Recent Advances in Plasmonic Probes

Lecture Notes in Nanoscale Science and Technology 33
Rajib Biswas
Nirmal Mazumder Editors
Recent
Advances in
Plasmonic
Probes
Theory and Practice
Lecture Notes in Nanoscale Science
and Technology
Volume 33
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Rajib Biswas • Nirmal Mazumder
Editors
Recent Advances
in Plasmonic Probes
Theory and Practice
Editors
Rajib Biswas Nirmal Mazumder
Department of Physics Department of Biophysics
Applied Optics and Photonics Lab Manipal School of Life Sciences
Tezpur University Manipal Academy of Higher Education
Tezpur, Assam, India Manipal, Karnataka, India
ISSN 2195-2159 ISSN 2195-2167 (electronic)

Lecture Notes in Nanoscale Science and Technology
ISBN 978-3-030-99490-7 ISBN 978-3-030-99491-4 (eBook)
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Preface
Plasmonic probes so far has come a long way. With the advent of sophisticated
fabrication process as well as coating process, it has become easier to make sensing
assays for various applications. Starting from measuring physical variables such as
temperature, pressure, and humidity, it has been applied in various disciplines such
as chemical, biological, civil, and architectural fields along with many other analyt-
ical schemes such as immunoassays, biomarkers, environmental indexing, and water
quality. In this context, we aim to provide a comprehensive glimpse of recent
advancements in plasmonic probes with a strong unification of theory and practices.
The main objective of the book is to present in-depth analysis of the theory,
properties, and practical implementations of novel probes based on plasmonics
that would be integrated with modern and future communications.
Recent Advances in Plasmonic Probes—Theory and Practice offers a unique
assimilation of theory and practices including principle of development, fabrication,
functionalization, integration, and implementation of these probes. With equal
emphasis on theory as well as practices, the book turns out to be synergistically
balanced. Although the book as a whole covers many aspects of plasmonic probes
with an intended bridge between theory, instrumentation, and applications, we have
taken utmost care to curate each chapter in order to make them more illustrative as
well as easily comprehensible. Hence, it is the outcome of extensive interactions and
fruitful discussion process, and this is meant for a wide spectrum of audience—
students, early-stage researchers, experts, scientists, etc.
The book is organized mainly into two parts: theory and applications. Chapters
“Fundamentals of Plasma Oscillation” and “Theory of Plasmonic Probes,” describe
the basic understanding of plasmonic techniques including plasma oscillation and
electronic excitations at metal surfaces. Chapter “An Analytic Overview of Equa-
tions of Substantial State in Plasmonic Perspective” briefs a compact overview of
diversified EoS extensively useful to characterize and describe different states of
matter in different physical conditions. The molecular scale plasmonic with the
enunciation of basic understanding of plasmonics have been comprehensively
discussed in chapter “Plasmonics Studies for Molecular Scale Optoelectronics.”
v
vi Preface
Chapter “Aluminum: A Sustainable Universal Plasmonic Material” deals with the

recent advancement of Al plasmonics in the UV, visible, and IR regime for surface-
enhanced Raman scattering, photo detection, color filters, photovoltaics,
photocatalytic, and nonlinear applications that are reported. Later, this chapter
explains Al plasmonics advanced applications in all the specific wavelength regimes.
The basic understanding of surface plasmon resonance (SPR) and its applications
in various fields are explained in chapters “Surface Plasmon Resonance Biosensors
Based on Kretschmann Configuration: Basic Instrumentation and Applications,”
“Plasmonic Nanoprobes for SERS-Based Theranostics Applications,” “2D
Nanomaterials-Based Surface Plasmon Resonance Probes for Biosensing Applica-
tions,” “Plasmonic Sensors: An Insight into Fundamentals, Compositions, and
Applications,” and “Improved Biosensor Device to Diagnose Malaria Based on
One-Dimensional Photonic Crystal”. Chapter “Surface Plasmon Resonance Bio-
sensors Based on Kretschmann Configuration: Basic Instrumentation and Applica-
tions” explains the basic instrumentation and reviews the recent trends in the
developments of Kretschmann configuration-based SPR biosensors with its appli-
cations. The various types of plasmonic nanoprobes that have been exploited for the
applications mentioned above and discussed their optical response upon interacting
with the electromagnetic wave have been briefed in chapter “Plasmonic Nanoprobes
for SERS-Based Theranostics Applications.” Chapter “2D Nanomaterials-Based
Surface Plasmon Resonance Probes for Biosensing Applications” summarizes the
recent advances in the development and applications of SPR sensors (integrated on
prism and optical fiber configuration) based on 2D nanomaterials. The basics of the
plasmonic optical principle, different types of plasmonic sensors based on propa-
gating SPR and localized surface plasmon resonances (LSPRs) are reviewed in
chapter “Plasmonic Sensors: An Insight into Fundamentals, Compositions, and
Applications.” Chapter “Improved Biosensor Device to Diagnose Malaria Based
on One-Dimensional Photonic Crystal” demonstrates one-dimensional photonic
crystal structure that can be used as a biosensor.
Development of different types of plasmonic probes, nanostructures, and
nanoparticles and their applications are demonstrated in chapters “U-Bent Fiber
Optic Plasmonic Sensors: Fundamentals, Applications, Challenges, and Future
Directions,” “An Appraisal on Plasmonic Heating of Nanostructures,” “Plasmonic
Nanoparticles for Polarization-Sensitive Analytical Techniques,” and “Synthesis,
Conjugation, and Applications of Chiral Nanoparticles as Plasmonic Probes.”
Chapter “U-Bent Fiber Optic Plasmonic Sensors: Fundamentals, Applications,
Challenges, and Future Directions” describes the development of U-bent plasmonic
probes with the highlight of a theory of sensing, fabrication methods, and important
sensor applications. A short review on thermo-plasmonic nanostructures with key
concepts in physics are highlighted in chapter “An Appraisal on Plasmonic Heating
of Nanostructures.” Chapter “Plasmonic Nanoparticles for Polarization-Sensitive
Analytical Techniques” discusses the applications and benefits of using various
types of plasmonic nanoparticles in polarization-sensitive spectroscopy techniques.
Also, the insight to the synthesis, conjugation, and application of chiral nanoparticles
as plasmonic probes are described in chapter “Synthesis, Conjugation, and
Preface vii
Applications of Chiral Nanoparticles as Plasmonic Probes.” Two chapters

(“Plasmonic Optical Imaging of Biological Samples” and “Deep Tissue High-
Resolution and Background-Free Imaging with Plasmonic SAX Microscopy”) are
dedicated to plasmonic optical imaging. Chapter “Plasmonic Optical Imaging of
Biological Samples” introduces the demonstration of plasmonic optical imaging
based on various microscopy techniques for biomedical applications. Saturation
Excitation (SAX) microscopy is developed to achieve improved resolution and
acquire background-free images from depths of animal tissues using nonlinear
plasmonic nanoparticle scattering as markers as explained in chapter “Deep Tissue
High-Resolution and Background-Free Imaging with Plasmonic SAX Microscopy.”
Chapter “Microfluidic Plasmonic Sensors: Theory and Applications” describes the
development of the microfluidic-based plasmonic sensors including their applica-
tions in biomedical engineering, chemical detection, environmental monitoring, etc.
Chapter “Polyoxometalate-Based Composite Materials in Sensing Applications”
presents the different classes of polyoxometalate-modified sensors alongside their
characterization and detection techniques in laboratory practices.
Chapter “Plasmonic Random Lasers” discusses and summarizes the research and
development efforts that are done to realize compact, high-power lasers using
plasmonic nanostructures.
Editing a contributed volume requires a great deal of coordination among authors,
reviewers, and editors for achieving this accomplishment. Barring aside a few
denials from solicited authors, it has been quite a satisfying journey. We express
our heartfelt gratitude to all authors who out of their busy schedule took time to pen
down their valuable contributions. Equally, we are highly indebted to all the referees
who with their meticulous scrutiny and suggestions helped us in revising the
contributions. We do believe that the readers of this book will be immensely
benefited from the aptly chosen titles and their corresponding versions. It is our
belief that we have been successful in unwinding the great potential of plasmonic
probes via in-depth discussion on theoretical treatment as well as varied practices.
Tezpur, Assam, India Rajib Biswas

Manipal, Karnataka, India Nirmal Mazumder
Acknowledgments
I am sincerely indebted to my mother, elder brother, and my spouse for their

relentless support and inspiration. I also owe special thanks to my brother cum
collaborator Dr. Nirmal Mazumder (Co-editor) for his invaluable effort and support
in editing this book. It is not an easy task to look for potential contributors as well as
persuading them to jot down their valuable contributions. Even after consent, there
happens to be declination from committed authors which put extra burden in finding
suitable replacements. Whatever may be the case, with continued support from my
co-editor, we have been able to pull this strain with combined and coordinated
endeavor. I am really indebted to all my contributors—without their help, this book
would not have been possible. We know that refereeing is a time-taking task without
any honorarium. Deep appreciation also goes to all esteemed referees who did their
job in the stipulated time and thus enabled us to get the revised manuscripts well
ahead of schedule. Most importantly, I sincerely express my heartfelt gratitude to Dr.
Sam Harrison for his constant guidance and support while preparing the edited
volume. His meticulous supervision in the drafting of the book proposal helped us
to design the best possible theme for the book. Last but not least, I express my
sincere appreciation to all who are directly or indirectly involved in preparing this
edited book.
Dr. Rajib Biswas
Tezpur, India
rajib@tezu.ernet.in
I am extremely grateful to the many people worldwide for numerous reasons
including discussion, inspiration, and help in preparing this plasmonic book. A
special thanks to Dr. Rajib Biswas (Editor) for his invaluable support in preparing
this book. I thank Prof. Fu-Jen Kao, National Chiao Tung Yang Ming University,
Taipei, Taiwan for his inspiration in many different ways. I am indebted to all
contributors, referees for their valuable time in preparing the chapters and reviewing
them in stipulated time. It would not be possible without them. I express my sincere
ix
x Acknowledgments
appreciation to all who are directly or indirectly involved in preparing this book. In
addition, I would like to thank Dr. Sam Harrison and the other editorial and
production team members of Springer. Their constant assistance during writing,
editing, and production cycles are much appreciated.
Nirmal Mazumder
Manipal, India
nirmaluva@gmail.com
Contents
Fundamentals of Plasma Oscillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

R. Moulick
Theory of Plasmonic Probes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
Tonmoy Gogoi, Sita Chettri, Prankrishna Borgohain, and Ritupan Sarmah
An Analytic Overview of Equations of Substantial State
in Plasmonic Perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
Pralay Kumar Karmakar and Siddhartha Saikia
Plasmonics Studies for Molecular Scale Optoelectronics . . . . . . . . . . . . . 121
Farhana Yasmin Rahaman, Anas Akhtar, and Abhijit Chandra Roy
Aluminum: A Sustainable Universal Plasmonic Materials . . . . . . . . . . . 171
Abhishek Dubey and Ta-Jen Yen
Surface Plasmon Resonance Biosensors Based on Kretschmann
Configuration: Basic Instrumentation and Applications . . . . . . . . . . . . . 191
Nishant Shukla, Pawan Chetri, Ratan Boruah, Ankur Gogoi,
and Gazi A. Ahmed
Plasmonic Nanoprobes for SERS-Based Theranostics
Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
Anindita Das and Rakesh S. Moirangthem
2D Nanomaterials-Based Surface Plasmon Resonance Probes
for Biosensing Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
Satya Pratap Singh, Siddharth Kaushik, and Umesh Tiwari
Plasmonic Sensors: An Insight into Fundamentals, Compositions,
and Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273
Bhavana Anchan, Gayathri Ajith Chakkadath, Ajeetkumar Patil,
Goutam Thakur, and Shounak De
xi
xii Contents
Improved Biosensor Device to Diagnose Malaria Based

on One-Dimensional Photonic Crystal . . . . . . . . . . . . . . . . . . . . . . . . . . 295
Ankita, Shivangi Bissa, Bhuvneshwer Suthar, and Anami Bhargava
U-Bent Fiber Optic Plasmonic Sensors: Fundamentals, Applications,
Challenges, and Future Directions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309
Christina Grace Danny, Hariharan Manoharan,
Sangeeta Yadav, V. V. R. Sai, and Jitendra Satija
An Appraisal on Plasmonic Heating of Nanostructures . . . . . . . . . . . . . 341
Upama Das, Nirmal Mazumder, and Rajib Biswas
Plasmonic Nanoparticles for Polarization-Sensitive
Analytical Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 355
Ishita Chakraborty, Soumyabrata Banik, and Nirmal Mazumder
Synthesis, Conjugation, and Applications of Chiral Nanoparticles
as Plasmonic Probes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 365
Manasa Gangadhar Shetty, Sindhoora Kaniyala Melanthota,
Nikhil Kumar Daimari, Rajib Biswas, Nirmal Mazumder,
and Kampa Sundara Babitha
Plasmonic Optical Imaging of Biological Samples . . . . . . . . . . . . . . . . . . 389
Priyal Dhawan, Priyasha De, K. M. Sindhoora, Nirmal Mazumder,
and Guan-Yu Zhuo
Deep Tissue High-resolution and Background-free Imaging
with Plasmonic SAX Microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 419
Gitanjal Deka, Bimalendu Deka, Kentaro Nishida,
Katsumasa Fujita, and Shi-Wei Chu
Microfluidic Plasmonic Sensors: Theory and Applications . . . . . . . . . . . 437
Rezoana Bente Arif and Tanujjal Bora
Polyoxometalate-Based Composite Materials
in Sensing Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 455
Sukanya Maity, Kumari Sweta, Partha Pratim Das, and Sib Sankar Mal
Plasmonic Random Lasers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 467
Pooja Naik, Al Ameen Abdul Nazar, and Junaid Masud Laskar
Contributors
Gazi A. Ahmed Department of Physics, Tezpur University, Tezpur, Assam, India

Anas Akhtar Department of Inorganic and Physical Chemistry, Indian Institute of
Science, Bangalore, Karnataka, India
Bhavana Anchan Department of Atomic and Molecular Physics, Manipal Acad-
emy of Higher Education, Manipal, India
Ankita Maharaja Ganga Singh University, Bikaner, Rajasthan, India
Department of Physics, Engineering College, Bikaner, Rajasthan, India
Rezoana Bente Arif Center of Excellence in Nanotechnology, School of Engineer-
ing and Technology, Asian Institute of Technology, Klong Luang, Pathumthani,
Thailand
Department of Electrical and Electronics Engineering, IUBAT-International Univer-
sity of Business Agriculture and Technology, Uttara, Dhaka, Bangladesh
Kampa Sundara Babitha Department of Biophysics, Manipal School of Life
Sciences, Manipal Academy of Higher Education, Manipal, Karnataka, India
Soumyabrata Banik Department of Biophysics, Manipal School of Life Sciences,
Manipal Academy of Higher Education, Manipal, Karnataka, India
Anami Bhargava Department of Physics, Govt. Dungar College, Bikaner, Rajas-
than, India
Shivangi Bissa Department of Physics, Engineering College, Bikaner, Rajasthan,
India
Rajib Biswas Department of Physics, Applied Optics and Photonics Lab, Tezpur
University, Tezpur, Assam, India
xiii
xiv Contributors
Tanujjal Bora Center of Excellence in Nanotechnology, School of Engineering

and Technology, Asian Institute of Technology, Klong Luang, Pathumthani,
Thailand
Prankrishna Borgohain Department of Physics, Tezpur University, Tezpur, India
Ratan Boruah Department of Physics, Tezpur University, Tezpur, Assam, India
Gayathri Ajith Chakkadath Department of Biomedical Engineering, Manipal
Institute of Technology, Manipal Academy of Higher Education, Manipal, India
Ishita Chakraborty Department of Biophysics, Manipal School of Life Sciences,
Pawan Chetri Department of Physics, D. R. College, Golaghat, Assam, India
Sita Chettri Department of Physics, Tezpur University, Tezpur, India
Shi-Wei Chu Department of Physics, National Taiwan University, Taipei, Taiwan
Brain Research Center, National Tsing Hua University, Hsinchu, Taiwan
Molecular Imaging Center, National Taiwan University, Taipei, Taiwan
Nikhil K. Daimari Applied Optics and Photonics Lab, Department of Physics,
Tezpur University, Tezpur, Assam, India
Christina Grace Danny Department of Electronics and Instrumentation Engineer-
ing, M.S. Ramaiah Institute of Technology, Bengaluru, Karnataka, India
Anindita Das Nanophotonics Lab, Department of Physics, Indian Institute of
Technology (Indian School of Mines), Dhanbad, Jharkhand, India
Partha Pratim Das Low Dimensional Physics Laboratory, Department of Physics,
National Institute of Technology Karnataka, Surathkal, Karnataka, India
Upama Das Applied Optics and Photonics Lab, Department of Physics, Tezpur
University, Tezpur, India
Bimalendu Deka North Eastern Hill University, Shillong, India
Gitanjal Deka Department of Physics, The Assam Royal Global University,
Guwahati, Assam, India
Priyasha De Graduate School of Medical Sciences, University Medical Center
Groningen, University of Groningen, Groningen, The Netherlands
Shounak De Department of Electronics and Communication Engineering, Manipal
Institute of Technology, Manipal Academy of Higher Education, Manipal, India
Priyal Dhawan Department of Biophysics, Manipal School of Life Sciences,
Abhishek Dubey Department of Materials Science and Engineering, National
Tsing Hua University, Hsinchu, Taiwan
Contributors xv
Katsumasa Fujita Department of Applied Physics, Osaka University, Osaka,

Japan
AIST-Osaka University Advanced Photonics and Biosensing Open Innovation
Laboratory, Osaka, Japan
Ankur Gogoi Department of Physics, Jagannath Barooah College, Jorhat, Assam,
India
Tonmoy Gogoi Department of Physics, Tezpur University, Tezpur, India
Pralay Kumar Karmakar Department of Physics, Tezpur University, Tezpur,
Assam, India
Siddharth Kaushik Department of Electrical Engineering, IIT Delhi, New Delhi,
India
Junaid Masud Laskar Nanophotonics Laboratory, Department of Physics and
Nanotechnology, SRM Institute of Science and Technology, Chennai, Tamil
Nadu, India
Sukanya Maity Low Dimensional Physics Laboratory, Department of Physics,
Sib Sankar Mal Materials and Catalysis Laboratory, Department of Chemistry,
Hariharan Manoharan Biomedical Engineering Laboratory, Department of
Applied Mechanics, Indian Institute of Technology Madras, Chennai, India
Nirmal Mazumder Department of Biophysics, Manipal School of Life Sciences,
Manipal Academy of Higher Education (MAHE), Manipal, Karnataka, India
Sindhoora Kaniyala Melanthota Department of Biophysics, Manipal School of
Life Sciences, Manipal Academy of Higher Education, Manipal, Karnataka, India
Rakesh S. Moirangthem Nanophotonics Lab, Department of Physics, Indian
Institute of Technology (Indian School of Mines), Dhanbad, Jharkhand, India
R. Moulick Centre of Plasma Physics, Institute for Plasma Research, Guwahati,
Assam, India
Pooja Naik Nanophotonics Laboratory, Department of Physics and Nanotechnol-
ogy, SRM Institute of Science and Technology, Chennai, Tamil Nadu, India
Al Ameen Abdul Nazar Nanophotonics Laboratory, Department of Physics and
Nanotechnology, SRM Institute of Science and Technology, Chennai, Tamil Nadu,
India
Kentaro Nishida Department of Physics, National Taiwan University, Taipei,
Taiwan
Department of Applied Physics, Osaka University, Osaka, Japan
xvi Contributors
Ajeetkumar Patil Department of Atomic and Molecular Physics, Manipal Acad-

emy of Higher Education, Manipal, India
Farhana Yasmin Rahaman Department of Physics, Indian Institute of Science,
Bangalore, Karnataka, India
Abhijit Chandra Roy Department of Physics, Indian Institute of Science, Banga-
lore, Karnataka, India
Siddhartha Saikia Department of Physical Sciences, Indian Institute of Science
Education and Research Kolkata (IISER-Kolkata), Mohanpur, West Bengal, India
V. V. R. Sai Biomedical Engineering Laboratory, Department of Applied Mechan-
ics, Indian Institute of Technology Madras, Chennai, India
Ritupan Sarmah Department of Physics, Tezpur University, Tezpur, India
Jitendra Satija Centre for Nanobiotechnology, Vellore Institute of Technology,
Vellore, Tamil Nadu, India
Manasa Gangadhar Shetty Department of Biophysics, Manipal School of Life
Sciences, Manipal Academy of Higher Education, Manipal, Karnataka, India
Nishant Shukla Department of Physics, Tezpur University, Tezpur, Assam, India
K. M. Sindhoora Department of Biophysics, Manipal School of Life Sciences,
Satya Pratap Singh CSIR-Central Scientific Instruments Organisation, Chandi-
garh, India
Bhuvneshwer Suthar Department of Physics, M.L.B. Govt. College, Nokha,
Bikaner, Rajasthan, India
Kumari Sweta Low Dimensional Physics Laboratory, Department of Physics,
Goutam Thakur Department of Biomedical Engineering, Manipal Institute of
Technology, Manipal Academy of Higher Education, Manipal, India
Umesh Tiwari CSIR-Central Scientific Instruments Organisation, Chandigarh,
India
Sangeeta Yadav School of Biosciences and Technology, Vellore Institute of
Technology, Vellore, Tamil Nadu, India
Centre for Nanobiotechnology, Vellore Institute of Technology, Vellore, Tamil
Nadu, India
Ta-Jen Yen Department of Materials Science and Engineering, National Tsing Hua
University, Hsinchu, Taiwan
Guan-Yu Zhuo Institute of New Drug Development, China Medical University,
Taichung, Taiwan
Fundamentals of Plasma Oscillation
R. Moulick
Abstract Plasma Oscillation is the most fundamental aspect of Plasma Physics. An

appropriate understanding and knowledge of the topic are important for those who
wish to begin studies on Plasma Physics. Moreover, the quantum of such plasma
oscillation is termed as the Plasmon. In this chapter, we intend to visualize the
plasma oscillation based on Particle-In-Cell (PIC) technique. Particle-In-Cell is a
particle-based computer simulation technique to simulate the bulk properties of
plasma. This chapter includes a discussion on the basic mechanism of the PIC
technique to visualize the plasma oscillation along with the code written in
MATLAB.
Key words Plasma oscillation · Plasmon · Particle-In-Cell (PIC) · Simulation ·

MATLAB
1 Introduction
Plasma is considered as one of the primitive states of matter in the universe.

Although it is termed as the fourth state of matter, it may be said as the first state
if we look at the evolution of the universe since the Big Bang. Almost 99% of the
visible universe consist of plasma state [1]. Plasma is a state of ionized gases with
neutral atoms dissociated in the form of ions and electrons. Thus, the state is much
like a soup of free electrons and ions. An important aspect of the plasma state is the
collective behavior, which means, the motion of particles not only depend on the
local conditions but the state of the plasma at far off distances also affect the motion.
However, plasma is quasi-neutral, by which we mean, although there may be a local
non-neutrality of charges, the plasma is overall neutral [1–4].
Electrons have low inertia and high thermal velocity, as a result, it is more mobile
than the ions. In many situations in modeling, especially regarding the plasma
R. Moulick (*)
Centre of Plasma Physics, Institute for Plasma Research, Guwahati, Assam, India
© The Author(s), under exclusive license to Springer Nature Switzerland AG 2022 1

R. Biswas, N. Mazumder (eds.), Recent Advances in Plasmonic Probes,
Lecture Notes in Nanoscale Science and Technology 33,
https://doi.org/10.1007/978-3-030-99491-4_1
2 R. Moulick
oscillation, the ions are considered to form a static background. The high thermal
velocity of electrons quickly sweeps the electrons away from the ionic background.
This act of separation forms an electric field which pulls the electrons back towards
the ions. However, due to the inertia of the electrons, they overshoot the location of
the ions and again generate an electric field in opposite direction to the previous one.
This electric field is responsible for the opposite motion of the electrons again. The
situation of electrons may be compared with a simple pendulum bob, which oscil-
lates about the mean position—much alike the electrons oscillate about the ions. This
oscillation is known as the plasma oscillation. Typical frequency of this oscillation is
dependent on the plasma density, however, in many situations it is of the order of
megahertz or gigahertz. This is a characteristic frequency of the plasma and is quite
important to achieve while preparing a laboratory plasma. A quantum of the plasma
oscillation is known as the plasmon. This is similar in concept as the light particles
are known as photons and the quantization of mechanical vibrations are known as
phonons. This chapter is dedicated to the understanding of fundamentals of the
plasma oscillation both theoretically and via numerical simulation.
We shall discuss in brief the Particle-In-Cell (PIC) technique which is a potential
simulation method in plasma [5–7]. There are a host of problems starting from
electric propulsion to magnetic fusion devices, which are solved using the Particle-
In-Cell technique [8–10]. As the name suggests, PIC is a particle-based technique,
where, raw simulation particles are sampled out of an appropriate velocity distribu-
tion such as Maxwell-Boltzmann and simulated over a numerical domain. From the
particle data, various field information such as density, velocity, and electric field are
collected. A particle mover computes the overall force acting on the particle and
pushes the particle forward in time. Along with this, a dedicated potential solver
solves for the electric potential and field.
2 Plasma Oscillation
Let us consider a small region in plasma. If the electrons are displaced from the
uniform background of ions, an electric field will be set up. The direction of this field
will be such that it tends to maintain the electrical neutrality of the charges. The field
produces a restoring force which is responsible for pulling the electrons back to their
original position. However, because of the inertia of the electrons, they overshoot the
location. Once again, an electric is produced opposite in direction to the previous one
and in this way an oscillation of electrons is sustained about the ions. The charac-
teristic frequency of this oscillation is known as the plasma oscillation. The ions, in
this case, are considered to form a static background.
In order to understand the process of plasma oscillation, let us follow the cold
plasma model, where the particle thermal motion and the pressure gradient force are
not taken into account [2]. We follow the procedure of linearization. Assuming the
amplitude of oscillation to be small, the higher powers of amplitude factors can be
neglected. All the dependent variables are separated into two parts, one, the
Fundamentals of Plasma Oscillation 3
equilibrium part and, the other, the perturbed part. Thereby, the electron density,
velocity, and the electric field are written as:
ne ¼ n0 þ n1
υe ¼ υ0 þ υ1
E ¼ E0 þ E1
Here, the suffix “0” denotes the equilibrium part and “1” denotes the perturbed
part. The equilibrium terms represent the state of the plasma in absence of the
oscillation. To obtain an expression for the plasma oscillation we follow the standard
fluid equations, viz., continuity equation, momentum equation coupled with the
Poisson’s equation.
The continuity equation is given by:
∂n ∂
þ ðnυÞ ¼ 0 ð1Þ
∂t ∂x
The momentum equation is written as:

∂υ ∂υ e
þυ ¼ E ð2Þ
∂t ∂x m e
And, the Poisson’s equation used for closing these set of fluid equations is
given by:

∂E e
¼ ðni ne Þ ð3Þ
∂x E0
Linearizing the continuity equation (1), we get,
∂ ∂
ðn0 þ n1 Þ þ ½ðn0 þ n1 Þðυ0 þ υ1 Þ ¼ 0
∂t ∂x
∂n1 ∂υ
) þ n0 1 ¼ 0 ð4Þ
∂t ∂x
Since, n0 is an equilibrium term, its first order derivative with time is zero. All
other terms arising in Eq. (4) are either higher order term or equilibrium term, and,
hence, neglected.
The oscillating quantities are assumed to behave sinusoidally. Thus, they can be
expressed as:
4 R. Moulick
n1 ¼ n1 exp ðiðkx ωt ÞÞ
υ1 ¼ υ1 exp ðiðkx ωt ÞÞbx
E ¼ E exp ðiðkx ωt ÞÞbx
Thus, we write for Eq. (4),
∂ ∂
ðn1 exp ðiðkx ωt ÞÞÞ þ n0 ðυ1 exp ðiðkx ωt ÞÞÞ ¼ 0
∂t ∂x
We write,
∂ ∂
! iω and ! ik:
∂t ∂x
Thus, simplifying we get,
ωn1 ¼ kn0 υ1 ð5Þ
Linearizing Eq. (2) we get,
∂ e
ðυ0 þ υ1 Þ ¼ ðE 0 þ E 1 Þ
∂t me
This eventually gives,
eE 1
iωυ1 ¼ ð6Þ
me
Again, from the Poisson’s equation, we get,
∂ e
ðE 0 þ E 1 Þ ¼ ððni0 þ ni1 Þ ðne0 þ ne1 ÞÞ
∂x E0
which we may write as:
ikE0 E 1 ¼ ene1 ð7Þ
The suffix “i” and “e” appears in the equation to differentiate between the ions
and electrons.
Combining Eqs. (5)–(7) we get,
rffiffiffiffiffiffiffiffiffi
n0 e 2
ω¼ ð8Þ
me E0
Equation (8) gives the required expression for the plasma frequency. It is seen that
the plasma oscillation frequency depends upon the equilibrium density only for a
specific type of plasma. If n0 ¼ 1018 m3, we have, f ¼ ω/2π ¼ 9 109 Hz.
3 Computational Modeling
Particle-In-Cell (PIC) technique provides an elite way of simulating the plasma. The
plasma oscillation can be tested for the oscillation of an electron surrounding the ion.
The brief algorithm for the Particle-In-Cell is as follows:
1. Load simulation particles to represent the real ions and electrons.
2. Use the particle position to compute the charge density.
3. Solve Poisson’s equation to get the plasma potential (∇2 ϕ ¼ Eρ0 ).
! !
4. Compute electric field (E ¼ ∇ϕ).
! !
5. Update particle velocity from Newton’s second law (m a ¼ qE ).
! !
6. Advance particle location using Δ x ¼ υ Δt.
7. Repeating the process 2–6.
The computational grid is as shown below (Fig. 1):
We have considered a periodic boundary condition, which computationally
means both of the red nodes are the same node only. This may be compared with
a torus, which is continuous in space. Particles leaving through the left boundary will
emerge into the domain through the right boundary. The electron is loaded at a
certain offset position from the ion. Since computationally it is difficult to simulate
every single ion and electron in the domain, Particle-In-Cell method works with the
concept of specific weight. Specific weight is defined as the ratio of the real numbers
of particles to the simulation particles. Thus,
N real
W¼
N sim
Total number of nodes present in the domain is:
ni ¼ Ion Slots Ion Spacing þ 1
Fig. 1 Computational domain. The domain contains 9 nodes and 8 cells. The first node is
considered as 0th node and the last is the 8th node. However, because of the periodic boundary,
0th and 8th nodes are the same nodes
6 R. Moulick
An important aspect of the plasma oscillation code is loading the ion density. In
this simulation, every 8 node is loaded with ions. For a quasi-neutral plasma, the ion
density should become equal to the plasma density and so is the electron density.
However, in this case, since ions are considered to form a static background, which
do not move, and hence the density of ions is present only on the loading nodes and
everywhere else it is zero. As a consequence, it is expected that the average ion
density over the nodes should become equal to the plasma density. Therefore,
ndi ¼ Plasma Density Ion Spacing
Please note that on the 9th node a new ion appears, and hence averaging is done
for the first 8th nodes. Thus, we load ndi ion density on the first node and the rest
7 nodes after the first has zero ion density. Again, on the 9th node there is ndi ion
density and so on. Thus,
ndi
W¼
1
We consider equal number of electrons as that of the ions to load in the domain
and set their velocity close to zero. The electrons are however positioned with some
offset to the ions so that an appropriate electric field is generated in order to start the
oscillation.
A MATLAB-based code is written to demonstrate the phenomenon of plasma
oscillation. In the following, Fig. 2 shows the phase space plot for the electron
oscillation and Fig. 3 depicts the positional oscillations with respect to time.
Fig. 2 Phase space plot of

the electron motion about
the ion
Fig. 3 Time evolution of the position of the electron
It is important to note that the density of the plasma is considered to be

n ¼ 109 m3. Accordingly, the theoretical plasma frequency is f ¼ 0.28 MHz. A
careful observation of the plot in Fig.3, shows the frequency in the order of MHz
thereby giving a pretty good benchmarking of the numerical results with that of the
theory. The reader is encouraged to play around with the code and observe the
parametric deviations in results. The OFFSET parameter is an important choice in
the code, which has been given a low value. Increasing the OFFSET parameter often
leads to the deviation of the simple harmonic behavior of the plasma oscillation.
4 Conclusion
This chapter deals with the understanding and visualization of the plasma oscillation.
Since plasmon is the quantum of plasma oscillation, it is important to understand the
nature of plasma oscillation in order to have a clear picture of the plasmon.
Furthermore, this chapter emphasizes on the use of the Particle-In-Cell technique,
which is a modern technique of particle simulation for rarefied and ionized gases.
Thus, this chapter will serve as an introduction for the novice.
8 R. Moulick
Acknowledgments The author would like to acknowledge Dr. Lubos Brieda, who taught the
author fundamentals of Particle-In-Cell technique. The basic ideas of much of the computational
techniques discussed in this chapter have been adopted from the course on “Fundamentals of the
Particle in Cell Method” delivered by Dr. Lubos Brieda.
Appendix: The MATLAB Code for Plasma Oscillation
clc; clearvars; close all;

%=============================================================
% The following program simulates a single electron in front of % a single
ion and shows the oscillations. Plasma density is
% restricted to 1E+9 per cubic meter. There are 9 grids and with % the
application of periodic boundary condition (PBC) the 1st % and the last
nodes are the same nodes. Ions are loaded every % 8th grid points from the
first. Gauss-Seidel Poisson solver
% is used.
%=============================================================
% Dr. Rakesh Moulick, (CPP-IPR)
%+++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++
format long
tic
%+++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++
% DEFINE PARAMETERS
%+++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++
EPS_0=8.85418782E-12;
ME=9.10938215E-31;
E=1.602176565e-19;
AMU=1.660538921e-27;
%-------------------------------------------------------------
PLASMA_DEN=1E9;
DH=1E-4;
DT=1E-9;
X0=0;
NUM_TS=10000;
ELE_PER_CELL=1;
ION_SPACING=8;
ION_SLOTS=1;
OFFSET=0.1;
%-------------------------------------------------------------
% INITIALIZATION
%-------------------------------------------------------------
ni=ION_SPACING*ION_SLOTS+1; % Number of grid points
% Define the field variables

phi = ones();
rho = ones ();
ef = ones ();
nde = ones ();

ndi = ones ();
% load ions
for i=1: ION_SLOTS+1
ndi((i-1) *ION_SPACING+1) = PLASMA_DEN*ION_SPACING;
end
% Set particle specific weight
spwt=(PLASMA_DEN*ION_SPACING*DH)/1.0;
% Number of electrons is same as the ions

num_ele=ION_SLOTS;
% Memory space for electrons

ele_pos(1:num_ele) = 1;
ele_vel(1:num_ele) = 1;
% Set domain length

XL=DH*(ni-1);
% load stationary electrons, offset by 4 nodes to the right from the ion
for i=1: ION_SLOTS
ele_pos(i)=X0+DH*(1+(i-1) *ION_SPACING+OFFSET);
ele_vel(i)=0.002;
end
% open file to trace electrons

file_trace=fopen('trace.txt','w');
%fprintf (file_trace,'Variables= time pos vel\n');
% open file for results

file_res=fopen('results.txt','w');
%fprintf (file_res,'Variables= x nde ndi phi rho\n');
%-------------------------------------------------------------
% MAIN LOOP
%-------------------------------------------------------------
TIME_START=0;
for ts=TIME_START:NUM_TS
format long
% clear data
nde(1:ni) = 0;
% Scatter particles to the mesh

for p=1:num_ele
li=(ele_pos(p)-X0)/DH;
i=floor(li);
di=li-i;
10 R. Moulick
nde(i+1) = nde(i+1) +spwt*(1-di);

nde(i+2) = nde(i+2) +spwt*(di);
end
% Divide by cell volume to get density

nde(1:ni) = nde(1:ni)/DH;
% Apply periodic boundary condition

nde(1) = nde(1) + nde(ni);
nde(ni)= nde(1)
% Compute charge density
rho(1:ni) = E*(ndi(1:ni)-nde(1:ni));
% Reset potential
phi(1:ni) = 0;
%=============================================================
% Poisson's Solver
%=============================================================
% Solve for potential
for solver_it=0:5000
% left and right nodes are at fixed 0 volts
phi(1)=0;
phi(ni)=0;
% Gauss seidel method
for i=2:ni-1
im=i-1; %if im<1, im=ni-1; end
ip=i+1; %if ip>ni, ip=2; end
phi(i)=0.5*(phi(im)+phi(ip)+DH*DH*rho(i)/EPS_0);
end
if (mod(solver_it,25)==0)
sum=0;
for i=2:ni-1
im=i-1; %if im<1, im=ni-1; end
ip=i+1; %if ip>ni, ip=2; end
R=-rho(i)/EPS_0 - (phi(im)+phi(ip)- 2*phi(i))/(DH*DH);
sum=sum+R*R;
end
L2=sqrt(sum/ni);
if(L2<1e-6)
break;
end
end
end
% Compute the electric field

ef(1)=-(phi(2)-phi(ni-1))/(2*DH); % Central difference at left
ef(ni)=-(phi(2)-phi(ni-1))/(2*DH); % Central difference at right
%ef(1)=-(phi(2)-phi(1))/(DH); % Forward Difference

%ef(ni)=-(phi(ni)-phi(ni-1))/(DH); % Backward Difference
for i=2:ni-1
ef(i)=-(phi(i+1)-phi(i-1))/(2*DH); % Central difference
end
% Push particles back by half time step the first time through
if (ts==TIME_START)
for p=1:num_ele
i=floor(li);
di=li-i;
% Gather electric field onto the particle position

part_ef=ef(i+1)*(1-di)+ef(i+2)*(di);
% Rewind velocity by 0.5*DT

ele_vel(p)=ele_vel(p)-0.5*DT*(-E/ME)*part_ef;
end
end
% Push particles
for p=1:num_ele
% Compute particle node position

i=floor(li);
di=li-i;
% Gather electric field onto particle position

part_ef=ef(i+1)*(1-di)+ef(i+2)*(di);
% Advance velocity
ele_vel(p)=ele_vel(p)+DT*(-E/ME)*part_ef;
% Advance position
ele_pos(p)=ele_pos(p)+DT*ele_vel(p);
% Take care of particle that left the domain

if (ele_pos(p)<X0)
ele_pos(p)=ele_pos(p)+XL;
elseif (ele_pos(p)>=(X0+XL))
ele_pos(p)=ele_pos(p)-XL;
end
pos = ele_pos(1);
% Adjust position to get continuous trace of particle

if (pos>=0.5*XL)
pos=pos-XL;
end
end
12 R. Moulick
if (mod(ts,100)==0)
disp(ts)
end
fprintf(file_trace,'%15.5g %15.5g %15.5g\n',ts*DT, pos,ele_vel
(1));
% Periodically save results

if (mod(ts,100)==0)
for i=1:ni
X(i)=(i-1)*DH;
fprintf(file_res,'%15.5g %15.5g %15.5g %15.5g %15.5g %15.5g\n',X
(i), nde(i),ndi(i),phi(i),rho(i),ef(i));
end
% Plotting figure
figure(1)
plot(X,nde,'r',X,ndi,'b','linewidth',2),grid on,
xlabel('x (m)'),ylabel('Number Density (m^{-3})')
title(ts)
pause(0.1)
end
TIME_START=TIME_START+1;
end
toc;
In addition to this code, the following code is used for processing the
generated file.
clc; clearvars;
load trace.txt;
t = trace(:,1);
x = trace(:,2);
v = trace(:,3);
figure(1)
plot(x,v,'r','linew',1), grid on
axis([min(x) max(x) min(v) max(v)])
axis('square')
xlabel('Position'), ylabel('Velocity')
figure(2)
plot(t,x,'r', 'linew',2), grid on
xlabel('Time'), ylabel('Position')
%----------------------------------------------------------
% Calculate the theoretical frequency
me=9.10938215E-31;
e=1.602176565e-19;
n0=1E12;
eps0=8.85418782E-12;
w0 = sqrt((n0*e^2)/(me*eps0));
f = w0/(2*pi);
fprintf('f: %10.2f MHz\n',w0/(2*pi*1e6));
References
1. F. Chen, Introduction to Plasma Physics and Controlled Fusion (Springer International Pub-
lishing, Cham, 2016)
2. J.A. Bittencourt, Fundamentals of Plasma Physics, 3rd edn. (Springer, New York, 2004)
3. D. Bohm, E.P. Gross, Theory of plasma oscillations. A. Origin of medium-like behavior. Phys.
Rev. 75(12), 1851–1864 (1949). https://doi.org/10.1103/PhysRev.75.1851
4. H. Motz, Plasma oscillations. Rep. Prog. Phys. 29(2), 305 (1966). https://doi.org/10.1088/0034-
4885/29/2/305
5. A.L. Langdon, C.K. Birdsall, Plasma Physics Via Computer Simulation, 1st edn. (Taylor &
Francis, New York, 2005)
6. D. Sydorenko, Particle-in-Cell Simulations of Electron Dynamics in Low Pressure Discharges
with Magnetic Fields, Jun 2006
7. L. Brieda, Plasma Simulations by Example, 1st edn. (CRC Press, Boca Raton, 2020)
8. M. Keidar et al., Electric propulsion for small satellites. Plasma Phys. Control. Fusion 57(1),
014005 (2015). https://doi.org/10.1088/0741-3335/57/1/014005
9. B. Scheiner, S.D. Baalrud, M.M. Hopkins, B.T. Yee, E.V. Barnat, Particle-in-cell study of the
ion-to-electron sheath transition. Phys. Plasmas 23(8), 083510 (2016). https://doi.org/10.1063/
1.4960382
10. S. Adhikari, R. Moulick, K.S. Goswami, Ion dynamics in a magnetized source-collector sheath.
Phys. Plasmas 25(9), 094504 (2018). https://doi.org/10.1063/1.5045186
Theory of Plasmonic Probes
Tonmoy Gogoi, Sita Chettri, Prankrishna Borgohain, and Ritupan Sarmah
Abstract Collective excitations of electrons at metal surfaces play a fundamental

role in a wide range of science ranging from physics to life sciences. With the recent
advent of miniaturization and the development of micro- and nanometer scale
technology, surface plasmon-based probes have become inevitable. Recent studies
demonstrate the effectiveness of surface plasmon sensors over conventional optical
sensors lifting its limitations. Here we present a brief review of the theoretical
description of various collective electronic excitations at metal surfaces.
Key word Collective behavior · Plasmons · Surface plasmon polariton · Localized

surface plasmons · Nanoparticle array
1 Introduction
The optical properties that emerge due to interactions between light and matter
manifest as wonderful displays in nature. The beautiful color display in peacock
feathers, colors of butterfly wings, and the appearance of mirages are some spectac-
ular examples in nature that have fascinated humankind since medieval times. There
also exist some artificial creations which baffled scientists for a long time. For
example, the stained-glass windows of Cathedrals and the Lycurgus cup from the
Roman empire (fourth century AD), shown in Fig. 1, appear greenish in reflected
light and red in transmitted light [1]. The mystery of the color change of the
Lycurgus cup was not solved until the end of the last century and is attributed to
Sita Chettri and Prankrishna Borgohain contributed equally with all other contributors.
T. Gogoi · S. Chettri · P. Borgohain · R. Sarmah (*)

Department of Physics, Tezpur University, Tezpur, India
e-mail: tonmoy@tezu.ernet.in; sitaphd@tezu.ernet.in; prankrishna@tezu.ernet.in;
ritupan@tezu.ernet.in

https://doi.org/10.1007/978-3-030-99491-4_2
16 T. Gogoi et al.
Fig. 1 The color display in the Lycurgus cup [2, 3]
the use of nano-sized metal particles by Roman glassmakers [1]. Artists have also
been using nanoparticles of different sizes in their artworks and artifacts for ages.
The discovery of Maxwell that light is an electromagnetic (EM) wave and that of
the electron as the elementary charge carrier by J.J. Thomson in the last century,
marked the beginning of modern science around which many areas of physics have
been developed, ranging from quantum mechanics to condensed matter physics. Due
to possible technological applications and academic interest, the interplay of light
and matter has continued to draw the attention of scientists till today [4–7]. The
invention of transistors mid last century has revolutionized the field of electronics.
With the advancement of technology, emphasis is on miniaturization and develop-
ment of micro- and nanoelectronics devices owing to their broad-ranged applica-
tions. However, the efficiency of electronic devices drops as size decreases due to
thermal noise as well as signal delay. On the contrary, photonic devices have high
efficiency in terms of speed as well as data-carrying capacity, but constraint by
device size is limited to about half of its operational wavelength governed by the
diffraction law. Thus, the need for alternative methods to probe into subwavelength
regimes arises and plasmonic devices have proved to be an excellent candidate since
the early 1990s. Standing at the interface of electronics, photonics, and nanotech-
nology, plasmonic have provided means to accomplish investigations in the
sub-nanometre length scales where the electronic and photonic devices are not
enough.
The field of plasmonics is concerned with the study and usage of plasmons in
various devices and applications. Plasmonic excitations represent collective modes
of vibrations of electrons within the conduction band of metal. Two types of
plasmonic modes are used for applications—one propagating, called surface
plasmon polariton and, the other, localized surface plasmon. The propagating
Theory of Plasmonic Probes 17
plasmons are generated and propagate usually on metal-dielectric interfaces. On the

other hand, the localized plasmons are confined within nanoparticles (NPs) and are
characterized by local enhancement of the electric field at optical frequencies
[8]. The coupling of these collective modes with light in metal NPs shows in brilliant
colors and gives rise to new optical effects at the nanoscales [4, 8]. The localization
and enhancement of electric fields find novel applications in nanoelectronics, tele-
communications, optical imaging, and biomedicines among others.
This chapter starts with a brief introduction to the field of plasmonics in Sect. 1,
followed by a discussion on the classical theory of plasmons in Sect. 2. Section 3
discusses the propagating collective excitations, SPP, and methods to excite these
modes. A similar treatment of localized surface plasmons is presented in Sect. 4. In
Sects. 5 and 6, we discuss the theoretical approach to address the plasmon-plasmon
coupling in simple and complex nanostructures with regard to classical and quantum
mechanical treatments. Finally, we conclude this chapter in Sect. 7. The area of
plasmonics is ever extending with emerging new concepts; however, the choice of
the topics in this chapter is to provide the readers a basic foundation in this field.
2 Classical Theory of Plasmons
For the sake of completeness, we briefly introduce the classical theory of plasmons,
derived using classical electrodynamics. The optical properties of metals, over a
wide range of frequencies, are explained using Drude’s free electron model and their
interaction with the electromagnetic (EM) fields [9]. Metals contain free electrons
that move in the background of ionic cores. When metals are exposed to EM
radiation, the oscillating electric field exerts a force on these negatively charged
free electrons and drives them to move in the direction opposite to the applied field
and tries to screen the radiation field. Under the suitable condition, as the momentum
of the incident EM radiation become comparable to that of the electrons, they
oscillate resonantly with the EM field. The quanta of these collective oscillations
of the electrons are called plasmons, more specifically bulk plasmons. Thus, classi-
cally plasmon represents a self-sustained spatially oscillating charge density wave
coupled with the EM field.
In the presence of an oscillating electric field E(x, t) E0 exp [i(k x – ωt)] of the
EM radiation, the free electrons start to oscillate. Their motion is damped through a
characteristic collisions time scale γ 1τ . At the room temperature, typi-
cally τ~1014 s. Mathematically, the equations of motion for such collection of
free electrons is described by
me€x þ me γ x_ ¼ eE ðx, t Þ ð1Þ
where x is the displacement, γ is the damping coefficient, and me and e are the
effective mass and charge of the electron, respectively. It is well known that the
optical properties of a system are governed by frequency response of its complex
18 T. Gogoi et al.
dielectric constant E(ω) ¼ Er(ω) + iEim(ω). Further, the complex refractive

pffiffiffiffiffiffiffiffiffi index and
dielectric constant is connected through ηðωÞ ¼ hηr ðωÞ þ iκ ðωÞ ¼ EðωÞ. This rela-
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi i
tion may further be simplified to write ηr ðωÞ ¼ Er ðωÞ þ Er ðωÞ þ E2im ðωÞ=2 1=2
2
and κ(ω) ¼ Eim(ω)/2ηr(ω). It is to note that while ηr(ω) accounts for the dispersion,
κ(ω) determines the absorption in the medium [8]. In the absence of an external
source, Maxwell’s wave equation in Fourier domain takes the form
ω2
kðk E Þ k 2 E ¼ Eðk, ωÞ E, ð2Þ
c2
where k represents the wave vector and c is the speed of light in free space. Note that
the dielectric constant, in general, depends both on wave vector as well as frequency.
However, in the limit of long wavelength compared to characteristic length scales
involved in the system, the response becomes homogeneous which reduces E(k, ω) to
E(ω). Further, we note that Eq. (2) supports two propagating modes depending on the
response of dielectric function to frequency and the polarization of the associated
electric field. The transverse mode represented by k E ¼ 0 results in the dispersion
k2 ¼ E(ω)ω2/c2, while it also supports a longitudinal mode (k k E) at frequencies that
satisfy E(ω) ¼ 0. Using the solution of Eq. (1), the frequency-dependent complex
dielectric response of the free conduction electrons is given by
ω2p τ2
E ð ωÞ ¼ 1 , ð3Þ
ω2 τ2 þ iωτ
qffiffiffiffiffiffiffi
where ωp ¼ ne2
E0 me , n and E0 represents electron density and permittivity of free
space, respectively. The characteristic frequency ωp at which the conduction elec-
trons oscillate collectively is called the plasma frequency [10]. For most metals and
noble metals, ωp 1016 s1 falls in the near-ultraviolet regime. The real and
imaginary parts of this dielectric constant become

1 þ ω2 ω2p τ2
E r ð ωÞ ¼ , ð4Þ
1 þ ω2 τ 2
ω2p τ
Eim ðωÞ ¼ : ð5Þ
ωð 1 þ ω 2 τ 2 Þ
The dispersion relation of the EM radiation in the metal is obtained using ω ¼

pffiffiffiffiffiffiffiffiffi
ck= EðωÞ. We can understand the role of characteristic collision frequency 1/τ on
the optical properties by studying the response of the dielectric functions as a
function of frequency at different regimes of frequencies.
At very low frequencies ωτ 1, Eim q Erffiffiffiffiffiffiffiffiffiffiffiffiffi
. As a consequence, metals absorb EM
radiation with absorption coefficient α ¼ 2ω2p ωτ=c. Since k is imaginary in this
Fig. 2 Dispersion relation

of Drude’s free electron gas
regime, the EM radiation field decays exponentially with distance inside the metal
with a skin depth δ ¼ 2/α [8]. However, the validity of the description is limited to
the fact that the mean free path of the electrons λ vFτ δ, where vF is the Fermi
velocity. At high frequencies ωτ 1, there are two possibilities (a) ω < ωp and
(b) ω > ωp. In case of ω < ωp, for a large range of frequencies, the approximation is
valid and the damping term iωτ can be neglected leading E(ω) to
ω 2
p
EðωÞ ¼ 1 : ð6Þ
ω
Thus,q
the dispersion ffi relation for the EM radiation in metal in this limit becomes
ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ωðkÞ ¼ ωp þ k c , as shown in Fig. 2. It is easy to see that, below plasma
2 2 2
frequency ωp, E(ω) becomes real and negative (see Eq. 6) that leads to total reflection
(Reflectivity R ¼ 1) which explains why metals appear shiny at the visible range. In
this range, EM radiation does not propagate inside the metals. However, for ω > ωp,
E(ω) is real and positive and k is real, and therefore the wave propagates into the
metals. It is clear from Fig. 2 that transverse mode is allowed only above ωp with a
group velocity falling below that of the EM radiation in free space.
Interestingly at ω ¼ ωp, corresponding to long wavelength limit k ! 0 for
negligible damping, E(ω) vanishes, suggesting the existence of a collective longitu-
dinal mode. Thus, at ω ¼ ωp, the electric field behaves as a pure depolarizing field.
The physical interpretation is that all the free electrons of the conduction electron gas
undergo a simple harmonic motion in phase with a collective oscillation frequency
of ωp in the fixed background of ions. The quantum of these collective modes of
charge oscillations are called plasmons or more specifically, bulk plasmons
[10]. These excitations are longitudinal and therefore do not couple to transverse
EM waves. We note that bulk plasmons exist only in regimes where the metal
becomes transparent to EM radiation and cannot be localized since ω(k) is larger
than the frequency of incident EM radiation. Therefore, they are considered to be
short-lived and also break down on internal defects or surfaces. On the other hand,
the existence of longitudinal bulk plasmons in metals depends on spatial dispersion
since the dielectric response is a function of wave vector as well.
20 T. Gogoi et al.
2.1 Interband Transition and Real Metals
Despite its simplicity and classical origin, the Drude model effectively describes the
optical properties of many metals at low frequencies. However, it fails significantly
to predict the properties of noble metals such as Cu, Au, and Ag in the near-infrared
and visible regime. Interestingly, these simple metals possess finite frequency
absorption that gives their beautiful colors attributed to the existence of high
dissipative loss arising due to interband transitions, where electrons from the filled
band below the Fermi energy are excited to a higher band [8]. Interband transition
refers to the transitions where the electrons in the metals are excited by the incident
photon to make a transition from one energy level to another. As the energy of the
incident photon of EM radiation exceeds the energy gap between valence and
conduction bands, one bound electron acquires it and jumps to an unoccupied
state in the conduction band that creates a transient dipole moment. The excited
electron may further transit to the valence band through stimulated emission or
spontaneously emitting the photon. Classically, the interband transition of the bound
electron is incorporated by replacing Drude’s model with a damped harmonic
oscillator called the Drude-Lorentz model given by
me€x þ me γ x_ þ me ω20 x ¼ eE ðx, t Þ, ð7Þ
where me is the effective mass of the electron, e is the charge of the electron, γ is the
damping coefficient, and ω0 is the resonance frequency of the bound electron
[10]. Then, the frequency-dependent dielectric response modifies to
f2
ω
EðωÞ ¼ 1 þ 2
p
, ð8Þ
ω0 ω2 iγω
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
where ωep ¼ e ne2 =mE0 with e n being the density of the bound electrons. The Drude-
Lorentz model lifts the limitation of the Drude model in describing the optical
properties of silver and gold in the visible regime [8].
In the following sections, the two collective modes of surface plasmons are
discussed in detail.
3 Surface Plasmon Polaritons
Surface plasmon polaritons (SPPs) are two-dimensional longitudinal propagating

evanescent EM waves confined at metal-dielectric interfaces [8]. The propagation
constant of these inhomogeneous plane waves in the orthogonal direction to the
interface is imaginary, and therefore the fields decay exponentially away from the
interface. These waves are coupled coherently with the collective oscillations of
conduction electrons on the surface of the metal. The emergence of SPPs at the
metal-dielectric interface is attributed to the long-range strong resonant Coulomb
coupling [8]. In two-dimensional surfaces, such as thin films or interfaces, these
oscillations are confined at the surface leading to a propagating surface charge wave
known as the surface plasmon polariton (SPP). Polariton refers to the transformation
of the volume oscillations occurring in bulk materials to propagating surface waves
at metal-dielectric interfaces [11]. The existence of such propagating surface waves
with the corresponding boundary conditions was first introduced by Zenneck [12]
while solving Maxwell’s equation (see Eq. 2) and subsequently the polaritons were
demonstrated by Ritchie, Powell, and Swan [13]. Due to this coherent interaction
with collective charge oscillations, SPPs have greater momentum than a free space
EM wave of the same frequency. Interestingly, SPPs can confine the energy of the
wave at the interface. The longitudinal nature of SPPs suggests that the translational
invariance of EM waves breaks down at the interface, to allow EM radiation a mixed
polarization. It ensures that SPP waves can only be excited through transverse
magnetic (TM) polarized EM radiation, under the condition that the phase of the
tangential wave vector matches that of surface plasmons along with the metal-
dielectric interface. We note that TM polarization is needed for the generation of
plasma distribution in the metal-dielectric interface while no surface mode exists for
transverse electric (TE) polarization [8]. Classically, SPPs can be studied by solving
Maxwell’s equation at the metal-dielectric interface.
Consider an interface at z ¼ 0, separating a semi-infinite dielectric medium
occupying the half-space z > 0, characterized by a positive and real dielectric
constant Ed, and a metal slab with a complex frequency-dependent dielectric constant
Em(ω) that occupies the other half-space z < 0, as shown in Fig. 3. The electric and
magnetic field of an incident wave of frequency ω in TM polarized state, propagating
along the x direction at the metal-dielectric interface can be written as

Es ðk, ωÞ ¼ E sksx , 0, E sksz exp ksz jzj exp i k sx x ωt ,

H s ðk, ωÞ ¼ 0, H sy , 0 exp ksz jzj exp i k sx x ωt , ð9Þ
Fig. 3 Interface separating

two semi-infinite dielectric
and metallic slabs with
dielectric functions Ed and
Em(ω), respectively
22 T. Gogoi et al.
where s ¼ m, d represent metal and dielectric and kz and kx are the z and x components
of the wave vector, respectively. Writing k ¼ k x ebx þ kz ebz and using sourceless
2 2
Maxwell’s wave Eq. (2), we arrive at ksz þ k sx ¼ Es ω2 =c2 . Thus, the inverse
decay length of the field in the two media, respectively, are given by
rhffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiiffi
d 2
kdz ¼ k x Ed ω2 =c2 , ð10Þ
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
h i
2
z ¼
km km x Em ðωÞω2 =c2 : ð11Þ
Applying continuity of fields at the interface, we get
km kd
z
þ z ¼ 0: ð12Þ
Em Ed
Using this relation together with the phase matching condition, i.e., kdx ¼ k m
x ¼ k x,
of the field along the propagating x direction, we arrive at the dispersion relation
1
ω Ed Em ðωÞ 2
kx ðωÞ ¼ kSPP : ð13Þ
c Ed þ Em ðωÞ
Substituting this result in Eqs. (10) and (11), the inverse decay lengths for the two
media become
1
ω E2d 2
kdz ðωÞ ¼ , ð14Þ
c E d þ E m ð ωÞ
1
ω E2m ðωÞ 2
z ð ωÞ
km ¼
c Ed þ Em ðωÞ
: ð15Þ
The wave vector kSPP(ω) in Eq. (13) represents the surface plasmon wave vector.
This relation is called
the dispersion
relation of the propagating SPPs. It is clear from
Eq. (9) that Re kdz and Re km z must be positive to represent a surface wave. This
condition may be achieved in two ways, (a) Em(ω) is real and negative and (b) Em(ω)
is complex with non-negative imaginary parts, which results in a complex wave
vector (see Eq. 13). The first condition is easily satisfied in the case of metals for
frequencies in the optical range. The second condition represents a lossy medium. In
both cases, a real surface plasmon wave vector can be obtained as long as dielectric
constants are of opposite sign and satisfy Re[Em(ω)] < Ed [8]. Replacing the
frequency-dependent dielectric constant of metals with the Drude model for the
conduction electrons in the non-dissipative limit, i.e., replacing Em(ω) by Eq. (6), the
dispersion relation for the SPPs in metal can be written as
Fig. 4 Dispersion relation

of SPP
2
1 þ Ed ðck SPP Þ
ω4 ω2 ω2p þ ðck SPP Þ2 þ ω2p ¼ 0: ð16Þ
Ed Ed
A plot of Eq. (16) is shown in Fig. 4. We can see that the dispersion equation has
two branches. The lower branch (shown in red) corresponds to the SPPs. At the low
pffiffiffiffi
value of ω, the dispersion curve approaches the light line ω ¼ ck= Ed of the
dielectric medium. In this branch, ω reaches a maximum value of ωSP ¼
pffiffiffiffiffiffiffiffiffiffiffiffi
ωp = 1 þ Ed for large k. The crossover between these two lines indicates the
formation of SPPs. The entire SPP branch lies below the light line meaning that
the SPPs carry more momentum and thus longer wavelength (λSPP ¼ 2π/kSPP) than
the incident radiation in the metal surface. The SPPs in this regime are non-radiative.
The propagation length for the SPPs reads
1
L¼ : ð17Þ
2Imfk SPP g
In the visible EM spectrum, typical range of L is 1–100 μm [14]. The penetration

depth, the length from
the interface at which the strength of SPPs falls by a factor of
1/e is lp ¼ 1= Re ksz . Both the propagation length and penetration depth depend on
frequency in this regime. The upper branch starts above plasma frequency ωp and
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
grows asymptotically as ωn ¼ ck ð1 þ Ed Þ=Ed indicating volume plasmons. In the
regime between ωSP and ωp, the EM wave suffers strong decay along the propaga-
tion direction, and therefore plasmon modes are forbidden.
3.1 Excitation of SPPs at Interfaces
Surface plasmon polaritons propagating at the metal-dielectric interface are confined

by the condition that propagation wave vector kSPP is greater than that of EM wave in
the dielectric. As seen from Fig. 4, the dispersion curve corresponding to SPPs lies
24 T. Gogoi et al.
below the light line in the dielectric (kSPP > k dx ) implying that direct illumination of
EM radiation on the metal-dielectric interface is not sufficient for the excitation of
SPPs. Special techniques must be employed in order to make up for this momentum
deficit. One of the ways to achieve this phase matching is by using a three-layer
system, where a thin metal film is inserted between two dielectrics with different
dielectric constants, E [8]. Usually, a prism is used as the dielectric with the higher E
and we can assume the other dielectric to be air (E ¼ 1). If a beam of photons with
momentum k is reflected at the prism-metal
pffiffi interface at an angle θ, then the in-plane
momentum in the metal will be k E sin θ. The fields of this beam will be tunnelled
through the metal to the metal-air interface by a process called attenuated total
internal reflection. The in-plane momentum of the tunnelled photons now is suffi-
cient to support SPPs at the metal-air interface.
Two geometries are used for prism coupling: Kretschmann configuration [15] and
Otto configuration [16]. In the Kretschmann geometry, shown in Fig. 5a, the metal
film is placed on top of the glass prism and a beam is incident through the prism. As
long as the angle of incidence is larger than the critical angle for total internal
reflection, the beam excites SPPs at the metal-air interface [8]. In some physical
systems where direct contact is undesirable, the Otto configuration, shown in Fig. 5b,
can be used. In this geometry, an air gap exists between the metal and the prism.
Similar to the Kretschmann geometry, a total internal reflection occurs at the prism-
metal interface for incidence angle greater than the critical angle, and SPPs are
Fig. 5 A schematic of different techniques used for the excitation of SPPs at metal-dielectric
interfaces (a) Kretschmann configuration, (b) Otto configuration and (c) grating coupling
excited at the air-metal interface after tunnelling through the air gap. However, it is
difficult to control the width of the air gap experimentally.
Apart from the prism coupling, an alternative way to excite the surface plasmons
is by using a grating coupler, as shown in Fig. 5c. Here the metal surface is patterned
with a periodic grating of grooves, separated by a distance a. If the incident light
makes an angle θ with the normal and has a wavevector k, the SPP excitation is
possible when the condition kSPP ¼ k sin θ ng is satisfied, where g ¼ 2π a represents
the reciprocal lattice vector of the grating and n ¼ 1, 2, 3, . . . is a positive integer.
4 Localized Surface Plasmons
Localized surface plasmons (LSPs) are non-propagating collective plasmon oscilla-

tions on metallic nanostructures. In Sect. 3, we discussed the two-dimensional
propagating plasmonic excitation SPPs and showed that the frequency of SPPs
depend on the dielectric constants at the interface and that these modes cannot be
excited by direct EM radiation. Typically, the local EM field corresponding to SPPs
extends ~100–200 nm into the dielectric.
Any difference in local environment at the interface within this distance bring
changes in the dielectric constant, causing a redshift of the oscillation frequency.
These limitations of SPPs are lifted by reducing the two-dimensional metal interface
to a zero-dimensional NP. For NPs smaller than the wavelength of incident EM
radiation, the oscillating electric field can be assumed to be constant across the NP,
inducing uniform displacement of the conduction electrons. These driven free
conduction electrons feel a strong effective restoring force from the background
positive ionic core, limited by the geometry of the NP, similar to a simple harmonic
oscillator. The resonance occurs when the frequency of these collective excitation
matches with the frequency of EM radiation in the metal NP. Since the surface
plasmon wave cannot propagate beyond the size of the particle, these modes are
localized. This phenomenon is called localized surface plasmon resonance (LSPR)
[4]. The resonance frequency depends strongly on the local environment, shape,
size, and composition of the particle [17, 18]. For Au and Ag NP, the resonance
frequency falls in the visible region [4]. The resonant enhancement of absorption and
scattering of LSPR results in the bright colors exhibited by metallic NPs both in
reflected and transmitted light. The staining of glass for windows of cathedrals and
Lycurgus cup of the Roman empire are some famous examples of LSPR. Unlike
SPPs, LSPs are excited by incident EM radiation. The additional momentum for
resonance is provided by the geometry of the NP. Due to its simplicity, LSPs can be
used as an alternative to SPPs in various applications such as light transformation
and light manipulation at the nanoscale level [19, 20], field concentrators [21],
nanotweezers [22], and active optical elements [23].
26 T. Gogoi et al.
Fig. 6 A schematic of oscillating dipoles created by the conduction electrons at the surface with
electric field during interaction of light with metallic NP
We now discuss LSPs by considering a simple model to arrive at resonant

conditions. For simplicity, consider a homogeneous, isotropic spherical metallic
NP of radius a with complex frequency-dependent dielectric constant Em(ω) located
at the origin is surrounded by a non-absorbing isotropic medium with dielectric
constant Ed. In quasistatic approximation, the size 2a of a particle is considered to be
much smaller than the wavelength (2a λ) of the incident EM radiation in that
medium [4]. Thus, the electric field corresponding to the EM radiation is assumed to
remain constant over the particle volume. This approximation allows to simplify the
problem of the spatial distribution of the field to a particle in a static electric field, say
E ¼ E 0 ebz . When the light is incident on the metallic NP, the associated EM field
exerts a force on the free electrons of the metal NP. As a result, the conduction
electrons move towards the NP surface as shown in Fig. 6. Thus, the accumulation of
opposite charges occurs on either side, giving rise to a transient electric dipole. The
resultant dipole creates a retarded electric field ER inside the NP, i.e., in the direction
opposite to that of the light, which acts like a restoring force [8].
The electric field of the spherical NP can be obtained by solving the Laplace’s
equation ∇2ϕ ¼ 0 in spherical coordinate and using E ¼ ∇ ϕ. Using azimuthal
symmetry and boundary conditions at the interface r ¼ a, the electric field, inside Ein
and outside Eout are given by,
3Ed
E in ¼ E , ð18Þ
Em þ 2Ed 0

! ! ! !
3n n p p 1
E out ¼ E0 þ , ð19Þ
4πE0 Ed r3
where n ¼ r =r is the unit vector and !

! !
p is the induced dipole moment [9]. In
presence of the external field, the induced dipole moment of the NP is expressed as,
! Em Ed !
p ¼ 4πE0 Ed a3 E : ð20Þ
Em þ 2Ed 0
Notice that the strength of the induced dipole moment inside the NP scales
linearly with the strength of the external field. Then, the polarizability α defined
! !
through p ¼ E0 Ed α E 0 become
Em Ed
α ¼ 4πa3 : ð21Þ
Em þ 2Ed
The polarizability corresponding to the spherical metallic NP in the quasistatic

approximation resembles the Clausius-Mosotti relation [9]. For small metallic NP
a λ the ideal dipole moment of quasistatic approximation is valid and the
oscillating electric field may be expressed as E(r, t) E0 exp (iωt). The complex
dielectric constant of the metallic NP for the incident EM radiation is Em(ω).
Equation (21) suggests that the polarizability experiences a resonant enhancement
when the denominator |Em + 2Ed| is minimized. For small and slow varying Im
[Em(ω)], the resonance condition is simplified to Re[Em(ω)] ¼ 2Ed. This condition
is known as the Fröhlich resonance condition [8]. The resonance frequency shows a
strong dependence on the dielectric constant of the medium and undergoes a redshift
as a function of increasing Ed. This suggests that metal NPs could serve as a good
candidate for optical sensing. In addition, the resonance in polarizability α(ω) also
implies a resonant enhancement of dipolar fields. The scattering cross section (σ sc) of
the spherical metallic NP [8] is given by,
2
8πk4 a6 Em ðωÞ Ed
σ sc ¼ , ð22Þ
3 Em ðωÞ þ 2Ed
where k ¼ 2π/λ. The absorption cross section is,

Em ðωÞ Ed
σ ab ¼ 4πka Im
3
: ð23Þ
Em ðωÞ þ 2Ed
Then, the extinction cross section [8, 24] is defined as the sum of the scattering
and absorption cross section. For the spherical NP of radius a and dielectric function
Em(ω) ¼ Er + iEim, the extinction cross section, i.e., σ ext ¼ σ sc + σ ab is given by,
3=2
24π 2 a3 Ed Eim
σ ext ¼ : ð24Þ
λ ðEr þ 2Ed Þ2 þ E2im
From Eqs. (22) and (23), it is clear that while scattering scales as a6, absorption
process scales with a3. As a consequence, large particles will be scattering EM
radiation whereas absorption dominates for smaller particles. The color change
effects appear at the transition between the two regimes. For example, small Au
28 T. Gogoi et al.
particles appear red as it absorbs green and blue, while large Au particles scatter in
the green, and thus appear greenish. However, the theory of the dipole NP plasmon
resonance breaks down for large particles since the dipole approximation is not valid
due to spatial inhomogeneity of the driving field over the volume of the particle. For
such systems, Gustav Mie had developed a complete theory for spherical NPs that
explains the colors of colloidal Au particles [25]. For the Mie theory, readers are
referred to the following textbooks on electromagnetism [9, 26].
4.1 Effect of Geometry and Medium on LSPR
The optical properties of LSPR are greatly affected by the geometry and surrounding
media (see Eq. 21) of the NP [27]. The geometry includes both size and shape of
NP. The effect of size of the NP can be understood by subdividing it into two distinct
regimes, (1) small NP (size λ of incident light) and (2) large NP, comparable to
the wavelength of light [27]. For small NP, radius a 50 nm, the quasistatic
approximation is valid and can be described by the oscillating dipole model
discussed in Sect. 4. The size of the NP in this regime primarily affects the intensity
and width of the resonance band [27]. The full width half maxima FWHM (Γ) is
found to be linearly proportional to the inverse of the NP radius (as shown in the
inset of Fig. 7b). The surface plasmon resonance (SPR) band of the NP is assumed to
follow the relation
n
Γ¼mþ ,
a
where m and n are material-dependent constants. Figure 7a shows dependence of the

absorption spectra of Ag NP for different sizes. It is clear from the figure that
Fig. 7 (a) Absorption spectrum for Ag NPs for different nanoparticle sizes calculated using the
Mie theory and (b) linear relationship between FWHM and the inverse of the radius. (Reproduced
with permission [27])
Fig. 8 Absorption
spectrum for Au NPs with
10 nm size in a dielectric
medium with different
dielectric functions
calculated according to the
Mie theory. (Reproduced
with permission [27])
intensity of the absorption band increases, while the FWHM at resonance decreases
with the size of NP.
For large NP (in the second regime), the quasistatic approximation fails and the
NP cannot be approximated by the dipole model due to inhomogeneous displace-
ment of the electronic cloud. Their description demands the inclusion of multipolar
terms. As the NP size is further increased, the SP becomes propagating with well-
defined modes.
The restoring force of SPs depends on the charge accumulated on the surface of
NP and is strongly influenced by the shape of the NP as well. In geometries such as
nanorods, cube, or triangular-shaped NP, resonance shifts towards a larger wave-
length in comparison to that of spherical NP [27, 28]. Apart from size and shape, it is
evident from Eq. (21) that the LSPs also get affected by its surrounding media. From
the Fröhlich condition of resonance, it is clear that at the resonance, intensity
depends on the dielectric response of the surrounding medium as well as on the
imaginary part of the dielectric constant of the metal NP. Figure 8 shows the
dependence of intensity of the resonance band for different values of the dielectric
function of the medium [27].
5 Nanoparticle Arrays and Plasmon-Plasmon Coupling
In this section, we focus our attention on an ensemble of metallic NPs ordered in

one-dimensional arrays. The effect of size and shape on LSPR of single NP suggests
that an additional shift from Fröhlich resonance condition is expected in the NP
30 T. Gogoi et al.
arrays due to the presence of EM coupling between the LSPR. Indeed, for small NPs
(radius a λ), the array of NPs can be approximated as an ensemble of coupled
dipoles. It has been found that when the metallic NPs are arranged in an array of
wavelength scales, a new resonance mode emerges that goes by the name surface
lattice resonance (SLR). SLRs attract attention for their interaction with emissive
species, both concerning light emission [29] and strong coupling between lattice
resonances and excitons [30]. In addition, metallic NP arrays find importance in
metamaterial research as well [31, 32].
We now discuss about the resonant condition for the array of NPs approximated
as an ensemble of coupled dipoles. Consider N spherical NPs, each of radius a are
arranged in a one-dimensional array separated by the interparticle spacing d such that
a d. In this case, the quasistatic dipole approximation is valid and each NP can be
treated to be point dipoles. In this approximation, known as coupled dipole approx-
imation (CDA), the NPs are substituted by an array of electric dipole p! i at position
!
ri (i ¼ 1, 2, 3, . . ., N ) with polarizability αi. When an EM wave Ein
! ! !
E 0 exp i k r is incident on this one-dimensional NPs array, the field induces
!i !i
electric dipole in each particle position ri given by !
pi ¼ αi E loc. Here, E loc represents
the local electric field experienced by each dipole at the position ri. The local field is
!i
the vector sum of incident (E in) and the retarded field created by the (N 1) dipoles
!i !i
(E dipole ) [4, 33]. Then, E loc is given by
!i
! X
N
E loc ¼ E 0 exp i k !
ri þ ξij !
p j, ð25Þ
j¼1, j6¼i
where ξij is the dipole interaction matrix and the second term may be expressed as
! !
!
r ij r ij p j
ξij !
p j ¼ k2 exp ik:r ij 3
exp ik !
r ij þ 1 ik:r!
ij
r ij
h i
r 2ij !
p j 3r! ! !
ij r ij p j
, ð26Þ
r 5ij
where !r ij is the separation between ith and jth dipole. For analytical solution of
Eq. (26), consider an infinite array of identical NPs of polarizability α with equal
induced polarization. Then, the polarization of each particle is given by
E0
p¼ ,
1=α S
where S represents the dipolar sum [33, 34]. The extinction cross section per particle
for such an array of NPs [4] can be written as,
Fig. 9 Extinction cross section per particle for an isolated single particle to that of an NP array.
(Reproduced with permission [33])

p
σ ext ¼ 4πkIm :
E0
A comparison of extinction cross section per particle [33] for an NP array to that
of a single NP is shown in Fig. 9. It can be seen from Fig. 9 that the resonance
response of the NP array shifts towards a longer wavelength accompanied by a
sharper resonance peak compared to that of a single particle.
The validity of CDA is limited by the size of the NPs. However, for larger
particles with typical size (size/λ ! 0.1), the dipole approximation is not sufficient
to interpret its optical responses and requires the inclusion of high order retardation
effects. Two key effects due to the retardation are dynamic depolarization and
radiative damping. Dynamic depolarization arises when retardation in electric fields
is created due to spatial variations of the charge distribution. The radiation damping
is attributed to the accelerating charges of the oscillating dipole produced by incident
EM radiation. Though the problem may be addressed within the context of Mie
theory [18], there is no simple approach to model the collective optical response of
NP arrays. Alternative approaches are also proposed recently to address the optical
responses of NP arrays [35–37].
32 T. Gogoi et al.
6 Plasmonics of Complex Nanostructures
In previous sections, we discussed the plasmonic resonance of NPs with simple

structures, such as single and periodic arrays. However, for a complex collection of
nanostructures, a shift in plasmon resonance is noticed compared to its single
constituents, suggesting the emergence of collective modes due to aggregation.
Further, even a pair of NPs, when placed extremely close to each other (separation
<10 nm), is sufficient to give rise to such a shift [38]. Understanding this plasmon
resonance, which is highly sensitive to the nanostructure geometry, helps in the
tunability and better designing of probes. Another interesting property of these
complex nanostructures is their unusual high local enhancement of EM fields
when irradiated with light. This remarkably high local field enhancement (~1014
times) finds its applications in plasmonics, namely the surface-enhanced Raman
scattering (SERS) [39, 40].
In an attempt to explain the plasmonic responses of complex nanostructures, a
plasmon hybridization model was developed [41]. The model accounts for the
coupling between plasmon modes of individual nanostructures in an analogy of
how individual atomic orbitals get hybridized to form molecular orbitals in the
molecular orbital theory [5]. In this model, the collection of free electrons in the
nanostructure is assumed to represent an incompressible, irrotational fluid in the
background of uniform positive ionic core and the plasmons are regarded as defor-
mations in this fluid [5]. Prodan et al. has successfully applied the plasmon hybrid-
ization model to calculate the resonance frequency of a hollow metallic nanosphere
or nanoshell [41]. In their analysis, plasmon interaction leads to the hybridization of
individual plasmon energies, resulting in the splitting of the plasmon resonance into
two new branches. One is with lower energy, symmetric or “bonding” resonance,
and the other is the high energy, antisymmetric, or “antibonding” resonance
[41]. Similar hybridization analyses have also been carried out for other
nanostructures such as NP pairs (called “dimers”), thin metallic films [42], nanostars
[43], and nano matryoshkas [41].
6.1 Nanoparticle Dimers
Interestingly, in the case of an NP dimer, when the incident light is polarized along
the interparticle axis, the collective plasmon mode acquires a redshift, due to the
hybridization of the individual NP plasmons [44]. In the first approximation, this
hybridization can be considered to be only between the dipolar modes. Similar to
nanoshells, the resultant plasmon resonance splits into “bonding” and “antibonding”
modes as well. The antibonding mode has higher energy compared to the bonding
mode. However, these two modes couple differently to incident EM radiation. The
lower energy mode is a result of the parallel alignment of NP dipoles, which creates a
large dipole moment that helps to couple strongly to the far-field [5]. This mode is
radiative and is called bright mode. While in the high energy, antibonding mode, the
dipoles align antiparallelly resulting in the net-zero dipole. In this case, the far-field
coupling is weak and is called a dark mode. The bright mode dominates the optical
properties of a plasmonic dimer. An important parameter of this dimer hybridization
is the separation between the NPs. The collective plasmon mode shows an increasing
redshift as the separation decreases. In contrast, if the exciting light is polarized
orthogonal to the interparticle axis, a progressive blueshift is observed with decreas-
ing separation [44]. Experimental as well as theoretical investigations on optical
properties of NP dimers (for longitudinally polarized light) show that in contrast to
the redshift as the NP gets closer, a blueshift is observed once it starts overlapping
[38, 45]. This suggests the existence of a crossover in the spectrum between the
non-overlapping and overlapping regimes. The blueshift in the overlapping region is
attributed to the flow of electrons between the two particles known as charge transfer
plasmon mode [45]. The classical electromagnetic approach successfully predicts
the extinction properties in both these regimes. However, the transition from the
non-overlapping to the overlapping regime, where electron starts tunneling cannot
be addressed by the classical approach. Hence, for a complete description, a quantum
approach is necessary.
Another inadequacy of the classical approach is its inability to properly calculate
the local field enhancement once the overlapping between the particles starts. In this
regime, increasing electron tunneling decreases the field enhancement, whereas in
the classical description further enhancements are predicted. The quantum
approaches try to overcome this shortcoming.
6.2 Quantum Mechanical Description
6.2.1 Density Functional Approach
The quantum mechanical approach to study the dynamics of plasmon hybridization

in complex nanostructures was first introduced by Zuloaga et al. in 2009. They have
applied the time-dependent density functional theory (TDDFT) [46] to model the
optical responses of an NP dimer. In the density functional theory approach, the
many-body wavefunction of the complex nanostructure is approximated by an
effective single-particle electron density scheme, called the Kohn-Sham scheme,
and the time evolution of the electron density is obtained by solving the Schrödinger
equation with an effective potential. They employed a jellium model within the time-
dependent local density approximation (TDLDA) framework to study the NP pairs.
In the jellium model, the charge distribution of the positive ion cores is replaced with
a constant positive background [47]. The approach successfully captures the
decreased field enhancement and a smooth transition from non-overlapping to
overlapping regimes for NP dimers with a small number of conduction electrons.
In their study, the uniform charge density replacing the positive ionic background
was taken to be n0, fixed at a Wigner-Seitz cell of radius rs ¼ 3b, where
b ~ 0.0529 nm is the Bohr radius. The effective potential for the electrons in the
metal was taken as follows,
34 T. Gogoi et al.
Z
nð r 0 Þ n0 ð r 0 Þ 0
V eff ðr Þ ¼ V 0 ðr Þ þ dr þ vxc ½n ,
jr r 0 j
where vxc[n] is the exchange-correlation potential, n(r) denotes the electron density,
and V0(r) is the uniform background potential from the ionic background. Within the
TDLDA, the linear response in the frequency-dependent density fluctuation Δn is
expressed as
Z h i
δV
Δnðr, ωÞ ¼ dr 0 χ 0 ðr, r 0 ; ωÞ vext þ eff Δn ðr 0 , ωÞ, ð27Þ
δn
where χ 0 is the unscreened density-density correlation function, Veff is the effective

potential, and vext(r, ω) is an external driving potential, which for an external EM
field can be written as, vext(r, ω) ¼ E0 ∙ reiωt. Equation (27) can be solved to obtain
Δn, and thereby the induced dipole moment
Z
pðωÞ ¼ rΔnðr, ωÞdr:
Assuming linear response, the induced dipole moment can be written as

p ð ωÞ ¼ b
αðωÞE0 , with bαðωÞas the polarizability tensor. Then the absorption cross
section σ(ω) can be calculated using σ ðωÞ ¼ ω=cIm½b αðωÞ .
Figure 10 shows the optical absorption spectra obtained in this approach for two
different systems of NP dimers with radii R ¼ 16b and 24b, containing 302 and 1018
conduction electrons. The optical absorption σ(ω) plots against the energy of
incident EM radiation as the separation d between the sphere’s changes. A mono-
tonic redshift is observed as the separation distance decreases until about d ¼ 10b,
expected since at this distance quantum effects can be ignored, to approximate it as a
classical system. However, as separation decreases, in the region 3b < d < 10b, the
Fig. 10 Absorption spectra

using TDLDA for two types
of nanoparticle dimers:
R ¼ 16b (left) and R ¼ 24b
(right); as the separations
change: d ¼ 0, 1, 2, 3, 4,
5, 6, 7, 8, 10, 12, 14, 16,
20, 24b from bottom to top.
(Reprinted with permission
from [46]. Copyright
© 2009, American Chemical
Society)
quantum tunnelling of electrons becomes dominant. The tunnelling of electrons

reduces EM coupling by reducing the electric field across the junction and sup-
presses the redshift. As the separation is lowered further, due to more overlapping,
the conductance of the gap increases and a blueshift is observed. These observations
suggest that by incorporating the quantum aspect of the junction, the TDDFT model
captures the gap between the non-overlapping and overlapping states of the NP
dimer.
6.2.2 Quantum Correction Model
A limitation of TDDFT is that the results are reliable only for small systems,
containing only a few thousand conduction electrons. However, in reality, systems
of NPs contain more than millions of such electrons. In 2012, a novel approach
called “Quantum Correction Model (QCM)” was introduced by Esteban et al. In the
model, they incorporate quantum corrections into the existing classical model
[48]. The central idea of QCM is to introduce a fictitious dielectric material in the
junction between the NPs that allows electron tunnelling. Similar to the classical
description, the NP boundaries are assumed to be sharp and abrupt. The electron
tunnelling probability is used to find the separation-dependent junction permittivity
E(l, ω), where l is the dimer separation, and, subsequently, the extinction cross
section is calculated. Within the context of this model, the conductivity σ(l, ω) and
the dielectric function of the fictitious material are related through,
ω
σ ðl, ωÞ ¼ i ½Eðl, ωÞ 1 : ð28Þ
4π
Assuming a Drude’s model response at resonance for the fictitious material, the
dielectric constant is represented by,
ωg 2
Eðl, ωÞ ¼ E1 , ð29Þ
ω ω þ iγ g ðlÞ
where ωg is the plasmon frequency of the material in the gap, E1 is the screening
effect from the bound electrons of the fictitious material and γ g(l) represents
damping of separation-dependent tunnelling. For simplicity, ωg and E1 can be
taken to be the same as that of the surrounding medium, i.e., ωg ¼ ωp, E1 ¼ 1.
Due to the high resistive nature of the gap (γ g ω), the static conductivity σ 0(l)
(ω ! 0) is used to obtain γ g(l) and is expressed as
ωg 2
γ g ðlÞ ¼ :
4πσ 0 ðlÞ
36 T. Gogoi et al.
The dependence of conductivity on separation can be obtained from the relation

between the current density J along the gap and the electric field E. Assuming a
homogeneous flow of the tunnelling electrons along the electric field, the approach
of static scanning tunnelling microscopy is used. Since the radii of curvature of the
NPs are much larger than the junction separation and electron’s Fermi wavelength,
the NP dimer can be approximated as two metal slabs separated by the fictitious
material. Then, the NP dimer reduces to a simple model of tunnelling between two
flat metal surfaces, which is used for the calculation of tunnelling current (see
Fig. 11a). Then, the dc conductivity and the tunnelling current is related by,
ZμF
l
σ 0 ðlÞ ¼ 2 T ðE, lÞdE, ð30Þ
2π
0
where μF is the Fermi energy and T(E, l) represents the energy-dependent electron
tunnelling
R μ probability. A plot of normalized tunnelling transmissions, defined as
T ðlÞ ¼ 0 F T ðE, lÞdE , is shown in Fig. 11b. The local permittivity E(l, ω) can be
calculated using Eq. (29) from γ g(l).
A comparison of extinction cross section and the local field enhancement of the
spherical NP dimer junction, in the three distinct approaches, TDDFT (a, b), QCM
(c, d), and classical EM (e, f), is shown in Fig. 12. Each of the NP is assumed to
contain Ne ¼ 1074 electrons. The extinction spectra show a redshift in the
non-overlapping regime ( 5 Å) and a blueshift in the overlapping regime ( 1 Å)
in all three approaches. However, the crossover between the overlapping and the
non-overlapping regime is predicted only by the quantum approaches TDDFT and
QCM. Figure 12b, d,and f shows the comparison of EM field enhancements in three
different approaches. It is easy to see that the classical description predicts high field
enhancement even in the overlapping regime. However, the quantum approaches
adequately capture the decreased field enhancements attributed to electron tunnelling
in the overlapping regime.
Fig. 11 (a) Simplified

model potential for the
plasmonic system: two
plane interfaces with a
dielectric of length l,
permittivity E(l, ω), and
tunnelling T(l ). (b)
Normalized tunnelling
transmission through the
junction. Red and blue
curves correspond to Na and
Au systems, respectively
[48]
Fig. 12 Comparison of extinction spectra and field enhancement among the three approaches:
QM-TDDFT (a, b), QCM (c, d), and classical (e, f). Note that D is used instead of l to denote the
shortest separation between the two jellium NPs [48]
We note that due to the limitations of system dimension in TDDFT calculation,

the QCM is preferable for physical systems of NPs with large numbers of electrons.
For a detailed discussion, readers may refer to [48].
7 Summary and Conclusion
In summary, we systematically presented the fundamental theories of plasmonics.

Exposed to EM radiation, the conduction electrons in metals undergo collective
oscillations, called plasmons. The interaction of plasmons with light often gives rise
to interesting optical effects. The classical Drude free electron model explains the
optical properties of metals in the low-frequency regime. However, it fails to capture
the properties of noble metals, such as Cu, Au, and Ag, in the near-infrared and
visible regime, attributed to the interband transition of electrons [8]. The Drude-
Lorentz model lifts the limitations of the Drude model by incorporating the interband
transition classically. Confinement of plasmons is possible by reducing the system
dimension. Indeed, a new propagative collective mode known as SPP emerges when
plasmons confined at the metal-dielectric interface are coupled strongly with EM
radiation. The SPP resonance shows a strong dependence on the dielectric response
of the surrounding media. The long-range Coulomb coupling enables the SPPs to
carry higher momentum than the EM radiation itself. Thus, direct illumination of
light cannot produce SPPs at the metal-dielectric interface. However, to overcome
the momentum mismatch, special techniques such as prism coupling and gratings are
used. Once generated, SPPs can guide as probes. The extreme confinement of these
38 T. Gogoi et al.
SPPs and the inability to excite with direct illumination of light put limitations on
their applications. By reducing the size of the metals to zero-dimensional NP, a new
localized plasmonic mode called LSP emerges in the metallic NP. Unlike SPPs,
these localized collective modes can be excited with direct light. Since these modes
are localized, and the resonance strongly depends on the surrounding medium,
LSP-based probes are preferable over SPP for practical applications. However, the
optical properties of the LSPs are affected by shape, size, and compositions as well.
While the absorbance peak increases with the size, the FWHM scales inversely with
the radius of the spherical NPs. The dependence on size leads to exploring the
possibilities of these NPs when arranged in an ordered array. The plasmonic
resonance of the NP arrays shows highly localized resonance bands with longer
wavelengths. As a result, the efficiency of devices using NP arrays increases
dramatically. The narrow bands displayed by the NP arrays at resonance are attrib-
uted to the strong coupling between LSPs of individual NPs. Remarkably, the
coupled dipole approximation adequately describes the highly localized plasmonic
resonance. However, in complex nanostructures, a shift in the plasmon resonance is
observed. In fact, a pair of NPs close to each other (separation <10 nm) is sufficient
to show the redshift. The NP dimer also shows a blueshift in the overlapping regions
of the dimer. Incidentally, the junction between the NP dimer shows a high enhance-
ment in EM radiation. This property is successfully applied to enhance weak Raman
spectra in SERS. In the classical approach, the plasmon hybridization model cap-
tures the redshift. However, as the two particles start overlapping, electrons tunnel
and a blueshift appear. Although the classical hybridization approach captures the
blueshift, it fails to demonstrate a smooth crossover from red to blueshift, since it
cannot account for electron tunnelling, and a quantum mechanical approach is
required to resolve this issue. Two quantum mechanical approaches are used to
describe the smooth transition between the red and blueshift. We briefly outline the
concepts of the two quantum approaches, TDDFT and QCM, which successfully
predict the optical properties of overlapping NP dimers. The limitations of the
number of electrons considered in TDDFT suggest that QCM is a preferred model
for large complex nanostructures.
The field of plasmonic probes is expanding rapidly in recent years, as new and
more exciting directions (e.g., strong coupling in the past decade [7]) are getting
explored, for efficient devices based on plasmonic properties.
Acknowledgments TG and SC would like to acknowledge Tezpur University, India for financial
support in carrying out this work. PB acknowledges support from DST-INSPIRE for the Fellowship
[IF190022].
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An Analytic Overview of Equations
of Substantial State in Plasmonic
Perspective
Pralay Kumar Karmakar and Siddhartha Saikia
Abstract It is a usual practice to assume that matter and its various phases in normal
configuration extensively obey a polytropic equation of state (EoS) with a general-
ized semiempirical pressure-density functional relationship, P ¼ f(ρ), a polytropic
law or a polytropic rule. This law is explicitly given as P ¼ KPρΓ, ¼ KPρ1+(1/nP);
where KP is called the polytropic constant, Γ is called the polytropic exponent, and
nP ¼ (Γ 1)1 is called the polytropic index. After this basic thermodynamical
coordinate relationship, there exists a wide variety of EoS, useful to describe and
map matter in various realistic phases. The various thermo-functional relationships
go fairly in accordance with various predicted experimental findings and observa-
tions, such as plasmonic probe measurements, Joulean calorimetric investigations,
and four-probe findings. This mobilized contribution briefs a compact overview of
diversified EoS extensively useful to characterize and describe different states of
matter in different physical conditions. The EoS piecewise relevance is appropriately
briefed and actualized. It ends up with comparative and critical analyses of the same
graphically alongside a clear indication of the possible future refinements for broad
applicability in various circumstances.
Key words Polytropic · Equation of state · Exponent · Thermo-functional ·

Plasmonic probe · States of matter
P. K. Karmakar (*)
Department of Physics, Tezpur University, Tezpur, Assam, India
e-mail: pkk@tezu.ernet.in
S. Saikia
Department of Physical Sciences, Indian Institute of Science Education and Research Kolkata
(IISER-Kolkata), Mohanpur, West Bengal, India

https://doi.org/10.1007/978-3-030-99491-4_3
42 P. K. Karmakar and S. Saikia
1 Introduction
It is well known that an equation of state (EoS) is an organic mathematical relation-

ship among the various relevant thermodynamic coordinates describing the distinct
states of matter in different thermophysical conditions macroscopically [1–5]. In
other words, it is usually a semiempirical functional relationship describing the
correlative connection among the various thermodynamical coordinates, such as
the pressure, volume, temperature, and/or entropy of a material [6–18]. It actually
depicts the interdependent functional correlations among the relevant thermody-
namic factors [19, 20]. It throws light on how the elastic properties of the composing
material of a system vary in response to contraction and/or expansion [8, 21]. Thus,
it can offer basic thermodynamic data needed to investigate the equilibrium phase
diagrams and the microphysical insights about the interatomic interactions in any
state of matter.
It is to be noted that most of the existing EoS available in the literature are focused
on describing the pure states of matter feasible for the application of the general
thermodynamical principles [21–24]. The EoS can be usually derived from the basic
postulates of the thermodynamical behaviors and thermostatistical mechanical laws
exhibited by the constituent building elements of the system [25]. An extensive
realization of the EoS mostly relies on the experimental precisional measurements of
the relevant physical properties obtained through various models describing differ-
ent exotic states of matter, and so forth.
The most general form of an EoS in terms of the usual thermodynamical variables
can be expressed in a usual generalized functional form as, f(P, V, T, S) ¼ 0; where
S represents the entropy of the system [1–7]. An EoS should be so constructed that it
could take care of the macroscopic phase behaviors on a global scale. Various
complications are bound to occur in the EoS if the collective thermo-mechanical
correlative effects among the constitutive species are to be exactly considered
without any quasi-classic approximation of the traditional type.
It may be pertinent to add further that the role of various probes and techniques,
such as plasmonic probes (two probe, four probe, NMR probe), can never be ignored
in the active context of experimental study of matter and its various states in different
thermophysical configurations [8, 26]. Application of various sophisticated fabrica-
tion techniques and coating processes has clearly offered a broad way to make
sensing assay for various technological exploration and large-scale uses [27]. Prob-
ing the relevant physical variables, such as temperature, pressure, humidity, and
internal energy, has extended to various interdisciplinary sectors, such as chemistry,
biology, nanoscience and technology, geophysics, architectural engineering, and so
for [26, 28–30]. The technological applications of various investigated EoS are yet to
be well understood in the mysterious world of smart materials in different states and
their socioeconomic applications promoting human civilization. In this context, the
developmental mechanism of the next generation of nanoscale optical devices and
other nanoelectromechanical sub-devices indeed requires new theoretical tools and
techniques that could include the prominent application features from the classical to
An Analytic Overview of Equations of Substantial State. . . 43
the quantum world [26]. Such tropical issues have interdisciplinary relevance,
including the thermophysical and electromagnetic properties of nanoparticles, and
so forth [28, 29]. It, hereby, empowers us to state that there has long been a great
necessity to put forward a systematic nontrivial study of the various EoS relevant in
various states of matter at least in a theoretical perspective, but bearing a top-rated
industrial and technological applicability yet to be well explored.
In the course of time, different kinds of EoS to illustrate matter and its distinct
phases have been extensively formulated in numerous emerging multidisciplinary
fields of science, engineering, and technology. The primitive form of an EoS has
been developed by an Irish physicist and chemist, Robert Boyle, back in 1662, while
performing a number of physical and chemical experiments on a fixed amount of
gas, trapped inside a J-shaped glass tube. Gradual addition of mercury through one
end of the tube has been performed to determine the volume and the pressure of the
subsequent gas [3]. Later, a number of EoS, such as those due to the laws proposed
by Jacques Charles, John Dalton, Amedeo Avogadro, and Emile Clapeyron, have
been presented to predict different thermodynamical behaviors of pure and hybrid
substances [1, 3, 5]. After several decades, a series of prominent EoS have been
developed to deal with the realistic concept mapping centered around the varied
atypical phase equilibria of diversified fluids substances and derived complex fluidic
admixtures [30–35].
It is worth mentioning that a plethora of EoS exists that deal with the attractive
forces among the constitutive molecules of substances [36–46]. Besides, there exists
a diversified spectrum of EoS which examines the repulsive term of the hard-sphere
models of fluids [47–58]. Many of the EoS are instrumental in predicting the P–V–T
relationships for numerous hydrocarbonaceous fluids, having large-scale implica-
tions and applications in the industrial sector of petroleum engineering and technol-
ogy [11, 12]. In parallel, the solid Earth’s minerals undergo large volume strain due
to gravity, whose behaviors, such as transitions from solid to crystalline form under
high compression [59–65], can be often predicted through a relevant isothermal EoS
[66–82]. Crucial behaviors of sea water under high pressure can be analyzed with the
help of well-defined EoS [83–85]. There exists a special EoS that can provide
essential thermophysical information about the targeted products obtained from
high explosives [86–88]. Moreover, one of the most important uses of the EoS in
cosmology is in modeling different interior structures of stars, dense exotic matter of
compact astronomical objects, and radiation hydrodynamical fields [82, 89–
99]. Such EoS are extremely successful in analyzing the existence of different
compact structural objects, their atmospheres, and their conjoint properties in
ultra-extreme physical conditions [82, 89–91, 96].
We, herein, present a good number of EoS relevant in the diversified emerging
fields of modern science, engineering, and technology. It starts from the underlined
fundamental concepts of thermophysical foundation having applied value. A uni-
form system of generic notations (Table 1) is used for the sake of convenience and
simplicity of the content presentation. A standard scheme of acronyms useful in our
study is adopted (Table 2). A critical analysis is piecewise presented followed by a
brief discussion on the future refinement and multidisciplinary scope with applied
value.
Table 1 Symbolic significance

S. no. Symbol Generic significance Physical significance (source) Units
1 a Correction over the Its magnitude shows the N m8 mol1
intermolecular attractive strength of the intermolecular
potential force between two molecules
[1]
2 α A function of temperature It is the cohesion factor that Unitless
and acentric factor, ω measures the accuracy of an
α ¼ f(ω, T ) equation of state to predict the
vapor pressure of pure com-
ponent and checks the T-
dependency of energy [1, 9]
3 b Correction parameter for It measures the excluded vol- L mol1
finite molecular size/volume ume of the gas or the volume
occupied by the gas particles
and checks the repulsive
force between two molecules
[1]
4 β Reciprocal temperature func- It is the thermodynamic park J1
tion (1/kBT ) that expresses the response of
entropy due to energy
increase [24]
5 c Vacuum speed of light, It serves as the upper bound m s1
c ¼ 3 108 m s1 to the velocity range of all
material particles [95]
6 Cp Heat capacity in an isobaric It is the heat capacity at con- J K1 mol1
process stant pressure that expresses
the response of the enthalpy
of a system to a change in
temperature [31]
7 Cv Heat capacity in an isochoric It is the heat capacity at con- J K1 mol1
process stant volume that expresses
the response of the internal
energy of a system to a
change in temperature [100]
8 E{np} Sum of energy eigenvalues in It is the total energy of all the J
ideality constitutive particles having
momentum p at a particular
state of an ideal system [24]
9 Ep Energy eigenvalue of a state It is the single-particle J
in an ideal system energy, commonly known as
level, that represents the
number of states present in a
system [24]
10 EF Chemical potential at abso- It is the Fermi energy that J
lute zero expresses the energy differ-
ence between the highest and
lowest occupied single-
particle states in a quantum
system of noninteracting Fer-
mions at absolute zero tem-
perature [24, 93]
(continued)
Table 1 (continued)
11 ε Internal energy per unit mass It is the specific internal J kg1
energy that measures the
kinetic energy of molecules
and atoms [81]
12 η Parameter indicating the var- It is the packing fraction, Unitless
iation of isotopic mass from signifying the stability of the
whole atomic mass nucleus relative to the bind-
ing energy per nucleon
[47, 50]
13 fE2 Negative ratio of the It is the Eulerian finite strain Unitless
pre-compression volume to that describes the compres-
the reference volume when a sion of the body under finite
body is compressed strain relative to the post-
compression state as a refer-
ence [85]
14 fN Logarithmic strain (for large It is the Hencky strain that Unitless
deformations) extended to a represents the degree of
three-dimensional analysis severe plastic deformation
based on the large simple-
shear deformation [62]
15 FE Decreasing thermodynamic It is the Helmholtz free energy J
quantity for spontaneous that measures the amount of
processes useful intrinsic energy
obtainable of a system in
isochoric and isothermal
conditions [85]
16 Γg Thermodynamic parameter It is the Grüneisen parameter Unitless
indicating the thermal pres- that expresses the response of
sure of a system of vibrating vibrational properties of a
atoms crystal lattice against an
isochoric change [59]
17 Γ Thermodynamic exponent It is the polytropic exponent Unitless
used in a polytropic equation that correlates the pressure
change inside a system with
its material density [91]
18 γ γ ¼ Cp/Cv is the ratio between It is the adiabatic index that Unitless
the isobaric and isochoric gives a measure of the num-
molecular specific heats ber of degrees of freedom of a
gas molecule [100]
19 kB Proportionality constant It is the Boltzmann constant J K1
measuring the conversion (kB ¼ 1.38 1023 J K1)
between the average kinetic that provides a coupling
energy and thermodynamic measure between heat
temperature corresponding to the random
thermal motions of particles
[24, 93]
(continued)
Table 1 (continued)
20 h Fundamental physical con- It is the Planck constant Js
stant used in quantum (h ¼ 6.62 1034 J s) that
mechanics relates the energy carried by a
single photon to its
corresponding frequency [24]
21 K Thermodynamic quantity It is the bulk modulus or N m2
giving the ratio of the infini- incompressibility that
tesimal pressure increase to describes the elastic proper-
the resulting relative volume ties of a solidified substance
decrease [8]
22 m Intrinsic property measuring Mass of an object determines kg
linear inertia the measure of its resistance
against an applied force [3]
23 n A standard unit, that mea- It is the mole that represents a mol
sures amount of substance definite amount of the sub-
stance and a definite number
(Avogadro’s number,
NA ¼ 6.02 1023) of atoms,
molecules, or ions of a sub-
stance (at NTP) [1, 3, 9]
24 np Number of particles having It is the number of particles in Unitless
momentum p a definite momentum state,
specified by p in linear
momentum space [24]
25 nP Exponent on density in a It is the polytropic index that Unitless
(large polytropic law measures the work done by
P) the system, which is different
in different thermodynamic
processes [91]
26 N Fundamental parameter in It is the particle number that Unitless
thermodynamics, conjugate represents the number of
to the chemical potential constituent particles in a
closed thermodynamic sys-
tem [3]
27 NA Number of atoms or mole- It is the Avogadro number Unitless
cules in 1 mol of a substance that signifies the total number
of constituent particles in
1 mol of any sample sub-
stance (22.40 L of its volume)
at STP (named after Italian
scientist Amedeo Avogadro)
[3, 24]
28 ω Geometric property measur- The acentric factor Unitless
ing the centricity of (|ω| 101) is a number,
molecules named after Kenneth Pitzer,
signifying molecular
non-sphericity (centricity)
[1, 9]
(continued)
Table 1 (continued)
29 p Mass-velocity product It is the linear momentum that kg m s1
represents the result of appli-
cation of a force [24]
30 P Intrinsic fluid scalar parame- It is the pressure that signifies N m2
ter measuring force per unit measure of stress, experi-
area enced by physical matter in
different forms [1, 9]
31 Pc Saturated vapor pressure at It is the critical pressure of a N m2
critical point substance that expresses the
amount of pressure required
to liquefy a gas at its critical
temperature [1, 4, 10]
32 Pr Ratio of the absolute pressure It is the reduced pressure that Unitless
to the critical pressure of a correlates the pressure of the
system system to its critical pressure
at near critical point [4, 14]
33 PTh Thermodynamic parameter It is the thermal pressure that N m1
depicting the random kinetic measures the thermal energy
degrees of freedom of the density (P ¼ nkBT, where n is
motional constituent particles the particle concentration or
of a system population density of the
system) [21, 59]
34 QN A thermodynamic state vari- It is the partition function that Unitless
able function represents the statistical
assets in thermal equilibrium
[24]
35 R Proportionality constant, It is the universal gas con- J K1 mol1
R ¼ NAkB stant (also known as the
molar gas constant, some-
times also as Regnault con-
stant, the symbol “R”
designating the involved
French chemist, Henri Victor
Regnault) that signifies the
work done on or by 1 mol of a
gas needed for a unit degree
rise in its temperature [1, 9]
36 ρ Intrinsic property measuring It is the density of a substance kg m3
mass per unit volume that measures the degree of
compactness and constitutive
tightness of the substance
[93]
37 ρc Thermodynamic parameter It is the critical density that m3
measuring the average den- gives a subsequent measure
sity of matter of the density of a substance
at its critical point [15]
(continued)
Table 1 (continued)
38 ρm Thermodynamic parameter It is the molar density that mol m3
measuring the molar mass per measures the number of
unit volume moles of a substance within
the volume occupied by the
substance [43]
39 ρN Intensive quantity measuring It is the molecular material m3
molecular mass concentration density that describes the
degree of concentration of
countable objects in physical
space [47, 49]
40 ρr Ratio of the specific volume It is the reduced density that Unitless
to the critical volume of a correlates the density of the
system system to its critical density at
its critical point [12]
41 S Intrinsic property measuring It is the entropy that describes J K1
the degree of disorderliness the unavailability of a sys-
or randomness tem’s thermal energy during a
thermodynamic process [59]
42 T Intrinsic property measuring It is the temperature that K
the degree of hotness and describes the average kinetic
coldness energy of the constitutive
particles in an object [1, 9]
43 Tc Temperature of a pure sub- It is the critical temperature K
stance at critical state of a substance at and above
which, the vapor of the sub-
stance cannot be liquefied,
irrespective of the pressure
applied [1, 4, 10]
44 Tr Ratio of the absolute system It is the reduced temperature Unitless
temperature to the critical that correlates the tempera-
temperature ture of the system to its criti-
cal temperature at its critical
point [4, 14]
45 U* Energy required to dissociate It is the lattice energy that kJ mol1
solid ions into its gaseous measures the cohesive forces
ions that bind ions, describing
volatility, solubility, and
hardness [68–70]
46 U Energy comprising of kinetic It is the internal energy of a kg m2 s2
energy, potential energy, and system that represents the
electric energy heat absorbed or released in
an isothermal and isochoric
reaction [21, 59]
47 V Extrinsic property which is a It is the volume that measures m3
conjugate variable to pressure the quantity of three-
dimensional space enclosed
by a closed surface [1, 9]
(continued)
Table 1 (continued)
48 Vm Vm ¼ V/n is the ratio between It is the molar volume of a gas m3 mol1
molar mass and volume that gives a measure of the
volume occupied by any
number of moles of that
respective gas at a certain
temperature and pressure [1]
49 Vr Ratio of the specific volume It is the reduced specific vol- Unitless
of a substance to its critical ume that correlates the vol-
volume ume of the system to its
critical volume at its critical
point [4, 14]
50 Vc Specific volume of a sub- It is the critical volume that m3
stance at critical state measures the volume occu-
pied by a unit mass of a sub-
stance at its critical point
[1, 4, 10]
51 Z Ratio of molar volume of a It is the compressibility factor Unitless
gas to that of an ideal gas at that represents the deviation
the same temperature and shown by the thermodynamic
pressure properties of a real gas from
an ideal gas behavior [1, 9]
52 Zc Compressibility factor at crit- It is the critical compressibil- Unitless
ical point ity factor that characterizes
the gas-liquid critical point
[1, 9]
53 Z(z, V, Function of the thermody- It is the grand partition func- Unitless
T) namic state variables in a tion that allows a system to
grand canonical ensemble exchange heat and particles
with the external environment
at fixed temperature, volume,
and chemical potential [24]
54 z Measure of chemical poten- It is the absolute activity or Unitless
tial in statistical mechanics fugacity that defines a grand
canonical ensemble and rep-
resents the effort of adding an
additional particle to the sys-
tem [24]
2 Various Types of EoS
It is widely seen that there exist numerous kinds of EoS, which, indeed, have been
useful in narrating the different states of matter in different situations, as reported in
the literature [2, 27, 29], for several decades. These EoS can be well utilized to
describe the distinct behaviors of both pure and impure substances, ranging over a
scale far greater than that of the perfect gas equation (equation), commonly known as
ideal gas equation [2]. Each EoS has been derived with the help of a stipulated model
Table 2 List of abbreviation S. no. Terminology Abbreviation

1 Beattie–Bridgeman BB
2 Birch–Murnaghan BM
3 Brennan–Stacey BS
4 Benedict–Webb–Rubin BWR
5 Benedict–Webb–Rubin–Starling BWRS
6 Christoforakos–Franck CF
7 Carnahan–Starling CS
8 Equation/Equations Eq./Eqs.
9 Equation of state/Equations of state EoS
10 Elliott–Suresh–Donohue ESD
11 Freund–Ingalls FI
12 Heilig–Franck HF
13 Hard-sphere HS
14 Jones–Wilkins–Lee JWL
15 Kumari–Dass KD
16 Lee–Kesler LK
17 Modified Benedict–Webb–Rubin m-BWR
18 Mie–Grüneisen MG
19 Peng–Robinson PR
20 Peng–Robinson–Babalola PRB
21 Peng–Robinson–Stryjek–Vera PRSV
22 Poirier–Tarantola PT
23 Redlich–Kwong RK
24 Rose–Vinet RV
25 Soave–Redlich–Kwong SRK
26 Schmidt–Wenzel SW
27 Van der Waals VdW
bearing with generalized postulates based on the physical kinetic properties of the
states of matter under consideration. The variations in such kinds of model stem
from their response characteristic variabilities in nature. In this direction, various
EoS, such as the thermic EoS (P ¼ f(V, T )) and caloric EoS (T ¼ f(U, Cp)), are
empirically specified for a given thermodynamic system as found in the
literature [31].
Two principal types of EoS have been categorized so far in the literature [31],
namely, general EoS and specialized EoS. A general EoS predicts properties over a
broad range of phase existence of substances [4, 31]. In contrast, a specialized EoS
predicts the thermophysical properties of specific substances under defined existen-
tial conditions and proves to be extensively useful to provide a good correlation with
the various experimental data on phase-equilibrium features [31]. Thus, it is repeated
that almost all the EoS that have been developed so far in the literature can be
summarily classified under these two specific categories largely.
As already stated above, it is the interparticle or intermolecular interaction

processes in any state of matter that ultimately modulates the structure of the EoS
useful in describing it. Such interaction processes significantly change the effective
pressure, volume, temperature, internal energy, etc. As a consequence, it enables us
to enlist and discuss the most relevant forms of the EoS for the sake of instant
reference of readers as the following.
2.1 Ideal Gas Equation of State
The ideal gas EoS (or perfect gas law) is one of the simplest EoS, which is
reasonably accurate for weakly polar gases at low pressure and moderate tempera-
ture [12]. This equation has been primarily derived by Emile Clapeyron, in 1834.
Here, “ideal gas” or “ideal fluids” means a hypothetical gas or liquid that interacts
with each other or the walls of the container through elastic collisions as point
particles. At higher pressures and lower temperatures, the EoS becomes inaccurate
and fails to predict the condensation from a gas to a liquid phase [3, 12, 15].
The ideal gas law can be derived using the fundamental postulates of statistical
mechanics [5], by assuming gases to be composed of a large number of point
molecules, with no intrinsic attractive or repulsive forces. In reality, gas molecules
do interact with attractive and repulsive forces, which are responsible for the
formation of liquids, and so forth [3, 4].
2.1.1 General Form of Equation of State
The ideal gas EoS has been developed to have a constructive analysis of an ideal gas
(molecules occupying negligible space with negligible forces, except at collisions)
and is an outcome of several gas laws such as the Dalton law, Avogadro law, Boyle
law, and Charles law [3]. A simple derivation for the EoS can be constructed as
follows: an ideal gas with n number of moles, which can exert pressure P is taken
into account. Let the volume occupied by the gas be V and the temperature at which
the gas exists along with the pressure P and volume V be T.
According to the Boyle law [1, 3], at constant n and T, the volume bears an
inverse relation with the pressure exerted by a gas, expressed as
1
V/ : ð1Þ
P
It should be noted that Eq. (1) is also known as the Mariotte law, named after its
discoverer, the French physicist, Edme Mariotte, in 1676 [3]. Its physical signifi-
cance is in the basic energy conservation principle ensured by PV ¼ Pressure
energy ¼ constant. As per the Charles law [1, 3], at constant P and n, the volume
of a gas bears direct relation with the temperature as
V / T: ð2Þ
According to the Avogadro law, when P and T are constant, then the volume of a
gas bears direct relation with the number of moles of gas, expressed as
V / n: ð3Þ
At lower pressure and moderate temperature, the three Eqs. (1)–(3) can be
combined into a single equation [3, 4, 15, 18, 25], given as
PV / nT, ð4aÞ
PV ¼ nRT, ð4bÞ
where R ¼ 8.314 J mol1 K1 is the Universal gas constant [1–10].
2.1.2 Outcome
The degree of validity of the ideal gas EoS increases with a decrease in the gas
density [4]. The ideal gas law is found on the basic assumption that the gas molecules
act as point particles while interacting with the containers and not with each other.
As the collisions are perfectly elastic, the fundamental laws of conservation of linear
momentum and energy are well obeyed during the collisions [3, 4, 15]. However, in
reality, real gas particles do occupy spaces, termed as spheres of influence thereby
resulting in mutual attraction [3, 4, 15]. As a consequence, the validity of the ideal
gas EoS falls short in the case of real gases thereby inviting future refinements for
better realistic implications and applications.
2.2 Van der Waals Equation of State
The Van der Waals (VdW) equation (or real gas law) has fundamentally been
developed to predict the critical behaviors of the phase transition between vapor
and liquid states [5, 15]. The EoS has originally been derived by Johannes Diderik
Van der Waals in 1873, who, consequently, received the Nobel Prize in Physics in
1910. The EoS is one of the first equations that has taken into account the interacting
forces acting between the real gas constitutive molecules [10, 12, 13, 15]. The VdW
equation has introduced two new parameters (a and b) due to the intermolecular
forces [1, 3–5, 9]. It has significantly improved the ideal gas law on the grounds of
the following two independent basic reasons:
(a) According to VdW, the real gas molecules are assumed to be particles
possessing finite volumes, which can move only in a limited part of the total
gas volume [3, 14, 15, 32].
(b) The gas molecules present near the wall have higher chances of being attracted
by other molecules due to the attractive forces between the molecules [3, 14, 15,
32]. Therefore, the attraction forces have decreased the pressure acting against
the walls or the surface of the entity.
The VdW EoS [1, 3, 4, 9, 10, 13–15, 32] is written as

a
P þ 2 ðV m bÞ ¼ RT, ð5Þ
Vm
where Vm ¼ V/n is the molar volume of the gas, b is the volume that is occupied by
1 mol of the molecules and a is a constant whose value depends on the gas. Further,
n is the number of moles of the gas and V is the total volume of the gas. Now, Eq. (5)
for n moles of the real gas can be written in a modified form as

an2
P þ 2 ðV nbÞ ¼ nRT: ð6Þ
V
The substance-specific constants, a and b, can be determined from the critical

properties of the gas under consideration [32], which can be given in terms of the
critical parameters as
a ¼ 3Pc V 2c , ð7Þ
Vc
b¼ : ð8Þ
3
Here, Pc, Vc, and Tc are respectively the critical pressure, critical volume, and
critical temperature. Therefore, the critical compressibility factor [4, 10, 14, 32] can
be given as
Pc V c 3
Zc ¼ ¼ : ð9Þ
RT c 8
Furthermore, the reduced form of the properties can be used to create the reduced
form of the VdW equation [4, 14, 32], as presented below

3
Pr þ 2 ð3V r 1Þ ¼ 8T r : ð10Þ
Vr
Here, Pr ¼ P/Pc, Tr ¼ T/Tc, and Vr ¼ Vm/Vc represent the reduced state variables
of a fluid. For a given Tr and Pr, Vr of the fluid can be determined using Cardano’s
root-finding method on Eq. (10) [4, 34]. The reduced form of the cubic EoS can be
expressed as

1 8T r 2 3V r 1
V 3r þ Vr þ ¼ 0: ð11Þ
3 3Pr Pr Pr
The reduced cubic EoS, as presented in Eq. (11), has obviously three distinct
roots (solutions in Vr). For Pr < 1 and Tr < 1, there exist three real roots of the cubic
equation, where the largest root corresponds to the gas and the smallest root
corresponds to liquid [34]. For Tr > 1, there exists only one real solution to the
equation.
2.2.2 Outcome
The VdW EoS has prominently shown more accuracy than the ideal gas EoS in
terms of predicting the thermodynamical behavior of the gases [3, 14, 15, 25]. The
EoS has displayed accurate results for real gases above the critical temperature.
However, in the case of the liquid-gas phase transition, it has demonstrated poor
performance [1, 4, 5]. The substance-specific constants a and b of the EoS have also
shown significant variation with change in temperature [15]. So, it seems that the
VdW EoS needs further refinements to achieve a better precision.
2.3 Redlich–Kwong Equation of State
The Redlich–Kwong (RK) EoS has been developed to predict the P–V–T relation-
ships of gas [25] and to understand the thermophysical behaviors of the gas-phase
transition. The EoS has shown high accuracy than the VdW EoS at a temperature
above the critical point. The RK EoS has originally been proposed by an Austrian
physical chemist, Otto Redlich and a Chinese chemical engineer, Joseph Neng Shun
Kwong, in 1949. Redlich and Kwong have improved the attractive parameter a of
the VdW EoS and modified its expression into a function of the temperature [1, 15,
25, 33], as given by Eq. (13).
The RK EoS [1, 4, 6, 9, 10, 15, 18] is written as
RT a
P¼ pffiffiffiffi : ð12Þ
ð V m bÞ T V m ð V m þ bÞ
Applying the critical conditions of gas, the constants a and b can be determined
and their expressions can be written, in terms of Pc and Tc [1, 4, 6, 10, 15], given as
0:42780R2 T 2:5
a c
, ð13Þ
Pc
0:086640RT c
b : ð14Þ
Pc
Furthermore, the EoS can be reduced to a cubic equation [25], which is given as

RT 2 1 1 ab
V 3m Vm þ pffiffiffiffi bRT Pb V m pffiffiffiffi ¼ 0:
2
ð15Þ
P P T P T
If the expressions of a and b are replaced with their reduced properties, one can
express Eq. (15) in terms of the compressibility factor Z ¼ PVm/RT [15, 25], given as
0 1
Pr B0:42748 0:007506Pr C 0:03704P2
Z3 Z2 þ @ qffiffiffiffiffi 0:08664 AZ qffiffiffiffiffi r ¼ 0: ð16Þ
Tr Tr
T 3r T 7r
2.3.2 Outcome
The RK EoS has been proved to be a better EoS than that of the VdW EoS in
predicting the thermodynamical behaviors of the fluidic substances in the high-
pressure range [4, 15, 25]. However, it is of poor performance with respect to the
vapor-liquid transition phase [33]. Nevertheless, the EoS can be utilized in conjunc-
tion with separate liquid-phase correlations encountered as in the case of the vapor-
liquid phase equilibria [10, 25].
2.4 Soave–Redlich–Kwong Equation of State
The Soave–Redlich–Kwong (SRK) EoS has been developed to determine the

thermal and volumetric properties of pure and impure substances [6, 7]. The EoS
has been especially able to show an accurate description of the thermophysical
behaviors of both liquid and vapor phases [1]. In fact, the RK EoS has been modified
by Soave in 1972 by expanding the attractive term, a, appearing in the RK EoS into
dependent parameter as a function of two independent variables, such as tempera-
ture, T and asphericality, ω [7, 9]. In other words, it is repeated that the attractive
term, a, has been modified to evolve as an explicit function of temperature, T and
geometric shape (sphericity) of the constitutive molecules with the help of the
Pitzer’s acentric factor, ω, given as [1, 7, 9, 33, 35, 36] in the following
a ¼ aðT, ωÞ: ð17Þ
The SRK EoS [7, 9, 10, 19, 20, 33, 35, 36] is given as
RT αa
P¼ , ð18Þ
V m b V m ð V m þ bÞ
where, the alpha term, α, represents the molecular cohesion factor. The term, 1/√T,
of the RK EoS is replaced by the function α ¼ f(T, ω) [10, 33, 36], which is
mathematically expressed as
pffiffiffiffiffi 2
α ¼ 1 þ 0:48508 þ 1:55171ω 0:15613ω2 1 T r : ð19Þ
Applying the critical conditions on Eq. (18), new expressions for the constants
a and b can be estimated, which are indeed found to be exactly the same as those of
the RK EoS [7, 35]. Assuming A ¼ αaP/R2T2 and B ¼ bP/RT, the cubic form of the
SRK equation can be obtained [35, 36] with the help of Eq. (18), as given below

Z 3 Z 2 þ A B B2 Z AB ¼ 0: ð20Þ
A close inspective comparison of the SRK EoS (Eq. 20) and RK EoS (Eq. 16)
reveals that the former is free from any kind of molecular cohesive influencers (likely
to enter via α).
2.4.2 Outcome
The basic notion behind using the α-parameter in the SRK EoS is to devise a proper
correlative analysis of the vapor pressure data obtained from different hydrocarbons
in different conditions [10, 35]. It has been reported that, in contrast to the RK EoS,
the SRK EoS can predict accurate results for the phase behavior of the mixture of
gases near the critical parametric region [6]. Besides, the dimension of the liquid
molar volume (from the SRK EoS) has been reported to be less accurate than that of
the gas molar volume (again from the same SRK EoS) [1, 7].
2.5 Equation of State Due to Peneloux Et al.
The EoS by Peneloux et al. has been developed to improve the volumetric properties
of fluids by introducing a constant volume translation in the cubic SRK EoS [9, 35,
36]. Peneloux et al. EoS has shown a better correlation of the P–V relationship at low
temperature than that of the SRK EoS [7]. It has been fundamentally proposed by
André Péneloux, Evelyne Rauzy, and Richard Fréze in 1982. The considerable
discrepancy shown by the SRK EoS is the calculated liquid molar volume, which
is significantly less accurate than that of the gas molar volume. Therefore, Peneloux
et al. have proposed a simple correlation of the volume translation without affecting
the vapor-liquid equilibrium calculations [7, 37], which is expressed as
V m,SRK ¼ V m C PEN, ð21Þ
where CPEN is the additional fluid component correction parameter [37].
The Vm term of the SRK EoS can be replaced by the volume translation Eq. (21).
Therefore, the EoS by Peneloux et al. can be written [37] as
RT αa
P¼ : ð22Þ
V m C PEN b ðV m C PEN ÞðV m CPEN þ bÞ
Here, the term, CPEN as in Eq. (22), is generalized as an expansion in terms of the
critical parameters [7, 37], which is now mathematically expressed as
0:40768ð0:29441 Z RA ÞRT c
C PEN ¼ , ð23Þ
Pc
where, the term ZRA is known as the Rackett compressibility factor [37], expressed
as
Z RA ¼ 0:29056 0:0877ω: ð24Þ
2.5.2 Outcome
The EoS by Peneloux et al. has subsequently demonstrated better performance in

estimating the liquid molar volume than most of the other cubic EoS. However, the
EoS by Peneloux et al. has not been found to be applicable near the critical point of
liquids [36]. As a consequence, Hoyos (2004) has reported that the relative deviation
of the saturated liquid volume, obtained from the SRK EoS, increases with an
increase in the temperature. The expression for the specific volume shift has not
taken this fact into account. As a result, the EoS after Peneloux et al. has failed to
show accurate results for the cases where the reduced temperature, Tr > 0.65 [37].
2.6 Peng–Robinson Equation of State
The Peng–Robinson (PR) EoS has been developed to predict the density behaviours
of liquids and other fluid properties over the critical regions [1, 6, 7]. This EoS has
been derived by the Chinese chemical engineer, Ding-Yu Peng and the Calgarian
chemical engineer, Donald B. Robinson, in 1976, who have executed a detailed
study of the SRK EoS in hydrocarbons and similar associated systems. Then, Peng
and Robinson have proposed a modification of the attractive term, a, of the SRK EoS
and found a reasonably good estimation in the vapor pressure for both the pure and
impure forms of the substances [6, 36].
The PR EoS [1, 4, 7, 9, 10, 18, 36] is given as
RT αa
P¼ 2 , ð25Þ
Vm b V m þ 2bV m b2
where the constants a, b, and the term α can be expressed [9, 10, 36] as
0:45724R2 T 2c
a , ð26Þ
Pc
0:07780RT c
b , ð27Þ
Pc
pffiffiffiffiffi 2
α ¼ 1 þ 0:37464 þ 1:54226ω 0:26992ω2 1 T r : ð28Þ
The EoS is further rearranged into the form of a cubic equation. Assuming
A ¼ αaP/R2T2 and B ¼ bP/RT [36], one can express Eq. (25) on the compressibility
factor [6, 12] given as

Z 3 ð1 BÞZ 2 þ A 2B 3B2 Z AB B2 B3 ¼ 0: ð29Þ
2.6.2 Outcome
The PR EoS has a critical compressibility factor of 0.307 (Zc of the RK equation is
0.333 and that of VdW is 0.375) [4, 6, 10, 33]. Also, the PR EoS is, generally,
superior to the other EoS in terms of predicting the liquid densities of different
materials, especially for nonpolar ones [38]. However, the PR alpha function tends to
diverge above the critical temperature [38]. So, a further refinement of the alpha
function for the molecular cohesive effects is looked forward.
2.7 Schmidt–Wenzel Equation of State
The Schmidt–Wenzel (SW) EoS has been proposed to improve the liquid density
and other fluid properties compared to the PR and RK EoS [39]. The EoS is designed
to predict the phase behaviors of pure components while providing the same
equilibrium compositions [7].
The SW equation [7] is given as
RT aα
P¼ 2 : ð30Þ
Vm b V m þ ð1 þ 3ωÞbV m 3ωb2
Using the boundary conditions at the critical points, the expression for the
parameters a and b can be projected [7] as
3
1 R2 T 2c
a¼ 1 ð 1 qÞ , ð31Þ
½3ð1 þ qωÞ Pc
1 RT
b¼ q c: ð32Þ
½3ð1 þ qωÞ Pc
Here, 1/[3(1 + qω)] ¼ Zc (critical compressibility factor) and q [7] is approxi-

mately given as
b
q¼ ¼ 0:25989 0:0217ω þ 0:00375ω2 : ð33Þ
Vc
2.7.2 Outcome
The SW EoS is a more generalized form of the cubic EoS and can be reduced to the
original RK EoS when ω ¼ 0, and to the PR EoS when ω ¼ 1/3 [7]. The EoS has
been proved to be superior to the PR EoS in predicting the liquid-phase densities of
different hydrocarbons [9, 38]. However, the SW EoS is not suitable for predicting
the varied thermodynamical features of polar and associating constituent fluids
because of heterogeneous dispersive effects [33].
2.8 Peng–Robinson–Stryjek–Vera Equation of State
The Peng–Robinson–Stryjek–Vera (PRSV) EoS (Eq. 34) has been developed to

amend the molecular cohesive α-term of the nonideal PR EoS (Eq. 25) for real fluidic
substances in both the liquid and gaseous phases [9, 40]. This EoS has widened the
horizon of applicability of this cubic PR EoS to different polar fluidic components, in
both the homogeneous and heterogeneous form in practical situations [9].
At first, an adjustable pure component parameter has been introduced to modify the
polynomial fit of the acentric factor, ω, appearing in Eq. (25) [9, 40]. As a result, the
PRSV EoS in an α-modified generic form [33] is derived and written as
RT αa
P¼ , ð34Þ
V m b V m ð V m þ bÞ þ bð V m bÞ
where, the α-term has an amended expression [33], which is given as

pffiffiffiffiffi2
α ¼ 1 þ k 1 T r : ð35Þ
Here, k* has two kinds of expression, each of the cases where the reduced
temperature, Tr > 0.7 and Tr 0.7. For Tr > 0.7, the expression of k* [33] is written
as
pffiffiffiffiffi
k ¼ k0 þ k1 1 þ T r ð0:7 T R Þ: ð36Þ
Here, k1 is an adjustable generalized empirical parameter used to characterize the

purity of component nature. It is recommended that when Tr > 0.7, k1 ¼ 0, and
k* ¼ k0 [33]; where,
k 0 ¼ 0:37889 þ 1:4897153ω 0:17131848ω2 þ 0:0196554ω3 : ð37Þ
For Tr 0.7, the k*-expression [33] is written as

pffiffiffiffiffi pffiffiffiffiffi
k ¼ k 0 þ k 1 þ k2 ðk3 T r Þ 1 T r 1 þ T r ð0:7 T r Þ, ð38Þ
where k0 has the expression as shown by Eq. (37). Furthermore, k1, k2, and k3 are the
three distinctly adjustable pure component parameters.
2.8.2 Outcome
The first form of the PRSV EoS (k*-modulated as in Eq. 36) has shown an advantage
over the PR model for describing the thermodynamic behaviors of real fluids; more
specifically, although, it has shown inaccurate results for phase-equilibrium calcu-
lations [33]. It is because of the highly nonlinear behaviors of the phase-equilibrium
calculations involving diversified thermodynamical coordinates [40]. As a conse-
quence, the second form of the PRSV EoS (k*-modulated as in Eq. 38) is more
favored than the former one in terms of realistic applications [33, 40]. However, the
two distinct forms of the PRSV EoS have shown poor performance in predicting the
thermodynamical behaviors of the real fluids in the critical regions, as the α-function
of the PRSV EoS tends to diverge from zero and becomes arbitrarily singular [9].
2.9 Fuller Equation of State
The Fuller EoS has been developed to modify the results obtained from the PRSV
EoS, which has shown errors in the critical regions of the fluidic substances [9]. The
EoS is proposed by a Canadian chemical engineer, Gerald Gendall Fuller, in 1976. It
has introduced three distinct parameters (a, b, d ) in the PRSV EoS [10] so that the
compressibility factor of the fluids becomes variable and the errors which are
obtained due to the α-parameter of the PRSV EoS can be neglected above the critical
regions under consideration.
As already mentioned, Fuller (1976) has proposed a three-parameter EoS [10], given
as
RT αa
P¼ , ð39Þ
V m b V m ðV m þ dbÞ
where d is the third parameter [10], which is defined as

rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi ! rffiffiffiffiffiffiffiffiffiffiffiffiffi
V Vm 3 3 1 1 3 3
d¼ m ¼ : ð40Þ
b b 4 2 βd βd 4 2
Here, βd ¼ b/Vm represents the ratio of the co-volume to the volume. Applying
the critical condition to Eq. (39), one can derive the expressions of a and b [10],
given as
Ωa R 2 T c
a¼ , ð41Þ
Pc
Ωb RT c
b¼ : ð42Þ
Pc
Here, the terms, Ωa(βd) and Ωb(βd), are expressed functionally [10] as
ð1 þ dβd Þ2 ð1 βd Þð2 þ dβd Þ ð1 þ dβd Þ3

Ω a ðβ d Þ ¼ , ð43Þ
ð1 βd Þ4 ð2 þ dβd Þ2
βd ð1 βd Þð2 þ dβd Þ ð1 þ dβd Þ
Ωb ð β d Þ ¼ : ð44Þ
ð2 þ dβd Þð1 βd Þ2
The α-function in the Fuller EoS [10] is expressed as

" (rffiffiffiffiffiffiffiffiffi ) #2
4 βd pffiffiffiffiffi
αðT Þ ¼ 1 þ 0:480 þ 1:5740ω 0:176ω 2
1 Tr : ð45Þ
0:26
2.9.2 Outcome
The two useful features shown by the Fuller EoS (Eq. 39) [10] are as follows:
(a) A variable critical compressibility factor can be obtained through the EoS.
(b) Both a and b parameters have been modified into a function of temperature.
The EoS has significantly improved the vapor-pressure deviations shown by the
SRK EoS [10]. However, Yei et al. (2000) have mentioned that complications of the
EoS are bound to occur due to the incorporation of more than two substance-specific
parameters. With additional inputs, the accuracy of the results on phase-equilibrium
behaviors shown by the Fuller EoS has gradually decreased against the practical
desirability [10].
2.10 Elliott–Suresh–Donohue Equation of State
The Elliott–Suresh–Donohue (ESD) EoS has been developed to seek the correctness
of the PR EoS by improving the inaccurate VdW repulsive term [11, 12]. The EoS
has been proposed by Jr. J. Richard Elliott, S. Jayaraman Suresh, and Marc
D. Donohue in 1990 [12]. The EoS has been able to consider the effects of the
geometric shape of a nonpolar molecule, which can, subsequently, be extended to
polymers and polymeric families [11, 12].
The ESD EoS has introduced a new term, g ¼ f(ω), in order to include the effects of
geometric shape of the molecular volumes. A new parameter, q, is included to
consider the shape and the interaction of the constitutive molecules [11]. The ESD
equation [11, 12] is summarily cast as
PV m
¼ Z ¼ 1 þ Z rep þ Z at þ Z as : ð46Þ
RT
Zrep and Zat signify the repulsive and attractive parts of the compressibility, Z,
respectively. Zas is widely used for understanding the analytical behaviors of poly-
mers and their associated intermixed states. It is to be noted that, for remaining cases
other than polymers, Zas can be omitted without any loss of generality. The other two
terms are represented [11, 12] as
4gμ
Z rep ¼ , ð47Þ
1 1:9μ
9:5qρr Y
Z at ¼ : ð48Þ
1 þ 1:7745μY
The Zrep has a g-term (commonly known as geometric shape factor) and ρr is the
reduced material density. The expression for ρr with all the usual notations [12] is
written as
kB T c n
ρr ¼ Φ : ð49Þ
Pc Vm
Here, kB is the Boltzmann constant signifying the energy-temperature coupling.

The expression for Φ-term [11, 12] can be written as
0:0312 þ 0:087ðg 1Þ þ 0:008ðg 1Þ2

Φ¼ : ð50Þ
1 þ 2:455ðg 1Þ þ 0:732ðg 1Þ2
Again, the expression for g [11, 12] can be written as

g ¼ 1 þ 3:535ω þ 0:533ω2 : ð51Þ
The Zat-term has two significant terms Y and q [11, 12], which can be represented
as
E
Y ¼ ekB T 1:0617, ð52Þ
q ¼ 1 þ 1:90476ðg 1Þ, ð53Þ
where E represents the depth of a fluid-solid square-well potential coupled with a

geometric shape factor correction, g. The expression for E/kB [12] as a function of
g can be given as
" #
E 1 þ 0:945ðg 1Þ þ 0:134ðg 1Þ2
¼ Tc : ð54Þ
kB 1:023 þ 2:225ðg 1Þ þ 0:478ðg 1Þ2
2.10.2 Outcome
The ESD EoS has subsequently proved its nontrivial importance over the PR EoS in
predicting the volumetric properties of gaseous substances at higher temperature
[11]. However, in an experiment, where pure substances, like methane and water, are
taken into account, Sebastián et al. (2016) have reported that the parameter g in the
Zrep-term for both these two substances is very sensitive due to the intermolecular
fluid-fluid interactions and cannot work effectively. As a consequence, the error rate
for specific volume of both these two pure substances has been found to be
significantly higher for the EDS EoS than in case of the PR EoS [11]. Therefore,
there is a need to refine the geometric shape factor of the ESD EoS as explained
above.
2.11 Peng–Robinson–Babalola Equation of State
The Peng–Robinson–Babalola (PRB) EoS has been developed to predict the ther-
modynamic properties of complex reservoir fluids for the sake of the P ¼ f(V, T )
modeling [12]. This EoS is a modified form of the PR EoS, which has been proposed
by the Nigerian chemical engineer, Faith Uchenna Babalola. He has interpreted the
attractive a-term of the PR EoS (Eq. 25) as a variable with respect to pressure,
improving its accuracy in predicting the thermodynamical properties of the heavier
fluidic substances [12].
The PRB EoS [12] is expressed in a generalized thermodynamical form as
RT ½V m ðV m þ bÞ þ bðV m bÞ a2 α
P¼ : ð55Þ
Vm b V m ð V m þ bÞ þ bð V m bÞ þ a1 α
The straight line designating the variable parameter a in the form of a ¼ f(-
P) ¼ a1P + a2 is a smooth linear regression curve, formed by using two straight lines
corresponding to the pressures below and above the certain reference pressure
point [12].
2.11.2 Outcome
The PRB EoS has subsequently shown accurate predictions about the thermody-
namical behaviors of complex reservoir fluids and their compositional properties
[12]. Babalola et al. (2014) have reported that the PRB EoS has successfully
increased the accuracy of the PR EoS for high density and low viscosity fluids
when the applied pressure range exceeds 30 MPa [12].
2.12 Dieterici Equation of State
The Dieterici EoS has been developed to amend the thermodynamical behaviors of
the fluids obtained from the VdW EoS over a broad range of temperature [13]. The
EoS has amended the first term of the VdW EoS, i.e., RT/(Vm – b) in Eq. (5), by
multiplying it with an exponential function, exp(C/RT), so that it can successfully
consider the pressure gradient of the fluidic substances near the critical regions
[13, 41]. Thus, the Dieterici EoS is an explicit EoS [41].
The Dieterici EoS [13] is given as
RT
eRT ,
C
P¼ ð56Þ
Vm b
where C-term is a measure of the work done by the molecules in penetrating into the
surface of the surrounding walls. Dieterici has assumed C ¼ a/Vm [41]. So, the final
EoS is written as
RT
eRTV m :
a
P¼ ð57Þ
Vm b
Applying the critical conditions to Eq. (57), the expressions for the critical
parameters characterizing the fluidic substances can be evaluated [13, 41] as
a
Tc ¼ , ð58Þ
4Rb
1 a
Pc ¼ 2 2 , ð59Þ
4e b
V c ¼ 2b: ð60Þ
It is therefore evident, from Eqs. (58)–(60), that the critical thermodynamical

parameters of the real fluidic substances are explicit functions of the VdW
constants [41].
2.12.2 Outcome
It has been reported that the Dieterici EoS has shown high accurate results in
predicting the thermodynamical behaviors of the real fluids at the critical regions
[13], in contrast to the VdW EoS that has shown invalid results at the critical state.
However, when the molar volume, Vm, of Eq. (57) is large, then Eq. (57) can be
expanded [13] as

RT a RT a
P¼ 1 þ ... ¼ : ð61Þ
Vm b RTV m V m b V m ð V m bÞ
Equation (61) is quite similar to that of the VdW EoS (Eq. 5). Both the Dieterici
EoS and the VdW EoS have the same expression when Vm 1, which is written as
RT
P¼ : ð62Þ
Vm b
Therefore, the Dieterici EoS and the VdW EoS can be reduced to the same
expression of the pressure at low densities. Besides, all the thermodynamical results
obtainable from the VdW EoS can be deducible from the Dieterici EoS when low
pressures are considered [13].
2.13 Virial Equation of State
The Virial EoS (or Kamerlingh Onnes equation) has been developed to deal with the
thermodynamical behaviors of diluted gases and the P–ρ–T properties of the fluids
[41]. The EoS is capable of expressing the pressure of many-particle system in
equilibrium as a power series expansion in terms of material density. The Virial EoS
has been proposed by the Dutch physicist and Nobel laureate, Kamerlingh Onnes
[14]. Kamerlingh has done some significant calculations useful for him to develop
the original VdW EoS and his own version of the EoS with the help of experimental
data for different substances at different temperatures [14].
The simple virial EoS [4, 14, 15] is expressed as
PV m B C D
¼Aþ þ þ þ ...: ð63Þ
RT V m V 2m V 3m
If the compressibility factor is considered as Z ¼ PVm/RT ¼ P/RTρm; where ρm

represents the molar density, then the EoS can be expressed as
P
Z¼ ¼ A þ Bρm þ Cρ2m þ . . . : ð64Þ
RTρm
Here, A, B, C, etc., are the virial coefficients expressible in a simple algebraic

form as
b2 b3 b4 b5
B ¼ b1 þ þ þ þ : ð65Þ
T T2 T3 T4
It is clearly evident from the above that the Virial EoS contributes additional
terms beyond that actually meant for an ideal gas due to the intermolecular interac-
tions. The first virial coefficient is A, which has been found to be a constant, i.e.,
A ¼ 1. This means that, with large volume, all fluids behave like an ideal gas
[14, 15]. So, this term is independent of the temperature.
The second virial coefficient is B, which relates the interactions between pairs of
molecules. Similarly, C depicts the interactions among triplets of molecules, and so
forth. Therefore, the virial coefficients of the virial EoS, other than the first A-term,
are the thermodynamic functions of the temperature parameter [14, 15].
2.13.2 Outcome
The dimensionless compressibility factor, Z, is beneficial for extracting relative

information about the real gases [14]. Most EoS can be reformulated into virial
equations and can be used for extracting valid information on the unknown param-
eters of the EoS. However, when the VdW EoS is considered, the term 1/(Vm b)
can be expanded into Taylor’s series [14, 15], and, thus, the final form of the VdW
EoS can be represented as a virial form, which is written as

P a
Z¼ ¼1þ b ρ þ b2 ρ2m þ b3 ρ3m þ . . . : ð66Þ
RTρm RT m
It can be estimated that the second virial coefficient, B ¼ (b – a/RT), of Eq. (66)
has a correct comportment, while the rest of the coefficients are independent of
temperature, which is indeed incorrect. Therefore, it can be estimated that the VdW
EoS is not very accurate as far as real fluidic situations are encountered [14]. Apart
from that, the general virial equation (Eq. 64) fails to provide accurate results at very
high pressures as the coefficients do not converge to a finite value [15]. Therefore,
further refinement of the virial EoS is looked forward.
2.14 Beattie–Bridgeman Equation of State
The Beattie–Bridgeman (BB) EoS has been established to predict the thermody-
namical behaviors of both gaseous and liquid states more accurately relative to the
above scenarios [15]. The EoS has been proposed by Beattie and Bridgeman in
1928. This EoS is closely related to the virial EoS, which uses several empirical
constants, in order to consider the significant decrease in the number of constitutive
molecules due to molecular aggregations [15, 16].
The BB EoS with all the usual notations for the used thermophysical variables [16] is
put as

RT c A
P¼ 2 1 3
ðV m þ BÞ 2 : ð67Þ
Vm V mT Vm
Here, the constants, A and B, are respectively expressed [16] as


a
A ¼ A0 1 , ð68Þ
Vm

b
B ¼ B0 1 : ð69Þ
Vm
It can be observed from Eqs. (67)–(69) that there are five experimentally deter-
mined constants characterizing the nature of the substances because of molecular
aggregative processes under consideration. These five empirical constants, i.e., A0,
B0, a, b, and c*, can be found experimentally [16] for different gases and liquids.
2.14.2 Outcome
The BB EoS has shown high accuracy in predicting the thermodynamical behaviors
of the real fluids up to 80% of their critical densities [15]. This EoS can be further
rearranged in terms of the compressibility factor [15, 16], which is expressed as

A c A a B0 bc 3
Z ¼ 1 þ B0 0 3 ρm B0 b 0 3 ρ2m þ ρm : ð70Þ
RT RT RT T3
It has been reported that the second virial coefficient, B ¼ B0 – A0/RT c*/RT3, in
Eq. (70) is quite accurate [15]; but, the third virial coefficient, C ¼ (bB0 – aA0/
RT3), has a negative sign as shown in the literature, implying that the third virial
coefficient of the BB EoS is very poor when compared to the best-accepted values.
As a consequence, the EoS has failed to express the relationship of the isotherms at
near Tc [16].
2.15 Benedict-Webb-Rubin Equation of State
The Benedict-Webb-Rubin (BWR) EoS has been developed to predict the thermo-
dynamical behaviors of the real fluidic substances with more precisions [15]. The
EoS has resulted in the improvement of the BB EoS (Eq. 70), by increasing the
number of empirical constants of the BB EoS [15, 17]. The increase in the number of
constants has subsequently increased the accuracy in capturing more indistinguish-
able behaviors of fluid dynamics. Manson Benedict, George B. Webb, and Louis
C. Rubin in 1940 have improved and rearranged the BB EoS and increased the
number of experimental constants from 5 to 8 [17].
The BWR EoS [16, 42] is expressed as

C c ρ3
P ¼ ρm RT þ B0 RT A0 20 ρ2m þ ðbRT aÞρ3m þ αaρ6m þ 2
T T
2
1 þ γ ρ2m eγ ρm : ð71Þ
Now, Eq. (71) can be expressed in a virial form [16, 42] as in the following

A0 C0 a 2 αa 5 c ρ2
Z ¼ 1 þ B0 3 ρm þ b ρm þ ρ þ
RT RT RT RT m RT 3
2
1 þ γ ρ2m eγ ρm : ð72Þ
Here, A0, B0, C0, a, b, c, α, and γ * are the empirical constants which are
experimentally found for different types of gases and liquids [16]. The exponential
part of Eq. (72) is to correct the third virial coefficient, C ¼ (bB0 – aA0/RT 3) in
Eq. (70), such that the isotherms in the liquid phase can be correctly represented
below Tc [16, 43].
2.15.2 Outcome
The BWR EoS has been emphasized as being one of the best equations in predicting
the thermodynamical behaviors of the gases. However, this EoS can be used only in
those cases of the substances where there is a sufficient amount of experimental data
in a wide-range variation of pressure and temperature [43]. The EoS has shown
accuracy for lighter hydrocarbons; as well as, for other fluidic substances when
ρ < 1.2ρc [15]. However, above this critical range, the BWR EoS fails to express
proper pure-substance critical isotherms.
2.16 Benedict–Webb–Rubin–Starling Equation of State
The Benedict–Webb–Rubin–Starling (BWRS) EoS has been developed to deal with

the behaviors of fluids in fluid dynamics and to improve the thermodynamical results
obtained from the BWR EoS [42, 43]. The BWR EoS has been modified by Kenneth
Earl Starling of the University of Oklahoma in 1973. The EoS has significantly
improved the BWR EoS by increasing the empirical constants in the BWR EoS
(Eq. 72) from 8 to 11 [42, 43].
The BWRS EoS [18, 43] is given as

C D E d 3
P ¼ ρm RT þ B0 RT A0 20 þ 30 04 ρ2m þ bRT a ρ
T T T T m

d 6 c ρ3 2
þα aþ ρ þ 2 1 þ γ ρ2m eγ ρm : ð73Þ
T m T
Now, Eq. (73) can also be expressed in a virial form as

A C D E a d
Z ¼ 1 þ B0 0 03 þ 04 05 ρm þ b 2 ρ2m
RT RT RT RT RT RT
2
a d cρ 2
þ α þ ρ5 þ 1 þ γ ρ2m eγ ρm : ð74Þ
RT RT 2 m RT 3
Here, A0, B0, C0, D0, E0, a, b, c, d, α, and γ * are the empirical constants which are
experimentally found for different gases and liquids [43].
2.16.2 Outcome
As stated above, the Starling version of the original BWR EoS has improved the T-
dependent eight empirical constants of the BWR EoS, by introducing three extra
empirical constants [18]. Mixing rules have been introduced for all the total
11 parameters involved in the BWRS EoS [18–20]. The mixing rule, for example,
in expressing A0, is a quadratic mole fraction as
X 1X 1
A0 ¼ xi A20i x j A20j 1 kij , ð75Þ
i j
where kij is an interaction parameter of the ith component [19, 20]. The BWRS EoS
has the exponential term as in the BWR EoS (Eq. 72) that corrects the third virial
coefficient of Eq. (74) in order to predict the correct representation of the isotherms
in the liquid phase below Tc.
2.17 The Modified Benedict-Webb-Rubin Equation of State
The modified Benedict-Webb-Rubin (m-BWR) EoS has been developed to predict

the thermodynamical properties of the real fluids in diversified practical areas of fluid
dynamics. The EoS is one of the several modified versions of the BWR EoS,
expressing the pressure in a summation form of the fluid material density, as already
reported in the literature [43]. This EoS has originally been introduced by Richard
T. Jacobsen and Richard B. Stewart, in 1987.
The m-BWR EoS [43] is given as
X
9
2
X
15
P¼ an ρnm þ eγ ρm
an ρ2n17
m : ð76Þ
n¼1 n¼1
Here, ρm is the molar density and γ * is expressed in terms of critical density, ρc,
written as
1
γ ¼ : ð77Þ
ρ2c
2.17.2 Outcome
2
The exponential term, eγ ρm , in the m-BWR has fundamentally represented the
isotherms in the liquid phase accurately, as similar to the BWR EoS and BWRS EoS
cases [16]. The m-BWR EoS has subsequently evolved into a 32-term equation and
the constants of the BWRS EoS can be estimated by fitting Eq. (76) into experi-
mental data for a given fluid [43].
2.18 Lee–Kesler Equation of State
The Lee–Kesler (LK) EoS has been developed to predict the thermodynamical
properties of fluids in both gaseous and liquid phases [44]. This EoS is also a
modification of the BWR EoS. The LK EoS has fundamentally been proposed by
Byung Ik Lee and Michael G. Kesler in 1975. This EoS has been proposed on the
basis of the principles of the corresponding states, which has been mentioned by
VdW as [44]: “Substances behave alike at the same reduced states. Substances at
same reduced states are at corresponding states.”
The LK EoS in the reduced form with all the generic notations [44] is given as

Pr V r B C D c4 γ γ 2
Zr ¼ ¼ 1þ þ 2þ 5þ 3 2 β þ 2 e : Vr
ð78Þ
Tr Vr Vr Vr Tr Vr Vr
Here, B, C, D, c4, β*, and γ * are the constants characterizing the fluid. It may be
noted that Eq. (78) is a general form of the LK EoS. The EoS can analytically be
expressed in any of the following forms with no loss of any generality

Tr B C D c γ γ
Pr ¼ 1 þ þ 2 þ 5 þ 3 4 2 β þ 2 e V 2r , ð79aÞ
Vr Vr Vr Vr Tr Vr Vr
1
V m Pc B C D c4 γ γ
Pr ¼ T r 1 þ þ 2 þ 5 þ 3 2 β þ 2 e V 2r , ð79bÞ
RT c Vr Vr Vr Tr Vr Vr

RT B C D c4 γ γ
P¼ 1 þ þ 2 þ 5 þ 3 2 β þ 2 e V 2r : ð79cÞ
Vm Vr Vr Vr Tr Vr Vr
2.18.2 Outcome
The LK EoS has been proposed to be one of the most accurate enthalpy models for
the gaseous phases of substances [18]. The EoS has Vr and Tr as the basic parameters
[44] because the reduced parameters are independent natural variables which are
useful in predicating the thermodynamical properties of the fluidic substances. These
reduced parameters, i.e., Vr and Tr, can be evaluated through the mixing rules as
explained above [44].
2.19 Berthelot Equation of State
The Berthelot EoS has been developed to predict the P–V–T relationships of the real
gases [45]. This EoS has been proposed in order to modify the attraction term, a, of
the VdW EoS. The Berthelot EoS is being derived by Pierre Berthelot in 1903, using
the Clapeyron-Clausius equation (displaying the exponential relationship between
vapor pressure and temperature).
The Berthelot EoS [45] is generally expressed in a generic form as
RT a
P¼ : ð80Þ
V m b TV 2m
Here, a and b are the constants of the Eq. (80), as in the case of the VdW EoS. At
the critical points, where

∂P
¼ 0, ð81Þ
∂V T¼T c
2
∂ P
¼ 0, ð82Þ
∂V 2 T¼T c
the expressions for these constants [46] are calculated as
a ¼ 3T c Pc V 2c , ð83Þ
Vc
b¼ : ð84Þ
3
Therefore, the compressibility factor Zc is found to be 0.375. At low pressure,

Berthelot has proposed another modified equation [46], which is given as

RT 9PT c 6T 2
P¼ 1þ 1 2c : ð85Þ
Vm 128Pc T T
It is interesting to note here that Eq. (85) involves no parameter dependent on

a and b unlike the previous cases consequent upon the standard EoS.
2.19.2 Outcome
It is usually found that the Berthelot EoS is able to describe only the evaporation
processes for real gases qualitatively. However, the value of the compressibility
factor for the Berthelot EoS at a critical state is the same as that of the VdW EoS. As
a consequence, it has been reported that the Berthelot EoS is not adequate to explain
the above processes significantly [46].
2.20 Carnahan–Starling Equation of State
The Carnahan–Starling (CS) EoS has been developed to deal with the fluid phase of
the hard-sphere (HS) model in a full thermodynamic form [47]. This EoS is a
non-cubic EoS, which is obtained by simple modification of the repulsive term of
the VdW equation (HS term of Eq. 5), in order to predict the accurate thermody-
namical behaviors of the densities of liquids and other fluid properties over the
critical regions. The CS EoS has primarily been proposed by the American chemical
engineers, Norman F. Carnahan and Kenneth Earl Starling, in 1969 [47].
2.20.1 Simple Derivation and Equation of State
Carnahan and Starling have proposed an accurate representation of the HS interac-

tions [47] with the help of several observations of the hard-sphere virial coefficients
values [10, 48]. The general virial expression for HS fluid [47, 49] is given as
P X 1
¼1þ Bnþ1 ρnN , ð86Þ
ρN k B T n¼1
where Bn+1 is the (n + 1)th virial coefficient and ρN ¼ N/V represents the molecular
material density. Thus, compressibility factor can be written [41, 49] as
PV
Z¼ ¼ 1 þ B2 η þ B3 η2 þ B4 η3 þ . . . : ð87Þ
Nk B T
Here, N is the number of particles and η is the packing fraction [47], given as
π Nσ 3
η¼ : ð88Þ
6 V
Here, σ is the diameter of the molecular HS. Through experimental observations,

the first seven virial coefficients for the HS fluids are estimated as B2 ¼ 4, B3 ¼ 10,
B4 ¼ 18.36, B5 ¼ 28.23, B6 ¼ 39.54, B7 ¼ 53.54, and B8 ¼ 70.78 [50]. Using the
first three virial coefficients, Carnahan and Starling have obtained a general form
[50] of the virial coefficients given as
Bnþ1 ¼ n2 þ 3n: ð89Þ
With proper approximations, the compressibility factor of the real fluids is

generalized into a function of η with the help of the general virial coefficient
expression (Eq. 87) [10, 47, 50] as
1 þ η þ η2 η3
Z¼ : ð90Þ
ð1 ηÞ3
In 1972, Carnahan and Starling have substituted the repulsive term of the VdW
EoS (RT/Vm b of Eq. 5) with Eq. (90) and subsequently improved the VdW EoS
[10], which is given as
1 þ η þ η2 η3 RT a
P¼ : ð91Þ
ð1 ηÞ3 V m V 2m
2.20.2 Outcome
The CS EoS has been emphasized as being one of the most widely used equations. It
is quite an accurate EoS in the stable region of the HS fluids. It has shown a good
performance in predicting the thermodynamical properties of the mixtures and
inhomogeneous fluids [48]. However, it has experimentally been shown that the
CS EoS deviates from the expected results when η > 0.55 [47]. Therefore, further
refinement of the HS term of the CS EoS is sought for better and brighter calculation
schemes in this direction.
2.21 Thiele Equation of State
The Thiele EoS has been developed to predict the thermodynamical behaviors of the
fluidic substances with the help of an accurate HS model [51]. The EoS has been
proposed by Ernest Thiele in 1963. This EoS is similar to the CS EoS; where, the
compressibility factor of the HS fluids is expressed in terms of their packing fraction,
η. Thiele has used the Percus-Yevick virial equation [52] to derive a modified
version of the EoS in order to improve the thermodynamical results obtained from
the VdW EoS for the real fluids.
The virial expression for the HS fluids can be written in terms of the virial coeffi-
cients (Eq. 87) and packing fraction ɳ ¼ πρNσ 3/6 (Eq. 87) [10, 49]. Thiele, with the
help of the Percus-Yevick virial equation, has successfully been able to establish his
own version of the HS expression in terms of ɳ [10], which is explicitly given as
1 þ η þ η2
Z¼ : ð92Þ
ð1 ηÞ3
Therefore, the Thiele EoS, after combining Eq. (92) with the attractive term of the
VdW EoS, can be derived and expressed as
1 þ η þ η2 RT a
P¼ : ð93Þ
ð1 ηÞ3 V m V 2m
2.21.2 Outcome
The Thiele EoS has successfully provided a better expression of the repulsive forces
between constitutive molecules than the VdW EoS [48]. It is quite a simple and
prominent EoS, which is analytical in the stable fluid region. However, in terms of
accuracy, the CS EoS has experimentally shown better performance than that of the
Thiele EoS [48].
2.22 Guggenheim Equation of State
The Guggenheim EoS has been developed as a simple and alternate expression of the
CS EoS, which has been proposed by an English physical chemist, Edward Armand
Guggenheim, in 1965 [53]. The Guggenheim EoS is formulated as a fused form of
two molecular interactive terms, constituting the modified HS repulsive term of the
VdW EoS and the VdW attractive term. This non-cubic EoS has been widely utilized
for critical equilibria calculations [10, 53].
The simple form of the Guggenheim EoS [10] is given as
1 a
Z¼ 4
, ð94Þ
ð1 ηÞ RTV m
where, it is repeated that a is the attractive parameter and η is the packing fraction
[10], put as
π Nσ 3 b
η¼ ¼ : ð95Þ
6 V 4V
The packing fraction can be also expressed in terms of the co-volume parameter
b. The expression for the parameters a and b can be estimated using critical
conditions [10], given as
0:49002R2 T 2c
a¼ , ð96Þ
P2c
0:18284RT c
b¼ : ð97Þ
Pc
At the critical point, the Guggenheim EoS has Zc ¼ 0.3611 [10], which is less
than that of the VdW case, given as Zc ¼ 0.375.
2.22.2 Outcome
The simplicity of the Guggenheim EoS has produced good results for the vapour-
liquid critical system [54]. Guggenheim has also stated that his method has shown
better results at higher densities than the VdW EoS [53]. The EoS has successfully
estimated the critical properties of immiscible gases over a large range of binary
mixtures [54]. However, the CS EoS has shown slightly better results in calculating
the vapour-liquid critical properties of binary fluidic mixtures than the Guggenheim
EoS [10].
2.23 Christoforakos–Franck Equation of State
The Christoforakos–Franck (CF) EoS has been developed to deal with the attractive
and repulsive terms of the HS fluids, specifically, for high-pressure equilibria
[55]. This EoS has come of merging the CS repulsive term (Eq. 90) with a square-
well intermolecular potential, depicting the attractive intermolecular interactions of
the constitutive fluid molecules [10]. The CF EoS has given accurate thermodynam-
ical properties of the fluid binary systems [55].
The CF EoS [10, 55] is written as
V 3m þ V 2m β þ V m β 2 β 3 4β 3 E
Z¼ λ 1 eRT 1 : ð98Þ
ðV m β Þ3 Vm
Here, E and λ depict the depth and relative width of the square-well intermolecular
potential, respectively. b is the repulsive parameter. β* is a T-dependent co-volume
term [10], given as
0:3
Tc
β ¼ b ð99Þ
T
At the critical point, the other state parameters of the CF EoS [10] are expressed
as
0:04682RT c
b¼ , ð100Þ
Pc

E 2:65025
¼ T c ln 1 þ 3 : ð101Þ
R λ 1
2.23.2 Outcome
The merged structure of two distinctive forms of the attractive and repulsive terms,
in case of the CF EoS, has significantly increased the accuracy in predicting the
thermodynamical behaviors of the supercritical phase equilibria of hydrocarbons
[10]. The CF EoS has successfully shown good performance in case of some relevant
binary aqueous mixtures with high polarity, at high temperature and pressure [55].
2.24 Heilig–Franck Equation of State
The Heilig–Franck (HF) EoS has been developed to predict the thermodynamical
properties of the fluidic substances at high-pressure equilibria [10]. The HF EoS has
fundamentally been proposed by M. Heilig and Ernst Ulrich Franck, in 1989. This
HF EoS is a modified form of the CF EoS, by introducing an alternative form of a
square-well (attractive force) potential representation [10]. This EoS has taken the T-
dependent CS form of the repulsive forces between two constitutive HS fluid
molecules [10].
The HF EoS [10, 56] is given as
V 3m þ V 2m β þ V m β 2 β 3 h i1
C
Z¼ þ B Vm þ , ð102Þ
ðV m β Þ3 B
where B and C represent the contributions from the second and third virial coeffi-
cients of a square-well fluid, respectively, due to the interaction of two HS fluids via
the square-well potential [10]. The β*-term in Eq. (102) has similar expression to the
β*-term in Eq. (98) [10].
The first part of the HF EoS is similar to that of the CF EoS, which is derived from
the CS EoS; whereas, the attractive term is obtained by using the Padé approxima-
tion of the virial coefficients of a square-well fluid and is specified through three
parameters, σ (interaction separation), E/RT (intermolecular attraction), and λ (width
of square-well) [10, 57]. At the critical point, the value of the mentioned parameters
[10, 57] is given as
λ ¼ 1:26684, ð103Þ
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
V
σ ¼ 0:24912 c , ð104Þ
3
NA
E
¼ 1:51147T c : ð105Þ
R
Here, NA (6.022 1023) is the Avogadro number and Vc is the critical volume of
the one-component pure fluid under consideration.
2.24.2 Outcome
Heilig and Franck have reported that calculations of the critical properties are
accurate in case of binary mixture [10, 56]. The same in case of ternary mixture
(consisting of water, ethanol, and methanol with various concentrations) has been
also reported. The HF EoS has successfully predicted the results more accurately
than any other combined form of the EoS, for calculating the vapor-liquid phase
equilibria involving a polar molecule [58].
2.25 Mie–Grüneisen Equation of State
The Mie–Grüneisen (MG) EoS (or Grüneisen EoS) has been developed to relate the
pressure and volume of a solid alongside the internal energy at a given temperature
[21, 59]. This EoS has been proposed by two German physicists, Gustav Mie and
Eduard Grüneisen. The MG EoS has been emphasized as being a special form of the
Grüneisen model which determines the pressure of a shock-compressed solid
[21]. The Grüneisen model is specifically designed for the Grüneisen parameter,
denoted as Γg, named after the pioneer, Eduard Grüneisen [59].
2.25.1 Simple Derivation and Equation of State
Mie (in 1903) and Grüneisen (in 1912) have developed a theory stating that the
pressure in solids could be a linear function of the internal energy [59]. They have
shown that the internal energy of a solid due to the interactions of atoms at rest can
be given as
U ¼ U K ðV Þ þ U Th ðV, T Þ, ð106Þ
where, UK(V ) is the potential energy at T ¼ 0 C and UTh(V, T ) is the thermal

vibrational energy [59]. The pressure of the solid material can also be expressed as
P ¼ PK ðV Þ þ PTh ðV, T Þ: ð107Þ
Now, the thermal pressure, PTh, is proportional to that of the thermal energy [59],
and PK(V )-term has a negative relation with the volume derivative of the potential
energy, given as
dU K ðV Þ
PK ðV Þ ¼ : ð108Þ
dV
In 1912, the Grüneisen parameter, Γg [59], has been introduced, which is

expressed as
d ½ ln ðϑÞ
Γg ¼ , ð109Þ
d½ ln ðV Þ
where ν is the vibrational frequency of the solid material. Using the virial theorem
and the Grüneisen parameter (Eq. 109), Eduard Grüneisen has given a pressure
equation [59] as
Γ g ðV Þ
PTh ðV, T Þ ¼ U Th ðV, T Þ: ð110Þ
V
Using Eqs. (106) and (107), Eq. (110) can be reformed into the MG EoS [59] as
Γ g ðV Þ
P ¼ PK ðV Þ þ ½U U K ðV Þ, ð111Þ
V
At the macroscopic level, Γg can also be expressed [59] as

dP ∂ ln ðT Þ
Γg ¼ V ¼ : ð112Þ
dU V ∂ ln ðV Þ S
2.25.2 Outcome
The P(V, U )-derived Grüneisen model is especially useful in shock wave physics. In
such cases, the conservation of energy in Eq. (111) involves pressure, volume, and
internal energy of the constitutive solid materials [59]. It may be seen that Eq. (111)
has also been utilized in describing the thermodynamical properties of many other
states of matter (e.g., in fluid dynamics, etc.) [59]. However, it does not allow to
access on the entropy and temperature of the solid system. As a consequence, more
modified form of the MG EoS has been introduced, for example, extending Eq. (111)
of the MG EoS into a complete form of S ¼ f(V, U ) [59].
2.26 Stiffened Equation of State
The stiffened EoS has been proposed to deal with the P–V relationships of water
under high compression [78, 100]. The EoS is a simplified form of the MG EoS that
deals with conditions when water is under very high pressure [78, 100], such as
underwater nuclear explosions or sonoluminescence (light emission from imploding
bubbles in a liquid when excited by sound).
The stiffened EoS [100] is given by
P ¼ ρðγ 1ÞC v T Pm , ð113Þ
where Pm represents the constant molecular attraction between constitutive water

molecules, Cv is the heat capacity at constant volume. As a consequence, γ ¼ Cp/Cv
is used to denote the ratio between the isobaric and isochoric specific heats (also
termed as the adiabatic index).
2.26.2 Outcome
The stiffened EoS has been widely used to predict various thermodynamical prop-
erties of water and like liquids at high-pressure equilibria [78]. However, it has
several demerits against the MG EoS. One of the main disadvantages lies in the
wrong prediction of water density [100].
2.27 Cole Equation of State
The Cole EoS has been developed to adiabatically modify the stiffened EoS for
liquids under the effect of high compressive pressure [79]. This EoS has primarily
been proposed by an American chemist, Robert Hugh Cole. The Cole EoS has
fundamentally been modeled in such a way that it can be well utilized in the field of
nearly incompressible fluidic environments.
The Cole EoS [80] is written in a generic form as

γ
ρ
P¼B 1 , ð114Þ
ρ0
where ρ0 is the reference (initial) material density and B is a pressure (stress)

parameter [80]. Using Eq. (114), the phase speed of sound propagating through
such liquids can be expressed with the help of the Newtonian formalism followed by
the Laplacian correction [80] as
rffiffiffiffiffiffi
γB
cs ¼ : ð115Þ
ρ0
Therefore, Eq. (114) can be further reorganized with the help of Eq. (115) as
γ
c2s ρ0 ρ
P¼ 1 : ð116Þ
γ ρ0
It may be, hereby, inferred that Eq. (116) is one of the simplest EoS in the P–ρ
plane modulated by both γ and ρ0 conjointly.
2.27.2 Outcome
The Cole EoS has been able to predict accurate thermodynamical properties of
fluidic substances and has been utilized in many hydrogeological and petroleum
applications [80]. The value of γ in Eq. (116) for liquids is taken as seven, in order to
enforce incompressibility to a compressible liquid [80]. In most common circum-
stances, γ ¼ 1 for gaseous substances.
2.28 Jones–Wilkins–Lee Equation of State
The Jones–Wilkins–Lee (JWL) EoS has been developed to deal with the thermody-
namical properties of both detonation products and unreacted high explosives
[81]. The EoS is similar to the MG EoS, which comprises of Γg and describes the
pressure-volume-energy relationships of the products obtained after explosions [81].
The JWL EoS [82] is of the form

Γg V 0 RV1 V Γg V 0 RV2 V Γg
P¼A 1 e 0 þB 1 e 0 þ ðε þ ΔεÞ: ð117Þ
VR1 VR2 V
Here, V0 is the initial volume of explosive and V is the volume of the detonation
product. A, B, R1, R2 are constraint parameters. ε stands for the specific energy
(energy per unit mass) and Δε stands for an offset in the origin of specific internal
energy [81]. Both A and B have dimensions of pressure, while R1, R2, and Γg are
dimensionless [81].
2.28.2 Outcome
The P(V, E) equation of the JWL EoS has been emphasized as being one of the most
widely used EoS, for modeling the detonation of explosives. There are several other
forms of the JWL EoS, which have been proposed by different authors [82]. One of
the most commonly found JWL EoS has subsequently been expressed as an
isentrope [82], given as

P ¼ AeR1 V þ BeR2 V þ C ðSÞV ðω þ1Þ
, ð118Þ
where S is the entropy. A, B, R1, and R2 are constant fitting parameters associated
with the model, ω* is a constraint parameter, and C is a nontrivial function of S [82].
2.29 Murnaghan Equation of State
The Murnaghan EoS has been developed to predict the thermodynamical properties
of the solidified substances [83]. This EoS has fundamentally been proposed by an
Irish mathematician, Francis Dominic Murnaghan, in 1937. The EoS has
subsequently been used to predict the behaviors of the solids at high-pressure

equilibria [83]. It is important to note that due to the compact nature of the solid
and its minimum intermolecular spaces, a solid cannot be compressed easily. Under
such circumstances, Murnaghan has proposed the EoS, which can specifically be
used in earth science and shock physics [8, 83].
The Murnaghan EoS can be derived with the assumption that the bulk modulus
varies linearly with the pressure [8, 83]. At constant temperature, bulk modulus
K [8, 83] is given as

∂P
K ¼ V : ð119Þ
∂V T
The linear expression for the bulk modulus of the substance, as formulated by
Murnaghan [83], can be mathematically recast as
K ¼ K 0 þ PK 00 : ð120Þ
Here, K0 is the modulus of incompressibility (or isothermal bulk modulus at

P ¼ 0) and K 00 ¼ (∂K/∂P)P ¼ 0 [83]. Substituting Eq. (119) in Eq. (120), one gets the
Murnaghan EoS as

0
∂P
K 0 þ PK 0 ¼ V : ð121aÞ
∂V T
Integrating Eq. (121a) between the limits V ¼ V0 at P ¼ 0 to V ¼ V at P ¼ P, one

gets
" K 00 #
K V
P ¼ 00 1 , ð121bÞ
K0 V0
where V0 is the initial volume of the vessel confining the substance. Thus, the normal
form of the Murnaghan EoS is given by Eq. (121b). The values of each of the
parameters in Eq. (121b) are obtained through a regression analysis on the volume
fitted as V ¼ f(P) experimentally [83].
2.29.2 Outcome
The Murnaghan EoS can also be expressed as V ¼ f(P) [83], which is given as
0 1=K 00
K
V ¼ V0 1 þ P 0 : ð122Þ
K0
This makes the Murnaghan EoS very effective in thermodynamical calculations,

as both Eqs. (121b) and (122) can be easily integrated [83]. For V/V0 > 90%, the
Murnaghan EoS can provide accurate experimental data [8, 83]. However, it has
been reported that the EoS is limited to only a certain range of pressure (for small
compressions up to about 10%) [8] and fails at great compression (greater than
10%). Therefore, further refinement of the Murnaghan EoS is sought for achieving
better thermodynamical calculations in this direction.
2.30 Birch–Murnaghan Equation of State
The Birch–Murnaghan (BM) EoS has been developed to deal with the P–V relation-
ships for solidified substances at high compression equilibria [84, 85]. This EoS has
been proposed by an American geophysicist, Albert Francis Birch, in 1947, based on
the work of Francis Dominic Murnaghan, as explained above. This isothermal BM
EoS is a new form of the Murnaghan EoS, which uses the finite elastic strain theory
in the Eulerian scheme, after Murnaghan [8, 84].
It is to be noted that, matter becomes increasingly incompressible with pressure

when strains are finite, as postulated by Murnaghan [84]. Against this backdrop, he
has introduced the Eulerian finite strain [8, 85], which is analytically expressed as a
volumetric function as
"rffiffiffiffiffiffiffiffiffiffiffiffiffi #
2
1 3 V0
f E2 ¼ 1 : ð123Þ
2 V
After that, Birch has extended this theory to conduct his own EoS, which has been
later termed as the BM EoS [85]. The application of the Helmholtz free energy, FE,
by Birch has resulted in the formation of different orders of the EoS, namely, the
second, third, and fourth-order BM EoS [85]. From the thermodynamical viewpoint,
the pressure is the volume derivative of the Helmholtz free energy, which is
mathematically written as

∂F E
P¼ , ð124Þ
∂V T
and FE has been expressed in terms of a series of the Eulerian finite strain [8, 85],
given as
F E ¼ a0 þ a1 f E2 þ a2 f 2E2 þ a3 f 3E2 þ . . . : ð125Þ
With accurate calculations, Birch has expressed the second-order BM EoS [85],
given as
"rffiffiffiffiffiffiffiffiffiffiffiffiffi rffiffiffiffiffiffiffiffiffiffiffiffiffi#
7 5
3 3 V0 3 V0
P ¼ K0 : ð126Þ
2 V V
Here, the FE-expression (Eq. 125) has been truncated to the second-order term.
Similarly, the third-order BM EoS [85] is given by
"rffiffiffiffiffiffiffiffiffiffiffiffiffi rffiffiffiffiffiffiffiffiffiffiffiffiffi#" (rffiffiffiffiffiffiffiffiffiffiffiffiffi )#
7 5 3 V 0 2
3 3 V0 3 V0 3 0
P ¼ K0 1 þ K0 4 1 : ð127Þ
2 V V 4 V
The difference between Eqs. (127) and (126) is that the FE-expression (Eq. 125),
in case of the third-order BM EoS, has been truncated to the third-order term only
(as evident in Eq. 125). Similarly, a fourth-order EoS can also be derived when the
FE-expression is analogously truncated to the fourth-order term only, and so forth
[8, 85].
2.30.2 Outcome
The third-order BM EoS has been emphasized as the most frequently used EoS in the
emerging areas of solid-earth sciences, shock-induced physical sciences, and so on
[8, 85]. The BM EoS can also be derived with the help of another scheme, commonly
known as the Lagrangian Scheme [85], which describes the compression of matter
using the pre-compressed state as a reference, rather than the post-compressed state
in the Eulerian case [85]. Both the Lagrangian and the Eulerian schemes have shown
a similar increase in the rate of change in pressure under low compression. However,
it has been well reported in the literature that the Eulerian finite strain rapidly
increases and diverges if and when V/V0 ! 0 [85], which has indeed shown better
agreement than the Lagrangian scheme, with the fact that both FE, P ! 1 as V/V0
! 0 [85].
2.31 Rose–Vinet Equation of State
The Rose–Vinet (RV) EoS (also known as the universal EoS) has been developed to
deal with the relationships between the volume of a substance and the pressure to
which it is subjected (or which it exerts) [86]. This EoS has been proposed, in order
to modify the BM EoS which has shown inaccurate volume variation of most of the
existing solids under very high compression [8]. This isothermal EoS has considered
the exponential dependence of the repulsion between two constitutive molecules of
the solid substance due to strong compression.
Rose et al. in 1983 have proposed that the binding energy of metals can be
represented [60] as
G ¼ G0 ð1 þ ar Þea , ð128Þ
where a is the reduction of the atomic spacing [60], written as
r r0
ar ¼ : ð129Þ
l
Here, l is the scaling length characterizing the relative separation of two consti-
tutive molecules. r0 and r are the interatomic distances at zero and high pressure,
respectively [87, 88]. Vinet et al. (1987) have used Eq. (128) in order to derive the
RV EoS. Assuming the volume of metals at zero and high pressure to be V0 ¼ r03
and V ¼ r3, respectively [60, 87, 88], Eq. (128) can be recast as
p ffiffiffiffi p ffiffiffiffiffiffi p ffiffiffiffi p ffiffiffiffiffiffi
3
V 3 V0 3
V 3 V0
G ¼ G0 1þ e : ð130Þ
l l
Therefore, the isothermal bulk modulus can be written as

∂P ∂ ∂GðV Þ
K ¼ V ¼ V , ð131aÞ
∂V T ∂V ∂V T
"pffiffiffiffiffiffi pffiffiffiffiffiffi pffiffiffiffi pffiffiffiffiffiffi # p ffiffiffiffi p ffiffiffiffiffiffi
V 2 þ ðl 3 V 0 Þ 3 V 2 3 V 0 l V 3 V0
3 3
G0
K¼ 3 p ffiffiffiffiffi
ffi e : ð131bÞ
9l 3
V2 l
Substituting V ¼ V0 when P ¼ 0 [60] in Eq. (131b), K0 can be written as

qffiffiffiffiffiffiffiffi
G0 3
V 1
∂P 0
K 0 ¼ K P¼0 ¼ V 0 ¼ : ð132Þ
∂V T,P¼0 9l2
Now, one can derive the expression for K0 from Eq. (131b) as
1
0 ∂K ∂K ∂P
K ¼ ¼ , ð133aÞ
∂P T ∂V T ∂V T
which can be expanded with the help of Eqs. (130)–(131b) as

" pffiffiffiffiffiffi p ffiffiffiffiffiffi pffiffiffiffiffiffi p ffiffiffiffi pffiffiffiffiffiffi 2 #
1 V þ ðl 3 V 0 Þ V þ l 3 3 V 0 l V 4 3 V 0 l
3 2 2 3
0
K ¼ p ffiffiffiffiffiffi pffiffiffiffiffiffi pffiffiffiffi pffiffiffiffiffiffi ð133bÞ
3l 3
V 2 þ ðl 3 V 0 Þ 3 V 2 3 V 0 l
Similarly, replacing V ¼ V0 in Eq. (133b), K 00 can be expressed [60] as

∂K 2p ffiffiffiffiffiffi 2r
K 00 ¼ ¼1þ 3
V0 ¼ 1 þ 0 : ð134Þ
∂P T,P¼0
3l 3l
As stated above, the expression for the pressure expression can be written as
p ffiffiffiffiffiffi p ffiffiffiffi p ffiffiffiffi p ffiffiffiffiffiffi
∂ G0
3
V0 3 V 3
V 3 V0
P¼ ½ G ðV Þ ¼ 2 p ffiffiffiffiffi
ffi e , ð135aÞ
∂V 3l 3
V2 l
s ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
2 rffiffiffiffiffiffi h32p3 ffiffiffiV0
ffin pffiffiffiffioi
G0 3 V 3 V 1 3 VV
P¼3 : ð135bÞ
2 3l 0
1 e
9l2 V0 V0
Thus, replacing K0 and K 00 in Eq. (135b), the RV EoS [8, 60, 87, 88] can be
expressed as
rffiffiffiffiffiffirffiffiffiffiffiffiffiffiffiffiffiffiffi h n pffiffiffiffioi

3 V 3 V 0 2 32ðK 00 1Þ 1 3 VV0
P ¼ 3K 0 1 e : ð136Þ
V0 V
2.31.2 Outcome
Vinet et al. in 1987 have conducted experiments on various metals, such as H2, D2,
Xe, Rb, and Mo, and confirmed that the RV EoS has shown good performance in
predicting the thermodynamical properties of the solids [60]. Both the RV EoS and
BM EoS have shown similar results at a moderate compression; whereas, at high-
pressure equilibria, the RV EoS has the most accurate predictions of the
thermodynamical behaviors than the BM EoS [87, 88]. However, it has been later
shown that no existing two-parameter EoS can totally agree with the measurements
of high-order elastic moduli of the solidified substances [60, 87, 88]. Therefore,
further refinements of the RV EoS are necessary to look forward and beyond in this
direction.
2.32 Poirier–Tarantola Logarithmic Equation of State
The Poirier–Tarantola (PT) logarithmic EOS has been developed to modify the
results obtained from the BM EoS, which has shown errors in finding the volume
variation of the solids under very high compression [8, 61]. This EoS has been
proposed by a French physicist, Jean Paul Poirier and a Spanish physicist, Albert
Tarantola, in 1998. They have expressed the substantial pressure with a logarithmic
strain rather than the Eulerian or Lagrangian finite strain [8, 61].
Poirier and Tarantola have defined another strain, called as natural strain or hydro-
static compression [8, 62], which is given as

1 V
f N ¼ ln : ð137Þ
3 V0
This natural strain is different from the Eulerian finite strain of the BM EoS
[8, 85]. With the help of the natural strain, the PT EoS is derived [61], now expressed
as
K 0 2 n o2
V0 V V
P ¼ K0 ln 0 þ 0 ln 0 : ð138Þ
V V 2 V
2.32.2 Outcome
The PT EoS has subsequently shown good performance in predicting the thermo-
dynamical properties of the solids at high-pressure range against the BM EoS
[61]. The inclusion of the Hencky logarithmic strain in the PT EoS has shown
equivalent results with respect to the Eulerian strain of the BM EoS, for a small
amount of applied strain. However, this Hencky strain has its benefits over the
Eulerian scheme at large strain [63]. It has later been shown however that the Hencky
strain, fN, proposed by Poirier and Tarantola, varies as a function of V0/V, which
indicates that an increase in the compression will increase the Hencky potential. This
resultant increase in the Hencky potential deviates from the other determined
parametric potential [63]. So, it has been reported that the PT EoS is valid only up
to a short range of compression [8, 63].
2.33 Kumari–Dass Equation of State
The Kumari–Dass (KD) EoS has been developed to predict the thermodynamical
properties of solidified substances. The KD EoS is, in fact, similar to the Murnaghan
EoS [64]. This KD EoS has considered an expression of the bulk modulus, K; where,
the ratio K/K0 is assumed to be independent of the pressure (Eq. 139) [64].
The expression for the bulk modulus K for the KD EoS [64] is given as
K 00
K ¼ K0 þ 1 eλP , ð139Þ
λ
where λ is a constraint parameter for the bulk modulus. Therefore, using Eq. (119) in
Eq. (139), one can derive the KD EoS as

K 00 ∂P
K0 þ 1 eλP ¼ V , ð140aÞ
λ ∂V T
which, on integration between the limits V ¼ V0 at P ¼ 0 to V ¼ V at P ¼ P, yields

" λK 0 þK 00 #
1 V K 00
P¼ K0 þ : ð140bÞ
λK 0 þ K 00 V0 λ
Thus, the normal form of the KD EoS is given by Eq. (140b) [64], which, clearly,
portrays the intimate relationship among P, V, and K.
2.33.2 Outcome
The KD EoS has shown a good performance in predicting the thermodynamical

properties of the solids to a volume compression of 0.7 [22, 65]. However, similar to
the Murnaghan EoS, the KD EoS cannot be applied to a very high temperature due to
its volume compression limit (greater than 0.7). It has been emphasiszed that such
EoS have to satisfy some basic criteria on the control parameters including their
extreme values, which have been set by an Australian geophysicist, Franck Donald
Stacey, in order to have a brief analysis of the thermodynamical behaviors of the
solidified substances at relatively high compression equilibria [65]. Clearly,
Eq. (140b) depicts that P ! 1 when V/V0 ! 0, which satisfies the first criterion
set by Stacey. It has been reported that K0 in Eq. (140b) is constant at high pressure,
while K remains nearly zero for the same [65]. This reference does not match with
the second criterion that invokes the fact that, at large pressure, one finds that K0 !
1. Thus, K should increase linearly with the pressure in order to reveal the actual
thermodynamic scenarios of greater applied interest [65].
2.34 Baonza Equation of State
The Baonza EoS has been developed to deal with the P–V relationships of solidified
substances, with the help of a model, similar to that of the Murnaghan EoS
[66]. Valentin Garcia Baonza et al. have primarily proposed a simple analytical
expression for K in order to predict the thermodynamical properties of the solids
accurately. It is equivalent to the description as in the case of the RV EoS [66]. This
Baonza EoS has also been able to provide a reasonable precision for the thermody-
namical behaviors of different molecular liquids at high-pressure equilibria.
The expression for K, as proposed by Baonza et al. [66], is given as

γ
K 00
K ¼ K0 1 þ P , ð141Þ
K0
where γ * is a constraint parameter that relates K and K0 via Eq. (141) [66]. Now,
equating Eq. (119) and Eq. (141) for K, one gets
γ
K 00 ∂P
K 0 1 þ P ¼V : ð142aÞ
K0 ∂V T
When Eq. (142a) is integrated between the limits V ¼ V0 at P ¼ 0 to V ¼ V at

P ¼ P, one gets
" 1 #
K 1 V 0 1γ
P ¼ γ 00 1þ K 00 1 ln 1 : ð142bÞ
K0 γ V
Thus, the normal form of the Baonza EoS is given by Eq. (142b), which is
obviously a logatropic barotropic EoS in nature [66]. It is clear from Eq. (141) that
the expression for K is of the explicit functional form K ¼ f(P), modulated by γ ,
playing the role as a binomial exponent. As an advantage, it helps us in accounting
for a large range of the pressure for the needful thermodynamical calculations to
proceed in different thermodynamical conditions of practical importance
[66, 67]. This relevant feature of thermodynamical interest makes the Baonza EoS
supersede other commonly used EoS, such as the BM EoS and Murnaghan EoS.
2.34.2 Outcome
It has been reported that the Baonza EoS is not applicable for predicting thermody-
namical properties at very high compression. However, in a comparable range of
pressure, this EoS has shown high precision, with results equivalent to those of the
RV EoS [66, 67]. Moreover, it has been shown that the EoS cannot provide accurate
values of the cohesive energy of the solidified substances [66, 67]. In other words,
the Baonza EoS cannot subsequently be used for physical descriptions of the energy
property of the solids in a unique cohesive perspective [66].
2.35 Shanker Equation of State
The Shanker EoS has been established to analyze and study the volume compression
of materials such as nanocrystalline materials (polycrystalline material with a crys-
tallite size ~nm) under different pressure conditions [68]. The EoS has been devel-
oped with the help of the Grüneisen theory of thermal expansion, formulated by Max
Born and Kun Huang in 1954 [68], which has been modified by Shanker et al. by
including the truncated Taylor series expansion of the lattice potential energy, U*,
asymptotically [68–70].
For a solid, the Shanker EoS in a generic form [68, 69] is given as
d
P¼ ½U ðV Þ þ PTh , ð143Þ
dV
where PTh is the thermal pressure. U* can be expanded in terms of Δ ¼ (V – V0). As

mentioned, Shanker et al. have used the concept of the Grüneisen theory of thermal
expansion to derive the EoS [68, 69]. They have truncated the Taylor series
expansion for U* into a Δ-polynomial expression in the customary notations [68–
70], presented here as
1 00 2 1 000 3
U ¼ U 0 þ U 0
0 Δ þ 2 U0 Δ þ 6 U0 Δ : ð144Þ
The derivative of U* with respect to V from Eq. (144) is given as
dU 1 000 2
¼ U 0 00
0 þ U0 Δ þ 2 U0 Δ , ð145Þ
dV
where the coefficient terms in the right side of Eq. (145) are the volume-derivative of
U* of their respective orders, under an extreme condition defined by Δ ¼ 0, i.e.,
V ¼ V0. Therefore, in equilibrium, we find that U 0 0 ¼ 0 [68, 70]. Also, the second-
order and the third-order volume derivatives of U* at V ¼ V0 [68, 70] are respectively
given as
K0
U 00
0 ¼ , ð146Þ
V0

000 K 0 K 00 þ 1
U 0 ¼ : ð147Þ
V 20
Now, with the help of Eq. (145), Eq. (143) can be expressed as
00 1 000
P ¼ U 0 Δ U 0 Δ2 þ PTh : ð148Þ
2
Substituting Eqs. (146) and (147) in Eq. (148) and assuming PTh 0, Shanker
et al. have finally obtained a new EoS with all the generic notations [68, 70], which is
expressed as
" ( 2 )#
V K 00 þ 1 V
P ¼ K0 1 þ 1 : ð149Þ
V0 2 V0
Thus, Eq. (149) represents the normal form of the Shanker EoS, which is
obviously an algebraic polynomial form in terms of the relative volume of the
substance under consideration [68, 70].
2.35.2 Outcome
Several analyses of the nanocrystalline materials have been performed with the help
of the Shanker EoS. Under such experiments, the Shanker EoS has displayed
suitably accurate results for volume compression under low pressure [68]. However,
at high pressure, this EoS has failed to provide reasonable and suitable results.
Therefore, a new modified version (on an empirical basis) of the Shanker EoS,
proposed in 2008 [71], has been introduced, which has improved the results of this
EoS when compared with the experimental data at high compression [68, 71]. The
newly modified Shanker EoS [68] is cast as
" ( 2 )#
K V V K 00 þ 1 V
P¼ 0 0 1 þ 1 : ð150Þ
V V0 2 V0
2.36 Freund–Ingalls Equation of State
The Freund–Ingalls (FI) EoS [72] has been developed to modify the results obtained
0
from the KD EoS, which has shown errors in finding K and K of the solids under
very high pressure [23]. It is one of the inverted EoS, similar to the Murnaghan EoS.
This EoS has two elastic parameters [23, 73], due to the presence of K0 and K 00 [73].
The generalized form of an inverted EoS, as far as seen in normal environs [73], is
given as
1
V A K 00 þ A A
¼ 1 0 ln 1 þ P , ð151Þ
V0 K0 þ A K0
where A is an adjustable parameter [72]. When A ¼ 1, the generalized Eq. (151) is

modified to the KD EoS, which is the simplest form. However, when A ¼ 1/3,
Freund and Ingalls have introduced a new EoS in terms of pressure [72], given as
"(sffiffiffiffiffiffiffiffiffiffiffiffi
ffi ) #
e ð K 0 þ 3Þ
9K 0 0 1 3 V
P¼ 1 1 : ð152Þ
3K 00 þ 1 V0
2.36.2 Outcome
From Eq. (151), the expression of K can be easily derived [73] as

A
A K 0 þA
0A V
1
V V0
K ¼ K0 e : ð153Þ
V0
The derivative of K with the help of Eq. (153) is given [73] as


dK 0 V A
K0 ¼ ¼ K0 þ A A: ð154Þ
dP V0
At P ! 1, V ! 0. As a result, V/V0 ! 0 and K0 ! K 01 [73]. Thus, K 01 can be

written as
K 01 ¼ A: ð155Þ
For the FI EoS, K 01 ¼ 1/3, which is not consistent with the thermodynamics of
the solids at extreme pressure conditions (or when V/V0 > 0.6) [73]. Therefore, the FI
EoS is not accurate for showing P–V relationships for solid materials subject to high
compression circumstances.
2.37 Tait Equation of State
The Tait EoS has been developed to predict the thermodynamical properties of the
liquids and to relate the liquid density to pressure. This EoS has been originally
proposed by Peter Guthrie Tait, in 1888 [74]. Tait has inclined for an EoS that relates
between pressure and volume of the liquids through a logarithmic function that has
the same ratio of V/V0 (or ρ/ρ0) for constant mass). The EoS is purely empirical and
originally proposed for dealing with water [18].
The expression for K [75], in case of the Tait EoS, can be considered as

1 ∂V 1 C
K¼ ¼ , ð156Þ
V ∂P T V ðB þ PÞ
where B and C are the parameters which are functions of temperature only and
independent of pressure [75]. With the help of Eq. (156), the Tait EoS [75] has been
derived as
Z V Z P
CdP
dV ¼ , ð157aÞ
V0 P0 BþP
which on simplification yields the Tait EoS as


PþB
V ¼ V 0 C log 10 : ð157bÞ
P0 þ B
In terms of pressure, the above Tait EoS can be rearranged as

Δ
P ¼ ðP0 þ BÞ10C B, ð158Þ
where Δ ¼ (V – V0) as already mentioned above. Thus, Eq. (158) represents the most
commonly used form of the Tait EoS. This EoS has also been further applied in
predicting the P–V relationships and the linking indicator phase diagrams for many
compressible solids [75].
2.37.2 Outcome
It is seen from Eq. (158) that, when V ! 1, then P1 can be expressed [75] as
P1 B: ð159Þ
The negative value of the pressure, as indicated from Eq. (159) when V ! 1,
makes it theoretically unsuitable [75], as it is not consistent with the thermodynamics
of the substances in extreme conditions. In other words, it violates the so-called
Boyle law (PV ¼ Pressure energy ¼ constant) and hence the usual form of the
energy conservation principle [1]. Therefore, this EoS needs to be further amended
so that it could be used in an extended range of pressure.
2.38 Brennan–Stacey Equation of State
The Brennan–Stacey (BS) EoS is one of the several isothermal EoS that studies the
volume compression relation of the solid materials [30]. This BS EoS has originally
been derived from the thermodynamic articulation of the Grüneisen parameter, Γg
[30]. The BS EoS is similar to that of the Shanker EoS since both EoS can be derived
from the lattice potential theory [30].
Assuming that Γg is proportional to volume, Stacey et al. have derived the BS EoS
[76]. With this assumption, K [30] has been expressed as
ffi h 0 5 V i
sffiffiffiffiffiffiffiffiffiffiffiffi
3 V ðK 0 3Þ 1V 0 4
K ¼ K0 e þ P: ð160Þ
V0 3
Now, K0 can be written [30] with the help of Eq. (160) as

0 dK 4 P 0 5 V 5 16 P
K ¼ ¼ 1 K0 þ þ : ð161Þ
dP 3 K 3 V0 3 9 K
Therefore, substituting K from Eq. (160) in Eq. (119), one gets
ffi h 0 5 V i
sffiffiffiffiffiffiffiffiffiffiffiffi
3 V ðK 0 3Þ 1V 0 4 ∂P
K0 e þ P ¼ V : ð162Þ
V0 3 ∂V T
As the homogenous differential Eq. (162) is solvable; therefore, integrating

Eq. (162) between the limits V ¼ V0 at P ¼ 0 to V ¼ V at P ¼ P, one gets
sffiffiffiffiffiffiffiffiffiffiffiffiffiffi
4ffi hn3K 00 5 V o i
3K 3 V 1V 1
P¼ 0 0 : ð163Þ
3 0
e
3K 0 5 V0
Therefore, the normal form of the BS EoS in a generic form [30] is given by
Eq. (163). Evidently, it represents a nonlinear relationship depicting the evolution of
pressure with change in volume and elasticity in case of solid materials. It may be
noted from Eq. (163) that, as V/V0 ! 0, P ! 1 (as above); thereby, satisfying the
first criterion of the control parameters for solidified substances at relatively high
compression equilibria set out by Stacey [65].
2.38.2 Outcome
The validity of the BS EoS lies on the fact that it can provide quite close to accurate
results of the thermodynamical properties of the solids when introduced to high
pressure [30]. From Eq. (161), K 00 can be formulated. As P ! 1, one finds K 01 [77]
as
4
K 01 ¼ : ð164Þ
3
However, it has been reported that K 01 of this EoS does not follow the criterion
that at extreme pressure, K 01 5/3 (e.g., Earth’s deep interior) [77]. Thus, this BS
EoS has failed to predict the actual behaviors of the solidified substances at high
pressures, or at high compressions [77].
2.39 Equation of State for an Ideal Fermi gas
The ideal Fermi gas EoS has been developed to deal with the thermodynamic
properties of the ideal Fermi gas. The EoS has been proposed to analyze the
invaluable insights of identical particles forming the Fermi system [24, 89]. An
ideal Fermi gas is said to be a state of matter which is a collection of several
noninteracting Fermions. Fermions are the noninteracting particles having spin-
½ћ, which form a Fermi system, ћ ¼ 1034 J s1 is the reduced Planck constant
[89]. The Fermi gas has been primarily discovered from the model proposed by an
Italian physicist, Enrico Fermi [24, 89].
To analyze the thermodynamic properties of an ideal gas, it is necessary to have a

thermodynamic potential expression. Therefore, for a system of N-identical Fermi-
onic particles, the use of a grand partition function (with fixed temperature and
volume) to derive the chemical potential is very useful [24]. For a grand canonical
ensemble, the canonical partition function for any ideal gas is given as [24]
X
QN ðV, T Þ ¼ g np eβEfnp g , ð165Þ
fn p g
where {np} is the set of occupational numbers which defines np number of particles
having p momentum in that state, g{np} is the number of states corresponding to
{np}, E{np} is the energy of states corresponding to {np}, and β ¼ 1/kBT is the
thermodynamic park. {np} and E{np} have to satisfy the given condition [24]
presented as
X
E np ¼ E p np , ð166Þ
p
X
N¼ np , ð167Þ
p
where N is the total number of particles in the corresponding state and Ep is the
single-particle energy (Ep ¼ p2/2m). For an ideal Fermi gas, np has value either 0 or
1. Therefore, the number of states corresponding to {np} is given as [24]

g np ¼ 1: ð168Þ
The grand partition function, Z(z, V, T ), in terms of QN is given as [24]

X
1
Z ðz, V, T Þ ¼ zN QN ðV, T Þ, ð169Þ
N¼0
where z is known as the absolute activity or fugacity. With the help of Eq. (165), the
grand partition function can be solved for the Fermi gas as
1 X
X P
Z ðz, V, T Þ ¼ zN eβ Ep np
, ð170aÞ
N¼0 fnp g
X
1 X P P
np β Ep np
¼ z e , ð170bÞ
N¼0
fP
np g
np ¼N
1 XY
X
¼ znp eβEp np ð170cÞ
N¼0 fnp g p
XXX h n0 n1 n2 i

¼ ... zeβE
0
0
zeβE
1
1
zeβE
2
2
... , ð170dÞ
n0 n1 n2
X βE n0 X βE n1 X βE n2
¼ ze0 0 ze1 1 ze2 2 ... ð170eÞ
n0 n1 n2
As mentioned, for an ideal Fermi gas, n ¼ 0, 1. Therefore, the grand partition

function for the Fermi gas, using Eq. (170e) is given [24] as
" #
Y X
βEp n
Z ðz, V, T Þ ¼ ze , ð171aÞ
p n¼0, 1
Y
¼ 1 þ zeβEp : ð171bÞ
p
The grand partition function can be used to estimate the EoS for the Fermi gas in
grand canonical ensemble. The EoS for the ideal Fermi gas can be expressed [24] as
( )
Y
PVβ ¼ log ½Z ðz, V, T Þ ¼ log 1 þ zeβEp , ð172aÞ
p

PVβ ¼ log 1 þ zeβE01 þ zeβE1 1 þ zeβE2 . . . , ð172bÞ
X
PVβ ¼ log 1 þ zeβEp : ð172cÞ
p
Huang (1987) has mentioned that as V ! 1, the possible values of the momen-
tum p change to continuum which can help to replace the summation over p to
integration over p, given as
X Z
V
! d3 p, ð173Þ
p h3
where h ¼ 2πћ is the Planck constant, designating the minimum unit of quantum
action. Therefore, the EoS (Eq. 172c) can be rearranged and presented [24] as
Z 1
4π βp2
Pβ ¼ p2 log 1 þ ze 2m dp, ð174aÞ
h3 0
1 X ð1Þ zl
1 lþ1
P¼ pffiffiffiffi : ð174bÞ
βλ l¼1
3
l5
Here, the parameter λ ¼ √(2πћβ/m). Also,

Z 1
1 N 4π 1
¼ ¼ 3 p2 βp2
dp, ð175aÞ
v V h 0 1 þ z1 e 2m
1 X ð1Þ zl
1 lþ1
1
¼ 3 pffiffiffiffi : ð175bÞ
v λ l¼1 l3
2.39.2 Outcome and Analysis
According to Huang (1987), at high temperatures and low densities, which is usually
given as Nλ3/V ¼ λ3/v 1, the average interparticle separation, v1/3 λ, i.e., the
thermal wavelength. Therefore, the ideal Fermi gas EoS (Eq. 174b) gets reduced [24]
as

v z2 1 λ3
Pvβ ¼ z p ffiffiffiffi
ffi þ . . . ¼ 1 þ pffiffiffiffiffi þ . . . : ð176Þ
λ3
25 25 v
Clearly, this is a form of thermodynamic virial expansion. While at low temper-

atures and high densities, where Nλ3/V ¼ λ3/v 1, the average interparticle
separation, v1/3 λ, i.e., the thermal De Broglie wavelength. Under such situation,
it is assumed that at absolute zero
z eβEF , ð177Þ
where EF is the electron Fermi energy at which the electronic occupancy probability
becomes exactly 50% (defined in Table 1). With some further calculations under
specific conditions, the EoS (Eq. 174b) in low temperature and high density [24] is
written as
" 2 #
2 EF 5π 2 1
P¼ 1þ þ ... : ð178Þ
5 v 12 βEF
It is seen from Eq. (178) that the pressure does not vanish even at absolute zero.
Thus, the Fermi gas is needed to be confined using fixed walls [24]. An ideal Fermi
gas with maximum energy depending on the Fermi level energy remains in the
ground state and the particles occupy all the quantum states at T ¼ 0 K [24]. How-
ever, the Fermi gas degeneracy occurs when the quantum states with energy greater
than the Fermi energy remains empty, and so forth [24, 89].
2.40 Equation of State for an Ideal Bose Gas
The ideal Bose gas EoS has been established to deal with the thermodynamic
properties of the ideal Bose gas. This EoS has been developed to study the critical
properties of a gas of noninteracting bosons [24, 90]. The bosons are the subatomic
particles with zero or integral spins, such as photons, phonons, and gluons [90]. The
capability of bosons to occupy the same quantum state without any kind of limit
marks the main difference between the bosons and the fermions. The model for the
ideal Bose gas has been primarily derived by an Indian mathematician and physicist,
Satyendra Nath Bose. The nomenclature “Boson” has been coined after him by Paul
Dirac in his paper [24, 90].
A thermodynamic potential expression is necessary to understand the thermody-

namic properties of any ideal gas. Therefore, a partition function, as stated above,
can be used for a system of N-identical bosons in a grand canonical ensemble. It is
important to note that, for an ideal Bose gas, n ¼ 0, 1, 2, 3, . . . [24]. Therefore, using
Eq. (171a), the grand partition function for an ideal Bose gas can be written and
presented as [24]
" #
Y X Y 1
βEp n
Z ðz, V, T Þ ¼ ze ¼ : ð179Þ
p n p ð1 zeβEp Þ
Therefore, with the help of Eq. (179), the EoS for an ideal Bose gas can be
expressed as [24]
" #
Y 1 X
PVβ ¼ log ½Z ðz, V, T Þ ¼ log βE
¼ log 1 zeβEp : ð180Þ
p ð1 ze p Þ p
However, Eq. (180) diverges at p ¼ 0 when V ! 1 [24]. Thus, this EoS is split at
p ¼ 0 and the rest part of the sum is changed to an integral (Eq. 173). Therefore,
Eq. (180) is written [24] as
Z 1
4π βp2 1
Pβ ¼ p2 log 1 ze 2m dp log ð1 zÞ, ð181aÞ
h3 0 V
1 X zl
1
1
P¼ pffiffiffiffi log ð1 zÞ, ð181bÞ
βλ3 l¼1 l5 V
and
Z 1
1 N 4π 1 1 z
¼ ¼ 3 p2 dp þ , ð182aÞ
v V h z1 e 2m 1
0
βp2 V 1z

1 X zl
1
1 1 z
¼ 3 pffiffiffiffi þ , ð182bÞ
v λ l¼1 l3 V 1 z
where, h ¼ 2πћ is the Planck constant and the parameter λ ¼ √(2πћβ/m).
To satisfy the EoS of an ideal Bose gas, Huang (1987) has clearly mentioned that z 2
[0, 1]. Therefore, for small z, the power series expanded form of Eq. (182b) can be
expressed [24] as
X1
zl z2 z3
t ðzÞ ¼ pffiffiffiffi ¼ z þ 3 þ 3 þ . . . : ð183Þ
l¼1 l3 22 22
At z ¼ 1, t(1) is found to be finite, i.e., t(1) ¼ 2.612 [24]. Therefore,
t ðzÞ < 2:612: ð184Þ
Let the expression of 1/v in Eq. (182b) be rearranged [24] as


λ3 λ3 z
t ðzÞ ¼ , ð185aÞ
v V 1z
λ3
t ð1Þ > 0: ð185bÞ
v
When λ3/v > t(1), a finite number/fraction of particles inhabit the region where
p ¼ 0 [24]. This conditional phenomenon which exists in a subspace region of the P–
v–T space of the ideal Bose gas at low densities and has a transition from the rest of
the region is known as the Bose-Einstein condensation (BC), also known as the fifth
state of matter [24].
Therefore, if Tc and vc are the critical temperature and critical volume, respec-
tively, at which λ3/v ¼ t(1), then the region of condensation can be defined as the
region in the P–v–T space of the ideal Bose gas at low densities where T < Tc and
v < vc. Thus, the ideal Bose gas EoS (Eq. 181b) can be further generalized with the
help of the specified regional range as [24]
8
1 X zl
1
>
>
>
> pffiffiffiffi , for v > vc ðor T > T c Þ,
< βλ3 l5
l¼1
P¼ ð186Þ
> 1 X
>
1
1l
>
> pffiffiffiffi , for v < vc ðor T < T c Þ,
: βλ3
l¼1 l5
where the linearity or nonlinearity of P clearly depends on the strength of v relative

to vc. The term log(1 z)/V is neglected in both of the cases [24]. The only kind of
Bose system known to exist at low temperature is He4. It is important to note that the
particle number conservation law is necessary for the occurrence of the Bose-
Einstein condensation [24].
2.41 Equation of State for Boltzmann Gas
The Boltzmann gas (or classical gas, or Maxwell-Boltzmann gas) EoS has been
proposed to deal with the thermodynamic properties of noninteracting particles over
various energy states in thermal equilibrium. The Boltzmann system has been
developed with the fact that the particles in the system are indistinguishable
[24]. Such system does not exist as there is no known particle that exhibits the
Maxwell-Boltzmann thermostatistical law.
As mentioned earlier, an EoS for an ideal gas can be derived from the grand partition
function. It is important to know that for a Boltzmann gas, n ¼ 0, 1, 2, 3, . . .
Therefore, the number of states corresponding to {np} is given [24] as
0 1
1 @QN! A
g np ¼ , ð187Þ
N! np !
p
Therefore, the partition function (Eq. 165) for the Boltzmann gas can be given
[24] as
0 1 P
X 1 β Ep np
QN ðV, T Þ ¼ @QN! Ae p , ð188aÞ
N! np !
fn p g p
X
eβEp np eβEp np . . .
¼ , ð188bÞ
n0 !n1 ! . . .
n0 , n 1 , n 2 , . . .
P
ni ¼ N
i
1 βE0 N
¼ e þ eβE1 þ eβE2 þ . . . , ð188cÞ
N!
!N
1 X βEp
¼ e : ð188dÞ
N! p
Therefore, the grand partition function (Eq. 169) for the Boltzmann gas can be
written [24] as
!N
1 X
X X
βEp
Z ðz, V, T Þ ¼ zN
e , ð189aÞ
N¼0 fnp g p
Y
¼ exp zeβEp : ð189bÞ
p
Therefore, the EoS for the Boltzmann gas can be derived [24] as
" #
Y
βEp
PVβ ¼ log ½Z ðz, V, T Þ ¼ log exp ze , ð190aÞ
p
1 X βEp
P¼ ze : ð190bÞ
βV p
Also, the number of particles, N, can be estimated [24] as
∂ X
N¼z ½ log fZ ðz, V, T Þg ¼ zeβEp : ð191Þ
∂z p
Therefore, the EoS can be written in the form of PV ¼ N/β. In other words, it can
be summarized that in case of the Boltzmann gas, the grand partition function is
trivial [24].
It can be noted that the trivialness of the grand partition function for the Boltzmann
gas has shown another way of proving the same EoS, by using the partition function
for the Boltzmann gas only [24]. If V ! 1, the summation of the exponential term
can be rearranged in a continuum set, which can be expressed as
X Z 1 3=2
βEp V 2 βp
2
m
e ¼ 3 4πp e 2m dp ¼ V : ð192Þ
p h 0 2πβћ2
Therefore, using Eqs. (188d) and (192), one can estimate the following expres-
sion [24]
" 3N2 # N
1 1 1 N m 1 α
log ðQN Þ ¼ V 2
¼ log , ð193aÞ
N N N! 2πβћ N N!
where α ¼ V [√(m/2πβћ2)]. Therefore, Eq. (193a) can be further broken as
1 1
log ðQN Þ ¼ log αN log ðN!Þ : ð193bÞ
N N
Using Starling’s approximation method in Eq. (193b), one gets

N
1 1 1 α
log ðQN Þ ¼ log αN N log ðN Þ ¼ log , ð194aÞ
N N N NN
" 32 #

1 α V m
log ðQN Þ ¼ log ¼ log : ð194bÞ
N N N 2πβћ2
Huang (1987) has reported that Eq. (194b) easily follows and satisfies the ideal
EoS, i.e., PV ¼ N/β in the generic form. Thus, the trivialness of the grand partition
function in the Boltzmann gas is true and we can neglect the use of this function
while deriving the EoS [24]. It may be noted that, at high temperatures, both the
Fermi and Bose systems tend to approach towards the Boltzmann system, where the
particles of the former systems become distinguishable [24].
2.42 Equation of State for Compact Astrophysical Objects
There could exist several EoS for compact astrophysical objects that have been
developed to deal with the properties and the extreme conditions of the compact
stellar remnants and other like objects in the polytropic fabric [91–99, 101, 102]. It
contextualizes brown dwarfs, white dwarfs, red dwarfs, neutron stars, magnetars,
black holes, and so forth. It is seen that compact stellar objects usually have a higher
mass than that commensurable to their size. It hereby results in their degenerate
states, which are indeed high-density configurations in real space [96]. Such struc-
tures consist of quantum plasmas so compacted with high density and low temper-
ature that the constitutive particles’ de Broglie wavelengths become significant
[99, 101]. These structures are consequent upon the counterbalancing mechanism
between the radially inward self-gravitational (non-quantum) pressure and the radi-
ally outward quantum-mechanical (nongravitational) degenerate pressure of the
constituent fermions. It seems to be extremely important to formulate an appropriate
EoS, which could connect the most relevant thermophysical variables for such
structures in a more refined way. This family of EoS is anticipated to be capable
of illuminating the proper conceptual framework about their inhomogeneous con-
centric constitutive multilayer coupling of the remnant stars and their ambient
degeneracy effects in diversified nonlocal astrocosmic scenarios [99, 101, 102]. It
would contribute to understand various collective instability processes and cooper-
ative phenomenology actively governed by the exotic properties of nuclear
matter [96].
2.42.1 A Brief Overview of Compact Astrophysical Objects
The compact stars can be explained as the gaseous stars in hydrostatic equilibrium
(state of fluids with surfaces at constant pressure and mass), which remain stable due
to their internal pressure support against gravity [91]. The internal pressure of such
stars could have originated under different circumstances, which as a result, would
lead to different compact families of stellar objects. Following are some of their
circumcised conditions [92]
(a) Degeneracy pressure of electrons, e.g., white dwarfs.

(b) Degeneracy pressure of neutrons and repulsive strong interactions above nuclear
density, e.g., neutron stars.
(c) Thermal pressure of the hot gas, such as shining stars.
(d) Pressure due to degenerate strange quarks along with their confined pressure
(also known as bag pressure), e.g., quark stars.
There are two distinct categories of the EoS [92] depending on the relativistic
effects in the constitutive matter in case of compact astrophysical object. They are
commonly named as
(a) Nonrelativistic regime;
(b) Relativistic or ultra-relativistic regime.
One may find it convenient to formulate the EoS for the white dwarfs as the
degenerate pressure of the constitutive electron gas is found to be a ρ-dependent
parameter. Such EoS are called polytropic EoS and are written symbolically [91] as
P / ρΓ , ð195Þ
which yields,
1
P ¼ K P ρΓ K P ρ1þnP , ð196Þ
where KP is known as the polytropic constant, which is replaced with Knr for
nonrelativistic stars and Kur for ultra-relativistic stars. Γ ¼ (1 + nP1) is called the
polytropic exponent and nP is called the polytropic index [91]. With the help of a
white dwarf model, interesting solutions of the hydrostatic equilibrium for a general
polytropic EoS (termed as the Lane-Emden EoS [91] coined after the American
astrophysicist, Jonathan Homer Lane and the Swiss astrophysicist, Robert Emden)
can be evaluated. It can subsequently be utilized to understand the internal dynamics
operating in other astrophysical objects in a broader perspective [92].
White Dwarfs
White dwarfs are said to be small, hot, and dim stellar objects which faint abruptly
due to their white color. These dwarfs represent the most common endpoints of the
stellar evolution as dying stars. It is known that about 90% of all the stars will end up
as such white dwarfs. The mass of heavy white dwarf stars scales from 1.2–1.4MJ,
where MJ ~ 1030 kg is the mass of the Sun and MCh ¼ 1.4MJ is the theoretical
upper mass limit of white dwarfs, known as the Chandrasekhar mass [99]. The lack
of brightness is specifically due to the used-up hydrogen and the presence of helium
under high-temperature conditions [24, 96]. The self-gravitational force exerted by
the star attracts and binds the whole heavier helium nuclei within the star against the
degenerate electron quantum pressure. So, white dwarfs are also known as
degenerate dwarf stars or compact stars due to the presence of ionized gases in a
dense matter form. The high temperature of the dwarf stars results in ionization of the
trapped gases thereby creating both nuclei and electrons [90–93, 96].
As stated above, the pressure expressions of the degenerate electron gas present
inside the white dwarf are characterized into two categories, which are ρ-dependent.
The general expression of the polytropic EoS is the same for both the nonrelativistic
and relativistic regimes parameterized via the polytropic exponent as 5/3 and 4/3,
respectively [93, 96–98].
White Dwarfs in the Nonrelativistic Regime
In the Sommerfeld picture, the expression for the nonthermal pressure for a fully
degenerate electron gas practically realizable for white dwarf stars [94] is given as
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
5
π h2 3 3ne
Pe ¼ , ð197Þ
60 m π
where ne represents the number density of the constitutive electrons and m is the
mass of this electron. The expression for ne available in the literature [94] is given as
ρ
ne ¼ ð1 þ f Þ1 , ð198Þ
μ mH
where ρ is the material density of the stellar object, mH is the mass of hydrogen atom,
μ is the molecular weight per electron of the ionized medium, and f is the ratio of the
ionic population and the electronic population [94]. With the assumption that μ ¼ 5/
2 for a fully ionized material (such as plasmas), the total pressure can be derived and
expressed [94] as
0 sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi 1
5 sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi5ffi
π h 3 2
3 A 3 5 ð1 þ f Þ1 ρ
P¼@
60 m πmH 2
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
5
5
ð1 þ f Þ1 ρ ,
3
¼ 9:84 1012 ð199Þ
2
If the above individual constant terms are collectively replaced with Knr, one can
write.
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
K nr ¼ 9:84 1012 ½2:5ð1 þ f Þ5 : ð200Þ
3
The total pressure, as a consequence, can be expressed in terms of material

density. This expression comes in the limit when the degenerate electron gas is
nonrelativistic. Therefore, the pressure is called the nonrelativistic electron degen-
eracy pressure [91–94], given as
5 ~5
Pnr ¼ K nr ρ3 ρ3 : ð201Þ
It is obviously needless to point out that Eq. (201) is in a standard form of the
polytropic EoS. Using Eq. (196), one gets nP ¼ 3/2. As Pnr / (ρ)5/3, the degenerate
electron gas is more resistant to the compression than that of an ideal gas [93]. There-
fore, in the nonrelativistic regime, the EoS for the white dwarfs is a stiff EoS (or hard
EoS) as already seen in the literature [96]. A more generalized construct to express
the dependency of the polytropic constant for the stellar ionized matter on the
relevant fundamental parameters (in terms of μ and NA) in the nonrelativistic regime
under consideration can be presented [91, 93] as
rffiffiffiffiffiffiffiffiffiffiffi sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
2 2 3 5 ~ 53
3 3 h NA NA
K nr ¼ : ð202Þ
π 20m μ μ
White Dwarfs in the Relativistic Regime
The expression for the nonthermal pressure for a fully degenerate electron gas (with
a supercritical electronic concentration related to the usual benchmark) in the ultra-
relativistic regime, as seen in the literature [95], is given as
rffiffiffiffiffiffiffiffi
ffi qffiffiffiffiffi
1 3 3
Pe ¼ hc 3 n4e , ð203Þ
8 π
where c ¼ 3 108 m s1 represents the vacuum speed of light. With the help of
Eq. (198) for ne, and assuming μ ¼ 5/2 for completely ionized material, the total
pressure is expressed [95] as
rffiffiffiffiffiffiffiffi sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ffi 3 4
1 3 5
ð1 þ f Þ1 ρ :
3
P¼ hc ð204Þ
8 π 2
Replacing the above individual constant terms, collectively as Kur, one [95] gets
rffiffiffiffiffiffiffiffi !qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ffi qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
1 3
½2:5ð1 þ f Þ4 ¼ 3:62 1014 ½2:5ð1 þ f Þ4 :
3
K ur ¼ ð205Þ
3 3
hc
8 π
Therefore, the expression for the ultra-relativistic pressure [91–94] is given as

4 ~4
Pur ¼ K ur ρ3 ρ3 : ð206Þ
Using Eq. (196) for evaluating the polytropic index, one gets nP ¼ 3 in the ultra-
relativistic regime. In the highly relativistic case, one finds Pur / ρ4/3. It means that
the expression for the total pressure in the ultra-relativistic limit depicts a non-stiff
EoS (or soft EoS) in comparison with that of the nonrelativistic limit portraying a
stiff EoS (or hard EoS) [93, 96]. This is because of the fact that a small increase in the
momentum of the constitutive particles in the relativistic regime here does not affect
their velocity distribution significantly [93]. As a consequence, the velocity of the
relativistic particles is considered to lie in the same common speed range at around c.
After all these reservations, a more generalized way to express the polytropic
constant in the ultra-relativistic regime can be written [91–93] as
rffiffiffiffiffiffiffiffi s
ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
4ffi ~ 43
ffi
3 3 hc 3 N A NA
K ur ¼ : ð207Þ
π 8 μ μ
A comparison of Knr (in Eq. 202) and Kur (in Eq. 207) yields as
13
K nr NA
¼ 3 1012 : ð208Þ
K ur μ
It is clearly evident from Eq. (208) that the radially outward electronic degeneracy
pressure support against the radially inward self-gravity is weaker in the nonrelativ-
istic case than that in the ultra-relativistic circumstances of compact astrophysical
objects.
2.42.2 Outcome
In the nonrelativistic regime, as the mass (M ) of the dwarf stars increases, the radius
(R) tends to decrease as R / M 1/3 [91]. However, in the relativistic regime, the
radius of the star tends to drop towards zero as mass increases abruptly. As a result,
the mass of the stars becomes independent of radius or central density in the
relativistic regime. Consequently, the white dwarf EoS in the ultra-relativistic limit
fails to stop the contraction of the stellar matter to grow denser against the self-
gravity action [91, 93, 96–98].
With the help of a polytropic model of a white dwarf star in the relativistic regime,
Indian-American astrophysicist, Subrahmanyan Chandrasekhar, has introduced a
limit to the mass of the dwarf star, above which the electron degeneracy pressure
in the stellar core is insufficient to balance the self-gravitational attraction of the star
[24, 96]. The famous Chandrasekhar mass expression [91–93, 96] is given as
5:836 J
M Ch ¼ M : ð209Þ
μ2e
Assuming μe ¼ 2 for a typical white dwarf, the Chandrasekhar mass limit

[91, 96–98] is cast as
M Ch 1:46M J : ð210Þ
Therefore, a white dwarf can exist only if the mass of the star <1.4MJ. If the
mass exceeds it, the stellar remnant collapses due to its own gravity and ends up as a
supernova [91, 93, 96]. It has been observed that as the mass of a remnant stellar star
crosses the Chandrasekhar mass limit, most of the nuclei in the core of the stellar
structures are squeezed out and turn into pure neutrons due to the thermonuclear
reactions [91, 97, 98]. This shrinks the stellar volume in size and results in the
formation of a neutron star. A neutron star is an extremely dense interstellar object
made up of exotic state of matter. They are characterized by strong magnetic fields,
ranging typically as 1011–1013 G [99]. It is held together by the nonlocal neutron
degeneracy pressure and short-range repulsive neutron-neutron interactions inter-
ceded by the strong force against the long-range long-local self-gravity action [91–
93, 96, 97]. However, if the mass of the neutron star surpasses the maximum mass
limit (called the Tolman–Oppenheimer–Volkoff (TOV) mass limit: 2.16MJ), it will
end up as a black hole, and so forth [91, 96, 97].
3 Graphical Comparative Analysis
After analyzing the qualitative features of the 43 multitasking EoS as above, it is

relevant to provide a graphical comparative platform to have their relative quantita-
tive glimpse. Accordingly, a composite common P–V indicator diagram is macro-
scopically constructed through computational means (as shown in Fig. 1). It nicely
enables us to perceive a total overview of their collective relative behaviors on a
mutual thermodynamic footing conjointly.
It may be pertinent to repeat that all the 43 EoS have been taken into account for a
brief analysis of their analytic structural representations. Each EoS has been
reassembled into a common expression of pressure and volume. Assuming the
Boyle-Mariotte law, the thermodynamical pressure term of each EoS is generalized
into a function of volume, neglecting all the fundamental terms minorly described in
the EoS (defined originally by their pioneers). However, the attractive term, a,
introduced by VdW, which is commonly being used in many other modified EoS,
has roughly been assumed as 0.1. A three-dimensional (3D) graphical representation
of each and every member of the EoS family in the specific conditions stated above
is generated and presented illustratively (Fig. 1).
Fig. 1 A graphical comparison of all the presented 43 EoS in the P–V indicator phase space on a
common terminal footing. The equation numbers (1–43) and the correspondingly yielded line
numbers (1–43) are clearly depicted with the help of various colors and numbers
It is found from Fig. 1 that the P–V indicator relationship of the MG (Line: 25),
stiffened (Line: 26), Murnaghan (Line: 29), KD (Line: 33), Fermi (Line: 39), Bose
(Line: 40), and Boltzmann (Line: 41) EoS have almost the same graphical represen-
tation as that of the ideal gas (Line: 1) EoS (P / V 1) on a common comparative
foundation. In contrast, other EoS, such as the RK (Line: 3), SRK (Line: 4),
Peneloux et al. (Line: 5), Fuller (Line: 9), and Berthelot (Line: 19) EoS have a
similar P–V phase graphical portrayal as that of the VdW (Line: 2) EoS (P / (1/V
0.1/V 2)). Parallelly, the two modified versions of the BB (Line: 14) EoS, i.e., the
BWR (Line: 15) and the BWRS (Line: 16) EoS, have a common extended mathe-
matical form. However, it can be noted that the PRB (Line: 11), Shanker (Line: 35),
and FI (Line: 36) EoS diverge from the usual P–V graphical form (i.e., polytropic
form P / V Γ). The two EoS for the white dwarfs in the nonrelativistic regime
(Line: 42) and relativistic regime (Line: 43) have almost the same P–V phase graph.
The rest of the graphic curves representing the other EoS (Line: 6–8, 10, 12–14,
17, 18, 20–24, 27, 28, 30–32, 34, 37, 38) depict a similar representative profile
pattern linking closely related thermophysical conditions. It is in a fair correlation
with that of the ideal gas EoS within their respective defined boundaries of physical
applicability.
4 Summary and Conclusion
In this chapter, an analytical review study of 43 relevant and prominent EoS in

generic forms, describing the thermodynamical and thermophysical properties of
different states of matter, is systematically carried out alongside a peek graphical
support on a common reference fitting. In a broader sense, a brief graphical analysis
of all the well-explained EoS has been presented in a P–V indicator illustrative phase
diagram. It concisely represents each EoS in a common fundamental polytropic
form, P ~ V Γ, with Γ defined as the polytropic exponent. A brief case-by-case

study of the outcomes obtained from the constructed graphical platform is briefly
analyzed. We present a highlight about the major strengths and weaknesses of the
diversified EoS, along with their applicability in different phase-equilibrium model-
ing studies bearing high applied value. This study is believed to be extremely useful
in understanding the different thermophysical processes that exist in Nature in
diversified extreme conditions in the mysterious wide-range astrocosmic Universe.
Finally, a new scopal direction to the plausible future refinement and applicability of
our exhaustive peek analysis, particularly for further improvement and amendment
of the relevant EoS which are extremely useful in describing the complex liquid-
solid interfacial phases in natural realistic circumstances, is concisely outlined.
Acknowledgments Active cooperation received from Colleagues and Friends in different places is
thankfully acknowledged. The financial support received (by the corresponding author) through the
SERB Project (Grant-EMR/2017/003222) is duly recognized.
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Plasmonics Studies for Molecular Scale
Optoelectronics
Farhana Yasmin Rahaman, Anas Akhtar, and Abhijit Chandra Roy
Abstract Molecular scale plasmonics (MSP) is associated with the area of molecular
electronics (ME) where the electronic property of molecules is exploited to generate
or modulate plasmons at sub-wavelength confinement. The MSP and ME both occur
at diffraction-limited regimes which gives an advantage of understanding both optical
and quantum mechanical properties simultaneously. Thus, this emerging field could
promise prospective applications in the field of ultrafast information processing,
computation, nonlinear and ultrahigh-resolution electronic display, optoelectronic
devices, etc. The combination of ME and MSP opens a window to understand the
interaction of electromagnetic waves at metal-molecule interface with the help of
recently emerging molecular electronic characterization tools in sub-wavelength
range. Here, we discuss molecular scale plasmonics with the enunciation of a basic
understanding of plasmonics. In addition to these, we systematically discuss various
methods of plasmon excitation and detection, using the quantum mechanical models,
because classical electrodynamics fails to illustrate the electromagnetic coupling in
the sub-nanogaps formed by molecular junctions. Also, we have showcased numer-
ous examples of recent advances in molecular electronic plasmonic including
sub-nanometer air/vacuum and molecular gap quantum plasmonic systems. Finally,
we conclude this chapter by mentioning the prospects and various challenges in terms
of making efficient characterization techniques or better models to explain MSP.
Key words Molecular scale plasmonics · Molecular electronics · Ultrafast · Metal-

molecule · Sub-wavelength
Farhana Yasmin Rahaman and Anas Akhtar contributed equally with all other contributors.
F. Y. Rahaman · A. C. Roy (*)

Department of Physics, Indian Institute of Science, Bangalore, Karnataka, India
A. Akhtar
Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore,
Karnataka, India
https://doi.org/10.1007/978-3-030-99491-4_4
122 F. Y. Rahaman et al.
1 Introduction
The performance of the modern electronic device has achieved tremendous improve-
ment since the first release of the electronic processing unit [1]. The main building
block of conventional electronics usually comprises of semiconductor materials. The
emergence of modern nanotechnology tools helps silicon-based electronics chips in
taking a great leap in miniaturization; however, these semiconductor components
shows some limitations when it became few nm in size [2, 3]. To overcome such size
limitation of semiconductor electronic components, scientists came up with the idea
of using molecules as building blocks of electronic components, resulting in emer-
gence of a new branch of science known as molecular electronics [4, 5]. In other
words, molecular electronics deals with the investigation and utilization of mole-
cules as a building block of electronic components. In addition to the size limitation
of the electronic components, the data processing and transportation are limited to
the range of GHz frequency [6]. On the other hand, photonic data transmission can
achieve speed as high as in the range of THz. However, the dimension of the
conventional data transmitting optical fiber is more than 1000 times larger than the
conventional electronic components inside a chip-based processing unit [7]. Hence,
there is a mismatch of the dimension of the nanoscale electronic components and
conventional photonic data transmission route. Various proposal has been reported
to integrate the photonic component in electronic circuitry, e.g., connecting optical
transmission component via air or optical fiber to various part of the electronic
circuits. Despite many interesting ideas, implementation in the reality is hindered by
bulky size of these optical components. Now the question remains whether we can
integrate photonic components to an electronic circuit in nanoscale below the
dimension of the wavelength of the optical light? To answer this question, one
very convincing idea is to incorporate nanoscale optical property, i.e., plasmonics
into processing unit associated with optical signal and electrical current. The surface
plasmon polariton (SPPs) in metallic nanostructure is one such example that prom-
ises sub-wavelength confinement, and a transmission capability more than hun-
dredth of THz. Now the question is whether the SPPs can be generated in case of
molecular electronics? In this chapter, we are going to discuss about the develop-
ment of the generation of the SPPs in various molecular electronic systems.
Mainly two broad categories of molecular junction namely single and ensemble-
based molecular junctions have been employed in molecular electronics to character-
ize the electrical [8], optical [9], chemical [10], or thermal and thermoelectric [11–13]
properties of various molecules in different junction configurations. The charge
transport molecular electronics occurs in quantum regime in various fashions namely
through tunneling [14–17], hopping [18–20], and through super exchange [21, 22]
mechanism both in the case of single molecular and ensemble molecular junction. We
define the single-molecule junction as SMJs and the ensemble molecular junction as
EMJs throughout this chapter. Single molecular junction is made and characterized by
various tools/techniques such as scanning tunneling microscope-based molecular
junction (STMJs) [23, 24], conducting probe-atomic force microscope-based
Plasmonics Studies for Molecular Scale Optoelectronics 123
molecular junction (CP-AFMJs) [25, 26], and mechanically controlled break junction
(MCBJ) [27, 28]. On the other hand, the ensemble molecular junctions are made by
various sophisticated as well as simple processes that include liquid metal hanging
drop [29–32], nanotransfer imprint [33–35], microfluidic channel [36, 37], cross wire
configuration [38, 39], nanoparticle bridge [40–42], graphene or carbon-based mate-
rial interlayer [43], etc.
The first idea of molecular electronics was theoretically proposed by Aviram and
Ratner in 1974 [44]. However, due to the limitation of experimental tools, the
experiments on molecular electronics flourished after the invention of the scanning
tunneling microscope in 1982 by IBM [45–47]. Initially, focus of the molecular
electronics was to study the electrical property of the molecules to scrutinize as a
potential electronic device/component [10, 48]. Till now many examples of mole-
cules showing electronic properties suitable for potential application as electronic
components have been reported by various research groups around the globe [8, 49–
54]. For example, many molecules have been found to show current rectification
properties both in single molecular junctions [55–59] as well as in large-area
molecular junctions [60]. In addition, both types of the molecular junction show
properties other than current rectification such as magnetoresistance [61–64], quan-
tum interference [65–68], thermoelectric [11, 12, 69, 70], and molecular plasmonic
[6, 71–73]. In addition, these molecular junctions have shown experimental evi-
dence of many charge transport mechanisms including, conductance switching [74–
78], magneto resistance [79–83], optoelectronics [84–88], and negative differential
conductance [89–91].
In this chapter, we will be discussing about the various aspects of the develop-
ment, progress, techniques, advantages, limitations, and future prospects of
molecular scale plasmonics (MSP). Broadly, three types of electrode configurations
can be seen deployed by various researchers, i.e., the nonplanar closely separated
electrodes, nonplanar and planar electrode, and planar-planar electrode configura-
tions as shown in Fig. 1a, d, and g, respectively. In the case of nonplanar electrodes,
numerous shaped electrode pairs or dimer structures have been used by various
groups. For example, spherical gold nanoparticle dimer [92], bowtie antenna struc-
ture [93], cubic nanostructures [94], etc. In addition, various device modules are
adapted to the molecular scale electronics for plasmon excitations, detections, and
applications which are shown in Fig. 1a–c.
Figure 1a shows the schematic representation of two nonplanar electrodes sepa-
rated below the diffraction limit of light and are interlinked by self-assembled
monolayers of the molecule. Upon incident light of distinct wavelength or electron
beam of certain energy, the excitement of plasmon occurs. As a result, an electric
field induced between the gap of the two electrodes causes the quantum mechanical
tunneling between the electrodes. The direct charge transfer between the particles
induces supplementary plasmons commonly known as charge transfer plasmon
(CTP) modes [71, 95–103]. The charge transfer plasmon mode carries lower energy
compared to the hybridized plasmon mode [102]. The signature characteristic of the
CTP mode is the generation oscillating electric current between the junction at
optical frequency either through classical conductive path or quantum tunneling
Fig. 1 Vital three operation principles of molecular scale plasmonic (MSP) devices. (a) Schematic
of SAM-linked plasmonic dimer, the tunneling current induces quantum plasmon resonances
(QPR) where incident light causes the tunneling current in the junction. (b) Application of bias
voltage in molecular electronics system for plasmon excitation. The excitation of plasmon emission
occurs due to tunneling current induced by an applied bias voltage (V ). (c) Application of plasmon
detection in molecular electronics. The detection plasmon excitation is conceived by measuring the
increase in tunneling current caused by incident light on the molecular junction. (d, e) Schematic
shows the respective diagrams of NonPlanar-Planar electrode and Planar-Planar electrode config-
uration for MSP. The tunneling junction’s energy level diagram (HOMO–LUMO gaps) is associ-
ated with conjugated (f) and aliphatic (g) molecules. HOMO represents the highest occupied
molecular orbital and LUMO represents the lowest unoccupied molecular orbital
based on the nature and shape of the junction [92, 104]. The oscillatory conductance
property of CTP mode promises possible application as an active device, such
examples include high-frequency nano switches [105] and terahertz (THz) photonic
devices [106]. Studies also show that the performance of the CTP mode relies on the
transport property of the junction [107]. One of the remarkable progress in under-
standing the molecular charge transport at optical frequency has been contributed by
CTP mode studies [94]. Besides, the CTP mode has assisted in achieving adaptable
plasmon resonance even in the infrared spectrum [102]. Another important aspect of
MSP is the techniques of plasmon excitation. In common practice, diffraction-
limited bulky optical elements such as aberration-corrected objectives lens, prisms,
and grating are used to excite the surface plasmons [108, 109]. However, these bulky
optical components are rarely suitable for making on-chip compact plasmonic
devices. Alternatively, fast and high-energy electron beams (~30 keV) also have
been used for very precise and localized plasmon excitation [110, 111]. Despite very
precise plasmon excitation method using electron beam, the involvements of
Fig. 2 Theory of quantum plasmonics. (a) Schematics on the left is the schematic representation of
volume-based Quantum corrected model (QCM) and on the right-hand side, the boundary-element-
based QCM (right). (Reproduced with permission from Ref. [103]). (b) The energy diagram of
plasmonic dimer with respect to their separation in terms of the classical local, classical nonlocal,
and QCM methods. (Reproduced with permission from Ref. [175]). (c, d) Nano Au dimer’s optical
response is calculated by CEM and QCM, respectively. (e) Simulation result of the field enhance-
ment of two oppositely arranged nanoantenna commonly known as bowtie antenna of dimension of
10 nm (radius of curvature). (Reproduced with permission from Ref. [71]). (f–i) Shape and gap
geometry induced charge transfer plasmon (CTP) mode bar dimers (Au) including both spherical
and flat-gap cases. (Reproduced with permission from Ref. [100]). BDP bonding dimer plasmons,
CTP charge transfer plasmons, CTP0 higher order charge transfer plasmons, LAP longitudinal
antenna plasmons
vacuum environment and high electric voltages limit their application in chip-based
compact environments. Therefore, as shown in Fig. 2b, the plasmon can be excited
through inelastic electron tunneling on the two-electrode molecular junction consist
of at least one electrode with the capability of holding plasmons and are separated by
an ensemble of single molecule. The application of bias voltages between the
electrodes causes plasmon excitation either due to electroluminescence from the
molecules or as a result of the direct tunneling between the electrodes. Figure 1b, c
shows distinct molecular junction configurations which are used for detecting
plasmons in molecular junction. External light source is used to excite the plasmons
in the molecular junction configurations. The light-induced plasmons generated in
the junction get coupled with the tunneling charge carriers which give rise to
increase in the tunneling current across the junction. The increase in tunneling
current is indicating the presence of plasmons inside the junction.
Although, we have shown a simple spherical electrode system for simplifications,

in practice various types of electrode systems including material variety [112, 113],
shape dissimilarity [114, 115], and electrode separation mechanisms [116–118] can
be employed in generating molecular plasmonics. The first theoretical formalization
of the tunneling effect between two arbitrary shaped electrodes/probes by a very thin
layer is proposed by John G. Simmons at the beginning of 1963 and is known as the
Simmons equation [119]. Many researchers in recent times uses a simplified form of
the Simmons equation (Eq. 1) to estimate the dependency of the tunneling barrier
width d, tunneling rate J (A/cm2), and height ϕ.
rffiffiffiffiffiffiffiffiffiffiffiffiffiffi
βd 2ϕ me
J ¼ J0e with β ¼ 2 ð1Þ
ћ2
1
where J0 represents pre-exponential factor with unit A/cm2, β (Å ) indicates the
tunneling decay coefficient, me represents the effective mass of an electron with the
unit of kg, and ћ indicates the reduced form of Planck’s constant. The β is an
important exponent which along with d determines the decay rate of tunneling
current density J. Also, tunneling barrier width d and height ϕ are associated with
the nature of the molecules embedded in the junction. Conjugated molecules are
those molecules that possess alternating single and multiple bonds. As a result of this
bond sequence, the conjugate molecules usually exhibit comparatively low tunnel-
ing barrier height due to the small gap between the HOMO and LUMO (Fig. 1d). As
the energy difference HOMO–LUMO of the conjugated molecules shows narrow
gap, coherent tunneling may be observed over for a large distance of up to 5 nm. And
1
the value of the exponent factor β is in the order of ~0.1–0.3 Å . On the other hand,
aliphatic molecules show a relatively large energy gap between the HOMO and
1
LUMO which is in the order of ~8–9 eV and with β ~ 0.8–0.9 Å . As a result, the
tunneling rates of aliphatic molecules-based junction decreases significantly com-
pared to the tunneling rates in case of a conjugated molecule. It has been observed
1
that the β value of tunneling through vacuum is inefficient is ~2.9 Å which results
in very poor tunneling. Interestingly, the tunneling occurrences can be overlooked in
the plasmonic system with a gap larger than 1 nm [71, 101]. Hence, molecular tunnel
junctions [55, 63, 65, 75–78, 83–88, 120–136] could be fascinating entrants for
various future applications in MSP.
2 Quantum Plasmonics for Molecular Electronics
Quantum plasmonics (QP) is a subbranch of nanometer scale photonics/plasmonics

where the interaction of electromagnetic wave (light) with nanometer scale matter
(metal, semiconductor) is described by the laws of quantum mechanics [2, 137]. The
term “quantum plasmonics” is usually used whenever either electromagnetic fields
in dielectrics or free-electron oscillations in metals show quantum signature
[138]. Quantum plasmonics has shown attractive possibilities in the field of quantum
information [9, 139, 140], the high-efficiency optoelectronic device [141–144], and
highly sensitive detection [145, 146]. However, in quantum plasmonic, discretely
generated bosons are known as quantum emitter (QE) which is very important for the
realization of single-photon source [137]. Single-photon sources have potential
application in various phenomenon including such as quantum sensing, cryptogra-
phy, and entanglement [147]. One of the important criterions to become a practically
useful single-photon source for quantum communication and information processing
is its high emission rates in the range of THz. However, the radiative lifetime of QE
is in the order of 10 ns which is far below the demand of the optical-communication
and information-processing systems. Therefore, many efforts have been adopted to
enhance the emission rate of such quantum emitters. One such example is by placing
a QE in a suitable photonic environment which can drastically increase the sponta-
neous emission (SE) rate [148]. Therefore, in this section, we shall be discussing
such molecular electronic system which might give possibility to introduce photonic
environment to resolve such problem. A closely separated pair of metallic
nanoparticles (say within 5 nm) works as a plasmonic dimer. The plasmonic dimers
have drawn sufficient attention due to their superior field enhancement capability at
the vicinity of the junction of the nanoparticle. This highly enhanced field leads to
the realization of even single molecular detection [149–161]. Recently, various types
of nanostructured plasmonic dimers have been exploited to study the quantum
mechanical tunneling phenomena-induced plasmon modes [71, 95–103]. In closely
separated dimers, the classical analysis demonstrates the induction of huge charge
densities on the oppositely facing sides of the dimer which generates red-shifted
bonding dimer plasmons (BDP) resonance [162, 163]. For the finite separation of
dimer of two nanospheres, BDP is the fundamental plasma mode the dimer in which
the plasmons are bonded by the Coulomb interaction between the oppositely signed
charge distribution of across the nanogap [164, 165].
However, in practice, negligible redshift or blueshift of the BDP resonances has
been observed in very closely separated dimers, i.e., the separation between the
nanoparticle in the range of less than or equal to 1 Å. In such condition, the
conductance through the junction shows a large value and the dimer behaves as if
a signal nonspherical unit. The discrepancies are caused by the non-consideration of
the nonlocal effects, i.e., the charge distribution spill and tunneling of electron
through the dimer [71, 73, 95–97, 99, 100, 102, 103, 166–171]. In such conditions
where nanostructure dimer is in sub-nanometer proximity and application of enough
high electric field generates novel charge transfer plasmon mode (CTP) [71, 73, 95–
97, 99, 100, 102, 103, 166–171] and higher order charge transfer mode (CTP0 ). The
notable characteristic of these modes is the flow of electrons between the particles.
2.1 Theoretical Studies for Quantum Plasmonics
The treatment of the plasmonics in the classical model applies to macroscopic

Maxwell’s equation to homogeneous media [108, 172–174] where boundaries are
well defined. The classical electromagnetic model (CEM) solely depends on a
frequency-dependent local dielectric function (ε) [163, 165]. However, the classical
electromagnetic plasmonic model fails to explain plasmonic occurrence of the
structures of diameter less than 5 nm [175]. In the classical electromagnetic
plasmonic model, the dielectric function (ε) at the juncture between various mate-
rials shows a sharp alteration, the explanation of plasmonic system of size greater
than 5 nm remains a challenge.
As the size of the plasmonic material reduces below 5 nm or so nonlocal
phenomenon such as density electron spill and electron tunneling between the
closely spaced nanostructure plays an inevitable role. The incorporation of such a
nonlocal phenomenon results in the non-abrupt change of the local dielectric func-
tion (ε) at the interface [73, 97, 166–171, 176]. Therefore, to incorporate such a
nonclassical phenomenon, a complete quantum mechanical treatment is employed to
mode such phenomenon. Although theoretically, the quantum mechanical treatment
shows possibilities however it might not be possible to estimate the analytics due to
the limitation of our calculating capabilities. The typical nanoparticle consists of
more than 10,000–30,000 atoms, considering such a huge number of atoms in the
analysis is currently almost impossible using basic quantum mechanical treatment
[73, 166]. To overcome such limitations, the quantum systems are modeled with a
classical nonlocal model [73, 97, 166–171, 176]. Such model is first introduced by
Pendry, Maier, and García de Abajo et al. [71, 73, 95–97, 99, 100, 102, 103, 166–
171]. In such a modified classical model, the response of the metallic quantum
structures is modeled using a hydrodynamic nonlocal approach without considering
charge transfer across the quantum structures [175]. In addition, Aizpurua et al. have
developed the quantum corrected model (QCM) [96]. In the QCM analysis, an
amalgamation of classical and quantum analysis has been exploited to model the
quantum plasmonic system. In the case of QCM, the system is defined using a
classical local dielectric constant with the consideration of electron tunneling across
the closely spaced quantum structure [71, 175]. Based on the description of tunnel-
ing of electron through the junction, the quantum corrected model is further extended
into volume-based [71, 73, 95–97, 99, 100, 166–171] and boundary-element-based
quantum corrected model. In the volume-based QCM model, artificial dielectric
materials are used throughout the junction [103]. On the other hand, nonlocal
boundary conditions are used only at the surfaces of the dimer gap in case of
boundary-element-based quantum corrected model (Fig. 2a).
The contrasting result of classical local, classical nonlocal, and QCM models, for
plasmonic nanoparticles closely separated by vacuum (plasmonic dimer) are shown
in Fig. 2b [175]. When the separation (d ) of the nanoparticle exceeds 5 nm, i.e., in
the local regime, it is clear from Fig. 2b that all these methods show identical output.
On the other hand, nanoparticle with separation less than 5 nm, i.e., in the regime of
nonlocality (0.3 nm < d < 5 nm), interestingly, the QCM and classical nonlocal
methods show identical result, and accurately predicts the redshift of the bonding
dimer plasmon modes compared to classical local method. On the other hand, at a
separation less than or equal to ~0.3 nm, the classical nonlocal and QCM shows
significant variation in the result, a blueshift has been observed in case of QCM
output compared to classical nonlocal model. In the quantum mechanical tunneling
regime, the blueshift in the spectra and charge transfer plasmon (CTP) and higher
order CTP0 modes have been predicted by QCM.
The charge transfer plasmon mode in touching dimers can be explained by both
the classical nonlocal and classical local methods where the mode is supported by
conduction through the plasmonic dimer contact but not vacuum tunneling. Quan-
tum correction model (QCM) can not only predict the blueshifted extinction spectra
in nearly touching plasmonic dimer but also it can describe the diminishing field
enhancement in the dimer gap at quantum regime where the plasmonic dimer are
separated by less than or equal to 0.3 nm [6]. Importantly, the combination of
hydrodynamic Drude model and finite element model (FEM) is used to formalize
the classical nonlocal modeling to describe the dielectrics of the metal [6]. On the
other hand, boundary element method (BEM) is used in the volume-based QCM
with the involvement of the time-dependent density function theory (TDDFT) which
engaged in estimating artificial dielectric material. However, in case of the
boundary-element-based QCM, a similar result is achieved as compared to
volume-based QCM by using modified nonlocal boundary conditions which also
simplify the simulations.
The importance of the introduction of QCM in near touching nanostructure
plasmonic has also been confirmed in realistic nanostructures of a gold bowtie
antenna [177–179]. Figure 2e shows simulation result of the field enhancement
plasmon such as gold bowtie antenna using CEM and QCM with a dimension of
cone length 100 nm and with edge radius ~10 nm. The CEM shows huge unrealistic
field enhancements ~38,000 for the atomic level separation of d ~ 0.5 Å. On the
other hand, the QCM models forecast a much realistic enhancements with a maxi-
mum ~3000 at the optimal separation of ~3 Å. To further understand the difference
between CEM and QCM, let us consider the result of the two methods on gold dimer
(diameter ~ 50 nm) as shown in Fig. 2c, d [71]. The calculation clearly depicts the
distinguishing outcome of the plasmonic resonance of nearly touching nano dimer
Au calculated by these two methods. The vital observation from the calculations is
(1) The CEM estimation shows a larger number of modes than the QCM. The reason
for such variation may be due to the less significant Fabry-Perot resonances in QCM
than CEQ modes arising as a result of large damping raised by electron tunneling
between the particles. (2) Also, the QCM calculations predict a first order CTP mode
(tunneling CTP/tCTP) and higher order CTP0 mode depending on the separation
between the particles. If the separation of the particle is d < 0.3 nm CTP0 modes are
seen considering the tunneling remains the prominent mode. Also, important to note
that the appearance of CTP mode not only depends on the separation d but also
depends on the tunneling barrier height which is depicted in Fig. 1. More precisely,
the transition of the BDP mode to CTP mode has been observed, when the air gap
decreases to below 0.3 nm, i.e., the resonance peak blue-shifts rather than red-shifts
as predicted by CEM and the peak intensity decreases. The decrease of peak
intensity at that small separation (~0.3 nm) is because of the enhancement of the
tunneling electron. The increase of the tunneling electron at the junction creates
hindrance in the plasmonic coupling due to the screening of the surface charges of
the localized plasmons. (3) Also, it has been predicted that the tunneling CTP mode
occurs at lower frequency, i.e., at infrared frequencies (<1 eV). The oscillation of
tunneling mainly generates the tCTP mode. The frequency of tCTP mode is far
greater than the resonance frequency of the plasmonic resonator. From the above
discussion, the quantum plasmon resonances become evident from the characteristic
of BDP and CTP modes near the particle separation 0.3 nm air gap. Noteworthy to
mention that the tCTP mode varies with the tunneling current density generated by
plasmonic field in the gap between the particles. As the plasmonic field induces the
CTP mode and tunneling current, the CTP mode is very sensitive to the texture/
geometry of the plasmonic particle/dimer. This geometry dependence of CTP mode
due to the plasmonic field in a plasmonic dimer is shown in Fig. 2f–i [109]. Both the
classical and quantum analysis shows no or negligible CTP mode in the case of flat
faced gold dimer compared to spherical pointed gold dimer.
2.2 Various Tunneling Barriers for Quantum Plasmonics
In this section, we are going to discuss some examples of plasmonic dimers

separated by air or vacuum. We have discussed the occurrence of quantum plasmon
resonance at the quantum regime of extremely small gap of order ~0.3 nm. In
practice, it is very difficult to fabricate such a very narrow gap using a conventional
top-down approach. However, a high-resolution electron beam lithography process
has been developed to study the modal spectra of plasmon with nanometer resolution
and then performing these systematic studies of a plasmon in metal nanostructures
using a high-resolution electron beam lithography process (EBL) [93]. Although the
technique was able to reach up to 0.5 nm gap between the gold electrode however the
technique failed to further reduce the gap to reach the quantum regime, i.e., below
the range of 0.3 nm (Fig. 3a). Using this technique, they also fabricated structures of
touching bowtie antennas as shown in Fig. 3a. Electron energy loss spectroscopy
(EELS) is employed to measure the plasmonic resonance under transmission elec-
tron tunneling microscope (TEM). As we have seen in the earlier discussion, the
quantum plasmonic mode such as tCTP mode can be observed when the gap
between the electrodes is in the range of ~0.3 nm however in this case, the distance
is greater than 0.3 nm. Therefore, they did not observe the transition of BDP mode to
CTP/tCTP mode to those bowtie antennas with gap greater than 0.3 nm. However,
the structure with a continuous touching bridge showed CTP mode. In a similar
fashion, two gold nanoparticle and their separation were controlled using a TEM and
the plasmonics resonance were captured by EELS by Scholl et al. [92]. In this work
however the transition of BDP mode to quantum induced CTP or CTP0 modes had
Fig. 3 Air/vacuum tunneling barrier induced quantum plasmonics. (a) Plasmonic resonances of
connecting and near touching Au bowtie antennas and electron energy loss spectroscopy (EELS)
spectrum. (Reproduced with permission from Ref. [93]). (b) Quantum plasmon resonance in Au
nanosphere dimers with sub-nanometer separation. (Adapted with permission from Ref. [92]). (c–e)
Quantum plasmon resonance in sub-nm plasmonic cavities formed between two Au-coated AFM
tips. (Reproduced with permission from Ref. [104])
been observed when the separation between the particles was in the range of
~0.27 nm (Fig. 3b). In another work, the distance of the two gold nanoparticle was
brought closer than 0.3 nm by using two conducting AFM tips attached with two
gold nanoparticles attached to an AFM tip (Fig. 3c) [104]. Interestingly, in this
experiment, they were able to manipulate the gap between them with the aid of a
piezoelectric positioner. As a result, they managed to reach a separation starting from
a few nanometers to sub-nanometer, i.e., below 0.3 nm quantum regime. As a result,
both the classical and quantum mode of plasmonics modes were observed by
analyzing darkfield scattering spectra of the closely separated nanoparticle junction.
As the separation between the nanoparticles decreases, initially, the observed BDP
modes get red-shifted till it reaches ~0.3 nm and below that gap a quantum behavior
became prevalent, i.e., a blue shift of the plasmonic resonance was observed
(Fig. 3d, e).
2.3 Molecular Tunneling Barriers for Quantum Plasmonics
An interesting way to separate two nanoparticles with sub-nanometer distance is by

separating them by incorporating molecules in between the gap. Using the same
strategy, many research works on quantum plasmonics have been published in recent
times. In such a technique, usually, either nanoparticles are coated with monolayer of
molecule usually, i.e., SAMs or a plain plasmonic film is coated with SAMs to study
the quantum plasmonic. One important advantage in this technique is the liberty of
modulating the sub-nanometer gap between the probes by tuning the length of the
molecule or substituting constituent atoms to make different molecular lengths
[168, 180–183]. As a result, the fabrication of such sub-nanometer gap drastically
reduces the complexity of such junction.
One of the early works on molecular gap-based quantum plasmonics was inves-
tigated by Ciracì et al. using a self-assembled monolayer of amine-alkane thiolates (S
(CH2)nNH2) on a gold film and a gold nanoparticle [168]. Interestingly, the authors
have modulated the separation between the nanoparticle and the gold film by just
changing the chain length of the molecule, i.e., altering the value of n (Fig. 4a).
Every subtraction of CH2 unit from the SAM molecule results in the occurrence of
red-shifting of BDP mode. Although the redshift of BDP mode was not obeying
according to CEM model, the experimental results show excellent fit using nonlocal
dielectric functions of gold. Importantly, they did not observe the quantum signature
in the experiments, i.e., CTP mode’s transition from BDP mode is not observed. The
reason for not showing quantum plasmonic mode characteristics for those mole-
cules’ bridged junction was cited to be due to the relatively large value of n which is
more from 2 to 16. Also, a large tunneling barrier raised from the gap comparatively
induces large energy gap (~8–9 eV) between the HOMO–LUMO is another reason
for the lack of quantum plasmonic mode in those plasmonic structure (Fig. 4a).
As shown in Fig. 4b, instead of using a plasmonic metallic film and a gold particle
separated by a SAM, the study of two gold particles separated by a layer of SAM
also was studied by Cha et al. [180]. In such studies, the authors made plasmonic
gold nanoparticle dimer by coating one of the gold particles with alkane dithiolates
(S-(CH2)n-S) molecule to make a molecular gap with another uncoated nanoparticle
on a glass plate (Fig. 4b, c). These junctions show the clear presence of both classical
plasmonic modes as well as quantum plasmonic mode depending upon the separa-
tion between the nanoparticles, i.e., depends on the lengths molecular which separate
the two nanoparticles (Fig. 4d). For the gap between the nanoparticles greater than
1 nm regime, as n decreases, i.e., separation between the nanoparticle decreases the
resonance peak of the BDP mode however as gap shrinks below ~1 nm, a blueshifted
of the plasmonic mode was observed. This prominent evaluation of BDP mode to
CTP mode clearly shows a quantum signature of the plasmon modes in such
nanoparticle junctions with molecular bridges (Fig. 4d). Another interesting work
published by Tan et al. [94], shows the evidence of quantum plasmonic modes on Ag
nanocubes dimer separated by SAM of different varieties (Fig. 4e–g). They used two
types of molecules namely 1,2-ethanedithiolates (EDT) or 1,4-benzenedithiolates
Fig. 4 Molecular tunneling barriers for quantum plasmonics study. (a) Schematic representation of
tunable molecular gap adjustable tunneling barrier using molecular chain modification. (b) Sche-
matic nanoparticle plasmonic dimer where the two gold nanoparticles are separated by monolayers
of molecules. (c) Scanning electron microscopy (SEM) photograph of the gold-gold nanoparticle
dimer separated by alkane dithiolates (S–(CH2)n–S) molecular gap. (d) The graphs show the
scattering peak wave position of the dimers vs separation. (Reproduced with permission from
Ref. [180]). (e) A representative image of the study of quantum plasmon resonance (tCTP) in Ag
nanocube dimers where the nanocubes are separated by EDT (1,2-ethanedithiolates) or BDT
(1,4-benzenedithiolates). (Original work done by Tan et al. [94])
(BDT) of similar length but different HOMO–LUMO gap to understand the effect of
HOMO–LUMO gap on quantum plasmonic modes. The authors observed the
presence of tCTP mode through EELS inside the TEM on those junctions. The Ag
nanocubes having flat surfaces enhances the surface cross sectional areas (~103 nm2)
between two such cubes, which results in the enhancement of the weak tCTP mode
due to the occurrence of increased tunneling events number across the junctions.
Results show that the BDT based SAM junction shows a peak tCTP mode of
having a peak at a lower energy range of ~0.5 eV, on the other hand, EDT SAM
junction shows a low energy peak at around 0.6 eV (Fig. 4g). This difference in the
peak energy is because of the higher conductance value of SAM of BDT compared
to the conduction of the EDT SAM citing the fact that the length of BDT and EDT is
the same. The shift of the energy of tCTP is also associated with the lower HOMO–
LUMO gap, i.e., tunneling barrier height of BDT (5 eV) compared to the HOMO–
LUMO gap of EDT molecules (8 eV). Interestingly, due to the higher tunneling rate
of the BDT SAMs due to its lower HOMO–LUMO gap and larger Ag junction cross
section, the tCTP mode was observed even at a separation of ~1.3 nm, which is not
possible in common dimer system.
3 Molecular Scale Plasmonics (MSP)
Interaction of electromagnetic radiations with the matter has been one of the most
decisive ways to characterize a material, both at bulk as well as at micro/nanoscale
since the dawn of optics as a branch of physics [184, 185]. Plasmonics is a subclass
of optics and a precipitous research field that deals creation, recognition, and
exploitation of surface plasmon polaritons (SPPs) along with metal-dielectric inter-
faces in the nanometer scale [186]. The fundamental aspect of plasmonics states that
the collective oscillations of charges in a material couple to a greater extent with
electromagnetic radiations as compared to the individual charges [187]. Deriving the
theoretical and experimental understanding for the mechanism(s) of this light-matter
coupling at nanoscale could be a great achievement and provide better opportunities
for radiation confinement beyond the traditional limitations of conventional optics
(such as diffraction limits and optical resolution). Since molecular junctions (MJs)
have already been proved to be an efficient platform to study the electronic interac-
tion or coupling with the metal electrodes [188], they could be utilized to scrutinize
SPPs and localized surface plasmons (LSPs) to comprehend the light-matter inter-
actions with the precision in quantum regime [137, 189, 190]. In an essence,
molecular electronics (ME) encompasses single molecules or an ensemble of mol-
ecules (such as self-assembled monolayer) as the active components of
nanoelectronic circuitry, either in standard two-electrode (source-drain) or in three-
electrode (source-gate-drain or transistor) configuration. Some of the recent research
findings suggested that these constructions for MJs can be exploited to demonstrate
various classical and nonclassical phenomena such as current rectification [55, 128–
130, 191–193], electrostatic [194–198] as well as electrochemical gating [198–201],
switches [202–205], memory devices [206–208], quantum interference [209–213],

negative differential resistance [214–217], Coulomb blockade/Kondo resonance
[218–221], and giant magnetoresistance [62, 63, 222–224]. Since the SPPs could
give a considerable improvement in the electric field enhancement at the surfaces of
metallic structures, they could be employed as molecular sensors [225] and energy
conversion [226]. Also, as the charge transport mechanism in MJs is based on
quantum tunneling in nano regime, one could follow a similar approach to realize
tunneling-based charge transfer between two SPPs when placed in the locale of a few
nanometers to reach the tunneling region which is known as quantum plasmon
resonances (QPRs) [6, 137] which play a vital role in the comprehension of quantum
plasmonics. This would further lead to the enhancement in the local field in SPPs
which could be a promising strategy to use them in nonlinear optics and molecular
optoelectronics.
In this section, various advancements and developments of plasmonics studies in
ME will be discussed in terms of single and ensemble-based MJs with a subclassi-
fication on the basis of the techniques (such as break junction and liquid metal-based
methods) that have been employed to realize the plasmonic resonances at molecular
scale. Open questions and decisive challenges regarding the experimental and
theoretical standpoints will be discussed with future expectations with MSP at the
end of this section.
3.1 Plasmon Excitation in MSP
Plasmon excitation occurs when the frequency of the collective oscillation of free
electrons in a metal follows the resonance condition with the incident electrons/
holes, photons, etc., as a source of energy [227–229]. There are numerous ways by
which plasmons can be electronically excited, e.g., by utilizing an electron beam
[230, 231], electromagnetic radiation [232], or X-ray irradiation [233]. The process
of excitation of surface plasmon follows primarily two kinds of mechanisms as
depicted in Fig. 5. The first pathway says that the tunneling electrons couple to the
plasmonic modes of the system of interest like a molecular junction. Since the
plasmons can be directly excited by utilizing the tunneling current, this is also
termed as direct plasmon excitation. Whereas the second method dictates a
two-step process for the excitation of plasmons. Due to the propagation of charge
carriers, electron–hole (e–h+) pair(s) are generated in the junction. These, so
formed, electrons and holes recombine with each other to emit photons of certain
frequencies. If the resonance condition is matched among photons and the plasmonic
modes, the excitation of plasmons occurs by virtue of these photons.
The above-mentioned routes for plasmon excitation show that the plasmons in
nanostructures are capable of coupling with the incident light and confine the light
below diffraction limit [234–236]. Several efforts [237] have been made towards
plasmon excitation in various materials, for instance, semiconductors such as
Fig. 5 Schematic representations of (a) Direct plasmon excitation in molecular junctions via
tunneling current and (b) Indirect plasmon detection in molecular tunnel junctions as a result of
electron–hole (e–h+) recombination
silicon-based sources [238, 239], GaAs superconductor [240], nanoantenna derived

from GaP [241], metamaterials (graphene-gold metasurface) [242], and other
nanomaterials [243]. But in this review, we shall be focusing only on molecular
junctions as the basis of direct and indirect plasmon excitations for the MSP because
of the distinctive energy signature of molecular orbitals (HOMO and LUMO) in the
tunneling process which could influence the plasmon excitation in the junctions.
Although the achievable nanoscale plasmonics with molecular junctions is an
interesting research area and could be advantageous to develop novel optoelectronic
devices [244–248], establishing the mechanisms of plasmon excitation is still a
challenging hurdle to overcome in MSP because of the systems with incompatible
energy levels of molecular orbitals with the plasmonic nanomaterials.
Various experimental testbeds (see Fig. 6) have been utilized to regulate the
excitation of plasmons by localizing the tunneling current with a sub-nanometer
resolution [249–255]. In the upcoming sections, we shall be discussing about these
instrumental methods such as scanning tunneling microscopy (STM), mechanically
controllable break junctions (MCBJ), nanoparticle-based molecular junctions, and
on-chip molecular devices to probe the quantum mechanical properties behind the
plasmonic excitation. These findings are crucial for the future developments of MSP
as an emerging candidate for VLSI applications in real-world optoelectronic
devices [185].
Fig. 6 Experimental testbeds for molecule-based tunneling junctions for MSP. Schematic repre-
sentations of (a) Scanning tunneling microscope (STM) based single-molecule junction. (Adapted
with permission from Ref. [273]). (b) Mechanically controllable break junction (MCBJ) for single
molecular junctions. (Adapted with permission from Ref. [280]). (c) On-chip molecular junction-
based device. (Adapted with permission from Ref. [305]). (d) Molecular assembly on nanoparticle
array. (Adapted with permission from Ref. [288])
3.1.1 Scanning Tunneling Microscopy (STM) in MSP
Scanning tunneling microscopy (STM) techniques have been shown to be versatile

testbeds for the elucidation of various electronic and optoelectronic characteristics of
molecular junctions with sub-nanometer resolution [256, 257]. Since molecules
tethered to the plasmonic sources (metal electrodes/nanostructures) were proved to
be an effective transporter of localized surface plasmons (LSPs) in their
nonradioactive decay [258–260], they can be utilized to perform control experiments
to collect information about the mechanism(s) of plasmon excitation in molecular
junctions. STM utilizes an extremely localized tunneling current which can excite
the plasmons in the proximity of the tip and the sample with a molecule present in the
junction.
Various experimental [261–263] and theoretical studies [264–266] have been
performed with the STM-based tunnel junctions which suggest the influence of
contact geometry of tip on the plasmon excitation due to the direct effects on the
local density of electronic and optical states which are crucial factors for the plasmon
mapping with sub-nanometer resolution. Electroluminescence of molecules present
in the junctions is an important parameter for the indirect excitation of the plasmons
at the electrodes [267, 268]. However, this luminescence produced by the applied
voltage is susceptible to quenching due to the electron capture via electronic traps
present in metallic lattice [269]. An electronic trap is any imperfection (whether

intrinsic or extrinsic) in a metallic or semiconducting lattice that creates localized
energy states spatially dispersed around that particular imperfection [270]. Therefore,
it becomes necessary to decouple the molecules from the top and bottom electrodes.
The decoupling of the molecular species has been realized in various ways such as
introducing a tripodal anchoring group as a “spacer” in between the metallic surface
and the molecule [271], insulating metal oxide layer between the junction [272], or
depositing a monolayer of C60 on the bottom substrate as support for physisorbed
molecules of interest [261]. Sometimes, simply lifting the molecular wire lying on
the bottom substrate with the help of STM could serve the purpose of decoupling the
molecule from the plasmonic modes of the metal electrode in the junction to avoid
the quenching of electroluminescence [273].
Plasmon-induced transformations in molecular junctions (such as bond dissoci-
ation/formation) could shed light on the mechanisms of plasmon excitation because
these changes may lead to chemical reactions in the molecules. For example,
Kazuma et al. [274] anticipated a mechanism involving a direct intramolecular
excitation in the dissociation of S–S bond of a dimer (CH3S)2 into CH3S species
by employing the STM setup. The experimental observations clearly indicated that a
strong electric field in the nanogap generated by LSPs—which themselves were
generated through radiating the system with p-polarized light (λ ¼ 532 nm)—excite
the (CH3S)2 single molecule present near the STM tip. As a result of the excitation of
the dimer, a first order dissociation reaction (CH3S)2 ! 2CH3S takes place. This
change can be seen in the STM images (Fig. 7), before (a) and after (b) the
irradiation. The bright spot—corresponding to the dimer (CH3S)2—in the STM
image (a) gets transformed into two identical ball-shaped protrusions which are
related to the dissociated monomer CH3S species. This dissociated species showed
the same appearance as that of the dimer when tunneling electrons are injected into
it. These experimental inspections along with the theoretical studies established that
the above-mentioned plasmon-induced chemical dissociation reaction followed the
direct plasmon excitation mechanism. Recently in the year 2020 [275], the same
group extended these single-molecule studies for the dissociation of O2 molecule
adsorbed on Ag(110) surface at cryogenic temperature (5 K) with the Au STM tip.
Real-space observation with the help of STM in these studies revealed that the
mechanism was based on hot-carrier transfer.
One of the biggest obstacles in the way of MSP as well as for the other subfields
of molecular electronics is the time period for which a single molecule persists in a
molecular junction. A recent study on single molecular junctions of metalloprotein
Azurin (Azu) has proved that the optical trapping of molecules with the help of a
combination of STM-based electrochemically gated plasmon-supported break junc-
tion (EC-PBJ) and nearfield gating effects on the localized surface plasmon reso-
nance (LSPR) of the junction nanogap could increase the lifetime of the individual
Azu junctions by a factor of 40 [276] (see Fig. 7c, d). These findings provide
fundamental knowledge about the interaction between molecules and LSPs, which
is necessary for designing and controlling plasmon-induced reactions for future
applications in molecular optoelectronics.
Fig. 7 (a, b) Pictographic representation of the real-time observation of the plasmon-induced

dimerization reaction. (Original experiments performed by Kazuma et al. from Ref. [274]). (c)
Pictorial depiction of the electrochemically gated plasmon-supported break junction (EC-PBJ)
setup for nearfield trapping of single metalloprotein junctions. (d) The Azu-protein molecular
junction is characterized by its distinctive current signature (Im) which is extracted by subtracting
the tunneling current of the Azu-free scenario (It) from the detected current (Id). (Adapted with
permission from Ref. [276])
3.1.2 Mechanically Controllable Break Junctions (MCBJ) in MSP
Mechanically controllable break junction or MCBJ is one of the most reliable

methods to control the nanogap between the two metal electrodes for the formation
of single-molecule junctions, with a sub-Å resolution MCBJ [27, 28]. The versatility
and adaptability of the open structure of MCBJ setup make it an ideal testbed for the
integration of other spectroscopic methods such as ultraviolet (UV) spectroscopy
[277], scanning electron microscopy (SEM) [278], and transmission electron
microscopy (TEM) [279]. It is a well-established fact that the physical, as well as
chemical characteristics of the isolated molecules, differ vastly from the molecules
present in a junction [4, 86]. Raman spectroscopy, assisted with laser-induced
surface plasmon resonance (SPR), is the most reliable technique to acquire the
physicochemical properties of a molecular junction.
An enhancement in the Raman scattering signals is observed by an electric field
generated by the SPRs upon plasmon excitation. This particular effect of SPRs on
the molecular junctions is utilized in a technique called surface-enhanced Raman
spectroscopy (SERS). This methodology enables the highly reproducible in situ
characterization of molecular junctions with MCBJ for the interpretation of
structure-property relationships based on electronic and vibronic behavior of the
molecules. First attempt in this direction was put forward, in 2006, by Tian et al.
from Xiamen University (Xiamen, China) in collaboration with Tao’s group from
Arizona State University (Arizona, USA) who have combined SERS with MCBJ
method that could characterize and detect molecules within two electrodes at
nanogap [280]. The hybrid SERS-MCBJ setup can be seen in Fig. 6b in which
1,4-benzenedithiol molecular junctions were studied through Raman signals. The
key finding here was that, upon decreasing the nanogap between the two
nanoelectrodes with the typical pushing/pulling cycles with MCBJ, an enhancement
in the Raman signals from the molecular junctions was observed. Strengthening of
the electric field inside the nanogap is a direct consequence of induced electromag-
netic field by the molecule present in the junction. This, further, confirms the
trapping of a single molecule between the electrode system of concern. Another
factor that could affect the plasmonic excitation is the direction of polarization of the
electromagnetic radiation used to obtain the SERS signals. It was affirmed by Tian
et al. [281] that there will be an enhancement in the Raman signals when the incident
laser is polarized in the direction parallel to the electrodes and reduces drastically by
perpendicular polarization of laser irradiated.
Modern electronics demands for the further miniaturization of the already existent
devices for better and faster functionalities and single molecular devices could prove
themselves as potential candidates for this purpose [282–284]. Recently, Guo et al.
[285] constructed a side-gated field-effect Raman scattering (FERS) device which is
a vital element of modern optoelectronic circuitry. They exploited molecular orbital
gating [194] to modulate the intensity of the Raman signals coming from a single-
molecule mechanically controllable break junction (MCBJ) via plasmonic enhance-
ment. In brief, the electromagnetic field was confined on a single molecular junction
by focusing a laser through a lens from the top of the MCBJ setup and the Raman
scattering signals were collected using the same lens (see Fig. 8). By precisely
controlling the nanogap, MCBJ setup was able to obtain Raman signals directly
from the molecular junctions without the noise signals coming from the surrounding
molecules present in the system. Furthermore, an enhancement in the intensity of
Raman signals was observed upon applying the electrostatic gate potential to the
molecular junction through the third electrode (in addition to the source and the drain
electrodes). Regulation over spectral intensity of Raman signals with the help of
electrostatic gating through plasmon excitation could detect some unforeseen phys-
icochemical characteristics of molecular species and could appreciate the signifi-
cance of Raman spectroscopy in characterization of molecule-based FET devices.
These ingenious ways of measuring the Raman shifts of the molecules provide us
a better understanding of vibrational behavior of molecules in molecular junctions
[286]. Also, it has become easier to visualize the dynamics of molecules when they
are present in the junction and hence it is reasonable to say that SERS in association
with MCBJ has been proved to be a kind of spectacles for researchers [255].
Fig. 8 (a) Illustrative image of the measurement setup for side-gating field-effect Raman scatter-
ing. Inset: SEM image of a MCBJ chip with a side-gated electrode. (b) SEM image (top) of a MCBJ
chip fabricated on a relaxed spring steel substrate (bottom) using e-beam lithography and reactive
ion etching. A gap was generated when the substrate was bent and this gap size can be precisely
controlled at sub-angstrom accuracy by the bending of the substrate through piezoelectric actuator.
(c) A 3D plot for showing the effect of gate voltage on the intensity of Raman shifts in the recorded
SERS spectra when the bias voltage between the source and drain electrodes is fixed at 100 mV. (d)
Intensity of Raman shift at 1568 cm1 decreases with an increase in the gap size and gradually
saturates to a maximum at d 1 nm. (e) Simulation-based graphics for the electric field distribution
due to an incident laser. The field was enhanced and confined with gap shrinking. (Adapted with
permission from Ref. [285])
3.1.3 Nanoparticle-Based Plasmon Sources in MSP
Nanocavities, nanoparticles, and nanopores have been employed to engineer the

optical characteristics of the plasmonic sources and to restrain the electromagnetic
fields to sub-nanometer regime for the circumvention of resolution limit with the
traditional optoelectronic devices [263, 287, 288]. These nanostructures were used
for modern applications in highly efficient optical tools such as plasmon-based
tweezers [289], lasers [290], photosensors [291, 292], and energy storage devices
such as solar cells [293].
Incorporating molecule(s) in these nano-assemblies could be a great strategy to
deploy the quantum mechanical effects associated with molecular junctions to excite
the plasmonic sources in proficient ways. For instance, Lv et al. [294] employed a
strategy to coat the Fe3O4 nanoparticles (NPs) with tetrathiafulvalene-fused carbox-
ylic ligands (TTF-COO) to achieve control over electronic conduction and mag-
netoresistance (MR) within the nanoparticle assemblies. Concisely, TTF-COO–
Fe3O4 NPs were prepared by replacing the oleylamine (OA) molecules—which
are present as capping on the Fe3O4 NPs—with TTF-COO via a ligand exchange
process to modify the NP surface composition from OA-Fe3O4 to TTF-COO–Fe3O4
(see Fig. 9a). One can control the interparticle distance between TTF-COO–Fe3O4
NPs through alteration in the length of the TTF-based core units. This leads to one
Fig. 9 (a) Schematic representation of surface modification of OA capped Fe3O4 NPs with
different molecular spacer groups. The –COO– group serves as the anchor between the ligand
and NP surface, binding to Fe–O surface via the monodentate form. (b) Temperature dependence
MR of L1-, L2-, and L3-NPs at magnetic field strength of 5.8 kOe. (c) Zero-bias resistivity ρ0 of
L1-, L2-, L3-, L10 -, and OA-NPs as a function of T-1/4. (Adapted with permission from Ref. [294]).
(d) Nanoparticle-on-mirror (NPoM) geometry with an 80 nm Au particle is used to elucidate field
enhancements required for single-molecule spectroscopy. (e) Molecular structures of six different
molecular tunneling junctions (I–VI) used in the hot electron reduction experiments. (f) Time scans
for SERS spectra from individual NPoM geometries, with different molecular tunnel junctions (I–
VI), in which the electron transport mechanism is changing from coherent tunneling to sequential
hopping. (g) Schematics for the mechanism of plasmon-induced hot electron transfer between Au
nanoparticles and unoccupied molecular orbitals of adsorbed molecules and the resultant reduction
route. (Adapted with permission from Ref. [295])
peculiar observation of this study, the shorter the interparticle distance through
decreasing the alkyl spacer chains, the better will be the conjugation between the
TTF’s HOMO and LUMO and consequently, higher will be the electrical conduc-
tivity and MR. Furthermore, it was also observed that the different NPs with
diversified capping molecular species behave as somewhat ohmic conductors
above 250 K whereas the typical Coulomb blockade behavior was shown below
150 K (see Fig. 9b, c). Further advantage of using the TTF-coating is the stabiliza-
tion of Fe3O4 NPs as opposed to their deep oxidation and loss in the spin information
(polarization) on Fe3O4.
Nanoparticle-based molecular tunneling junctions were also explored to compre-
hend the redox behavior of the SAM under the illumination of light. De Nijs et al.
[295] uncover the role of hot electrons in the photoinduced redox reaction by
recording the Raman spectra of molecular junctions formed with a gold
nanoparticle-on-mirror (NPoM) geometry in their device (refer Fig. 9d–g). The hot
electrons were created in the nanogap with the help of irradiation by a 633 nm laser
and the transport of these hot carriers through the molecular junctions causes the
redox reaction in the SAM. Time-evolved Raman spectroscopy was performed to
elucidate the effects of electron transfer mechanism for all the different types of
molecular junctions. If the charge transport relies on hopping mechanism, the main
peak in the Raman spectrum fluctuates drastically. On the other hand, molecular
junctions with coherent tunneling mechanism show stable spectroscopic signatures.
The fluctuations in the Raman spectra for hopping-dominated junctions can be
assigned to the hot electron-induced redox reactions. This strong correlation between
Raman shifts and redox states is noteworthy to examine the chemical behavior at the
single-molecule scale. Conductance modulation of single molecular junctions
through hot electrons could be a potential candidate to unravel the nano-
photochemistry and SPR-induced photocatalysis.
Recent studies have also demonstrated the importance of hot carriers in the
realization of photocatalysis induced by plasmonic sources [296]. Active research
in the field of nanoparticle-based plasmonic excitation could provide a better
platform for the understanding of various optoelectronic applications such as
photocatalysis, sensors, optical fibers, and high-speed spectroscopy with the hope
for future spintronics applications [297–299].
3.1.4 On-Chip Plasmon Sources in MSP
Various efforts have been made to employ SPRs in an on-chip plasmonic device for
superior performance and better power-efficient nanoscale implementation for opto-
electronic applications [300]. Current research on electrically driven plasmon-based
electroluminescence through indirect excitation with nanoscale semiconductor has
given the required impulse to this research field towards real-life applications in
optoelectronics industries [301, 302]. Nevertheless, plasmon sources—via electron–
hole (e–h+) recombination—lack with respect to the timescale as these excitations
are comparatively slower than the direct electrical plasmons excitation [303]. Direct
plasmon excitation occurs at quantum mechanical timescale (pico- to femtosecond)
whereas a typical timescale for the recombination of e–h+ pairs is circa nanosec-
onds [304]. But then, it has been demonstrated that plasmonic sources can be
splendidly stabilized in microfluidic channels and could be used in various charac-
terization methodologies such as molecular overtone spectroscopy [305] and label-
free SPR-based imaging microscopy [306]. In this direction of microchannel-based
devices, an attempt towards the realization of an optoelectronic device with molec-
ular monolayers was put forward by Du et al. [307] utilizing the metal-molecule-
metal junctions as plasmon sources on an electrically driven on-chip design. Briefly,
a molecular monolayer was assembled on an ultraflat template stripped gold sub-
strate (AuTS) as bottom electrode and a liquid alloy of gallium (Ga) and indium
(In) in eutectic (E) composition (also called as EGaIn)—confined in a through-hole
in a transparent rubber (poly-dimethylsiloxane; PDMS) channel—as the top elec-
trode (Fig. 10a, b). A suitably thin Au film (~50 nm) was deposited for the reliable
detection of surface plasmon polaritons (SPPs) and LSPs. A range of two kinds of
molecules were taken—one type of molecules is S(CH2)n1CH3 (SCn, n ¼ 10,
12, 14, 16, and 18) and (4-((4-(ferrocenyl)-phenyl)ethynyl)phenyl)methanethiol
(S-OPE-Fc)—to study the effects of symmetry of tunneling barriers on plasmon
Fig. 10 (a) Schematic of the SAM-based molecular junctions stabilized in microchannels formed
in PDMS with the Ga2O3/EGaIn top electrode and an ultra flat AuTS bottom electrode. An optical
adhesive (OA) was used to glue the AuTS onto the glass substrate. (b) Representation of the
molecular junctions with a SAM of SCn (left) and S-OPE-Fc (right). The blue arrow specifies the
tunneling direction along the molecular backbone, α corresponds to the tilt angle of the SAM with
respect to the surface normal to the substrate and d is the tunneling barrier width (or molecular
length, so to say). (c) Absorption spectra of plasmons excited in molecular junction with a SC12
SAM on a 50 nm AuTS film at different applied bias. (d, e) Real plane and back focal plane images,
respectively, of plasmons excited in a SC12 molecular junction at 1.8 V. (f) Defocused image of
plasmon excitation spots in the molecular junction with a SC12 SAM on the AuTS substrate
recorded at an applied bias of 2.1 V with an acquisition time of 5 s. (Reproduced with permission
from Ref. [307])
excitation. Fermi levels of both top and bottom electrodes are around 4.2 eV which is
almost half of the HOMO–LUMO gap of these molecules (~8–9 eV). Hence, it was
found that the microchannel devices with SCn junctions showed symmetric tunnel-
ing current response and could be modulated through changing the decay constant
by varying the length of the molecules. However, S-OPE-Fc junctions were accom-
panied by asymmetric charge transport characteristics similar to molecular diodes. In
case of S-OPE-Fc junctions, a positive bias leads to a downward shift in the HOMO
energy below the Fermi levels of both the electrodes and consequently, a direct
tunneling-based mechanism predominates for charge transport. On the other hand,
when a negative bias is imposed on the SAM present in the device, HOMO pro-
gresses in between the Fermi levels of the two electrodes involved in the molecular
junctions. As a result of this alteration, electronic transport follows sequential
hopping instead of direct tunneling mechanism.
As far as the plasmonic properties are concerned, it was found that plasmons in
these molecular junctions come into existence from the diffraction-limited single
spots obeying power law-based statistical distribution of photons [308]. It was also
affirmed that one can have a directional control over polarization of light by altering
the tilt angle of the molecular monolayer and applied bias. The polarization of the
plasmon sources was recognized on the defocused images (see Fig. 10d–f) of
different SAMs on the bottom electrode and different orientation of the dipole in
plasmons were indicative of polarization via through-bond (and NOT through-
space) tunneling. Also, there was an inhomogeneity in the emission pattern of the
plasmons, viz., the excitation of SPPs ensued at the edges of the molecular tunnel
junctions and propagation occurred in the direction of Au-SAM-air and Au-SAM-
PDMS interfaces, while SAM-based molecular junctions were the epicenter of the
excited LSPs. On the other hand, S-OPE-Fc SAM-based plasmon sources—which
behaved like molecular diodes—exhibited switching behavior by changing the sign
of the voltage. The key finding was the discretization of excitation spots which could
enable the engineering of plasmons for molecular diodes for better power efficiency.
Numerical simulations settled on the fact that the orientation of the plasmon
emission (via polarization) was around 30 with respect to the normal to the substrate
surface and matches with the tilt angle of the molecular monolayer. This also
indicates that the plasmon excitation propagated along the tilted molecular junctions
of the SAM via through-bond tunneling. Additional evidence for this observation
came by the replacement of bottom electrode from AuTS to AgTS which resulted in
the change in the tilt angle by ~20 (tilt angles are ~30 and 10 for SCn on AuTS and
AgTS, respectively [309]), and because of this, the directional excitation was found
to be at ~10 .
This work is an excellent example of operating and modulating the dynamics of
plasmonic excitation of molecular junctions and could be an essential scheme toward
the implementation of molecular tunnel junctions in viable and functional optoelec-
tronic devices. Because of the ease in quenching of molecular fluorescence, to date,
molecular diodes have been realized either at cryogenic temperature or high vacuum
[267, 273]. On-chip optoelectronic devices consisting of junctions with molecular
monolayer might miniaturize a light-emitting diode (LED) in the foreseeable future
for operation in ambient environment.
3.2 Plasmon Detection in MSP
Plasmons are intricate entities and their generation, as well as detection, require
sophisticated methodologies and instrumentation [137]. In this section, we shall be
discussing the approaches to perceive the plasmons in MJs (Fig. 11). After the
creation or excitation of plasmons, it becomes necessary to detect the same as it is
crucial for the study of optoelectronic properties of the MJs under investigation.
There are two ways of detecting the plasmons in the system of interest namely direct
plasmon detection and indirect plasmon detection [310, 311]. Direct plasmon detec-
tion entails plasmon/photo-assisted tunneling, also known as PAT, whereas indirect
plasmon detection involves a two-step process which comprises of generation of
electron–hole (e–h+) pairs followed by separation and collection of these pairs in
order to get photoinduced current. We will address both the ways for the detection of
plasmons in MJs along with their applications in the modern world in the upcoming
subsection.
3.2.1 Direct Plasmon Detection in MSP
Excitation of plasmons by irradiating them through electromagnetic radiation can

generate an exceptionally high localized electric field in the host nanogaps of the
metal electrodes [312–314]. This results in the enhancement of charge transport at
nanoscale by a process termed as photoemission in which an electron—generated by
the photonic excitation, also called as photoelectron—gains adequate momentum to
Fig. 11 Pictorial representations of (a) Direct plasmon detection through photon-assisted tunneling
(PAT) and (b) Indirect plasmon detection in tunnel junctions as a result of electron–hole (e–h+)
separation
tunnel form one end of the nanogap to the other [6, 185]. This is termed as photon-
assisted tunneling or PAT, since the plasmonic detection utilizes the electromagnetic
radiation stipulated by the plasmon, it could also be termed as plasmon-assisted
tunneling. The proficiency of PAT is directly related to the energy of the incident
photons (ħω) and the effective work function (Φ0) of the metal electrodes [188]. As a
result of this, there exists a net charge imbalance between the two electrodes due to
the photoemission which consequently leads to the emergence of photocurrent even
in the absence of applied bias. This whole process is characterized as direct plasmon
excitation and is crucial for the realization of modern optoelectronic devices for
applications in quantum plasmonics.
The explanation(s) for the above-stated phenomenon was put forward by Tien
and Gordon in 1963 [315]. According to this model, the time-dependent modulation
of electronic energy levels occurs due to a periodic potential VP generated by the
plasmonic field across the metal nanogap. An electron coming from the left electrode
(say), with an initial energy E, tunnels through the junction either by absorbing or
emitting n photons with the plasmonic frequency ω. This leads to an effective energy
of electron as E nħω after the completion of the tunneling process. Since the
transmission probability is an instructive function of electronic energy, one can alter
the “amount” of tunneling across the junction, and hence the DC current of the
junction. Strictly speaking, VP acts as an external bias (in addition to the applied DC
bias VDC) to regulate the transmission probability of the electron tunneling across
the MJs.
Numerous researches have been performed to understand the mechanism of PAT
through the excitation of SPPs by photons when the resonance condition of momen-
tum is fulfilled [296, 316–318]. One of the successful experiments towards this
objective was carried out by Vadai et al. [232] where they have constructed a
“squeezable” platform for the break junction procedure as shown in Fig. 12a. The
setup consists of two vertically facing gold electrodes (40 nm Au deposited on glass
slides) and self-assembled monolayers (SAMs) of the interested molecular system
were prepared on the bottom electrode. An initial gap of ~500 nm was maintained
between the two glass slides and with the help of a mechanical configuration, the gap
between these two slides can be precisely controlled over the range of nanoscale. By
bending and relaxing the top slide, one can create standard break junctions of the
structure Au–SAM–Au by repeating the said process. In order to create SPPs within
the nanogap, MJs can be excited with the illumination of polarized light by
employing a glass prism in Kretschmann-Raether geometry [319–321]. The inten-
sity of the reflected light from the glass prism was measured continuously with
respect to the variation in angle θ between incident laser and normal to the surface.
The plasmon resonance condition advocates that the maximum coupling between
SPPs and the incident radiation will correspond to a drastic drop in the reflectivity of
laser by the prism. Consequently, an enhancement in the conductance of MJs was
observed under laser irradiation than in the dark and this is termed as
photoconductance [85]. Since the molecules under investigation have a wide energy
gap (>3 eV) between highest occupied molecular orbitals (HOMO) and lowest
occupied molecular orbitals (LUMO), the enhancement in the conductance
Fig. 12 (a) Schematic illustration of squeezable break junction setup. (b) Conductance histograms
depicting the effect of plasmons and light polarization on the conductance at 781 nm without
illumination (shown by black solid line), with p-polarized light for which plasmons are created
(shown by red colored area), and with s-polarized light for which no plasmons should be created
(shown by green dashed line). Inset of (b) represents the conductance traces with (red) and without
(black) laser illumination. (Adapted with permission from Ref. [232])
(photoconductance) cannot be described solely in terms of photoionization of

electrons by laser radiation (781 nm 1.59 eV, almost half of the HOMO–
LUMO gap and hence insufficient to cause photoionization). This shows that the
photoconductance observed in the MJs may be affected by the oscillating optical
field generated by SPPs. This novel strategy for the enhancement of conductance via
illumination could open a way towards the photodevices based on optical gating for
nanoelectronics [205, 254].
Various studies on plasmon excitation in molecular tunnel junctions have also
been performed to investigate the effects of length and conformations/configurations
of the molecules involved [295, 296, 322]. Information about the behavior of
molecules with respect to their geometry in the MJs could enable us to tune the
directional excitation of SPPs. In recent times, Du et al. [323] reported the conse-
quences of chemical structures and the tilt angle (with respect to the surface normal)
on the excitation of SPPs which is based on quantum mechanical tunneling across
molecular double-barrier junctions.
They showed that one can have directional control over the SPPs excitation by
modulating the double energy barrier via adjusting the tilt angle of an active unit,
using well-established odd–even effects [324]. In case of SAMs of S(CH2)nBPh
(BPh ¼ biphenyl, n ¼ 1–7) on Au, the tilt angle of the BPh unit with respect to the
surface normal is 45 when n is even and 23 when n is odd. To study the plasmonic
characteristics of MJs, the authors performed leakage radiation microscopy
[307, 325] in which the light emission can be detected from these junctions in the
far-field through the bottom electrode (SAM with the EGaIn stabilized in
microchannels of PDMS [307]). The resultant image for the light emission (see
figure, recorded at 2.0 V) shows that the photons originate as a result of the
discretization of emission spots. In order to evaluate the excitation of SPPs in a

particular direction, defocused images of the light emission were obtained from the
junctions by moving the objective—an oil immersion objective with a numerical
aperture (NA) of 1.49—away from the image plane by approx. 1 μm.
The directional excitation of SPPs can be quantified by defining directivity of the
SPP excitation with the help of the following mathematical expression:
ðI L I R Þ
D¼
ðI L þ I R Þ
where IL and IR are the respective maximum intensities of the left and right lobes of
the defocused spot which can be obtained by analyzing the cross section intensity
profiles of the defocused spots from the defocused images (as shown in Fig. 13c).
Highest value of D (~0.40) was found to be with n ¼ 2, lowest value of D (~0.22)
with n ¼ 1 and 3 whereas intermediate values of D (~0.30) were obtained with
n ¼ 4–7. These sort of examinations of plasmonic excitation are fascinating and
could open the doors for the advancement of nano-optoelectronics for future VLSI
applications.
Fig. 13 (a) Different configurations of the molecular junctions depending upon the number of
carbon atoms in aliphatic chain of the molecules. (b) For n > 3, tunneling direction, which is shown
by the solid red line, is defined by the tilt angle of the alkyl unit (αalk) along with Energy level
diagram of the double-barrier junction. (c) Experimentally defocused images of junctions with
n ¼ 2 (even) and n ¼ 3 (odd) recorded at 2.1 V bias. (d) Intensity profiles of the cross section of
defocused patterns obtained for junctions with n ¼ 2 and n ¼ 3. In insets, shown the corresponding
defocused images from which the profiles were taken. (Adapted with permission from Ref. [323])
3.2.2 Indirect Plasmon Detection in MSP
Light-induced plasmons can contribute towards the conductance of a single MJ by

exciting the electrons for tunneling across the junctions when these junctions are
impinged by light. These excited electrons are thus perceived as photoelectrons and
lead to photocurrent. Additionally, under the influence of externally applied bias, the
electron undergoes radiative transitions resulting in the formation of electron–hole
(e–h+) pairs. As a result of the recombination of these e–h+ pairs,
photoluminescence occurs which could be detected by various spectroscopic tech-
niques [326]. But there are some intrinsic difficulties associated with the MJs for the
real-time operative plasmon detection in an indirect way. For the formation of the
e–h+ pairs, a small bandgap between the HOMO and the LUMO orbitals is required
which is a characteristic of electronically decoupled conjugated molecules. This
smaller HOMO–LUMO gap of the molecular system results in a shorter detection
bandwidth. Another problem is the non-conformity in the timescales of measure-
ment response and the generation of e–h+ pairs. These issues constraint the
experimental viability of the indirect detection of plasmon excitation in MJs. Some
of these limitations to achieve indirect plasmon detection has yet to be overcome but
Zhou et al. [327] came up with the experimental verification along with the theoret-
ical explanation for the indirect detection of plasmonic excitation in MJs. They took
a highly conjugated molecule with a narrower HOMO–LUMO energy bandgap
(~2.5 eV) and demonstrated that the enhancement in the conductance of the molec-
ular system under the light illumination (photoconductance) can be understood in
terms of energy profile of the molecular structure and Coulombic interactions
between e–h+ pairs which are evolved in the MJ upon irradiation of light with
their corresponding energy signature.
In brief, they have employed perylene tetracarboxylic diimide (PTCDI) mole-
cules chemisorbed to gold electrodes via amine anchoring groups and the junctions
were created using scanning tunneling microscopy break junction (STM-BJ) tech-
nique (see Fig. 14a). The photons of certain energy (~495 nm wavelength
~2.5 eV) were bombarded on the system of concern with the help of a monochro-
mator for the realization of resonance condition with HOMO–LUMO bandgap of
PTCDI molecules. An ultrathin optical fiber cable was exploited to illuminate the MJ
in the toluene solution and the sufficient number (>1000) of corresponding
conductance-distance traces were acquired for the statistical analysis measured
electronic/optoelectronic properties (see Fig. 14b).
Two types of STM-BJ measurements for conductance were performed with the
MJs, one was in the dark (gray curves in Fig. 14c) and the other was under
illumination (shown as blue curves). There was a clear-cut distinction between the
blue and gray curves in terms of the positions of the plateaus in them. Blue plateaus
were present a higher value of conductance than that of the gray plateaus and the
corresponding conductance histograms evidently showed the enhancement in the
conductance upon shining the light on the MJs (photoconductance) as compared to
the nonilluminated MJs. The peak in the conductance histograms was centered
Fig. 14 (a) Schematic illustration of an STM-BJ setup in which a NH2-PTCDI-NH2 molecule is

trapped and illuminated with laser light. (b) Corresponding conductance histogram (blue: light ON
and grey: light OFF), and (c) Conductance traces that were used to create the histograms.
Representation of charge transport mechanism through a molecular junction in dark (d) and
under illumination with light (e). (Adapted with permission from Ref. [327])
around ~1.25 105 Go in case of MJs under “dark” conditions whereas the
irradiated ones showed a peak around ~1.75 105 Go. Since the molecule is not
structurally photoactive (does not change its structure upon illumination) and is a
perfectly symmetric rigid molecule, all the other factors (such as in-built asymmetry)
for the change in conductance upon irradiation can be neglected. The authors
formulated a modest mechanism of charge transport based on coupling between
HOMO/LUMO orbital with the metal electrodes that harmonizes with their exper-
imental observations. Assuming the hole-dominated transport through HOMO
orbital, when the MJ is lightened with the radiation having a near-resonance
frequency of the HOMO–LUMO energy gap, the electrons were most likely to get
excited from HOMO to LUMO. Consequently, hole transport from electrode to the
HOMO level leads to Coulombic attraction between hole (in HOMO) and electron
(in LUMO). This interaction leads to a push on HOMO energy level towards LUMO
level, resulting in the reduction of the HOMO–LUMO gap. This, in turn, decreases
the tunneling barrier for the charge transport and hence an enhancement in the
conductance (photoconductance) is observed.
Realization of photoconductance in these types of exclusive molecular assem-

blies could have a great potential to be wired into real-life electronics as switches
[328] as well as light sensors [274] in future technological advancements
[329]. There are still some serious challenges for single molecule optoelectronics
which should be tackled with novel strategies and methodologies for the realization
of steadfast molecular devices. For example, when plasmonic nanogaps are irradi-
ated with the light, numerous other processes come into the picture such as thermal
expansion of the electrode material [330] and photothermoelectric response of the
MJs [330, 331] which could lead to discrepancies in measuring the desired charge
transport properties of the MJs. There are several ways [332–334] to quantify these
physical effects, out of which the Raman spectroscopy is one of the most important
techniques to probe the real-time fingerprints on the MJs [81–86]. Direct acquisition
of structural information with physical as well as chemical dynamics of single MJs
can be precisely determined by using surface-enhanced Raman spectroscopy (SERS)
[335–340] incorporating with mechanically controlled break junction (MCBJ) tech-
nique [341–343]. These studies are of utmost importance when it comes to under-
standing the fundamental concepts behind single- or ensemble-based molecular
optoelectronics devices and applications. Quantum plasmonics by deploying the
molecular junctions is one of the bottom-up approaches in creating the plasmons in
nanostructures [344] but there are several top-down approaches as well that have
been performed to study the optoelectronic properties of the nanomaterials
[345, 346]. Future objective of nanoscale plasmonics could be an amalgamation or
“crossbreed” of top-down and bottom-up methodologies [347, 348] to engineer the
improved nanostructures for further applications in high-resolution optical devices
[187, 205, 310], photocatalysis in light-induced chemical reactions [295], efficient
photovoltaics [348–352], and photosensors for biomedical applications [353–357].
4 Future Perspective and Challenges
We are looking forward to a better future for MSP and hence it becomes crucial to
develop innovative methods to fabricate molecular devices that can address the
inadequacies conjoined with the present devices based on molecular assembly for
plasmonic studies. In this chapter, we have discussed numerous novel techniques
and the recent technological advancements in the device fabrication methodologies
that helped a lot in understanding the fundamental phenomena related to the quan-
tum world of MSP which could lead to the significant development in competent
optoelectronic devices. This growth is crucial for elucidation of charge transport
mechanism for plasmon excitation as well as the implementation of these devices in
modern electronics. Better understanding of phenomenon related to MSP could help
in diminishing the unnecessary energy losses and undesirable effects, resulting in the
modernization of device fabrication and superior electrode materials. Furthermore,
since modifications in chemical identity of molecules are quite straightforward and
they are easily available, one could find countless approaches to control the ways
charge flows through molecular junctions. MSP, being a unification among various
scientific disciplines, requires extensive alliance among the ambitious researchers
from the scientific community of physics, chemistry, material science, electronic
engineering, biology, and biochemistry in order to reach the desired goals.
Despite the copious endeavors, unresolved difficulties continue to exist. The
majority of the techniques for the characterization SPPs and LSPs are indirect and
involve a diverse range of severe approximations, which often ensue either misin-
terpretation of results or make it challenging to explain the outcomes of experiments.
Future direction of MSP demands efforts to resolve these issues related to the
fundamental studies of plasmonics to enunciate the mechanism of charge injection.
Along with this, the improvements in material design, and augmenting the stability
of device structure, could lead to better functioning electronic devices and could be
realized with their full proficiency in modern optoelectronics. All these devices and
techniques, that have been developed by creative researchers around the globe,
somehow provided an optimistic portrayal of MSP with a promise of a lucid future.
Rapid development in the expansion of the research field would be a path that could
fulfill the dream of participation of MSP in real optoelectronic marketplace and
changing the direction of industries from hard to soft electronics. Enthusiastic and
creative activities in the past few years in the field of MSP are the real motivation to
achieve the long-term goals and to create a broad perception for upcoming advances
in this interdisciplinary line of work, which is growing with an unceasing
progression.
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Aluminum: A Sustainable Universal
Plasmonic Materials
Abhishek Dubey and Ta-Jen Yen
Abstract In recent years, many alternative plasmonic materials have emerged in the
plasmonic research field. Among them, aluminum (Al) is one of the most suitable
and sustainable plasmonic material with a broad plasmonic working wavelength
range in contrast to well-known noble metals such as silver (Ag) and gold (Au).
Additionally, high plasma frequency, low loss, native oxide protection, and CMOS
compatible benefits of Al make it a potential candidate for plasmonic-based appli-
cations. Here in this chapter, we will report the recent advancement of Al plasmonics
in the UV, visible, and IR regime for surface-enhanced Raman scattering,
photodetection, color filters, photovoltaics, photocatalytic, nonlinear applications,
etc. To lay the foundation of Al plasmonic effects, first, we commence by explaining
the physics of surface plasmons behavior in the Al film and nanostructures. Later,
this chapter explains the application of Al plasmonics advanced applications in all
the specific wavelength regimes.
Key words Aluminum plasmonics · Epitaxial aluminum film · Aluminum

nanostructures · UV plasmonics
1 Aluminum: An Introduction
Over the past decade, aluminum (Al) has attracted much attention due to its
plasmonics profile over the broad wavelength spectra that can be utilized to dramat-
ically enhance the light-matter interactions from UV to IR regime. Primarily, it is
very important to know what parameters make a material an appropriate plasmonic
material. In particular, the real part of the dielectric function which determines the
near-field intensity, and the imaginary part of the dielectric function which elucidates
the intrinsic loss of the materials are major important parameters. Bearing this in
mind, many researchers have devoted themselves to look for suitable and sustainable
A. Dubey (*) · T.-J. Yen

Department of Materials Science and Engineering, National Tsing Hua University, Hsinchu,
Taiwan
https://doi.org/10.1007/978-3-030-99491-4_5
172 A. Dubey and T.-J. Yen
plasmonic materials for all over the wavelength spectrum [1–4]. As a result, Al
appeared as one of the most abundant plasmonic material on earth with excellent
stability, complementary metal-oxide-semiconductor (CMOS) compatibility, and
wide availability as compared to prevalent plasmonic material such as silver
(Ag) and gold (Au) [5].
For the study of surface plasmon, the Drude model for metal/air interface
describes the surface plasmon frequency for the system as following [6]
ωp
ωsp ¼ pffiffiffi ð1Þ
2
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
where ωsp is surface plasmon frequency and (ωp ¼ ne2 =ε0 m) is the bulk plasma
frequency. Therefore, the major advantages for Al are the high electron density, with
three electrons per atom in comparison for Au and Ag have one electron per atom [7]
and plasma frequency (ωp) is at ~15 eV, in comparison ωp for Ag and Au is 8 and
9 eV [8]. Therefore, high plasma frequency can accompany broad wavelength range
for surface plasmons. Further for optical behavior, we can see in Fig. 1a, b, the
comparison of the dielectric constants of Al, Ag, and Au were demonstrated by
Gerard et al. [9]. The real part of the dielectric function of Al keeps a negative value
(ε1< 1) from UV to IR regime and exhibits metallic behavior. However, for Ag and
Au it approaches zero below 300 and 500 nm, respectively. Consequently, it loses
the surface plasmon behavior properties.
In particular, Al shows an interband transition (IT) at around 800 nm and “Drude-
like” behavior in the entire regime of the spectrum. In Fig. 1b, we can see that IT is at
around 800 nm where Al has a peak behavior. However, the IT for Au and Ag are at
around 310 and 500 nm, respectively, which exhibit threshold behavior. For Au, the
incident photons with higher energy than 2.4 eV (~500 nm) excite the electron-hole
pairs due to exciting the d band and s–p band [10]. But for Al, incident photons
higher than the interband transition energies are unable to excite electron and hole
pairs. Because the bands involved in the IT transition of Al are parallel with
transition energy ~1.5 eV (~800 nm) and similar like conduction and valance band
of direct band semiconductor [11]. On the other hand for the imaginary dielectric
part which is the less favorable of the Al, nevertheless Al exhibited comparable
performance for many applications in the visible regime as compared to Ag
[12]. Specifically, for the deep UV (DUV) regime (<300 nm) Al overpasses the
Ag and become the only suitable choice for this regime. Therefore, Al can work as a
plasmonic material at UV, visible, and IR regimes [13].
We have already described that Al can possess the LSP resonance on both sides of
the IT peak (~800 nm). But when LSPR reaches 800 nm, a coupling among IT peak
and LSPR peaks is observed by Pakizeh et al. [14]. In this work, the author has
described the coupling behavior using Drude-Lorentz model using the following
dielectric equation
Aluminum: A Sustainable Universal Plasmonic Materials 173
Fig. 1 (a) Real part of the dielectric function. (b) Imaginary part of the dielectric function of Al,
Au, and Ag with respective wavelength. (Adapted with permission from [8]. Copyright 2015 IOP
publishing). (c) Scattering spectra of Al nanodisk with various oxide percentages (solid lines are
simulated spectra). (Reprinted with permission [11]. Copyright 2013 American Chemical Society)
" #
ω2p G0 ω20
ε ð ωÞ ¼ 1 þ 2 ð2Þ
ωðω þ iγ c Þ ω0 ω2 iΓω
where γ c is the collision rate in the first term and in the second term G0, ω0, and Γ are
gain in the Lorentzian term, central frequency, and damping factor, respectively. In
Eq. (2), the first term represents the Drude-like behavior of Al and the second term
defines the IT transition at frequency ω0. As a result, the authors also observed that
optical absorption of Al NPs is enhanced near to IT transition due to the coupling of
these two modes. Further, Schwind et al. demonstrated the experimental realization
of noncrossing behavior in the coupling of LSPR and IT band in Al film using
nanohole [15]. Therefore, the coupling event between IT and LSP resonance in Al is
accomplished due to the narrow spectral IT band, unlike Au and Ag.
Al is always underrated for plasmonic applications due to oxidation concerns.

The native oxide layer is always coated on Al, despite native oxide thickness
depending on the preparation method [16]. Knight and coworkers demonstrated
the oxide effect on Al nanodisk prepared by electron beam lithography [17]. The
darkfield emission spectra for D ¼ 100 nm nanodisk which is covered by SiO2 as an
oxide layer are plotted in Fig. 1c. For 0% oxide layer Al resonance peak is observed
at 405 nm and at 40% oxide layer peak is red-shifted to 550 nm with lower scattering
amplitude. It means that the oxide fraction can be also used to tune the resonance. In
terms of native oxide, many researchers claimed that oxide thickness is around
2–5 nm and stable for many months [18]. Such analyses claim that native oxide
prevents the bulk oxidation like Ag and show sustainable behavior of Al in the
environment.
2 Aluminum Film and Nanostructure
As we know, size and shape are the most critical parameters for tuning the
plasmonics resonance applications [19]. Firstly, McClain et al. demonstrated the
facile synthesis of monodisperse, icosahedral, and trigonal bipyramidal Al
nanocrystals having DUV to visible plasmonic resonance [20]. In this work, the
author controlled the size of Al nanocrystals by increasing the fraction of tetrahy-
drofuran (THF) in the 1,4-dioxane/THF solutions (Fig. 2a). For these various sizes of
Al nanocrystals, the simulated and dark field scattering spectra were shown in
Fig. 2 (a) Al NCs synthesis reaction and different size TEM image of Al NCs with tuned THF
volume fraction. (b) Measured and simulated scattering spectra of different diameter Al NCs.
(Reprinted with permission [20]. Copyright 2015 American Chemical Society). (c) Scanning
electron microscope (SEM) and CCD image of Al nanohole array with different diameters. (d)
Measured and simulated scattering spectra of Al/GaAs nanohole array. (Reprinted with permission
[23]. Copyright 2015 American Chemical Society)
Fig. 2b, where dipolar resonance was dominated for 80, 120, 155, and 220 nm Al
nanocrystal. However, for 120 and 150 nm authors also observed higher order mode
(i.e., quadrupole mode) at 5 and 4 eV, respectively. Afterward, single-crystalline Al
nanorods were also synthesized by Clark et al. [21]. Here, Al nanorods showed two
adjacent {111} facets separated by {100} facets which exhibited polarization-
dependent plasmon resonance covering the visible and UV regime. Further, Renard
et al. developed a robust method to functionalize Al nanocrystals with silica as a
protection layer in H2O from hours to weeks for photothermal heating [22].
The performances of plasmonics materials do not only depend on the structure
and shape but also the material quality. Mostly, plasmonics devices are fabricated
using lithography methods where polycrystalline Al is used which suffers from
strong scattering loss and short surface plasmon polariton propagation length. As
we know, Al is extremely sensitive to deposition methods. Therefore, the epitaxial
growth of Al is most important to realize for advanced applications. Firstly, for
plasmonics applications, ultra-smooth epitaxial Al film is grown on semiconducting
GaAs substrate by molecular beam epitaxy (MBE) [23]. In this work, authors
realized plasmonic mode from near UV to all over the visible regime by designing
periodic nanoslit and nanohole arrays. In this work, LSPR and photonic mode of Al
nanohole and GaAs, respectively, are tuned from 400 to 800 nm using the various
diameter of nanohole, as we can see in Fig. 2c, d. Further, Cheng et al. grew the
epitaxial Al film on Si, which showed lower loss and higher electric field confine-
ment compared to palik-Al film [24]. Likewise, Cheng et al. also grew the single-
crystalline Al film on sapphire and showed plasmonics lasing behavior in the UV
and visible regime using ZnO nanowire and InGaN nanorod, respectively [25].
3 Applications in the Broad Spectrum

3.1 Ultraviolet Regime
Many researchers showed interest in the Al plasmonics because Al’s plasma fre-
quency is higher than that of Au or Ag and this profoundly allows for significant
surface plasmon responses to strike in the UV regime. As result, Al is the best choice
for UV plasmonics. So here, we will discuss various recent applications of Al
plasmonics in the UV regime.
Very recently, Dubey et al. have reported UV plasmonics enriched ultrasensitive
photodetector with the help of epitaxial Al film and Gallium nitride (GaN)
[26]. Their design is a combination of epitaxial Al nanohole array on GaN/Al2O3
substrate (see Fig. 3a). We can see at the interface of epitaxial Al and GaN in the
Transmission electron microscopy (TEM) image in Fig. 3b where (111) plane of Al
is aligned with (0002) plane of GaN. Further, an optimized Al periodic nanohole
array is fabricated to excite LSPR around the bandgap edge of GaN which is
confirmed by reflectance spectra (see Fig. 3c) and this LSPR decays
non-radiatively and transfers into the GaN substrate. In addition, the nanohole
Fig. 3 (a) Schematic design of the device. (b) TEM image of Al and GaN interface. (c) Simulated
and experimental reflectance/transmittance spectra of Al nanohole array. (d) Band alignment of
proposed device. (e) Responsivity and detectivity of photodetector with various incident optical
power. (f) Spectral photoresponse of photodetector. (Reprinted with permission [26]. Copyright
2021 John Wiley and Sons)
array supports extraordinary transmissions (EOT), which coupled the incident pho-
tons to the GaN surface more efficiently to eject photoelectrons from GaN as shown
in Fig. 3d with band alignment. Such unique combinations have shown ultrahigh
detectivity 1.48 1015 cm Hz1/2/W and maximum responsivity 670 A/W as shown
in Fig. 3e. In Fig. 3f, we can see, optimized nanohole array also enhanced
responsivity from all over the UV spectrum due to excitation of higher-order
resonance mode among Al nanohole.
A first attempt is reported by Zhang and coworkers for room temperature plasmon
laser using Al film and GaN nanowire at 370 nm [27]. In this work, GaN nanowire is
used as a gain medium on Al film with ~8 nm SiO2 separation. The authors observed
that SPP-lasing modes are very delicate to incident polarization. In Fig. 4a, we can
see the schematic of the geometry of lasing device design and plasmon lasing
selected by incident polarization. When the incident polarization light is parallel to
the nanowire, the single-mode plasmonic lasing is excited at 369 nm with contrast to
the perpendicular to the nanowire where multimode lasing is excited at 372 nm (see
Fig. 4c, d). Besides that, for the effect of Al film, authors have demonstrated time-
resolved two-photon pump emission of GaN nanowire on SiO2/Al and SiO2 sub-
strates. As a result, spontaneous emission of GaN nanowire is enhanced in the
plasmonic substrate due to the Purcell effect. We can see in Fig. 4e GaN emission
lifetime is decreased from 698 to 78 ps on a plasmonic device.
Fig. 4 (a) Schematic and absolute electric field distribution of the plasmonic device. (b) Schematic
of single mode (upper panel) and multimode (lower panel) Plasmonic lasing using incident
polarization. (c, d) Experimental spectra of lasing when the incident polarization is along and
perpendicular of GaN nanowire. (e) Time-resolved emission lifetime of the GaN nanowire.
(Adapted with permission from [27]. Copyright 2008 American Chemical Society)
Recently, Li et al. have demonstrated a low threshold plasmon laser the usage of
metal (M), insulator (I), and graphene (G) structure, whereas in metal Al and Ag
were used [28]. Here, graphene causes a variation in the electron density at Al and
Ag surface which results in change in the plasmon resonant frequency. This variation
can be attributed to the lower work function of Al than graphene, so more electrons
are accumulated at the Al surface. In Fig. 5a, b, we can see the schematic design and
SEM image of this surface plasmon polariton (SPP) nanolaser which confirms the
laser cavity is around 0.8 μm. The authors also demonstrated that after using
graphene, the propagation wavelength of SPP waves can be increased two-fold
and the threshold of nanolaser is reduced by 50% in comparison to without
graphene. To determine the lasing behavior, PL spectra were recorded at 77 K, in
the case of Ag template multimode emission and large spontaneous emission factor
(β) are observed (Fig. 5c–f). However, for Al a single mode emission and small
value β is acquired. In conclusion, such a plasmonic device is capable of modulating
the plasmonic wire laser for an essential role in quantum plasmonics devices.
Since 1970, SERS is the most prominent application for plasmonics research.
Since UV SERS have not been explored much as visible and IR SERS due to the
limitation of plasmonic materials in the UV regime. Especially, the DUV regime has
more potential due to the Raman scattering cross-section increasing with the fourth
Fig. 5 (a) Schematic design of the SPP nanolaser. (b) Scanning electron microscopy image of ZnO
nanowire on Graphene/Al2O3/Al film. (c–f) Photoluminescence measurement of ZnO nanowire on
with and without graphene on Al and Ag film at 77 K. (Reprinted with permission [28]. Copyright
2019 American Chemical Society)
power of the frequency [29]. Moreover, many biological molecules such as oligo-
nucleotides have absorption in the DUV regime as a result DUV surface-enhanced
resonance Raman spectroscopy (SERRS) can be beneficial [30].
Firstly, in 2007 researchers have demonstrated crystal violet SERS behavior on
Al film having 244 nm incident laser [31]. Further, Jha and coworkers demonstrated
more clear evidence of DUV SERRS using Al nanoparticle array as plasmonic
substrate and 1 nm thick adenine as an analyte [32]. In this chapter, Al nanoparticle
array fabricated over a large area (400 μm 400 μm) using extreme UV interference
lithography which shows the far-field extinction spectra having a height of 70 nm,
periodicity of 200 nm with various particle sizes (Fig. 6a). The authors observed two
strong plasmon resonances which are attributed to dipolar resonance (350 nm) and
quadrupolar resonance (250 nm) as shown in Fig. 6b as a result of strong evidence of
tunable and sharp plasmon resonance in the UV and DUV regions. Further, they
measured the Raman signal of 1 nm thick adenine on fused silica and Al nanoparticle
array as shown in Fig. 6c. In comparison, the Raman signal of adenine on nanopar-
ticle arrays with the same diameter was ~13 times higher than that on the fuse silica
substrate. The author assessed that the detection efficiency of such substrate can go
up to 50 zmol (~30,000 molecules) of adenine. Here, DUV SERRS promises to be
highly useful for ultrasensitive analytical biological detection.
Sharma et al. also took the advantage of resonance Raman spectroscopy and Al
plasmonics for ultrasensitive detection of adenine, tris(bipyridine) ruthenium(II),
and trans-1,2-bis(4-pyridyl)-ethylene [33]. In this work, authors used Al film over
nanosphere (AlFON) substrate with different sizes for DUV SERRS using incident
laser wavelength at around (~229 nm). In Fig. 6d, we can see the remarkable
enhancement in all the aforementioned analytes in comparison to Al film (green
Fig. 6 (a) SEM image of Al NPs array. (b) Extinction spectra of NPs array with various particle
diameters. (c) DUV Raman spectra of 1 nm thin adenine on Al NPs array and fused silica substrate.
(Reprinted with permission [32]. Copyright 2012 American Chemical Society). (d–f) SERS and
resonance Raman spectra of BPE (d), RU(bpy)32+ (e), and adenine (f) using 229 nm incident laser
on AlFON and Al mirror (green) with different diameters 179 nm (red) and 210 nm (blue).
(Reprinted with permission [33]. Copyright 2016 American Chemical Society)
curve), and on the other hand AlFON 210 nm (blue curve) showed the greater signal
enhancement over AlFON 170 nm (red curve). In this chapter, the authors defined
that the total enhancement factor (EF) is a contribution of resonance Raman and
electromagnetic EF. In this work, averaged EFs were calculated for all adsorbates,
which are 1.96 106, 2.76 107, 1.55 106, and 2.02 105 EFs for Ru(bpy)32+,
BPE, adenine, and nonresonant molecule 6-mercapto-1-hexanol (MH), respectively.
These are the highest EFs yet reported for DUV SERRS using excitation of 229 nm
laser.
3.2 Visible Regime
The visible regime is the most reported regime for Plasmonics applications. So far,
Ag and Au are the two most reported plasmonic materials for this regime. As we
have realized from spectroscopic ellipsometer data stated in Fig. 1a, b, Al has the
capabilities to show the plasmonics behavior in the visible spectrum owing to the
negative value of the real part of the dielectric function [17]. Consequently, several
researchers have taken the wager to accomplish the demand.
Firstly, to demonstrate the main key of Al being the CMOS compatibility is
harvested by Zheng et al. [34]. In this work, the author demonstrated color selective
and CMOS compatible photodetection with the best photoresponse using Al–Si
Fig. 7 (a) Schematic design of Al–Si–Al MSM photodetector. (b) Band alignment and mechanism
of photodetector. (c) Responsivity of as-fabricated detector for red, green, blue wavelength. (d)
Calculated power absorbed for red, green, and blue color in the Si. (Reprinted with permission
[34]. Copyright 2021 John Wiley and Sons). (e) Simulated transmittance spectra at the interface of
Al nanohole and Si. (f) Measured responsivity of as-fabricated color filter at zero bias for blue,
green, and red color. (g) Relation between the photocurrent and tuned incident optical power for all
three colors. (Reprinted with permission [35]. Copyright 2016 American Chemical Society)
MSM geometry (Fig. 7a). Here Zheng et al. reported a new strategy by taking the
advantage of intrinsic gain to improve photodetection efficiency. In particular, as
shown in Fig. 7b, accumulated charges at Al and Si junction generate mirror charges
thus reduction of Schottky barrier height induces an exponential increase in photo-
current for amplifying photoresponse. Above all, the tuning of the pitch of Al grating
from 500, 400, and 300 nm can make color selective photodetection for the red,
green, and blue regime. In Fig. 7c, spectral response measurements show the
maximum responsivities are 12.54, 12.07, and 11.18 A/W for blue, green, and red
detectors, respectively. Moreover, measured spectral response curves are also well-
matched with absorbed power in the Si, as we can see in Fig. 7d. However, a
photodiode with 100% quantum efficiency can have only 1.3 A/W responsivity.
Such gain in such device geometry is owing to near-field enhancement due to Al
grating. This is an innovative illustration of Al plasmonics for visible regime
applications.
Further, Lin et al. also demonstrated a low-power color filter sensor using an Al
nanohole array with Si, where Al behaves as a top electrode and a color filter [35]. In
particular, in this research article the authors demonstrated high pixel density,
superior quantum efficiency, efficient color splitting, and low power consumption
color-image sensor. In this work, the authors have optimized the diameter and
periodicity of the Al nanohole array to achieve maximum EOT at 445, 555, and
595 nm. In Fig. 7e, we can see, simulated transmittance spectra at Al and Si interface
having peaks at around 445, 555, and 595 nm with the support of the EOT. For the
major color-image sensor result, responsivities as a function of wavelength at zero
bias for 445, 555, and 595 nm are shown in Fig. 7f. This measurement confirmed the
Fig. 8 (a) Schematic design of chiro optical-based plasmonic vortex lens. (b) Chiral SHG peaks for
885 and 1200 nm. (c, d) SHG intensity with tuned incident optical power at 885 nm (c) and 1200 nm
(d). (e) The measured SHG-CD for two chiral SPP bands. (Reprinted with permission [36]. Copy-
right 2020 American Chemical Society)
self-bias behavior of this color filter. Moreover, the authors observed, various low
power (femtowatt to picowatt per square micrometer) incident light has a linear
response with generated photocurrent (see Fig. 7g) for all three aforementioned
wavelength regimes. Therefore, such a concept behind this device would expand
the effective area of color-image sensor to advance the pixel density.
The Al plasmonic also emerges as a versatile approach for nonlinear applications.
Recently, Guo et al. have endeavored to combine spiral Al vortex with tungsten
disulfide (WS2) to enhance the chiral Second-harmonic generation (SHG) efficiency
of WS2 (Fig. 8a) [36]. In this work, epitaxial Al plasmonic spiral structures were
designed for dual-band resonance at 442 and 600 nm, where 442 nm resonance is
well-matched with C-exciton of WS2 which does not show the valley excitons based
chiroptical properties. Therefore, enhancement of chiral SHG efficiency is caused by
the plasmonic enhancement effect under the optical spin-orbit interaction. We can
see in Fig. 8b, c, the authors have demonstrated two distinct chiral SHG peaks with a
strong dependence on the incident circular polarization states. Here, the authors
observed at 885 nm, SHGRCP SHGLCP due to the plasmonic vortex lens effect
which follows the quadratic behavior with excitation power density. On the other
Fig. 9 (a) Schematic design of the SERS substrate with 2D material. (b) Experimental reflectance
spectra of Al and Ag plasmonic nanogroove. (c) SERS spectra of the monolayer MoS2 on the
grating and bare metal substrate. (d) Raman mapping of A1g mode of MoS2 on Al grating. (e)
Average Raman spectra from Raman mapping. (f) Al nanogroove orientation Raman spectra for
A1g mode of the MoS2 monolayer. (Reprinted with permission [12]. Copyright 2020 American
Chemical Society)
hand, at 1200 nm SHGRCP < SHGLCP and SHG intensity fluctuates from quadratic
dependence. The measured SHG-circular dichroism (SHG-CD) for different power
and two resonance bands are shown in Fig. 8e and SHG-CD is recorded as high as
1.2 for two chiral bands. Above all, this chapter is a suitable demonstration of a
hybrid combination with 2D materials for quantum architectures.
In the visible regime, Al appeared as a suitable alternate material for SERS
application. Recently, epitaxial Al as a visible SERS for large-scale 2D materials
characterizations are demonstrated by Raja et al., where remarkably Al performed
comparably with Ag (Fig. 9a) [12]. In particular, here Al and Ag grating were
designed for 532 nm resonance which is well-matched with the incident Raman
laser (i.e., ~532 nm) (see Fig. 9b). Here, the authors used monolayer MoS2 as an
analyte to assess the performance of SERS substrate. As we can see in Fig. 9c Raman
measurements of Al grating and Ag grating are comparable due to the atomically
smooth nature of epitaxial Al film. Further, highly uniform Raman enhancement is
confirmed by Raman mapping in Fig. 9d, e. The enhancement exclusively comes
from Al grating which is confirmed by substrate orientation dependent Raman
spectra. As in Fig. 9f, we can see a two-fold symmetry pattern due to the plasmonic
gap mode of grating on the other hand on bare Al, a perfect circle exhibited the
isotropic Raman intensity form MoS2. In conclusion, the extraordinary performance
of Al film is attributed to its atomically smooth nature, a protective native oxide
layer, and facile functionalization scheme.
3.3 IR Regime
It is so unpredictable to see that one material has the capability to cover the all-over
spectrum from UV to IR. Even though Al is lossy and has an interband transition at
around 800 nm in the IR regime still several applications have given promising
results to use Al in this spectrum.
Firstly, Tian and coworkers used Al nanocrystals (NCs) for SERS application
using 785 nm incident laser [37]. In this study, Al NCs is used as a label-free coupler
for single-stranded DNA (ss-DNA) for SERS analysis in comparison to Au. In
Fig. 10a–d, SERS spectra of ss-DNA molecules with different bases on Al NCs
and Au NCs compared with normal Raman scattering. As a result, Al showed better
functionalization than Au without losing the major characteristics of ss-DNA. In
particular, ss-DNA is attached through phosphate band (PO2) at 1087 cm1 on Al
NCs due to the native oxide layer. However, Au is binded through nitrogen-
constituent groups thus shifting their Raman peaks (Fig. 10e, f). For clinical diag-
nostics purposes, the authors demonstrated quantitative analysis of individual base
content into mixed ss-DNA sequences using a multivariate regression model. In
Fig. 10g–i, we can see for two different ss-DNA sequences reference and experiment
results are in good agreement. This study explains the usage of Al NCs as suitable
and efficient SERS substrate for a wide variety of sensing, analyzing, and diagnostic
applications in comparison to Au NCs.
Firstly, Chen et al. demonstrated an Al metamaterial-based plasmon-enhanced
infrared perfect absorber [38]. Here, the authors used conventional Metal-Insulator-
Fig. 10 SERS spectra of ss-DNA molecules on Al NCs, Au NCs, and normal Raman (a) cytosine,
(b) adenine, (c) thymine, (d) guanine. Surface binding mechanism of ss-DNA on (e) gold, (f) Al
substrates. (g) Sequence of two ss-DNA oligomers used in the experiment. (h) SERS spectra of
mentioned two ss-DNA on Al NCs. (i) Quantification result of mentioned two ss-DNA oligomers
with nucleobase content (%) with reference value. (Reprinted with permission [37]. Copyright 2017
American Chemical Society)
Fig. 11 (a) Schematic design of Al-based PA. (b) Simulated near-field confinement in the PA. (c)
Measured reflectance spectra of absorber with different disk parameters. (d) Absorbance spectra of
the BSA on PA (black) and Al planer film (red). (Reprinted with permission [38]. Copyright 2015
John Wiley and Sons). (e) SEM image of self-assembled UCNP layer Al lattice. (f) UC
photoluminescence spectra of core-ishell on the Al lattice and glass substrate at 4 W/cm2 incident
laser power. PL intensity of UCNPs on Al lattice with various incident laser power for different
emission wavelength (g) 540 nm, (h) 658 nm. (Reprinted with permission [39]. Copyright 2021
John Wiley and Sons)
Metal (MIM) geometry of Al as metal and Al2O3 as a spacer, especially here the
perfect absorber (PA) is designed by scalable nanofabrication technique colloidal
lithography and dry etching (Fig. 11a). For perfect absorption, the reflectance
measurement of three different diameters based PA showed in Fig. 11c where nearly
perfect absorption (~96–97%) is exhibited with the same spacer thickness. More-
over, in Fig. 11b, simulated near-field simulation results are shown which confirm
the confinement of electric field around Al disk at resonance wavelength. Such PA is
an appropriate choice for biosensor application owing to surface functionalization of
biomolecules due to the native oxide layer, i.e., Al2O3. In this work, the authors
explored this phenomenon with standard protein bovine serum albumin (BSA),
which has amide bands located in the IR regime. In Fig. 11d, we can see the
absorbance spectra of the adsorbed BSA molecules on PA and Al film. In conclu-
sion, amide II and amide I bands of BSA are 60 times and 8 times larger in
comparison to the plane Al film, respectively. This reason can be credited to better
overlapping of the plasmon resonance with the amide II band which also demon-
strates spectral selectivity of the enhancement from PA. Therefore, such PA can be a
potential biosensor.
As we know, upconversion-based nanoparticles (UC NPs) are mostly excited
through using IR regime laser (i.e., ~980 nm), so as a result combination of UC NPs
and Al plasmonics can boost the upconversion photoluminescence. Recently, Yuan
Gao et al. demonstrated Al for near IR plasmonics for amplifying of UC

photoluminescence using three types of core-shell nanoparticles namely as a core
only (NaGdF4: Er3+, Yb3+), active core-ishell (NaGdF4: Er3+, Yb3+ as a core, and
NaYF4 as a shell), and core-ashell (NaGdF4: Er3+, Yb3+ as a core and NaYF4: Yb3+
as a shell) [39]. Firstly, Al disk height, periodicity, and diameter were optimized
using the FDTD simulation method to support LSPR resonance at around
800–1000 nm. In Fig. 11e, we can see the homogeneous dispersion of UC NPs on
a fabricated Al nanodisk array. For such a homogenous sample results are shown in
Fig. 11f, where UC photoluminescence spectra of core-ishell with Al nanodisk array
are enhanced 103 and 102 times higher at 540 and 658 nm, respectively, using
980 nm excitation in contrast to the glass substrate. Further, UC intensity vs
excitation power shows the linear relation in logarithmic scale on glass in contrast
to Al disk array in Fig. 11g, h. This shows that population reaches the saturation in
the UC process due to the higher density of localized photons in the plasmonic
structure. For understanding charge transfer in detail, core-ashell NPs were also
measured. However, the luminescence of core-ashell is higher than on core-ishell on
glass but on Al disk array UC enhancement factor is only 24. Here authors explain
that charge transfer from Yb3+ to metallic surface leads to lower UC intensity. Above
all, here Al is shown as an alternative material for IR regime plasmonics.
The proper comparison of plasmonics behavior of Al with Au for IR regime is
done by Li et al. [40]. In this work, surface lattice resonance of Al and Au were used
to demonstrate lasing characteristics. As a result, Al exhibited comparable
nanolasing behavior as Au. Here, Li et al. used spacing a ¼ 580 nm, average
diameter d ¼ 110 nm, and height h ¼ 50 nm for Al and Au NP array (Fig. 12a).
For lattice plasmon laser, in Fig. 12b, transmittance spectra show sharp modes at
840 and 844 nm for Al and Au NP array, respectively. This blue shift in the Al NP
array is attributed to higher energy localized surface plasmon of Al NPs. Charge
distribution at resonance in Fig. 12c confirms that these sharp modes are owing to the
dipolar resonance of NPs with near-field enhancement at around ~400. Further, for
lasing characteristics, authors pumped LDS-765 dye with 600 nm femtosecond
pulsed incident laser for both Al and Au NPs array. The authors observed a narrow
lasing peak at 839 nm (FWHM ¼ 0.5 nm) and 843 nm (FWHM ¼ 0.4 nm) for Al and
Au NPs array, respectively, which is very close to the dipolar resonance. This slight
difference in FWHM is because of roughness in the NPs array. Likewise, the
comparable lasing threshold for Al and Au NPs array are also counted at around
0.11 and 0.10 mJ/cm2, respectively (see Fig. 12d, e). In addition, the authors also
demonstrated a comparable lasing threshold for higher order resonance mode, i.e.,
quadrupolar resonance in Al and Au NPs array. We can conclude due to thermal
stability and native oxide, Al plasmon nanolasers can be potentially used in the
CMOS compatible IR laser where noble metals are incompetent.
Fig. 12 (a) SEM image of Al and Au NP array. (b) Transmission spectra of Al and Au NP array
and lasing spectra using LDS 765 dyes. Measured lasing spectra with various incident optical power
for (c) The electric field distribution of Al and Au NP at the resonance wavelength (d) Al NP array,
(e) Au NP array. (Reprinted with permission [40]. Copyright 2019 Optical Society of America)
4 Limitation, Challenges, and Future Prospective of Al

Plasmonics
Nowadays, Al plasmonics has become an advanced and excellent field, boosted by

technological advances in film preparation, fabrications, and numerical methods
[41]. It has made a substantial contribution in all over the spectrum for numerous
applications, as well as providing a strengthen from essential to realistic realizations
[42]. However, the major limitation with Al is it suffers from native oxide coverage
which deteriorates the optical performance [43]. On the other hand, native oxide also
served as a protection layer. In addition, Al is lossier than Ag and Au in the visible
and IR regime which also limits application range. Moreover, Al is also a poor
conductor of heat, so there is a major drawback to use in thermo-plasmonic appli-
cations [44]. The major challenge with Al is the fabrication of nanostructures.
Despite Al being CMOS compatible, nanofabrication of Al needs very delicate
fabrication procedures. Above all, Al is the better choice especially for the UV
regime over the Ag and Au. There are numerous needs which can satisfy the usage of
Al in plasmonics-based applications. Likewise, Al can be advantageous for design-
ing the SPACER (Surface Plasmon Amplification by stimulated emission of radia-
tion) based DUV laser [45]. In bioscience, detecting many biomarkers is a great
challenge without damaging them. Al as a SERS substrate has the capability to fulfill
this demand [12]. In the future, Al opens multiple windows to realize the
plasmonics-based applications in the industry [46].
5 Conclusion
In this chapter, we made an effort to demonstrate the recent advancement in

Plasmonics probe using Al film. Al has shown promising consequences for various
applications from UV to IR spectrum owing to high plasma frequency and native
oxide protection. We tried to reveal the potential of Al as a potential candidate as an
alternative plasmonic material. Still, there is a giant room for Al to explore and
comprehend for better and exciting outcomes. Conclusively, Al has demonstrated
itself as a universal, sustainable, and broad wavelength plasmonic material.
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Surface Plasmon Resonance Biosensors
Based on Kretschmann Configuration:
Basic Instrumentation and Applications
Nishant Shukla, Pawan Chetri, Ratan Boruah, Ankur Gogoi,

and Gazi A. Ahmed
Abstract Surface Plasmon Resonance (SPR) offers a powerful tool for label-free
and noninvasive characterization of biomolecular interactions. To date, several
experimental configurations, based on two fundamental physical phenomena, e.g.,
attenuated total reflection and diffraction, have been developed to measure the SPR
signal generated due to the resonant interactions between incident light and plasma
waves on the metal surface. These configurations are divided into three categories:
grating-based, prism-based, and waveguide-based coupling. Among such tech-
niques, one of the prism-based SPR coupling schemes, popularly known as
Kretschmann configuration, is most widely used due to its high sensitivity, opera-
tional simplicity, lower cost, and real-time detection. This chapter explains the basic
instrumentation and reviews the recent trends in the developments of Kretschmann
configuration-based SPR biosensors with its applications.
Key words Surface Plasmon Resonance (SPR) · Attenuated total reflection ·

Resonant · Prism · Kretschmann configuration · Biosensors
1 Introduction
The great Czech medical scientist Johannes Purkinje coined the term “Plasma” for
the clear liquid that remains after removing various corpuscles of the blood. In 1927,
the term was borrowed by the Noble prize-winning American chemist Irving
Langmuir in order to describe the electrified fluid-carrying electrons and ions as an
N. Shukla · R. Boruah · G. A. Ahmed (*)

Department of Physics, Tezpur University, Tezpur, Assam, India
e-mail: gazi@tezu.ernet.in
P. Chetri
Department of Physics, D. R. College, Golaghat, Assam, India
A. Gogoi (*)
Department of Physics, Jagannath Barooah College, Jorhat, Assam, India
https://doi.org/10.1007/978-3-030-99491-4_6
192 N. Shukla et al.
analogy to blood plasma carrying red and white corpuscles [1]. During the investi-
gation related to the extension of the lifetime of a filament [2], he developed the
theory of plasma sheaths and Langmuir waves—the periodic variations of the
electron density [3]. In 1932, Steenbeck, applied the theory of Tonks and Langmuir,
suggesting the existence of plasma oscillations in metals [4]. The free conduction
electrons in the metal interact with electromagnetic radiation and can sustain surface
and volume charge density oscillations called plasmons distinct resonance frequen-
cies. The first such behavior was observed in 1902 by Wood, who suggested
implementing the idea of polarization to explain the singular behavior of grating
[5]. Later, the different roles of surface and their importance were envisioned in the
work of Zenneck (in 1907) [6] followed by Sommerfeld (in 1909) [7], Fano
(in 1941) [8], and Bouwkamp (in 1950) [9], who analyzed the solution of Maxwell’s
equations that had “surface-wave” (plasmons) properties. The subject gained its
realization after a series of publications by Bohm and Pines during the 1950s [10]. In
1968, Otto manifested the coupling of light waves to surface plasmon waves by
using the method of frustrated total reflection [11]. In the same year, Kretschmann
and Raether, through their practically developed method based on total internal
reflection advanced for the advertised use of SPR [12].
SPR technique relies on the measurement of the change in the refractive index of
the sensing layer due to molecular interactions on the sensor surface [13]. This
technique relies on the certitude that, for certain defined conditions, surface
plasmons on a metallic film can be excited by photons at the interface of two
materials [14]. The certainty of the condition relies on the analysis of a metal/
dielectric interface by Maxwell’s equations. Although the history of biosensors
goes back to 1962 with Leland C. Clark developing the enzyme electrodes [15], it
was in 1983 that Liedberg, Nylands, and Lundstroem for the first time demonstrated
the physical methods for the label-free, real-time detection of biomolecules using
SPR technique [16–18]. Basically, biosensors are devices that analytically convert a
biological response into an electrical signal [19]. In SPR sensors, the extent of
coupling between the incident wave and the surface plasmons are elucidated through
angular, wavelength, intensity, phase, and/or polarization modulation schemes by
measuring the parameters that yield the strongest coupling, which is subsequently
used as the sensor output (calibrated to refractive index) [20]. Since its first attempt
in the field of biosensors by Liedberg et al. [17] in 1983 and the induction of the first
commercial SPR instrument (BIAcore) by Pharmacia Biosensor in 1990 [21, 22],
SPR sensing has become a gold standard for the measurement of various biomolec-
ular interactions [23]. Starting from the study of binding kinetics and affinity of
protein–protein or protein–lipid interactions to viral diagnostics, the profound suc-
cess of SPR has been documented by more than 30,000 research works, registered in
PubMed, since 1980s.
Notably, among various SPR sensor types, Kretschmann configuration-based
sensors are the most widely used biosensor due to their inherent advantages, such
as high sensitivity, operational simplicity, and real-time detection capability. In this
chapter, a brief discussion on the instrumentation and various applications of
Kretschmann configuration-based SPR biosensors are presented.
Surface Plasmon Resonance Biosensors Based on Kretschmann Configuration. . . 193
2 Theoretical Background
The collective charge (electron) density oscillation occurring on a metal surface is

called plasma oscillation and the quantum associated with this oscillation is known
as surface plasmon (SP) [24]. SPs can be excited by electrons [25, 26], phonons [27],
and photons [28, 29]. Under specific conditions, such as when light of suitable
wavelength is shone at the interface between a semi-infinite metal layer and a
dielectric medium, the phase-matching conditions between the optical and surface
plasma wave (SPW) vector are achieved and SPs are excited. Such a condition is
known as surface plasmon resonance (SPR) and the resultant surface trapped
electromagnetic oscillation due to the resonant coupled interaction between the
incident light and SPW is defined as a surface plasmon polariton (SPP) [30–
33]. The excitation of SPs in case of metallic nanostructures is known as localized
surface plasmon resonance (LSPR).
The wavevector associated with a SPW at a metal-dielectric interface is given by
[29, 34–36]:
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
Em Ed
k spp ¼ k0 ð1Þ
Em þ Ed
where, k0 ¼ ωc is the wavevector of the incident wave, ω is the incident frequency,

c is the speed of light, Em and Ed are the metal layer permittivity and dielectric
(analyte) permittivity, respectively. Notably, the dielectric constant of the metal is a
= == = ==
complex quantity, i.e., Em ¼ Em þ iEm , where Em and Em represents the real and
imaginary parts, respectively. Thus, the wave vector of the SPW is also a complex
quantity, i.e., k spp ¼ k=spp þ ik ==
spp with [29]
!12 !12
= = 2
ω E E 2π E n
k=spp ¼
m
m d
¼ d
ð2Þ
c E=m þ Ed λ E=m þ n2
d
!32 !32
= == = ==
ω Em Ed Em 2π Em n2d Em
k== ¼ ¼ 2 ð3Þ
spp c E=m þ Ed =
2 λ E=m þ n2 =
2 Em d 2 Em
where, Ed ¼ n2d [37], nd being the refractive index of the dielectric (analyte).
As can
= = =
be seen from Eq. (2), for real values of kspp , one must have Em < 0 and Em > Ed .
Notably, metals, such as gold and silver, satisfy this condition [38–40]. Moreover,
k==
spp determines internal absorption, which is responsible for the dissipation of the
energy of the SPs on smooth surfaces [29].
On the other hand, merely shining light on a smooth metal surface may not excite
surface plasmons since the wavevector of photons in free space, k0, is smaller than
that of SP [40, 41], as shown in the dispersion relation curve (Fig. 1). Thus, there is
Fig. 1 Graphical representation of the dispersion relation of light in (a) free space, (b) dielectric
medium, and (c) surface plasmon polaritons. Here, ωp is the frequency of bulk longitudinal electron
excitations, i.e., the plasma frequency. The wave number, k, of a photon is always less than that of
SPP at all frequencies. Excitation of SPs can be achieved by the judicious use of dielectric materials
that increase the light wave vector so that the dispersion lines intersect. (The figure is reproduced
from Zhang et al. [34], Copyright © The Author(s) 2021, Creative Commons Attribution 4.0
International License)
always a mismatch between the momenta of the incident light photon (ħk) and SP
(ħkspp), for the same frequency. Nevertheless, several momentum-compensation
coupling mechanisms have been developed, as described in the next section, to
increase the wave vector of incident light in the dielectric medium (given by Eq. 4) to
achieve the matching conditions for the excitation of SPs.
pffiffiffiffi 2π
k ¼ k 0 Ed ¼ n d ð4Þ
λ
In the case of Kretschmann configuration, the wave vector of the incident light is
modified as [40].
2π
kx ¼ n sin θ ð5Þ
λ p
where np and θ are the refractive index and angle of incidence in the prism,
respectively.
At resonance condition [42, 43].
!12
=
2π 2π Em n2d
k x ¼ np sin θr ¼ ð6Þ
λ λ Em þ n2
=
d
8 !1 9
< E = n2 2 =
1
θr ¼ sin 1
m d
ð7Þ
: np Em þ n2d ;
=
where, θr ¼ coupling angle (i.e., angle at which resonance condition is satisfied).
3 SPR Sensor Configurations

3.1 Experimental Principle
At SPR, most of the incident light energy is resonantly coupled into the SPP mode,
resulting in a dip in the observed reflectance profile. This resonance condition is
localized at the metal-dielectric interface and susceptible to any change in the optical
properties (e.g., refractive index) of the dielectric triggered by the binding interac-
tions between sensor-immobilized ligands and sample biomolecules (analyte), and
therefore can be exploited as a method for detecting external medium near the
interface (Fig. 2A) [45–49]. For instance, when a biomolecular binding event occurs
on a gold surface, the mass of the accumulated biomolecules increases. While this
leads to an increase in the refractive index of the sensing surface, the prism refractive
index remains the same [50], resulting in significant changes in the resonance angle,
wavelength, intensity, and/or phase of the reflected light which is typically detected
by measuring the variation in the reflected light (Fig. 2B). In addition, time rate of
change of the resonance or response units (RU), that signifies the increase or
decrease in the signal, can also be measured in the form of a sensorgram, as
shown in Fig. 2C. Such capabilities of SPR biosensors allow for real-time quantifi-
cation of the amount of surface concentration of the analyte molecules and binding
affinity, and, thus, label-free monitoring of biomolecular reaction kinetics. Typi-
cally, 1000 RU represents an angular shift of 0.1 [44, 51, 52]. A SPR biosensor is
schematically represented in Fig. 2.
3.2 Basic Instrumentation
The keystone in the construction of a SPR sensor is the efficient coupling between
the incident light wave and the SPs at the metal-dielectric interface. Since SPW is a
TM wave (p-polarized wave, i.e., the electric field vector is parallel to the incident
plane), SPR is possible only when the wavevector of the incident light parallel to the
interface (i.e., TM or p-polarized light) becomes equal to that of the SPW. Notably,
the wavevector of incident (p-polarized) light can be increased and matched with that
of SPW to facilitate efficient coupling by using specially designed optical coupling
Fig. 2 Schematic representation of SPR biosensing principle. (A) Prism-coupled configuration-

based SPR instrument set up. (B) Shift of the resonance angle from a to b when analyte molecules
bind to receptor molecules. (C) Four phases of a typical SPR sensorgram: association phase,
equilibrium phase or steady-state, dissociation phase, and regeneration phase. Kon: rate of associ-
ation, KD: binding affinity, Koff: rate of dissociation. (The figure is reproduced with permission from
Patching [44], Copyright © 2013 Elsevier B.V.)
Fig. 3 Basic configurations of SPR sensors: (a) grating-coupled SPR system; (b) optical
waveguide-coupled SPR system; prism-coupled (c) Otto configuration and (d) Kretschmann con-
figuration. (Figures (a) and (b) are reproduced from Gupta et al. [53], Copyright © 2016 by the
authors; licensee MDPI, Basel, Switzerland, Creative Commons Attribution (CC-BY) license.
Figures (c) and (d) are reproduced from Yesudasu et al. [39], Copyright © 2021 Elsevier Ltd.,
Creative Commons Attribution (CC BY-NC-ND) license)
configurations. There are three coupling configurations that can be used to optically
excite surface plasmons: grating-based, prism-based, and optical waveguide-based
coupling (Fig. 3) [24].
In a grating coupler-based configuration, first demonstrated by Wood [5, 54] in
1902, the resonance condition is achieved by diffraction of the incident light. Briefly,
a light beam incident on a periodically distorted metal-dielectric interface (like a
grating) gets diffracted in different directions with an increase or decrease of the
incident light wave vector by integer multiples of the grating wave vector kg
(kg ¼ 2π/λ). A diffracted beam becomes evanescent when the diffracted order has
a wave vector greater than that of the incident grazing radiation. SPR is achieved
when the wavevector of the parallel component of the diffracted light matches that of
the SPs [49].
Otto [11], Kretschmann and Raether [12] introduced the excitation of SP by using
prism coupling in 1968. Otto configuration is based on the principle of total internal
reflection occurring at the prism/dielectric (air) interface and subsequent penetration
of an evanescent field into the outer layer. When a nano-dimensional metal film is
brought close to the outer layer of the prism, the electromagnetic field of the SP at the
metal/dielectric interface couples to the incident evanescent wave provided the
resonance condition is reached [11]. This technique is called the attenuated total
internal reflection (ATR) technique since the evanescent wave is generated by the
phenomenon of total internal reflection in the prism and subsequently coupled with
the SPs. On a similar basis, Kretschmann and Raether configuration (popularly
known as the Kretschmann configuration) relies on ATR. Nevertheless, in contrast
to Otto configuration, the Kretschmann configuration involves the deposition of a
nano-dimensional metal thin film directly on the hypotenuse surface of a right-angle
prism. The evanescent fields produced by total internal reflection pass through the
nano-dimensional metal film and if the thickness of the metal film is less than the
skin depth of the material, the SP can easily couple to the outer layer. Notably,
optimum coupling at visible light wavelengths can be achieved for a metal film
thickness in the range of 10–70 nm [55].
Similarly, an optical waveguide-coupled SPR configuration is also based on
ATR. The waveguide guides a light wave to the region deposited with a metallic
thin film. If the surface plasma wave (SPW) and the guided light wave that
evanescently penetrate the metal layer are phase-matched, the light wave excites
the SPs at the outer interface of the metal film [49].
Although all these configurations have their unique advantages and limitations, as
summarized in Table 1, prism-based coupling is the most widely used method,
especially for biosensing, due to its high sensitivity and operational simplicity
[56]. Notably, between the two prism coupling strategies, Kretschmann configura-
tion is the most conventional approach for the fabrication of SPR-based sensors [60],
since more efficient plasmon generation is possible in this configuration due to the
presence of the metal layer directly on top of the prism surface [31]. In contrast, Otto
configuration requires the metallic layer to be brought within a few microns of the
prism and maintain a constant air gap over the entire surface, which is very difficult
to accomplish [61]. However, Otto configuration is found to be efficient in the study
of single-crystal surfaces, since such surfaces would not be affected by the prism due
to the presence of the air gap between the prism and metal surfaces [57].
Table 1 Comparison of different SPR coupling configurations

SPR
coupling
configuration Advantages Disadvantages
Grating- Higher integration capabilities, possi- Sensitivity is comparatively low; com-
based bility of miniaturized sensor fabrica- plicated manufacturing process [38]
tion for lab-on-a-chip applications [56]
Prism-based Highly sensitive, easy to use [56] Complicated opto-mechatronic instru-
mentation, especially for angular mod-
ulation; miniaturization is usually
difficult since the size of the prism is
large [53, 56–59]
Waveguide- Miniaturized sensor size [57, 58], Angular modulation is not applicable,
based highly sensitive, no moving parts [45] SPR reflectivity profile can be obtained
with polychromatic light only [43]
3.3 SPR Measurement Methodologies
Notably, biochemical interactions at the sensor surface trigger local changes in the
refractive index of the dielectric near the metal layer, leading to alterations in the
propagation constant of the SPs. Consequently, the coupling condition between the
light wave and SPs gets altered, which affects the characteristic properties of the
light wave after interacting with the SPs. Notably, at SPR, both amplitude and phase
of the p-polarized light change significantly due to the momentum transfer between
light and SPs, while those of the s-polarized light are changed slightly [62]. Based on
these changes and depending on the intended characteristics of the light wave to be
measured, SPR sensors can be classified into angular, wavelength, intensity, phase,
and/or polarization modulation sensors [14, 43, 63, 64], as shown in Fig. 4.
Fig. 4 SPR measurement methodologies: (a) angular, wavelength, intensity modulation, and (b)
phase modulation method for SPR measurements. (The figure is reproduced from Prabowo et al.
[43], Copyright © 2018 by the authors, Creative Commons Attribution (CC BY) license). (c) The
phase difference Δφ between the p- and s-polarization components produce a shift α0 in the
orientation angle of the light ellipse, (d) Schematic representation of the SPR experimental setup
used for polarization modulation SPR measurement method. (The figure is reproduced with
permission from Wong et al. [65], Copyright © 2013 Elsevier B.V.)
In angular modulation, a monochromatic light source is used and the intensity of

the reflected light is found by scanning throughout the angular range. Likewise, a
broadband light source is used in wavelength modulation and the reflected light
intensity is measured by varying the wavelength at a fixed incident angle. Thus, if the
output signal in the form of normalized reflected intensity (R) is measured as a
function of incident angle (θ) or wavelength (λ), by keeping other parameters and
components (e.g., the thickness of the metal and dielectric layers) unaffected, then a
sharp dip is observed at resonance angle θsp of wavelength λsp due to an efficient
transfer of incident photon energy to SPs. On the other hand, intensity modulation is
primarily used for SPR imaging and is based on the detection of reflectance intensity
variation at a fixed incident angle or wavelength [64, 66, 67]. As the name suggests,
the phase interrogation method involves the detection of the phase shift in the
reflected optical beam with respect to the incident beam [68, 69] and the polarization
modulated SPR sensors exploit the polarization ellipse orientation caused by the
phase difference between the p-polarization and s-polarization components [63, 70].
3.4 Performance Parameters
The performance of any SPR sensor can be defined by various parameters, e.g.,
sensitivity, resolution, detection limit, linearity, dynamic range. Although these
parameters have been covered by several excellent publications [39, 45, 50, 71–
75], the major performance parameters (viz., sensitivity, resolution, and limit of
detection) in case of a Kretschmann configuration-based (prism-coupled) SPR
sensor operated in angular and wavelength modulation modes are briefly described
here, in this section.
Sensitivity of a SPR sensor signifies the detectable fluctuations in the magnitudes
of the SPR parameters of interest (e.g., resonant angle, wavelength, intensity) with a
change in refractive index of the sensing layer. The larger the shift, the higher is the
sensitivity. For a Kretschmann configuration-based SPR sensor, the sensitivities for
angular modulation and wavelength modulation can be derived from Eq. (6) and are
given by [31, 42, 72, 76],
qffiffiffiffiffiffiffiffiffi
= =
dθ Em
Em
Sp,θ ¼ ¼ r ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ffi ð8Þ
dnd =
=

E m þ nd
2 E m nd np nd np
2 2 2 2
2
=
dλ Em
Sp,λ ¼ ¼ ð9Þ
dnd n2d dE=m þ E= þ n2 E= dnp nd
2 dλ m d m dλ np
Resolution is the minimum change in the SPR parameter (e.g., refractive index)
that can be resolved by the sensor. It depends on the standard deviation of the output
noise (σ so) and bulk refractive index sensitivity (SRI) of the sensor, and is expressed
as [72, 73, 77],
σ so
σ RI ¼ ð10Þ
SRI
where,

δθr δneff
SRI ¼ ðfor angular modulationÞ
δneff δn
δλr δneff
¼ ðfor wavelength modulationÞ
δneff δn
λr ¼ coupling wavelength
k
neff ¼ kspp
32
0
=
δneff Em
δn ¼ =
Em þnd 2
¼ sensitivity of the effective index of SP to a bulk refractive change.
Finally, the limit of detection (LOD) or detection limit, is defined as the minimum
concentration of the analyte that produces the smallest resolvable change in the
measured SPR parameter with reasonable certainty and reproducibility [78–80].
4 Applications of Kretschmann Configuration-Based SPR

Biosensors
SPR sensors have proven to be a highly efficient tool for label-free, noninvasive,
real-time monitoring of biomolecular interactions [81]. Recent years have witnessed
tremendous advancements in SPR biosensors [82–85] that have already found
widespread applications in diverse fields including detection and characterizations
of bacteria and viruses [86–88], analysis of biomolecules [33, 89] (e.g., protein-
nucleic acid [90, 91], nuclear receptor-DNA [92], DNA–DNA interactions [93]),
immune recognition [94], drug screening [44], etc. In this section, although a
comprehensive review of the applications of SPR biosensors based on Kretschmann
configuration will not be presented, as they have been covered by many other works
[44, 95, 96], a brief review of the most recent applications of Kretschmann
configuration-based SPR biosensors on the following important domains will be
discussed. In addition, a representative list of different applications of Kretschmann
configuration-based SPR biosensors using different modulation techniques are
presented in Table 2.
Table 2 Representative list of the biosensing applications of Kretschmann configuration-based SPR sensors using different measurement methodologies
202
Measurement
methodology Subject of study Sensor chip used Performance parameter(s) References
Angular Serum YKL-40 estimation CM5 sensor chip LOD: 0.33 ng/mL [97]
modulation Acetylcholine binding protein (AChBP) CM5 and NTA sensor chips S/N: 36 [98]
screening
Detection of apple stem pitting virus (ASPV) Aptamer-modified sensor chips LOD: 250 nm [99]
coat protein (PSA-H, MT32)
Detection of 2,4-dichlorophenol, a type of Anti-(2,4-dichlorophenol) antibody- LOD: 20 ppb [100]
dioxin precursor modified sensor chip
Detection of cytokeratin 19 fragment Carboxyl-MoS2-based chip LOD: 0.05 pg/mL [101]
(CYFRA21-1), a biomarker related to lung
cancer
Detection of breast cancer cell line MCF-7 Aptamer-modified gold chip LOD: 136 cell/mL [102]
Wavelength Detection of soluble vascular endothelial Vascular endothelial growth factor (VEGF- LOD: 25 ng/mL [103]
modulation growth factor receptor (sVEGFR-1), a plas- A) immobilized gold-coated replaceable
matic protein marker of myelodysplastic sensor chip
syndromes (MDS)
Detection of tau-Aβ biomarker of Mixed self-assembled monolayer (SAM) LOD: 1 pM [104]
Alzheimer’s disease modified chip
Measurement of specific antigen-antibody Mouse IgG and goat IgG integrated gold Dynamic range: 7.67 103 [105]
binding chip RIU
Resolution: 1.89 106 RIU
IgG antigen–antibody interaction Rabbit IgG immobilized chip RI resolution: 1.27 106 RIU [106]
Dynamic range: 4.63 102
RIU
Intensity Avian influenza A H7N9 virus H7-mAb immobilized Ag/Au (35/10 nm) LOD: 144 copies/mL [107]
modulation chip
Nine common respiratory viruses—influenza Virus-specific oligonucleotide immobilized LOD: [108]
A and influenza B, H1N1, respiratory gold chip Influ A—5 nM
N. Shukla et al.
syncytial virus (RSV), parainfluenza virus 1– Influ B—1 nM
3 (PIV1, 2, 3), adenovirus, and severe acute PIV1—1 nM
respiratory syndrome coronavirus (SARS) PIV2—2.5 nM
PIV3—3.5 nM
RSV—3 nM
ADV—0.5 nM
SARS—2 nM
H1N1—3 nM
Detection of lung cancer biomarkers EGFR Antibody attached gold biochip Sensitivity: 9.258 103%/RIU [109]
(epidermal growth factor receptor) and Resolution: 8.311 106 RIU
PD-L1 (programmed death-ligand 1)
Phase Bovine serum albumin (BSA) antibody– BSA immobilized gold chip LOD: 0.5 ng/mL [110]
modulation antigen interaction
BSA/anti-BSA binding interaction Protein immobilized gold sensor surface Resolution: 8.8 10–7 RIU [111]
LOD: 7.7 104 mg/mL
Interaction of streptavidin–BSA complex Biotin–protein immobilized gold chip Sensitivity: 1.3 nM [112]
Rabbit IgG–goat–anti-rabbit IgG interaction Rabbit IgG spotted microarray sensing chip Phase resolution: 0.2 [113]
RI resolution: 3 105 RIU
Polarization Detection of single-stranded DNA (ssDNA) Graphene/gold nanoparticle-based sensor Dynamic range: 1015–107 M [114]
modulation hybridization chip LOD: 500 aM
Detection of lysozyme/antibody interaction Lysozyme immobilized CM5 chip LOD: 106 RIU [115]
Detection of influenza (H3N2) virus protein– H3N2 virus protein/DNA immobilized gold Sensor resolution: 4.36 107 [116]
antibody and DNA–DNA interaction surface RIU
Detection limit: 8.6 nM
(320 ng/mL), in the case of
Surface Plasmon Resonance Biosensors Based on Kretschmann Configuration. . .
virus antibodies
LOD limit of detection or detection limit, S/N signal to noise ratio, RI refractive index, RIU refractive index unit
203
4.1 Analysis of Lipid/Protein Molecules
Lipids and proteins are the key building blocks of life. In addition to forming cell
membranes, storing up energy, acting as chemical messengers, maintaining temper-
ature, etc., these molecules play vital roles in the structure and function of living
cells. For instance, whereas the structure of cellular membranes is composed of
lipids, their specific functions are mainly controlled by proteins. Apart from partic-
ipating in the distribution and localization of membrane proteins and thereby
regulating the cellular signaling and trafficking processes, many membrane lipids
act as ligands for different signaling proteins and enzymes [117]. On the other hand,
membrane proteins account for approximately 30% of the human genome and
constitute more than half of the current drug targets. They also take part in many
physiological functions, e.g., molecular recognition, cell adhesion, etc. [118–
122]. Therefore, protein–protein, protein–lipid and lipid–lipid interactions are
important not only to understand the science behind the physiology of cells but
also for the validation and discovery of newer drugs.
Notably, most of the traditional methods used to study the kinetics of biomolec-
ular interactions, e.g., ELISA (Enzyme-Linked Immunosorbent Assay), MicroScale
Thermophoresis (MST), Equilibrium Dialysis, and Affinity Chromatography,
require labeling and are therefore complicated and time-consuming [123, 124]. In
this context, SPR-based biosensing has found widespread application in the study of
real-time binding kinetics, affinity, concentration, etc., without labeling the ligand or
the analyte thereby keeping the molecular properties unchanged. Through its tech-
nique of immobilizing a ligand on a surface with monitored interaction of analytes,
SPR is successfully used for the study of various protein/lipid mechanisms with high
sensitivity and high throughput of samples [96, 125–130].
Kretschmann configuration-based SPR biosensors have been used extensively for
the study of the interaction of proteins and/or lipids with each other and with other
biological macromolecules [131–135]. Many of these works used BIAcore™ tech-
nology which is one of the pioneering commercial instruments for SPR biosensing
[44, 95, 133, 136, 137]. The standard BIAcore™ setup for SPR experiments is based
on prism-coupled Kretschmann configuration and is shown in Fig. 2a. Besides, these
biomolecular interactions are typically studied at specially prepared surfaces known
as “sensor chips” that enable the attachment of analytes on the surface-bound ligands
[138–142]. A large number of commercial sensor chips have been developed till date
[96, 128, 143, 144]. Notably, the sensor chips HPA (hydrophobic association
analysis) and L1 are the most widely used chips developed by BIAcore™ to study
protein–membrane interactions [95, 127]. Similarly, CM5 is another all-purpose
sensor chip from BIAcore™ where different types of ligands including proteins,
nucleic acids, carbohydrates, etc., can be attached by using covalent coupling
technique [145, 146]. In one such work, Currie et al. [140] created a lipid monolayer
on a chip by injecting extruded lipid vesicles to measure the binding kinetics of
100 nM PDK1 (3-Phosphoinositide-dependent protein kinase-1) and PKB (Protein
kinase B). The kinetics then help in the identification of various PtdIns whose
presence make the protein kinase phosphorylate. Notably, phosphoinositides are

acidic phospholipids in cell membranes with their principal role in the activation,
suppression, regulation of the integral protein activities. Similarly, Bahloul et al.
[147] used CM5 sensor chips to immobilize harmonin-a and CDH23 (cadherin-23)
to study harmonin-a/myosin VIIa and cadherin-23/myosin VIIa interactions by
allowing myosin VIIa tail to flow over the chip at a rate of 30 μL/min for 120 s. In
the same work, the group used a lipophilic L1 chip to capture large unilamellar
vesicles (LUVs) and monitor protein–lipid interactions by allowing proteins to flow
over the LUVs at a rate of 10 μL/min for 300 s.
In addition to the commercially available chips, development of other sensor
chips has also been reported [39, 43, 148]. Recently, Vala et al. [149] used a novel
plasmonic chip prepared by depositing 1.5 nm Ti adhesion layer and 50 nm gold
layer on a glass (BK7) substrate. On the top layer, another SiO2 layer was grown by
using atomic layer deposition to facilitate the efficient binding of the myelin
particles. In this work, a Kretschmann configuration-based SPR sensor was used
in wavelength modulation mode to study the binding kinetics of human IgM
antibodies to central nervous system (CNS) myelin particles. Notably, myelin is
mainly composed of lipid (70–85% of dry mass), protein (15–30% of dry mass), and
has water content of about 40% [150]. Ryu et al. [151] reported the development of a
novel and versatile membrane platform, which is continuous but spatially heteroge-
neous, to monitor the time-lapse dynamics of lipid–lipid interactions during the
transient raft functional domain formation and sequential raft-associated receptor–
ligand interactions. Regarding protein–protein interaction studies, a detailed proto-
col for the protein immobilization on the sensor surface, analyte-binding analysis,
affinity/kinetic measurements, as well as data analysis by using a BIAcore T200
system is described by Douzi [152]. Furthermore, Kim et al. [153] used
Kretschmann configuration-based SPR spectroscopy to demonstrate the binding of
poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) or PEO–
PPO–PEO triblock copolymer to the model cell plasma membrane composed of
supported lipid bilayer (SLB). Such studies are particularly important for the proper
understanding of the cell membrane protective mechanism of poloxamer 188 (P188)
triblock copolymer that involves polymer-membrane interaction kinetics. Most
recently, Belkilani et al. [154] demonstrated multiparametric surface plasmon reso-
nance (MP-SPR) technique to investigate the interactions of mono-rhamnolipids
(mono-RLs) with biomimetic membranes. Using this technique, the group success-
fully characterized the evolution of liposome architecture from monolayer to phos-
pholipid bilayer induced by mono-RL interactions with a detection limit of 2 μg/mL.
Figure 5 shows the sensorgram measured during mono-RLs–liposome interaction, at
670 nm wavelength. Notably, several other reviews on the use of SPR as a method
for the study of interactions involving proteins and lipids can be found in the
literature [96, 155, 156].
Fig. 5 SPR angle versus time sensorgram, measured at 670 nm wavelength, during the interaction
of mono-RLs with liposomes. (The figure is reproduced with permission from Belkilani et al. [154],
Copyright © 2021 American Chemical Society)
4.2 Detection of Biomarkers
Biomarkers give vital information about the progression or regression of a disease

and therefore have high clinical significance. Proper screening of different bio-
markers, e.g., nucleic acids, hormones, proteins, and other biomolecules, is essential
for the detection, diagnosis, and treatment of a disease to prevent its further spread
thereby significantly reducing the death rate. A number of strategies, including
enzyme-linked immunosorbent assay (ELISA), polymerase chain reaction (PCR),
immunofluorescence, western blotting, etc., have been already developed for the
detection of disease biomarkers. Although efficient, these techniques are mainly
limited by their operational complexity, the requirement of large sample volume, and
longer processing time [157–159]. Recently, SPR-based sensors have attracted much
attention due to their simplicity, cost-effectiveness, and capability to offer highly
sensitive, and biomarker-specific real-time measurement even with low sample
concentration. This section intends to cover some of the recent applications of
Kretschmann configuration-based SPR sensors for biomarker detection.
While the standard clinical protocols for evaluating cancer typically rely on tissue
biopsy, which involves painful strategies using special needles and surgeries, SPR
biosensors are emerging as a promising alternative capable of offering noninvasive
liquid biopsy [160]. SPR sensors based on Kretschmann configurations have been
exploited by many researchers for the analysis of cancer-related biomolecules
[161]. With its robustness and versatility, SPR sensors perform analysis in a broad
range including plasma, serum, and saliva [162]. Detection of baculoviral inhibitor
of apoptosis containing protein biomarker BIRC4 in dog-serum has also been
reported [94]. Moreover, SPR assays are used for the detection of protein biomarkers
in human sera in cases of pancreatic cancer [163, 164], ovarian cancer [165], and
coronary artery disease [166–168]. For early detection of cancer, SPR is used to
detect cancer biomarkers through the development of point-of-care immunosensors.
In one such work, Uludag et al. [169] successfully detected prostate cancer total
prostate-specific antigen (tPSA) with a detection limit of 0.29 ng/mL (8.5 pM) by
using PSA antibody-modified Au nanoparticles of size 40 nm. Recently, a high
precision SPR (HP-SPR-3D) system is reported for the phenotypic screening of anti-
cancer drugs using cancer cell lines [170].
The kidney is one of the most vital organs of the human body that removes waste
products from our body and maintains the balance of fluids and other chemicals.
Alarmingly, kidney failure, which affects 10% of the worldwide population, is one
of the leading causes of millions of deaths every year. Notably, the functioning of the
kidney is generally monitored by observing the levels of urea and creatinine bio-
markers [171, 172]. In this context, SPR biosensors have shown enormous potential
for application in such biomarker detections. Recently, a nano-laminated gold film-
based SPR sensor (50-nm thick) in Kretschmann configuration was used to detect
urea and creatinine at various concentrations [171]. The group employed finite
difference time domain (FDTD) simulation to determine the thickness of the nano-
laminated gold film (that gives the best reflectivity), incident wavelength, and source
angle for obtaining optimum SPR coupling and reflectivity. As shown in Fig. 6,
enhanced sensitivities were obtained for both enzymatic urea-urease sample (16.2 /
M at 670 nm and 10.4 /M at 785 nm) and creatinine-creatininase sample (10 /M at
670 nm compared to 6 /M at 785 nm). In another work, Said et al. [173] used
graphene-coated copper-based SPR sensor in Kretschmann configuration for urea-
detection. Notably, the primary role of graphene in this work was to act as the
Fig. 6 Sensitivity of 50 nm-thick nano-laminated gold film vs concentrations of (a) urea-urease

and (b) creatinine-creatininase samples at 670 and 785 nm optical wavelengths. (The figure is
reproduced from Menon et al. [171], Copyright © 2018 Menon et al. Creative Commons Attribu-
tion License)
preventive layer for Cu oxidation and enhance SPR reflectance intensity. Due to the
high adsorption efficiency of graphene and the cost-effectiveness of copper over
gold and silver, such a bio-recognized engineered device promises itself as an
efficient SPR sensor, especially for biomolecules with carbon-based ring structure.
Moreover, biosensors utilizing graphene-MoS2 under Kretschmann-based SPR con-
figuration have also shown promising results for urea-detection in gas chromatog-
raphy and calorimetric, fluorimetric, and their respective analysis [174, 175]. In the
case of creatinine detection, Pothipor et al. [172] demonstrated an electrochemical
(EC)-SPR instrumentation, with a detection limit of 0.19 μM, that used conducting-
polymer-based SPR sensor chip made of polypyrrole (PPy). The work involved the
electropolymerization of a PPy film on the gold-coated SPR chip and subsequently
monitoring the aggregation of starch-stabilized AgNPs induced by creatinine. The
selectivity and specificity of the technique were ensured by investigating the effect of
other substances, e.g., uric acid, albumin, etc., with Ag nanoparticles.
On the other hand, the excess of glucose in the blood causes diabetes. With a large
population suffering from insulin resistance or insufficient insulin production by the
body, the need for blood glucose levels monitoring has become necessary. The most
conventional technique is the fringe prick blood test method which involves sam-
pling blood through test strips and glucometer. Although effective, this method
proves to be inconvenient for patients with self-monitoring glucose management.
Propositions of Kretschmann configuration-based SPR sensors for such analysis
have already been done as an alternative. Recently, glucose detection by using
Kretschmann configuration-based SPR approach in angular modulation mode was
demonstrated by Menon et al. [176]. The group utilized a nano-laminated (thickness:
50 nm) Au-Cr SPR sensor to evaluate the refractive indices of glucose levels at
various concentrations. Another bimetallic Ag (30 nm)/Au (17.5 nm) thin film-based
SPR glucose sensor was reported by Mulyanti et al. [177] that showed sensitivity
and figure of merit values of 4.7993 /RIU and 0.5173 at 633 nm incident wavelength
for a glucose concentration of 0.08 g/dL. Most recently, other multilayer, e.g.,
chromium/gold [178], Ag/Si3N4/Au [179], and SiO2/gold/silver [180] thin film-
based SPR biosensors have shown excellent performances in the detection of
glucose in blood or glucose/water solutions. Notably, different methods, including
Taguchi method, FDTD simulation, COMSOL simulation, were used in such works
to optimize the sensor design considerations.
The next major concerning malady is stroke. It mainly occurs when a blood vessel
that carries oxygen and nutrients to the brain bursts or gets blocked by a clot
[181]. Early diagnosis and appropriate treatment are of paramount importance for
the prevention of strokes [182]. Several researchers have reported the reliability of
SPR biosensors for the recognition of biomarkers related to stroke and their under-
lying mechanism [183–187]. Recent work by Harpaz et al. [188] on SPR biosensors
for detecting stroke biomarkers is one such notable example. The group used a novel
antibody functionalized SiO2 plasmonic chip to detect stroke biomarkers n-terminal
pro brain natriuretic peptide (NT-proBNP) and S100β. With a limit of detection less
than 1 ng/mL, the reported sensor was found to be highly efficient for diagnosing
strokes.
Impressively, SPR-based biosensors are also used for the diagnosis of neurode-
generative diseases such as Alzheimer’s disease (AD). Amyloid-beta are peptides
that form polymorphic fibrils and are active participants of diseases like AD and thus
prove to be a very important biomarker for AD. For instance, Ryu et al. [189]
demonstrated the capability of SPR biosensor in the label-free monitoring of
Alzheimer’s β-amyloid (1–42) fibrillation from the initial monomeric conditions
on a solid surface. Recently a review article concerned with the applications of
SPR-based biosensors has highlighted the detection of different biomarkers, e.g.,
aggregated β-amyloid and tau proteins, related to AD [190].
4.3 Viral Diagnostics
With the first discovery of the yellow fever virus in 1901, at present, approximately
219 virus species are known to infect humans. There have been a complicated range
of highly infectious viruses, e.g., influenza, dengue, human immunodeficiency,
swine flu, Ebola, severe acute respiratory syndrome coronavirus (SARS-COV),
SARS-COV-2 (COVID 19), etc., that are capable of producing severe health issues.
They have special binding enzymes that bind to the host cells through a pathogenic
process, weakening the immune system. With unprecedented challenges emerging
from such new viruses, effective global surveillance mechanisms need a boost in the
subject [191].
Remarkably, among many other optical and/or nonoptical techniques, SPR has become
one of the most widely used optical techniques for viral diagnostics [192–204]. In a
comparative study among SPR, resonant waveguide grating biosensing, and ELISA in the
immunoassay evaluation of dengue virus, Hu et al. [197] found that Kretschmann
configuration-based SPR sensor is capable of providing accurate association (kass) and
dissociation (kdiss) rates for the interaction between dengue virus (DENV) nonstructural
1 (NS1) monoclonal antibodies (mAbs) with immobilized DENV NS1 proteins
(a serological marker used for the early detection of the disease). The group further studied
the affinity of antigen–antibody interactions. Interestingly, in a recent work, highly sensitive
detection of DENV-2 E-proteins was demonstrated by performing SPR measurements at
concentrations as low as 0.08 pM of the proteins (Fig. 7) [196]. For this work, an SPR sensor
thin film of Au/dithiobis succinimidyl undecanoate/reduced grapheneoxide-
polyamidoamine dendrimer/monoclonal antibody IgM (Au/DSU/NH2rGO-PAMAM/
IgM) was fabricated that offered excellent selectivity and enhanced penetration depth of
evanescent waves for efficient SPR coupling. Moreover, Palau et al. [201] demonstrated the
capability of SPR sensors in the real-time monitoring of interaction of RNAs of Hepatitis C
virus (HCV) genome by immobilizing 5BSL3.2 on a sensor chip. In contrast to previously
reported results, the group successfully demonstrated the complex formation of 5BSL3.2
with stem-loop SL2.
Fig. 7 (a) Sensorgram obtained during the real-time detection of DENV-2 E-proteins in contact
with Au/DSU/NH2rGO-PAMAM/IgM sensor film at different concentrations; (b) Selectivity of
Au/DSU/NH2rGO-PAMAM/IgM sensor for different target antigens. (The figure is reproduced
from Omar et al. [196], Copyright © The Author(s) 2020, Creative Commons Attribution 4.0
International License)
Regarding coronavirus infections, although the reverse transcriptase quantitative

polymerase chain reaction (RT-qPCR) is considered the gold standard for detecting
coronaviruses, it is time-consuming, requires a sophisticated testing facility, and
sometimes give false results. In addition, while other sensing mechanisms, e.g.,
computed tomography (CT) scan and FET-based sensor topology using nasopha-
ryngeal swabs, are still being explored [205, 206], the need for real-time, ultra-
sensitive technique could be fulfilled by SPR-based sensors. In this context, in a
pioneering work published in 2005, Chen et al. [202] used Biacore 3000 instrument
to study the interaction of nonphosphorylated/phosphorylated nucleoprotein
(N protein) of avian infectious bronchitis virus (IBV), which is a type of coronavirus,
with a variety of target RNAs. Recently, Kretschmann configuration-based SPR
sensors were studied for real-time detection of severe acute respiratory syndrome
coronavirus 2 (SARS-COV-2) [195]. Integrated layers of Si and BaTiO3 on
Ag-metal layer with thiol tethered DNA as receptor has been proposed for sensing.
The work was based on the numerical analysis performed by using transfer matrix
theory FDTD technique to characterize the performance parameters of the proposed
sensor architecture. Moreover, another study, based on simulation, showed that a
Kretschmann configuration-based SPR sensor can detect 3.615 nm of virus concen-
tration [207]. Furthermore, significant advances have also taken place for tackling
pandemic by studying receptor recognition mechanisms of the coronavirus and
angiotensin-converting enzyme 2 (ACE2). Through the SPR technique (Biacore
2000 instrument), bindings kinetics of the receptor binding domains (RBDs) of
SARS-CoV, SARS-CoV-2, and chimeric SARS-CoV-2 with ACE-2 receptors
were analyzed [203]. By understanding the receptor recognition mechanisms of
the viruses, one can regulate their host range and infectivity. Importantly, it has
been reported that ACE-2 is the receptor in humans that is recognized by both
SARS-COV and SARS-COV-2 [208, 209]. In a recent work by Das et al. [210], a
sandwich-type SPR immunoassay model based on Au nanorods has been proposed

in order to amplify the output signal. The group showed that evanescent field
enhancement of 376.33% can be achieved for a 10 nm diameter Au nanorod coupled
SPR sensor compared to the traditional Au nanosheet-based sensors.
5 Conclusion
The last few years have witnessed spectacular advances and facilitation in molecular
biochemistry, materials science, and optoelectronics leading to the invention of
several efficient laboratory-based and commercial SPR instruments [211]. Many
commercially available SPR instruments, including SPRAutolab ESPRIT, Biocore
series, Multiskop, and NanoSPR, have their principal based on prism coupling
design. Notably, prism-coupled Kretschmann configuration is the most widely
used configuration among different coupling schemes used in such SPR instrumen-
tations. This chapter reviews the basic principles, instrumentation, and the most
recent applications of Kretschmann configuration-based SPR biosensors.
SPR biosensors have now gained a promising and accomplished stature. Apart
from their advanced analyzing capability, their continuous progress and evolution
towards the development of a highly accurate, sensitive, and user-friendly biosensor,
they have been manifested as one of the most multifaceted devices for applications in
diverse fields of molecular biology and biotechnology, particularly for the monitor-
ing of dynamics and affinity of biomolecular interaction. The future of this technique
lies entirely in the research and development of strategies related to antifouling,
miniaturization, and initiations regarding the designing of innovative chemical
chips. The real challenge which the field faces is its high-cost platforms and
components. Once scientists and engineers develop a low-cost, high-performance
SPR sensor platform, SPR will be an irreplaceable tool for biological analysis and
diagnosis.
Acknowledgments AG acknowledges the University Grants Commission (UGC), India (Grant

No. F.5-376/2014-15/MRP/NERO/2181), and Assam Science Technology and Environment Coun-
cil, India (Grant No.: ASTEC/S&T/1614/8/2018-19/1159), for their support to the biophotonics
research projects at JBC.
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Plasmonic Nanoprobes for SERS-Based
Theranostics Applications
Anindita Das and Rakesh S. Moirangthem
Abstract Over the last decade, considerable interest has been made in plasmonics
for nanotheranostics which can provide optical multiplexed disease detection and
therapy in a single modality. The concept of light confinement in sub-wavelength
volumes makes plasmonic nanoprobes a noninvasive alternative for oncological
studies, including drug designing, imaging, tumor targeting with localized therapeu-
tic effects, etc. Here in this chapter, with an overview of basic plasmonic phenom-
ena, we concisely described various types of plasmonic nanoprobes that have been
exploited for the applications mentioned above and discussed their optical response
upon interacting with the electromagnetic wave. Later, this chapter will focus on
surface engineered nanoscale materials fabrication and their applications specific to
Surface-Enhanced Raman Spectroscopy (SERS)-based diagnostics, imaging, and
plasmonic photothermal therapies (PTT). This chapter also is concluded by summa-
rizing the collective use of SERS imaging and PTT using plasmonic probes to meets
the challenges and clinical needs.
Key words Plasmonics · Nanoprobes · Noninvasive · Localized · Nanoscale ·

SERS · PTT
1 General Considerations
1.1 Fundamental Optical Properties of Metals
The electromagnetic response of metals can be firmly understood in the classical

regime. The most fundamental model to explain the optical properties of metal is the
Drude model, which is based on the two core assumptions that free electrons in
metals experience viscous damping due to electron lattice collision, and the only
A. Das · R. S. Moirangthem (*)

Nanophotonics Lab, Department of Physics, Indian Institute of Technology (Indian School of
Mines), Dhanbad, Jharkhand, India
e-mail: rakeshap@iitism.ac.in
https://doi.org/10.1007/978-3-030-99491-4_7
224 A. Das and R. S. Moirangthem
active force is the applied electric field [1]. These free electrons in metals which are
considered as free electron gas response to the optical excitations as longitudinal
electromagnetic charge density waves and their quanta are known as plasmons or
plasmon polaritons.
Plasmons can be existed in two forms, i.e., bulk plasmons and surface plasmons
and can be distinguished by the system geometry [2]. In case of bulk metals, the most
fundamental plasmon excitation that exist is known as bulk plasmons, whereas the
plasmon excitation on metal surface interfaced with dielectric medium, which can
propagate as an electromagnetic wave across the metal-dielectric interface is known
as surface plasmon polaritons (SPP). But in the case of nanoscale metallic geometry,
the plasmon excitations result from electric dipole oscillation in response to the
incident electromagnetic wave and such plasmon excitation are localized in nature,
which is known as localized surface plasmons (LSPs) [3]. We first analyze the
physical phenomena of LSPs in a classical framework without accounting quantum
mechanics due to the high density of free electrons results in small spacing of
electronic energy levels. However, to describe the damping mechanism, the quantum
mechanical treatment is necessary as metal nanoparticles have multiple oscillation
modes; each differs in its charge and electric field distribution.
1.2 Qualitative Description of Theory of Localized Surface

Plasmons
In metal nanostructure that is much smaller than the wavelength of the incident light,
the electromagnetic field can penetrate throughout the volume of the metal. This
resulted the free conduction electrons to experience a local restoring force exerted by
positive ion core inside the volume. The coherently shifting of free electrons in
response to the external electric field and subsequently acting restoring force con-
stitute a dipole oscillation having a resonance frequency with that of the incident
light. Such coherently oscillating free conduction electrons in metal nanostructures
are called as localized surface plasmon resonance (LSPR). The induced surface
plasmon oscillation generally decays within a few femtoseconds and can be
maintained by introducing an alternating electric field. The simple free electron
oscillation model can explain most of the phenomena associated with surface
plasmons in metallic nanoparticles [3, 4].
The interaction of an isolated spherical metal nanoparticle with an electromag-
netic radiation can be explained using quasi-static approximation, providing that the
particle size (a) is much smaller than the wavelength of the incident light (λ), i.e.,
a λ. In this regime, the external electromagnetic radiation fully penetrates the
volume of the nanostructure, and the phase of the harmonically oscillating electric
field is constant over the nanoparticle volume. This uniform electric field induces
dipole moment inside the sphere. Under electrostatic approximation, the polarizabil-
ity (α) of the sub-wavelength sized nanosphere is
Plasmonic Nanoprobes for SERS-Based Theranostics Applications 225
εðλÞ εm ðλÞ
αðλÞ ¼ 4πa3 ð1Þ
εðλÞ þ 2εm ðλÞ
where ɛ and εm are the frequency-dependent dielectric functions of metal and the
surrounding medium, respectively. Maximum polarizability occurs when ε-
(λ) 2εm(λ). This condition is known as the Fröhlich condition. The real part
of the dielectric function of metal poses a negative value with a negligible imaginary
part variation that can be ignored. Under this condition, nanoparticle attains maxi-
mum extinction value and plasmon resonance occurs [5].
This simple quasi-static approximation approach also reveals the influential factors
associated with surface plasmon resonance on metal nanoparticles such as particle shape
and dielectric functions of both metal and its surrounding medium. However, for large
particle size the phase of electromagnetic field is not constant throughout the volume and
varies significantly. In that case, Mie theory provides a correct theoretical description of
the scattering and absorption of electromagnetic radiation by a sphere of any arbitrary
size. Mie theory is an analytical solution to Maxwell’s equations for sphere, and the
scattered fields are expressed as an infinite series of vector spherical harmonics [6]. Fur-
ther, Gans theory provides an analytic expression for rod-shaped nanoparticles with
dual LSPR modes, one longitudinal resonance mode along the major axis and another
transverse resonance mode across the rod [7]. For metal nanostructures with anisotropic
shapes and sizes, the commonly adopted numerical methods for investigating surface
plasmon properties includes discrete dipole approximation (DDA) [8] and finite element
method (FEM) [9]. Since the aforementioned theoretical models for surface plasmons
on metallic nanostructures are treated quantitatively in various books, a much more
detail description of the models is not required here [10].
1.3 Probing Basic Plasmonic Effects
By investigating the optical characteristics associated with metal nanoparticles, the

quantification of the surface plasmon phenomena in far field and near field is possible
[2]. If the optical responses are recorded from a distance much larger than the nanopar-
ticle itself or the wavelength of the incident electromagnetic radiation, then it is known
as far field spectra. Most of the general optical experiments rely on far field measure-
ments that include reflection, transmission, absorption, scattering, extinction, etc. [11]
Although significant information can be obtained from far field study, they do not reveal
optical phenomena associated with the nanoparticles. Whereas, near field measurement
deal with the electromagnetic fields within a sub-wavelength spatial domain from the
nanoparticle surface. Near field study reveals optical quantities related to the local
electromagnetic field pattern at the nanoparticles vicinity. Some of the common exper-
imental techniques such as surface-enhanced Raman spectroscopy (SERS), fluores-
cence microscopy, and scanning nearfield optical microscopy (SNOM) efficiently
exploit the near field optical properties of metal nanoparticles and utilize the benefit of
plasmonic effects, particularly in spectroscopic problems [12, 13].
1.3.1 Enhanced Local Electric Field Effects
The incident electromagnetic radiation interacts with a sea of free electrons and
causes momentary displacement with respect to static positive charges by creating a
dipole. The oscillating dipole generates an electric field which is a function of
distance from the nanoparticle surface. In this, the microscopic local electric field
(ELoc) is a function of incident wavelength. It induces the microscopic local electric
field (ELoc) due to the interaction between the incident field (EInc) with free electrons
in nanoparticles (see Fig. 1). The incident field can be enhanced into several orders
of magnitude due to the surface plasmons of metallic nanoparticles, and hence the
resultant field experienced by absorbed molecule at the surface is significantly
enhanced. Such effect encourages the surface-enhanced Raman scattering of analyte
molecules upon interacting with enhanced local field and strongly enhanced the
Raman signals. Subsequently, reradiation occurs due to the interaction between the
Fig. 1 Schematic of photoexcitation of nanoparticle and associated plasmonic effects.

(i) Electromagnetic enhancement contributing towards SERS enhancement through (1) A metallic
nanoparticle is kept in a dielectric medium. The metal permittivity is ɛmetal and the dielectric
permittivity is ɛdielectric. (2) A local field Eloc induced due to incident field E0 at a wavelength
λ0 and directly proportional to E0 and to the local enhancement factor Mloc(λ0). (3) Analyte molecule
at the locality of the nanoparticle. (4) A scattered field Escat is produced due to molecule and local
field interaction at the Raman wavelength λR and Escat is proportional to the molecule polarizability
α. (5) A reradiated field Erad is created due to interaction between Escat and Eloc and proportional to
enhancement factor Mrad(λR). (Reproduced with permission from the Elsevier article [14]).
(ii) Radiative decay via reemission of photons. (iii) Nonradiative decay of plasmons through
(1) transition of electrons from filled to unfilled states creates nonequilibrium heating. Generated hot
carriers then redistributed energy via electron-electron scattering process. (2) Energetic charge
carriers cool down over time by transferring energy to particle’s phonon modes causes a rapid
increase in nanoparticle temperature. (3) Finally, heat is dissipated to the surrounding over a longer
timescale
scattered field (Escat) with the local electric field of the nanoparticle. Thus, the
radiated field enhancement factor (Mrad) nearly goes up to the fourth power of the
enhanced local electric field of the nanoparticle. Apart from dipolar excitation, the
enhancement of local field can be affected by particles’ sharp edges and corners due
to the lightning rad effect, which creates hot spots by concentrating dipolar fields at
tip regions [15].
1.3.2 Plasmon Damping Effects
The LSPR spectral line width, which can be obtained by measuring optical cross-
sections as a function of photon energy, the plasmon resonance amplitude, and their
decay, is greatly influenced by the SPR damping process. The plasmon relaxation
happens at tens of femtosecond by radiative or nonradiative damping effects, which
depend on the particle shape and material nature. For a large, isolated nanoparticle
located in an unreactive surrounding, the plasmonic decay is mainly due to the
radiative damping process by photon reemission through scattering. However, for a
small isolated nanoparticle (size <20–30 nm) the decay is dominated by
non-radiative Landau damping [16]. The LSPR line width is also negligibly affected
by the pure dephasing process where phase matching condition breaks between
collective plasmon oscillation and incident electromagnetic radiation due to the
elastic scattering of plasmons from electrons and phonons [17].
Radiative Damping: Scattering
The resonant scattering involves energy loss due to radiative photons (re)emission.
The radiative damping of plasmon modes is a function of particle size and surround-
ing dielectric media. The reemitted photons can cause new excitations in other
neighboring plasmonic nanoparticles. The radiative spectral linewidth of LSPR
gradually increases as NP size increases. For small nanoparticles, the plasmon
enhancement is limited by the surface scattering process due to an increase in
electron screening as particle size decreases [18]. Theoretical evidence shows both
the radiation damping and surface scattering effects play an important role in
limiting the maximum attainable electromagnetic SERS enhancement in plasmonic
NPs [19].
Non-radiative Damping: Absorption
In smaller plasmonic nanoparticles, the extinction is dominated by resonant absorp-

tion due to relatively weak light scattering. The plasmons decay into energetic hot
electron-hole pairs non-radiatively by Landau damping, as photo-excited electrons
jumped from filled states below the fermi level to unfilled states above the fermi level
and lead to a nonthermal e-distribution. The e–e scattering thermalizes the
distribution by elevating the carrier temperature. Further, these hot carriers cool
down further by transferring the energy with nanoparticles phonon modes. It causes
local heating of nanoparticles over a few picosecond time scale (see Fig. 1) [20, 21].
The damping process causes the nanoparticles to act as plasmonic nano-heaters,
which gradually dissipate the heat energy to the surrounding. The heating effect of
photo-excited plasmonic nanoparticles is vastly used in noninvasive targeted
photothermal therapies [22].
1.3.3 Polarizability and Particle Shape Effects
The nature of the light–matter interaction of metallic nanoparticles and associated

local electric field enhancement, absorption, as well as scattering of light, are
strongly depending on the quasi-static polarizability. Absorption and scattering
cross-section of a particle with size below the incident wavelength can be calculated
from the polarizability (α) as,
C abs ¼ k Im½α ð2Þ

k4 2
C scat ¼ jαj ð3Þ
6π
Under quasi-static approximation, Eq. (1) shows that the polarizability directly
depends on particle volume and Eqs. (2) and (3) reflects that optical cross section
vary directly with particle polarizability. Hence, the radiative damping process is
dominated by absorption for small particles While in case of large particles, the
radiative damping is mostly dominated by photon reradiation through light scatter-
ing from large particle volume [23].
The LSPR spectral peak position depends on the dielectric environment of metal
nanoparticles and their local environment. In addition, LSPR characteristics of metal
nanoparticles is associated with particle’s shape and size. Intrinsically any variation
in metal nanoparticle shape or size can alter the surface polarization causes an
alteration in plasmonic resonance. Whereas the increase in particle size affects the
relative magnitude of the particle’s optical cross-sections (absorption and scattering).
The LSPR peak shift due to changes in the aspect ratio from spherical to an elliptical
shape is relatively higher as compared to the LSPR peak shift due to an increase in
the overall size of nanoparticles. Further, nanoparticles with the same shape and size
show different resonance conditions due to their different dielectric functions. For
example, gold and silver nanoparticles of the same size have different resonance
wavelengths due to their difference in the frequency-dependent dielectric constants.
Also, variation in the dielectric constant of the surrounding medium of metal
nanoparticles causes the shifting of LSPR peak position [24, 25]. Further, the
LSPR effect is mainly responsible for the Raman signal enhancement of the analyte
molecules. Upon laser irradiation, the plasmon-induced local electric field across the
nanoparticles interacts with the nearby analyte molecules, and their Raman
scattering cross-section can enhance to many folds. Sometimes molecules within

plasmonic hot spots can experience enormous enhancement that even single-
molecule detection at ultra-low concentration can also be possible. But in the
absence of plasmonic substrates, it is difficult to detect molecules at low concentra-
tions using the normal Raman technique due to very weak Raman signal from the
molecules [26, 27].
2 Nano-Engineering of Plasmonic Probes
2.1 Methods for Fabrication of Nanomaterials
Two different physicochemical approaches have been developed for the fabrication
of desired nanostructures. First, the top-down method involves external mechanical
force to break up or successive cutting of bulk material into smaller particles. In
contrast, the second approach is the bottom-up method, which is based on molecular
condensation or atomic transformations, starting from atoms or nuclei to clusters by
self-assembly of atoms and then forming nanostructures. Top-down approach
includes milling, grinding, etching, lithography, and other techniques which are
listed in Fig. 2 [28].
Among all the methods, the fabrication of periodic nanostructures over a large
area mostly employed conventional lithography techniques such as Photolithogra-
phy. However, the traditional photolithography method has limitations for fast
processing and cost-effective fabrication. Also, it has a feature resolution of around
100 nm [29]. Other traditional lithography methods such as electron beam lithogra-
phy (EBL) [30], focused ion beam (FIB) [31], interferometric lithography (IL) [32],
nanosphere lithography (SL) [33], and maskless lithography [34] are used for
Fig. 2 Schematic of the top-down and bottom-up approaches for fabrication of nanomaterials
nanoscale feature fabrication and has nanometre resolutions; however, these lithog-
raphy techniques are not feasible for fabrication of large-scale nanoprobes. To fulfill
the requirement for fast, low-cost, and large-scale fabrication, Nanoimprint Lithog-
raphy (NIL) was introduced. NIL has a standard nanoscale resolution of 10 nm with
an extremely high throughput of approximately 1 m2/s [35, 36].
As the bottom-up approach starts from atomic-scale, the materials prepared using
bottom-up techniques are expected to have narrow size distributions (1–20 nm) with
various possibilities to tune their shapes and geometries. Some of the common
bottom-up synthesis techniques such as chemical reduction, solvothermal, biosyn-
thesis, and Sol-gel are summarized in Fig. 2.
2.2 Preparation of Plasmonic Nanoprobes
Plasmonic nanoprobes with excellent optical properties and high stability are highly
demanding for their applications in the biomedical field, spectroscopy, sensors,
energy harvesting, etc. Manipulation of plasmonic material constituents, composi-
tion, size, and shape significantly affects the associated electric field, which enable
us to engineer plasmonic materials as per our requirement. The engineered
plasmonic materials can be either a single metal NPs or a composite NPs consisting
of core-shell structures. Depending on their geometries, plasmonic nanoparticles can
be further classified into quasi-spherical and anisotropic NPs.
2.2.1 Metal Nanoparticle-Based Plasmonic Probes
Spherical gold and silver nanoparticles have been known for years and are widely
employed as plasmonic probes. Since Faraday’s first research in 1857, several
approaches have been reported to synthesize gold NPs with controllable size and
good monodispersity [37]. Typically, wet chemical reduction of metal salts is useful
for large-scale production of inorganic nanoparticles. In an aqueous medium, reduc-
tion of gold chloride using sodium citrate as a reducing and stabilizing agent was
proposed by Turkevich [38]. Frens later synthesized different sizes of gold NP by
varying the sodium citrate and precursor ratio [39]. Further, it was reported that the
nanoparticle size can be controlled by varying the strength of reducing agents. Brust
et al. developed another standard synthesis protocol to synthesize silver nanoclusters
using NaBH4 as a reducing agent and it was found that bigger size silver
nanoparticles were obtained when mild reducing agents like ascorbic acid and
sodium citrate were employed [40]. It was found that the LSPR band maxima for
both gold and silver nanoparticles falls in the spectral range between 400 and 600 nm
and exhibits red shifting of LSPR peak with increasing nanoparticles size (see
Fig. 3b) [41]. Further, it was reported that silver nanoparticles demonstrate higher
SERS enhancement up to 10–100 folds higher than gold nanoparticles. Because gold
has both interband transition and plasmon band in same spectral region. Whereas
Fig. 3 Representative shape engineered single metal nanoparticles. (a) Transmission electron
microscopy (TEM) image of spherical Au NPs and field profile of Au NP inset at the corner.
(Copyright 2007, American Chemical Society [46]). (b) Absorption spectra of gold nanoparticles
(NPs) of different size. (Copyright 1999, American Chemical Society [47]). (c) TEM images of Au
nanorod [48] and electric field profile of an individual Au nanorod inset at the corner [49]. (d)
Extinction spectra with multiple red shifted LSPR peaks of nano bars with three different aspect
ratios [25]. (e) Scanning electron microscopy (SEM) image of silver nano prisms [50] and simulated
field profile of a nanoprism displayed at the corner. (Copyright 2018, American Chemical Society
[51]). (f) The shape dependant spectral redshift of silver NPs with their corresponding high-
resolution TEM images. (Reproduced with permission from the AIP Publishing [52]). (g) TEM
images of Au nano-bipyramids (Copyright 2019, American Chemical Society [53]) and electric
field map inserted at the corner. (Reproduced with permission from the IOP Publishing [54]). (h)
SEM images of little truncated silver nanocubes (Reproduced with permission from the John Wiley
and Sons [55]) and simulated electric field map of a silver nanocube inset at the corner. (Copyright
2014, American Chemical Society [56]). (i) TEM image of Au nanostars (Copyright 2019,
American Chemical Society [57]) and simulated local electric field distribution displayed at the
corner [58]. (j) TEM images of Au nanodimers modified with COOH-alkanethiols of C5, C7, C10,
C15, and its corresponding absorbance spectra [59] and in the middle, an illustration of the hot spot
for the dimer system showing the change in electric field enhancement factor w.r.t. distance.
(Reproduced with permission from the Elsevier article [60])
silver interband transition is in the UV region and well separated from its plasmon
band causes lesser plasmon damping [42, 43]. However, SERS enhancement factor
in the large-sized silver nanoparticles is also affected by the radiation damping
effects. Hence, the optimum nanoparticle size one can consider is in the range
between 30 and 100 nm [44]. Another disadvantage of silver nanoparticles is their
poor stability and lesser biocompatibility, limiting their biological applicability as
compared to gold nanoparticles [45].
Although there are well-established synthesis protocols of spherical gold and
silver NPs, their optical properties are limited to the visible range. To this end,
nanoparticles having complex morphologies can meet the demand with at least one
NIR SPR band [61]. Several groups have reported the synthesis of silver and gold
nanoparticles having complex morphologies. For example, anisotropic metal
nanoparticles, mostly silver or gold, can be fabricated through seed-mediated syn-
thesis, i.e., nucleation phase, where strong reducing agents are used, and the growth
phase to get selective crystal facets growth. The fabrication of anisotropic
nanoparticles requires better control on the surface energy, growth kinetics of
different crystal facets. Therefore, specific capping agents or stabilizers play an
important role in controlling reaction parameters such as reaction rate, reagent
concentration, solubility, and diffusion rate [62].
Among reported anisotropic plasmonic nanoparticles, nanorods are the most
efficient and commonly adopted plasmonic probe for SERS and PTT applications.
For instance, gold nanorods possess dual LSPR modes including one weak trans-
verse band at the visible region and one longitudinal band at the NIR region. The
electric field confinement around the longer axis was found much stronger than the
transverse one (see inset of Fig. 3c) [49]. Unlike transverse mode, the longitudinal
mode can be altered with varying aspect ratios (see Fig. 3d) [47]. Fabrication of gold
nanorods by the seed-mediated method was first reported in 2001 by Murphy’s
group [63]. In the growth phase, varying the silver nitrate concentration, gold
nanorods of different aspect ratios were achieved [64]. Further, nanoprism shows
stronger Raman enhancement than nanorods counterparts due to wavy edges and
sharp corners (see Fig. 3e). Also, nanoprism having rough edges with sharp corners
exhibits SERS signal enhancement of the order of 2–12 than nanoprism with the
smooth edged [50]. S. Schultz group smartly introduced the shape transformation
from colloidal silver nanospheres to nanoprisms and observed the spectral redshift
(see Fig. 3f) [52]. Again, the shape of anisotropic nano-bipyramids can give large
SERS enhancement as compared to NRs. Such enhancement is due to the enor-
mously strong local field confinement across the nanoscale tip regions and due to
smaller plasmon damping (see Fig. 3g) [53, 65]. In case of nano-bipyramids, LSPR
peak varies more dominantly with respect to the aspect ratio over the volume. Also,
the maximum light scattering was obtained along the direction perpendicular to the
incident electric field orientation [54]. Furthermore, anisotropic nanocubes can
provide SERS enhancement up to the order of 108, which is highly applicable in
single-molecule detection [66]. The theoretical simulations of silver nanocube found
that the electric field was intensely localized around the corners (see inset of Fig. 3h).
Earlier reported works suggest that the synthesis of silver nanocubes with high
crystallinity is relatively easier whereas it is quite challenging to prepare gold

nanocubes. Nevertheless, Matteini et al. successfully synthesized the gold concave
nanocubes on PDMS film to detect proteins, insulin, and cytochrome c [67]. Xia’s
group reported a novel fabrication method to prepare hollow gold nanocages through
galvanic replacement between silver nanocubes and chloroauric acid in aqueous
medium. Such multifunctional hollow gold nanocubes with porous walls (size range
30–200 nm) are promising for cancer theranostics including hypothermia treatment,
optical imaging, and drug encapsulation and delivery [68, 69].
The electric field distribution can be extremely strong across nano tip regions of
multibranched metallic nanostars and nanoflowers. The synthesis of gold nanostars
using gold seeds, ascorbic acid, NaBH4, and CTAB was first reported by Sau and
Murphy [70]. Yuan et al. further reported the synthesis of citrate stabilized gold
nanostar using silver ions and ascorbic acid [71]. In such gold nanostar, the induced
localized surface plasmon field from the core and its dendrimer arms are coupled
together and provide better optical field enhancement than metal nanorods and
nanospheres [72, 73]. Furthermore, the sharp dendrimer spikes of nanostar effec-
tively act as electromagnetic hot spots, as shown in the inset of Fig. 3i. Such sharp
spikes are utilized in tip-enhanced Raman spectroscopy [58]. In addition to these
structurally engineered nanoparticles, plasmonic dimers and multimers are also
attractive because of intense electric field confinement at nanogap regions known
as hot spots. Interestingly, gold nanodimers and multimers were fabricated using
spherical gold NPs modified with COOH-terminated alkanethiol [59]. Such gold
nanodimers possess dual LSPR, which can easily tune up to the NIR region (see
Fig. 3j). Furthermore, gold nanodimers are advantageous over gold nanorods in
terms of size, interparticle hot spots, and biocompatibility [74].
2.2.2 Composite Plasmonic Nanoprobes
Besides single metal nanoparticles, composite nanoparticles are emerging as an

efficient alternative due to their unique quantum confinement, surface functionality,
and biocompatibility. Bimetallic nanocomposites such as Au/Ag [80], Au/Cu [81],
Ag/Cu [82], and Ag/Pt [83]. either alloyed or in the core-shell form are demonstrated
as plasmonic probes and exhibit their plasmonic signature in a broader optical
window ranging from visible to NIR spectral region. The synthesis of gold-silver
(Au@Ag) bimetallic nanoparticles was first reported using the co-reduction process
of chloroauric acid and silver nitrate with sodium citrate in an aqueous phase [84],
and many other techniques have been proposed thereafter for the preparation of
Au@Ag or Ag@Au bimetallic nanoparticles of various shapes including spherical,
cubic, rod, pyramids, etc. [85–87] Interestingly Au@Ag hollow nanocubes have
shown greater SERS enhancement of the order of 109 due to the presence of multiple
hot spots across sharp tips, edges, and empty nanogaps between the core and hollow
shell region. Moreover, such structural modifications enable tuning the LSPR
absorbance band from visible to NIR spectral region as shown in Fig. 4a
[75]. Wang et al., reported the synthesis of core-shell Au@Ag nanorods using Au
Fig. 4 Representative (a) TEM image of Au core with spherical solid and hollow Ag shells, Au
core with cubical solid and hollow shells and their corresponding absorbance spectra. (Reproduced
with permission from the Elsevier article [75]). TEM micrographs for (b) Au@Ag rod like
nanomatryoshkas embedded with 4-nitrobenzenethiol (NBT) reporter (Copyright 2017, American
Chemical Society [76]) and (c) dye encapsulated Au-nanomatryoshka model. (Copyright 2014,
American Chemical Society [77]). (d) TEM image of Au980-CuS yolk-shell NPs with UV-Vis NIR
absorbance spectra. (Copyright 2018, American Chemical Society [78]). (e) TEM image of
mesoporous Au nano-frameworks and NPs absorbance spectra by changing gold precursor con-
centration. (Reproduced with permission from the John Wiley and Sons [79])
nano-dipyramids as seed [80]. Choi et al. reported synthesis of Au@Bi2Se3 core-

shell nanoparticles using two-step seed-mediated process and such core-shell
nanoparticles act as bifunctional plasmonic probe for SERS-PTT applications
[88]. Further, Au/Ni bimetallic nano-pyramids fabricated using phase-shifting pho-
tolithography offers multipolar resonance conditions [89].
On the other hand, metal-dielectric nanocomposites such as Au@TiO2,
Au@SiO2, and Au@Al2O3 [90] are also reported as potential plasmonic probes
for many biomedical applications due to their improved optical, thermal, and
biostability properties. It was observed that despite the excellent SERS activity of
silver nanoparticles, its practical applicability is mainly affected by low stability
issues as rapid oxidation and sulphuration occur in the air. However, if an ultrathin
layer of TiO2 is coated over the silver nanorods, it significantly improves particle
stability and recyclability [91]. The encapsulation of metal nanoparticles with
dielectric layer coating enables reusability of SERS substrates. SiO2 coated
plasmonic star-shaped Au and Au@Ag NPs on Pt substrate were reported for shell
isolated NPs enhanced Raman spectroscopy [92]. Plasmonic probes consisting of
metal core, Raman reporter layer, and a protecting shell are employed as SERS tag
for biological applications. Mesoporous silica encapsulated Au@Ag nanorods were
successfully designed for SERS imaging and PTT applications (see Fig. 4b) [76]. Sil-
ica encapsulation porous nanoparticles improve the biostability, solubility, and
provide additional tag loading capacity of fluorescent dye or drug molecules. A
unique gold nanomatryoshka consists of Au core enclosed by a thin SiO2 layer,
covered with Au shell layer was investigated to enhance the fluorescence of the
fluorophore (see Fig. 4c). In such NPs the reporter molecules are entrapped between
spacer layer and positioned within few nanometers of metallic surface which can
lead to a strong SERS signal with NIR absorbance [77].
Furthermore, metal-semiconductor nanocomposites including Au@CuS [93],
Ag@CuS [94], Au@CuSe [78], Au–ZnO [95], Au/Ag@Cu2O [96], and
Fe3O4@Au NPs [97] have two distinct plasmon bands covering from visible to
NIR regions. Zhu et al. have adopted a modified self-limiting and self-assembled
hydrothermal route for fabricating monodisperse dual Plasmonic Au@Cu2xS,
Au@Cu2xSe NPs with two distinct plasmon bands from visible to NIR [93]. The
unique Au–CuS yolk-shell nanoparticles as shown in Fig. 4d can provide excellent
enhanced absorption in the NIR region [78]. Further, Au/Ag and Fe2O3-based
magneto-plasmonic nanocomposites exhibit both optical and magnetic properties.
Recently multifunctional magneto-plasmonic probes consisting of core-shell struc-
ture, i.e., AgNP@Fe3O4, encapsulated with a fluorescent silica layer was reported
for SERS-based multiplex detection and separation of carcinogenic cells [98]. Sev-
eral other techniques for the preparation of magneto-plasmonic nanoparticles
consisting of Fe3O4@Au spherical and polyhedral core@shell nanostructures were
also reported [97, 99]. Other plasmonic probes consisting of metal-polymers com-
posites (Au-RaR@PMA, Ag-PVP, Au@PMMA, AuNR@PEG/PLGA, etc.) [100–
102] exhibit excellent properties like high colloidal stability, good plasmonic
response, good surface functionality, shape and size tunability, etc. The encapsula-
tion of more than one plasmonic nanoparticles within the polymer vesicle can
produce plasmon coupling leading to hot spot generation, resulting in effective
heating and SERS imaging. The solid colloidal metal-polymeric nanocapsules
attached with therapeutic drugs can protect active materials inside the biosystem
and fulfil target delivery with higher efficiency [103]. For multimodal therapeutic
application, mesoporous gold nano-frameworks with pore size around 40 nm were
prepared using liposomes polymeric micelle as a templet (see Fig. 4e) [79]. Further-
more, several two-dimensional (2D) materials were also widely use in SERS-based
sensors. For example, 2D materials such as graphene (G), graphene oxide (GO),
boron nitride (h-BN), molybdenum disulfide (MoS2), tungsten diselenide (WSe2),
black phosphorus (BP) with unique features such as in-plane symmetry, edges,
charge carrier concentration shows excellent SERS signal enhancement with the
suppression of background fluorescence signal. Hybrid nanostructures composed of
plasmonic metal and 2D materials further improves plasmonic properties in an
exclusive way for several SERS-based sensing applications [104, 105].
3 Surface Functionalization
Surface functionalization of plasmonic probes are essential for altering surface

properties of nanomaterials to achieve biocompatibility, multifunctionality, resorp-
tion behavior, and stability. Material functionalization strategies are based on the
interaction phenomena between chemical linker and nanoparticle surface. Their
interaction can be classified as, (1) physisorption—relatively weak interactions
(e.g., electrostatic attraction) and (2) chemisorption—involving strong and direct
interaction often covalent attachments [106]. The interaction between noble metals-
thiolate groups (Au–S bond) is the most common spontaneous and strong interaction
at room temperature [107]. Also, surface salinization is a covalent coating that
increases biocompatibility and solubility [108].
Surface functionalization facilitates to introduce a variety of ligands over the
surface of the nanoparticles that enable nanoparticles for intercellular targeted
delivery and detection of disease biomarkers. For instance, nanoparticles
functionalized with positively charged ligands increase nanoparticles internalization
and improve cellular uptake as compared to neutral and negative charged ligand
functionalized nanoparticles. PEGylated nanoparticles support passive targeting of
tumor tissues by EPR effect and enhance materials biocompatibility [109]. Other
linkers such as aptamers, antibodies, folic acid, and the arginine–glycine–aspartic
acid (RGD) motif are used to make passive targeting NPs to active targeting
[110]. Oligonucleotide functionalization of nanoparticles such as DNA-Au NPs
and siRNA-Au NPs improves the biocompatibility, effective internalization of
cells, and significantly reduces the cytotoxicity [111, 112]. Further, the capping of
silica layer over metal nanoparticles provides easier functionalization of various type
of ligands and accommodate drug molecules due to their mesoporosity nature. Silica
encapsulation also allows to trap Raman reporter molecules into the pores for
enhancing SERS signal [113]. Besides, plasmonic sensing platform requires suc-
cessful protein immobilization over the sensor surface and several chemical linkers
have been adopted, which includes carboxyl (–COOH) groups, amine (–NH2), or
hydroxyl (–OH) groups enabling the development of lab-on-chip biosensors [114].
4 Theranostics Opportunities and Challenges
The understanding of interactions between the nanoscale optical fields associated

with plasmonic nanoprobes with cells, biomarkers, small or large molecules enable
us to study many complex biological processes, progression of diseases, and their
treatment. Engineering the geometry and material compositions of plasmonic probes
enhances the contrast of optical imaging modalities like confocal imaging,
photoacoustic imaging, SERS imaging, fluorescence imaging, etc. One can design
plasmonic probes with efficient therapeutic effects like photothermal transduction
efficiency, photodynamic therapy, targeted drug delivery, etc. Further, plasmonic
probes can be loaded with biomolecules (e.g., proteins, genes) and therapeutic drugs
for gene and chemo-photo therapies. Plasmonic probes with very strongly confined
nearfield optical field have showed multimodal imaging modalities with improved
spatial-lateral accuracies [115].
A large number of preclinical studies using plasmonic probes have been reported
for theranostics applications. Some of the latest advances in SERS-guided PTT
studies are illustratively summarized in Fig. 5. One of the earliest reports employed
SERS signal collected from skin and tumors labeled gold nanorods to develop a
SERS-based tumor detection technique by differentiating the SERS response
between skin and tumor cells. The in vivo thermal imaging also confirmed the
hypothermic effect of gold nanorod formulations inside the MDA-MB-435 tumor-
bearing mouse, which can be seen in Fig. 5a [116]. Further designing of plasmonic
probes by combining non-stoichiometric copper chalcogenides with noble metals
can provide high photothermal transduction ability along with improved SERS
enhancement. For example, a hollow core CuS with spiky Au shell NPs are
extremely useful for SERS-guided real-time monitoring of the biochemical response
during thermal therapy (see Fig. 5b) [117]. Also, dual plasmonic Au@Cu2xE NPs
show promising application potential in multimodal imaging and PTT. The inter-
nalized Au@Cu2xE NPs can create 90% of temperature-induced cancer cells death
within 10 min of 0.75 W/cm2 laser irradiation at wavelength of 808 nm (see Fig. 5c)
[93]. Zhu et al. studied the SERS spectra recorded from human breast cancer cells
incubated with gold nano colloids. Intense Raman band assigned for cytoplasm and
the Raman map at 1030 cm1 signifies the strong affinity between gold NPs with
phenylalanine (see Fig. 5d) [118]. The first illustration of in vivo SERS imaging
using ScFv EGFR-conjugated malachite green labeled spherical gold nanoparticles
was reported by Nie and coworkers. Their study has revealed the nonspecific uptake
of gold nanoparticles by liver tissue (see Fig. 5e) [119]. Later, several studies
demonstrated the combination of two noninvasive techniques namely SERS and
PTT, which provided good opportunities in developing different theranostics
systems.
However, one of the major challenges to overcome is the limited penetration
depth of tissues, which makes it difficult in conducting in vivo SERS imaging
[120]. A spatially offset surface-enhanced Raman scattering spectroscopy can par-
tially address such issues [121, 122]. Understanding of interaction mechanisms
between NPs with intracellular components benefits in target cancer therapies.
Designing nanoprobes with NIR absorbance in the spectral region between
700 and 1350 nm is important because of their transparency towards biological
tissues and blood. Vijayaraghavan et al. [123] reported a multibranched gold
nanoechinus with an extremely high extinction coefficient in the NIR region
(800–1700 nm) covering both the biological windows (BW I and II) to study the
in vivo dual-modal photothermal and dynamic therapy using B16F0 melanoma
tumor-bearing mice model upon irradiating both 915 and 1064 nm lasers. Wang
et al. showed that the mesoporous gold NPs exhibit a large number of hot spots and
light absorption at NIR-II (1000–1350 nm) in Infrared optical window and such
mesoporous HA-4-ATP-AuNFs are used to eradicate the MDA-MB-231 tumor with
Fig. 5 (a) Schematic diagram illustrating cooperative NP system for combined therapeutic. Along
with optical and thermal images of MDA-MB-435 tumor-bearing mice. The corresponding SERS
spectra were acquired from the tumor and nontumor regions. (Reproduced with permission from the
John Wiley and Sons [116]). (b) Schematic illustration of SERS-based intercellular imaging-guided
PTT with HCCuS@spiky Au NPs and in vitro SERS mapping image and corresponding spectra of
HeLa cells. (Reproduced with permission from the Royal Society of Chemistry [117]). (c) Cell
viability and photothermal efficiency results of Au@Cu2xS NPs using 4T1 murine breast cancer
cells, after 10 min laser irradiation (0.75 W/cm2, 808 nm). (Copyright 2017, American Chemical
Society [93]). (d) Photomicrograph and SERS mapping image of fixed breast cancer cell at
1030 cm1 Raman band and the corresponding SERS spectra recorded from point a, b, and c
[118]. (e) ScFv EGFR-conjugated malachite green-labeled spherical gold NPs used to get in vivo
SERS spectra from both targeted and non-targeted tumor sites under 785 nm laser excitation.
(Reproduced with permission from the Springer Nature [119])
chemo-photo therapy using NIR-II laser source [79]. Recently, Wai et al. [124]
reported an optimized gold nanoprobe for SERS-based intraoperative detection and
photothermal ablation of SKOV3 ovarian tumors. Authors have also investigated the
role of adjuvant photothermal therapy (aPTT) after surgery through pre- and
intraoperative Raman mapping. Such combined Raman imaging-guided surgery
and aPTT advancement can be able to remove the residual tumors after surgery
that are difficult to detect by naked eyes. In future, we believe that the plasmonic
probes with multi functionalities will enable to fulfill multimode therapies like
integration of chemo-photo therapy, photodynamic therapy (PDT), photothermal

therapy (PTT), etc., with imaging techniques for cancer theranostics applications.
However, there are still many challenges that need to be addressed before bringing
the plasmonic probes-based theranostics to clinical setting. Most of the in vivo
studies have been conducted on tumor-bearing mouse models and are located
underneath the skin where light is accessible. But extensive studies are necessary
for targeting tumors lying deep inside the tissue regions Furthermore, the long-term
biocompatibility, cytotoxicity, and excretion of plasmonic probes after therapy also
need to be carefully addressed before employing them for in vivo applications.
5 Conclusion
This chapter focused on the fundamentals of optical properties of plasmonic

nanoparticles and associated influencing factors (e.g., electric field, plasmon
damping, polarizability, morphology, material composition, and dielectric surround-
ing) for understanding the light–matter interaction. An elaborated assembly of
various reported plasmonic nanostructures are included in this chapter for designing
of multifunctional plasmonic probes. We also discussed the potential theranostics
applications of these advanced nanoprobes in SERS, photothermal therapy, chemo-
photo therapy, and their associated challenges. Conclusively, we believe that
multifunctional plasmonic probes will certainly provide many new opportunities in
the technological advancement of theranostics methods.
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2D Nanomaterials-Based Surface Plasmon
Resonance Probes for Biosensing
Applications
Satya Pratap Singh, Siddharth Kaushik, and Umesh Tiwari
Abstract Surface plasmon resonance (SPR) technology involves the interaction

between the incident light wave and free electrons that reside at the metal-dielectric
interface. Globally, the SPR-based sensing platforms have drawn considerable
attention due to their versatility, high sensitivity, and reusable probes. In recent
years, 2D nanomaterials (particularly graphene and transition metal dichalcogenides
[TMDCs]) have been studied extensively for tuning the sensing properties of
plasmonic sensors. These low bandgap nanomaterials enable efficient absorption
of photons for exciting the electrons directly from the valence band to the conduction
band, without the requirement of phonons. The sensitivity of plasmonic probes
towards the surrounding medium increases significantly due to the high surface-to-
volume ratio of the 2D nanomaterials. The lattice vibrations, charge transfer, and
functionalization properties of 2D nanomaterials can be tuned to achieve optimal
response in biosensing applications. This chapter summarizes the recent advances in
the development and applications of SPR sensors based on 2D nanomaterials. This
chapter also presents the fabrication, intrinsic features, and sensing mechanism of
different SPR sensors based on prism and optical fiber configuration. This chapter
provides insights for researchers to do in-depth study and explore further the 2D
nanomaterial-based SPR sensors.
Key words Surface plasmon resonance · 2D nanomaterials · Transition metal

dichalcogenides · Biosensing applications
S. P. Singh · U. Tiwari (*)

CSIR-Central Scientific Instruments Organisation, Chandigarh, India
e-mail: umeshtiwari@csio.res.in
S. Kaushik
Department of Electrical Engineering, IIT Delhi, New Delhi, India
https://doi.org/10.1007/978-3-030-99491-4_8
246 S. P. Singh et al.
1 Introduction
Biosensors have gained a lot of potential in recent years as they possess desirable
features such as good stability, high sensitivity, easy operation, better selectivity, fast
response, and cost-effective [1]. For sensitive and precise detection of chemical
substances and biomolecules, a variety of biosensing systems have been described,
including photoelectrochemical [2–5], impedance-based [6–8], and optical [9, 10].
In recent years, the optical biosensor had made tremendous progress and has been
applied in several areas including security, health sector, food safety, and environ-
mental monitoring [11–14]. Recent advances in light sources and detectors have
promoted portable and more practical systems. In biosensing applications, the
optical transducer has been established in both routine monitoring of analytes and
for quantitative analysis of biological compounds [15]. Fiber-optic biosensors are
reliable optical transduction methods having great potential to offer real-time, label-
free, and multiparameter analysis [16]. The fiber optic biosensors including SMS
structures, SPR sensors, and LPG sensors are gaining considerable attention of
researchers and are being employed for pathogen detection.
The optical fiber SPR sensors have been explored widely for the detection of
several biomolecules. For targeted analytes, the optical fiber biosensors must be
functionalized using biorecognition molecules, such as proteins, RNA, DNA, and
cells. The attachment of biomolecules over the fiber surface is generally attained
through some chemical linkers (3-Aminopropyl) triethoxysilane, N-Succinimidyl
4-Maleimidobutyrate, etc. The abovementioned surface modification approaches are
generally tedious and achieving a homogenous bio coating is difficult. However, to
overcome these issues the 2D transition metal dichalcogenides (TMDs), i.e., MoS2,
have been used due to their high electron conductivity, tunable bandgap, and high
optical absorption efficiency [17, 18]. The hydrophobic characteristic of MoS2, as
well as its high surface area and availability of free sulfur atoms, make it a promising
material for biosensing interfaces [19, 20].
1.1 Surface Plasmon Resonance (SPR)
The SPR phenomenon was initially observed by Wood in 1902 as “anomalies” or

absence of spectrum in the reflected light by a diffraction grating. Since 1968, after
Kretschmann and Raether provided a detailed explanation of the SPR phenomenon,
these sensors have revolutionized the sensing technology and have become the
reliable platform for environmental monitoring and medical applications. They
observed that when light interacts with the substrate metal interface, it excites the
surface plasmon waves which propagate through thin metallic layer coated over the
dielectric substrate. Surface plasmon polaritons (SPPs) are electromagnetic waves
that are excited by charge density oscillations at the metal–dielectric interface.
Surface plasmon waves (SPW) are related to SPR, which is the quantum of these
2D Nanomaterials-Based Surface Plasmon Resonance Probes. . . 247
oscillations. The SPWs travel along the interface in a transverse manner and decay
exponentially in both the dielectric and metal medium. At the phase-matching
situation, TM polarized light excites the surface plasmon. Surface plasmon reso-
nance (SPR) is generated when the propagation constant of TM polarized light
equals the propagation constant of the SP wave. The normalized transmission
power of the fiber optic SPR sensor is presented in Eq. (1) [21]
Z π
2
RN ð∅Þ n1 2 Sin2∅
d∅
2 ð1n1 2 Cos2 ∅Þ
2
T:P: ¼ Z ∅πcr ð1Þ

2
n1 2 Sin2∅
d∅
2 ð1n1 2 Cos2 ∅Þ
2
∅cr
where n1 is the refractive index of the core and ∅ is the angle of the incidence of the
light with the normal at the core-cladding interface in the sensing region. The total
reflection by the incident light is represented by N(∅). As seen in Fig. 1, the SPR
intensity decays exponentially, resulting in a dramatic dip in the transmitted light’s
spectral response. As a result, changes in the RI of the sensing area are caused by
interactions between immobilized bioreceptors (e.g., antibodies, aptamers, lectins,
etc.) and target molecules, which can cause the resonant wavelength to vary [22–24].
Label-free biosensing can be achieved through SPR as no radioactive or fluores-
cent dyes are required for labeling the biomolecules [25, 26]. The SPR sensors
determine the mass of binding analyte on the surface of the sensor, and hence it is
particularly employed for detection of small analytes [27]. In recent years, SPR
sensors have been explored for a wide range of applications including medical
diagnosis [28, 29], studying ligand–receptor interactions [30], and environmental
monitoring [31].
Fig. 1 The schematic representation of the fiber optic SPR sensor with sensing layer (antibodies)
1.2 Molybdenum Disulfide (MoS2): Structure and Properties
MoS2 is a prominent member of the family of Transition Metal Dichalcogenides

(TMDs) and most widely explored due to its widespread distribution in nature. The
MoS2 are structurally analogous to graphene; the molybdenum (Mo) atomic layers
are sandwiched between two sulfur (S) atomic layers with S–Mo–S bonding. The
interlayer atom is bonded by the weak van der Waal interactions whereas the
intralayer atoms are bonded via strong covalent [32]. It has some advantageous
semiconducting properties than well-established 2D materials including graphene
particularly thickness-dependent bandgap which serves more potential in several
device applications. MoS2 with an indirect bandgap (~1.2 eV) becomes a direct
bandgap (~1.9 eV) semiconductor when thinned down to monolayer. This feature
explains why quantum confinement in layered d-electron materials manifests differ-
ently from quantum confinement in sp-bonded semiconductor nanostructures. The
notable properties like intrinsic large bandgap (1.2–1.8 eV) and MoS2 atomic layers
tunability let this material be used in nanoelectronic and optoelectronic devices on
both conventional and flexible substrates [33–40]. Further thickness-dependent
fluorescence [41] or fluorescent quenching ability [42] found to be predominant in
atomically thin MoS2 and MoS2 nanosheets also exhibit strong near-infrared region
(NIR) absorbance and high NIR photothermal transduction efficiency [43]. The Mo
atoms are hexagonally arranged with surrounding S atoms; the bond lattice constant
and bond length of Mo–S are 3.18 and 2.42 Å, respectively [44]. MoS2 can be
generally categorized into four different poly-types on the basis of lattice arrange-
ments of Mo and S atoms [45–47]. These includes 1T MoS2, 1H MoS2 (single-layer
MoS2), 2H MoS2, and 3R MoS2 (few-layer MoS2). Among these, 2H MoS2 is the
most stable and most abundant poly-type, whereas 1T MoS2 and 3R MoS2 tend to be
metastable [48]. Raman spectroscopy has emerged as a very useful and convenient
characterization tool for the study of the interlayer stacking order in 2D layered
materials like MoS2. It facilitates the identification of different MoS2 poly-types
[49, 50].
In recent years, a significant upsurge has been witnessed in activities dealing with
the synthesis of large area MoS2 layers with target applications in the fabrication of
next-generation biosensor devices, flexible electronics, industrial catalyst, and so on
[51–53]. MoS2 nanosheets are synthesized via different methods including chemical
exfoliation method, hydrothermal, and vapor deposition methods [45]. Researchers
have used chemical exfoliation via lithium intercalation method to grow 1T-MoS2
poly-type nanosheets from its predecessor 2H-MoS2 nanostructures
[54]. Researchers have utilized the organic solvents to control the crystalline phase
and morphology of MoS2 and attained an average size of 90 nm, and a thickness of
about 10–20 nm [55]. Researchers have reported a chemical vapor deposition (CVD)
method to grow monolayer MoS2 [56]. They used the three-zone furnace with
temperature control to grow MoS2 monolayer with MoO3 and sulfur powder as
precursors MoS2 has been considered as an excellent material of choice in a wide-
ranging application as field effect transistors (FETs) [57], photovoltaic [56]
industrial lubrication [58], catalyst [54], wearable/flexible electronics [19, 59], and
optoelectronics devices [60]. Some of this material’s main properties can be listed
out as: high chemical and thermal stability (even up to 1200 C), large available
surface area (even upto 2630 m2/g) [61], high carrier mobility (μ ~ 700 cm2/V/S)
[62, 63], and intercalation-based tuneable features [64]. MoS2 nanosheets have
drawn tremendous research interests in biosensor fabrication due to large surface
area, strong photoluminescence, definite electronic bandgap, and possibility of
surface functionalization for bioconjugation [60]. Researchers have functionalized
2D nanomaterials such as MoS2, graphene and graphene oxide (GO) on multimode
fiber coated with silicon particles (overlayer) to study the performance and detection
accuracy of the developed SPR sensor. Moreover, through Transfer Matrix Method
(TMM) they observed enhancement in sensitivity, resolution, Figure of Merit
(FOM), and electric field intensity of the developed sensor due to coating of
nanomaterials. It was reported that the addition of MoS2 enhances the electric field
by 3.72 104 and sensitivity increases to 199.4 nm/RIU [65]. Researchers have
studied theoretically the effect of MoS2 nanosheets on the sensitivity of SPR sensors.
The relationship between dielectric constant and MoS2 has been studied. The MoS2
monolayer was functionalized in conjugation with Si layer (7 nm) on 50 nm Au
metallic layer. The sensitivity was 10% higher in MoS2/Si/Au/prism as compared to
Au/prism. It was observed that MoS2 functionalized SPR sensor have three times
better performance in comparison to graphene functionalized SPR sensor [66].
Food-borne diseases caused by E. coli and S. typhimurium are leading diseases
affecting human health to great extent. The detection of these bacteria can be
achieved with laboratory-based methods (e.g., microscopic analysis, ELISA, PCR,
etc.) but adequate disease management demands the intervention of rapid technol-
ogies, i.e., biosensors. Among all of the different kinds of biosensors, the optical
fiber biosensors are the promising platforms to provide a technologically more
feasible solution in terms of simplicity, real-time monitoring, specificity, and min-
iaturization. However, the performance of these sensors is affected by the sensor
characteristics including cylindrical geometry with respect to biofunctionalization,
sensitivity, and selectivity. Hence, it is imperative to investigate alternate methods
utilizing nanomaterials for the development of rapid and sensitive optical probes to
detect bacteria in water and food. The MoS2 nanosheets have been utilized for rapid
interfacing antibodies on the surface of SPR probe as it is particularly attractive for
the development of highly sensitive biosensors due to its excellent properties.
In this chapter, we explore the fiber optic sensors for bacteria detection in water,
milk, and juice samples. The large surface area, availability of surface sulfur atoms
as well as the hydrophobic nature of the MoS2 nanostructures have been investigated
to successfully attain the biofunctionalization of the SPR probe with the bacteria-
specific antibodies. These nanostructures could also be further explored for bio
interfacing and sensitivity enhancement of optical fiber SMS sensors, LPG, and
FBG sensors. The reported optical fiber biosensors can be introduced for real-time
monitoring of bacteria in food and beverages processing industries.
2 Experimental Studies
2.1 Synthesis of MoS2 Nanosheets
In our experiments, first MoS2 nanosheets were synthesized by two different

methods (1) electro-dissolution method and (2) chemical exfoliation method. In
first method, the cathode having molybdenum sheet was intercalated with Na+
ions. The Ag/AgCl, molybdenum sheets, and Pt wire have been used as the reference
cathode (working) and anode (counter) electrodes, respectively, in an electrochem-
ical cell having 1 M sodium sulfide (Na2S) solution as the electrolyte. The chrono-
amperometry mode has been applied, keeping the potential constant at 1 V. To
obtain better product yield, the electrolysis process was repeated many times. The
hydroxyl and oxygen radicals produced by water oxidation react with the grain
boundaries and edge locations of the molybdenum sheets, causing defects. Interlayer
separation occurs when Na+ ions intercalate at these defective sites. The disintegra-
tion of the Na+ intercalated MoS2 sheets was clear, as the colorless electrolyte
organic solution became light yellow and then dark yellow as the MoS2 sheets
trickled into the solution. The centrifugation at 20,000 rpm for 30 min was
performed to separate the extracted material. The supernatant which is suspended
after washing three times with DI water followed by centrifugation results in the
exfoliation of Mo into few-layered MoS2 nanosheets utilizing ultrasonication for 2 h.
This process is highly effective to produce homogenous MoS2 nanosheets. The
exfoliated MoS2 nanosheets obtained at different time intervals during the electro-
dissolution method are shown in Fig. 2.
The MoS2 nanosheets were exfoliated from bulk MoS2 flakes utilizing an ultra-
sonic aided liquid exfoliation process with n-methyl pyrrolidone (NMP) as an
organic solvent in the second procedure. In this method, MoS2 flakes (30 mg)
were added to NMP (10 mL) in a 20 mL beaker and sonicated for 3 h in an ultrasonic
bath sonicator. Subsequently, probe sonic tip at an output power of 125 W was used
to sonicate the dispersed solution for 10 min at 25 C. It causes more dispersal of
stacked layers of MoS2. To avoid the overheating effect, the tip was pulsed for ON
Fig. 2 Exfoliated MoS2 nanosheets obtained through electro-dissolution method after different
time intervals. The dimensions of MoS2 nanosheets decrease from sample A1a to A3 [67]
Fig. 3 Exfoliated MoS2 nanosheets obtained through chemical exfoliation method after different
time intervals [67]
(7 s) and OFF (5 s). The obtained solution was centrifuged at 5500 rpm for 1 h at
10 C. One-third of the supernatant was collected and stored at room temperature in
a glass vial. The exfoliated MoS2 nanosheets obtained at different time intervals
during this method are shown in Fig. 3. We have considered the ultrasonication
assisted liquid exfoliation technique for generating MoS2 nanosheets as it offers a
simple and rapid extraction method. The second method is simple and does not
require an electrochemical cell. Therefore, we have used MoS2 nanosheets produced
through abovementioned second method for optical fiber functionalization process.
The proper synthesis of the MoS2 nanosheets was confirmed through morphological
and spectral analysis [67].
2.2 Sensor Fabrication
A plastic cladded multimode step-index fiber with 400 μm core diameter was used to
develop the sensing zone for SPR sensor. In this regard, the 1 cm cladding layer was
removed by thermal process. After removal of the polymer clad layer, the core
region of the optical fiber was exposed to Hydrofluoric acid (HF) (48% w/w) for
38 min at room temperature (25 2 C). The uniform etching is achieved by
keeping the etch rate approximately at 3 μm/min through an optimized etch process.
The tapered optical fibers were stored in a glass desiccator under dry conditions after
washing with methanol and deionized water.
For gold thin film coating over the tapered optical fiber, a DC Magnetron
Sputtering deposition equipment with a DC sputter source (Excel Instruments,
India) as illustrated in Fig. 4a was utilized. The optical fiber was placed at 10 cm
in front of the target as depicted in Fig. 4b. A high voltage was applied to accelerate
the argon ions to a pre-mounted gold target surface that led to the ejection of gold
particles, resulting in coating of metal layer onto the optical fiber. The sputtering gas
Fig. 4 (a) Photograph of the DC magnetron sputtering unit for deposition of gold thin films on
optical fiber; (b) Inside view of coating chamber during coating process [67]
(Argon) was injected in the chamber with a flow rate of 30 standard cubic centimeter
per minute (SCCM) at a pressure of 2.1 Pa during the experiment. Under inert
circumstances, 7 cycles of rotation were used to create a homogeneous coating. The
optical fiber was originally coated with chromium (5 nm) in order to bind gold to
it. The DC power was kept at 40 W during the deposition. The thickness of the gold
layer was measured to be 50 4 nm which is comparable to the thickness in the
earlier reported studies [68].
Using a dip coating method (5 cycles), MoS2 nanosheets were deposited on the
gold-coated optical fiber SPR sensor. A 1 mL solution of MoS2 nanosheets was
incubated with the gold-coated fiber. The scanning electron microscopy and Raman
spectroscopy characterization confirmed the uniform interfacing of the MoS2 on the
gold-coated fiber [67].
2.3 Biofunctionalization Process
The MoS2 functionalized surface of the optical fiber was incubated with the 80 μg/
mL solution of anti-E. coli (monoclonal antibodies) in PBS solution (pH 7.4) for 2 h
at room temperature. After immobilization of anti-E. coli antibodies (size: 10 nm),
the sensing platform was incubated for 30 min with 2% BSA solution as a blocking
agent to block the nonspecific sites of the sensing probe [69]. After incubation, the
fiber was rinsed three times with DI water to remove unattached molecules. The
MoS2/Au/optical fiber was sliced with a surgical blade before being placed on the
glass slide for Raman spectroscopic investigation. The laser beam at a wavelength of
514 nm is focused with 50 objective and Raman signal is collected at room
temperature.
2.4 E. coli Culture Process
E. coli was grown under ideal circumstances at 37 C in a sterilized medium of

nutritional broth (pH: 7.2). In a conical flask with 1000 mL solution of nutritional
broth (13 g) in DI water, 0.5 mL of cultured E. coli was transferred. The solution was
incubated for 24 h at 37 C under a continuous shaking process as depicted in
Fig. 5a. Bacterial growth was seen in the broth after 24 h of incubation, as evidenced
by the development of yellow turbidity. The concentration of the cell suspension was
1.5 108 CFU/mL as calculated by measuring optical density (OD 600). The pellet
from a 10 mL E. coli culture was resuspended and successively diluted (1:20
dilution) in sterile phosphate buffer (0.1 M; pH 7.2) as illustrated in Fig. 5d after
centrifugation at 3000g for 15 min at 8 C. Determination of E. coli concentration in
terms of colony forming units/milliliter (CFU/mL) was done by plating the serial
dilutions on the surface of the nutrient agar plates shown in Fig. 5b, c. The detection
range of 1000–8000 CFU/mL was selected from the dilutions [70]. The Anti-E. coli
monoclonal antibodies were diluted in PBS solution (pH 7.2) at a dilution factor of 1:
1000 and stored at 4 C. S. typhimurium was cultured and buffer solutions with
different bacteria concentrations were prepared according to the procedure discussed
in the preceding chapter. Both the bacteria have similar dimensions with diameter
between 0.5 and 1 μm and length of 1–2 μm.
The SPR biosensor experiments were carried out using experimental setup
presented in Fig. 6. The developed sensor (Ab/MoS2/Au optical fiber) was placed
in a flow cell made up of glass with definite inlet and outlet passages. Polychromatic
and nonpolarized light from a broadband source (wavelength range: 360–2400 nm;
output power: 6.7 mW; Ocean Optics, HL-2000) was launched at one end of the
Fig. 5 (a) The culture process of bacteria; (b) the nutrient agar plates with different concentrations
of bacteria; (c) bacteria counting in the incubated plates; (d) PBS solutions with different concen-
trations of bacteria selected for sensing experiments [67]
Fig. 6 Schematic diagram of the experimental setup of optical fiber SPR biosensor for the detection
of E. coli [69]
optical fiber sensor. The transmission spectra were recorded through charge-coupled
device (CCD) spectrometer (wavelength range: 200–1160 nm; resolution:
0.09–20 nm; Avantes, ULS2048XL-EVO) connected to another end of the sensor.
The computer was interfaced with the spectrometer to record the spectral response at
different concentrations of the E. coli/S. typhimurium [69].
2.5 Sensing Studies
The performance of the antibody grafted MoS2 optical fiber sensor was compared
with a conventionally designed antibody grafted gold optical fiber sensor. In con-
ventional design, the gold-coated optical fiber was modified with
3-mercaptopropionic acid (3-MPA) by immersing in 10 mM ethanolic solution of
3-MPA for 6 h, followed by the incubation of the monoclonal antibodies at 37 C for
an hour. The self-assembled monolayers (SAMs) of 3-MPA can be prepared easily,
they are highly organized and have a high affinity with gold metallic layer. Owing to
strong Au-S bonds, they act as stable linkers for biofunctionalization of SPR sensing
probe. To block the unbind sites of the sensing probe the developed sensor was
treated with 1 M ethanolamine hydrochloride (pH 8.6) for 45 min. Before being used
for bacteria detection, the designed biosensor probe was carefully cleaned three
times with distilled water, dried with nitrogen gas, and kept at 4 C. Figure 7 shows a
schematic of the whole procedure for fabricating a normal SPR sensing probe and a
MoS2-assisted biofunctionalized SPR sensing probe. Different concentration of
bacteria (E. coli/S. typhimurium) was prepared for successive detection experiments.
The antibody immobilized MoS2/gold/optical fiber sensor was interacted with for
Fig. 7 Schematic delineation of the process involved in the development of conventional optical
fiber SPR biosensor and the MoS2 modified optical fiber SPR biosensor [71]
15 min using a carefully engineered flow cell, and the resulting transmission spectra
were recorded. The sensor’s spectral response was then correlated with the varied
bacteria concentrations evaluated via wavelength interrogation.
3 Result and Discussion
3.1 Optimization of Parameters
The gold layer thickness is a key parameter to obtain the good sensitivity of the SPR
sensing probe. The gold layer deposition was optimized by rotating the fiber for
different cycles (~4–9) to achieve best results. However, it was observed that the
sensitivity of the fabricated sensor for 6% w/v sucrose solution (RI: 1.3420 at 25 C)
was highest for 7 cycles as compared to the other rotations of a certain time interval
as shown in Fig. 8a. The dip coating was performed for 4, 6, 8, 10, 12 cycles to
optimize the nanosheets functionalization process. In each cycle the optical fiber was
dipped in the MoS2 nanosheets solution for 20 s, followed by its drying for 120 s.
The MoS2 functionalized sensing probe was annealed for 1 h at 60 C after various
cycles to ensure that the MoS2 interface with the gold layer remained stable. The
MoS2 biofunctionalized sensing probes were evaluated for detection of E. coli and
S. typhimurium after being further treated with particular antibodies.
Fig. 8 Optimization graphs displaying the (a) relationship between sensitivity and gold layer
thickness. The optimum sensitivity was achieved at 50 4 nm thickness (7 cycles); (b) effect of
MoS2 layer thickness on spectral response for detection of definite concentration of bacteria; (c)
correlation between antibodies concentration and sensitivity; (d) effect of pH value on sensitivity of
immunosensor [67]
The best resonance wavelength shift was obtained at the optimal thickness of
MoS2 layers corresponding to 8 cycles of dip coating process for the development of
proposed sensor as shown in Fig. 8b. The concentration of antibodies on the surface
of sensing platform is one of the important parameters which determines the
sensitivity of a biosensor. To optimize the concentration of antibodies, different
concentration (20–100 μg/mL) was immobilized on MoS2/Au/optical fiber to detect
samples having E. coli in defined concentration (1000 CFU/mL). The resonance
wavelength shifted gradually with increase in concentration of immobilized anti-
bodies as shown in Fig. 8c; however, after 100 μg/mL the shift in wavelength
decreases due to antibodies agglomeration hindering the formation of antibody-
antigen complex. The antibody-antigen interactions are pH-dependent and we
have performed pH optimization as shown in Fig. 8d for obtaining high sensitivity
of the developed sensor towards target bacteria. The best results were obtained at pH
range (7.0–7.5). It was noted that beyond this range, the sensitivity decreases due to
the conformational alterations in the structure of antibodies affecting the sensing
mechanism. We have conducted all experiments at pH 7.2.
3.2 Structural and Spectral Analysis
The microscopic and spectroscopic techniques were used to characterize the exfo-
liated MoS2 nanosheets. Due to direct transitions at the K point of the Brillion zone
[72] the exfoliated MoS2 nanosheets have shown the UV-Vis absorption spectrum
(Fig. 9a) peaks at 617 and 672 nm. According to the published research [73], a wide
peak at 395 about 453 nm occurs when electrons linearly migrate from the deep
valence band to the conduction band. The TEM images as shown in Fig. 9b manifest
the formation of the nanostructures with uniform dimensions. The TEM image
clearly shows the sheets-like shape of the exfoliated MoS2. The FESEM analysis
as shown in Fig. 9c, d signifies morphological changes on the sensing probe’s
surface after MoS2 functionalization. The dip coating technique is shown to be
suitable for homogeneous deposition of MoS2 nanosheets on optical fibers. In
comparison to the conventional optical fiber SPR sensor, the FESEM scans indicate
the homogeneous interfacing of MoS2 nanosheets, resulting in increased antibody
binding sites.
Fig. 9 (a) UV-Vis spectra of exfoliated MoS2; (b) TEM analysis of the exfoliated MoS2
nanosheets; (c) FESEM Image of SPR sensor to show the functionalized layers of MoS2 nanosheets
on the gold-coated optical fiber; (d) Enhanced view of functionalized MoS2 nanosheets [69, 71]
Fig. 10 (a) XRD analysis of exfoliated MoS2 nanosheets; (b) Raman spectrum of bulk MoS2
powder (black color), exfoliated MoS2 nanosheets (red color), MoS2 nanosheets interfaced gold-
coated optical fiber sensing probe (purple color). Characteristic in-plane E12g (384 cm1) and out-
of-plane A1g (404 cm1) Raman vibrational modes [69, 71]
The XRD spectrum of the bulk MoS2 powder contains many peaks that corre-
spond to the lattice plane reflections from the multiple layers of MoS2 (Fig. 10a).
However, the XRD spectra of exfoliated MoS2 nanosheets show the strong charac-
teristic peak (002) of bulk MoS2 (shifted from 14 to 9 ), indicating lattice expansion
owing to increased lattice strain and reduced crystallite size. Exfoliation increases
the interlayer distance of the (002) lattice plane, resulting in a reduced angle of
diffraction. The occurrence of 33 XRD peaks corresponds to planes of (100) in a
typical hexagonal MoS2 structure. The reduction of particle size in the corresponding
planes is linked with the widening of these peaks [74]. The electronic and vibrational
states of synthesized MoS2 nanosheets were measured using Raman spectroscopy.
The thickness dependence of the breathing and shear modes (interlayer vibrational
modes) in MoS2 is well defined. Layer thickness affects the intensity and frequency
shift of both modes. The peak position of in-plane (E12g) and out-of-plane (A1g)
modes provide precise identification of individual and few layers of MoS2
[75, 76]. The laser power was kept to a bare minimum to prevent heating the
nanomaterials and causing damage to them. The Raman spectrometric analysis of
exfoliated nanosheets with MoS2 nanosheets functionalized sensing probe is shown
in Fig. 10b. The vibration modes of the exfoliated MoS2 sample showed a frequency
change when compared to MoS2 powder. The A1g peak is blue-shifted from 408.7 to
405.2 cm1 while E12g peak was red shifted from 381.8 to 384.7 cm1 which is
similar to previous studies [77–79]. Raman analysis was also used to validate the
functionalization of MoS2 nanosheets on gold-coated fiber, as evidenced by the red
spectrum. The characteristic in-plane E12g (384.6 cm1) and out-of-plane A1g
(405.5 cm1) vibrational modes were in accordance with standard exfoliated
MoS2. These nanosheets were further investigated for use in the manufacture of a
fiber optic SPR immunosensor, and Raman analysis verified the functionalization of
MoS2 nanosheets over the sensing probe, with significant E12g and A1g visible in the
purple spectrum [71].
Fig. 11 The water contact angle of (a) silicon substrate (SiO2), (b) gold (Au), and (c) MoS2 layer to
show hydrophobic characteristics of different substrates [71]
Drop shape analysis was used to measure the hydrophobicity of the exfoliated
MoS2 nanosheets. As illustrated in Fig. 11a–c, the contact angle was calculated
using a picture of a sessile water drop at the locations of contact with the target
surface. The hydrophilic glass substrate has a mean contact angle of 32.55 . When
compared to MoS2 nanosheets functionalized surface (73.85 ), the mean contact
angle of gold-coated surface (71.95 ) is less hydrophobic. MoS2 nanosheets have a
greater hydrophobicity, which aids in the appropriate adsorption of proteins and
antibodies without cross-likers. As a result, MoS2 nanosheets are prospective 2D
nanomaterials for antibody immobilization that is quick and easy [67].
3.3 Comparative Study of Response Characteristics
In a control experiment, when antibodies were not immobilized on the sensing

platform, the shift in the resonant wavelength was 0.3 nm and it was due to the RI
of the E. coli sample as shown in Fig. 12. The spectral response of Ab/Au/optical
fiber and Ab/MoS2/Au/optical fiber were tested for known concentrations of E. coli
in buffer solution to explore the spectral properties of the constructed SPR biosensor.
The same process was considered for S. typhimurium detection however instead of
Anti-E. coli monoclonal antibodies, Anti-S. typhimurium monoclonal antibodies
were immobilized on the sensing platform. The reference peak was defined as the
resonance wavelength seen after the antibodies had been immobilized. The SPR
spectra attained with conventional SPR sensor for different concentrations of E. coli
ranging from 1000 to 8000 CFU/mL in PBS solution are depicted in Fig. 13a. After
15 min of analyte addition in the flow cell, the transmission spectra were measured.
The resonance wavelength was measured for each sample with a specific concen-
tration. A redshift in the resonance wavelength may be observed when the E. coli
concentration rises. Figure 13c shows the corresponding shift in the resonance
wavelength with each sample (E. coli) by developed biosensor.
The error bar graph depicted in Fig. 13b, d clearly shows the increase in the
resonance wavelength increases linearly with the E. coli concentration; however, the
resonant wavelength shift is relatively more in PBS solution by Ab/MoS2/Au/fiber
compared to PBS solution by Ab/Au/fiber. The experiment was carried out in
triplicates for the analysis of each individual sample. After each experiment, the
probe was cleaned with DI water to remove any bound molecules. The contact
between the target bacteria (E. coli/S. typhimurium) and particular antibodies results
Fig. 12 (a) Transmission spectrum of MoS2/Au/optical fiber without antibodies for E. coli con-
centration (1000 –8000 CFU/mL); (b) shift in resonance wavelength of MoS2/Au/optical fiber
immunosensor with respect to the concentrations of E. coli [67]
Fig. 13 Spectral characteristics of E. coli in PBS solution of the (a) conventional and (c) developed
SPR biosensor; Standard calibration plot of (b) Ab/Au/fiber; (d) Ab/MoS2/Au/fiber for different
concentrations of E. coli in PBS solution (pH 7.4); the error bars represent the standard deviation
[3, 69]
Fig. 14 (a) Transmission spectrum of conventional Ab/Au/optical fiber biosensor for

S. typhimurium concentration (5000 –50,000 CFU/mL), (b) shift in resonance wavelength of
Ab/Au/optical fiber biosensor vs. concentrations of S. typhimurium with standard deviation as
error bars, (c) transmission spectra of Ab/MoS2/Au/optical fiber biosensor corresponding to the
different concentration of S. typhimurium, (d) shift in resonance wavelength vs. concentrations of
S. typhimurium with standard deviation as error bars [67]
in the development of an immune complex, which alters the characteristics of the

interacting evanescent wave and shifts the resonance wavelength.
The SPR spectra attained with conventional SPR sensor for different concentra-
tions of S. typhimurium ranging from 5000 to 50,000 CFU/mL in PBS buffer is
depicted in Fig. 14a. The detection of S. typhimurium performed by the Anti-
S. typhimurium immobilized MoS2 interfaced optical fiber SPR sensor is shown in
Fig. 14c, the redshift in the resonance wavelength is proportional to the increase in
the concentration of the S. typhimurium in different samples. The error bar graph
depicted in Fig. 14b, d, clearly shows the increase in the resonance wavelength
increases linearly with the S. typhimurium concentration.
The concentration of bacteria is proportional to the change in refractive index and
the difference in refractive index is shown by a shift in the transmission spectra’s
resonance wave length. As demonstrated in Fig. 15a, b, the suggested Ab/MoS2/Au/
optical fiber has a greater amount of wavelength shift, indicating enhanced sensor
Fig. 15 Graphs presenting comparative shifts in resonance wavelength by both the sensors (a) for
E. coli detection; (b) for S. typhimurium detection [67]
sensitivity. The density of functionalized antibodies increases as the surface-to-

volume ratio of functionalized MoS2 nanosheets increases, resulting in the binding
of a large number of target microorganisms. It is also important to note that the MoS2
monolayer has a higher refractive index (4.49 @ λ ¼ 651 nm) as compared to gold
layer [80]. The MoS2 nanosheets can support evanescent waves even at lower
thicknesses due to their high RI. As a result, thin layers (8 2 μm) of these
nanosheets can transmit a large fraction of the evanescent field in the biorecognition
zone. Similarly, because sensitivity is proportional to the electrical intensity overlap
integral in the surrounding medium, which is dependent on the interaction between
analytes and guided waves, the biosensor’s sensitivity rises as the interaction
between guided waves and analytes increases. It is evident from the spectral results
that the developed SPR biosensor provides better sensitivity for E. coli detection
with LOD of 94 CFU/mL [(calculated by 3 SDBlank/slope of calibration curve)
with R2 ¼ 0.9960] as compared to conventional optical fiber SPR biosensor LOD of
391 (with R2 ¼ 0.9935). Likewise, the LOD of 229 CFU/mL of Ab/MoS2/Au/optical
fiber (with R2 ¼ 0.9972) for S. typhimurium detection was better than Ab/Au/optical
fiber biosensor LOD of 477 CFU/mL (with R2 ¼ 0.9744) [67].
3.4 Performance Studies
A good biosensor must have selectivity for the analyte being measured. The spec-
trum analysis was done in the presence of several closely related interferents such as
S. typhimurium and S. aureus with two sets of concentrations, i.e., 1000 and
2000 CFU/mL, to examine the selectivity of both the standard SPR sensing probe
and the proposed MoS2 modified SPR biosensor. Figure 16a–d depicts the measured
response of both sensing probes as a change in resonance wavelength towards each
compound. The high-affinity binding of the epitopes of antigen with the paratopes of
Fig. 16 Comparative specificity of (a) Ab/Au/optical fiber and (b) Ab/MoS2/Au/optical fiber for
different bacteria in PBS solution [67]
antibodies occurs only when they are complementary to each other in shape, size,
and orientation resulting in highly specific antibody-antigen immunocomplex. The
shift in wavelength as observed by Ab/Au/optical fiber in Fig. 16a for 1000 CFU/mL
of S. typhimurium was 0.26 nm and for 1000 CFU/mL of S. aureus, it was 0.22 nm
whereas 1.84 nm was noted for target E. coli. Similarly, the observed values of shift
in resonance wavelength evident in Fig. 16b by Ab/MoS2/Au/optical fiber for
1000 CFU/mL of S. typhimurium was 0.69 nm and for 1000 CFU/mL of S. aureus,
it was 0.32 nm whereas a significant shift of 2.05 nm was observed for target E. coli
for the same concentration. Comparison of the performance of the conventional
Ab/Au/optical fiber SPR biosensor with the developed Ab/MoS2/Au/optical fiber
SPR biosensor is presented in Fig. 16c, d in case of S. typhimurium sensing
experiment indicates that the MoS2-based developed biosensor is more sensitive
and specific towards the detection of target bacteria as MoS2 nanosheets provide
large surface area for attachment of higher number antibodies thereby increasing the
specificity of the biosensor. Both these sensors are immobilized with Anti-
S. typhimurium monoclonal antibodies. The shift in resonance wavelength for
5000 CFU/mL of S. typhimurium was 10.167 nm as against the 3.74 and 2.10 nm
shift for similar bacteria E. coli and S. aureus with the same concentration.
To investigate the response time of the developed Ab/MoS2/Au/optical fiber

immunosensor, the resonance wavelength was recorded at 620.898 nm before and
after the introduction of solution containing E. coli of different concentration in the
flow cell. The decrease in transmission intensity and shift in wavelength was
observed in the presence of analyte with no change when the measurement was
repeated after 2 min. After cleaning the glass flow cell, the spectral response was
found to be nearly identical to its initial value. As a result, the immunosensor’s
reaction time is said to be less than 2 min. The precision of the immunosensor was
investigated by measuring the standard error (SE) of the resonance wavelength
obtained at each concentration of E. coli. The smaller value of the SE indicates
higher precision. The results shown in Table 1 show high precision of developed
immunosensor at each concentration of target analyte.
The mean wavelengths were compared using a one-way ANOVA to see if there
was a statistically significant difference. The ANOVA test results indicate a statis-
tically significant difference in wavelength across at least one of the samples of
bacteria at the concentration of 1000 CFU/mL (F 3, 8 ¼ 213.719, p < 0.001) and
2000 CFU/mL (F 3, 8 ¼ 330.225, p < 0.001). To perform pairwise comparisons,
Tukey’s Honest Significant Difference (HSD) post hoc test was employed, with the
family-wise alpha set to 0.05. Mean wavelength in the detection of E. coli at 1000
and 2000 CFU/mL is observed to be significantly different from that of other
interferent bacteria viz. S. typhimurium ( p < 0.001), S. aureus ( p < 0.001), and
blank sample ( p ¼ 0.175 and p < 0.001). We observed no significant difference in
mean wavelength in the detection of S. typhimurium ( p ¼ 0.175 and 0.140) and
S. aureus ( p ¼ 0.369 and 0.624) at 1000 and 2000 CFU/mL, respectively, when
compared to blank samples. A p < 0.05 was significant. Table 2 provides a pairwise
comparison of mean resonance wavelength across different bacteria samples and the
forest plot demonstrates the same (Fig. 17). The statistical analysis of data was
performed by SPSS version 15.0 (SPSS South Asia, Bangalore) and R software. The
Table 1 Precision analysis of developed immunosensor for E. coli detection in standard buffer
solution
Precision of Coefficient of
conventional Precision of Coefficient of variation
SPR developed SPR variation (CV)b (CV)b of
E. coli immunosensor immunosensor of conventional developed
concentration (Standard (Standard SPR SPR
S. no. (CFU/mL) Errora) Errora) immunosensor immunosensor
01. 1000 0.007 0.091 0.026 0.089
02. 2000 0.006 0.210 0.025 0.106
03. 4000 0.007 0.053 0.029 0.110
04. 6000 0.006 0.228 0.025 0.140
05. 8000 0.015 0.408 0.058 0.141
a pffiffiffi
The estimate of standard error was obtained using SD/ n, where SD is the standard deviation of
resonance wavelength measured at each concentration of E. coli
b
Coefficient of variation ¼ (Standard Deviation/Mean) 100
Table 2 Pairwise comparison of mean resonance wavelength in detection of different interferent

bacteria, E. coli and blank samples
1000 CFU/mL 2000 CFU/mL
Mean difference (95% Mean difference (95%
Comparison CI) p Value CI) p Value
E. coli—Blank 2.000 (1.708, 2.292) <0.001* 4.580 (5.124, 4.032) <0.001*
S. typhimurium— 0.220 (0.082, 0.502) 0.175 0.420 (0.967, 0.125) 0.14
Blank
S. aureus—Blank 0.158 (0.134, 0.450) 0.369 0.210 (0.335, 0.757) 0.624
S. typhimurium—S. 0.053 (0.239, 0.345) 0.936 0.211 (0.335, 0.756) 0.624
aureus
E. coli—S. 1.790 (1.498, 2.082) <0.001* 4.160 (3.611, 4.702) <0.001*
typhimurium
E. coli—S. aureus 1.840 (1.55, 2.135) <0.001* 4.367 (3.821, 4.913) <0.001*
*Significant difference in mean wavelength in the detection of E. coli, when compared to blank
samples. A p < 0.05 was considered to be significant
Fig. 17 The forest plot outlines the 95% confidence interval for difference in mean resonance
wavelength of different samples of bacteria at 1000 CFU/mL concentration [67]
findings of the statistical analysis support the constructed immunosensor’s excellent

specificity for E. coli detection [67].
3.5 Recovery Test
To measure the practical utility of the developed SPR immunosensor, the real sample
analysis was done using drinking water and orange juice samples spiked with a
known concentration of E. coli. The juice samples were diluted five times with DI
water before the addition of E. coli whereas no pretreatment was done for water
samples.
The recovery test on spiked water and juice samples under the optimized condi-
tions. The recovery percent for spiked water and orange juice samples was observed
in the range of 94–123% as shown in Table 3. The recovery test result demonstrates
the sensitive and selective detention of E. coli by the developed Ab/MoS2/Au/optical
fiber immunosensor even in the presence of several interfering compounds in
drinking water and juice samples [81].
4 Summary
In this chapter, a novel scheme is proposed and demonstrated that utilizes MoS2
nanosheets for simple and rapid biofunctionalization of optical fiber SPR sensor. The
developed optical fiber SPR sensors have been studied for specific detection of
E. coli and S. typhimurium, respectively. Different analytical methods, including
Raman spectroscopy, TEM, UV-Vis spectroscopy, FESEM, and XRD analysis,
were used to characterize the sensing probe functionalization using nanosheets and
antibodies immobilization. To achieve high analytical performance, the parameters
were optimized throughout the construction of the sensing probe. The sensing
capabilities of the developed biosensor were compared with the conventional optical
fiber SRP biosensor. The sensitivity of the designed probe (LOD for E. coli: 94 CFU/
mL and LOD for S. typhimurium: 229 CFU/mL) was better as compared to the
conventional probe (LOD for E. coli: 391 CFU/mL and LOD for S. typhimurium:
477 CFU/mL). Even in the presence of cross-reactive chemicals, the developed
sensing probe was highly selective for target microorganisms. The practical appli-
cation of the developed sensor has been presented by the detection of E. coli in real
samples. Though the current study yielded some encouraging findings, there are a
few drawbacks to be aware of, including the brittle nature of optical fiber and the
time-consuming gold coating procedure. The alternative approach of easy
biofunctionalization might open up new avenues for the creation of next-generation
optical fiber sensors that enable real-time monitoring and ultra-low quantitative
analysis while being simple to fabricate.
Acknowledgments The authors gratefully acknowledge the Director CSIR-CSIO Chandigarh for
the encouragement. The authors also acknowledge support from the CSIR for funding under CSIR
mission project on Medical Instruments & Devices titled “Diagnostic system for circulating tumour
cells (CTC) in prostate cancer detection using optical fiber sensor.” One of the authors also thanks
CSIR, New Delhi for the funding support under Senior Research Associateship (file no. 13(9134-
A)/2020-Pool).
Table 3 The recovery percent for spiked water and orange juice samples
Conc. of
E. coli in Concentration of Concentration of
standard Mean λ value E. coli recovered E. coli recovered
buffer Mean λ value obtained with from spiked water λ value obtained from spiked juice
samples obtained with spiked water samples (in CFU/ with spiked juice samples (in CFU/
S. no. (in CFU/mL) standard samples samples mL) Recovery % samples mL) Recovery %
01. 1000 622.951 0.158 623.004 0.091 1194 119 0.032 623.109 0.157 1232 123 0.056
02. 2000 625.528 0.364 625.581 0.328 2114 105 0.058 625.739 0.091 2171 108 0.016
03. 4000 629.995 0.091 630.257 0.240 3785 94.6 0.02 630.415 0.241 3842 96 0.020
2D Nanomaterials-Based Surface Plasmon Resonance Probes. . .
λ: Resonance wavelength. All the information reported herein are mean of triplicate analysis
Recovery % ¼ (Recovered concentration/actual concentration) 100
267
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Plasmonic Sensors: An Insight into
Fundamentals, Compositions,
and Applications
Bhavana Anchan, Gayathri Ajith Chakkadath, Ajeetkumar Patil,

Goutam Thakur, and Shounak De
Abstract Plasmon resonance principle has become a very important tool for the
development of plasmonic sensors, particularly in the case of biosensing and
chemical sensing. In this chapter, we will review the basics of the plasmonic optical
principle, different types of plasmonic sensors based on propagating surface
plasmon resonances (SPRs), and localized surface plasmon resonances (LSPRs).
Different types of plasmonic materials that include metal, nonmetal, polymer-based
nanomaterials have been discussed. Geometries of the nanomaterials like planar
nanofilm, nanoholes, nanoislands, and nanoparticles have been discussed which
have profound effects on the plasmonic sensing applications. Plasmonic sensors
have been successful in overcoming conventional limitations.
Key words Plasmon · PSPR · LSPR · Plasmonics · Sensors · Metal nanoparticles ·

Polymer nanoparticles
Bhavana Anchan, Gayathri Ajith Chakkadath, Ajeetkumar Patil, Goutam Thakur and Shounak De
contributed equally with all other contributors.
B. Anchan · A. Patil (*)

Department of Atomic and Molecular Physics, Manipal Academy of Higher Education,
Manipal, India
e-mail: ajeetkumar.p@manipal.edu
G. A. Chakkadath · G. Thakur (*)
Department of Biomedical Engineering, Manipal Institute of Technology, Manipal Academy of
Higher Education, Manipal, India
e-mail: goutam.thakur@manipal.edu
S. De (*)
Department of Electronics and Communication Engineering, Manipal Institute of Technology,
Manipal Academy of Higher Education, Manipal, India
e-mail: shounak.de@manipal.edu
https://doi.org/10.1007/978-3-030-99491-4_9
274 B. Anchan et al.
1 Introduction
Metal-dielectric interfaces are growing interest for the last two decades as they
provide unique properties of electromagnetic radiation. Plasmonic optical phenom-
ena where the sub-wavelength confinement and optical field enhancement when
close to nanostructures are being studied extensively. Electromagnetic field interac-
tion in thin film/nanostructures has shown tremendous potential in various disci-
plines/applications. Increasing interest in the applications/fields such as in
engineering, biomedical, biology, and material science with specially synthesized
nanomaterials of various sizes/shapes such as thin film, nanorods, nanospheres,
nanoflowers, and so on enhanced the plasmonic optical phenomena.
According to the collective electromagnetic nature of sub-wavelength consider-
ation and “meta-atoms” as building blocks have spawned extensive research over the
past decade which created a lot of interest in composite materials tunability, viz.,
near-zero material parameters, high material parameter value, unconventionally
characterized by bulk and surface properties. The Plasmonics field can be divided
into one that deals with the mode of propagating plasmonics, and, secondly, that
deals with localized plasmonic modes.
Physical phenomena with surface waves have been proven for numerous appli-
cations such as nanoelectronics, biomedicine, telecommunications, optical imaging,
photovoltaics, and photocatalysis [1–3]. The discovery of metamaterials with tun-
able electrical and magnetic properties [4] has enabled a rich phenomenon, namely
the expansion of the broad spectrum of structures that can carry surface waves.
Polaritons (SPP) are electromagnetic excitations that occur at the junction between a
conductor and a dielectric. These are evanescent to a limited extent in the vertical
direction [4, 5]. It is possible to mimic the properties of SPPs that are limited by
geometry-induced SPPs known as interfering SPPs. The phenomenon can occur at
lower frequencies. One could conclude that the surface structure can open a door to
counterfeit surface plasmons. The former serves as the perfect prototype for struc-
tured surfaces.
Manipulating the optical properties under the presence of metal nanostructures
(Particles) at the nanoscale level is called plasmonics and such nanoparticles are
called plasmonic nanoparticles. It is due to the interaction between the light and
electrons at the metal surface or in the presence of nanostructures resulting in an
optical enhancement. Plasmonic nanoparticles such as gold and silver particles are
discrete metallic particles that have unique optical properties dependent on their size
and shape (Fig. 1). As a result, tunning of the size and shape can be possible to
optimize the performance required for a specific application without changing the
chemical composition of the materials. Recent studies have shown that metal
nanoparticles doped with other metals show tunable and good efficiency of plasmon
resonances. Two main elements of plasmonics are
1. Surface Plasmon Resonance (SPR) and
2. Localized Surface Plasmon Resonance (LSPR)
Plasmonic Sensors: An Insight into Fundamentals, Compositions. . . 275
Fig. 1 Plasmonic nanoparticles showing optical properties based on their size and shape (https://
nanocomposix.com/pages/the-science-of-plasmonics)
1.1 What Are Plasmons? “A Plasmon Is a Quantum

of Plasma Oscillation”
Plasmon can be defined as the quantization of a discrete range of plasma oscillation.

As a photon is the unit for quanta of light, a phonon is the unit of lattice vibrations,
the basic unit of plasma oscillation is plasmon. It is a quasi-particle that originates
due to the interaction between the light and the free-electron density present at the
metal surfaces. To understand the generation of plasmons, one can imagine light as a
wave with changing electric and magnetic fields interacting with the free electrons
on the metal surface. During this process, the electric-magnetic field forces the freely
moving electron to align and move along the field directions. This gives a very
interesting phenomenon as the moving free electrons are confined to move in a
specific path based on the wavelengths which lead to resonance behavior between
incident light and wavelength of the metal sheet (thin films/nano-sized structures).
The plasmonic phenomenon occurs when the polarized light graces the thin film
surface at the interface with different refractive materials. SPR is a phenomenon in
which the propagation of plasmons at the metal-dielectric interface resonates with
the oscillation of the metal’s surface conduction electrons. LSPR occurs when the
incident frequency of the photon is resonant with the oscillation of conductive
electrons in metallic nanoparticles. The dispersion curve of the plasmon (shown in
Fig. 2) lies below that of the free space in the dielectric. Therefore, direct excitation
of SPP by light beams is no longer possible, except for unique strategies which are
used to achieve phase matching.
Fig. 2 Typical Surface Plasmon Resonance (SPR) measurement scheme
1.2 Electromagnetics on Metal Surfaces
The mechanism of plasmon and plasmonic interaction can be best understood by

solving the classical Maxwell’s equations together with the corresponding boundary
conditions that lead to the solution referred to as a surface wave.
Metal interaction with electromagnetic fields can be defined in the context of
classical Maxwell equations [6].
∇D¼ρ ð1Þ
∇B¼0 ð2Þ
∇ E ¼ ∂B=∂t ð3Þ
∇ H ¼ J þ ∂D=∂t ð4Þ
where dielectric displacement (D), external charge density (ρ), magnetic induction
(B), electric field (E), magnetic field (H ), and current density (J ). For dielectric,
where there is no magnetic media the material dependent relations:
D ¼ E0 E E ð5Þ
B ¼ μ0 H ð6Þ
where E0 is known as the permeability of free space, μ0 permittivity of free space.

With a dielectric constant E to a frequency-dependent function: E(ω) ¼ E0 + iE00 and is
coupled to the refractive index complex via n(ω) ¼ n + iκ ¼ √E.
So, we can write the following expressions:

E0 ¼ n2 κ2 , where E00 ¼ 2nκ ð7Þ

2 2
n2 ¼ E0 =2 þ 1=2√ E0 þ E00 , where κ ¼ E00 =2n ð8Þ
where n(ω) is the real part of the refractive index for the dispersion in the medium,
κ(ω) the imaginary part responsible for attenuation of electromagnetic waves, which
is also known as the absorption constant or extinction coefficient. Extinction coef-
ficient can be determined as α(ω) ¼ 2κ(ω)ω/c from Beer’s law, which signifies an
exponential decrease in the light intensity propagating along with the x direction in
the medium: I(x) ¼ I0eαx.
1.3 Plasma Model
1.3.1 Bulk Plasmons
Optical properties over a wide frequency range can be described based on the
plasmon model. According to the model, it is assumed that the electron gas of the
effective electron mass “m” with the density “N” spreads freely behind a positively
charged atomic background. Under the influence of the electromagnetic field, E-
(t) ¼ E0eiωt, the electron vibrates and dampens through collisions with a charac-
teristic speed where γ ¼ 1/τ (typically τ 1014 s at room temperature).
Equations of motion based on the plasmon model reads as,
m€x þ mγ x_ ¼ eEðt Þ ð9Þ
with the solution

e
xð t Þ ¼ P E ðt Þ ð10Þ
½mðω2 þ iγωÞ
Polarization P ¼ Nex which give rise to the dielectric displacement (D), and the
dielectric constant (E(ω)) as follows
D ¼ E0 E þ P ¼ E0 E E ð11Þ
!
ω2p
¼ E0 1 2 ð12Þ
ðω þ iγωÞ
! !
ω2p ω2p τ2
EðωÞ ¼ 1 2 ¼ 1 2 2 ð13Þ
ðω þ iγωÞ ðω τ þ iωτÞ
where ωp plasmon frequency ω2p ¼ Ne2 =E0 m.

For lower frequencies κτ 1, metal absorbs strongly and the penetration depth of
the electromagnetic field, according to Beer’s law, becomes δ ¼ 2/α and it is called
the skin depth.
For higher frequencies, ωτ 1 approximation is valid and the damping term

(iωτ) can be neglected and E(ω) becomes approximately real:
EðωÞ ¼ 1 ω2p =ω2 ð14Þ
and the electromagnetic field dispersion can be obtained from k2 ¼ |k|2 ¼ Eω2/c2:

ωðkÞ ¼ √ ω2p þ k2 =c2 ωðkÞ ¼ √ ω2p þ k2 =c2
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ffi
ωð k Þ ¼ ωp þ k =c Þ
2 2 2
ð15Þ
For ω > ωp, waves propagate with a group velocity vg ¼ dω/dk < c.
Further for ω ¼ ωp, where for low damping ε(ωp) ¼ 0, quanta of oscillation of
charges are called plasmons. Bulk plasmons cannot couple to transversal electro-
magnetic fields, so direct irradiation cannot be used for excitation. Generally, the
plasma frequency lies in the ultraviolet regime with energies ~5–15 eV, based on the
metal band structure in most metals.
1.3.2 Surface Plasmons (SP)
SP are electromagnetic excitations that travel along with the interface between a
dielectric medium and a metal. To obtain these excitations we again start with
Maxwell’s equations and solve them separately for the metal and dielectric parts.
Considering metal surface extending infinitely in the xy plane at z ¼ 0 as shown in
Fig. 3.
Fig. 3 Interface along the x–y plane between a dielectric E1 and a metal E2
The normal and transversal field components on this interface are given by [6]:
B1,z ¼ B2,z , D1,z ¼ D2z , ð16Þ

H 1,x=y ¼ H 2,x=y , E 1,x=y ¼ E2x=y , ð17Þ
Under the above conditions, no transverse electric (TE) modes are significant and
transverse magnetic (TM) modes for the field which progress in the x direction.

E i ¼ E ix , 0, Eiy eiðki riωtÞ ð18Þ

H i ¼ 0, H iy , 0 eiðki riωtÞ ð19Þ
Di ¼ E0 Ei E i ð20Þ
The wave vector
ki ¼ ðβ; 0; ki; z Þ
where β ¼ kx—along x.
In absence of charges and currents (ρ ¼ 0, J ¼ 0), we can write:
k 1,z =E ¼ k2,z =E ð21Þ
The field exponentially decays into the respective half-spaces: Ei ! exp(ki;z).

Comparing this with the relation (21), when the dielectric constants of the two
materials are of the opposite (i.e., E1 ¼ E2). SP can only exist at the interface
between a metal (E < 0) and a dielectric medium (E > 0) [4–6].
In general, the exponentially decaying evanescent nature of the electromagnetic
wave that propagates at the interface between the dielectric plasma and oscillating
electrons in a metal leads to the formation of surface plasmons, also known as
surface plasmon polaritons.
The penetration depth of the field into the dielectric medium is typically of the
order of half wavelength in the medium.
In surface plasmon, these oscillations in which light is focused onto a thin metal
film through a glass prism and reflection is detected as shown in Fig. 4.
Fig. 4 (a) Light focused onto a metal thin film through a glass prism and reflection is collected and
analyzed. (b) Graphical representation of the LSP and absorbance spectra obtained on nanoparticles
In 1983 Liedberg, Nylander, and Lundström introduced SPR into immune sen-
sors ever since surface plasmon optical biosensors are studied more in detail and
widely used. Technology was developed to study the interaction and changes in SPR
angles with the surface refractive indexes (RI) could help in detecting the molecular
mass of the biomolecule attached to the metal surface at higher sensitivity [7].
2 Plasmonic Sensors
Here, we discuss two main elements of Plasmonics: SPR or LSPR effects. Surface
plasmon supports two modes of operation, i.e., PSPRs [8] and LSPRs [9], respec-
tively as shown in Fig. 5 [10]. PSPRs are bounded by planar metal-insulator
interfaces (evanescent electromagnetic waves) resulting in oscillations of the con-
duction electrons. LSPRs are oscillating electromagnetic waves on metallic
nanostructures (i.e., nanoarrays, nanocavities, and single nanoparticles). In both
PSPR- and LSPRs-based sensors they respond to change in refractive index when
any targeted species bind to the surface. The process does not require any labels like
in the case of chromophore and fluorophore as visible in other optical sensors.
Fig. 5 Schematics of PSPR (left) and LSPR (right) sensing system (Jatschka, J., Dathe, A., Csáki,
A., Fritzsche, W., & Stranik, O. (2016). Propagating and localized surface plasmon resonance
sensing—A critical comparison based on measurements and theory. Sensing and biosensing
research, Volume 7, March 2016, Pages 62–70. Open access article, under a Creative Commons
CC-BY license) [10]
As in Fig. 5 in the case of SPR, polarized light graces the thin film surface at the
interface with different refractive materials. After striking the surface, the reflected
light becomes evanescent. Due to Kretschmann configuration [11], the SPP waves
on gold or silver films are optically excited. The change in surface property results in
an attenuated reflectance through the shift in angle in SPR signal. Kang et al. [12, 13]
can detect the biomolecules by adsorption of metal ions. In Fig. 5 (LSPR), SPR
sensitiveness is due to the shift in angle due to the change in the concentration of
target metal ions.
Modification of PSPR has been done by changing the surface structure and
molecular binding sites within the evanescent field. In LSPR-based sensor, tuning
of shape, composition, and size helps sense the analytes in nanoparticle-based
sensing which is an advantage over PSPR-based techniques. Recently, researchers
have [14–18] explored nanoparticle sensors with tunability, sensitivity, and in vivo
applicability which serves as an excellent probe.
2.1 PSPR Thin Film-Based Nanosensors
In this type of sensor, the substrate surface is covered with a metal layer. Surface
plasmon polaritons (SPPs) are generally excited onto the surface of thin films using
grating or prisms couplers [8] by propagating from a dielectric-metal interface with
an exponentially decaying curve up to a few micrometers. On account of this, there is
a change in the refractive index which changes the plasmons resonance conditions. It
is interpreted as a change in intensity, wavelength, or angle shifts required for
sensing applications. Otto [19] in 1968 had conceptually demonstrated the surface
Plasmon phenomenon. Moon et al. [20], done sensing of metal ion adsorption on
functionalized thiols surface, have shown increment in sensitivity by adding hydro-
philic molecules which increases adsorption rate.
Mesoporous thin films (MTFs) based devices have high specific surfaces and
easy manufacturability in their composition. They can be easily deposited onto a
wide variety of substrates. MTFs [21, 22] are characterized by their thickness,
refractive index, pore size, pore spatial distribution, pore accessibility, wall crystal-
linity, and mechanical properties. Kang et al. [13] have used MTF for observing the
change in optical contrast due to the placement of the sample at different distances
from the sensor surface. Massad-Ivanir et al. [23] have studied mesoporous Si film,
fabricated through an electrochemical anodization process, has been used as a
sensing element of the biosensor. Monoclonal antibodies are attached to detect
Escherichia coli K12 bacteria. The biosensor is exposed to the target which is
trapped onto the antibody-modified porous Si surface. The change in the optical
spectrum proves the possible detection of 104 cells/mL.
Sometimes PSPR and LSPR techniques have been combined to get another type
of biosensors. PSPR requires prism couplings which depend on another component.
With the advent of new lithographic techniques, surface plasmons excitation can be
done using sub-wavelength structures. Nanoholes and nanoislands work like prism
coupling. Arrays of nanoholes have been fabricated on gold film surfaces [24]. It had
been used to monitor the binding event on a gold surface. A sensitivity of 400 nm per
refractive index unit has been reported. Plasmonic biosensor based on the multiwall
reader has been designed [25] and tested for the detection of Ig. A 96-well hole of
gold has been fabricated in 4-in. glass photolithographically for reading read several
prostate-specific (PSA) antibodies. Optical biosensing platform based on plasmonic
nanoholes array, fabricated by deep lithography technique, with varying pitch size
( p ¼ 500, 500 and 600 nm), hole diameter (d ¼ 200, 220, and 240), and gold
thickness (t ¼ 100, 150 and 200 nm) have been demonstrated [26]. A sensitivity of
409.4 nm/RIU and the surface mass sensitivity is 1.802 nm/ng/mm2 have been
reported.
Nanoislands from the metallic material have been fabricated for plasmonic
biosensing. Solid-state dewetting or agglomeration process of minimization of
surface energy w.r.t. surface interface required for the formation of nanoislands of
gold films. Abbott et al. [27] have studied the solid-state dewetting process for the
formation of nanoislands from the deposited films which is further studied by other
authors [28, 29] on thermodynamics and kinetics of the films. Nanoislands from Ag,
Pt, Pd, and Cu films have been also prepared apart from the gold films
[30, 31]. Bathini et al. [32] have fabricated gold nanoislands for early detection of
cancer. They have used the LSPR technique with gold nanoislands where there is the
interaction of exosomes and peptides called Venceremin or Vn96. Preliminary
results have shown the shift in the plasmonic peak with changes in the exosomes
concentration. This demonstrates label-free detection. Ozhikandathil et al. [33] have
studied the bovine growth hormone detection by fabricating the three-dimensional
gold nanostructures using the convective assembly method. This is based on the
LSPR. The assembly has been integrated with a microfluidic structure and spectral
measurements have been carried out using the ultraviolet visible spectrophotometer.
In conclusion, PSPR-based methods have been successfully commercialized for
many field applications. However, it is less suitable for in vivo detection.
2.2 LSPR-Based Nanosensors
Localized surface Plasmon resonance (LSPR) is a simple, effective, label-free, cost-

effective, and rapid method of bio-detection with nanoscale spatial resolutions. It is
robust and selective in nature. The basic principle is a resonant oscillation of
electromagnetic waves (delocalized conduction electrons) on metallic nanostructure
like an array of metallic nanoislands [34], nanorings [35], nanoholes [36] thin films.
Even nonmetal-based (e.g., graphene, silica, and carbon nanotubes) nanoparticles
have been used to analyze various biological analytes [37, 38]. The spatial
nanostructures are fabricated by techniques like Wet seed-mediated chemical reduc-
tion method, electron beam lithography, nanosphere lithography process, and
nanoimprint lithography [39, 40].
Fig. 6 Schematic of LSPR

detection technique
LSPR signal detection depends on three major parts: a light source, a sensor chip,
and a spectrometer optical detector as shown in Fig. 6. The light source is incident on
the sample chip. The sample chip is covered with conducting layer. It is
functionalized with the ligand. Then, the whole construction is fed to the target
environment where the analyte is attached to a ligand. When light is passed through
this combination, wavelength shifting is observed which is detected by a detector.
This is the principle used for biosensing applications. Change in extinction wave-
length maximum, λmax, is observed which is the change in the refractive index.
Reflection-based optical systems have been used for nontransparent substrates.
Haes and Van Duyne [41, 42] had fabricated the borosilicate glass substrate. On
the substrate, they made the biotin attachment on triangular silver nanoparticles
through a linker. They have measured the antibody-antigen, nucleic acid hybridiza-
tion, and protein-carbohydrate through the LSPR measurements in transmission
mode. Haes et al. [43] have used this for the detection of a biomarker for Alzheimer’s
disease. Alivisatos et al. [44] have mixed the single-strand DNA withNPSs which
form aggregation. The color change indicates different DNA strands. The combina-
tion of microfluidics and optical fiber for integrated techniques of detection is a very
elegant mechanism. Yonzon et al. [45] have studied the integrated design with metal
NPs on-chip for low sample volumes and monitored the shift in LSPR peaks. Cheng
and Chau [46] have developed fiber-based LSPR detection technology. Cheng et al.
have attached the gold NPs on the fiber end for detection. That is the advantage of
LSPR for small volume detections.
Various researchers [9, 47, 48] have sophisticated nanoscale detection techniques
with dark-field microscopy-based optical systems. The advantage of using this
resolution is up to the nano level which can detect molecules at the very lowest
dimensions making the systems very sensitive, parallel detection, real-time tracking,
as imaging by nanoparticles without any additives and low volume requirements.
3 Plasmonic Materials and Its Applications
Here, the section mainly discusses plasmonic materials that cover metal, polymer-
based nanomaterials, and their application in various fields such as drug delivery,
imaging, sensing, and photothermal therapy.
3.1 Metals
Metallic nanoparticles, due to their excellent optical, catalytic, and photothermal

properties, have gained immense interest especially for, optical switching,
nanocatalysis, nano sensing, magneto-plasmonic systems, drug delivery, and cancer
diagnosis and treatment. The intense plasmonic electromagnetic fields arising from
LSPR could be accounted for photonic and photothermal properties (mainly gold
and silver) of plasmonic nanoparticles [49–54].
The two criteria that need to be tailored for the nanoparticle form such as
optimizing the strength of the plasmonic field and distributing the nanoparticle
chosen for the plasmonic enhancement and tuning the LSPR peak to the optical
absorption in regions of the visible spectrum and NIR are necessary for different
optical enhancement applications. The radiative process can be enhanced in the
visible and NIR regions using symmetrical shapes (such as circles, cones, triangles,
shells) or asymmetrical forms (viz., wires stars and rods). Owing to the wide range of
wavelengths for the tenability of LSPR and the presence of a strongly enhanced
strong field, gold nanocages and nanorods (AuNCs and AuNRs) are usually help-
ful [49, 50, 54].
The LSPRs of gold nanorods are controlled by altering the aspect ratio, whereas
resonance of gold nanocages is modified by reducing the wall thickness and altering
the outer size.
Solid metallic nanoparticles have catalytic properties owing to the presence of
numerous atoms which are kinetically active on the sides, the presence of defects on
their surface. Their properties are further enhanced by a high surface-to-volume ratio
and numerous kinetically active atoms on the sides or defects that are present on the
surface of the nanoparticle. Further, hollow or porous particles intensify the catalytic
properties. The confinement cage effect is likely to be the cause of these changes
[52, 53].
3.1.1 Preparation of Solid and Hollow Nanoparticles
The seedless and seed-mediated approaches (with various shapes, sizes, and com-
positions) have been usually employed to prepare metallic nanoparticles. Both
techniques involve the development of a small cluster seed followed by the growth
within the seedless solution or seed-mediated solution. The size and shape of the
nanoparticles can be put in order by tuning the capping rate [49, 54]. Further, to
modify the dimensions of the nanocrystals various techniques including physical-
chemical and optical methods have been employed. The physical method used for
annihilating the symmetry of growth of nanocrystals depends on the difference in the
kinetics of crystallization and also its thermodynamic stability. These effects could
be modulated by a change of the amount of precursor used that is silver and/or also
by modifying the capping material. During the growth of nanocrystals changing their
reduction kinetics can be used for breaking/altering its symmetry [55, 56].
Also adding oxygen ions or chloride ions to modify the seed sites can be used to
derive a single crystalline structure of nanoparticles and the growth symmetry is
broken [56, 57]. A new mechanical method that employs high stirring speed to break
the growth symmetry of silver nanocrystals has been found to be in recent use
[58, 59].
The abovementioned methods are used for manufacturing nanostructures which
are solid and hollow nanostructures that cannot be prepared using these techniques.
There are three alternative methods used for the preparation of hollow
nanostructures.
Mohwald and his group had introduced a method based on a template that
involves the use of silica beads for the deposition of metal atoms and then etching
the same template using H2O2 and HCl. However, the nanoparticles are thus
prepared to have a rough surface which renders them less useful [60]. Kirkendall
metallurgical effect was used to develop the second method This involves a reaction
interface without equilibrium which facilitates diffusion of counter atoms. As the
flow rates and sizes of elements are nonidentical, within the nanoparticle, it leads to
the formation of an internal vacancy. However, only composite nanoparticles (hol-
low) could be synthesized using this method [53, 61].
However, the galvanic replacement approach is the most competent technique
used to produce hollow nanoparticles. This approach is based on galvanic oxidation
of ions of nanoparticle template by an ion of metal in solution. Oxidation of multiple
atoms followed by dissolution of the same on the surface renders the production of
the cavity. Further, this results in the retention of nanoparticles’ dimensions along
with the formation of a central cavity [50, 62].
The technique was upgraded in 2014 by Mahmoud et al. to prepare transition
metal nanocages. They performed galvanic replacement carried out at an optimum
temperature and optimized the rate at which the salt was added to template solution
to develop nanoparticles that were hollow and also possessed catalytic potential.
Application of galvanic replacement to nanoparticles with a hollow structure and
having double-shell resulted in the production of bimetallic nanoparticles containing
plasmonic and non-plasmonic metals. EDX-SEM mapping along with HR-TEM was
employed to examine the structure of the double-shell hollow nanoparticles precisely
[49, 63–66].
3.1.2 Assembly of Nanoparticles on a Substrate
Small size and challenges encountered while handling nanoparticle and their recov-
ery is the main limiting factor in their application. To resolve the inefficient handling
of nanoparticles, different techniques have been proposed. For example, if
nanoparticles are to be formed substrates surface, nanosphere, and electron beam
lithography techniques could be explored [49].
Colloidal chemical techniques are extensively used to synthesize nanoparticles.
These methods have been used to prepare nanoparticles with various structural
features. Colloidal nanoparticles however also have stability and recycling concerns.
To solve these issues, Mahmoud et al. proposed microparticle supports for loading
and the Langmuir-Blodgett techniques.
3.1.3 Plasmonic Surface Enhancement by Sensors Based on Raman

Scattering (SERS)
Raman signal of analyte molecules that are adsorbed or present within their electro-
magnetic plasmon field on their surfaces could be increased by plasmonic
nanoparticles. This is caused by electromagnetic and chemical mechanisms. Surface
enhancement is observed mostly by the electromagnetic plasmonic process [54, 67].
For a single particle, it is possible to have an increase of 106 in the Raman signal.
However, the presence of the molecule in hot spots of the plasmonic aggregates in
the solid plasmonic region can lead to an increase of the Raman signal by 1014. Tight
coupling of the two solid adjacent nanoparticles between the plasmon fields is
attributed to the much higher surface plasmon field. Therefore, for experiments
using SERS nanoparticle aggregates are preferably used [51, 67, 68].
The distinct SERS action of hollow and solid nanoparticles can be understood by
measuring the increase in plasmon field in the case of AuNFs and AgNCs and their
study in form of dimers having limited separation gap using discrete dipole approx-
imation (DDA). However, combined dimers of the hollow AuNFs indicate compar-
atively lower coupling enhancement [49].
3.2 Polymers
Films made of polymers can have a variety of properties, depending on their

monomer constituents and polymer architecture, varying from protection from
corrosion to reduction of adsorption over the surface of the material. Nanoparticles
can be assembled with a much higher immobilization density than monolayer
assemblies. Scientists credit the neutralizing effect of polymer brushes on

nanoparticles for this result. Due to the synergistic effect created by the polymer
and nanoparticle combination, this platform can possess both classes of material’s
properties [69].
LSPR-based plasmonic sensing is one area that benefits from this combination.
Alteration in the local dielectric environment (5–10 nm) brings about shifts in the
peak wavelength of LSPR. LSPR peak wavelength would redshift if biomolecules
are attached to the nanoparticle surface, whereas blue shift would be the result in
case of detachment [70].
The extent of red- or blueshifts produced could be linked based on a substantially
high number of molecules that are either attached or detached. A refractive index-
based LSPR sensor is commonly used to detect single nanoparticles using dark-field
microscopy. Links between two or more nanoparticles lead to “plasmonic coupling”
in addition to refractive index variations. There are even visible changes in the LSPR
spectrum with the naked eye. This phenomenon has been explored for precise
detection of DNA owing to the occurrence of colorimetric changes in the nanopar-
ticle solutions [42, 71].
Nanoparticle assemblies having a high density can be formed with the aid of
polymers. Polyelectrolyte-nanoparticle-polyelectrolyte assemblies are one of the
easiest ways to achieve this. Either a positive or negative charge usually ensures
the stability of most nanoparticles. Further, these nanoparticles could be arranged
between oppositely charged polyelectrolytes.
3.2.1 Hydrogen Sensing Using Metal-Polymer Nanoparticles
For hydride-forming metal nanoparticles, it has been found that polymer coating
layers enhance the sorption rate of hydrogen and sensitivity. This mechanism
enables the arrays of plasmonic nanoparticles to function as optical hydrogen sensors
with unique response metrics. Metal–polymer optical hydrogen sensors with
plasmonic metal-polymer structures presented here are superior to existing hydrogen
sensing technology [72].
4 Applications
4.1 Photothermal Therapy
Due to its minimally invasive nature, photothermal therapy has become a promising
alternative to current cancer management. Photo-absorbers interact with light and
then convert the light energy to heat (as explained above), which causes thermal
damage to the tumor cells. Plasmonic nanoparticles used as phototherapy agents
when compared to the conventional agents can result in a substantial increase in the
light absorption efficiency in the visible range and NIR, along with significantly high
photostability. Simple to perform, this treatment allows patients to recover quickly,

reducing their hospital stay. Photothermal contrast agents of the next generation will
be plasmonic nanoparticles with these properties. It turns out that causing a local
temperature increase damages and eventually destroys cells. Hence, to improve a
target-specific treatment with minimal damage to healthy tissues, it is needed to
increase the contrast of optical absorption between healthy and neoplastic tissues.
Indeed, plasmonic nanoparticles provide the necessary selectivity since they are
capable to be bound or can be internalized into tumor cells following an active or
passive targeting mechanism [73].
4.2 Drug Delivery
The use of light-responsive materials to control drug release precisely and selectively
has emerged as an effective modality to improve treatment selectivity and lower
unwanted side effects. A variety of light-activated nano-carriers that are capable of
preventing the drug from degrading before they reach their target have been devel-
oped. These carriers minimize premature drug release in the circulatory system and
improve drug efficacy. A common nanomaterial used for this purpose is plasmonic
nanoparticles (Au NP). These plasmonic NPs can act as a simple carrier system
where they can bind the drug directly to them or can also act as an active element
when exposed to a laser beam, they can release the drug. To achieve high spatial and
temporal resolution, different approaches have been used. As one example,
functionalizing the surface of nanoparticle using molecules has the ability to bind
the required drug to facilitate the release with the temperature change. Further, NIR
laser irradiation and high intracellular glutathione content can induce controlled
cytosolic gene release [74].
The use of polymeric nano-carriers to control drug release can be coupled with
light-responsive plasmonic nanoparticles, to produce photo-triggered therapies.
Polymer-based nanoparticles, dendrimers, micelles, liposomes, conductive mate-
rials, and capsules have been explored for this purpose. A drug can be loaded into
the inner cavity of polyelectrolyte multilayer capsules, and plasmonic nanoparticles
can be added to their outer walls so that irradiation with NIR light could trigger the
drug release. Several studies have shown that multifunctional capsules can trigger
cytosolic reactions, making them useful as model systems for understanding and
controlling processes that are taking place within cells and the release of the drug.
Besides, lowering the size of these capsules is essential to use these smaller capsules
as an alternative to their use in some applications. Liposomes which are produced
with sizes of 100 nm or even smaller, and can contain plasmonic nanoparticles,
appear as a promising candidate for drug delivery [73].
4.3 Imaging and Sensing
These nanoparticles can act as transducers because PR is highly dependent on the

dielectric environment at the local level. This is achieved by the small changes in the
refractive index (RI) into shifts of scattering and extinction characteristic curve. The
RI of biomolecules is usually greater than that of buffer solution. A target molecule
binds to the surface of the nanoparticle, increases the local RI, and shifts the
wavelength of the PR to red, resulting in increased refraction PR shift used as an
initial input signal for chemical and biosensors that follow this phenomenon. As a
result of this principle, transmission or resonance scattering spectrometry could be
employed to monitor binding events in real-time with high sensitivity. It has been
shown in the first studies that the binding of biopolymers to the surface of CG
nanoparticles has a small effect on the scattering and extinction maxima (about
10–20%) as well as a slight redshirting of the plasmon resonance wavelength over
1–20 nm. Owing to the local electrodynamic nature of PR shifting, shape, size, and
structure of the particle will substantially impact the sensing sensitivity [75].
5 Summary
In this chapter, we discussed the basics of Plasmonics and sensors exhibiting

remarkable sensitivity based on SPR or LSPR effects. The development and pro-
gress over the years in the field of surface plasmonic sensors have been discussed.
The plasmonics interaction between the metallic micro and nanostructures have
paved the way to a promising field of study that has been discussed. This chapter
also discussed the various geometries of the nanomaterials like planar nanofilm,
nanoholes, nanoislands, and nanoparticles, which have profound effects on
plasmonic sensing. The discussion further continues with the integration of such
nanostructure onto the physical, chemical, and biological sensing applications. In the
end, plasmonic applications in the biomedical fields such as photothermal therapy,
drug delivery, and image sensing have been discussed. Overall, the importance of
plasmonics theory, plasmonic materials, and sensing application have been
discussed in this chapter.
Acknowledgments Ajeetkumar Patil grateful to Dr. D.C.Pavate Foundation for Pavate Memorial
Visiting Fellowship to visit University of Cambridge, UK and Prof. Sir. David Klenerman, Yusuf
Hamied Department of Chemistry, University of Cambridge for being the host and Sidney Sussex
College, Cambridge, UK for all the local hospitality.
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Improved Biosensor Device to Diagnose
Malaria Based on One-Dimensional
Photonic Crystal
Ankita, Shivangi Bissa, Bhuvneshwer Suthar, and Anami Bhargava
Abstract In this chapter, we would study one-dimensional photonic crystal struc-

ture that can be used as a biosensor. In order to diagnose, an infected blood sample
has been used as a defect layer in the analysis. It has been observed that the refractive
index of blood changes with the infection stage, which can be identified with the
transmission peak. The study has been further extended to improve the sensitivity of
the biosensor by taking an infected blood sample sandwiched between
metamaterials. The sensitivity of the improved biosensor has been studied with the
thickness and plasma frequency of the metamaterial.
Key words Biosensor · Photonic crystal · Metamaterial · Defect · Transfer matrix

method (TMM)
1 Introduction
Photonic crystal (PhC) has a periodic optical structure that affects the motion of
photons same as semiconductor affects the electrons in solids [1]. PhCs consist of a
periodic structure of alternative high and low refractive indices. The optical period-
icity of PhC is similar to periodic potential in a semiconductor which causes allowed
and forbidden energy bandgap for the electron [2]. Similarly, optical periodicity of
the refractive index also causes allowed and forbidden wavelength or frequency
Ankita
Maharaja Ganga Singh University, Bikaner, Rajasthan, India
S. Bissa
B. Suthar (*)
Department of Physics, M.L.B. Govt. College, Nokha, Bikaner, Rajasthan, India
A. Bhargava
Department of Physics, Govt. Dungar College, Bikaner, Rajasthan, India
https://doi.org/10.1007/978-3-030-99491-4_10
296 Ankita et al.
region of electromagnetic waves. The photon corresponding to the wavelength of the

forbidden region is not allowed to propagate in PhC. Such forbidden wavelength or
frequency region are known as photonic bandgap (PBG) [1, 3]. PBG causes tremen-
dous control over the propagation of photons in PhC. The periodicity of PhC
structure must be of the order of the wavelength of electromagnetic waves. So, the
dimension of PhC structure is micrometer to nanometer as per the wavelength of
electromagnetic wave used to study.
In 1887, Lord Rayleigh experimented with periodic multilayered dielectric stacks
showing bandgap in one dimension. Later in 1987, scientists worked on periodic
optical structures with two dimension after that called photonic crystals (PhCs)
[4, 5]. Researchers are attracted to PhC due to their potential applications as optical
filters [6–8], optical switches [9–12], WDM [13–17], optical logic gates [18–20],
sensors [21–25]. Optical sensor application of PhC is important due to high sensi-
tivity, ultra-fast response, and ultra-compact size [23, 24, 26, 27]. Various kinds of
sensors are studied such as temperature sensors, pressure sensors, and biosensors
[25, 28–31]. Various materials have been used to study PhC such as dielectric,
chalcogenide, plasma, metal, and metamaterial [3, 32–37].
Recently, optical biosensors based on PhC is a great deal of interest to the
research community due to their ultra-fast response and high accuracy. Many
researchers worked on biosensor application of PhC for cancer cell detection, the
various component of blood, various virus detection, etc. [28, 38–40]. Porous
dielectric is also used in 1D PhC for biosensor application by various researchers
[41, 42].
According to WHO report 2019, 228 million cases of Malaria were reported
worldwide and 405,000 deaths were reported in 2018 [43]. Malaria is spread to
humans through mosquito bites from infected female Anopheles mosquitos. Delay
in treatment is a root cause for death because due to that a patient can reach a stage
where recovery is difficult and death may occur [44]. An effective detection device is
required to diagnose infection at an early stage with high accuracy. Therefore, we
focus on the optical biosensor device 1D PhC with defect structure to diagnose
Malaria at an early stage. The sample is taken as a defect layer in PhC to study sensor
application. Next, the defect layer of the blood sample is sandwiched between
metamaterials to improve the sensitivity.
2 Theoretical Model and Method
The schematic geometry of 1D PhC with periodic multilayer structure is shown in

Fig. 1. The structure can be expressed as (AB)N, where A and B represent the layers of
high and low refractive index medium and N represent the number of layers. Layer
A and layer B have a refractive index as n1 and n2, respectively. The thickness of
layer A and layer B is defined as d1 and d2, respectively. The complete structure is
achieved by the repetition of combined layer A and layer B. The combination of layer
A and layer B is known as unit cell and its thickness d1 + d2 ¼ a is defined as lattice
constant.
Improved Biosensor Device to Diagnose Malaria Based on One-Dimensional. . . 297
Fig. 1 The schematic diagram of 1D PhC with (AB)N structure
In optics and acoustics, transfer matrix method (TMM) is used to study transmis-
sion and reflection of electromagnetic or acoustic waves across a stratified medium
[45–47]. In TMM, space is divided into small discrete cells. The field on both sides is
coupled through a characteristic matrix, which is known as transfer matrix and the
method as TMM. Here, photonic band structure and transmission spectrum are
calculated using TMM. The characteristic transfer matrices are defined as
2 3
i sin β j
cos β j
Mj ¼ 4 nj 5 ð1Þ
in j sin β j cos β j
where βj ¼ (2π/λ)njdj ( j ¼ 1, 2), nj is refractive index of jth layer, and λ is the

wavelength of incident light. The transfer matrix for the unit cell of 1D PhC is given
as
Md ¼ M1 M2 ð2Þ
If the electromagnetic wave is propagating along z-direction in 1D PhC, then the

field on both sides of the unit cell is coupled by transfer matrix Md as
M d φjz¼0 ¼ φjz¼a ð3Þ
where
3 2

E ðzÞ
E ðzÞ
φðzÞ ¼ ¼ 4 i ∂EðzÞ 5
BðzÞ
kz ∂z
Due to periodicity along the z-direction, Bloch’s theorem is used with Eq. (3) as
298 Ankita et al.

M d φjz¼0 ¼ φz¼a ¼ eika φz¼0 ð4Þ
Using the properties of the transfer matrix, determinate of Md is unit and solve
further. The photonic band equation is obtained as

1 n1 n2
þ sin β1 sin β2 þ cos β1 cos β2 ¼ cos ðkaÞ ð5Þ
2 n2 n1
The complete transfer matrix for 1D PhC structure with N multilayers is given as
Y
N
M 11 M 12
M¼ Mj ¼ ð6Þ
j¼1 M 21 M 22
The transmission coefficient for 1D PhC structure is defined as [47]

2
2ni
T ¼ ð7Þ
ðM 11 þ ns M 12 Þni þ ðM 21 þ ns M 22 Þ
where ni,s are refractive indices of incident and substrate medium, respectively. Here,
the incident and substrate both are taken as air.
3 Photonic Bandgap
As silicon is one of the most common elements in the universe, it rarely exists in the
crust of the Earth as pure form. The majority of silicon has been used commercially
without being isolated and also with little natural mineral processing. Silicon is a
stable element thermally and chemically too. The refractive index of silicon is also
high and real in the IR region. The refractive index value of silicon is 3.669 at
800 nm and constant in the neighboring region [48]. So, we have chosen silicon as a
high dielectric material for this study. The low dielectric region has been taken as air
(with refractive index 1) due to the high contrast of refractive index between silicon
and air. The photonic gapmap has been plotted 1D PhC of (Si/air)N multilayered
structure using the transfer matrix method (TMM) [1, 47]. The photonic gapmap
diagram is shown in Fig. 2.
The photonic gapmap diagram has been plotted with the fill factor. The fill factor
( f ) is defined as the thickness ratio of the silicon layer to lattice constant [1]. The
thickness of the silicon layer changes in such a way that the lattice constant remains
the same. From Fig. 2, the lowest photonic bandgap is wider compared to the upper
band. So, the lower photonic bandgap has more potential application. It is found
from Fig. 2 that the photonic bandgap opens as the fill factor starts from zero and
closes as the fill factor at 1. This is due to the uniform medium at the fill factor both
Fig. 2 The photonic gapmap diagram for 1D PhC
as 0 and 1. As the fill factor increases the photonic bandgap starts to increase but
shifts towards the lower frequency region. The lowest photonic bandgap achieves
the highest photonic bandgap at 0.16 value of fill factor. After this, the photonic
bandgap decreases with the fill factor but still shifts towards the lower frequency.
The photonic bandgap shows a redshift with the fill factor.
The photonic band structure of 1D PhC of (Si/air)N multilayered structure (with
N ¼ 10) is plotted using TMM. The thickness of silicon and air layers are taken as
0.16a and 0.84a, respectively. The photonic band structure diagram is shown in
Fig. 3.
From Fig. 3, it is seen that the lowest photonic bandgap is from 0.217 to 0.475 at
the normalized frequency (ωa/2πc). The widest photonic bandgap is achieved as
0.257 at the normalized frequency (ωa/2πc). The lattice constant (a) is chosen as
250 nm to obtain the mid value of photonic bandgap at 800 nm. In this case, the
photonic bandgap exists from 526 to 1152 nm. The photonic bandgap value is equal
to 626 nm. This photonic bandgap has been used for the next sensor application.
300 Ankita et al.
Fig. 3 The photonic band structure of 1D PhC of (Si/air) multilayered structure
4 Photonic Crystal as Optical Sensor

4.1 Defect in Photonic Crystal
Defect in PhC can be introduced by changing the thickness or refractive index of a

single layer in 1D PhC structure. A defect in 1D PhC is defined as (AB)ND(BA)N.
Here, D is a defect layer between 1D PhC multilayered structure and N is taken as
5. The thickness and refractive index of defect layer D are taken as dd and nd,
respectively. The 1D PhC with defect layer is as shown in Fig. 4.
The break in periodicity of regular structure may introduce a localized state in the
PBG. The localized state allows transmission through the structure in PBG region.
The localized state depends on the thickness and the refractive index of the defect
layer. The transmission peak corresponding to the localized state shifts with the
variation in the thickness as well as the refractive index of defect layer. Therefore,
the localized state can be shifted with the change in the refractive index of defect
layer while the thickness is taken as constant. Such properties of 1D PhC with defect
layer can be used to detect or sense the refractive index of the defect layer. In this
way, 1D PhC with defect layer can be used for sensing applications such as pressure
sensor, temperature sensor, and biosensor [21, 24, 25, 28, 49].
Fig. 4 The schematic diagram of 1D PhC structure with defect layer
5 Biosensor Application
The refractive index of RBC is an optical parameter, which can be used to access the
concentration and biochemical information of the RBC [44]. Here, we have consid-
ered a blood sample to detect. The parasite Plasmodium falciparum is known to
replicate in infected RBCs, leading to three stages described in our work. As the
thickness of the defect is fixed, the refractive index is measured by the density of
cells. Here, the simulation has been done for the pure phase of RBC which exists at
wavelength λ ¼ 800 nm [50]. Hemoglobin (32%) and water (65%) are the main parts
of RBC, so the concentration of hemoglobin leads to a change in the refractive index.
The concentration of hemoglobin in RBC CHb(x, y, z) can be used to find refractive
index nz(x, y) as

nz ðx, yÞ 1
CHb ðx, y, zÞ ¼ 1 ð8Þ
nwater βðλÞ
Here, nwater is refractive index of water and β(λ) ¼ 0.001939 dL/g at wavelength
of 800 nm.
Now, we have used the above 1D PhC with defect as a biosensor to diagnose
Malaria. For different infection stages of Malaria, i.e., Ring, Trophozoites, and
Schizont stage, the refractive index has been obtained using hemoglobin concentra-
tion with β(λ) of a healthy person. The defect layer has been taken as the blood
sample for various infection stages of Malaria to diagnose. The thickness of the
defect layer was taken as dd ¼ 4 μm fixed. The rest of the parameters of PhC has been
taken the same in the previous study. Therefore, the transmission peak of the
localized state has been plotted using the transfer matrix method corresponding to
various infection stages of Malaria. The plot of transmission is as shown in Fig. 5.
302 Ankita et al.
Fig. 5 Transmission spectra of 1D PhC with defect for different stages of Malaria
Table 1 Refractive index of blood cells, wavelength of defect state, quality factor in different
stages of Malaria
Infection stage of Malaria Refractive index Wavelength (nm) Quality factor
Normal stage 1.408 803.15 3.92 106
Ring stage 1.396 796.75 3.94 106
Trophozoite stage 1.381 788.77 3.98 106
Schizont stage 1.371 783.45 4.02 106
The transmission peaks obtained are quite separated corresponding to blood

samples of various infection stages of Malaria and a healthy person. So, the infection
stage of Malaria can be easily diagnosed in the early stage. The early stage diagnosis
helps in medical treatment and can save a life. As the thickness of the defect layer is
fixed, it is found that the transmission peak depends on the refractive index of the
blood sample. In a blood sample, the concentration of RBS is distributed in a quasi-
homogenous manner. When the cells become infected with parasites, then the
structural and biochemical changes in RBCs cause the heterogeneous spatial distri-
bution. Thus, asymmetrical distribution of the hemoglobin occurs, which leads to a
change in the refractive index. An infected RBC’s optical properties are also affected
by the presence of hemozoin corresponding to low values of refractive index as
compared to microscopy [51]. The calculated mean values of the refractive index are
shown in Table 1.
The important qualitative parameter of an optical sensor is a quality factor (Q),

which is defined as the ratio of central wavelength and wavelength difference at full-
width half maximum (FWHM)
Central wavelength λ
Q¼ ¼ ð9Þ
FWHM Δλ
The transmission peaks and the quality factors for various infection stages of
Malaria and healthy blood samples are tabulated as shown in Table 1.
From Table 1, it is seen that the wavelength for the blood sample of a healthy
person is obtained at 803.15 nm. While the transmission peak corresponding to the
first infected stage of Malaria (Ring stage) is obtained at 796.75 nm. Next, the peaks
are obtained at 788.77 and 783.45 nm in the Trophozoite stage and Schizont stage,
respectively. The transmission peak shows a blue shift with the increase in parasite
concentration infection due to Malaria. The quality factor is achieved very high
(order of 106) [21].
The other very important parameter of the sensor device is sensitivity. The
sensitivity is defined as the shift in transmission peak wavelength per unit refractive
index. To obtain the sensitivity of the proposed biosensor device, the wavelength of
defect state is plotted with the refractive index of the defect layer as shown in Fig. 6.
From Fig. 6, it is seen that the wavelength of the transmission peak shows linear
shifting with the refractive index of the infected blood sample. With the linear curve
fitting in transmission peak and refractive index, the slope of the curve, i.e., the
sensitivity is obtained as 532.54 nm/RIU. The sensitivity is quite high. So, 1D PhC
with the defect can be used to diagnose the infection of blood in an early stage of
Malaria.
805
y = 532.54x + 53.33
R2 = 1
800
Wavelength (nm)
795
790
785
780
1.365 1.37 1.375 1.38 1.385 1.39 1.395 1.4 1.405 1.41
Refractive Index
Fig. 6 Transmission peak wavelength with refractive index of blood sample

304 Ankita et al.
6 Improved Sensitivity of Biosensor Device
In the last section, we have discussed 1D PhC with defect structure as a biosensor for
Malaria diagnosis application. The high sensitivity has been achieved, which helps
to diagnose infection of Malaria in an early stage. Here, we are introducing a new
structure to improve the sensitivity of the device. For this, the infected blood sample
is taken as sandwiched between two metamaterial layers and used as the previous
defect layer. Now, the structure is defined as (AB)NMM/D/MM(BA)N, where MM is
a new layer of metamaterial is introduced on both sides of the defect layer as shown
in Fig. 7.
Here, we have used double negative metamaterial as MM layers. The permittivity
and permeability of double negative (DNG) metamaterial are defined as
ω2ep ω2mp
εmm ¼ 1 and μmm ¼ 1 ð10Þ
ω2 ω2
where ωep is electric plasma frequency and ωmp is magnetic plasma frequency. The
refractive index of DNG is defined as
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
nmm ¼ ðεmm μmm Þ ð11Þ
From Eq. (10), it is clear that above the plasma frequency, the permittivity and
permeability both are positive and it behaves like normal dielectric material. But
below plasma frequency the permittivity and permeability become negative and it
behaves similar to metal or more. The thickness of the MM layer is defined as dmm.
In this case, the transmission peak depends on both the thickness of the MM layer
and the plasma frequency. Therefore, the effect of plasma frequency and thickness of
the MM layer has been studied separately.
Fig. 7 The schematic diagram of (AB)NMM/D/MM(BA)N

6.1 Effect of Plasma Frequency
Here, we have studied the effect of plasma frequency on the transmission peak for
the structure shown in Fig. 7. For this, the thickness of the MM layer is taken fixed as
dmm ¼ 100 nm. Both electronic and magnetic plasma frequency values are taken
equal (i.e., ωep ¼ ωmp). The rest of the parameters are taken the same as the previous
study. The plasma frequency values are taken as 2.5 1014, 4.5 1014, 6.75 1014,
8.75 1014, 10 1014 Hz for this study. For these plasma frequencies, the
sensitivity and quality factors are tabulated as shown in Table 2.
From Table 2, it is seen that the sensitivity is small compared to the previous
study without MM layer at low plasma frequency. The sensitivity increases with the
plasma frequency of metamaterial. The sensitivity has been achieved up to
773.10 nm/RIU at plasma frequency 10 1014 Hz. Whereas the quality factor
decreases with the plasma frequency of metamaterial. The higher value of a quality
factor is desired to unwanted loss of resonant mode. It also helps to increase the
detection power. Therefore, the plasma frequency 8.75 1014 Hz is quite optimized
to have a good sensitivity as 634.30 nm/RIU and good quality factor of 2.61 106.
6.2 Effect of Thickness
In this section, we have studied the effect of the thickness of the MM layer on the
transmission peak for the structure shown in Fig. 7. For this, the plasma frequency of
the metamaterial is taken as ωep ¼ ωmp ¼ 8.75 1014 Hz. The remaining parameters
of the structure are taken the same as the previous study to observe the effect of the
plasma frequency of the MM layer.
Table 2 The sensitivity, quality factor with various plasma frequencies

Plasma frequency (1014 Hz) Sensitivity (nm/RIU) Quality factor (106)
2.50 511.11 3.27
4.50 565.68 3.10
6.75 625.35 1.53
8.75 634.30 2.61
10.00 773.10 1.25
Table 3 The sensitivity, quality factor at the various thickness of the MM layer
Thickness of MM layer (nm) Sensitivity (nm/RIU) Quality factor (106)
50 592.27 1.59
100 634.30 2.61
140 835.26 1.13
230 1369.07 0.69
275 931.75 2.05
306 Ankita et al.
From Table 3, it is seen that the sensitivity increases with the thickness of the MM
layer. At a certain thickness of MM layer 230 nm, the sensitivity attains the highest
value equal to 1369.07 nm/RIU. After that, the sensitivity decrease with an increase
in the thickness of the MM layer. The quality factor achieved the maximum value at
the thickness of 100 nm and the minimum at the thickness of 230 nm. So, the highest
sensitivity is achieved at the thickness of 230 nm, while the highest quality factor is
achieved at the thickness of 100 nm. On the other hand, the moderate value of the
sensitivity and the quality factor are achieved at the thickness of 275 nm.
7 Conclusion
In this chapter, we have studied 1D PhC with defect layer as optical biosensor to
diagnose Malaria. The sensitivity and quality factor are achieved as 532.54 nm/RIU,
4.02 106, respectively. Next, the sensitivity of the optical biosensor has been
improved by taking infected blood sample sandwiched between MM layer as
complete defect layer of 1D PhC. In this way, the sensitivity is improved and
attained as 1369.07 nm/RIU. So, such sandwiched defect structure may be applied
to other sensor devices to improve efficiency.
Acknowledgments One of the authors (Ankita) is thankful to UGC, New Delhi for financial
support as Junior Research Fellowship.
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U-Bent Fiber Optic Plasmonic Sensors:
Fundamentals, Applications, Challenges,
and Future Directions
Christina Grace Danny, Hariharan Manoharan, Sangeeta Yadav,

V. V. R. Sai, and Jitendra Satija
Abstract Plasmonic fiber optic sensors have garnered immense interest in the past
two decades owing to their inherent structural, functional, and operational benefits.
In particular, U-bent fiber optic sensors with their high evanescent wave absorbance
sensitivity offer a unique advantage of efficient monitoring of the optical extinction
properties of the plasmonic nanoparticles for the development of a variety of sensing
applications. This chapter describes the fundamentals of sensing in the LSPR-based
U-bent fiber optic probes. Various factors affecting the performance of plasmonic
U-bent probes such as nanoparticle size, shape, geometrical design, and other fiber
parameters are discussed in detail. In addition, this chapter provides in-depth cov-
erage of various sensing strategies developed for U-bent plasmonic fiber optic sensor
and their applications towards a variety of chemicals and biosensors. Although these
plasmonic sensors could achieve the detection limit down to the attomolar levels of
the analyte, concerted efforts are needed towards the translation and commerciali-
zation of U-bent plasmonic fiber optic sensors to devise a low-cost, field-deployable,
point-of-care diagnostic system.
Key words U-bent probe · Localized surface plasmon resonance (LSPR) · Optical
biosensor · Metal nanoparticle · Plasmonic fiber optic sensor
C. G. Danny
Department of Electronics and Instrumentation Engineering, M.S. Ramaiah Institute of
Technology, Bengaluru, Karnataka, India
H. Manoharan · V. V. R. Sai (*)
Biomedical Engineering Laboratory, Department of Applied Mechanics, Indian Institute of
Technology Madras, Chennai, India
e-mail: vvrsai@iitm.ac.in
S. Yadav
School of Biosciences and Technology, Vellore Institute of Technology, Vellore, Tamil Nadu,
India
Centre for Nanobiotechnology, Vellore Institute of Technology, Vellore, Tamil Nadu, India
J. Satija (*)
Centre for Nanobiotechnology, Vellore Institute of Technology, Vellore, Tamil Nadu, India
https://doi.org/10.1007/978-3-030-99491-4_11
310 C. G. Danny et al.
Plasmonic fiber optic sensors have garnered immense interest in the past two
decades owing to their inherent structural and functional advantages. Typically, a
plasmonic fiber optic sensor comprises of an optical fiber probe decorated with metal
nanoparticles (MNP), where the MNP plays an important role in the sensor and the
optical fiber serves as the transducer to measure the change in the MNP optical
properties, while this combination enhances the sensitivity and overall sensor per-
formance. To date, a variety of fiber optic plasmonic sensors have been realized by
employing various combinations of optical fiber probe design, type of MNP, and
sensing modalities. These include straight, tapered, coiled, and bent fiber probes with
MNP like gold, silver copper, platinum, etc. [1–3]. Among these, U-bent optical
fiber probe-based plasmonic probes have received considerable attention due to their
ultra-high sensitivity, ease of construction and use, compact ergonomic design with
an option to operate remotely and perform real-time analysis. In addition, the U-bent
configuration allows the ultra-low concentrations of the analyte detection in a very
low sample volume (<50 μL). These plasmonic probes are highly sensitive and have
been extensively used to detect a variety of analytes such as proteins, DNA, small
molecules, pathogens, and toxic compounds. This chapter describes the develop-
ment of U-bent plasmonic probes with the highlight of a theory of sensing, fabrica-
tion methods, and important sensor applications.
1 The Concepts of a Plasmonic U-Bent Fiber Optic Sensor
Light travels in an optical fiber by virtue of total internal reflection (TIR). The
propagation of light can be viewed as different modes (transverse field distributions
of electromagnetic wave) or rays propagating at different angles in a cylindrical
waveguide. For light to propagate without loss inside the optical fiber, the propaga-
tion constant of the mode (eigenvalue solution of the Maxwell equation) needs to be
real (modes with complex values are lossy), or the angle that the ray makes with the
normal of the interface should be higher than the critical angle. In U-bent optical
fiber probes, the propagation of light and thereby the sensitivity is influenced by the
decladding and bending parameters.
1.1 Effect of Decladding
In a straight optical fiber, the lower order modes (rays that travel along the optical
axis) have almost all their optical power confined within the fiber core. However, the
higher order modes (rays that travel with propagation angle close to the critical
angle) have a significant fraction of their optical power guided close to the core-
cladding interface. When an optical fiber is decladded and placed in an aqueous
solution, the refractive index (RI) of the aqueous solution is incorporated in Max-
well’s equations (instead of the cladding RI) to estimate the propagation constants
U-Bent Fiber Optic Plasmonic Sensors: Fundamentals, Applications. . . 311
Fig. 1 Light propagation showing the (a) refractive losses and (b) evanescent power availability in
whispering gallery rays of a U-bent fiber optic probe. Figure 1a is reproduced with permission from
[5]
and optical power. Typically, the RI of aqueous solutions is much lower than the RI
of cladding; therefore, some of the previously guided modes become leaky or
radiating modes. The transmission coefficient of these modes can be estimated
using Fresnel’s equations. The optical power in these modes is lost to the aqueous
solution and this is known as “refractive loss” (Fig. 1a).
Additionally, as the optical power in the higher order modes is confined to the
core-aqueous solution interface, it is available for interaction with the aqueous
solution. In wave optics, this portion of the light that is exponentially decaying
and propagating almost parallelly to the core-cladding interface is known as “eva-
nescent wave” (Fig. 1b). All the guided modes in an optical fiber have an associated
evanescent wave and the power available in the evanescent region varies based on
the mode distribution which drops exponentially from the interface. The depth of
penetration (dp), representing 1/e times the value of evanescent wave intensity at the
interface is given by Eq. (1). Within this distance from the interface, the presence of
any absorbing molecules such as chromophores causes light loss due to absorption.
This phenomenon is known as evanescent wave absorbance (EWA).
λ
dp ¼ 1=2 ð1Þ
2πn1 sin θz sin 2 θc
2
where n1 is the refractive index of the fiber core, θz and θc are the angle of
propagation and critical angle, λ is the wavelength of propagating light [4].
1.2 Effect of Bending
When optical fibers are bent with a large radius of curvature, their effect on the
optical power distribution is negligible. However, as the radius of curvature is
decreased, the light propagation in the optical fibers is significantly affected, increas-
ing the refractive losses and the evanescent power available at the core-aqueous
solution interface. This is due to the combined effect of geometry and bend-induced
refractive index inhomogeneity (BIRI inhomogeneity) [5].
1.3 Geometric Effects
In a straight optical fiber, the propagation angle remains constant throughout the
length of the optical fiber; however, in a bent optical fiber, the angle of propagation
varies in the bent region. Bending always results in the reduction of the propagation
angle at the outer curvature and this modification of the angle is given by Eq. (2) [6].

1 Rþh
φ ¼ sin sin θ ð2Þ
R þ 2ρ
where φ and θ are the modified and incident angle, R and ρ are bend and fiber core
radii, h is the distance at which the ray is incident on the entrance of the bent region
from the core-cladding boundary.
If the modified angle is lower than the critical angle, those rays are lost due to
refraction, and this principle is utilized in a decladded, bent optical fiber probe to
develop a refractive index sensor by placing the bent region in an aqueous solution
whose RI is to be measured. Typically, coupling of light to the optical fiber results in
uneven distribution of optical power to various rays (or modes). Thus, based on the
power of the rays lost due to refraction, the refractive index sensitivity differs and is
observed more prominently in a decladded-bent optical fiber, being more sensitive to
the RI of the surrounding solution, than a decladded-straight optical fiber.
In a bent optical fiber with a sufficiently low bend radius, all the rays that are
propagating in the bent region propagate by reflection only with the outer curvature.
These rays are known as whispering gallery rays (due to the similarity in propagation
with respect to whispering galleries) (Fig. 2a). This shift in propagation is due to the
reduction in the effective RI at the inner curvature (given by Eq. (3)) such that light
can be guided by only a small part of the optical fiber [7]. This outward shifting of
the light propagation further increases the evanescent field availability and thus the
EWA in a bent optical fiber probe (Fig. 2b).
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
h i
Rþx 2
NA ¼ nco 2 ncl 2 ð3Þ
Rx
where NA is the numerical aperture at x distance from the center of bend axis, nco
and ncl are core and cladding RI, R is the bend radius.
1.4 Material Inhomogeneity Effects
The process of bending uses mechanical and thermal energy to permanently modify
the geometry of the optical fiber causing a shear strain and bending moments in the
plane of bending. Particularly, the strain incurred during the fabrication process is
Fig. 2 (a) Whispering gallery modes (WGM) represented in microspheres—visual, ray propaga-
tion and modes; (b). Whispering gallery rays represented in U-bent optical fiber core. Figure 2a
(right image) is reproduced with permission from [8]
not uniform. It is highly tensile at the outer curvature and highly compressive at the
inner curvature resulting in alteration of the refractive index of the optical fiber core
material. This effect is termed as BIRI inhomogeneity and the equation for deter-
mining the local RI of the fiber core is given as per Eq. (4) and plotted in Fig. 3.

n 2x
neffective at x ¼ ncore 1 core ½P12 νðP11 þ P12 Þ ð4Þ
2R
where x is the distance of the point from the center of the bend axis, ν is the Poisson
ratio, P11 and P12 are Pockels or elasto-optic coefficients. The material inhomoge-
neity effects are pronounced when the bend radius is within five times the fiber core
radius. In this regime, the RI of the fiber core at the outer curvature is significantly
reduced and results in significant refractive losses.
Fig. 3 Gradient refractive

index of plastic optical fiber
core (made of PMMA,
RI ¼ 1.49) due to significant
bending. Reproduced with
permission from [5]
2 Plasmonic Sensing in U-Bent Fiber Optic Probes
The RI- and EWA-based sensitivity of the U-bent optical fiber probes can be
significantly improved using plasmonic nanoparticles/nanostructures which possess
high values of optical extinction and are efficient optical labels due to strong
electromagnetic field confinements. The plasmonic enhancement occurs for
nanoparticles of sizes approximately one-tenth that of the wavelength of the incident
light [9]. Hence, for visible light of approximately 400–700 nm, the sizes of the
nanoparticles are restricted to (approx.) <70 nm.
2.1 Basics of SPR and LSPR
The electromagnetic radiation that is guided in the optical fiber induces charge
separation in the nanoparticles giving rise to a dipole moment. This results in
coherent oscillation of the conduction band electrons at the frequency of incident
radiation. These oscillations exist in the metal-dielectric interface and are collec-
tively known as “localized surface plasmon (LSP)” when they are due to
nanoparticles, and as “surface plasmon polaritons (SPP)” when they are due to
continuous nanostructures (Fig. 4). The extent of optical enhancement achieved
depends on the polarizability (α) of the nanoparticles or the surface plasmon wave
vector (β) of the nanostructure, which is significantly affected by the immediate
sensing environment as explained in Eqs. (5) and (6).
Fig. 4 Schematic representation of (a) localized surface plasmon and (b) surface plasmon polariton
ε εm
α ¼ 4πa3 ð5Þ
ε þ 2εm
rffiffiffiffiffiffiffiffiffiffiffiffiffi
ω εεm
β ðor kx Þ ¼ ð6Þ
c ε þ εm
where a is particle size, Eo is applied electric field (input light), εm is dielectric

constant of the surrounding aqueous medium, ε is the dielectric constant of metal
nanoparticle/nanostructure, kx is surface plasmon wave vector, ω is the frequency of
light used, and c is the velocity of light in vacuum.
2.2 Influence of Shape and Size of Nanoparticles
The near-field and far-field properties of nanomaterials are significantly determined

by their shape, size, and exposed crystal planes. These properties include the extent
of the bulk frequency-dependent dielectric function, multipolar polarizability, skin
depth, near-field electromagnetic coupling, and effective dielectric of

nanoaggregates. The size of the plasmonic nanoparticles affects the dielectric con-
stant and hence the RI of the nanoparticles. The collisions of free electrons, inter-
band electronic transitions, contributions of bound electrons are also modified by the
size of the nanoparticles and affect their optical properties [10]. These properties
have been modeled effectively for spherical particles; however, as the shape gets
complex, discrete dipole approximation (DDA), finite-difference time-domain
(FDTD), or boundary element method (BEM) simulation approaches must be
taken into account for evaluation [11].
As the size of the nanoparticles is increased, a redshift in the wavelength of peak
absorption is observed. Moreover, as the particle diameter approaches the wave-
length of incident radiation, retardation effects become prominent and quadrupole or
higher order modes are excited [11]. With regard to the shape, it is known that
nanoparticles with a high aspect ratio (e.g., nanorods) excite longitudinal plasmon
bands apart from transverse bands. Correspondingly, anisotropically shaped
nanoprisms show four different plasmon resonances (in-plane, dipole, quadrupole,
out of plane dipole); and nanoflowers, triangles, and hexagons with multiple sharp
corners demonstrate increased plasmonic enhancement due to optical antenna effect
[12, 13].
Complex nanostructures such as dimers, trimers, core-shell, and bimetallic
nanoparticles have also been modeled, synthesized using shape-controlling addi-
tives, and used for tuning the absorption peak or generating multi-layered structures
for a variety of applications [12]. However, reproducibility, long-term stability,
biocompatibility, and assembly into appropriate functional architectures are still
challenges that need to be addressed [14].
2.3 Influence of Fiber Optic Probe Parameters

on the Refractive Losses and EWA
The four important parameters that influence the performance of plasmonic U-bent
optical fiber sensors are: (i) geometrical design, (ii) fiber material, (iii) nanomaterial
characteristics, and (iv) optical coupling.
2.3.1 Geometrical Design
The sensitivity of the U-bent optical fiber probes is majorly determined by the bend
ratio, i.e., the ratio of bend diameter to optical fiber core diameter. As the value of the
bend ratio becomes lower, the probe sensitivity increases till it reaches saturation.
This increase in sensitivity is attributed to the geometrical effects as the optical fiber
probe changes from being a two-boundary waveguide to a single-boundary wave-
guide, resulting in the reduction of the light propagation width. With further
reduction in the bend ratio, material aspects become prominent and due to BIRI
effects, a significant increase in the RI sensitivity of these probes occurs [5]. The
reduction in bend ratio also confines the light propagated to the outer curvature of the
probe, resulting in increased evanescent depth and EWA. Hence, while designing a
plasmonic U-bent optical fiber probe, it is important to note that the inner curvature
of the bent region does not contribute to light propagation or EWA. The effect of
other geometrical parameters such as the probe length and the ratio of input length of
the straight region to the output length is also found to be negligible [15].
2.3.2 Fiber Material Parameters
The RI of core and cladding material, elasto-optic coefficients, and the Poisson’s
ratio of the optical fiber core influence the sensitivity of the fiber optic sensors
significantly. Typically, plastic-clad silica fibers have core and cladding RI of 1.45
and 1.42, respectively, whereas PMMA-based plastic optical fiber has core and
cladding RI of 1.49 and 1.41, respectively. Though the cladding is removed in the
sensing region, the numerical aperture and hence the number of modes that are
guided by the optical fiber are determined by the difference in RI between core and
cladding. The difference in the RI between the core and the sensing medium or the
plasmonic material determines the sensitivity of the probe. Additionally, the elasto-
optic coefficients and the Poisson’s ratio affects the extent of the gradient of core RI
due to bending-related deformation [5].
2.3.3 Nanomaterial Parameters
The wavelength-dependent dielectric function or refractive index of the

nanoparticles or nanostructures is the most important parameter that determines
the probe sensitivity. Typically, the effect of nanoparticles on the U-bent optical
fiber probe is estimated through modeling the system as a multilayered structure. For
example, on top of a fiber optic core (layer 1), a layer of functionalizing material
(such as silane) is added (as layer 2) to facilitate the immobilization of plasmonic
nanoparticles. This is followed by nanoparticles (of height/diameter h) (layer 3) and
the probe is surrounded by an aqueous sensing medium (layer 4). In this case, the
effective RI of the surrounding is given by Eq. (7).

1 h h
neff ¼ nsilane þ nAuNP þ nsensing medium 1 , ðh λ Þ ð7Þ
2 λ λ
For nanostructures that are sputtered or deposited directly on top of the optical
fiber core, the system comprises of fiber optic core (layer 1), a thin film of metallic
nanostructure (layer 2), and the surrounding medium (layer 3) as shown in Fig. 5.
The dielectric function of the metallic nanostructure inclusive of the surface
Fig. 5 Schematic showing reflections at core-metal and metal-medium interface, where Fresnel’s
equations are used (S and D refer to light source and detector, respectively)
roughness could be estimated using Maxwell Garnett theory [16]. The size and shape
of the nanoparticles or nanostructures affect the frequency-dependent dielectric
function. The reflection at each layer is estimated through Fresnel’s equations. The
reflection coefficient at the sensitive film interface is given by Eq. (8).
r 1,2 þ r 2,3 e2ikz1 h

r¼ ð8Þ
1 þ r 1,2 r 2,3 e2ikz1 h
where rm,n is the reflectivity of the interface between layers m and n (e.g., m ¼ 1,
n ¼ 2 represents reflection at fiber optic core and metallic nanostructure interface),
h is the height of plasmonic nanostructure, kzn is wave vector in the z-direction on the
nth layer which is dependent on the dielectric function of the respective layers [17].
2.4 Types of Assay

2.4.1 Label-Free Sensing
Label-free detection involves analyte binding on gold nanoparticles coated optical

fiber probes. For intensity-based sensors, absorbance is measured throughout the
assay time using photodetectors [18] or spectrophotometers at selected wavelength
[19]. Time-resolved absorbance response is used to study binding kinetics of
bioreceptors, where a combination of intensity change and redshift can be used to
understand the kinetics, equilibrium state, and dose-response [20]. Other LSPR-
based sensors measure the shift in the peak absorbance wavelength using a spec-
trometer [21]. Label-free assays are usually simple and require a lesser number of
steps. However, one of the disadvantages of label-free sensing is its lower sensitivity
in comparison to labeled assays, limiting the possibility of trace molecule analysis.
2.4.2 Labeled Sensing
Labeled sensing involves the binding of chromophores or plasmonic labels to the

analyte, and the binding of the resulting complex to the optical fiber sensor, which
evokes a much higher absorbance response. This is typically achieved using a
suitable probe in a sandwich assay format, as in the case of a typical lateral flow
assay (LFA) technology. The target analyte is made to specifically bind to the
plasmonic labels, and the resultant complex specifically binds to the optical fiber
probe precoated with (bio)receptors. This results in a higher EWA response than that
achieved using a label-free technique for the same analyte concentration. A variety
of strategies for the implementation of sandwich assay including sequential or
simultaneous assay formats are available and explained elsewhere [22].
2.5 Types of Sensing Techniques
The most common realization of plasmonic U-bent optical fiber sensors is based on
the LSPR absorbance phenomenon. Herein, a plasmonic label is used for amplifying
the evanescent wave absorbance (EWA) response due to the binding of the analyte
on the sensor surface. The binding changes the local refractive index around the gold
nanoparticles such that the absorbance characteristics of the plasmonic layer change.
This modification is either measured as an increase or decrease in the LSPR
absorbance, or (typically) as a redshift in the peak absorbance wavelength.
EWA-based sensing can be achieved in a few different ways as described below.
2.5.1 SPR-Based Sensing
The decladded U-bent region is coated with a thin film of plasmonic material such as
gold or silver. The resonant absorption peak is sensitive to the localized environment
in which the probe is placed. The sensor response, i.e., change in the absorbance
intensity or peak absorbance wavelength, is measured for sensing either analyte
concentration or local refractive index changes. The sensitivity of these probes
depends on the thickness and morphological structure of the thin film [23, 24]. Typ-
ically, SPR-based sensors are fabricated by deposition of a thin film of gold or silver
through sputtering or evaporation. Laser-induced deposition of silver nanoparticles
followed by dip coating of graphene has also been reported to act as SPR sensors for
refractive index measurements [25].
2.5.2 LSPR-Based Sensing
This approach is based on intensity modulation and occasionally measurement of the

peak absorbance wavelength shift [26]. The plasmonic particles are coated on the
fiber probe and optimized for making it sensitive to the analyte of interest [27]. Usu-
ally, prior to the deposition of nanoparticles, physical/chemical functionalization of
the optical fiber probe surface is required to obtain uniformly distributed NP without
their leaching. Additionally, functionalization is required for coating the
nanoparticles with biomolecules such as DNA probes or antibodies to develop the
specific biosensor.
2.5.3 Whispering Gallery Mode (WGM)-Based Sensing
A special form of tunneling ray, with reflection only at the outer core-medium
interface, is termed as whispering gallery ray. When the bend diameter is sufficiently
lowered light propagates as whispering gallery rays concentrated to a limited fraction
of the cross-sectional area of the core. Since the power carried by these rays is mostly
confined close to the core-medium interface, the power in the evanescent field is
high, producing significant loss if the surrounding solution contains highly absorb-
ing molecules. WGM-based sensors are developed on the interference principle.
Macro-bend or micro-bend in the optical fibers are used as WGM based sensors by
analyzing the variation in transmission amplitude in the wavelength spectrum
[28]. These sensors have been developed and tested for the detection of glucose
[28], salt [29], and temperature measurement [30]. Recently, WGM-based sensors
have been used for electric field and magnetic field sensing [31, 32].
2.5.4 Interferometry
Mach Zehnder Interferometer-based sensors have also been developed using bent
single-mode optical fibers. These have been reported to measure micro-displacement
[33], concentration of levofloxacin (using tapered bent optical fibers) [34], and
humidity measurement [35].
2.5.5 Other Sensing Methodologies
Typically, U-bent optical fiber sensors are used in the intensity modulation or shift in
the resonant absorption wavelength mode. However, several other sensing method-
ologies can be realized using U-bent optical fiber sensors. For example, the
decladded U-bent probes have been used for level sensing through scattering-
based optical losses [36]. Plasmonic U-bent fiber optic sensors of PMMA and silica
have been utilized for SERS-based applications, with free-space excitation and
signal collection [37, 38]. Trace molecular detection of explosives has been achieved
using the U-bent optical fiber platform with fluorescent porous film coating [39]. In a
different approach, a long-period grating refractometer sensor has been fabricated by
introducing multiple notches on a PMMA optical fiber using the die-press-print
method followed by bending the fiber in U-shape [40]. A single-mode U-bent optical
fiber coated with magnetic fluid could be used as a fiber loop ring-down (FLRD)-
based sensor for measuring magnetic field [41].
3 Device Instrumentation
To design a miniaturized optical fiber-based device/instrument, the simplest

approach is to interface one terminal of a straight portion of the bent probe to the
light source while the other one is coupled to a detector. The decladded bent region is
dipped in the sample solution for interaction analysis. Therefore, from the device
instrumentation point of view, it is important to understand the four important
aspects of fiber optic sensors, i.e., (i) light source and optical coupling,
(ii) detector and data acquisition, (iii) sample introduction assembly, and
(iv) device packaging.
3.1 Light Sources and Coupling
3.1.1 Optical Coupling
Typically, a polychromatic light source is coupled to one end of the optical fiber
through appropriate coupling optics such as collimators and microscopic objectives.
The power distribution in the optical fiber is such that the rays traveling parallel to
the optical axis will have maximum power in comparison with rays traveling with an
angle close to the critical angle [6]. In addition, if the illumination condition couples
more number of skew rays (traveling near the exterior of the optical fiber with a
higher number of reflections per unit length) in comparison to meridional rays, the
light propagation and the excitation of plasmons will be significantly affected [42].
3.1.2 Light Sources
The light sources that can be used with U-bent fiber optic sensors could be classified
into two categories, i.e., broadband and narrow band. The selection of the light
source depends on the type of sensing and, in turn, determines the type of detector
that has to be used alongside. Typically, for physical sensing, the measurement is not
affected by the wavelength of light used. Hence, any broadband or narrowband light
source with light at a wavelength that is not absorbed by the optical fiber core
material can be used. However, for biosensing applications, the wavelength of the
light source is chosen based on the absorption profile of the analyte (for label-free
sensing) and plasmonic or chromophore label (for labeled sensing). Consequently,
the choice of whether to use broadband or narrowband light source depends on
whether the sensing methodology is based on intensity or shift in the wavelength.
The broadband optical sources that are widely used include tungsten halogen lamp
(360–2000 nm) [21] or white light-emitting diode (430–700 nm). Narrowband light
sources include LED sources of specific wavelength like green LED (λmax ¼ 532 nm)
or red LED (λmax ¼ 630 nm). While selecting the light sources it is important to
verify the suitability of the following parameters for the sensing application at hand.
(i) The intensity profile of the light source should match the analyte chosen. The
intensity at the wavelength of interest should be at least 80–90% of the
maximum intensity offered by the light source. Otherwise, while trying to
increase the intensity of light at the required wavelength, the detector might
reach saturation at other wavelengths. If the sensing application measures shift
in wavelength of peak absorption, it is important to ensure that the light
intensity at the range of wavelength does not differ significantly, affecting the
sensitivity of the detector, and the accuracy of the measurement. Thus, the full
width half maximum (FWHM) range for a narrowband light source has to be
chosen accordingly.
(ii) The intensity of the light source should remain constant throughout the mea-
surement. Typically, the reference readings are taken at the beginning of the
measurement. Thus, the intensity of the light source must be consistent
throughout the experiment. In the case of high-power light sources, provisions
for cooling must be provided so that the source does not get heated up
destabilizing the light source.
(iii) The optical output power of the light source should be chosen based on
applications. For label-free sensing using plasmonically active surfaces,
sources with tunable light intensity are preferred to ensure sufficient light
coupling even after the initial significant absorption by the plasmonic materials.
(iv) Optical coupling of sources such as LEDs should be done using microscopic
objective or collimator for focusing light. The focused light is then coupled to
the optical fiber sensor using an X-Y fiber positioner and bare fiber
adaptors [43].
3.2 Detectors and Data Acquisition System
For measurement of wavelength shift, a fiber optic spectrometer is used as a detector,

whereas for intensity-based measurement applications, a photodiode or CCD detec-
tor is used. The intensity at the detector is deduced from the measured voltage output
[18]. Photodetectors of a large dynamic range can also be used to observe light
intensity loss over four orders [22]. For assays involving measurement of very low
concentrations, amplification of the signal becomes a necessity to obtain a high SNR,
for which a lock-in amplifier is used. Alternatively, smartphones can also be used for
optical coupling, with flash used as a light source and rear camera as the detector.
Signal acquisitions are usually done through proprietary software that allows the
user to set the signal accumulation time and averaging. Signal acquisition time is set
based on the saturation characteristics of the detector and the intensity of the optical
source, to ensure that the detector is not saturated, while the signal is sufficiently
distinguishable from the noise throughout the sensing experiment. Normally, if
averaging is performed for more than over 50 acquisitions, a signal-to-noise ratio
(SNR) of 100 or more can be achieved [43].
3.3 Sample Introduction Assembly
Accurate sampling is important for obtaining reliable measurements. For surface-

sensitive probes like U-bent fiber optic sensors, reliability cannot be improved by
just increasing the sample volume. Integration of microfluidics with U-bent fiber
optic sensor allows: (i) large sample volumes through minute channels, (ii) enhanced
analyte transport and binding kinetics [44] using convection and diffusion, and (iii)
improved mixing of the reagents by suitably designed secondary structures. The
design of a microfluidic device for EWA-based U-bent FOS should consider a
suitable fabrication protocol that is scalable, cost-effective, and reproducible and
can provide efficient sample interaction with the waveguide. In parallel, the
microfluidic device should be chemically, mechanically, and thermally stable with
negligible nonspecific interactions and adequate shelf-life.
Typically, almost all the U-bent fiber optic sensors that have been reported to
date, use a cuvette-type assembly for introducing the samples. The geometry of the
U-bent probes makes it challenging to design and fabricate microfluidic channels
that fit a bent probe. However, considering the benefits and the possible improve-
ment in accuracy and reliability, efforts need to be made for the integration of
microfluidics with U-bent fiber optic sensing.
3.4 Device Packaging
The U-bent optical fiber sensors have a wide dynamic range and can be employed for
a variety of applications. Hence, depending on the utilization, the device packaging
requirements can be varied conveniently. Different device configurations including
hand-held and bench-top device capabilities have been reported. In most cases, an
LED or tungsten halogen light source and a spectrometer are connected to the U-bent
optical fiber probe with additional optical accessories such as collimators and
microscopic objectives. The signal is measured and recorded using the software.
For example, Nair et al. reported a portable optical device setup using narrowband
LED, a driver circuit, voltage-controlled current source, photodetector,
transimpendance amplifier, an analog filter, microcontroller unit, display, and USB
interface [45]. Arcas et al. reported a simpler optical setup with IR light source and Si
photodetector connected to required driver circuits and signal conditioning circuits,

with processing performed using Arduino or any other microcontrollers
[46]. Recently, Murugan et al. developed a P-FAB (plasmonic—fiber optic absor-
bance biosensor) platform for monitoring the optical power loss in a U-bent optical
fiber probe with removable and replaceable cartridge [47]. P-FAB uses gold
nanoparticles as labels and is highly sensitive with a detection capability of a few
hundred analyte molecules in 25 μL of the sample within a 15 min assay. Wen et al.
reported the packaging of U-bent probes in a quartz tube and could be maintained in
position using UV curable glue [48]. This packaging reduces the environmental
impact and allows for easy handling. Additionally, as the sensitivity of the device
depended significantly on the bend diameter, proper and rigid packaging of the
biosensor helped in reproducible and reliable measurements.
4 Fabrication of Plasmonic Fiber Optic U-Bent Probes

4.1 Fabrication of U-Bent Probes
The design of U-bent probes requires an appropriate choice of optical fiber material,
fiber core diameter, and bend diameter. Fused silica glass optical fiber is widely used
to develop optical sensors, but recently plastic optical fibers have gained significant
attention due to their low cost, ease of handling, and high durability. Usually, the
choice of fiber core diameter varies between 200 and 1000 μm, whereas the bend
diameter at the U-region is maintained at 2 to 8 times that of the fiber core diameter.
Both silica and plastic optical fiber can be fabricated in a U-shaped probe in a
multistep procedure as explained.
4.1.1 Fabrication of Silica Glass-Based U-Bent Probes
This technique is based on controlled heat exposure-based bending of the silica

optical fiber near its glass transition temperature. The following steps are adopted to
get the U-bent fiber optic probe of silica fibers (Fig. 6).
(i) Step-I: A piece of an optical fiber of a known length, usually in the range of
30–40 cm, is taken and both the ends are polished to get the efficient light
coupling.
(ii) Step-II: A 1–2 cm middle portion of the optical fiber is mechanically
decladded using a fiber stripper which exposes the core region and serves as
the sensing region of the probe.
(iii) Step-III: This is the critical step in the fabrication of the U-bent probe. The
decladded portion of the fiber is manually bent in the U-shape using a butane
flame at a temperature from 700 to 1000 C. The bend diameter can be tuned by
controlling the flame temperature and the exposure time.
Fig. 6 Schematic illustration of the U-bent fiber probe fabrication
Fig. 7 Fabrication of PMMA U-bent fiber optic probe; (a) Glass capillary tube, (b) Glass capillary
tube containing manually bent PMMA optical fiber, and (c) the PMMA U-bent fiber optic probe
with decladded bent region
4.1.2 Construction of U-Bent PMMA Probe
The PMMA-based plastic optical fiber can be fabricated in the U-shape probe at a
much lower temperature (~100 C) as their glass transition temperature is very less
compared to fused silica. The following method is typically used to fabricate a
U-bent probe of PMMA optical fiber (Fig. 7).
(i) Step-I: A straight optical fiber (~0.5 mm fiber core diameter) of 30–40 cm
length is polished at both end.
(ii) Step-II: The piece of the plastic fiber is manually bent and inserted into a glass
capillary (Fig. 7a and b) of appropriate length and then placed inside a hot air
over at 100 C for 20 min. This heating process creates a permanent deforma-
tion that leads to the formation of a U-bent probe.
(iii) Step-III: The bent region of the probe is dipped in ethyl acetate solution to
remove the cladding material and get the sensing region exposed (Fig. 7c).
4.2 Activation and Functionalization of U-Bent Fiber Probe
The silica glass probe is usually cleaned with piranha solution (70% conc.
H2SO4 + 30% H2O2) for 30 min followed by extensive rinsing with DI water and
drying in a hot air oven at 100 C for 1 h. This helps in generating the silanol groups
at the fiber surface which can be used for covalent attachment of silane molecules
that facilitate the chemisorption of plasmonic nanoparticles. For example, Satija
et al. have reported the immobilization of 3-aminopropyl-triethoxysilane (APTES)
by immersing the cleaned U-bent probe in the 1% APTES solution (prepared in
ethanol:acetic acid mixture) for 5 min followed by excess ethanol wash and oven
drying at 105 C for 60 min [15]. The loosely bound silane molecules are removed
by sonicating the probes in ethanol for 5–15 min. Thereafter, the probes are kept in
the hot air oven at 100–120 C for 60 min to crosslink the immobilized silane
molecules. The silane concentration, incubation time, and condensation temperature
can be tuned as per the application requirement. The silane-functionalized probes
can be stored in the nitrogen ambiance till further use.
The PMMA fiber probes are cleaned by immersing in H2SO4 solution (1 M) for
5 min to generate carboxylic groups on the surface. To generate the amine function-
alities at the sensor region, the probe is incubated in 10% HMDA solution (prepared
in 100 mM borate buffer of pH 11.5) for 2 h. Subsequently, the probe is treated with
NaOH (1 M) for 5 min that reduce the NH3+ groups of HMDA. Finally, the probe is
washed with excess DI and stored in a nitrogen atmosphere till further use.
4.3 Plasmonic U-Bent Probe Preparation
Metallic nanoparticles exhibit excellent optical properties due to the plasmon reso-
nance phenomenon which is extensively studied and utilized for a variety of
applications. In order to generate a plasmonic fiber optic probe, physical vapor
deposition (PVD) and solution-based dip-coating techniques are being widely used
to immobilize/create the desired metal nanoparticles/nanostructures on the surface of
the fiber.
PVD technique includes metal/metal-oxide pulse vapor deposition, sputtering
and thermal evaporation. In this technique, the U-bent probe is placed inside the
metal evaporator chamber as shown in Fig. 8. The metal coating thickness is
controlled by varying the deposition power, time and chamber. To date, gold, silver,
copper oxide, molybdenum disulfide, or zinc oxide coatings have been developed on
U-bent probes using the PVD technique [23, 24, 49, 50].
In the dip-coating technique, the functionalized U-bent probe is immersed in the
colloidal solution of metal nanoparticles for a known duration. Metal nanoparticles
such as gold nanospheres, gold nanoshells, hollow gold nanostructures, gold
nanoflowers, silver nanospheres, and silver nanotriangles have been used to develop
plasmonic U-bent fiber probes through chemisorption or electrostatic interactions
[19, 20, 26, 51–53]. Few reports have advocated the seed-mediated in situ growth
approach to prepare the plasmonic probes (Fig. 9). In this approach, at first gold or
silver seed nanoparticles (<5 nm in size) are chemisorbed on functionalized U-bent
probe. Thereafter, the probes are immersed in the growth solution (containing metal
precursor, reducing agent, and surfactant/stabilizer) which promotes the growth of
the nanoparticles by means of redox catalytic reaction. Modification of seed and
Fig. 8 Sputter deposition of

metal on the U-region of the
probe
Fig. 9 Seed-mediated in situ growth of plasmonic nanoparticles for U-bent optical fiber probe
growth solution composition provides good control of shape, size, and distribution
of plasmonic nanoparticles [38].
5 Applications of the LSPR-Based Optical Fiber Sensors
Advantages of plasmonic U-bent fiber probes, including their low cost, wavelength
multiplexing capability, electromagnetic immunity, low transmission losses, small
size, and low weight, have made them an attractive choice of platform to develop
into a variety of chemical and biochemical sensors. To date, these have been
successfully developed for the quantitative and qualitative detection of biological
molecules (i.e., disease biomarkers, endotoxins, etc.), physical parameters (i.e.,
relative humidity and refractive index), and chemical parameters (i.e., heavy metals)
(Table 1).
328
Table 1 Summary of U-bent fiber optic probe explored for various sensor applications
Optical Nanomaterial
fiber Analyte Matrix Detection principle used Performance parameters References
Silica HIgG PBS buffer Absorbance (plasmonic) AuNPs LOD ¼ 0.17 zM [54]
DR ¼ 1 fg/ml–1 pg/mL
Silica Cephalosporins Simulated human LSPR-based absorbance AuNPs LOD ¼ 0.5 μg/mL [19]
(antibiotics) urine DR ¼ 0.5–10 μg/mL
Silica Cephalosporins Tap water LSPR-based absorbance AuNPs LOD ¼ 10 ng/mL
(antibiotics) DR ¼ 1 ng/mL–1 μg/mL
PMMA Plasmodium Potassium phos- SPR-based absorbance Au film LOD ¼ 264 pM [55]
falciparumglutamate phate buffer DR ¼ 5–250 nM
dehydrogenase (PfGDH;
protein)
Silica Mannosylated PBS buffer and syn- LSPR-based absorbance AuNPs LOD ¼ 1 fg/mL (buffer) [56]
lipoarabinomannan thetic urine LOD ¼ 10 fg/mL (synthetic
(glycolipid) urine)
DR ¼ 5 fg/ml–10 pg/mL
(buffer)
DR ¼ 10 fg/mL–10 pg/mL
(synthetic urine)
Silica Glucose solution Glucose solution LSPR–based wavelength shift GO/AgNPRs Refractive index sensitiv- [26]
and transmission rate ity ¼ 1116.8 nm/RIU
(AgNPRs)
Silica Bacterial Endotoxin free Change in the transmitance AuNPs LOD ¼ 100 ng/mL (direct [57]
lipopolysacchride (EF) water (< 0.001 method), LOD ¼ 0.4 ng/mL
EU/mL) (Sandwich method)
DR ¼ 0.1–100 ng/mL
(direct method)
Silica Mercury Drinking water LSPR-based wavelength shift AgNPs LOD ¼ 2 ppb [27]
DR ¼ 0–200 ppb
C. G. Danny et al.
Silica Mercury Different water LSPR-based absorbance AuNPs LOD ¼ 0.1 ppb (tap water) [58]
sources, sea fish, and LOD ¼ 0.2 ppb (sea fish and
vegetable samples vegetable samples)
DR ¼ 0.1–540 ppb (tap
water)
Silica Mercury and cadmium Tap water and LSPR-based absorbance AuNPs LOD ¼ 0.5 ppb [59]
spiked DI water DR ¼ 0.5–2000 ppb
PMMA HIgG PBS buffer LSPR-based absorbance AuNPs LOD ¼ 0.25 μg/mL [60]
DR ¼ 0.25–10 μg/mL
PMMA Lead (Pb2+) Water Change in output voltage, AuNPs LOD ¼ 2.10 ppb [61]
power, and intensity DR ¼ 1–20 ppb
Silica KMnO4 Aqueous SPR (wavelength and Ag film DR ¼ 102–108 M [24]
absorbance)
Silica Gasoline vapors Air RI change causes a change in AuNPs and LOD ¼ 11 ppm (AuNPS) [62]
LSPR characteristics of AgNPs and 21 ppm (AgNPs);
nanoparticles (wavelength shift) DR ¼ 0–153 ppm (AuNPS)
and 0–144 ppm (AgNPs)
Silica HIgG PBS buffer LSPR-based absorbance change AuNPs LOD ¼ 0.3 ng/mL [63]
DR ¼ 1–105 ng/mL
PMMA Dopamine Milli-Q water LSPR-based absorbance change AgNPs LOD ¼ 0.16 μM [64]
and wavelength shift DR ¼ 0–50 μM
Silica Bisphenol A Water SPR (wavelength and Ag film LOD ¼ 0.0037 ng/mL [65]
U-Bent Fiber Optic Plasmonic Sensors: Fundamentals, Applications. . .
absorbance) DR ¼ 0.01–50 ng/mL

Silica Sugar Fruit juice LSPR-based absorbance change AuNPs RI sensitivity ¼ 1.333– [66]
1.387 RIU
Silica HIgG PBS buffer LSPR-based absorbance change HGNS DR ¼ 1 ng/mL–6 μg/mL [20]
329
5.1 Detection of Biological Parameters
ELISA-based immunoassays have been extensively studied on the plasmonic U-bent

probe to develop both labeled and label-free fiber optic biosensors that offer high
sensitivity and precise detection of the analyte of biological origin via specific
immunoreaction. For example, Ramakrishna et al. developed a rapid, wash-free
dip-type plasmonic sandwich immunoassay-based U-bent fiber optic sensor for
highly sensitive and selective detection of the analyte molecule (Fig. 10) [54]. In
this study, the plasmonic sandwich immunoassay could be realized by dipping the
anti-Human immunoglobulin G (aHIgG) antibody functionalized U-bent fiber optic
probe in the sample solution containing human immunoglobulin G (HIgG), followed
by the addition of Goat anti-Human (GaHIgG) antibody conjugated AuNP. The
formation of the plasmonic sandwich immunocomplex on the U-bent region of the
fiber probe could be correlated with the drop in intensity of light collected at the
other end of the fiber probe. This assay gave rise to an unprecedented detection limit
down to 0.17 zeptomole of HIgG in buffer solution within an assay time of 25 min.
Further, the signal could be amplified by silver enhancement of AuNP labels over
5 min resulting in the limit of quantitation down to 0.17 zeptomole.
Using a similar approach, Divagar et al. developed a low-cost, sandwich ELISA-
based screening platform for on-site detection of lipoarabinomannan (LAM), a
potential TB biomarker present in the urine at the early stage of the disease
[56]. The plasmonic sandwich assay was realized by interacting various concentra-
tions of Mtb LAM between 1 fg/mL and 1 ng/mL with the capture antibody anti-Mtb
LAM immunoglobulin M (IgM) immobilized on U-bent optical fiber, followed by
incubation with detector antibody anti-Mtb LAM immunoglobulin G conjugated
Fig. 10 Schematic showing analyte detection using plasmonic U-bent fiber optic probe-based
absorbance biosensor where AuNP-based labels were used as a probe in a sandwich assay format
(left). The sensor response is depicted in terms of absorbance by normalizing the optical intensity
signal from the photodiode with respect to its initial value at the beginning of the experiment.
Reproduced with permission from [54]
Fig. 11 Fabrication of optic fiber probes, preparation of simulated malaria samples, and analysis of
the captured images. Reproduced with permission from [55]
with AuNP. Further, the change in the optical power loss in the U-bent region of the
fiber probe due to the formation of plasmonic sandwich immunocomplex could be
quantified to measure the concentrations of the Mtb LAM in urine solution.
In a different study, Sanjay et al. reported a novel strategy for the development of
a multichannel, smartphone-based optical fiber sensing platform for the detection of
Plasmodium falciparum glutamate dehydrogenase (PfGDH), i.e., a disease bio-
marker for malaria (Fig. 11) [55]. To fabricate the sensing platform, the gold-
sputtered U-bent region of the optical fiber probe was functionalized with the
aptamers specific to the PfGDH. Thereafter, the images of the optical fiber after
interaction with the stimulated malarial samples were collected and processed to
calculate the blue histogram value (B-Value) using image J software. The developed
sensor exhibited the detection limit of 264 pM, with a linear (at log scale) detection
range (DR) of 5–250 nM. Further, the developed sensor demonstrated high speci-
ficity towards the detection of PfGDH and could discriminate the interferent such as
Plasmodium lactate dehydrogenase, human glutamate dehydrogenase, Histidine
Rich Protein-II, and Plasmodium falciparum.
Manoharan et al. developed an antibiotic-mediated U-bent fiber optic sensor for
the detection of lipopolysaccharides (LPS), which is the most insidious bacterial
endotoxins contaminant found in pharmaceutical and consumer products [57]. In
this study, the bent sensing region of the probe was functionalized with a self-
assembled layer of octadecyltrichlorosilanes (OTS), which could hydrophobically
entrap LPS from the aqueous solutions. Like a sandwich assay format, the bounded
LPS molecules were tagged with highly specific AuNPs-antimicrobial polymyxin B
conjugate and plasmonic wavelength response of AuNPs under evanescence wave
excitation was measured. After the silver enhancement reaction, the limit of detec-
tion (LOD) value of 0.4 ng/mL could be achieved. The developed assay showed high
Fig. 12 (a) Optical detection assembly (b) Schematic representation of the sensing mechanism of
antibiotics with bacterial cells. Reproduced with permission from [19]
sensitivity towards LPS detection even in the presence of common biopharmaceu-

tical components and thus could serve as an efficient sensing platform for the
detection of endotoxin for quality control testing during the therapeutic
development.
In an interesting study, LSPR-based U-bent fiber optic sensor has been tested to
assess the drug susceptibility on P. aeruginosa and E. coli by Nag et al. (Fig. 12)
[19]. The sensing was carried out by dipping the bacterial cells immobilized AuNPs-
coated U-bent fiber probe in a solution containing a potential drug. The bacteriolysis
signatures of P. aeruginosa RS1 showed that the sensor is selectively sensitive
towards the commonly used third-generation drugs (e.g., cephalosporins ceftriax-
one, cefotaxime, and ceftazidime). In the same study, the authors reported the
development of P. aeruginosa captured plasmonic U-bent fiber optic for quantifica-
tion of cephalosporins, which showed a linear detection range from 0.01 to 1 μg/mL
and the LOD value of 0.01 μg/ml in the tap water. Further, therapeutic monitoring of
these antibiotics in the real human serum could be successfully performed in the
therapeutic relevant range of 0.5–10 μg/mL (R2 ¼ 0.987) using the plasmonic
U-bent probes.
5.2 Physical and Chemical Sensing Application

of U-Bent FOS
5.2.1 Detection of Physical Parameters
Optical Fiber Refractometers
The plasmonic U-bent fiber probe-based sensors have received immense attention
due to their high sensitivity towards the refractive index (RI) change and thus have
been utilized to realize the various physical sensors. For example, Gowri et al.
suggested an evanescent wave absorbance-based U-bent fiber optic sensor for RI
sensing [53]. The RI sensitivity was observed to be maximum when the diameter of
the U-bent probe was kept 2–3 times the fiber core diameter. The fiber probes of
500 μm core size and 1.25 mm bend diameter displayed the highest sensitivity
(5.57ΔA560nm/RIU) when the RI was changed from 1.33 to 1.47, with a resolution
better than 1 103 RI units. Moreover, the LSPR-based RI sensor developed by
immobilizing AuNP on silanized U-bent PMMA probes showed an eightfold
improvement in the RI sensitivity and thus offering their applicability as a highly
sensitive refractive index sensor. In another study by Manoharan et al., U-bent
plasmonic fiber probes were developed by in situ growth of silver and gold
nanoparticles [38]. The RI sensitivities of these probes were found to be 15.8 ΔA/
RIU (for 22 AgNPs/μm2) and 18.9 ΔA/RIU (for 1424 AuNPs/μm2) for AgNP FOS
and AuNP FOS probes, respectively.
Zhang et al. developed a graphene/AgNPs modified U-bent fiber probe-based
LSPR sensor for the detection of alcohol [25]. The RI sensitivity of the developed
plasmonic U-bent probes was studied by observing the change in the spectral
characteristics at resonance wavelength when interacted with 90% aqueous ethanol
and 20% aqueous glucose. The corresponding redshift of 32 nm and 16 nm at the
resonance wavelength were observed for 90% aqueous ethanol and 20% aqueous
glucose, respectively. Further, the RI sensitivity was calculated to be 1198 nm/RIU
with response and recovery time of 3 s and 80 s, respectively. Similarly, Song et al.
presented a graphene oxide (GO)/triangular silver nanoparticle modified plasmonic
U-bent fiber optic probe as RI sensor, wherein the LSPR property of triangular silver
nanoparticles were utilized due to their high sensitivity, while the GO was used to
protect the inner triangular silver nanoparticles [26]. The local field intensity and
extinction efficiency of silver nanotriangles were found to be 10 times and 4 times
higher than the spherical nanoparticles. Further, The RI sensitivities were found to be
342.7 nm/RIU and 1116.8 nm/RIU for spherical and triangular nanoparticles,
respectively.
Optical Fiber Humidity Sensors
The measurement of relative humidity (RH) is an important parameter for various

industrial process control. In comparison to the conventional electrical humidity
sensor, the optical fiber sensors have become the most rapidly developed technology
for the measurement of moisture due to their high sensitivity, corrosion resistance,
electromagnetic interference resistance, easy construction, and remote sensing.
Jagtap et al. developed a U-bent optical fiber-based humidity sensor using a
PVA-activated fiber surface with silver decorated ZnO nanostructure [67]. The
basic phenomenon behind the sensing could be explained as at high humidity,
more number of water molecules are absorbed in the cladding region of the fiber,
which eventually dissociates into surface oxides and hence the boundary conditions
at the cladding interface changes, which further increases the beam confinement in
the guide. The refractive index of the clad may get increased and thereby transmitted
output becomes minimum and thus giving the lowest responsivity. The performance
of the designed sensor was successfully evaluated by interacting with different
humidity levels in the range of 20–95% RH at room temperature. The response
time and recovery time for the developed humidity sensor were found to be 10 s
(20–90% RH) and 1 min, respectively, calculated by considering the time taken by
the sensor to attain 90% of the total output change. The output signal at the cladded
guide was found to be highest for low humidity and it decreased with an increase in
the humidity of the surrounding medium.
5.2.2 Detection of Chemical Parameters
Environmental contamination by toxic heavy metals is a serious issue worldwide, as

these can cause several adverse effects to the environment and humans even at very
low concentration levels. At present, various conventional methods such as atomic
emission spectrometry, atomic absorption spectrometry, inductively coupled plasma
mass spectrometry (ICP-MS), and high-performance liquid chromatography
(HPLC) are being used for selective and highly sensitive detection of heavy metals.
However, the requirement of sophisticated laboratories, expensive instrumentation,
sample pre-processing, and specialized personnel to perform the analysis limits the
field deployability of these techniques. For all these reasons, the utilization of optical
fiber sensors for the detection of heavy metals can be a potential alternative due to
the possibility of real-time analysis with a high degree of precision and relatively
faster response. In this regard, recently, Shukla et al. reported the fabrication of
glucose capped silver nanoparticles (AgNPs) coated U-shaped fiber optic sensor for
label-free detection of mercury ions (Hg2+) in aqueous sample [27]. When aqueous
solutions of different concentrations of Hg2+ ions interacted, a concentration-
dependent change in the plasmonic absorbance of the AgNPs was observed. The
developed sensor could detect Hg2+ concentration down to 2 ppb level, which is
lesser than the WHO acceptable limit for Hg2+ in drinking water. Boruah et al.
proposed a technique for lead ions (Pb2+) detection using oxalic acid-modified
AuNPs-coated U-bent fiber optic sensor [61]. Here, the oxalic acid not only served
as a stabilizer for the nanoparticles but also acted as a sequestering agent for Pb2+
ions due to their strong affinity. Under optimized conditions, the LOD values of
1.87 ppb could be achieved.
In a different approach, Sadani et al. used chitosan capped gold nanoparticles
(AuNPs) on bovine serum albumin (BSA) coated optical fiber probe for the selective
and sensitive detection of mercury ions, in environmental and biological samples
[58]. The AuNPs-BSA complex immobilized on U-bent optical fiber served as a
receptor for specific binding of Hg2+. The LOD values were found to be 0.1 ppb in
the tap water, and 0.2 ppb in both sea fish and vegetable samples. The sensor could
be successfully validated and the recovery ranges were found to be 90–114% for tap
water (coefficient of variation <9%), 89–102% for seawater (coefficient of variation
<8.3%), and 110–119% for digested soil sample (coefficient of variation <8.2%).
Using a similar approach, Halkare et al. fabricated AuNPs-coated U-bent fiber optic
probe for the sensing of mercury (Hg2+) and cadmium (Cd2+) ions in water using
E. coli bacterial cells as a receptor (Fig. 13) [59]. The authors explained that the
interaction between the metal ions and the thiols and other groups present on
bacterial surface resulted in localized RI change around the AuNPs, causing a
metal ion concentration-dependent change in the plasmonic characteristic of
AuNPs. The LOD value of 0.5 ppb could be achieved using this sensor when sensor
response was monitored after interaction with metal ions spiked deionized (DI) water
and tap water.
6 Summary and Future Perspectives
In this chapter, the theory of plasmonic U-bent fiber probes, design and fabrication of
U-bent probes, and their potential application towards the development of plasmonic
sensors are discussed. The high sensitivity of the U-bent probes and their integration
with plasmonic nanoparticles, possessing the unique advantages of LSPR property
and greater extinction coefficient, provides wide possibilities in the realization of a
variety of sensors with improved measurement accuracy, sensitivity, and stability.
These sensors have shown the detection limit down to attomolar level of the analyte.
Besides the numerous advantages and significant progress in this field, there is still a
long way to go as most of their use is still limited to the research laboratory settings
only. Global and concerted efforts are needed towards the translation and commer-
cialization of U-bent fiber optic sensors, at various levels including (i) large-scale
fabrication of the U-bent probes (ii) ease of functionalization of multiple probes (iii)
convenient transportation and storage, and (iv) multiplexed sensing.
Further, integration of the multifunctional hybrid plasmonic nanomaterials to
develop a functional fiber optic probe may achieve ease of probe fabrication.
Moreover, the realization of advanced optical bioassays such as plasmonic-ELISA
based on etching or growth of the plasmonic nanoparticles on the U-bent fiber optic
probes might have vast potential in various sensing domains with distinct advantages
Fig. 13 Schematic illustration of (a) bacteria-based heavy metal detection and (b) experimental
set-up. OL represents objective lens, FP represents fiber positioner and BFTU represents bare fiber
terminator unit (not to scale). Reproduced with permission from [59]
of high sensitivity, real-time analysis, ease in handling, and flexibility. Application

of machine learning techniques and artificial intelligence in order to develop U-bent
plasmonic probes-based multiplexed sensors for drug discovery and drug evaluation
would be quite interesting for future studies. Similarly, the realization of cloud-based
remote sensing (both software and hardware) can be an innovative futuristic appli-
cation, where the signals from the U-bent probes can be remotely processed and
recorded. Overall, the future developments of U-bent plasmonic biosensors require
significant attention in the miniaturization particularly for flow cell and full integra-
tion of the fiber probe with inexpensive optoelectronics devices to obtain a low-cost,
field-deployable, point-of-care diagnostic system.
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An Appraisal on Plasmonic Heating
of Nanostructures
Upama Das, Nirmal Mazumder, and Rajib Biswas
Abstract Remarkable photothermal properties of plasmonic nanostructures, led to

the evolution of a new branch of nanoscience termed thermo-plasmonics, based on
plasmonic heating of structures in nanoscale by external electromagnetic illumina-
tion. This heating generally occurs in noble metallic nanostructures, when localized
surface plasmonic resonance (LSPR) condition is satisfied resulting in amplified
oscillation of the electrons present in the conduction band resulting in heat produc-
tion, which depends upon size, shape, structure of nanoparticles and type of source
used for illumination. Earlier generation of heat by the plasmonic nanostructure was
considered to be a side effect, but recent developments in this field have laid
foundation towards the emergence of new branches and applications of this field
such as nano-thermodynamics and photothermal therapy. This chapter will present a
short review on thermo-plasmonic nanostructures, in which some key concepts
related to the physics behind its occurrence will be highlighted and then its targeted
applications will be emphasized.
Key words Photothermal · Nanostructures · Thermo-plasmonics · Electromagnetic

illumination · LSPR · Amplified oscillation
1 Introduction
The quantum world predominates the classical world when it comes to nano regime
as the size of the nanoparticles is in order of the wavelength of incident radiation,
leading to some exceptional properties exclusively different from their bulk
counterparts [1].
U. Das · R. Biswas (*)

Department of Physics, Applied Optics and Photonics Lab, Tezpur University, Tezpur, India
e-mail: rajib@tezu.ernet.in
N. Mazumder
Department of Biophysics, Manipal School of Life Sciences, Manipal Academy of Higher
Education (MAHE), Manipal, Karnataka, India
https://doi.org/10.1007/978-3-030-99491-4_12
342 U. Das et al.
Considering the case of metallic nanoparticles, the conduction band (CB) -

electrons under constant irradiation of electromagnetic field starts oscillating with
a constant phase with the incident field, and the oscillation of the electrons gets
intensified at resonance when both the frequency of incident electromagnetic radi-
ation and oscillation of the electrons becomes equal [1, 2]. This condition is termed
as localized surface plasmon resonance (LSPR) and under this condition absorption
by the nanostructures gets significantly enhanced [1, 2] (Fig. 1).
As a result of the intensified oscillation of (CB) electrons, the collision frequency
of these electrons with the lattice atoms also increases resulting in “Joule heating.”
Where, energy absorbed from the incident electromagnetic radiation is converted as
heat to the environment, acting as an efficient source of light-to-heat converters
whose efficiency becomes maximum at the resonance [1] (Fig. 2).
Fig. 1 Graphical representation of surface plasmon resonance (SPR) displayed by nanoparticles [1]
Fig. 2 Schematic representation illustrating light to heat conversion by plasmonic nanostructures.

“Modified from (Hussein et al. 2018)” [8]
An Appraisal on Plasmonic Heating of Nanostructures 343
Ample number of applications in various branches are associated with thermo-

plasmonics such as photothermal cancer therapy [3–8], hyperthermia therapy [4],
solar energy harvesting [4], water desalinization [4], drug delivery [3, 4, 7], fusion of
cells and vesicles [1], materials science [3], nano-fluidics [3], photonics [3], and
thermo-voltaic [4].
This chapter will basically focus on the modes of synthesis of plasmonic
nanostructures, followed by fundamentals of thermo-plasmonics, and finally signif-
icant applications of thermo-plasmonics and their features will be highlighted.
2 Synthesis Techniques for Preparation of Plasmonic

Nanostructures
Shape, size, structure, and morphology play a pivotal role in determining the
plasmonic properties of nanomaterials. Recent advancements have resulted in a
large number of modes for synthesis of plasmonic nanostructures of various shapes,
sizes, and compositions in order to tune their thermo-plasmonic properties [1]. Out
of top-up and bottom-up approaches, the latter one is the solely used method for
preparation of plasmonic nanostructures, where formation of large structures is
facilitated by assembling of smaller units by the use of physical or chemical forces,
where homogeneous nucleation of the smaller units is preceded by secondary
nucleation [9] (Table 1).
3 Principles of Thermo-plasmonics in Nanostructures
Earlier the heat production by the nanostructures was considered to be a curse but
with recent developments in the field, heating effect in nanoplasmonics has paved its
way towards generating a large number of applications in various fields [27].
Due to the LSPR phenomenon in metal nanoparticles, at resonance condition,
amplification of movement of conduction band electron occurs due to their collective
oscillations which are responsible for the increase in surface temperature of the
nanoparticle by “Joule Heating” [1, 28].
In this part of this chapter, we will be focussing on the physics behind the heat
generated by plasmonic nanostructures.
344 U. Das et al.
Table 1 Various modes for synthesis of plasmonic nanostructures of different shapes and sizes
Shape of
plasmonic
nanostructures Mode of synthesis Particle size References
Spherical Seed particle method by laser 10–80 nm Pyatenko et al. [10]
treatment
Physical synthesis (Electrical arc 14–27 nm Ashkarran et al.
discharge) [11]
Chemical synthesis 10–20 nm Turkevich et al.
(Turkevich Method) [12]
Nanostars Seed-mediated growth method – Li et al. [13]
Chemical reduction by seed growth 40–70 nm Kumar et al. [14]
Nanoshell Seeding method – Oldenberg et al.
[15]
One-pot synthesis Below 36 nm Storti et al. [16]
Nanoframe Galvanic replacement technique – Mahmoud et al.
[17]
Nanomatryoshka Reduction method 90 nm Ayala-Orozco et al.
[18]
Nanorod Seeded wet-chemical synthesis 4–5 nm Edgar et al. [19]
Wet-chemical 2–6 nm Aslan et al. [20]
Nanocages Galvanic replacement method 35–45 nm Skrabalak et al. [21]
Nanowires Polyol chemical synthesis 30–80 nm Garnett et al. [22]
Nano prisms Microwave-assisted – Darmanin et al. [23]
Khodashenas et al.
[24]
Nanocubes Chemical method 30–50 nm Young et al. [25]
Huang et al. [26]
Photochemical method 2–8 nm Khodashenas et al.
[24]
Huang et al. [26]
3.1 Heat Generation of Nanoplasmonic Structure
3.1.1 Illumination from a Continuous Source
At resonance condition, when a constant source of electromagnetic wave falls on the

nanoplasmonic structure Joule heating effect occurs in them and the heat generated
in the nanoparticle can be expressed in terms of absorption cross section and heat
power density by using Poynting’s theorem given by,
Z
Q ¼ σabs I ¼ qðr Þd3 r ð1Þ
V
Where σ abs, I and q(r) represent absorption cross section, irradiance of the
incoming light (power/surface area), and heat power density inside the nanostruc-
ture, respectively [1–3].
Due to Joule’s heating in the nanostructure, density of heat power can be further
expressed as.
1
qð r Þ ¼ Re ½J ðr Þ E ðr Þ ð2Þ
2
Here, E(r) is complex amplitude of electric field and J*(r) denotes the complex
conjugate amplitude of current density inside the nanostructure and is given by,
J ¼ i ω P ð3Þ
E ðr Þ ¼ P=ðε0 εðωÞÞ ð4Þ
where P is power absorbed from light by the nanoparticle, ε0 represents permittivity

of free space, and ε(ω) represents frequency-dependent permittivity of nanostructure
[2, 3].
By using Eqs. (2), (3), and (4), we get a new equation of heat power density given
by,
ω
qðr Þ ¼ ImðεðωÞÞε0 jEðr Þj2 ð5Þ
2
Now by putting Eq. (5) in (1), we can justify that heat generated in plasmonic
structure is directly dependent on square of E(r) [2].
Spherical nanostructures whose size is much less than the wavelength of the
incident light are considered to be electromagnetic dipoles and absorption cross
section of this type of structures can be calculated from the expression [2],
k4 2
σ abs ¼ kImðαÞ jαj ð6Þ
6π
Where polarizability α(ω) by using Clausius-Mossotti relation is given by [2],
ε ð ωÞ ε s
αðωÞ ¼ 4πR3 ð7Þ
εðωÞ þ 2εs
Where εs is the frequency which is dependent on permittivity of the medium and

ε(ω) is the frequency which is dependent on permittivity of the nanoparticle and the
radius of the metal nanosphere is denoted by R. By using the Eqs. (1), (6), and (7)
one can calculate the value of heat generated by the small spherical nanostructures,
but not for structures with complicated morphologies. For them, we need to take the
help of some computational estimation to calculate E(r), to finally get the equation of
q(r) and based on it we can calculate the heat generated by the nanostructure [2].
346 U. Das et al.
3.1.2 Illumination from a Pulsed Source
Whenever the external source of illumination is in the range of femtosecond to

nanosecond they are termed as pulsed source. The physics behind the heat genera-
tion of plasmonic nanostructure under this type of illumination is slightly complex
and will be demonstrated in this section in three steps.
Electronic Absorption: Under pulsed illumination, a small portion of incident
pulsed radiation is absorbed by the free electron gas of the nanoparticles, electron gas
being lighter in weight compared to the ions, thermalizes fast resulting in
nonequilibrium state of the nanoparticle. This results in increase in temperature of
electrons, but the lattice phonons temperature remains constant [2, 29].
Electron–phonon thermalization: Due to nonequilibrium and high-temperature
state of electron gas they try to cool down by electron–phonon interaction for
achieving inner equilibrium. But the nanostructure is still in nonequilibrium state
with the external surrounding [2].
External Thermal Diffusion: To achieve complete equilibrium with the sur-
rounding, the energy is diffused in form of heat to the surrounding, which causes
cooling effect in the nanostructure and the surrounding becomes hot [2].
Energy absorbed by the nanostructure is given by the expression,
σ abs hI i
E¼ ¼ σ abs F ð7Þ
f
Here, f is termed as the pulsation rate and F represents fluence of the laser.
All the three steps mentioned above will occur simultaneously, and thus absorp-
tion and delivery of heat to the surrounding will be simultaneous [2, 30].
3.2 Surface Plasmonic Resonance in Metallic Nanostructures
Under resonance conditions at a particular frequency, the surface plasmons display

localized surface plasmonic resonance (LSPR) phenomenon which majorly depends
on structure, morphology, and the type of dielectric environment of the metallic
nanostructure. It originates in spherical nanoparticles, where diameter (d ) and
wavelength of the incident radiation (λ), satisfies this condition, d λ, which results
in uniform polarization of the particle, and, thus, results in electromagnetic dipole.
At resonance condition, for a particular value of frequency, the condition ε(ω) ¼ 2εs
must be satisfied [2].
The amount of heat generated by the nanostructures is identified by the amount of
heat absorbed which is quantified by the absorption cross section as given in Eq. (6).
The expression of extinction and scattering cross sections is given by,
σ ext ¼ σ scat þ σ abs ð8Þ

k4 2
σ ext ¼ jαj ð9Þ
6π
The ratio of absorption and scattering cross section gives the photothermal
efficiency μ, represented as [2],
σ abs
μ¼ ð10Þ
σ scat
For nanostructures, of size <90 nm, absorption becomes dominant than scattering
and we get high photothermal efficiency. But for bigger nanoparticles, scattering
becomes more dominant than absorption as a result photothermal efficiency
decreases [2, 31].
3.3 Temperature Profile for Thermo-plasmonics

of Nanostructure
3.3.1 Continuous Source of Illumination
Temperature profile of the heat generated by nanostructures can be explained by the

time-dependent heat transfer equation which is given by,
∂T ðr Þ
ρC p þ ∇ ½k∇T ðr Þ ¼ qðr Þ ð11Þ
∂t
Here, ρ represents density of mass and Cp is specific heat capacity at constant

pressure and T(r) is absolute temperature and k represents surrounding medium’s
thermal conductivity [32, 33].
By solving Eq. (11) by dimensional analysis we get Eq. (12), which gives the time
required by the nanostructure to reach steady temperature [33],
R2 ρCρ R2
τ ¼ ð12Þ
k D
Where R is the radius of NP or length of the system and D represents thermal

diffusivity. When the state of the system becomes steady, the equation of heat
diffusion becomes,
∇:½kðr Þ∇T ðr Þ ¼ qðr Þ ð13Þ

∇:½k ðr Þ∇T ðr Þ ¼ 0 ð14Þ
Which represents distribution of steady state temperature inside and outside the
nanostructure, respectively. But comparatively the surrounding medium’s thermal
348 U. Das et al.
conductivity is less than thermal conductivity of metal, km ks, and hence the
diffusion of heat is faster inside the nanoparticle [2, 32, 33].
Thus, the increase in temperature in the surrounding and in the nanoparticle is
given by,
σ abs I
ΔT ðr Þ ¼ ð15Þ
4πks r
σ abs I
ΔT NP ¼ ð16Þ
4πks a
Where r ¼ radial coordinate and a ¼ radius of the nanoparticle. Here, the change
in temperature of the surrounding medium is inversely proportional to r and thus
with increase in value of r the temperature decays uniformly [32].
But Eq. (16) is only valid for spherical nanostructure, as there is no general closed
form equation present till now for nanoparticles of other geometry except for
nanoparticle morphologies like rods, discs, ring, and ellipsoid one can use Eq. (17)
to calculate the increase in temperature in the nanoparticle given by,
σ abs I
ΔT NP ¼ ð17Þ
4rk s βaL
Where aL is the affective radius of the nanostructure. And β depends on the type
of structure of the nanoparticle, which can be calculated from the following expres-
sions, given by [32, 33] (Figs. 3 and 4),
Fig. 3 Figure demonstrating the aspect ratio D/d of ellipsoid, nanorod, ring, and disk [33]
Fig. 4 Graphical representation of radial profile of change of ΔT(r)/(ΔTNP) around a spherical

nanoparticle of radius (a) “Modified from (Baffou et al. 2017)” [32, 34]
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
For Ellipsoid, β ¼ exp 1 þ 0:0416 ln ðD=dÞ þ 0:092 ln ðD=dÞ 1 ð18Þ
For Rod, β ¼ 1 þ 0:09657 ln ðD=dÞ ð19Þ

For Disk, β ¼ exp 0:040 0:0124 ln ðD=dÞ þ 0:0677 ln 2 ðD=dÞ 0:00457 ln 3 ðD=dÞ
ð20Þ
For Ring, β ¼ 1:021 þ 0:17442 ln 2 ðD=d 0:625Þ ð21Þ
3.3.2 Pulsed Source of Illumination
Under pulsed source of illumination, the initial increase in temperature in the

nanoparticle is given by,
σ abs F
δT NP ¼ ð22Þ
Vρm cm
From Eq. (22), it is clear that δTNP is dependent on 1/r3, and on pulse energy per
unit area F, which is given by hfI i [2, 35].
Gain in temperature under pulsed illumination is given by a dimensionless
number η0 given by [35],
ΔT 0np 3βa
η0 ¼ ¼ 2 w ð23Þ
ΔT cw
np f R ð1 þ λ k Þ
Where T 0np and T cw

np are change in temperature of nanoparticles under pulsed and
continuous wave illumination, respectively.
Equation (23) is valid only for large value of η0, as for very low value of η0, the
denominator (R or f ) becomes very high, which may result in overlapping of the
successive pulses, and, thus, single-pulse illumination cannot be considered [35].
3.4 Collective Thermal Effects Displayed by a Bunch

of Nanostructures
Illuminating a large number of nanoparticles together results in the generation of

heat fluxes from individual nanoparticles which are added altogether resulting in a
strong enhancement of thermal effects, where each nanoparticle acts like a point
source of heat. There are two regimes where thermal hot spots exist, one is the
temperature localization regime, and another is the regime of the presence of a
dominant overall temperature due to the thermal collective effects. The occurrence
350 U. Das et al.
of each regime is dependent on a dimensionless number which depends only on the

geometry and properties of the nanoparticle system [32, 35].
For a 2D system of nanoparticles this dimensionless number, ζ is given by [32],
p2
ζ¼ ð24Þ
3La
Here, p is the inner distance between the nanoparticles, L gives the nanoparticle
size distribution and 2a represents the characteristic size of the nanostructures
[32, 35]. For large ζ, the temperature increase is considered in the localization
regime, but when ζ < 1 then there is a presence of dominant overall temperature
offset which causes thermal collective effects [32].
4 Application
This section of the chapter gives light on some of the applications based on
plasmonic heating of nanostructure.
Working
Branch Application Utilization principle Advantage Reference
Physical Heat-assisted To increase Plasmonic Increased stor- Zhou et al.
science magnetic storage capacity nanostructures age density [36]
recording of hard drives act as near field beyond 1 Tb/
transducers, in2
applies local
heating to the
media which in
turn decreases
the coercivity
Thermo-vol- Converts light Light energy Display highly Lenert
taic devices from the entire from the sun is efficient et al. [37]
band of the converted to plasmonic
solar spectrum heat directly by absorption with
into thermal using the hot high scalability
emission which absorber– and
is converted to emitter compactness
electricity
Life Photothermal Plasmonic Plasmonic Plasmonic Chatterjee
science therapy nanostructures nanoparticles nanostructures et al.[38]
as nano heat are injected into can be reused to Jauffred
source to kill the infected site repeat the et al. [1]
the cancerous which gener- therapy
cells ates heat to kill
the cancerous
cells upon
illumination
(continued)
Working
Branch Application Utilization principle Advantage Reference
Nano surgery Accurate and Uses pulsed Increase in Jauffred
precise manipu- source to heat local tempera- et al.[1]
lations of cells up the nano- ture and Baffou
structure which absorption et al. [4]
may cause pro-
tein denatur-
ation or even
cell death
Plasmonic- Manipulation Local melting Study of per- Jauffred
Nanoparticle- lipid mem- of the mem- meability of et al. [1]
Mediated branes and branes by the membranes
Membrane plasma thermo-
membranes plasmonic
nanostructures
to study the
permeability of
membranes
Chemical Plasmon Increases the Local heating in Boost reaction Bin Ai
science induced nano- yield of a plasmonic kinetics et al. [39]
chemistry reaction nanoparticles
results in the
enhancement of
chemical
reactions
Plasmon- Thin film depo- Laser-induced High-quality Baffou
assisted sition of high heating in thin film et al. [32]
chemical grade and plasmonic Boyd et al.
vapor quality nanostructure [40]
deposition
Thermo- Endothermic Pulsed illumi- Large amount Adleman
plasmonic- catalytic nation to gener- of heat is et al. [41]
assisted processes ate a rapid generated Fasciani
catalysis increase in tem- et al.[42]
perature in
nanostructures
5 Salient Features of Plasmonic Heating
In this part of this chapter, we will address the various features which affect the
thermo-plasmonic properties of nanostructures.
Type of thermo-
plasmonic
nanostructure Features Application References
Spherical • Strongly enhanced absorption and • Catalysis Pustovalov
nanoparticle scattering • Laser nano et al. [43]
(continued)
352 U. Das et al.
Type of thermo-
plasmonic
nanostructure Features Application References
• Increased absorption efficiency in biomedicine Jauffred
small NPs • Nanotechnology et al. [1]
based
Light-to-heat
conversion
Metallic • Absorption spectra depends on the • Photothermal Tuersun
nanoshells ratio of coreshell applications et al. [44]
Jauffred
et al. [1]
Composite metal- • Possess excellent light-to-heat con- • Efficient source of Jauffred
lic nanostructures version efficiency light-to-heat et al. [1]
• High absorption band near infrared converters
region
Metallic • Absorbs light in the NIR region • Photothermal Chen et al.
Nanocages • Higher amount of absorption com- therapy [45]
pared to nanoshells • Biomedical Jauffred
applications et al. [1]
Metallic nanorods • Length to width ratio determines • Thermo- Ma et al.
transverse and longitudinal resonance plasmonic heaters [46]
condition. Jauffred
• Resonance occurs in NIR frequency. et al. [1]
Metallic • Plasmonic coupling depends upon • Nano tweezing Romero
nanodimers strongly enhanced near-fields • SERS et al. [47]
• Close placed nanostructures result in • Nano rulers Juan et al.
strong electric hot spots [48]
Zheng et al.
[49]
Chen et al.
[50]
6 Conclusion
In this chapter, a brief introduction on thermo-plasmonics, physics behind its

occurrence, and some important applications and features are demonstrated. Absorp-
tion and scattering of light at a specific wavelength significantly contribute towards
some unique characteristic of plasmonic nanostructures, which makes their scatter-
ing and absorption capability tuneable depending on their geometry. The energy
absorbed by them is released as heat making them useful for photothermal applica-
tions. Plasmonic nanostructures such as gold nanoshells, nanomatryoskhas,
nanocages, nanorods, nanostars, and nanodimers are the most popularly known
plasmonic structures for their unique temperature profile and features resulting in
plasmonic heating. It was found out that the plasmonic heating displayed by the
nanostructures have a large no. of applications in various fields such as Photothermal
therapy, medical therapy, nanosurgery, Thermophotovoltaics, and Plasmonic-

assisted Chemical vapor deposition.
Acknowledgment Author UD acknowledges the financial assistance received as INSPIRE Fel-

lowship from DST [No. DST/INSPIRE Fellowship/2019/IF190914].
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Plasmonic Nanoparticles
for Polarization-Sensitive Analytical
Techniques
Ishita Chakraborty, Soumyabrata Banik, and Nirmal Mazumder
Abstract Plasmonic nanoparticles are metal-based nanoparticles with the efficient

ability to absorb and scattering of light. These are extremely strong absorbers and
scatters of light and used in diagnostics, imaging, surface-enhanced spectroscopy,
labeling, and color changing sensors. In this chapter, we discuss the applications and
benefits of using various types of plasmonic nanoparticles in polarization-sensitive
analytical techniques including polarization microscopy, fluorescence polarization
spectroscopy, and polarization-sensitive Raman spectroscopy.
Key words Plasmonic nanoparticles · Polarization-sensitive microscopy ·

Fluorescence spectroscopy · Raman spectroscopy
1 Introduction
When light interacts with metal nanoparticles, a novel phenomenon occurs leading
to the excitation of surface plasmons [1]. These metal nanoparticles are thus known
as plasmonic nanoparticles since they are extremely efficient in absorbing and
scattering light. Plasmonic metal nanoparticles are usually gold, silver, or platinum
nanoparticles. Colloidal solutions of these metal nanoparticles exhibit a variety of
colors due to the phenomenon of surface plasmon resonance (SPR) [2, 3] (Fig. 1).
SPR arises when incident light strikes the surface of the metal nanoparticles. The
plasmonic metal nanoparticles are 10–50 nm in diameter [4]. Adjusting the shape,
size, and surface coating of the nanoparticles assists in altering the color of the
nanoparticles within the visible and infrared regions of the electromagnetic spec-
trum. For instance, colloidal spherical gold nanoparticles appear ruby red since it
absorbs and scatters light in the green region of the spectrum [5]. Further, silver
nanoparticles appear yellow due to the absorbance and scattering of light in the blue
region. This property of plasmonic nanoparticles is applied in surface-enhanced
I. Chakraborty · S. Banik · N. Mazumder (*)

Education, Manipal, Karnataka, India
https://doi.org/10.1007/978-3-030-99491-4_13
356 I. Chakraborty et al.
Fig. 1 (a) Schematic description of localized surface plasmon resonance in metal nanoparticles, (b)
photophysical processes of plasmonic nanostructures: light absorption vs resonant light scattering,
and (c) imaging through a medium of plasmonic nanoparticles
spectroscopy, lateral flow diagnostics, color changing sensors, imaging, and labeling
[6]. In addition, the shape and size of nanoparticles can predict their optical proper-
ties. Maneuvering the dimensions of nanoparticles can be used to fabricate
nanoparticles that resonate at the desired wavelength [7]. Imaging sensors, solar
cells, optical detectors in biomedicine are mainly dependent on the surface area, size,
and shape of the nanoparticles [8].
Several techniques have been employed for the detailed study and characteriza-
tion of plasmonic nanoparticles [9]. High spatial resolution microscopic techniques
such as transmission electron microscopy (TEM) reveal the size, shape, morpholog-
ical details, and interparticle interactions of the nanoparticles. X-ray diffraction
(XRD) is used to study the crystallinity and crystallite structure of nanoparticles.
Fourier transform infrared (FTIR) spectroscopy exhibits the molecular structure and
the functional groups attached to the metallic nanoparticles [9, 10].
2 Introduction to Polarization
Light is an electromagnetic wave in nature, where the electric field oscillates

perpendicular to the direction of propagation. As the director of the electric field
fluctuates randomly in most cases, light is called to be unpolarized. On the contrary,
polarized light has well-defined the direction of the electric field. Polarized light is
Plasmonic Nanoparticles for Polarization-Sensitive Analytical Techniques 357
linear, circular, or elliptical (Fig. 2a). When the electric field vector remains within a
single plane, light is linearly polarized. On the other hand, circularly polarized light
comprises two electromagnetic plane waves of equal amplitude which are perpen-
dicular to each other with a 90 difference in phase. Similarly, elliptically polarized
light also comprises two perpendicular waves with 90 difference in phase, but of
unequal amplitude [11].
A polarizer is used to attain a specific polarization state of light. Polarization is
commonly implemented in spectroscopy/imaging applications, classification and
recognition of chemical isomers, and materials as well as analyzing reflections
[12]. Polarimeters, are devices used to separate, filter, quantify, separate, and
regulate polarized light. Polarization microscopes assist biologists in visualizing
things that exhibit optical anisotropy or birefringence, that would otherwise not be
evident under traditional light microscopy. Polarimeters consist of a polarization
generator to produce a beam of a known polarization state and an analyzer. The
analyzer is essentially a rotatable polarizer and can be used to observe the incoming
polarized light and determine the optical rotation of the sample.
The challenge lies in recognizing the forms of polarization and making the use of
a semiconductor-based imaging device that converts polarization information into
intensity, that may be distinguished by the detector (Fig. 2b).
Fig. 2 (a) Three types of polarized light, linear, circular, and elliptical; (b) Schematic diagram
showing a basic setup of a polarimeter
Some objects tend to show only poor contrast in general light microscopy.
However, polarized light microscopy can bring out additional relevant information
of the sample by increasing the image contrast. Incorporating polarization elements
into analytical systems enables high contrast polarization imaging where the polar-
ization state of light or the polarization property of the sample is considered. Both
organic and inorganic materials display polarization sensitivity. Polarization sensi-
tive analytical techniques find applications in microscopy, imaging, astronomy, and
biomedical diagnosis. This chapter deals with applications of plasmonic
nanoparticles in polarization-sensitive analytical, imaging, and microscopy
techniques.
3 Application of Plasmonic Nanoparticles
3.1 Plasmonic Nanoparticles in Polarization-Sensitive

Microscopy
Several studies on the applications of plasmonic nanoparticles for improved imaging

have been conducted. Usually, plasmonic nanoparticles suspended in a medium are
positioned between the sample and the observer’s or imaging system’s image plane.
The absorption spectra of the medium offer important but partial data about the
quality and characteristics of the transmitted image [13].
Influencing the properties of light at the nanometer scale is challenging but
fundamental for designing optical or other analytical devices. For instance, tradi-
tional near-field optical microscopy falls short of the sensitivity of in-plane polari-
zation. Therefore, polarization-sensitive near-field probes provide sensitive
information on the characteristics of nanoparticles and emitters. Recently,
nanoplasmonics is emerging as a division of photonics that proposes ways to
influence light by employing surface plasmon excitations on metal nanostructures.
A combination of stellated nanoparticles and polarization-sensitive darkfield micros-
copy was applied to detect and study molecular assemblies and epidermal growth
factor receptors in live cells. Linear polarized light was efficiently depolarized by
stellated nanoparticles as compared to spheroidal nanoparticles. Here, efficient
depolarization was used to detect stellated nanoparticle labeled molecules. In
cross-polarized imaging, the scattering of light was significantly reduced by cells
labeled with stellated nanoparticles (Fig. 3). A combination of plasmonic
nanoparticles and polarized light may be used to differentiate between epithelium
and connective tissue. Further, it could be incorporated into advanced endoscopic
techniques in diagnostics such as confocal reflectance microscopy and optical
coherence tomography for higher resolution [14]. Again, Stender et al. studied the
optical characteristics of gold nanorods using differential interference contrast (DIC)
microscopy. The nanorod was rotated with respect to a polarized light source under
Fig. 3 In (a), polarization-sensitive darkfield images of A431 cells labeled with spherical (top row)
and stellated (bottom row) particles are shown. Labeled cells were mixed in a 1:1 ratio with
unlabelled cells which appear blue due to intrinsic scattering from cells. Polarization-sensitive
darkfield images of the labeled/unlabeled cell mixtures were obtained with no polarizers (left),
parallel (middle), and perpendicular (right) orientation of a linear polarized illumination and an
analyzing polarizer. (b) shows scattering spectra of cells labeled with spherical (left) and stellated
(right) nanoparticles. The spectrawere obtained in parallel (blue) and perpendicular (red) orientation
of polarizers in illumination and detection pathsusing a PARISS hyperspectral imaging system
(Lightform, Inc.) coupled to the Leica DM6000 microscope. Figure reproduced from [14]
DIC, darkfield, and polarized light microscopy. Out of the three, strong diffraction
patterns were obtained using DIC. The behavior of these patterns can be altered by
varying the polarizer and analyzer set. As a result, patterns were absent while linear
and crossed polarizations were used. Further, adjusting the polarization is essential
in DIC microscopy since it impacts image contrast and bias retardation. The
non-plasmonic diffraction bands can be used for rotational tracking using nanorods
and the polarization setting with DIC microscopy [15]. F1-ATPase is a catalytic
complex of the ATP synthase or a molecular motor that consumes ATP to rotate the
γ-subunit inside the ring of three αβ-subunit heterodimers. Recently, this F1-ATPase
rotation was detected using a sensitive method that achieves acquisition rates with a
time resolution of 2.5 μs. Gold nanorods were attached to an individual F1-ATPase
molecule where rotation was envisaged using polarized light scattering in darkfield
microscopy. The light scattered from the gold nanorod was split by a birefringent
crystal into two polarization channels, resulting in spots being imaged at the same
time [16].
3.2 Plasmonic Nanoparticles for Polarization-Sensitive

Fluorescence Spectroscopy
Fluorescence polarization spectroscopy is an analytical technique, that reveals the

relationship between the polarization of light used for excitation and the fluorescence
signal. Polarization-sensitive spectroscopy can be used to measure the rotation of
molecules to examine molecular interactions in solution [17]. This can be efficiently
utilized to quantify the binding and dissociation of two molecules, only if one of the
molecules is fluorescent and small. Fluorescent plasmonic nanoparticles are essential
functional materials widely used in biosensing and bioimaging. The efficiency of
fluorescent nanoparticles is highly useful in biomarker detection. Recently, a fluo-
rescent silver nanoparticle immunoassay (FSNIA) was developed using streptavidin
bio-conjugated to fluorescent silver nanoparticles which can be used with biotin
labeled antibodies or antigens to detect the target [18] (Fig. 4).
Fig. 4 Simplified schematic diagram of plasmonic nanoparticle fluorescence spectroscopy.

Figure reproduced from [19]
3.3 Plasmonic Nanoparticles for Polarization-Sensitive

Raman Spectroscopy
Plasmonic nanostructures are extensively utilized in surface-enhanced Raman spec-

troscopy (SERS), in various applications. Polarization-sensitive Raman spectros-
copy is employed to assign and characterize vibrational modes by measuring the
depolarization ratio and optical activity. Polarization-sensitive measurements have
been combined with coherent Raman scattering, resulting in substantial progress in
both aspects of speed and sensitivity. Knowing the molecular structure is extremely
essential in polymorph analysis and synthetic chemistry. Hence, polarized Raman
spectroscopy is generally used to study macromolecular orientation in crystal lattices
of polymers. Furthermore, this technique is nondestructive and appropriate for
detailed analysis.
Plasmonic nanostructures such as metallic nanoantennas, nanospheres,
nanocubes, nanorods, nano triangles, and irregularly shaped nanoparticles are com-
monly used for SERS. In a recent study, single-wall carbon nanotubes were used as
polarization-sensitive probes to capture the transverse near-field components of an
optical Hertzian dipole antenna. Due to the Raman antenna effect in the nanotubes,
only the near-field elements were exclusively observed. The Raman antenna effect
occurs especially in nanowires and nanotubes due to the small diameter of the
nanoparticle when the electric field of the incident laser is parallel to the axis of
the nanoparticle. This revealed that carbon nanotubes can be used as polarization-
sensitive near-field detectors [20].
3.4 Plasmonic Nanoparticles for Surface Plasmon Resonance
Display technologies are developing towards improved resolution and miniaturiza-

tion. Plasmonic nanoparticles can contribute to this evolving technology given their
strong resonances as well as scattering and absorption at selective wavelengths.
Metal nanosphere dimers support plasmon resonances that span the entire visible
spectrum. Rasheed et al. exhibited bright colored polarized pixels and tuned metal
nanosphere dimers on a glass substrate that resulted in RGB pixels in the reflection
mode. The pixel color is a result of the longitudinal plasmon resonance of the
nanospheres which was further enhanced by far-field diffractive coupling. This
approach is simple and includes bright coloration, as well as exceptionally high
polarized function. Further, it can be used to develop transparent display screens by
projecting monochromatic light resonant wavelengths [21].
More effort has been devoted to understanding the polarization-sensitive behav-
iors of anisotropic plasmonic nanoparticles such as gold nanorods (Au NRs). Au
NRs are excellent directional plasmonic emitters with localized surface plasmon
resonance (LSPR). The three-dimensional nature of Au NRs is used to intricately
study biological transportation processes, molecular interaction, and intracellular
activity [22]. Researchers use a variety of microscopic techniques to observe and

track anisotropic nanoparticles in real-time. Recent studies in the plasmonic field
emphasize controlling the characteristics of light including propagation direction,
and intensity. This was achieved through surface plasmon propagation in metal
nanoparticles and transmission through nanoholes in metal films. Regulating the
intensity and spectrum of light requires enhancement of the local electromagnetic
field by LSPR and plasmon coupling.
4 Conclusion
Polarization-sensitive analytical techniques enhance the contrast and improve the

quality of the obtained information when compared to other techniques. Enhancing
the contrast manipulates the optical properties specific to anisotropy and provides
comprehensive information on the composition and structure of the sample, essential
for diagnostics. Plasmonic metallic nanoparticles are used to manipulate light on the
nanoscale. The application of plasmonic nanoparticles combined with polarized light
and polarization-sensitive detection systems can be expanded into in vivo applica-
tions. Manipulation of light by plasmonic nanoparticles can offer molecular-specific
imaging with superior quality of early disease detection, tissue imaging, and func-
tional diagnostics.
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Synthesis, Conjugation, and Applications
of Chiral Nanoparticles as Plasmonic
Probes
Manasa Gangadhar Shetty, Sindhoora Kaniyala Melanthota,

Nikhil Kumar Daimari, Rajib Biswas, Nirmal Mazumder,
and Kampa Sundara Babitha
Abstract Chirality has always been an interesting topic in science. At present,

chiral nanoparticles are in increased demand because of their unique chiroptical
properties. Collective oscillations of free electrons in nanostructures result in
plasmonic effects. Plasmonic has enabled the confinement of light to the nanoscales
resulting in increased chiroptical interactions. Several strategies are developed to
synthesize nanoparticles and impart chirality to them. Researchers are now more
interested to explore diverse applications of chiral nanoparticles in various biological
and pharmaceutical industries. We provide insight into the synthesis, conjugation,
and application of such chiral nanoparticles as plasmonic probes in this chapter.
Key words Chirality · Plasmonics · Circular dichroism · SERS · Colorimetry
1 Introduction
The chirality of a molecule is a geometrical property based on the spatial arrange-

ment of atoms within a molecule. The molecule exhibiting chirality is called a chiral
molecule. The mirror images of a chiral molecule are nonsuperimposable with each
other, and they are referred to as enantiomers. DNA, amino acids, and sugars are
some of the naturally occurring chiral biological molecules [1]. The enantiomers
share the same physical and chemical properties, such as melting points and boiling
points. However, they behave differently in a chiral environment. Each enantiomer
of a chiral drug molecule exhibits different chemical and pharmacological actions in
M. G. Shetty · S. K. Melanthota · N. Mazumder · K. S. Babitha (*)

e-mail: babitha.ks@manipal.edu
N. K. Daimari · R. Biswas
Department of Physics, Applied Optics and Photonics Lab, Tezpur University, Tezpur, Assam,
India
https://doi.org/10.1007/978-3-030-99491-4_14
366 M. G. Shetty et al.
biological systems. For example, one enantiomeric form of penicillamine is benefi-

cial as an anti-arthritis agent but the other form is a neurotoxin [2].
One of the very interesting aspects of chiral molecules, which make them
extremely important to be used in various fields is their interaction with circularly
polarized light. Each enantiomer interacts differentially with circularly polarized
light. To be precise, each enantiomeric form can rotate the direction of polarized
light in opposite directions. This property is called optical activity and therefore
chiral molecules are optically active. The optical activity of a chiral molecule can be
used to characterize and determine the purity of a molecule [2]. When chirality is
observed in nanoscale, they are called chiral nanostructures. However, the presence
of an equal amount of each enantiomer makes the macroscopic nanostructure
ensembles exhibit zero net chirality. The first chiral gold nanoclusters conjugated
with L-glutathione were prepared by Whetten et al. in 1988. This finding led to the
further development of various chiral inorganic nanostructures [1].
Collective oscillations of free electrons in nanostructures result in plasmonic
effects at the nanoscale. When plasmonic nanostructure possesses structural chirality
in the presence of a circularly polarized light, the resonance for one circular
polarization is more than the other. This leads to chiral plasmonic effects
[3]. Plasmonics has enabled the confinement of light to the nanoscales resulting in
increased chiroptical interactions. Nanostructures made up of gold are among the
highly used plasmonic nanomaterials with chirality. Usually, amino acids are used as
structure-directing agents to impart chirality to individual gold nanoparticles
[3]. Researchers have followed various strategies to induce chirality into
nanoparticles with strong chiroptical activity. Asymmetric chiral nanoparticles
with innate optical activity are also successfully being synthesized and used. After
being efficaciously able to synthesize different types of chiral nanostructures of
different shapes and sizes and investigating their mechanistic characteristics,
researchers are now focusing on the uses of chiral plasmonic nanostructures in
several fields such as biomedicine, solar cells, stills, and collectors. In this chapter,
we discuss details of synthesis and uses of chiral nanostructures where the plasmonic
signals are used [4].
2 Gold-Based Chiral Nanoparticle
Chiral ligands such as glutathione, penicillamine, cysteine, and thiols are used to
induce chirality to gold nanoparticles (Fig. 1(a); Table 1).
2.1 Glutathione (GSH) Protected
A group of huge nanoclusters with a gold core and a GSH adsorbent were prepared
using glutathione in distilled water and chloroauric acid (HAuCl4) in methanol. The
resultant mixture was a cloudy white suspension of Au(I)SG polymer, which was
Synthesis, Conjugation, and Applications of Chiral Nanoparticles. . . 367
Fig. 1 Synthesis and conjugation of chiral gold (a), silver (b), and cadmium (c) nanoparticles with
chiral ligands
then reduced by the addition of sodium borohydride (NaBH4). It was then added into
aqueous methanol with stirring, resulting in the formation of GSH capped chiral gold
nanoclusters [5]. Amino acids and peptides are used for the synthesis, along with
chiral gold to control the optical activity by preparing cubic and octahedral seed
nanoparticles. Chiral nanoparticles started to develop by the blend of amino acid/
peptides and seed solution into a solution containing tetrabromoaurate (AuBr4)
complex that is formed by combining of hexadecyltrimethylammonium bromide
solution (CTAB) and AuCl4H7O3 in deionized water (DI), followed by the rapid
injection of L-ascorbic acid solution to reduce Au3+ to Au+. Sequential addition of
glutathione into the growth and seed (cubic) solutions gave rise to the formation of
432 helicoid II. Similarly, 432 helicoid III was prepared by adding glutathione into
the growth and seed (octahedral) solutions. The temperature maintained was 30 C.
It was then centrifuged to eliminate unreacted reagents and was added to CTAB
Table 1 Summary of chiral gold nanoparticle synthesis and conjugation [5–7, 9–15]
Chiral Concentration Concentration Reducing Concentration
molecule (mM) Precursor (mM) agent (mM)
Glutathione 1.0 Chlorauric 1.0 Sodium 10.0
acid borohydride
2.0 Gold chlo- 10.0 L-ascorbic 100.0
ride acid
trihydrate
2.8 Gold chlo- 5.0 L-ascorbic 20.0
ride acid
trihydrate
2.0 Chlorauric 0.5 Sodium 5.0
acid borohydride
trihydrate
2.0 Chlorauric 0.5 Sodium 5.0
acid borohydride
trihydrate
Penicillamine 1.0 Chlorauric 0.5 Sodium 200
acid borohydride
Cysteine 5.0/100.0 Gold chlo- 10.0 L-ascorbic 100.0
ride acid
trihydrate
4.0 Chlorauric 1.0 Sodium 2100
acid borohydride
trihydrate
25/600 Gold 0.25/0.33 Sodium 100
chloride borohydride
4100 Chlorauric 1.01 Sodium 2100
acid borohydride
Thiol 1.5 Chlorauric 0.25 Sodium 200
acid borohydride
~3 equivalents of Chlorauric 0.3 Sodium 0.9
the moles of gold acid borohydride
trihydrate
[6]. Even though this method of chiral plasmonic gold nanoparticles (432 helicoids)
synthesis using aqueous-based amino acid/peptide had a great chiroptic response, it
was discovered that the whole chiroptic potential of a chiral gold nanoparticle is
limited with its total synthetic symmetry through single-nanoparticle dark-field
scattering analysis. Therefore, a multi-chirality-evolution step synthesis method
was introduced to enhance the chiroptic response by increasing particle uniformity.
Gold octahedral nanoparticles of uniform size enclosed with a {111} facet and
glutathione were used to form chiral seed nanoparticles with smaller size and then
it was followed by the further step that allowed second chiral growth helping to
stimulate uniform 432 helicoid III with improved chiroptic response [7]. Monodis-
perse Au38(SC2H4Ph)24 nanoclusters were prepared by mixing AuCl4H7O3 and
GSH powder in the presence of an organic solvent (acetone) at room temperature
(rt) under robust stirring causing the yellowish cloudy suspension to form. Addition
of an aqueous solution of NaBH4 to the mixture made the solution suddenly turn
black indicating the formation of gold nanoclusters soluble in water. Further, the
addition of Aun(SG)m in water with ethanol, toluene, and excess 2-phenylethanethiol
(PhC2H4SH), followed by heating the mixture led to the conversion of initial
polydisperse gold (Au) nanoclusters into monodisperse Au38(SC2H4Ph)24 clusters.
Finally, Au38(SC2H4Ph)24 nanoclusters were separated by extraction with
dichloromethane or toluene. Proper mixing of AuCl4H7O3 and GSH at rt. under
stirring conditions resulted in the formation of a yellowish cloudy suspension. The
mixture was cooled to 0 C and a fresh solution of NaBH4 in water (cold) was
quickly added to the above solution. Black colored Aun(SG)m nanoparticles precip-
itated and the precipitate was dissolved in water. The aqueous solution of Aun(SG)m
was mixed with ethanol, toluene, and benzyl mercaptan (PhCH2SH), and the mixture
was heated (80 C). Heating resulted in phase transfer of nanoparticles from the
aqueous phase to the organic phase. The resultant polydisperse Aun nanoparticles
obtained converted to monodisperse Au38(SC2H4Ph)24 nanoparticles due to a
prolonged etching process. The product was then washed with ethanol or methanol
and separated by extracting with dichloromethane or toluene. The product was
subjected to crystallization in toluene/ethanol, which resulted in the formation of
black crystals [8].
2.2 Penicillamine Protected
Gold nanoclusters protected with L, D, DL-penicillamine were synthesized in 2013

by Yang et al. [9]. HAuCl4 and penicillamine were added to methanol. The mixture
was reduced by the brisk addition of NaBH4 solution. The solution was kept
overnight. Upon adding ethanol into this solution, crude precipitate (dark-brown
colored) was formed, which was then subjected to water/ethanol and ethanol wash.
The washings formed nanocluster powder [10].
2.3 Cysteine Protected
Chiral nanostructure 432 helicoid I was prepared by adding cubic seed solution into
the growth solution and cysteine following the method mentioned by Lee et al. in
2018 [6]. Two different synthetic methods followed are (a) coating after Au nano-
particle synthesis and (b) coating during Au nanoparticle synthesis. For the previous
type of synthesis, aqueous solutions of gold chloride (AuCl3) and sodium citrate
(Na3C6H5O7) were prepared and the solution of NaBH4 was added into it and stored
overnight in the absence of light yielding Au nanoparticles. The solution was diluted,
and the cysteine was supplemented with the diluted solution. Cysteine coatings were
done in three different types (using D-, L-, and racemic forms of cysteine). An
aqueous solution of AuCl3 and Na3C6H5O7 were combined in the synthetic method
(a), NaBH4 was then gradually added at rt. The solution was kept overnight in the
dark. The Au nanoparticle solution formed was diluted, and cysteine was added to
it. In the latter synthetic method (b), an aqueous solution of AuCl3and Na3C6H5O7
was prepared in a round-bottom flask (RB flask). NaBH4 (ice-cold) was then added
with the instantaneous addition of cysteine. The solution was kept overnight in a vial
made of glass covered in aluminum foil to prevent photodegradation. The coated Au
nanoparticles solution was again diluted before use. Both the synthetic approaches
yielded products with identical net concentrations [11].
HAuCl4 and N-acetyl-L-cysteine (C5H9NO3S) were dissolved in methanol and
acetic acid in the ratio of 6:1, generating a red solution, which quickly turned into a
suspension of white cloudy color. This specifies the formation of Au (I) - C5H9NO3S
polymer. Fresh aqueous NaBH4 solution was added slowly to the mixture to reduce
the polymer under fast stirring. Polytetrafluoroethylene (PTFE) membranes
(0.2 mm) were then used to filter the solution. The product was dried. The particles
obtained were refined by subjecting the particles to sequential ethanol precipitations
and PTFE membranes (0.2 mm) filtrations followed by dialysis. Finally, the particles
were dissolved in water. The black solution obtained was evaporated to give a black
powder [12].
2.4 Thiol Protected
Thiolate-protected gold clusters were prepared by treating a methanolic solution of

HAuCl4 with thiol. The addition of aqueous NaBH4 solution with vigorous stirring
resulted in the formation of Au:SG and Au:S(SA) clusters. Au:S(PG) cluster was
synthesized by the addition of a methanolic NaBH4 resulting in the formation of a
precipitate. Washings with methanol, followed by drying the precipitate formed
yielded the desired nanoparticles [13]. N-isobutyryl-cysteine (C7H13NO3S) mono-
layer protected nanoparticles (MPNs) were synthesized by adding HAuCl4 and the
corresponding enantiomer of C7H13NO3S in methanol/acetic acid solution, resulting
in the formation of a suspension of cloudy white color, indicating the development of
Au (I) - N- C7H13NO3S polymer. It was then reduced by the addition of an aqueous
NaBH4 solution. A dark-colored solution formed was filtered using PTFE membrane
(200 nm) to eliminate insoluble reactants and consequently evaporated resulting in
precipitation, which was filtered with ethanol using the same PTFE membrane.
Further, the thiols or disulfides that remained unreacted were eliminated through
dialysis (Spectra/Por CE) in a bag (with molecular weight cutoff of 3500 Da). The
black colored solution obtained was further vaporized under a vacuum to give black
powder. The nanoparticles were separated using polyacrylamide gel electrophoresis
(PAGE) [14]. Chiral thiol protected Au25(SR)18 nanospheres were prepared by
dissolving AuCl4H7O3 in nano pure water with tetraoctylammoniunm (C32H68N+)
in toluene and the mixture was vigorously stirred. It was followed by the addition of
2-phenylpropane-1-thiol (C9H12S) under stirring conditions. An aqueous solution of
NaBH4 was quickly added to the clear mixture. Further, the addition of methanol
resulted in the formation of a turbid solution containing gold nanoparticles. The

precipitate obtained was allowed to stand overnight and later, the precipitate was
collected. Further, highly pure gold nanoparticles were obtained by extracting the
dried precipitate collected with acetonitrile (CH3CN). Similarly, the Au25
nanoparticles protected by (S) - C9H12S or racemic C9H12S were synthesized. The
reaction was performed under a nitrogen atmosphere. Further, they synthesized
chiral Au25 rods by combining and vigorously shaking the solutions of AuCl4H7O3
in nano pure water and tetraoctylammonium bromide (C32H68BrN) in toluene.
Triphenylphosphine (C18H15P) was added to the toluene resulting in the conversion
of a clear solution into a whitish cloudy colored solution. Further addition of an
aqueous NaBH4 in ethanol made cloudy white suspension suddenly become a dark
solution yielding black product. The product was then washed with hexane to
remove impurities, and the product obtained was dissolved in chloroform, followed
by the addition of pentane resulting in the formation of precipitation of unreacted Au
(I) salt comprising of polydisperse Au nanoparticles. It was then converted to
monodisperse Au25 rod clusters by the addition of (S)–C9H12S or racemic C9H12S
and dissolved in dichloromethane and the solution was rapidly stirred at rt, followed
by washing with hexanes and hexane/dichloromethane (1:1). The monodisperse
Au25 nanorods were extracted from the precipitates with ethanol [15].
3 Silver-Based Chiral Nanoparticle
Chiral ligands such as poly(dG)-poly(dC) double-stranded (ds) scaffold, GSH,

phosphines, thiols, and halogens (Cl and Br), bovine submaxillary mucin, and
dihydrolipoic acid (DHLA) are used to induce chirality to silver nanoparticles (Fig. 1
(b); Table 2).
3.1 Poly(dG)-Poly(dC) Double-Stranded (ds) Scaffold

Protected
Poly(dG)-poly(dC) double-stranded (ds) chiral skeleton was used to prepare a chiral

silver nanoparticle by the reduction of silver (Ag+) bound to 700 base pairs poly
(dG)-poly(dC). The elongated homopolymer of poly (dG)-poly (dC) was created
using Klenow exo-fragment of DNA polymerase [16].
Table 2 Summary of chiral silver nanoparticle synthesis and conjugation [16–20]

Chiral
molecule Concentration Precursor Concentration Reducing agent Concentration
a a a
Poly(dG)-poly Silver Sodium borohydride
(dC) double-
stranded
(ds) scaffold
GSH 50 mM Silver 20 mM Tetrabutylammonium 100 mM
nitrate bromide
a a
Multiple Silver Sodium borohydride 50 mg/mL
[phosphines, nitrate
thiols and hal-
ogens (Cl and
Br)
BSM 10 mg/ml Silver 1 mg/ml Bovine submaxillary 10 mg/mL
nitrate mucin
Lipoic acid 5.0 104 mol Silver 100 mM Sodium borohydride 5.0 104
nitrate mol
a
No data available
3.2 GSH Protected
Aqueous solutions of silver nitrate (AgNO3) and GSH were mixed with ultrapure
water under mild stirring conditions resulting in the formation of an Ag(I)–SG
complex. Cold tetrabutylammonium borohydride (TBAB) and sodium hydroxide
(NaOH) were added to the reaction mixture with vigorous stirring, a deep
red-colored solution of silver nanoparticles was formed. The solution was then
incubated resulting in the gradual decomposition, resulting in the development of
a colorless solution. A brown Ag nanoclusters solution was again added with TBAB
and NaOH with vigorous stirring to form a brown solution, which was then
incubated. The resultant raw red-emitting solution was collected, dialyzed, lyophi-
lized, and stored at 4 C [17].
3.3 Multiligand Protected
Tetrahydrofuran solution (THF) with (C32H68ClN) was added to AgNO3 in metha-

nol, followed by the addition of bis(diphenylphosphine)methane (Dppm,
C25H22OP2) and 1-adamantanethiol (HSAdm, C10H16S). The solution was stirred
for 30 min. NaBH4 was supplemented to the mixture and the reaction was sustained
for 4 h. Solvents were decanted, and the product obtained was solubilized in
dichloromethane. The solvent was evaporated and the black colored crystals of
[Ag32(Dppm)5(SAdm)13Cl8]3+ were formed. Likewise, the
[Ag45(Dppm)4(S-But)16Br12]3+ nanocluster was prepared using tert-butyl mercaptan
(HS-But) and tetraoctyl ammonium bromide (TOABr) as surfactants [18].
3.4 Bovine Submaxillary Mucin (BSM) Protected
A stable chiral Ag nanoparticle within a natural mucin glycoprotein was synthesized

by combining an aqueous solution of AgNO3 and bovine submaxillary mucin
(BSM) at rt. (24 h). The reaction caused the formation of a complex, which was
then purified by size exclusion chromatography using Sephadex G-25. After purifi-
cation, the pH was adjusted using sodium borate buffer (pH 10.0). The reaction
mixture was stirred and filtered through a 0.45 mm filter. In this synthesis, BSM
itself acts as a reducing agent [19].
3.5 Dihydrolipoic Acid (DHLA) Protected
Chiral silver nanocluster was prepared using DHLA as a capping ligand. NaBH4 was
added to the solution of α-lipoic acids which resulted in the instant formation of a
turbid solution of brown color. NaBH4 reduces enantiomeric α-lipoic acids to
DHLA. Further, nanoclusters with discrete numbers of silver atoms and ligands
were developed by size-focusing of nonluminescent nanoparticles [20].
4 Cadmium-Based Chiral Nanoparticle
Chiral ligands such as penicillamine, horse spleen ferritin, cysteine, and a few
carboxylic acids thiols are used to induce chirality to gold nanoparticles (Fig. 1
(c); Table 3).
4.1 Penicillamine Protected
Penicillamine stabilized cadmium sulfide (CdS) nanocrystals using a solution of

penicillamines (D-, L-, or racemic forms), cadmium perchlorate hydrate
(Cd (ClO4)2.H2O), and thioacetamide (CH3CSNH2) were synthesized under micro-
wave irradiation (850 W). Nanoparticles were precipitated using 2-propanol
[21]. Chiral Cd-Pen complex was formed by the addition of Cd (ClO4)2 to penicil-
lamine (D-, L-, or racemic forms). A highly luminescent CdS nanocluster of 5 nm
size range was formed upon the addition of CH3CSNH2 under microwave irradiation
to the above mixture [22]. Penicillamine and cadmium chloride (CdCl2) solutions
were mixed in water. The pH was maintained at 11.5–12 by adding NaOH to the
mixture. Followed by the addition of CH3CSNH2 solution to the mixture and it was
refluxed for 2 h. The mixture was allowed to cool in the absence of light. The
solution was concentrated and filtered through evaporation and ultracentrifugation,
374
Table 3 Summary of chiral cadmium nanoparticle synthesis and conjugation [21–38]

Chiral molecule Concentration Precursor Concentration Reducing agent Concentration
Penicillamine 2 105 mol Cadmium perchlorate hydrate 1.0 102 M Thioacetamide 8 103 M
– Cadmium perchlorate – Thioacetamide –
0.01 M Cadmium chloride 0.01 M Thioacetamide 0.01 M
1 102 M Cadmium perchlorate hydrate 1.0 102 M Sodium selenosulfate 1 102 M
0.01 M Cadmium perchlorate 10 mM Sodium borohydride 1M
Horse spleen ferritin 0.05 M Cadmium acetate 1.0 mM – –
Cysteine 0.04 g/4 ml TOPO/OA–cadmium selenide 0.05 mM – –
0.10 g/10 ml Cadmium acetate (cadmium selenide NPLs) – – –
– Cadmium perchlorate hexahydrate 0.013 M – –
0.50 g/50 ml Cadmium oxide 0.2 mmol – –
1.0 M Cadmium perchlorate hydrate 0.985 g/125 ml – –
0.2 M Cadmium selenide NPLs 0.15 mmol – –
0.062 M Cadmium telluride/selenide QDs – – –
0.5 g/50 ml Cadmium selenide NPLs – – –
3.0 103 mol Cadmium chloride hemipentahydrate 1.25 103 mol – –
Carboxylic acid 0.056 M Cadmium selenide QDs 0.03 mM – –
0.057 M Cadmium sulfide QDs – – –
50 mg/0.5 ml Cadmium sulfide – – –
M. G. Shetty et al.
respectively. The precipitate formed was then washed with a mixture of water and
ethanol and then it was resuspended in water. The chiral CdS nanotetrapods were
stored in the refrigerator at 4 C [23]. Degassed Millipore water was added to an
aqueous D-, L-, or racemic-penicillamine solution at a constant flow of argon gas by
maintaining the pH of 11.5 using NaOH. It was followed by the addition of Cd
(ClO4)2.xH2O and sodium selenosulfate (Na2SeSO3) with vigorous stirring. The
mixture was then irradiated with microwave (40 s, 1500 W). This resulted in a clear
yellow solution. It was kept in dark condition followed by rotor evaporation.
2-propanol was added to the concentrated solution to precipitate the nanoparticles.
The nanoparticles were centrifuged and washed with a propanol water mixture and
added to water [24].
CdS quantum dots were synthesized by the addition of aqueous Cd(ClO4)2.H2O
and L-penicillamine to water with fast stirring (pH 11.5). Aqueous thioacetamide
was quickly added to it. The product was incubated for 24 h in the dark (rt) and
separated and purified using a C 6/40 column of Sephadex G-25. It was useful for the
separation of sizes of quantum dots. The D-enantiomer was also prepared similarly
by shifting enantiomer from L- to D-form. Likewise, CdSe quantum dots were also
synthesized by preparing sodium hydrogen selenide by dispersing selenium powder
in ice-cold water, followed by the addition of sodium borohydride by vigorously
stirring. The solution became translucent and was immediately used. Different
samples were prepared using aqueous solutions of cadmium perchlorate hydrate
and penicillamine and the pH was raised to 11.5 using an aqueous solution of sodium
hydroxide and immediately sodium hydrogen selenide (NaSeH) solution was added.
The sample was passed through the Sephadex column as mentioned above. Different
fractions of elution were collected [25].
4.2 Horse Spleen Ferritin Protected
CdS quantum dot (QD) in a horse spleen ferritin was prepared as a hollow chiral
template using thioacetic acid in a horse spleen apoferritin/reaction solution (pH 6.5)
along with cadmium acetate in ammonia (Aq.). This formed chiral CdS QDs in the
apoferritin cavities [26].
4.3 Cysteine Protected
The ligand exchange method is followed to prepare an optically active cadmium

QDs. TOPO/OA–CdSe in toluene was added to an aqueous solution of cysteine in
DI water (pH maintained at 12 and purged with nitrogen gas). The reaction mixture
was kept in dark condition (stirring at rt. for 24 h). There was phase transfer as the
cysteine capped CdSe settled down in an aqueous phase and TOPO/OA–CdSe was
found not solubilized in water. The crude cysteine–CdSe QDs were then filtered by
precipitation [27]. CdSe nanoplatelets capped with cysteine molecules were pre-
pared by dissolving cysteine (D- or L-) hydrochloride monohydrate in water
(pH 12.0). It was followed by the addition of CdSe solution in hexane. Ethanol
was then added into the solution, its addition brings about the transfer of CdSe
quantum dots into the water layer. It was then properly stirred and added with
isopropanol at room temperature which resulted in the precipitation and the resultant
product was dissolved in water [28]. Water-soluble (D, L)-Cysteine-Stabilized CdTe
nanocrystals were synthesized following the Rogach-Weller method. An aqueous
solution of Cd(ClO4)26H2O was saturated with nitrogen and maintaining the pH at
11.2. Addition of (D, L)-cysteine acts as a stabilizing agent. The solution was then
refluxed (110 C) in an oil bath under a nitrogen atmosphere with the flow rate of the
nitrogen gas was 100 ml/min during synthesis [29].
Classic thermal injection technique was followed to prepare wurtzite CdSe
quantum rods using trioctylphosphine oxide (C24H51OP). Stabilizers such as
tetradecylphosphonic acid (C14H31O3P), octadecylphosphonic acid (C18H39O3P),
and hexylphosphonic acid (C6H15O3P) were used to control the growth rate of
CdSe quantum rods. Followed by ligand exchange with L- or D-cysteine. The
exchange allows the complete transfer to the aqueous phase from organic solvent
[30]. D- or L -cysteine stabilized CdTe nanoparticles were synthesized using alumi-
num telluride (Al2Te3) with H2SO4 as precursor molecule under nitrogen atmo-
sphere. H2Te was passed through Cd (ClO4)26H2O in water containing D- or
L-Cysteine/GSH as the stabilizing agent by maintaining the pH at 12.0. The reaction
mixture was refluxed at 110 C in nitrogen atmosphere (flow rate: 100 ml/ min, 8 h).
Chiral CdTe nanoparticles were centrifuged and purified using 2-propanol and
redispersed in PBS [31]. Cysteine (L- or D-) hydrochloride monohydrate was
dissolved in water (pH 12.0) using tetramethylammonium hydroxide (TMAH)
resulting in the formation of cysteine solution. Cysteine solution was added with
hexane solution containing CdSe nanoplatelets followed by stirring at room temper-
ature (24 h). Phase separation occurred when the reaction mixture was allowed to
stand for 1 h. Nanoplatelets were formed and were purified by precipitation by
adding water. The purified cysteine nanoplatelets were redispersed in water and
stored in dark at room temperature [32]. CdS, CdSe, and CdTe QDs dissolved in
toluene were mixed with an aqueous solution of L-cysteine solution, maintained at
the pH of 10.5 under vigorous stirring. Acetone was added dropwise which allows
the phase transfer (6 h under dark). The reaction mixture was then incubated for
30 min which resulted in phase separation. The QDs were purified using the first
centrifugation. The resultant QDs were dissolved in water [33].
Cysteine (D- or L-) hydrochloride monohydrate in ultrapure water maintained at
pH 12.0 with TMAH to form the cysteine solution was added to wurtzite CdSe
nanoplatelets in chloroform or zinc blende CdSe nanoplatelets in hexane solution. It
was followed by the addition of ethanol. It was further stirred at room temperature
(1 h) and then isopropanol/ultrapure water was added to the mixture, the cysteine-
CdSe nanoplatelets were precipitated. It was then purified by centrifugation and
finally, the product was redissolved in water [34].
Cysteine (D- or L-) modified CdTe QDs were prepared by dissolving cadmium
chloride hemipentahydrate (CdCl22.5H2O) in water and cysteine (D- or L-) was
added under nitrogen atmosphere by maintaining the pH at 11.0. A freshly prepared
oxygen-free NaHTe was added to the reaction mixture under vigorous stirring and
the resulting mixture was refluxed (100 C) for 8 h. The solution was then cooled to
room temperature and deaerated by applying nitrogen gas. CH3CSNH2 in water was
added to crude CdTe and heated at 80 C for 6 h to form CdTe@CdS core@shell
structure. It was purified by adding ethanol until the solution turned turbid, which
was stirred and CdTe@CdS quantum dots were separated by centrifugation and
dried. The dried precipitate was redispersed in water [35]. The L- and D-cysteine
capped CdSe QDs were synthesized using OA-CdSe and TOPO/OA-CdSe quantum
dots as precursors following phase transfer ligand exchange. L-cysteine hydrochlo-
ride monohydrate was dissolved in water (pH 12.0) using tetramethylammonium
hydroxide. It was further added to OA-CdSe QDs in toluene, deaerated, and stirred at
room temperature under dark conditions for 24 h. Phase transfer occurred, and
L-cysteine capped quantum dots settled at the bottom of the water layer. The mixture
was then allowed to proceed for one more hour for the completion of phase transfer.
The settled layer was collected and purified by precipitation using acetone/DI water.
The precipitate was redissolved in DI water. It was further precipitated with acetone
centrifuged. The precipitate finally obtained was redissolved in DI H2O and stored in
the absence of light under dark conditions [36]. L-Cysteine derivative in water
(pH of 12.0, maintained using tetramethylammonium hydroxide) was added with
the solution of OA-CdSe QDs in toluene. The reaction mixture was deaerated using
nitrogen gas and stirred at room temperature under dark conditions (24 h). The
reaction mixture was further incubated for the complete phase transfer followed by
the separation of CdSe quantum dots capped with cysteine derivatives by precipita-
tion upon addition of acetone. The precipitate formed was isolated by centrifugation
and redispersed in DI water (2 mL) and stored under dark conditions. Similarly,
cysteine capped CdS quantum dots were prepared [37].
4.4 Carboxylic Acid Protected
Post synthetic ligand exchange method was used to synthesize chiral CdSe quantum
dots with carboxylic acids exhibiting chirality. Oleate and myristate ligand-bound
CdSe was added to chiral carboxylic acid and carboxylate bound CdSe QDs
dissolved in toluene. Nanoparticles were found aggregated and the supernatant
was discarded. It was redispersed in dimethylformamide, dimethyl sulfoxide, or
methanol. Some of the carboxylic acid chiral ligands used in the study are
C5H9NO3S, aspartic acid, tartaric acid (D-and L) (C4H7NO4), malic acid (D- and
L) (C4H6O5), L-lactic acid (C3H6O3), (S)-()-2-chloropropionic acid (C3H5ClO2),
and (R)-()-phenylsuccinic acid (C10H10O4) [38].
5 Applications of Chiral Nanoparticles
5.1 Chiral Gold Nanoparticles as Plasmonic Probes
Self-assembled gold nanoparticles (AuNPs) stabilized with chiral ionic liquid (CIL)
monolayer were fabricated as surface-enhanced Raman spectroscopy (SERS) sub-
strates which generated enhanced SERS signal for Rhodamine 6G (R6G). S-3-
hexadecyl-1-(2-hydroxy-1-methylethyl)imidazolium bromide ([C16hmim]Br) as
CIL was utilized to synthesize the AuNPs. The CIL stabilized AuNPs were fabri-
cated on quartz slides and then drop-casted with aqueous solution of R6G to prepare
SERS samples. It was found that the AuNPs self-assembled to form ring-like
structures in air/water interface attributing to “surfactant-enhanced Marangoni-
Benard instability.” Raman spectra with solid R6G on quartz slide exhibited rela-
tively weak signal while SERS activity of R6G on AuNPs patterned substrate
showed a significantly enhanced response. The enhancement of SERS signal was
mainly due to the interaction of aromatics rings of R6G with CIL imidazole groups
on AuNPs. The SERS intensities were also found to be significantly increased in
the concentration range 105– 104 M of R6G attributing to aggregation of
nanoparticles. The surface enhancement factor was calculated to be ~7.28 104
implying that CIL stabilized AuNPs could be employed as reliable SERS
substrates [39].
AuNPs synthesized by means of chemical reduction method and functionalized
with glutathione (GSH) and Rhodamine 6G (R6G) molecule to form GSH-AuNPs-
R6G SERS substrate for determination of As3+ was reported. The wine-red color of
stabilized GSH-AuNPs turned blue upon addition of As3+ by formation of As-O
bonds. It was observed that SERS activity of GSH-AuNPs-R6G-As3+ exhibited
more intense signals compared to other substrates attributing to enhanced electro-
magnetic interaction among the aggregated AuNPs. The SERS activity of
GSH-AuNPs-R6G with 1 ppb As3+ solution also found that R6G signal increased
with increasing concentration of GSH 29–95 nM suggesting that GSH ligands
replaced the citrate ions on the surface of AuNP causing aggregation. Thus, the
prepared AuNPs provided an exquisite SERS substrate with abundant hotspots for
detection of As3+ using R6G probe providing an limit of detection (LOD) of
0.14 ppb [40].
L-cysteine adsorbed on AuNPs surface were investigated by means of SERS
method. AuNPs colloids were fabricated by two methods: 1) reduction by sodium
borohydrate and 2) reduction by sodium citrate. Cysteine solutions of 2 104 M
were mixed with Au colloids and the mixture were taken on a quartz slide for SERS
measurement. It was found that the SERS experiments on Au colloids prepared
under different methods provided similar spectra. The SERS spectra also showed the
unavailability of 490 cm1 band from S-S stretching of cysteine which suggested
that no aggregation of cysteine took place. Also, the absence of band at 2570 cm1
due to S-H stretching indicated the ionization of thiol at Au surface. Theoretical DFT
simulations were performed and compared with experimental SERS spectra which
affirmed that cysteine adsorbed on the surface of AuNPs through S and O sites [41].
Circular dichroism (CD)-active spectra of AuNPs post synthesized using

1,3-disubstituted diamino calix[4]arene chiral ligands named 2a (distally distributed
with R chiral centers) and 2b (distally disubstituted with S chiral centers) was
studied. Initially, AuNPs were synthesized in dichloromethane stabilized with
tetraoctylammonium bromide and then followed by addition of each
aminocalixarene enantiomeric solution to AuNPs solution. UV-visible absorbance
spectra of AuNPs capped with 2a and 2b exhibited redshift of SPR band at about
520 nm indicating calixarene ligands adsorbed on AuNP surface. The CD band
ellipticities at 280 nm and 520 nm also increased with increasing total calixarenes
ligand concentration. The interaction of the adsorbed chiral ligand with the elec-
tronic states of the AuNP was attributed to the emergence of CD-active SPR
band [42].
Chiral gold nanoflowers (AuNFs) fabricated using L-ascorbic acid (L-AA) in the
presence of chiral guanosine 50 -monophosphate (50 -GMP) was reported as SERS
enhancement substrate. AuNPs were also prepared with reducing agents sodium
citrate and NaBH4 but they did not exhibit any chirality. UV-Visible spectroscopy of
50 -GMP capped chiral AuNFs found a characteristic LSPR band at around 636 nm.
For SERS activity measurement, 2-mercaptopyridine (2-Mpy) was used as a probe
molecule in the range of 1 103 1 106 mol/L and added with AuNFs
solution to form SERS substrates. The Raman spectra discerned enhanced SERS
intensity in 1 103 mol/L 2-Mpy AuNFs caused by production of large numbers
of “hotspots” from the surface area of AuNFs [43].
Selective enantiomeric determination of tyrosine using AuNPs surface capped
with chiral N-acetyl-L-cysteine (NALC) molecule was proposed. NALC was
adsorbed on the surface of AuNPs by forming Au-S covalent bond. The AuNPs
showed a noticeable color change to purple from red when L-tyrosine (L-Tyr) was
added indicating the aggregation of NALC-AuNPs. This was verified by the appear-
ance of new absorption peak in 630 nm with a slight reduction in intensity at 522 nm.
The extinction ratio (A630/A522) also discerned an increasing trend with an increase
in logarithmic value of L-Tyr concentration from 2.5 to 250 μM. However, no such
effect can be observed upon addition of D-Tyr confirming the chiral selectivity of
NALC-AuNPs on Tyr. The enantiomeric selectivity was attributed to electrostatic
interactions and hydrogen bonding of NALC ligands through carboxylic, amino, and
hydroxyl groups [44].
Chiral gold nanocubes (AuNCs) as colorimetric sensor for detection of D/L-
Leucine (Leu) enantiomers was reported. The AuNCs synthesized by aqueous seed-
mediated growth method exhibited red color and good stability. The AuNCs solution
turned colorless from red in presence of L-Leu, while no change was produced by
D-Leu. UV-Visible spectroscopy showed reduction of absorbance intensity at
540 nm and emergence of new peak at 710 nm upon addition of L-Leu. The
absorbance ratio (A710/A540) versus enantiomeric excess (ee) of L-Leu found a
correlation coefficient of 0.9908 within ee range 100% to 100% indicating that
the colorimetric probe can quantitatively determine Leu enantiomers. Circular
dichroism (CD) spectroscopy also presented strong CD signal intensity at 540 nm
inferring that AuNCs possessed intrinsic chirality attributing to the presence of point
defects in nanostructure [45].
Bovine serum albumin (BSA)-based LSPR probe was proposed for ultrasensitive
determination of Hg (II) using AuNPs capped with chitosan (ChGnP). Electrostatic
interaction between the amino groups of chitosan and AuCl4 solution ensued the
formation of the AuNPs where chitosan acted as both reducing and protecting agent.
A U-bend optical fiber platform by incorporating ChGnP and BSA was used as a
sensing probe. The selectivity and sensitivity of the sensing probe towards Hg
(II) were hypothesized to be due to the following factors: chemisorption, electro-
static interactions, hydrophobic, and Van der waals interactions. Due to the adsorp-
tion of Hg(II) on nanoparticles, a peak at 520 nm was observed in the absorbance
spectra. The sensor probe produced a linear response in the concentration range
0.1–540 ppb of Hg(II) providing excellent performance in tap water with a limit of
detection of 0.1 ppb and 0.2 ppb in sea samples [46].
AuNPs functionalized with glutathione (GSH) on an indium tin oxide (ITO)
substrate was developed as a plasmonic sensor for Pb2+ ions. ITO-AuNPs substrate
was fabricated through the self-assembly method using poly-dimethyl diallyl ammo-
nium chloride (PDDA) and calcined. The ITO-AuNPs substrate was then
functionalized with GSH molecules (ITO-AuNPs-GSH). An LSPR band peak was
noticed at 524 nm in the absorption spectra of ITO-AuNPs. This peak red-shifted to
532 nm with an increasing concentration of GSH attributed to the formation of Au-S
bond. A strong linear response was also calculated from 1010 M to 105 M Pb2+
concentration with red-shifted peak induced chelation between Pb2+ ions and GSH.
This plasmonic probe showed high selectivity towards Pb2+ ions with an LOD of
5 1011 M [47].
5.2 Chiral Silver Nanoparticles as Plasmonic Probes
Glutathione (GSH) stabilized silver nanoparticles (AgNPs) were prepared by the

green synthesis method to study the effect of different reaction times on the
nanoparticle mean size. Due to Van der Waals forces, weak molecular bonds were
formed between GSH molecules and AgNPs through thiol and acetyl groups. The
AgNP colloids collected at different reaction times 1 h, 3 h, 6 h, 18 h, 36 h, 48 h, and
72 h were subjected to UV-Visible spectroscopy which showed characteristics SPR
band around 344–354 nm indicating the formation of spherical AgNPs. The SPR
peak intensities also gradually increased from 36 h to 72 h suggesting an increase in
the concentration of AgNPs. This agreed with trasmission electron microscope
(TEM) results which determined a mean diameter of 3.20 0.71 nm,
4.83 1.15 nm, and 6.19 1.59 nm for 36 h, 48 h, and 72 h, respectively. However,
the occurrence of redshifts was hypothesized to be due to the reduction of electron
conductivity in the outermost atomic layer [48].
Uridine 50 -triphosphate (UTP)-capped AgNPs were utilized as a colorimetric
biosensor for enantioselective detection of D- and L-Cysteine (Cys). UTP consisting
of amines, carbonyls functional groups interacted with the surface of AgNPs and the
negatively charged phosphate groups which stabilized the nanoparticles through
electrostatic repulsion. When D-Cys was added to UTP-AgNPs it turned to red from
yellow color while no such alteration was observed in the case of L-Cys. With time
course UV-Visible spectroscopy the visual observation was confirmed which
showed D-Cys induced shift of SPR peak from 400 nm to 520 nm with a gradual
decrease in intensity at 400 nm. The performance of the colorimetric probe was
studied through absorption ratio A520/A400 which increased from 0.1 μM to 100 μM
for D-Cys; however, very low variation of A520/A400 ratio was calculated for L-Cys.
The colorimetric probe demonstrated a responsive selective chiral detection with
LOD of 100 μM and separation of cysteine enantiomers [49].
Silver nanoparticles capped with chitosan (CS-AgNPs) were fabricated as color-
imetric discrimination methods of L- and D- Tryptophan enantiomers. CS polymers
were utilized as stabilizers during the reduction of silver nitrate by sodium borohy-
dride for the preparation of CS-AgNPs. An SPR characteristic peak appeared at
around 404 nm with a mean diameter of 15 2 nm which indicated the uniform
dispersion of nanoparticles. From visual investigation, a gradual change of color was
observed with L-Trp from yellow to brown but not in D-Trp. It was confirmed by
TEM image and redshift of SPR peak at 550 nm indicating possible aggregation of
CS-AgNPs attributing to the helical structure of CS interacting with Trp through
hydrogen bonding. RGB (red, green, blue) and CMYK (cyan, magenta, yellow,
black) values obtained through scanometry determined good linearity within
1.3 105 4.6 104 mol L1 concentration of L-Trp with LOD
2.1 106 mol L1, 2.4 106 mol L1, and 3.8 106 mol L1 corresponding
to R, G, and B values, respectively. However, through spectrophotometry an LOD of
1.8 106 mol L1 was found for L-Trp [50].
Colorimetric recognition of D/L-deoxynucleoside enantiomers based on AgNPs
using calixarene chiral oligomers (CA[n]P-Ag NPs where n ¼ 4, 6, and 8) as capping
agents were developed. CA[n]P were initially fabricated and then mixed with
AgNO3 solution to form bright yellow colored CA[n]P-AgNPs in the presence of
NaBH4. An intense negative CD peak and UV-Visible absorption peak emerged at
425 nm attributed to characteristic SPR. The sensing performance particularly of CA
[8]P-AgNPs probe showed appreciable selectivity towards L-dC (β-L-2-
0
-deoxycytidine) and L-dT (β-L-20 -deoxythymidine) confirmed through color
change to red from yellow. The emergence of a new SPR peak at 539 nm due to
aggregation of CA[8]P-AgNPs realized a linear response of A539/A425 with respect
to concentration producing an LOD of 2.67 μM for L-dC and 3.28 μM for L-Dt,
respectively. The chiral probes also showed high selectivity towards L-
deoxynucleoside in the following decreasing performance CA[8]P-AgNPs > CA
[6]P-AgNPs > CA[4]P-AgNPs [51].
A simple low-cost colorimetric sensor probe using L-cysteine capped AgNPs
(L-Cys-AgNPs) for enantioselective detection of ketoprofens was developed. L-Cys
formed self-assembled monolayers on AgNPs which exhibited intense SPR peak at
409 nm in UV-Visible range. The chiral recognition ability was confirmed from
UV-Vis spectra when R-ketoprofen induced the appearance of a new peak around
600 nm in L-Cys-AgNPs. This selectivity was attributed to the bonding of
R-ketoprofen and AgNPs leading to agglomeration confirmed visually by a color
change to dark green. Although, no such prominent change was noticed with
S-ketoprofen in L-Cys-AgNPs. Raman intensities were also observed to be more
in R-ketoprofen than in S-ketoprofen ascribing to L-Cys being moved away from
metal surface due to conformational change of L-Cys on the addition of
S-ketoprofen. The L-Cys characteristic peaks observed at 498 cm1, 785 cm1,
and 1408 cm1 corresponding to S-S stretching, COO bending, and COO sym-
metric stretching respectively indicated that even with R-ketoprofen the interaction
between L-Cys and AgNPs prevailed. Additionally, the appearance of other peaks at
1002 cm1, 1599 cm1, 1649 cm1, and 3065 cm1 were related to alteration of ring
structure, stretching of C-C, stretching of C═O, and stretching of C-H respectively
confirming L-Cys and R-ketoprofen near nanoparticle surface-induced its aggrega-
tion. From the absorbance ratio A600/A409 curve, the linear range was calculated to
be 8.33–33.3 μM revealing an excellent sensitivity of the probe with LOD 4.52 μM
and LOQ 13.69 μM for R-ketoprofen [52].
Glutathione (GSH) capped fluorescent silver nanocrystals (AgNCs) were synthe-
sized by sonochemical method for detection of S2 ions. Blue fluorescence emission
was observed under UV light while during daylight the AgNCs appeared colorless.
UV-vis spectra found an intense peak at 350 nm followed by a weak peak at 274 nm
relating to d-sp band transitions while fluorescence spectra presented a single
emission peak at 430 nm at an excitation wavelength of 350 nm. It was observed
that longer exposure to ultrasonic irradiation decreased the emission intensity by
generating nonfluorescent AgNCs. When S2 ions were employed to AgNCs,
fluorescent quenching with increasing concentration of S2 was observed due to
formation of Ag2S which induced color change to yellow in AgNCs. The sensor
probe provided high selectivity towards S2 over other anions and exceptional
sensitivity with a limit of detection of 2 nM [53].
5.3 Chiral Cadmium Nanoparticles as Plasmonic Probes
Fabrication of chiral DPA-Cys-CdS QDs as glucose biosensor by utilizing

D-penicillamine (DPA) and achiral cysteamine capped cadmium sulfide quantum
dots (Cys-CdS QDs) was reported. CD spectroscopy was used as a sensing strategy
for the detection of glucose. It was observed that no CD signals appeared in Cys-CdS
QDs but upon introduction of DPA to Cys-CdS QDs solution, strong CD intensities
were recorded due to binding interaction between CdS QDs and DPA. The amount
of hydrogen peroxide (H2O2) produced from the reaction between glucose and
glucose oxidase (GOx) is directly responsible for the oxidation of DPA-Cys-CdS
QDs impairing its chirality which ensued a decrease in CD response. It was observed
that the CD signals decreased linearly with increasing concentration of glucose from
50 to 250 μM. The CD-active sensor probe proved to possess a remarkable sensi-
tivity with a limit of detection of 31 μM as well as high selectivity towards glucose
over other sugar compounds [54].
L-/D-cysteine capped CdTe quantum dots (L-/D- QDs) with gold nanorods
(GNRs) were prepared as fluorescent probes for trace detection of cysteine. When
L-Cyst or D-Cyst were introduced to L-QDs and GNRs containing solution, the QDs
and GNRs formed tight dynamic nanoparticles-nanorods assemblies leading to
fluorescence resonance energy transfer (FRET) from QDs to GNRs. It was observed
that L-Cyst exhibited more efficient quenching of fluorescent signal than D-Cyst in
L-QDs resulting in selective detection of one of the enantiomers. When investigated
with D-QDs it was concluded that heterochiral (D- and L-QDs) interaction led to
higher FRET efficiencies relative to homochiral (L- L-QDs or D- D-QDs). By
analyzing the fluorescence spectra of both the chiral QD-GNR/FRET sensing plat-
forms, the concentration and proportion of cysteine could be well determined [35].
CD spectroscopy method was introduced for sensing of Ni2+ and Co2+ metal ions
using cadmium sulfide quantum dots capped with L-cysteine (L-Cyst CdS QDs).
With the introduction of Ni2+ or Co2+ to L-Cyst CdS QDs solution, the CD spectra
appeared strikingly different than those without the metal ions. It was found that in
Ni2+, CD peak at 324 nm switched to the positive direction while in the case of Co2+
the CD peak at 352 nm enhanced in the positive side attributing to the development
of chiral complexes between Ni2+ or Co2+ and L-Cyst. The proposed sensor probe
exhibited a wide linear range from 10 to 60 μM and 4–80 μM and excellent
sensitivity with a low LOD of 7.33 μM and 1.13 mM for Ni2+ and Co2+
respectively [55].
Chiral cysteine capped CdSe(ZnS) quantum dots were fabricated as a fluores-
cence sensor for the selective determination of cartinine enantiomers. Fluorescence
emission spectra discerned extensive quenching of fluorescence intensity in L- and
D- Cys CdSe(ZnS) QDs upon addition of D-cartinine and L-cartinine respectively
about the same wavelength. The possible mechanism was ascribed to the alteration
of Cys structures on QD surface when cartinine enantiomer interacted with Cys
through carboxylic, amino, and hydroxyl groups leading to attenuation of fluores-
cence signal. The chiral probe described excellent selectivity towards one enantio-
mer in the presence of other (1:100 mixtures) with precision <2.3% and error
<2.7% [56].
Chiral carboxylic acid-modified CdSe quantum dots (CdSe QDs) were synthe-
sized to study CD spectra. CD signals of CdSe QDs bonded with N-acetyl-L-aspartic
acid were compared to those by a thiolate group (N-acetyl-L-cysteine). It was found
that CD peak of N-acetyl-L-aspartic acid CdSe QDs blue-shifted by ~ 10 nm
producing a larger g-factor of 6 104 in comparison to N-acetyl-L-cysteine QDs
with a g-factor of 1.9 104. The shift in CD spectra was ascribed by splitting of
excitons due to chiral–ligand interactions leading to the generation of two sublevels,
each absorbed by opposite circularly polarized lights giving sharp CD peaks. CD
responses using other carboxylate bound CdSe QDs were also compared with
thiolate bound CdSe QDs which exhibited stronger signals with g-factors upto
7 104. However, a 30-fold range in g-factor was also observed emphasizing
that tuning of chemical structures of chiral ligands was significant [38].
CdSe nanoplatelets (CdSe NPLs) were fabricated having 4 atomic monolayers by
replacing oleate (OA) ions with chiral cysteine for highly selective detection of lead
(Pb) ions. After ligand exchange, redshift, and broadening of the two exciton peaks
at 498 nm and 528 nm were noticed in L-Cys CdSe NPLs attributing to delocaliza-
tion of wave function from NPLs to ligands and alteration of ligand density. The
chiroptical response showed mirrored CD spectra in Cys CdSe NPLs with L- and
D-Cys ligands respectively on contrary to weak signals in the presence of OA or the
same amount of both enantiomers. When Pb ions were introduced to L-/D-Cys CdSe
NPLs, large quenching of CD signal was observed ascribing to the formation of Pb-S
bonds and weakening of Cys and CdSe interactions. The chiral probe offered a
detection limit of 4.9 0.3 nM from the linear concentration range of 0.01 μM–
1 μM and excellent selectivity towards Pb ions among other metal ions [57].
6 Conclusion
Chirality is an essential characteristic feature of a molecule that plays an important

role in many biological and chemical processes [58]. The functions played by these
chiral molecules are interpreted using techniques such as SERS, colorimetric anal-
ysis, and other chiroptical methods. As a result, a number of chiral plasmonic
nanostructures are fabricated as sensing tools in various research areas. Majority
of them exhibit detection limits that are appropriate in environmental and health
sensing [59]. This chapter summarizes advances in many aspects of chiral
nanoparticles including chemical synthesis, conjugation protocols, and various
applications.
Chiral gold nanoparticles are designed as SERS substrates with the enhanced
SERS signal for the detection of rhodamine 6G, As3+. They are used as colorimetric
sensors for the detection of D/L-Leucine (Leu) enantiomers, LSPR probe for
ultrasensitive determination of Hg (II), plasmonic sensor for the detection of Pb2+
ions, and the selective enantiomeric determination of tyrosine [39–47]. Chiral silver
nanoparticle are used to study the effect of different reaction times on the nanopar-
ticle mean size. They are used as a colorimetric biosensor for enantioselective
detection of D- and L-cysteine, tryptophan, deoxynucleoside, and ketoprofens.
They are also used for the detection of S2 ions [48–53]. Similarly, chiral cadmium
nanoparticles are fabricated as glucose biosensors. They are used for sensing of Ni2+
and Co2+ metal ions, to study circular dichroism spectra and for the highly selective
detection of Pb2+ ions [35, 38, 54–57]. Altogether, chiral nanoplasmonics is a
promising field as it serves as the most efficacious method to get strong chiroptical
signals.
Acknowledgments Authors are grateful to the Department of Biotechnology (DBT) [Grant ID:
BT/PR20046/BIC/101/683/2016], Government of India for providing DBT BioCare Fellowship.
Authors thank Technology Information, Forecasting and Assessment council (TIFAC)-CORE,
Department of Science and Technology (DST), Government of India and Manipal Academy of
Higher Education (MAHE), Manipal, India for infrastructure.
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Plasmonic Optical Imaging of Biological
Samples
Priyal Dhawan, Priyasha De, K. M. Sindhoora, Nirmal Mazumder,

and Guan-Yu Zhuo
Abstract Plasmonic nanoparticles, particularly gold and silver, are significant for
various biomedical applications as they have unique plasmonic properties due to
their interactions with light and functions as excellent and stable bioimaging agents.
The plasmonic properties of nanoparticles have kindled researches and applications
in in vitro and in vivo imaging and diagnosis as well as therapy. Hence, they have
been employed in the development of imaging probes and therapeutic carriers.
Optical imaging is crucial in numerous biological studies but still, there are chal-
lenges in terms of sensitivity, resolution, depth of penetration, and speed. Few
techniques for plasmonic nanoparticle-based imaging are dark-field microscopy,
differential interference contrast microscopy, fluorescence-based microscopy,
surface-enhanced Raman scattering microscopy, interferometric scattering micros-
copy, and saturated excitation microscopy. Optical microscopy is a fundamental part
of biophotonics and biomedical research, and hence numerous groundbreaking
techniques like super-resolution optical microscopy have been developed. It has
led to the techniques exploiting plasmonic nanoparticles used in quantitative and
sensitive tracking of biological particles to investigate various cellular mechanisms.
Progress has been made in plasmonic imaging using different shapes of
nanoparticles as they are advantageous in regulating image resolution and specific-
ity. Thus, using plasmonic nanoparticles in microscopy paves the way towards the
development of non-toxic, highly sensitive, high resolution, photobleaching-free,
and rapid biological sample imaging and tracking. In the following sections, we
introduce the current demonstrations for plasmonic optical imaging based on various
P. Dhawan · K. M. Sindhoora · N. Mazumder

P. De
Graduate School of Medical Sciences, University Medical Center Groningen, University of
Groningen, Groningen, The Netherlands
G.-Y. Zhuo (*)
Institute of New Drug Development, China Medical University, Taichung, Taiwan
e-mail: zhuo0929@mail.cmu.edu.tw
https://doi.org/10.1007/978-3-030-99491-4_15
390 P. Dhawan et al.
microscopy tools, which are performed in different schemes for anticipated biomed-
ical applications.
Key words Plasmonic nanoparticles · Surface plasmon resonance · Optical

microscopy · Biological sample imaging · Particle tracking
1 Introduction
The small size of nanoparticles and distinctive optical, chemical, and physical
properties have increased their biomedical applications in recent years. Particularly,
metallic nanoparticles such as gold nanoparticles (AuNPs) and silver nanoparticles
(AgNPs) are extensively used. They are plasmonic nanoparticles and as a result of
localized surface plasmon resonance (LSPR), resulting in unique electromagnetic
radiation and interactions [1]. These plasmonic properties are due to metallic
nanoparticles’ interaction with the electromagnetic radiation giving rise to LSPR,
which is a combined oscillation of electrons in the conduction band that is in
resonance with a specific wavelength of the incident light [1, 2]. When the parti-
cle size is similar to the incident light’s wavelength, the interaction affects the light
absorption and scattering property of the nanoparticle and consequently the color of
it. This was known since ancient Roman times when the glass manufacturers used
silver and gold to present different colors for the glasses when light fell on them from
different directions like the Lycurgus cup. Then Faraday demonstrated the scientific
approach when he showed the ruby red color of gold colloids, which was later
explained theoretically by Mie. Many studies since then have investigated the optical
properties of plasmonic nanoparticles [2], revealing that LSPR depends on the shape,
size, and composition of nanoparticles as well as the dielectric function of the metal
and the medium. At the surface of nanoparticle, LSPR leads to localized electro-
magnetic field enhancement that is highly utilized in various applications like
surface-enhanced spectroscopy. A nanoparticle’s enhanced plasmonic field (electric
field) interacts with the adjacent nanoparticle’s field leading to plasmon coupling,
which then enables stronger plasmonic field enhancement in comparison to that of an
individual nanoparticle [1].
The plasmonic behaviors of nanoparticles have kindled researches in fundamen-
tal physics and the major applications in biomedical research such as sensors for
diagnostics, in vitro and in vivo imaging, and diagnosis as well as therapy. In
general, a functional material is often used alongside plasmonic nanoparticle syn-
thesis to create multifunctional nanomaterial for developing a wider range of appli-
cations. Other properties of nanoparticles that are enhanced apart from plasmonic
properties are luminescence, dispersibility in aqueous solutions, magnetism, and
stability [2]. Optical imaging and visualization are crucial in numerous biological
studies and there have been advances in these fields but still, challenges are
remaining in terms of sensitivity, resolution, depth of penetration, and speed
[3]. Along with the development of plasmonic nanoparticles, significant challenges
like real-time imaging and diagnostic techniques that are noninvasive with high
Plasmonic Optical Imaging of Biological Samples 391
precision are growing. Fluorescence imaging is a widely used technique and is

sensitive but the high toxicity, quick photobleaching of fluorophores, and in vivo
imaging of deep tissues have created the need for the development of new imaging
techniques using plasmonic nanoparticles. The scattered light from AuNP is a
million times stronger than the light generated from fluorescent color and Rayleigh
dispersion is five times larger than fluorescence emission, thus improving the
efficiency of imaging [4]. The various imaging methods based on the plasmonic
properties of nanoparticles are light microscopy, surface-enhanced Raman scatter-
ing microscopy, nonlinear response techniques, interferometric scattering micros-
copy, plasmon-enhanced fluorescence, and other imaging techniques. The shape
change of nanoparticles is also useful in regulating image quality and there has been
groundbreaking development of super-resolution optical microscopy, which
received the 2014 Noble Prize in Chemistry and facilitates nanoscale observation
of live cells [3, 4]. This chapter gives an overview of different optical microscopies
that are employed in the visualization of plasmonic nanoparticles and biological
samples as well as how plasmonic imaging can help in tracking biological particles.
In addition, plasmonic applications in super-resolved optical imaging in the near-
and far-field have also been discussed along with the progress made in plasmonic
imaging using different shapes of nanoparticles.
2 Plasmonic Nanoparticles Visualized in Different Kinds

of Microscopes
Measurement of the light transmission in a nanoparticle suspension as a function of

wavelength has helped to understand the optical properties of nanoparticles as well
as their plasmon resonance. But one question that is still being researched is how
these images of biological samples are transmitted through a suspension of scatterers
and absorbers. Earlier research shows that the optical properties of a plasmonic
nanoparticle suspension affect the transmission image while imaging and analying
biological and non-biological samples. The image contrast and resolution, as the two
main factors of image quality, are both dependent on the absorption and scattering of
light by the constituent nanoparticles [5]. Various types of microscopy techniques
have shown to improve the image quality as well as the sensitivity and specificity of
biosensing in the presence of plasmonic nanoparticles attached to different sub-
strates. These metallic nanoparticles like AuNPs and AgNPs as well as biological
samples like tissues and cells can be subjected to improved imaging by these
microscopy techniques like dark-field microscopy, differential interference contrast
(DIC) microscopy, fluorescence-based microscopy, surface-enhanced Raman scat-
tering (SERS) microscopy, interferometric scattering (iSCAT) microscopy, and
saturated excitation (SAX) microscopy, mainly due to LSPR as described below.
2.1 Dark-field Microscopy
Plasmonic biosensors use plasmonic nanoparticles like gold or silver nanoparticles

that can increase the specificity, detection range, and sensitivity of samples by using
single nanoparticle assays. LSPR is a characteristic of plasmonic nanoparticles that
has helped in overcoming the detection limit of these biosensors to single molecules.
LSPR also helps in imaging the light scattered by these nanoparticles using dark-
field microscopy, in which the inclined light passes through a specimen and
then the diffracted light enters the objective lens, forming a bright image against a
dark background. This microscopy is very useful for unstained samples
[6, 7]. Dark-field microscopy based on LSPR facilitates to observe various experi-
mental phenomena because it is a photobleaching-free biological imaging technique
[8]. Dark-field microscopy imaging of nanoparticles helps to construct a biosensor
that can detect and count single molecules in the sample by single nanoparticle
assays. In earlier studies, dark-field microscopy has been used in monitoring inter-
actions of single proteins on gold nanorods [9]. Apart from dark-field microscopy,
other methods to analyze single nanoparticles and their interactions include single-
particle spectroscopy and laser imaging. But for biosensors, obtaining specific
information from many single nanoparticles is much more important than spectral
details. Hence, rapid and high-throughput biosensors for single nanoparticle analysis
are the need of the hour [7].
A new colorimetric analysis to monitor plasmonic nanoparticle properties by
analysis of the color of scattered light in dark-field microscopy images has been
developed. This scattered light wavelength is related to the nanoparticle’s LSPR as
well as its size and shape, which is observed as a colored point-spread function
(PSF). RBG (red, green, and blue) analysis of the light scattered by the plasmonic
nanoparticles has been used to determine the size of nanoparticles as well as to detect
antigen-antibody binding reactions. This colorimetric analysis of single plasmonic
nanoparticles using LSPR can be carried out by the coupling of a commercially
available complementary metal-oxide-semiconductor (CMOS) camera and a dark-
field microscope. MATLAB software is then used for the analysis of these dark-field
microscopy images. Intensity-based processing helped to find out the point with the
highest intensity in each nanoparticle. CMOS cameras are of great advantage
because λmax of up to 5000 nanoparticles could be obtained in seconds. Thus,
thousands of nanoparticles can be processed within seconds, which is much better
than the long time required for this processing using conventional spectroscopic
methods [7]. CMOS also has other advantages like lower production costs, fast read-
out speed capability as well as it is widely available in cameras and smartphones,
which would allow our smartphones to be used as biosensors and point-of-care
devices when needed [10].
This technique can also be used in the detection of an analyte, interleukin-6 (IL-6)
that is associated with the inflammatory process of many diseases like Alzheimer’s
disease. The potential of this colorimetric analysis of dark-field microscopy tech-
nique used in plasmonic biosensing was demonstrated by a core-satellite antibody
sandwich assay where IL-6 binds to anti-IL-6 antibodies on the nanoparticle surface,
which then helps in the binding of another antibody that is conjugated to a satellite
nanoparticle. This plasmon coupling induces a red-shift in the digital analysis of
colors and helps in IL-6 detection [7].
Change in the refractive index of the surrounding medium of the nanoparticles
affects the LSPR shift, which can also be quantified by this digital analysis tech-
nique. Thus, it highlights the sensitivity and use of this high-throughput single
nanoparticle digital analysis technique in colorimetric analysis and dark-field
microscopy. This technique is mainly useful for sphere and cube-shaped
nanoparticles, which have a single scattering peak. Polarizing filters can be added
to separate the plasmon modes for nanoparticles like nanorods that have multiple
scattering peaks [7]. Polarization-dependent surface plasmons from these nanorods
are monitored by orientation sensors. Dark-field microscopy helps to differentiate
between and present both the transverse and longitudinal surface plasmonic reso-
nance from nanoparticles with more than one scattering peak like gold nanorods.
The gold nanorods with more than 30 nm diameters have a lot more unique optical
properties than the ones with smaller diameters. Thus, depending on the polarization
angle, the optical images taken from the microscope can show a rainbow of colors
for all the types of nanoparticles. Therefore, polarization-controlled colorimetric
nanoparticles can help in the biosensing of single-particle tracers in live cells [11].
Dark-field microscopy based on LSPR was also used as an in situ imaging
technique for human epidermal growth factor receptor 2 (HER2) protein on cell
surfaces. Modified asymmetric AuNPs with no LSPR were used as probes. Thus, in
the presence of the target analyte, plasma nanoaggregates with higher scattering
efficiency were formed. The AuNP probes were modified with DNA and anti-HER2
antibodies for dark-field microscopy imaging of HER2 protein on the cells. An
aptamer was designed to introduce rolling circle amplification (RCA) in the HER2
dark-field microscopy imaging of the cells for obtaining a much brighter image
signal. Therefore, the target signal could be distinguished easily from the back-
ground noise in the image making this useful tool in cell imaging and molecular
diagnostics [8]. Dark-field microscopy imaging along with a plasmonic biosensor
was used to detect Staphylococcus aureus in the presence of excess Escherichia coli
by using bacteriophages as the biorecognition element and the light scattered from
the aggregated gold nanospheres as the signal transducer [12].
Label-free imaging of objects at the nanoscale faces huge challenges, which can
be solved by techniques using LSPR. But dark-field microscopy with LSPR imaging
for metallic nanoparticles suffers from insufficient imaging quality and low light
throughput. Therefore, PlAsmonic NanO-apeRture lAbel-free iMAging (PANO-
RAMA) uses unscattered light to detect the nanoparticles and provides wide-field
imaging, higher sensitivity as well as diffraction-limited resolution. PANORAMA
can also count and size single dielectric nanoparticles beyond 25 nm as well as find
out their distance from the plasmonic surface making it an effective plasmonic
biosensor [13].
Fig. 1 Dark-field microscopy images of AuNPs internalization in Vero cells. Nuclei of the cells
were stained with 40 ,6-diamidino-2-phenylindole (DAPI). (a) Negative control of Vero cells. (b)
Vero cells treated with nanoprisms of plasmon band at 1100 nm (1100NPr/NS). (c) Vero cells
treated with 1100NPr/NS selectively precipitated using GSH and PEGylated (1100NPr-GSH-PEG).
(d) Vero cells treated with 1100NPr-GSH-PEG functionalized with a Gly-Arg-Gly-Asp-Ser (RGD)
sequence (1100NPr-GSH-PEG-RGD). Scale bars ¼ 50 μm. Figure adapted from Ramirez-Jimenez
et al. [14]
Gold nanoprisms made up of plasmonic AuNPs can be highly useful in optical

imaging and medical biotechnology applications using dark-field microscopy. But
the shape-selective synthesis of these gold nanoprisms requires toxic surfactants or
even very long purification procedures, which limits their applications. Ramírez-
Jiménez et al. showed how gold nanoprisms can be easily purified by precipitation
using glutathione ligand that is not toxic. This new method provides nanoprisms of
similar LSPR wavelengths. Crucially, the gold nanoprisms isolated using this
methodology show fewer nonspecific interactions with cells and lower cellular
internalization, which paves the way for a higher selectivity in therapeutic applica-
tions (Fig. 1) [14].
2.2 Differential Interference Contrast Microscopy
Differential interference contrast (DIC) microscopy depends on the wavelength and

enables nanoparticles’ (SPR or non-SPR) wide-ranging optical response using
illumination wavelength. It is based on the interferometry principle and to collect
differential data on the refractive indices of the sample and the surrounding medium,
using two mutually displaced beams of illumination (Fig. 2). Contrast theoretically
in DIC is directly proportional to the phase difference between sample and reference
beam [16, 17]. DIC microscopy has been employed in selective imaging of various
particles such as microparticles, AuNPs and AgNPs as well as multiplexed detection
of SPR and non-SPR particles [17, 18]. It is also utilized to investigate the geometry
of gold nanorods upon the optical response in live cells, showing the nanoparticles’
rotational movements on cell membranes and the typical rotational dynamics of drug
delivery vectors [16]. In unstained live cells, DIC microscopy facilitates the direct
observation of organelles with adequate high contrast [3].
Fig. 2 Schematic representation of (a) conventional far-field DIC, (b) near-field differential
interference contrast microscopy (NFDIC) excitation, which has similar functionality as conven-
tional DIC facilitating illumination of two adjacent spots on the sample, and (c) NFDIC detection,
which has similar functionality as conventional DIC facilitating interference information that con-
tains optical signals by photoinduced force microscopy. Figure adapted from Heydarian et al. [15]
Live-cell imaging via nanoparticle probes is still a key hurdle. Dark-field micros-
copies have acquired a lot of attention nevertheless differentiating tracer
nanoparticles is difficult from debris/cell components that also produce scattering
light. DIC microscopy for AuNPs presents brilliant spatial resolution as well as
contrast and can acquire enhanced cell images with the probes simultaneously
thereby circumventing the requirement of correlating cells and probes by changing
modes in microscopy. Therefore, they have been employed in single-particle track-
ing (SPT) with high lateral precision and temporal resolution in live-cell imaging
[17, 19–22]. DIC microscopy has extensive application in cell biology to explore cell
division, dynamics of microtubule (dis)assembly, and organelle trafficking. AuNPs
have exceptional photostability as well as high absorption and scattering due to
LSPR. Therefore, for DIC imaging of AuNPs in the cell, low light illumination is
enough. This aids in long-term constant observation of dynamic interactions with
nominal disturbance [3].
Distinguishing probes and subcellular particles are still a problem in DIC micros-
copy. A study demonstrated that immobilized Au/AgNPs on glass slides can be
distinguished and imaged individually due to the illumination wavelength and size
of the particle. They took advantage of the dependence of DIC contrast of Au/AgNPs
on wavelength and modified the DIC microscope to operate simultaneously at two
illumination wavelengths. It also showed that high contrast live-cell images both
with and without the illumination on AuNPs can be acquired facilitating conclusive
identification of probe. Therefore, dual-wavelength DIC microscopy is a new
approach for simultaneous multiple probe detection for rapid live-cell imaging
[17]. Various experimental setups that consist of light-cell or light-tissue interactions
consider cytoplasm’s refractive index as a significant parameter. A study demon-
strated the application of DIC microscopy in single live cell refractometry with
polystyrene microparticles (PSMPs) of 400 nm, which acts as a sensor. DIC micros-
copy is exploited to quantify the cytoplasm’s refractive index as an alternative to the
single live cell refractometries [16]. To explore cellular processes, the interaction
between biomolecules and nanoparticles can be studied using DIC microscopy and
plasmon resonance energy transfer (PRET). Therefore, in the future DIC will be
integrated with other imaging technologies, which will help in deciphering complex
interactions and dynamic cellular processes [3].
2.3 Fluorescence-based Microscopy
Fluorescence microscopy is a very important tool in biological imaging. It allows

imaging samples to have a high degree of specificity and selectivity. However, even
with the use of photostable and bright markers, unspecific background because of
scattering, imperfect labeling as well as auto-fluorescence affect the imaging of these
biological samples adversely [23]. The common method for spatial selectivity in
fluorescence is mainly based on total internal reflection fluorescence microscopy
(TIRF-M). But there is another concept that uses evanescent fields and mediates
fluorescence significantly originating from the areas close to a metal interface, called
surface plasmon-coupled emission (SPCE). SPCE efficiency depends mainly on the
fluorophore–nanocoating distance; therefore, it can help to distinguish between
signals that are close and the ones from larger distances. The coating with plasmonic
nanoparticles and its SPR illumination can also enhance TIRF field excitation
[24, 25]. Fluorescence imaging combined with SPCE has not been much successful
because of limited photon yield due to metal-induced energy transfer.
Therefore, Schreiber et al. tried to find out the optimal operational conditions for
SPCE due to its successful application in biosensing [26]. They showed that
fluorescence microscopy imaging for a live cell in a noisy and extremely high
photon background can be improved by SPCE. The determined image contrast
was decoupled from the enhancement excitation. For this, firstly the film thicknesses
of plasmonic AuNPs were compared to find the best combination between SPR
excitation, the efficiency of SPCE, and coating transparency. Secondly, the scientists
showed how fluoplasmonics (f-Pics) microscopy using AuNPs coated coverslips can
improve imaging by background suppression. Fluorophore concentration of
20–500 nM would be unfavorable to fluorescence microscopy imaging techniques
like TIRF-M; however, SPCE provides high selectivity and helps in fluorescence
imaging of biological samples or other nanoparticles in extremely noisy background
environments [23, 26].
Fluorescence microscopy imaging along with SPCE could be highly helpful in
high-throughput screening as well as cell-growth and near-surface binding studies. A
combination of SPCE and fluorescent dyes can be used to study these receptor
interactions even if there is extreme background light due to high marker concen-
tration inside the cell that could outshine the signal of cell membrane receptors [26].
Mostly like other optical imaging technologies, fluorescence microscopy is also
used in the imaging of two-dimensional cell culture systems. Therefore, imaging
multicellular specimens are very challenging, mainly for the three-dimensional
(3D) cell cultures used in drug discovery research. The main issues shown in
common fluorescence microscopy are phototoxicity, fluorophore bleaching, and
limited light penetration [27]. These drawbacks can be overcome by light-sheet-
based fluorescence microscopy (LSFM) that uses an orthogonal arrangement of
fluorescence with different lenses for illumination and detection. The specimen is
illuminated on a particular side using a thin light sheet overlapping with the focal
plane of a wide-field fluorescence microscope. LSFM also helps to achieve mini-
mum photobleaching and damage due to phototoxicity. Thus, LSFM is a useful
imaging technique for imaging biological 3D samples in life sciences. This imple-
mentation of LSFM is known as a single (or selective) plane illumination micro-
scope (SPIM), in which the sample is illuminated by a sheet of laser light and this
method can also be used in the visualization of nanoparticles [28].
The conventional laser-scanning confocal microscopy (LSCM) can penetrate to a
depth of about 150 μm below the brain surface and the two-photon excitation
fluorescence (TPEF) microscopy can penetrate deeper for about 500–800 μm from
the brain surface [29]. Better optical imaging methods for visualizing the projections
inside a brain and other organs are constantly needed, which can deal with the light
scattering coming from the deeper brain structures. Therefore, Hama et al. developed
a clearing reagent called Scale used for imaging the fixed brain tissues with it. They
found that Scale helped to make the biological samples optically transparent and
preserved the fluorescent signals from the labeled cells. Thus, Scale helped to
achieve better depth of imaging, which in turn helped in the 3D reconstructions of
cortical and hippocampal regions of the brain. It also helped in measuring the
distances of neural stem cells to blood vessels. The finding mainly suggested that
the Scale method can be very useful for light microscopy-based connectomics
mainly on the cellular networks of the brain along with the help of plasmonic
nanoparticles [30].
As discussed previously, f-Pics microscopy using coverslips coated with AuNPs
can improve the imaging of biological samples. Other optical techniques using
nanotechnology for plasmonic biosensing based on linear and nonlinear excitation
can also be used for imaging of biological tissues. But it was seen that the steady-
state fluorescence imaging method has a major limitation because it can provide only
morphological information. Spectroscopic methods based on lifetime measurement
of tissue fluorescence can help to find out functional information about these tissues
like pH, redox state, etc. Measuring fluorescence lifetime as well as analyzing this
data is a major step toward biological tissue characterization, which can be of the
utmost importance in the field of biophotonics and sensing when plasmonic
nanoparticles are used too [31].
2.4 Surface-enhanced Raman Scattering (SERS) Microscopy
Nanostructure plays a very important role in the macroscopic chemical behavior of

samples, which is important in the design and development of new catalysts,
membranes and sensors. Conventional microscopy analytics lacks the high specific-
ity and sensitivity required to detect interesting features. Raman spectroscopy
combining confocal microscopy and surface-enhanced detection helps in the molec-
ular characterization by measuring their vibrational modes but they suffer from
limitations like lower sensitivity and diffraction-limited spatial resolution
(200–300 nm). This can be improved by the LSPR effect by generating a localized,
intense electric field at the nanoparticle surface illuminated by the light that matches
the nanoparticle’s natural plasmon frequency [32]. This is the phenomenon that is
used in tip-enhanced Raman spectroscopy (TERS) making it an important
nanoanalytical tool for the chemical characterization of nanoparticles [33]. Other
imaging techniques like scanning tunneling microscopy (STM) can help in provid-
ing morphological information but without any chemical insights. Therefore, TERS
helps in overcoming this limitation as it is label-free and nondestructive as well as
can be used in both air and liquid systems making it a very important imaging
technique for various biological samples [34].
TERS, which can also be called a special type of SERS, is basically a combina-
tion of LSPR and the lightning rod effect for producing an electromagnetic field at
the tip of a sharp scanning probe microscopy (SPM) probe positioned at the focal
point of excitation laser. Transmission mode atomic force microscopy (AFM)-based
TERS can be applied for imaging of both biological and non-biological samples on
various substrates [32, 34]. The main procedure includes plasmonically active TERS
probes as well as nanoscale imaging using probes. TERS requires experimental
expertise in various disciplines like plasmonics, biosensing, SPM, optical alignment
as well as confocal Raman spectroscopy and it can be useful in obtaining
information about different nanoparticles and biological samples like self-assembled
monolayers of organic molecules, small molecules within biological cells, and
single-walled carbon nanotubes in both air and liquid environments [32].
SERS microscopy can be useful for diagnosing and monitoring cancer heteroge-
neity, being helpful in personalized medicine. This method has been well known for
the analysis of liquid biopsies. These optical nanosensors based on SERS and TERS
reach a high level of refinement using various plasmonic nanoparticles that help in
real-life applications. They can also be categorized into different classes based on the
tumor biomarkers they can sense like cells, proteins, or nucleic acids. These
nanotechnology-based SERS microscopy imaging can overcome the limitations of
other microscopy techniques in terms of sensitivity, multiplicity, specificity, rapid-
ity, and cost [35].
2.5 Interferometric Scattering (iSCAT) Microscopy
Sandoghdar and Kukura groups developed interferometric scattering (iSCAT)

microscopy, which was great for label-free nanoparticle tracking with elevated
temporal resolution. It was based on interference reflection microscopy, which has
been optimized to reflection interference contrast microscopy (RICM) [36]. Single-
molecule level imaging facilitates the direct visualization of interactions and behav-
iors of individual molecules without getting missed as in group observation. The
finite emission rate of light from fluorophores restricts the precise determination of
labeled protein’s position. The rate of photon emission by the labels is crucial in SPT
for the determination of precise location of the emitter and the best resolution
obtained per millisecond is in tens of nanometers for nanosecond lifetimes. The
vulnerability of fluorescent dyes to various processes is another demerit resulting in
no light emission that is unfavorable for tracking microscopies. Photobleaching and
blinking can also take place, which brings in the need for label-free imaging
techniques for biomembranes. An emerging technique, iSCAT microscopy, success-
fully deals with these problems and is compatible for imaging the diffusion of
membrane proteins with nanometric precision in 3D spatial and microsecond tem-
poral resolution, which is better than the resolution obtained using fluorescent
labels [37].
As an alternative to fluorescence, light scattering overcomes the impediments as

all the materials scatter light rather than fluorescence. Thus, it is not susceptible to
bleaching and blinking. The photon-electron interaction is nearly in an instant,
which in metal nanoparticles is at 10 fs implicating the generation of a million
photons that are scattered in the same time taken for one fluorescence photon
generation [37]. The detection of light scattering from nanoparticles is challenged
by weak scattering signals along with background noise, and iSCAT microscopy is
advantageous in extremely weak scattering signal detection [38]. Light scattering is
coherent, which means that there is no change in the phase difference the whole time
between the scattered light and the illumination light, implicating that the two
light beams can be combined efficiently in a process called interference. This is
advantageous as interfering two light beams can enhance the amplitude when one
beam is weak by combining it with the other stronger beam leading to enhanced sen-
sitivity in the detection. This principle is followed by microscopies known as
interferometric microscopies and iSCAT optimizes the detection sensitivity of
individual nanoparticles [37]. Since iSCAT microscopy is an optical detection of
scattered light, the selectivity and specificity of chemical information are not pro-
vided by iSCAT [36].
Independent of the duration of exposure or the scattering area of the imaged
object, the ability of iSCAT to keep up the enhanced contrast opens up its applica-
tions in imaging of (dis)assembly of lipid or peptide-based nanoobjects, high-speed
SPT as well as single-molecule imaging, and quantitative characterization. They can
also be used in mechanistic studies and has the potential to reveal the dynamics and
interactions of biomolecules. In a study, gold labels of 20 nm were bound to motor
domains and imaged using iSCAT after that comprehensive signature of an inter-
mediate state was observed constantly on a side of the actin filament. High temporal
resolution and spatial precision enabled the examination and characterization of the
state essential for mechanistic studies. Tracking precisely to nanometer scale with
exposure time in submillisecond is achievable by iSCAT because there is no
saturation of the scattering signals facilitating the access of temporal systems. In
U2OS cells and axons, it is possible to track 40 nm AuNP labeled membrane
proteins with a precision of 3 nm at 40 kHz. In a tube-like structure of axon, the
3D motion of the molecule was observed using iSCAT due to its interferometric
nature. For observing single virus particle assembly, an increase in the local con-
centration of capsid assembly protein was visualized by label-free, sensitive iSCAT
imaging [39]. Tracking the mobility of lipids and proteins provides insight into their
function as well as path, and the structure and functionality of membranes are
studied by tracking membrane proteins. To image mobility of proteins in live cells
and observe the molecular interactions occurring at the nanoscale in millisecond to
microsecond time, high frame rates are essential as in low frame rates they are not
detectable. iSCAT microscopy offers highly sensitive detection and a great signal-to-
noise level with 100–1,000,000 frames per second (fps). Using iSCAT microscopy
with wide-field reflection incorporated with confocal fluorescence microscopy,
HeLa and COS-7 cells were investigated to track epidermal growth factor receptor
(EGFR) and COS-7 membrane, in which iSCAT image was obtained with a
Fig. 3 (A) Schematic representation of the iSCAT setup used in the experiment. (B) Single GM1
lipids are labeled with 20 nm AuNPs and their diffusion across lipid bilayer was documented for 5 s
at 1 kHz frame rate with a localization precision of 2 nm. (a) The trajectory of particles depicts free
diffusion as well as nanoscopic and orbital confinement. (b) The trajectory of orbital confinement.
Temporal evolution is depicted by color coding for all the trajectories. (c) Trajectory presenting
Brownian diffusion. Arrow and red circle—150 nm void area at the center implying that the
supported lipid bilayer has small defects. (C) AuNP labeled high-speed tracking of lipid diffusion.
(a) 5 nm (b) 20 nm AuNP combined with biotinylated DOPE lipid and the corresponding trajectory
is documented (a) for 0.44 s at 23 kHz. (b) for 0.152 s at 913 kHz. (a) Upper inset—zoomed-in
confinement region. Lower inset—5 nm AuNP background-corrected iSCAT image on a lipid
membrane. Figure adapted from Spindler et al. [41]
speckled pattern. The incorporation of nanoparticles with strong scattering such as

AuNP as a label is essential to track the membrane-fused proteins and lipids (Fig. 3).
To eliminate the imaging background of the cell, the discrepancies between the
random patterns of the speckled background and gold probes’ imaged symmetric
circular pattern was utilized. COS-7 cell membrane with an AuNP probe bound to it
was imaged interferometrically and a series of alternating contrast rings were
observed that are denoted as interferometric PSF (iPSF) because nanoparticle is
smaller than the diffraction limit. The alternating contrast ring pattern was exploited
to estimate the height of the AuNP probe from the coverslip [37]. Using
interferometric-based techniques, reflection phase imaging facilitates high-
resolution, rapid, and label-free visualization of thin biological samples. They are
significant in measuring the backscattered field that has high-frequency sensitivity to
fine details and can be used for thick and thin samples [40].
A study demonstrated the significance of iSCAT microscopy in the investigation
of refined signaling protein mobility in live-cell membrane, in which EGFR was
used as the candidate. The 48 nm AuNP probe used in this study offers a permanent
scattering signal and interferometric SPT (iSPT) contours the trajectory of the
nanoparticle in 3D across a wide axial range facilitating the visualization of entire
process. Fine details about the EGFR trajectories in various processes like endocy-
tosis were uncovered by the high temporal and spatial resolution of iSPT. There is
complete wavelength flexibility usage implicating the used wavelengths can be
less harmful to the cells while providing high frame rate and adequate signal-to-noise
ratio. It was also demonstrated by a study that the EGF-AuNP probe of 48 nm did not
affect the signaling pathway of EGFR or endocytosis mediated by clathrin
[37]. Observing cytoplasmic organelles and their complex structures in live cells is
still a challenge without fluorescent labels. A study conducted label-free, rapid and
live-cell imaging of yeast, E. coli, and mammalian cells using iSCAT. It revealed
various underlying structures of cytoplasmic organelles’ complex along with those
underneath the cell. For the cells that are attached to the glass substrate, their contact
areas such as filopodia and focal adhesions were distinctly visible as well as in the
cytoplasm there were fringe-like structures. Significant sensitivity of iSCAT facili-
tates weak scattering signal detection from very thin filopodia or minor fluctuations
in the refractive index of biomaterials. Label-free iSCAT microscopy is a potent
technique to visualize in vivo structures and intracellular dynamics. Visualization of
the intracellular structure was clearer and more enhanced in iSCAT than RICM due
to the coherent light source and interference. [36]. Under laser illumination, metal
nanoparticles supporting LSPR are typically resonant for applications such as SERS.
However, the nano-sized objects are visualized using current iSCAT microscopy are
typically non-resonant under illumination and the contrast of the iSCAT signal is
merely proportional to the object’s volume and weight. A study was done to enhance
the iSCAT microscopy in terms of resonant scattering. They used nanoparticles with
tunable longitudinal LSPR, gold nanorods, which were imaged under the illumina-
tion near resonance using laser light. In the optical resonance setting, the polariz-
ability of gold nanorods is strongly dependent on a specific wavelength, which
explains that the drastic disparity in the contrast of iSCAT signal occurs when the
narrow range resonance wavelength of gold nanorods is scanned across a certain
range of illumination light wavelength. Theoretical analysis and numerical simula-
tion of various factors that influence the iSCAT signal were helpful to understand
how optical resonance affects the nanoparticles’ iSCAT signal. This study paves
way for iSCAT microscopy development toward nano-objects imaging, resonant
sensing and spectroscopy [38].
2.6 Saturated Excitation (SAX) Microscopy
Metal nanoparticles have linear scattering, which has been extensively used in
imaging and detection of cancer cells; however, the resolution of the far-field optical
imaging techniques used in these applications are limited by diffraction. To over-
come this shortcoming, various groundbreaking ideas based on saturation of fluo-
rescence have emerged [42]. Saturated excitation (SAX) microscopy is an alternative
technique to visualize any kind of fluorescent sample. Saturation of the excited state
of fluorescent molecules through the high-intensity excitation results in intense
fluorescence signals that are nonlinear, which improves the 3D spatial resolution.
High-resolution images can be obtained using fluorescent probes for various appli-
cations with SAX microscopy because of the inherent saturation effect of fluorescent
molecules [43]. The principle of SAX microscopy is that there is a stronger intensity
at the center of the laser spot in comparison to the edge. Thus, the fluorescence
signals at the center are saturated, while signals at the edges remain unsaturated. By
extracting the saturated portion, enhancement in spatial resolution takes place
successfully [42]. This is a significant advancement as it has applications in an
array of fluorescence probe-based microscopic observations [43].
Under strong laser irradiation, fluorophores exhibit nonlinear responses, which is
the basis of SAX, but the fluorescent molecules experience photobleaching quickly
under strong irradiation. It can cause phototoxicity and photodamage to biological
samples such as protein defunctionalization and inhibition of cellular processes. This
brings in the need for contrast agents that do not bleach and the LSPR structures with
strong scattering are ideal candidates. Integrating LSPR with light generates a strong
local electromagnetic field that enhances the nonlinear optical properties of the
surrounding objects significantly. The nonlinearity of the comparatively weak host
materials is enhanced due to the plasmonic nanostructures. Nonlinear interactions
with light are inherent to plasmonic nanoparticles and they can be used as con-
trast agents in optical microscopy [42]. Such nonlinearity used in SAX microscopy
is without any surge in excitation wavelength, which enhances the spatial resolution
beyond the diffraction limit [43]. Large excited-state absorption (ESA) effect or
transient absorption is exhibited by noble metal and graphene/plasmonic
nanoparticles. Without using fluorescence, the saturation of transient absorption in
graphene has been taken up for spatial resolution enhancement that can break the
diffraction limit. When the wavelength of the strong laser light matches the
nanoparticles’ LSPR band, scattering saturation of a single AuNP can be even
achieved. For resolution smaller than the diffraction limit, saturated and unsaturated
portions of the nanoparticle’s PSF can be differentiated. When the saturated signals
in SAX microscopy are used for spatial resolution enhancement, higher harmonic
signals are selectively collected and laser beam scanning of the sample is done to
form an image, which demonstrates the enhancement in resolution by the scattering
from separated AuNPs [42].
For physiology and cell morphology investigation of biological samples such as
tissues and drug metabolism observation, volumetric imaging is essential. Light
scattering and aberration in volumetric samples due to refractive index distribution/
mismatch diminish the imaging quality [44]. The contrast in deep tissue images is
degraded due to the out-of-focus signals that overwhelm the signal generated from
the focal region, and to surmount this obstacle nonlinear optical responses of probes
have been employed such as saturation of fluorescence excitation and two-photon
fluorescent excitation [45, 46]. Nonlinearity in fluorescence induced by SAX pre-
serves contrast at high depths in SAX microscopy. A study assessed optical transfer
functions for evaluating the depth contrast ability of SAX microscopy and also
calculated the edge responses for thick samples. It demonstrated that there was an
enhancement in the contrast and resolution of sample components, while from out-
of-focus regions, the background fluorescence signals were prohibited via
the nonlinear response detection of higher order fluorescence. Thus, a strong
nonlinear relationship between the fluorescence signal and excitation intensity not
Fig. 4 (A) Fluorescence images in the x–z plane of 3D matrix cultured HeLa cells with ATTO488
phalloidin stained actin filaments were observed by (a) SAX and (c) confocal microscopy. (b) and
(d) are magnified images of the boxed area in (a) and (c), respectively. (B) Fluorescence images of
cultured HeLa cells stained with ATTO Rho6G phalloidin were taken by (a–c) SAX and (d)
confocal microscopy. The above SAX images were all reconstructed by 2fm demodulation.
Figure adapted from Yamanaka et al. [44]
only plays a crucial role in signal enhancement but also facilitates the elimination of
background signals [43, 44]. Further, the z-direction distortion of the image was
curbed. Cultured 3D cell clusters were imaged using SAX microscopy, which
confirmed the improvement in resolution both at 40 μm depth and near the surface
(Fig. 4). The excitation intensity’s modulation frequency increased to 50 kHz
decreased the effect of photobleaching during observation for the high-speed
image acquisition as well as reduction in pixel dwell time. The fluorescent probe,
nanodiamonds are photostable and can additionally improve the spatial
resolution [44].
SAX microscopy has the potential for imaging deep areas of biological specimens
at super-resolution [44]. The localization of signal generation offers the ability for
optical sectioning in the imaging of deep tissues. It thus facilitates 3D and cross-
sectional images with enhanced contrast of thick samples. Due to LSPR’s intense
light scattering and stable structure, high photostability is exhibited by AuNPs probe
that facilitates the detection of signals from deep tissues [46]. In a study 80 nm gold
nanospheres as contrast probes were used for SAX microscopy at 561 nm excitation.
It enhanced contrast and spatial resolution in nanoparticle probe imaging, which is
under the 200 μm thick muscle tissue [47]. For biological tissues, the near-infrared
(NIR) light has a lower attenuation coefficient than visible light, and the excitation
and scattering light have more effective tissue propagation than visible light,
enabling deeper tissue access. A study developed SAX microscopy taking advantage
of nonlinear NIR scattering of plasmonic nanoparticles such as gold nanoshells and
nanorods to acquire images of high contrast from deep tissues and improve the
penetration depth. Nanoparticle probes that are present in the center of the laser’s
fcous spot generate scattering signals, in which the nonlinear components are
detected by SAX microscopy. This helps in eliminating the background signals
from the out-of-focus region. There is efficient transmission of NIR signals from the
nanoparticle probes through tissues, which is well suited for deep tissue imaging.
Individual gold nanoshells and nanorods have scattering intensities that exhibit
nonlinear responses at 780 and 1064 nm excitation, respectively. In a phantom
muscle tissue at 400 μm depth, the contrast and spatial resolution in images were
enhanced because of the selective detection of scattering signals that are nonlinear
from nanoshells [46]. By integrating SAX microscopy with two-photon microscopy,
the resolution enhancement was well demonstrated in this study. Resolution-
enhancement and the sidelobe effect in PSF were estimated theoretically, show-
ing that the 3D spatial resolution was enhanced significantly and the sidelobe effect
was suppressed by integrating SAX and core-ring illumination. It is efficient in
observing 100 μm depth in a phantom tissue and 3D observation of samples with a
much better spatial resolution [48].
3 Plasmonic Imaging for Tracking Biological Particles
To improve the outcome of patients in response to various therapeutic interventions,

investigation of various mechanisms fundamental to cell-based therapies and how to
enhance their therapeutic efficiency can be facilitated by quantitative and sensitive
tracking of biological particles [49]. Cell labeling methods such as fluorescence
microscopy, magnetic resonance imaging, and positron emission tomography are
not efficient for quantifying biodistribution and are not sensitive for imaging at the
single-cell level [49–51]. This brings to the development of gold nanostars (GNS)
fabricated from AuNPs without employing any toxic surfactants. For highly sensi-
tive optical imaging, these GNS have improved plasmonics and enhanced
two-photon photoluminescence (TPL). Since the gold mass can be measured, GNS
facilitates the quantitative analysis of biodistribution in vivo, and therefore, GNS
functionalized by peptide transactivator of transcription (TAT-GNS) is employed in
labeling and examining immune cells in the murine model after systemic adminis-
tration of macrophage cells. It demonstrated that this strategy enables sensitive
single-cell level imaging as well as quantitative tracking of biodistribution of
macrophage cells (Fig. 5). It is superior to other methods and is essential in
optimizing dose and administration to improve therapeutic efficiency. There was
no negative effect of loading GNS on immune cells; therefore, it has the potential in
future biomedical applications as a sensitive tracking technique [49]. TAT-GNS
emits ultra-bright TPL helpful in tracking mesenchymal stromal cells (MSCs) in
mice by high-resolution optical imaging and expresses greater retention in the cells
because of their star shape. To enhance the contrast and specificity, the labeling of
GNS can be used. In stem cell research, these plasmonic nanoplatforms are of a
useful method for tracking cells [52].
Fig. 5 (a) GNS nanoprobe-loaded primary immune cells and its TPL imaging after incubation for
2 h and 16 h exhibited a strong signal. DAPI stained cell nucleus—blue and GNS—white. DC—
dendritic cells; MDSC—myeloid-derived suppressor cells. (b) Quantitative biodistribution of
GNS-loaded macrophage cells after their systemic administration into mice with tumors.
Biodistribution was quantified at 4 h, 24 h, and 120 h after administration. Analysis done by the
ICP-MS method showed major macrophage uptake in the liver, spleen and lung, with the tumor
having the least accumulation of macrophages. % ID/g—percentage injected dose per gram tissue
(c) Tacking GNS-labeled macrophage cell via TPL imaging. After systemic administration, TPL
imaging was done at 4 h, 24 h, and 120 h. Red arrow—GNS-labeled macrophages; GNS—white.
Figure adapted from Liu et al. [49]
Another optical technique, interferometric plasmonic microscopy (iPM) is used

for exosome size analysis and imaging. It is highly sensitive and achieves much
better spatial resolution via enhanced detection and visualization [53]. Plasmonic
microscopy discards the extra noise and visualizes the biological particles within
200 nm of the surface [54, 55]. iPM is effective in visualizing, tracking and
analyzing single exosomes. It facilitates the quantitative assessment of the interac-
tions between exosome and antibody as well as liposomes and exosomes membrane
fusion. It also has potential applications in exosome identification as a biomarker for
cancer, cell-to-cell communication, and regulation of tumor microenvironment by
exosomes and delivery systems when they are targeted [53]. Inverse molecular
sentinels (iMS), a class of SERS nano-biosensors employ DNA functionalized
silver-coated GNS that are plasmonic-active. It identifies the nucleic acid biotargets
by altering the conformation of the functional DNA [56, 57]. SERS biosensing
technique can be combined with X-ray fluorescence (XRF) and plasmonics-
enhanced TPL for localization and quantification of the nanoparticle.
Multifunctional plasmonic-active nanoprobes can be utilized for in vivo SERS
imaging and observing the concentrations of miRNA biomarkers, especially in
biosystems of the plant [58].
Fig. 6. (a) Schematic representation of the experimental setup. Cultured cells are positioned on a
fluidics device after attaching them onto the gold chips. The images are taken by two cameras, one
for bright-field images and the other for SPR images. (b) The captured bright-field and SPR image.
(c) Schematic illustration for simultaneous analysis of binding affinity and kinetics by edge tracking
and SPR methods. Ligands introduced to the cells result in edge deformation due to binding, which
is quantified and simultaneously compared to the obtained SPR signals. (d) Simultaneous edge
tracking and analysis of SPR kinetic response curve of wheat germ agglutinin (WGA) binding to the
same cell. Comparison between the bright-field and SPR image (the insets) (e) Different WGA
concentrations and the average response curve of their binding to the cells employing SPR and edge
tracking. Figure adapted from Jing et al. [59]
In drug discovery, it is required to quantify the binding efficiency of the drug to

proteins on the cell membrane, which can be done by SPR imaging with a single-cell
resolution. Deformation of the cell membrane can be tracked to quantify the dynam-
ics of ligands binding onto it. Integrating these two methods facilitates the synchro-
nized data collection from both techniques. SPR signal can detect the mass of ligands
as well as measure the density of membrane proteins, while binding of small
molecules can be detected because of the tracking cell edge technique (Fig. 6). It
was found that the kinetic constants at the single-cell level of these two techniques
were in harmony and their combination enhances the reliability and quantifica-
tion ability [59]. A nuclear emulsion that is of fine grained known as Nano Imaging
Tracker (NIT) is helpful to ionizing particle detection with a resolution in the order
of nanometers. It documents the moving trajectories using AgNPs, which can be
observed and analyzed using super-resolution plasmonic imaging microscopy
(SRPIM). Due to LSPR, SRPIM exploits the optical response dependent on polar-
ization and tracks nanograins with a nanometer resolution [60].
Traceable spherical nucleic acids (SNAs) are constructed using AuNPs, which are
spherical and covered with DNA labeled with a fluorophore. They function as both
plasmonic and fluorescent nanoparticles. The distribution of these SNAs in a cell can
be analyzed by correlative imaging using fluorescence and dark-field microscopy.
Clustering states of SNA can be quantified and distinguished by integrating dark-
field microscopy and scanning electron microscopy (SEM) but they are lack of pre-
cision. In different accumulation states, plasmonic nanoparticles’ distribution in a
cell and endocytosis can be monitored in real-time and the targets can be visualized
quantitatively in live cells [61].
4 Plasmonics for Super-resolved Optical Imaging

in the Near- and Far-field
Optical microscopy is a fundamental part of biophotonics and biomedical research.

An ideal imaging modality is expected to provide high-resolution images of any
biological entity for its detailed investigation. However, the spatial resolution of
current far-field optical microscopy techniques is restricted roughly to half of the
excitation wavelength of light by the diffraction limit. It is the major setback in
imaging biological samples in their natural environments. Combining the image
resolution provided by electron microscopy with the contrast provided by light
microscopy is a topic of discussion [62]. In this regard, the concept of near-field
imaging was first introduced by E. H. Synge back in 1928; however, he could not
build a working model, as it demanded highly advanced instrumentation. Ever since
many researchers were working in this field and the first breakthrough was made by
the Nobel laureate Eric Betzig in the year of 1988 with his first near-field optical
microscope [63]. The near-field microcopy achieves the super-resolution in imaging
various biological entities; however, the region of interest (ROI) being illuminated in
this technique is very limited. This could be overcome with regular far-field imaging;
however, a suitable illumination source is desirable to surpass the diffraction limit.
The light with wavelength λ emitted from a source propagates through the space
in an unconditional manner. If the object/sample is kept at a shorter distance less than
the λ from the source (Fig. 7a), the spatial features with higher frequency can be
imaged using a near-field microscope. However, in far-field microscopy, this high-
frequency spatial information is filtered out due to the diffraction limit (Fig. 7b) [64].
Fig. 7 Comparison of a focused beam spread in the imaging process: (a) far-field, (b) near-field.
λ—wavelength of incident light; h—separation between sample and light source
Plasmonic nanoparticles such as gold and silver have remarkable absorption and
scattering properties due to the presence of conduction band electrons. On the
incidence of electromagnetic radiation at a particular frequency, which is equal to
the natural frequency of the material, the electron cloud resonates to produce SPR.
This phenomenon enhances the localized electromagnetic fields and acts as an
intense near-field illumination source for the molecules in their close vicinity. In
addition, the Rayleigh scattering caused by the plasmonic excitation allows single-
particle imaging [65].
5 Progress in Plasmonic Optical Imaging with Different

Shapes of Nanoparticles
The acquired SPR in plasmonic nanoparticles enhances their properties; therefore,

they have applications ranging in different fields of biology and medicine. Biocom-
patibility, synthesis, modification of the surface, and optical properties that can be
modified and/or enhanced have increased the use of AuNPs in cancer research.
AuNPs with different structures and shapes have been developed using various
synthetic technologies and have diverse applications (Fig. 8). Hollow AuNPs, gold
nanorods, or nanoshells are a few examples of different AuNPs, which mainly
demonstrate red-shifted properties. The electromagnetic field increased in the case
of SPR enhances Raman scattering and hence facilitates to differentiate adjacent
molecules, while the enhanced absorption/scattering facilitates molecular imaging of
cancer. Particle shape, size, composition, distance, and relative positioning can help
determine the induced field by Raman enhancement [67]. Asymmetric AuNPs
facilitate large Raman enhancement due to increased curvature surface (lightning-
rod effect). Adsorbed molecules on nanorods had enhancement factors, whereas in
similar conditions nanospheres showed no such enhancement [68]. AuNPs conju-
gated with anti-EGFR facilitate cancer imaging due to EGFR overexpression on
cancer cells. The spherical nanoparticles exhibit green-yellow color as on the cell
monolayer with SPR present at around 540 nm. Similarly, Au nanorods
presented intense SPR absorption at 800 nm and facilitated the diagnosis of cancer
cells [69, 70]. The quality of imaging human embryo kidney cells is enhanced by
cubic AuNPs by 200-folds in comparison to gold nanorods because the effect
of scattering is more than that of absorption [4].
Plasmonic nanoparticles have a strong SPR band and their intensity and wave-
length are governed by Mie theory which states that various factors including
composition, particle size, shape, metal type, structure, and dielectric constant of
the medium disturb the charge density of electrons on the particle surface which
affects the SPR band (Table 1) [76]. Sphere to rod shape change of AuNPs results in
SPR band to split into the longitudinal band in the NIR region (a strong band
corresponding to the oscillation of electrons adjacent to the long axis) and transverse
band in the visible region (a weak band with comparable wavelength to gold
Fig. 8 Illustration of imaging modes based on NIR gold nanomaterials such as gold nanorods,
nanocages, nanoshells, and assemblies. The characteristics of photothermal imaging (PTI), SERS
imaging, and photoacoustic imaging (PAI) for in vivo diagnosis and therapy. AuNPs can be
modified with biopolymer, biofunctional molecules, hydrophobic drug molecules, and other
amphiphilic ligands. Figure adapted from Tian et al. [66]
Table 1 LSPR and ASPR of different types of gold nanostructures. ASPR—axial surface plasmon
resonance; ext—extinction; LSPR—localized surface plasmon resonance. Table adapted from
Bansal et al. [71]
Peak SPR LSPR molar ASPR molar
Type of Dimension wavelength ext ext
nanocrystal (nm) (nm) (M1 cm1) (M1 cm1) Reference
Gold 5–100 LSPR— 1.10 107 to – [72]
nanoparticles 515–572 1.57 1011
Nanoshells 10–400 520–900 – – [73]
Gold nanorods Axial diame- ASPR—512 8.99 108 to 2.25 108 to [74]
ter—10 1.02 109 2.55 108
Longitudinal LSPR—
length— 700–808
29–41
Axial diame- ASPR—530 9.15 108 to 5.72 108 to
ter: 25 4.58 109 2.29 109
Longitudinal LSPR—
length— 550–700
34–73
Gold 20–200 400–1200 – – [75]
nanocages and
boxes
Branched gold 45–300 550–800 – – [73]
nanostructures
nanosphere). With increasing length to width ratio, i.e., aspect ratio, red-shift takes
place in the longitudinal band from the visible to NIR region resulting in blue to red
color change, whereas transverse band is not affected by size change at all
[77]. There is a linear red-shift in the SPR maximum when there is an increase in
aspect ratio in the case of nanorods, but in the case of spheres there is a slight
red-shift when particle size increases. The efficiency of scattering increases signif-
icantly and the absorption wavelength increases linearly when the aspect ratio
increases in the case of nanorods. This is similar in gold nanospheres [67, 78]. Scat-
tering quantum yield which is a ratio of scattering and total extinction efficiency
increases with a rise in aspect ratio. In the case of rods elongation leads to a decrease
in scattering quantum yield but in the case of spheres enlarging the shape increases
the quantum yield [67]. Hybridization of inner sphere and outer cavity plasmons
leads to red-shifts; therefore, by modifying the thickness of the shell SPR wave-
length can be modified [79, 80].
There are different plasmonic nanostructures namely, nanoantennas, optical
waveguides, photonic crystal resonators, and nanoapertures [81]. Studies have
been done on nanoantennas of different geometries (nanorods, V- and T-shaped
antennas, gap dipole antennas, cross antennas, and bowtie antennas) which demon-
strated that T-shaped nanoantennas have great optical properties. T-shaped
nanoantennas that are coupled have refined tunability and have powerful light
focusing capability in nanometer range via morphology alteration in the structure
[81, 82]. The study demonstrated that coupled copper T-shaped plasmonic
nanoantenna in optical trapping of a dielectric nanosphere can be used to explore
its optical and plasmonic characteristics. This study validated the robustness of
copper T-shaped nanoantennas as nanophotonic devices for nanoscale manipulation
of optical data [81].
To optimize plasmonic nanoparticle-based systems we can modify optical
responses, such as the strength and decay length of focused electric field in spectros-
copies and the refractive index minimization of peak width in effective sensing.
They can be manipulated by shape, size and composition creating interests in crystal
growth and shapes. LSPR enhances the interactions between light and matter as well
as manipulates light and plasmon resonance at subwavelength level, which is
supported by magnesium. Crystalline hexagonal close-packed (HCP) structure of
magnesium that is not common in plasmonic metals provides a range of twin planes
possibly resulting in unique shapes such as kite and fold predicted by Wulff model
[83]. Nanostructures of magnesium that are fabricated via a top-down approach
maintain LSPRs; for example, chiral photoresponse is displayed by magnesium
helices and the rate of fluorescence radiation is improved by aperture films
[84, 85]. These fabricated structures have various disadvantages such as fluctuating
transformation kinetics, higher oxidation, and reduced plasmon resonances quality
[83]. Single crystal, tent, chair, taco, and kite structures were synthesized and studied
employing dark-field scattering and STEM-EELS (scanning transmission electron
microscope electron energy loss spectroscopy) [86, 87]. Spanning visible, UV and
NIR, a range of modes were exhibited by discrete dipole approximation (DDA) for
optical and electron excitation, which supported previous studies [88–90]. STEM-
EELS data parallels the e-DDA predicted modes. Modes that have nodes present
along the long axis have more stability than those that have nodes along the short
axis, and an increase in aspect ratio results in a decrease in energy of long axis nodes.
STEM-EELS demonstrated that when the aspect ratio rises past 2.2, the longitudinal
modes become dominant and abundant for magnesium nanorods. Along with the
magnesium twin plane, folding and extension lead to upregulated aspect ratio, which
lifts the hexagonal plates’ degeneracy resulting in richer modes [83]. Among differ-
ent aspect ratios, the relative energy and intensity of higher order modes differ sig-
nificantly [86, 91]. Throughout various high-order modes, the different shapes due to
twinning of magnesium nanoparticles open up new prospects to sculpt the localiza-
tion and energy of electromagnetic hot spots [83].
6 Summary
The quality enhancement of imaging for biological samples in various kinds of

microscopy is due to the localization of plasmonic nanoparticles and the overlap
between their plasmonic fields. These metallic gold and silver nanoparticles have the
ability to scatter the light strongly, which makes them easily detectable under dark-
field illumination as well as other optical microscopy techniques. Thus, they can be
used in many in vitro biological applications and biomedical techniques, more
particularly for investigating and understanding the nanoparticle-cell interactions
helping in enhanced imaging of biological tissues. These plasmonic nanoparticles
are also advantageous over the more commonly used fluorophores and organic
fluorescent dyes because these fluorescent dyes are known to exhibit photobleaching
as well as decompose during imaging. Whereas, plasmonic nanoparticles are known
for their photostability. Therefore, they can be used as bionanoprobes for monitoring
various dynamic events in the cell over a long period of time and produce a very
high-quality stable signal that assist researchers to monitor the effects of drugs on
cells as well as to identify specific pathways. The most important requirement for
these special probes is that they should not be toxic to these biological sample. In the
case of toxicity, recent advancements have shown that encapsulation of these
nanoparticles with a thin and biocompatible silica coating can minimize their
toxicity and help in enhanced imaging. Future research can also focus more on
multifunctional plasmonic nanoparticles and their advantages over the traditional
ones in terms of imaging and biosensing. Hybrid nanoparticles with quantum dots or
superparamagnetic nanoparticles anchored on the conventional plasmonic
nanoparticles can be employed in multiple imaging techniques and guided to a
specific desired area for imaging by external magnetic stimulation. Therefore, it
can be definitively concluded that these nanoparticles have a wide range of biomed-
ical applications like in vitro and in vivo imaging as well as theranostics and are ideal
bionanoprobe candidates for further research in noninvasive diseased cell imaging
and treatment. The design and engineering of these “smart” plasmonic probes have
made live-cell imaging of biological samples much easier and have helped to
enhance the already existing microscopy techniques.
Acknowledgments We thank the Global Innovation and Technology Alliance (GITA), Depart-
ment of Science and Technology (DST) [Project Number—GITA/DST/TWN/P-95/2021], Govern-
ment of India, and the India-Taiwan international cooperative research project of Ministry of
Science and Technology (MOST), Taiwan [Grant Number—110-2923-M-039-001-MY3] for
financial support.
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Deep Tissue High-resolution
and Background-free Imaging
with Plasmonic SAX Microscopy
Gitanjal Deka, Bimalendu Deka, Kentaro Nishida, Katsumasa Fujita,

and Shi-Wei Chu
Abstract In the field of clinical biology, imaging biological tissues play a crucial
role in understanding the nature of structural and physiological changes in their
content. Traditionally, for physiological and morphological studies of infected
tissues, two-dimensional surface imaging of tissue sections was the standard. How-
ever, in many situations, 3D imaging of an entire tissue region becomes mandatory
for a better understanding of the condition. This requires an imaging modality that
can image deep inside the tissues with better resolution. But animal tissues are
notorious for scattering visible light thus making it difficult to see any anomalies
beyond 100 μm depth. To decrease the scattering by the tissue, IR light can be used.
But according to Abbe’s law, the resolution of a microscope system is inversely
proportional to the wavelength of light used. So, as two-photon excitation uses
approximately twice the one-photon wavelength, the resolution becomes approxi-
mately half of the single photon. Moreover, as we try to observe deeper, scattering
G. Deka (*)
Department of Physics, The Assam Royal Global University, Guwahati, Assam, India
e-mail: gdeka@rgu.ac
B. Deka
North Eastern Hill University, Shillong, India
K. Nishida
Department of Physics, National Taiwan University, Taipei, Taiwan
K. Fujita
AIST-Osaka University Advanced Photonics and Biosensing Open Innovation Laboratory,
Osaka, Japan
S.-W. Chu
Department of Physics, National Taiwan University, Taipei, Taiwan
Brain Research Center, National Tsing Hua University, Hsinchu, Taiwan
Molecular Imaging Center, National Taiwan University, Taipei, Taiwan
https://doi.org/10.1007/978-3-030-99491-4_16
420 G. Deka et al.
makes it difficult to cope with the decrease in the contrast between the object of
interest and the unwanted part of the tissue. In this chapter, we will discuss one
recently developed technique called Saturation Excitation (SAX) microscopy to
achieve improved resolution and background-free images from depths of animal
tissues using nonlinear plasmonic nanoparticle scattering as markers. Herein, we will
discuss the working principle of the SAX technique and review its potential in
imaging as deep as 400 μm with improved resolution and background-free contrast.
Key words Clinical biology · Biological tissues · Physiological changes · Two-

dimensional surface imaging · Scattering · Two-photon excitation · SAX technique ·
Resolution
1 Introduction
In research and diagnosis of tumors and cancers, tissue imaging has gained tremen-
dous interest for achieving exact structural identification of the infected tissue [1–
3]. And noninvasive histological approaches are at the forefront of this field, as they
are favored over invasive ones. For noninvasive approaches, optical imaging tech-
niques are the best candidate to image tissues and cells in their natural state.
However, 3D optical visualization of structures of interest within deep intact tissues
with high resolution is a challenging task due to the highly scattering nature of
biological tissues. In the recent decade, various optical imaging techniques have
been developed to investigate the anomalies in deep tissue.
Studying intact tissues with great detail requires techniques that can provide good
contrast and high-resolution images even at a depth of more than 100 μm to a
millimeter [4–6]. Techniques such as magnetic resonance imaging (MRI) and
ultrasound imaging can image much deeper. However, they are limited by very
poor resolution [7, 8]. On the contrary, optical imaging provides much better
resolution. Optical imaging techniques such as confocal microscopy, multiphoton
fluorescence microscopy, and harmonic generation microscopy have tried their
hands in imaging the deep part of the tissues [4, 9–11]. But, with an increase in
depth beyond 100 μm, resolution and image contrast degrades significantly, because
the background signal from out-of-focus region gradually dominates the signal from
the focal spot due to the increase in scattering [12, 13]. High-resolution optical
imaging approaches, such as stochastic localization-based PALM and STORM
techniques, structured illumination-based STED techniques have demonstrated
much improvement in resolution but failed in deep tissue imaging. PALM and
STORM are applicable only to a depth of a few micrometers [14]. Even though
STED microscopy had shown some promises due to its confocal nature, depth of
more than 120 μm has not been reported using this technique [15, 16]. STED
techniques usually require beam shaping but spatially modulated beams get distorted
while penetrating through tissue, limiting their applications to only superficial layers.
To overcome these difficulties Fujita et al. have developed a high-resolution tissue
imaging technique called saturation excitation (SAX) microscopy based on
Deep Tissue High-resolution and Background-free Imaging with Plasmonic. . . 421
saturation of fluorescence emission, and a temporal modulated excitation light

[17]. Unlike spatial modulation, temporal modulation of laser beams is less affected
by tissues, making it ideal for deep tissue imaging.
However, all the abovementioned techniques are based on fluorescence as a
contrast mode. Fluorescence microscopy has some inherent limitations, such as
phototoxicity, photo-bleaching, auto-fluorescence, and low photostability, which
arise majorly due to the basic requirement of molecular labeling [18–20]. It is due
to this reason that alternative contrast agents, such as scattering nanoparticles are
desirable to develop deep imaging techniques. The most ideal material being metal-
lic plasmonic nanoparticles which have physical properties such as high
photostability, biocompatibility, and tunability of the surface plasmon resonance
(SPR) [21, 22].
In this chapter, we will review the resolution enhancement and background-free
imaging ability of SAX microscopy using scattering from plasmonic gold
nanoparticles as markers at various tissue depths. We will also discuss the working
principle of the technique and its potential applications in deep tissue imaging.
Through this chapter, we intend to provide an idea about a novel alternate minimally
invasive method for background-free deep tissue imaging with high resolution and
contrast.
2 A Brief Account on Microscopy Techniques

and Resolution Enhancements in Deep Tissue Imaging
In the nineteenth century, German physicist Ernst Abbe calculated that one could
only resolve two objects distinctly if they were no closer than half the wavelength of
the light used to look at them, which was called the diffraction limit. For over a
century, scientists were limited in their investigation of the microscopic world, due
to the diffraction limit. This meant that the microscopic world beyond 250 nm
(as visible light has a central wavelength of 500 nm) was invisible to scientists
[23]. However, the invention of electron microscopy and scanning probe microscopy
techniques overcame this limit at the cost of being unable to in vivo imaging of the
biological sample; or simply put, compromising the sample for better resolution
[24, 25].
With the advancements in light microscopy, researchers were able to image cells
and tissues, with better contrast but only at submicron resolution. Till the late 1960s,
the resolution limits of the best wide-field microscope were, laterally ~250 nm and
axially ~800 nm [26]. This limit was overcome by Marvin Minsky’s invention of the
confocal microscope, which blocked the out-of-focus light using a pinhole [27]. Due
to its optical sectioning capability, it leads to great improvement in axial contrast and
3D volume imaging.
422 G. Deka et al.
Another optical sectioning technique; first theorized by Maria Goppert-Mayer in

her 1931 paper, called multiphoton microscopy, greatly improves penetration depths
[28]. In principle, two photons arrive simultaneously at a molecule combine their
energies to promote the molecule to an excited state, which then proceeds along the
normal fluorescence-emission pathway. It was in the 1990s when Dank et al.
investigated the potential of imaging two-photon excited fluorescence in a scanning
microscope with ultrafast pulsed lasers [9, 29]. With further improvements in
multiphoton microscopy instrumentation, three photon fluorescence imaging has
been possible to image intact mouse brain as deep as 500 μm [10]. With the help
of IR excitation wavelength, researchers have been successful in reaching deeper
parts of tissues [4, 9, 10]. Moreover, as the nonlinear optical response is induced only
at the center of the laser-focused spot, the signal light is restricted within a volume
smaller than the focal spot itself. The small-signal volume provides optical section-
ing capability in deep tissue imaging and allows obtaining 3D images of thick
samples with improved resolution and contrast [11]. But with further increase in
depth beyond 100 μm the contrast and resolution degrade rapidly due to scattering.
Additionally, the fluorophores suffer photo-bleaching once they are subjected to
prolong light illumination require to gather more signals.
With the invention of selective plane illumination microscopy (SPIM) or light-
sheet microscopy, the axial resolution improves by two times compared to confocal,
2.5 times compared to wide-field, and three times compared to two-photon micros-
copy, while the lateral resolution is the same as wide-field microscopy [30]. How-
ever, all the abovementioned techniques are still considered diffraction-limited, as
they are unable to resolve beyond the classical diffraction limit.
Those that can go beyond the classical diffraction limit are called super-resolution
microscopy techniques, which can be divided into near-field and far-field
[31, 32]. Near-field microscopy techniques include near-field scanning optical
microscopy (NSOM) and total internal reflection fluorescence microscopy
(TIRFM), which uses fiber optic probe to funnel light to nano-dimensions and
evanescent waves to excite fluorophore, respectively [33, 34]. NSOM can resolve
20 nm laterally and about 5 nm axially, and TIRFM can resolve up to depths of
100 nm. However, NSOM has its limitations, such as small depth of field, zero
working distance, and long scan times. In the field of far-field techniques, Dickson
et al. contrived a super-resolution microscopy technique called Photo-Activated
Localized Microscopy or PALM [35, 36].
This single-molecule localization technique relies on the principle of stochasti-
cally activating, localizing, and then photo-bleaching synthetic or genetically
encoded photo-switchable fluorophores. PALM originally used photo-activable or
photo-convertible fluorescent tags targeted to subcellular structures at high density to
achieve the localization precision necessary to generate image resolution as high as
10 nm [22]. A similar technique was then reported later in 2006 by Rust et al. based
on high-accuracy localization of photo-switchable fluorophores, called stochastic
optical reconstruction microscopy or STORM with an imaging resolution of 20 nm.
They claim that STORM can (in principle) reach molecular-scale resolution
[37]. The imaging process consists of a series of cycles, wherein each cycle, a
selected number of the fluorophore are switched on, such that each of the active
fluorophores is optically resolvable from the rest; thus, resulting in inaccurate
determination of the position of the fluorophore and hence a well-resolved image.
But being a wide-field imaging technique, both PALM and STORM are mainly
applied to cell imaging and limited to only a few micrometer depths. Concurrently,
Stefan Hell invented the stimulated emission depletion (STED) microscopy tech-
nique in the 1990s [38]. Here, all the fluorophores are transferred back to their
ground state by means of stimulated emission, except the center most fluorophores
within the diffraction-limited illumination volume. By using a spatially modulated
laser spot of a scanning microscope to induce stimulated emission of fluorescence at
the edge of the illumination focal spot, STED achieves a lateral resolution of
30–50 nm, which is at the cost of fluorophore photostability. Additionally, the
spatially modulated light gets distorted rapidly while imaging intact tissues. STED
can image maximally 100–120 μm depths with addition of few adaptive optics
improvements [16]. In far-field super-resolution optical microscopy, localization
and STED techniques are leading the way.
In 2007, Fujita et al. developed a high-resolution tissue imaging technique, which
is SAX microscopy, based on saturation of emission, along with a temporal modu-
lated excitation light [17]. Unlike STED, which is spatial light modulation-based
super-resolution techniques, temporal modulation of laser beams distort less in
tissues; hence it is ideal for deep tissue imaging [39]. With SAX technique, they
have demonstrated imaging living cells with fluorescence nano diamonds and dye
fluorophores [40, 41]. However, the resolution enhancement with this technique was
limited by the order of nonlinearity required to achieve high resolution. Conse-
quently, higher order nonlinearity requires higher excitation intensity, which the
fluorescence markers might not endure [32]. Hence, a robust and non-bleaching
contrast such as scattering from metallic plasmonic nanoparticles is desirable to
achieve high-resolution imaging with SAX microscopy [21, 22]. These metallic
nanoparticles are highly photo-stable, and their surface plasmon resonance (SPR) is
tuneable by geometry [22]. In the year 2014, our group has reported the nonlinear
scattering from single plasmonic gold nanoparticles and the resolution enhancement
through plasmonic SAX microscopy using the nanoparticles as probes [17].
Then half a decade later, for the first time, we demonstrated a three-fold resolution
enhancement inside a tissue sample up to a depth of 200 μm, using plasmonic SAX
microscopy [42]. In our experiment, we used a temporal modulated laser of 561 nm
to match the plasmonic resonance peak of 80 nm gold nano spheres (GNS). More
recently, to improve the penetration depth even further, we have demonstrated the
scattering saturation of gold nano shells and nano rods with near-infrared (NIR)
lights. We have achieved resolution enhancement at depth 400 μm inside a tissue
phantom, with complete background-free images [43]. The technique is useful in
imaging both static and dynamic cell systems. Also, it allows us to obtain a
multicolour image of more than two discrete nanoparticle probes by alternating the
excitation wavelength, which opens the possibility of multi-target observation in
deep tissue.
424 G. Deka et al.
3 Principle of Plasmonic SAX
3.1 Surface Plasmon Resonance (SPR) and Optical

Nonlinearity in Gold Nanoparticles
Surface plasmons are collective oscillations of electrons present on metal surfaces. In

metallic nanoparticles, surfaces plasmons localize within the nanoparticle. One
interesting feature of surface plasmons is their tendency to oscillate in phase with
an external applied field [44]. Hence, if the oscillation frequency of the external field
matches with the collective plasmon oscillations, the surface plasmons attain reso-
nance. This can greatly enhance the localized light intensity, meaning they have a
very high photon density [42, 43]. Due to this, intensity-dependent effects, such as
scattering, Raman scattering, magneto-optics, and fluorescence emission also get
enhanced [45–47]. The SPR facilitating the photothermal effect causes the saturation
in scattering signals from various metallic nanoparticles when shined with a light of
appropriate resonance wavelength [39, 43, 48].
Among all the plasmonic materials, gold nanoparticles stand out due to large
scattering cross section, photostability, nontoxicity, and biocompatible nature
[49]. Additionally, with different shape and size, gold nanoparticles provide
plasmonic resonance at various wavelengths. It was interesting to find that upon
illumination with resonant wavelengths, the scattering signal from the nanoparticles
saturates at relatively lower power [42]. Hence, these nanoparticles can be manip-
ulated in shape to get scattering saturation at different wavelengths. For example,
80 nm gold nano spheres yield better saturation at 561 nm, and nano shell and nano
rods saturate at 780 nm and 1064 nm, respectively [43]. As evident by the findings
described in Fig. 1(a), where extinction spectra of 40, 50, 80, and 100 nm
nanoparticles demonstrate clear SPR peaks at different wavelengths [18]. In addi-
tion, Fig. 1b, c, and d demonstrated the intensity dependence of scattering saturation
of 40 nm, 50 nm, 80 nm, and 100 nm gold nanoparticles for three different incident
wavelengths 405 nm, 532 nm, and 671 nm. These curves show a clear nonlinear
relationship of scattering signal with the excitation intensity. Since 405 nm lay
beyond the SPR region of all the nanoparticle types, none of them shows saturations
as evident from the linear curves. But for 532 nm lights, all the different sized
nanoparticles show scattering saturation after a certain higher intensity. However,
intensity requirement for saturation of 80 and 100 nm particles are much less than
that of 40 and 50 nm particles (Fig. 1c). This is because 532 nm lights do not overlap
well with the SPR band for 40 and 50 nm gold nanoparticle but overlap very well for
80 and 100 nm particles.
Similarly, in Fig. 1d for 671 nm light, the intensity requirement for scattering
saturation increases sharply as this wavelength is not exactly fit to SPR region of
those particles sizes. In separate experiments, we have examined the nonlinearity of
scattering of gold nano shells and nano rods. In gold nano shells the resonance
wavelength is governed by the ratio between silica core diameter and the gold shell
thickness [43]. As the thickness of the gold shell decreases, the SPR wavelength
Fig. 1 (a) Representative extinction spectra of 40, 50, 80, and 100 nm spherical gold nanoparticles,
which demonstrate clear SPR peaks at different wavelengths. (b–d) Demonstrate intensity depen-
dence curves of scattering saturation of those gold nanoparticles when illuminated with light of
wavelengths 405 nm, 532 nm, and 671 nm, respectively [18]. (e and g) Show the extinction spectra
of gold nano shells and nano rods, respectively. (f and h) Represents nonlinear response curves of
nano shells and nano rods, respectively [40]
moves towards the longer wavelength side. In our experiment, the nano shells were
of around 20–30 nm thick gold shells surrounding a silica core of diameter around
120 nm. They have an SPR resonance wavelength at about 780 nm and produce a
strong scattering signal at this wavelength. In the case of gold nano rods, the SPR
peak wavelength is determined by the aspect ratio (length to diameter ratio) of the
rods. With the increase in the aspect ratio, the resonance peak of gold nano rods
moves towards longer wavelengths. We used 70 nm long gold nano rods with
diameter 10 nm, which shows peak SPR scattering at 1060 nm. Figure 1e and g
show the extinction spectra of gold nano shells and nano rods, respectively. Their
corresponding nonlinear response curves are demonstrated in Fig. 1f and h, which
show deviation from linear trend as laser power increases. These plasmonic
nanoparticles whose SPR peaks lie in the IR region provide the advantage of
imaging deeper than visible SAX microscopy, due to less absorption and scattering
of IR light by biological tissues.
3.2 Principle of SAX Microscopy
SAX microscopy is based on saturation of emission, achieved with a temporal

modulated excitation light [17]. Similar to fluorescence SAX, which requires satu-
ration of fluorescence emission, plasmonic SAX microscopy exploits saturation of
scattering signal from plasmonic nanoparticles [17, 18]. The scattering saturation
elucidates the nonlinear relationship between excitation and scattering intensity.
When the plasmonic particles are illuminated with the laser, saturation starts at the
426 G. Deka et al.
Fig. 2 Schematic of the working principle of SAX microscopy. (a) Representative PSF in X-Z
plane, showing a typical elongated profile along Z. (b) Sinusoidal time varying signal extracted
from the PSF, which is unsaturated at the periphery, represented above and saturated towards center
represented bellow. (c) Represents the respective Fourier transform of the curves in (b), showing
only linear frequency components from the periphery and with nonlinear harmonics components
from center. (d) Demonstrate the effectively reduced PSF [32]
center of the laser focal spot, where intensity is the maximum and remains unsatu-
rated at the boundaries leading to a deformed point spread function (PSF). This PSF
carries structural information and can be used for improving the three-dimensional
spatial resolution of the image. Figure 2a shows the PSF of a laser focal spot in X-Z
plane, where the bright color in the centre represents higher intensity and decreases
gradually towards the periphery. Hence, if the saturation has just started at the center,
in the periphery the signals are still linear. Therefore, the trick to improve resolution
in SAX microscopy is to add a sinusoidal temporal modulation of frequency suppose
fm, to the excitation laser. Since the periphery follows the linear trend, the signal from
this region is unsaturated, as demonstrated in the top curve of Fig. 2b. On the other
hand, the signal from the central region is saturated as demonstrated at the bottom of
Fig. 2b. By taking the Fourier transform of the temporal modulation carried into the
scattered signal from the central region, the frequency components of fm and its
harmonics, such as 2fm, 3fm, can be observed as shown in the bottom plot of Fig. 2c.
As expected, in the top plot only the fundamental frequency ( fm) signal is observed
due to the linear response of the periphery. By selectively extracting only the higher
harmonic signals from a mixture of fundamental and harmonic signals with the help
of a lock-in-amplifier, the effective PSF can be reduced in all three dimensions thus
enhancing the resolution in the process (Fig. 2d). This feature of removing the
fundamental or linear harmonic signal has made SAX technique a much desirable
modality in high contrast, background-free, deep tissue imaging with improved
resolution.
3.3 SAX Instrumentation
In a typical SAX microscopy, a continuous wave (CW) light from a laser source
passed through a beam splitter (BS). Figure 3a shows the schematic diagram of the
experimental setup. The two diverged beams were then allowed to pass through two
acousto-optic modulators (AOM) with modulation frequencies at 40.00 and
40.01 MHz, respectively. The first-order diffraction beams from the individual
AOMs were then recombined with the help of the second beam splitter (BS2). By
this technique, sinusoidal modulation of the incident light beam intensity at beating
frequency (10 KHz) was obtained [40, 46]. A part of the modulated light was sent to
a photodetector, which fetched the modulated 10 KHz electric signal into the lock-in
amplifier (LA) as the fundamental ( fm) reference signal. The other part was guided
into a confocal microscope system to scan the sample with a pair of galvanometer
mirrors through an objective. The combined linear and nonlinear scattered lights
were then collected with the same objective and detected with a photomultiplier tube
(PMT) through the third beam splitter (BS3) [42]. The electrical signals from the
PMT carried both fundamental and higher harmonic signals to the LA. With the help
of the reference signal, the LA can extract the higher harmonic signals. These
harmonic signals then form the image in the computer with proprietary imagining
software. Figure 3b and c schematically show the process of imaging the gold
nanoparticles through the tissues and a reconstructed image of those particles
dispersed in the tissue with fundamental frequency signal respectively.
Fig. 3 (a) Ray diagram of a

typical SAX setup. (b)
Schematic of the imaging
procedure through tissue
section; O oil, CG cover
glass, T tissue section, GNS
gold nano sphere, SG slide
glass, S stage. (c)
Representative SAX image
of GNSs dispersed over
chicken breast tissues,
reconstructed with 1f
scattered harmonic signals
with sarcomere lines
indicated by the white arrow
[30]
428 G. Deka et al.
4 SAX Microscopy of Deep Tissue
4.1 Resolution Enhancement
Light scattering and absorption in tissues increase with penetration depth, which
deteriorates imaging resolutions rapidly [50]. Our group has shown that image
resolutions of GNSs decrease gradually as we try to image deeper in a tissue section
with visible light (λ ¼ 561 nm) [42]. Figure 4a (the blue histogram) elucidate the
increase in full width at half maximum (FWHM) of the gold nanoparticle images,
i.e., decrease in resolution with imaging depth. The images were formed by detecting
the fundamental 1f harmonic signals. However, SAX microscopy improved the
resolution at the depth of 50 μm, 100 μm, 150 μm, and 200 μm. The FWHM of
GNS images through the abovementioned thicknesses for 2f and 3f harmonic signals
were also measured for the same set of nanoparticles. Figure 4a shows a clear
decrease of FWHM in a specific thickness for 2f and 3f images. We observed
maximum of 1.8 and 3 times resolution enhancement by using 2f and 3f harmonic
signals respectively at maximum depth of 200 μm with visible excitation light.
Figure 4b quantifies the FWHM enlargement with imaging depth, and how much
Fig. 4 Column plot of (a) E1/2 ¼ 1f/2f and E1/3 ¼ 1f/3f, resolution enhancement factors while
imaging through different tissue thicknesses. (b) Variation of FWHM of GNS images with imaging
depth. The error bars represent the standard deviation from the average value.
Fig. 5 (a) Schematic of the

sample condition for the
observation of gold nano
shells in a tissue phantom.
(b) Photograph of the tissue
phantom. (c) Scattering
images of gold nano shells
obtained by SAX
microscopy at different
observation depths. First
column: observation depth
of 80 μm, second column:
240 μm, third column:
400 μm. Images of the first
row were reconstructed by
demodulating the 1f
scattering signal and the
second row with 2f signal.
White arrows in each image
indicate the positions of
gold nano shells
it can be minimized by collecting the higher harmonic signals in SAX microscopy.

The resolution enhancement factors (REF, E1/2 ¼ 1f/2f and E1/3 ¼ 1f/3f) as shown in
Fig. 4b, defined by the ratio of FWHM measured with 1f signal to 2f signal and to 3f
signal respectively are independent of tissue thickness and it is maintained through-
out the complete depth of the tissue.
In comparison to visible light, FWHM enlarges less with NIR light due to less
scattering and absorption and hence improves the penetration depth without image
distortion. We have demonstrated the use of 780 nm excitation lights for gold nano
shells as scattering markers [43]. For this purpose, we developed an artificial tissue
phantom by using agarose gel, intra-lipid, and water in a proper proportion to mimic
the scattering condition of animal tissue. A schematic of the imaging scheme with
dispersed nanoparticles in the tissue phantom is represented in Fig. 5a and the
phantom in Fig. 5b. The dispersed gold nano shells were imaged with 780 nm
excitation light. The average spatial resolution of gold nano shells was improved
from 486 nm to 363 nm by detecting the 2f signals when they are imaged directly
over a glass slide without any tissue [43]. The resolution improvement was also
achieved through tissue phantom of thicknesses 80 μm, 240 μm, and 400 μm
(Fig. 5c). The resolution was improved from 580 nm to 392 nm with the same
order of harmonic signal through 400 μm thick tissue phantom placed over the
nanoparticles [43]. By demodulating the 3f harmonic signals the resolution of gold
nano shells without any tissues was improved to 203 nm supplementary information
430 G. Deka et al.
of [43]. However, with the 400 μm thick tissue, the third-order harmonic signal
intensity decreases drastically. Hence, imaging based on third and higher harmonic
signals could not provide practical imaging solution at that depth.
The above results indicate that even though the spatial shape of the image formed
with linear signal is affected by the depth of the tissue, the nonlinear signals are less
affected. The FWHM of the nano shells degrades from 486 nm to 580 nm in linear
signal while imaging through 400 μm thick tissue, but it degrades only to 392 nm
from 363 nm in second-order harmonic signal. This had been possible only due to
the robust scattering property of plasmonic nanoparticles that allows detecting strong
harmonic signals. These findings open up new frontiers in tissue imaging, by
providing much more improved visibility in a region which was fuzzy earlier.
4.2 Contrast Enhancement
Contrast is the virtue by which an object is differentiated from its environment. In

microscopy, an image is comprised of background light which comes out of the
tissue. For a good contrast image, there must be a well-defined way to justify the
position of the region of interest and the background. In various microscopy
techniques, it is achieved with wavelength difference, polarized light sensitivity,
fluorescence lifetime difference, and intensity [51]. In plasmonic SAX microscopy,
nonlinear scattering intensity is the underlying principle to create the contrast
mechanism. Due to the plasmonic property, gold nanoparticles can scatter
nonlinearly modulated (2fm, 3fm,....) lights. On the other hand, the tissue being linear
can scatter only the linearly modulated ( fm) light. By demodulating only the higher
harmonic signals, the background signals coming from the tissue can be efficiently
removed. Thus, in theory, SAX microscopy can provide completely background-
free high contrast imaging, by creating a huge intensity difference between the
markers and the background.
4.2.1 Deep Tissue Background-free Imaging with Visible Light
Animal tissue is a highly scattering media thus signals from the tissue may interfere
with the signals from markers, giving a very low contrast image. With more imaging
depth, the scattering also increases, which deteriorates the contrast even further due
to high background signal coming from out-of-focus region. The background signals
can be effectively removed by demodulating 2f and 3f harmonic signals in SAX
microscopy [41, 48]. Figure 6 compares the contrast of the plasmonic gold nano
sphere markers in an environment of tissue at various depths. Figure 6a demonstrates
the SAX images of gold nano spheres, imaged with 561 nm laser through tissues of
various thicknesses. The first row shows the presence of tissue background while
images are formed with 1fm signal. However, the backgrounds are removed in the
images formed with 2fm and 3fm signals in the second and third rows. The signal-to-
Fig. 6 (a) Representative SAX images of GNSs through tissues of different thicknesses, left to
right: no tissue, 50 μm, 100 μm, 150 μm, and 200 μm. The first row is the images of the fundamental
harmonic signal; the second and third row represents the corresponding images formed by second
and third harmonic demodulated signals, respectively. (b) Column plot of SBR in log scale against
tissue thickness. The error bars represent the standard deviation from the average value. (c) Scatter
plot of signal-to-background ratio vs. NIR imaging depth of gold nano shells reconstructed by linear
signal (black), by a linear signal obtained through a 1.3 Airy confocal pinhole (red), by second-
order nonlinear signal (blue). N ¼ 5. Error bars are the first standard deviations [43]
background ratio (S/B) in 1fm, 2fm, and 3fm signal images are quantified and
compared in Fig. 6b. The S/B increases 20–40 times with harmonic signals. The
higher value of S/B in 2f than 3f is due to the lower signal strength of third-order
nonlinearity than the second-order. The background counts in these two sets of
images are equivalent and arise mainly due to the shot noises from the electronic
detection system and not from the tissue. Additionally, the white arrow in the third
column of Fig. 6a indicates two inseparable particles in 1f image. They are resolv-
able in 2f and 3f images, demonstrating the resolution enhancement ability along
with background removal. These findings provide the proof of double benefit of
SAX microscopy in simultaneous improvement of contrast and resolution.
432 G. Deka et al.
4.2.2 Deeper Tissue Background-free Imaging with NIR Light
Background-free images of gold nano shells as markers are obtained at 400 μm

maximum depth with 780 nm excitation light. Images formed by the 2f signals at all
the measured depths give a much higher contrast as compared to that of the 1f signal
by removing the background (Fig. 5c). The S/B of both linear 1f and nonlinear 2f
signals are measured at each observation depth and are compared with the direct
confocal images in Fig. 6c. The figure elucidates that the confocal detection with
NIR light provides much higher signals over background at shallow depth; however,
with depth, signals from tissue dominates but using 2f demodulated signal, S/B can
be kept at satisfactory value even at very deep tissue. In case of 1f signal, the
background is very huge at all the measured depths. Interestingly, the 3f signal is
very weak with NIR excitation above 200 μm depth, making it impractical to
construct the images.
5 Conclusion
Keeping in mind, the pivotal role of contrast and resolution, the plasmonic SAX
microscopy is an appropriate candidate for deep tissue imaging. Firstly, talking
about the contrast, it is an archetypal technique; since the background signals from
tissues were removed completely. The reason is the inability of the tissue in
scattering nonlinear signals and SAX images are constructed with nonlinear
scattered light by the plasmonic markers. Secondly, the resolution enhancement
can be achieved much more than fluorescence SAX, as they can survive the
prolonged illumination of high-power incident light required to achieve higher
order nonlinearity. Nonlinearity as high as tenth-order can be detected with this
technique (Fig. 5 of Ref. [42], Deka et al.), providing a vision for high-resolution
imaging as deep as 1 mm inside intact tissue. Thirdly, the possibility of optical
manipulation of resonance wavelength with size variation makes plasmonic
nanoparticles a perfect candidate for deep tissue imaging. As particles that have
resonance wavelength in the NIR region can be synthesized easily for achieving
deeper penetration of the excitation light, plasmonic SAX microscopy made deep
tissue, background-free, and high-resolution imaging a reality.
Even though two-photon and three-photon techniques can image much deeper in
comparison to confocal microscopy or SAX microscopy as we have presented here.
But these two techniques have resolution of cellular dimension that is from 1 to
20 μm. But on the other hand STED, PALM, and STORM techniques have a very
good resolution but cannot image deep. That is why SAX microscopy fills in the
niche of a deep imaging technique with a few 10s to a few 100 nm. Moreover, SAX
technique can be amalgamated with confocal, two-photon and three-photon imaging
techniques with very little modification.
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Microfluidic Plasmonic Sensors: Theory
and Applications
Rezoana Bente Arif and Tanujjal Bora
Abstract This chapter gives a brief overview of plasmonic sensors integrated with
microfluidic systems for the detection of chemicals, biological substances, and
physical properties of matter. Plasmonic sensors are one of the most promising
optical sensing techniques that can provide high detection sensitivity and can be
engineered to become highly selective. Integration of the plasmonic sensors with a
microfluidic system can further enhance its attraction by making them suitable for
point-of-care type applications and allowing to construct lab-on-chip type sensors
that is easy to use and portable. In the last decades, significant research and
development are transpiring in the field of microfluidic plasmonic sensors and
some of them are even commercialized recently. This chapter discusses the basic
theory of surface plasmon resonance and reviews briefly the recent research and
development of the microfluidic plasmonic sensors including their applications in
diverse fields, such as biomedical engineering, chemical detection, and environmen-
tal monitoring. The advantages, limitations, and future perspectives of the
microfluidic plasmonic sensors are also considered.
Key words Surface plasmon resonance · Plasmonic sensor · Microfluidic sensor ·

Optical sensor · Biosensor
R. B. Arif
Center of Excellence in Nanotechnology, School of Engineering and Technology, Asian
Institute of Technology, Klong Luang, Pathumthani, Thailand
Department of Electrical and Electronics Engineering, IUBAT-International University of
Business Agriculture and Technology, Uttara, Dhaka, Bangladesh
T. Bora (*)
Center of Excellence in Nanotechnology, School of Engineering and Technology, Asian
Institute of Technology, Klong Luang, Pathumthani, Thailand
e-mail: tbora@ait.ac.th
https://doi.org/10.1007/978-3-030-99491-4_17
438 R. B. Arif and T. Bora
1 Introduction
Microfluidic systems with controlled fluid flow at microscale level are extensively
used nowadays in various fields ranging from analytical chemistry to biomedical or
bio-nano engineering to food and agriculture industries [1, 2]. A microfluidic device
typically contains fluid flow channels or paths in a micrometer scale that allows
precise control over the flow usually in microliters per unit time scale. Their use
offers numerous advantages over conventional macroscale systems mainly because
of their much-reduced size, ability to handle microvolumes of samples, high sensi-
tivity, accuracy, simultaneous processing of multiple analytes, and flexible design
that allows their greater pertinence over several traditional benchtop applications [3].
Application of microfluidics in sensing field is not new and they are most
commonly used in two different ways: one in which sensing takes place inside the
microfluidic system, and the other in which sensing takes place with the help of an
externally integrated microfluidic system. In the first type, the sensor element is
typically integrated with the microfluidic channels. The most commonly used
sensing elements integrated with microfluidic systems are optical- and
electrochemical-based [4, 5]. Among these, optical sensors are of great interest
due to their high sensitivity, compactness, and faster response. Optical sensors
using Surface Plasmon Resonance (SPR) concept is especially gaining attention in
the field due to its extreme sensitivity and tunable optical properties [6]. SPR effect is
observed at a metal-dielectric interface and it is the oscillation of the collective
charge densities at this interface due to the interaction of the electron cloud of the
metal with an incoming electromagnetic wave. The SPR effect is observable only at
the nanoscale level (< 100 nm) and has been extensively studied in the past few
decades for various applications.
SPR sensors can provide highly sensitive and label-free real-time detection of
chemicals and biological substances, and integration with microfluidics further
offers the advantages of miniaturization, automation, and rapid processing with
compact design. In this chapter, we first briefly discuss the fundamentals of
plasmons and surface plasmon resonance (SPR) phenomenon, followed by a review
on recent developments in the field of SPR sensors integrated with microfluidic
systems and their sensing mechanism. The discussion also involves various appli-
cation areas of these microfluidic plasmonic sensors. At the end, their advantages,
limitations, and future perspectives are also discussed.
2 Plasmons and Surface Plasmons
Plasmons are quasiparticles arising due to the quantization of plasma oscillations,

analogous to the photons that are quantization of light wave. In another word, a
plasmon is a collective electromagnetic and quantized oscillation of free electrons,
where the wave nature of the plasmons can be described using Maxwell’s Equation
Microfluidic Plasmonic Sensors: Theory and Applications 439
[7]. Plasmons are responsible for the optical properties of metals and semiconduc-
tors. For example, the shiny nature of most of the metals is due to their high plasmon
frequencies that lie typically in the ultraviolet region, reflecting frequencies lower
than the plasmon frequency. Some metals, such as gold and copper, can absorb
specific energies of visible light through electronic interband transitions, giving their
specific colors. The plasmon energy, Ep of a material is often estimated using the free
electron model and is given by,
ne2
E p ¼ ħωp ¼ ħ ð1Þ
mEo
where ħ is the reduced Planck constant, ωp is the plasmon frequency, n is the

conduction electron density, e is the elementary charge, m is the electron mass,
and Eo is the permittivity of free space.
When the term “Surface Plasmon” is used, it signifies those plasmons that are
confined to the surface of a metal. The surface confinement is stronger when the size
of the metal particle is much smaller than 100 nm due to the high surface-to-volume
ratio of the particle. Polarization is observed when surface plasmons strongly interact
with an incoming light with a wavelength comparable to the dimension of the
particles. Surface plasmon requires a very thin layer of metal or highly doped
semiconductor consisting of negative real permittivity with another medium of
positive real permittivity, such as a dielectric. When the light incident on the surface
of the metal film fulfilling the total internal reflection condition, the positively
charged photon of the incident light and the negatively charged electrons of the
metal surface get coupled resulting in an electric field. Due to the attraction and
repulsion between the electrons and the alternating electric field an oscillation occurs
that results in a resonance, known as surface plasmon resonance (SPR) at a specific
incidence angle known as SPR angle [6, 8]. It creates a transitory or evanescent wave
of the electrons at the interface of the two media considered. The SPR oscillation is
highly dependent on the SPR angle and whenever there is a change of medium or
presence of analyte at the proximity of the metal surface the SPR conditions changes.
This is the primary mechanism of the SPR technology in the sensing field, and
depending on this phenomenon, different kinds of chemicals, biomedical antigens,
food, and environmental toxic substances can be detected.
Figure 1 depicts the commonly used Kretschmann configuration in SPR applica-
tions where a thin metal film (typically gold or silver) is inserted at the interface of
two dielectric media. Generally, medium 1 is a prism with a high refractive index
(n1) and medium 2 represents the surrounding air or a solution of interest with a
lower refractive index (n2). When light propagates from the higher refractive index
medium 1 to the lower refractive index medium 2, the total internal reflection (TIR)
can take place within medium 1 as long as the incident angle, θ, is greater than the
critical angle, θc, where sinθc ¼ n2/n1. Under this condition, evanescent waves are
formed and propagate towards medium 2, and the intensity of the evanescent wave
decays exponentially with distance from the dielectric interface. If the thickness of
Fig. 1 Schematic
representation showing the
surface plasmon resonance
phenomenon on a thin metal
film upon excitation with
incident light at resonance
angle (θ). The excited
surface plasmons can
propagate along the x- and y-
directions, known as
propagating surface
plasmon or surface plasmon
polariton (SPP). The
evanescent wave propagates
in the z-direction decaying
exponentially with distance.
Any analyte that binds to the
metal surface causes a
change in the effective
refractive index near the
surface of the metal film
resulting in a shift in the
resonance angle (Δθ) which
can be used for the detection
of the analyte
the metal film at the interface of the two dielectric media is small enough the
evanescent wave can penetrate it exciting the surface plasmons in the metal film.
The magnitude of the evanescent wave vector, kevan,k, parallel to the metal film is
given by,
2π
kevan,k ¼ ðn sin θÞ ð2Þ
λ 1
where, λ is the wavelength of the incident light.

If nm is the refractive index of the metal film, then the magnitude of the surface
plasmon wave vector (ksp) is given by,
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
2π n22 n2m
ksp ¼ ð3Þ
λ n22 þ n2m
At resonance, these two wave vectors become equal and therefore from (2)
and (3) we can write,
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi!
1 n22 n2m
θspr ¼ sin 1 ð4Þ
n1 n22 þ n2m
where θspr is the resonance angle which is related to the refractive index of the
surrounding (n2). Any change in n2 due to adsorption/desorption in the surrounding
medium will therefore alter the θspr and monitoring this change one can analyze the
adsorption/desorption at the metal surface.
2.1 Localized Surface Plasmon Resonance (LSPR)
Localized surface plasmon resonance (LSPR) is almost similar to SPR with a few
discrepancies, such as LSPR occurs when the metal consists of nanoparticles or in
the case of metal nanoparticulate thin films where the size of the nanoparticles is
smaller than the incident light wavelength [9]. In LSPR, a very small evanescent
wave is generated within a very small range of nanoparticles, unlike SPR. Further-
more, SPR is sensitive to a wider range of refractive indices than LSPR is [10]. At
resonance, metal nanoparticles exhibit enhancement in the local electric field and the
phenomenon has been exploited extensively for various optical sensing applications,
e.g., surface-enhanced Raman scattering (SERS), as depicted in Fig. 2. The
enhanced local E-field contributes several fold increments to the Raman signal
enabling detection of extremely low concentrations of chemical and biological
substances [11]. LSPR integrated with microfluidics for biomedical applications
have been also reported recently showing rapid, multiplex, and multi-parallel con-
tinuous measurements of biomarkers [12].
The dependence of the LSPR extinction peak on the surrounding dielectric
environment is governed by the following equation,
18πε3=2
m V ε2 ð λ Þ
σ ext ¼ ð5Þ
λ ½ε1 ðλÞ þ 2εm 2 þ ε2 ðλÞ2
where σ ext is the excitation cross section, V is the particle volume, εm is the dielectric
constant of the surrounding medium, ε1 and ε2 represents the real and imaginary part
of the complex dielectric function of the metal particle, respectively. The excitation
cross section will be maximized when ε1 ¼ 2εm. Using Drude model of the
electronic structure of metals, the frequency-dependent form for ε1 can be written as,
Fig. 2 Schematic representation of metal nanoparticles showing the locally oscillating electron
clouds around the nanoparticles generating localized surface plasmon resonance (LSPR). The near
filed interaction of the enhanced local E-field from the resonantly excited nanoparticles with an
analyte at near proximity produces enhancement in the inelastic scattering of light which can be
used as a probe for SERS-based sensing applications
ω2p
ε1 ¼ 1 ð6Þ
ω2 þ γ2
where ωp is the plasma frequency and γ is the damping parameter of the bulk metal.
Most of the metals exhibit LSPR conditions in the visible and NIR region in which
γ ωp and hence Eq. (6) can be further reduced to,
ω2p
ε1 ¼ 1 ð7Þ
ω2
At resonance, when ε1 ¼ 2εm, one can further obtain:
ωp
ωmax ¼ pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi ð8Þ
2εm þ 1
where, ωmax is the LSPR peak frequency. Converting the frequency terms in (8) to
wavelength using λ ¼ 2πc/ω where c represents the speed of the light and dielectric
constant to refractive index using εm ¼ n22 , the above equation can be rewritten as,
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
λmax ¼ λp 2n22 þ 1 ð9Þ
where λmax is the LSPR peak wavelength and λp is the wavelength corresponding to
the plasma frequency of the bulk metal. Therefore, any change in the surrounding
medium refractive index n2 due to adsorption/desorption or association/dissociation
will result in a change in the LSPR peak wavelength λmax.
3 Microfluidic Plasmonic Sensors
Continuous development of micro- and nanoscale technologies have provided broad

applications of plasmonics and microfluidics, especially in sensing applications.
Combining the two can lead to a high level of sensing performance through proper
system design, reduced diffusion time, multiplexing, and precise control over reac-
tion stages. While a significant amount of research is ongoing in this field almost
daily reporting novel techniques and ideas, commercialization of the technologies is
also happening at the same time. Table 1 summarizes some of the commercially
available plasmonic microfluidic sensors predominantly in the fields of biochemical
and biomedical engineering.
3.1 Plasmonic Flow Sensors
Because of simplicity, high sensitivity, robustness, and point-of-care (POC) settings,

the demand for plasmonic biosensors has been going in a progressive path.
Plasmonic flow sensors are beneficial from the detection of biomedical biomarkers
to the detection of food adulteration as well as other microfluidic applications.
Generally, microfluidic channels are fabricated on top of a metal layer, such as
gold or silver, because of its high stability in terms of reaction and high conductivity.
Table 1 List of some of the commercially available microfluidic plasmonic sensors in the fields of
biochemical and biomedical engineering
Model no. Application area Company, Country
BI-2500 series Microfluidic flow control Biosensing instru-
ment, USA
MP-SPR Navi™ Detection of organic molecules, nanoparticles, BioNavis, Finland
200 OTSO and proteins
SR7000DC lgG detection in human serum albumin Xantec, Germany
SPR-24 pro Life science Sierra sensors,
SPR-32 pro Germany
Plex Array system Protein detection from cell flow Plexera bioscience,
USA
Initially, there exists a reference intensity of light reflectance from the SPR sensor
when there is no flow of fluid in the microchannel. Once there is a flow at different
rates or there is a change of density of the flowing fluid due to the presence of a
chemical or a biomarker or other particles which is to be analyzed, the intensity of
the reflected light shifts. Plasmonic nanoparticles, as well as nanohole or nanorods,
are highly sensitive [13] to the presence of the analyte providing a significant shift of
the reflectance angle. Recently the work of Deng et al. [14] have demonstrated a
novel microfluidic flow rate detection method based on the SPR temperature imag-
ing and reported detection of water flow rates within a wide range of tens to hundreds
of μL/min. Calorimetric flow rate measurement was used by the novel system which
can be easily produced with high robustness and resistance to disturbances.
3.2 Biomedical Flow Analysis
In the race of biosensors for manifold biomedical specimen analysis, plasmonic

sensors are adding well-being exploitations. From the microfluidic cell flow analysis,
the concentration of apolipoprotein E (apoE) present in the human body can be
detected employing SPR shift with respect to the change in reflectance intensity
index which is extracted from the cell flow [15]. This is beneficial to detect the
imbalance of apoE (normal range in the human body is 23–49 μg/mL [16]) in gastric
cancer and Alzheimer’s disease. Not only plasmonic flow sensors are capable of
protein analysis, but also some of them are efficient in human enzyme level sensing
[17, 18]. Human enzyme level can be measured from the enhanced SPR on reverse
fluorescent coupling in microfluidic cell flow. Besides, LSPR can be utilized to
detect DNA polymerase reaction which is a very important enzyme in DNA repli-
cation. Again, an approach of single-cell analysis on the various membrane was
proposed by Perozziello et al. [19] by combining a microfluidic single-cell trap and
Raman spectroscopy from SPR analysis which is favorable in the characterization of
heterogeneity of single cells individually. Several plasmonic biosensors are capable
of analyzing antigen and other medical diagnoses, such as a simple, cheap, versatile,
and easily reproducible nanostructured microchannel was developed to detect anti-
gen level from human serum flow [20]. Also, in order to detect the analytes in
different medical diagnoses, the change in reflectance index in plasmonic sensors is
taken into an advantage [21]. Utilizing the electrophoresis capillary effect along with
the SPR sensor [22] where the gold layer is used as the grounding electrode, protein
separation can be performed for nanoliter per minute human serum flow.
Unexpected drugs from human saliva as well as from human plasma flow can be
detected utilizing Surface-Enhanced Raman spectroscopy of plasmonic particles in
microfluidic laminar saliva flow and microfluidic diatomite analytical devices,
respectively [23, 24]. Likewise, from measuring the exosome concentration in a
micro range urine sample lung cancer can be detected [25] in the initial stage with the
help of studying the Rayleigh Scattering of plasmonic nanoparticles. SPR, as well as
SERS, are also a blessing to investigate the high number of different medicines used
for the treatment. For example, Liu et al. [26] presented a model using SERS and Hu
et al. [27] demonstrated a process to detect and keep a beady eye on the amount of
propranolol and dopamine respectively since their excessive presence in patient’s
body is considered to be embodied pollution. Also, some LSPR microfluidic sensors
[28] are capable of sensing the outgrowth of various hormones in the human body.
3.3 Lab-On-Chip (LOC) Analysis
For micro and nanofluidic characterizations, on-chip analysis has been growing its
popularity due to its simple, expedient, and cost-effective circumstances. It provides
a mimic miniaturized environment which is required to perform the analysis
on. Plasmonic behaviors of particles have been utilized in lab-on-chip in terms of
micro and nanofluidic flow. For example, by fabricating gold nanoholes inside a
microfluidic channel on a bio-chip, the cell can be trapped from cell flow. And with
the varying reflectance as well as the plasmonic behavior, the cancer cell growth can
be identified [29]. In addition, optical image analysis from the diverse color illus-
tration of the plasmonic nanoparticle from their various level of flow can be analyzed
[30]. Not only SPR is used for microfluidic phenomena analysis, but LSPR is also
not less feasible in the detection of different biomolecules from various microlevel
fluidic flow using the same lab chip [31] which is easy to operate, handy, reusable as
well as inexpensive.
Presently research is under process to understand the nature, mutation behavior,
and effects of Covid-19 on humans. Besides magnetic, calorimetric, and different
fluorescent biosensors LSPR plasmonic flow sensors are catching the attention of the
researchers due to their high affinity towards the biomarkers of the virus with a very
low change in energy [32]. However, as it is not possible to test the virus on the
human body, researchers are taking assistance of on-chip human cell flow for this
analysis. Furthermore, LOC is used for plasmonic flow sensors for investigating the
magnetic [33] as well as the metallic [34] behavior of nanoparticle flow. LOC can be
considered as the backbone of the point-of-care medical diagnosis. POC is nothing
but a certain kind of bedside test, such as pregnancy test and urine strip test.
Although POC is a convenient process for instant diagnosis of any disease, there
are a few diseases or phenomena that can be detected using the POC system. Using
SPR flow biosensor chip, various bacteria, e.g., E. coli, S. aureus can be detected
[35] from phosphate-buffered saline (PBS) which is easily portable, user-friendly,
fast responsive, and cost-effective. Another POC that Hemmi et al. demonstrated
was the detection of immunoglobulin A (IgA) from a biofluidic sample [36]. Here,
the overflow of the fluid due to centrifugal force for rotation causes the change in the
intensity of light reflectance which was utilized to characterize the plasmonic sensor.
3.4 Food Quality Assessment
Plasmonic sensors have been quite well-established in various sectors of life science
for detecting the adulteration in daily used goods, food, cosmetics, and so on. For
example, the technique of SERS along Raman spectroscopy plasmonic sensor can
detect Listeria monocytogenes, one sort of food spoilage [37, 38]. In this regard, the
spoilage is parted from the significant change in their optical behavior in the
microfluidic system under SERS as well as Raman microscopy. Another approach
to detecting the bacteria present in the soft drink was made in conjunction with SERS
and Raman scattering. In replacement of gold nanoparticles, here, a super crystal of
plasmonic nanorod was utilized to trap the bacteria [39] to identify them from the
microfluidic flow. Apart from that, a collective mechanism of SERS and LAMP was
proposed by Teixeira et al., the distinct bacterium microorganic [40] that causes
harm to the human body from milk. Both of the mentioned systems work based on
the gold nanoparticle to detect pathogens.
Plasmonic Sensors have been contributing not only to food adulteration findings,
but also to maintain the quality of proper usage of human body-friendly commod-
ities. The misuse of lactam type medicine, Amoxicillin which is worldwide popular
to produce antibodies against different diseases can be detained by detecting its
usage limit with the help of SERS [41] plasmonic flow sensor. This mechanism is
possible to execute on only a few microliters per minute flow of flow taking
advantage of the change in Raman intensity with respect to the change in concen-
tration of amoxicillin. Moreover, due to the high sensitivity, low-cost features
plasmonic sensor SERS is also used to detect the access amount of Sudan I [42], a
red color temperament material used in real red chili oil using the chromatography
analysis of the output spectrum.
3.5 Chemical Detection
In order to actualize a hypothesis, to understand the material behavior, and to

fabricate things, chemical synthesis and analysis, as well as their detection, are
some important processes. The presence of heavy metals, e.g., mercury can be
detected using a gold SPR plasmonic sensor [43] as it is convenient for the heavy
metals to get attached to the gold surface, and, thus, illustrates the variation in the
surface plasmon resonance. To detect the organic chemical, photonic fiber (crystal)
and gold layer with a sandwich of a very narrow layer of TiO2 D-shaped sensor [44]
were used where chemical analytes get caught from the fluidic flow through the
channel. Depending on the quantum theory, optical sensors are capable of measuring
the salinity [45] of seawater with prominent resolution. Detection of some chemical
levels in the human body points towards diseases such as the downfall of immunity
and optical power respectively by SPR and SERS [46, 47]. Graphene with carboxyl
functionalization capable of enhancing the SPR property detects some particular
protein which indicated the condition of the immune system of the human body from
the affinity of carboxyl graphene and gold. In the other case, using SERS with
computer numerical analysis, the retinal albumin and glucose level are sensed to
conclude the condition of central vision of the retina. For this purpose, the
microfluidic flow of retinal serum is used.
Nanocomposites made up of diverse plasmonic nanoparticles are now becoming
popular for sensing chemical material in the microfluidic system using SERS. For
example, metallic graphene oxide-gold nanocomposite SERS plasmonic sensor [48]
is capable to detect kanamycin, one kind of antibiotic used for the treatment of
various types of oral, intermuscular infections, with a significant amount of lower
fluctuation in SERS response with respect to Raman shift. Another example of
nanocomposite is silver-gold nanocomposite which is applied in plasmonic SERS
plasmonic sensor [49] in order to detect alpha-fetoprotein which is a useful protein in
the growth of the fetus of a pregnant woman. This rapid detection sensor includes six
microfluidic channels within PDMS mold wherein the detection process takes an
average of the received data of the SERS spectrum from the individual
microchannel. Besides SPR and SERS plasmonic sensors, LSPR plasmonic sensor
is also able to detect some sort of nano chemical from the microfluidic sample within
a short period with significant sensitivity [50].
3.6 Environment Monitoring
Microfluidic plasmonic sensors are, in recent times, on the one hand contributing to
wastewater treatment and on the other hand becoming notable in air filtration. It is
complex to measure the waste in microfluidic air or water flow using conventional
systems. However, using the shift in the resonance of plasmonic nanoparticles for
the very small wavelength changes the diclofenac which is harmful to the water plant
can be detected and separated [51]. Herein, the water sample with the diclofenac is
passed through a microchannel where the antibody against the waste is already
generated. While having the flow through the channel there will be an affinity
created between the antigen and gold nanoparticle which will shift the plasmonic
response and thereby the waste can be detected with a very simple mechanism.
Another waste detecting sensor for water was fabricated by Qu et al. [52] with two
metallic zones separated by insulator ink. First, the Raman spectrum was observed
without the waste flow, and later the surface-enhanced plasmonic resonance signal
was observed and compared. The change in their response paves the way to detect
the waste as well as separate it from the water.
Day by day the pollution in the air has been in a growing phase due to numerous
chemical exposures in the environment. Some of these particles may cause long-term
harmful effects on human, animal as well as on plants. It is necessary to detect the
concentration of these harmful chemicals in the air for its purification which in some
cases can be done by cost-effective, reproducible, and robust plasmonic microfluidic
sensors. Using plasmonic Au/ TiO2 photocatalyst-based plasmonic sensor the
removal of formaldehyde from the air was demonstrated in the literature [53]. On top
of that, waste from the organic microfluidic sample can be isolated [54] with the
combination of Surface Plasmonic Polarization which is sensitive to change in
refractive index and polymer which is sensitive to the ultraviolet. When the organic
fluid sample passes through the microchannel due to the presence of analyte on the
metallic Au film SPP senses the change in refractive index and isolates the waste
from the sample.
3.7 Others
Mostly the wide range of applications of microfluidic systems along with optical
operations, SPR, SERS, LSPR, etc., are related to biomedical liquid exploration,
organic pollution analysis in food, environment as well as other natural and chemical
fluidic samples. Alongside these conventional applications of plasmonic flow sen-
sors, there are few areas of electronic signal manipulation methods [55] using this
sort of optical sensors. Since the plasmonic properties are highly sensitive to the
refractive index variation, fluid characteristics such as flow rate as well as attenuation
can be measured depending on the changes in this property with the frequency of the
electrical signal. Moreover, photon flow can be determined [56] using a plasmonic
waveguide combined with electronic signals in nano-optical devices.
4 Advantages, Limitations, and Future Perspectives

of Microfluidic Plasmonic Sensors
4.1 Advantages
Among the emerging technologies of immuno-bio-sensors, where the analyte of the

sensor apprehends a specific antibody, SPR-based sensors along with microfluidic
systems have been becoming desiring and gaining increasing attention. The reasons
behind their traction regarding biofluidic or chemical sample analysis are quite a lot.
For example, compared to other microfluidic sensors, they are much more reliable
and sensitive [57]. They provide mostly the advantages of a simple mechanism,
label-free detection, versatility, roughly estimating sensitivity in the case of
nanohole array system [58] in some cases. Moreover, SPR microfluidic biosensors
with multi-waveguide or fiber-optic are less sensitive to mechanical vibration [59];
thus, they can be miniaturized with a simple mechanism further. Besides, using the
surface optical characterization, colorimetric microfluidic sensors exhibits lower
execution and operating cost and better quantitative as well as qualitative analysis.
On top of that, this sort of microfluidic sensor provides the scope of label-free and
reusability properties [60] which minimizes the cost of the sensor explicitly.
Regarding the flow rate detection of the fluidic sample, SPR biosensors have
achieved the limit of a few microliters per minute through temperature gradient
image analysis [14]. Due to the miniaturization of SPR microfluidic sensors, repro-
ducibility, and mass production [61] are feasible. Therefore, with this type of bio-
sensors not only a lab-on-chip sample is analyzed, but also they are well suited for
POC or in situ [35] biomedical, chemical, or environmental microfluidic analysis or
detection. These POC SPR microfluidic sensors are robust, easy to carry and store
[62]. Different types of SPR microfluidic sensors such as prism-based [63], grating-
based [36], fiber-optic-based [64], or LSPR sensors [65] mostly take 10–20 min to
analyze the fluidic sample. Therefore, microfluidic antigen or antibody can be
detected or analyzed within a very short period of time as well as with an easy and
convenient method on spot. Integration of SPR mechanism in the microfluidic
system has made the microfluidic analysis and measurement further facile for the
usage of general people within comparatively low cost.
4.2 Limitations
Although there is a wide range of benefits of SPR-based microfluidic sensors, they

also possess some drawbacks which hinder their proper imposition in practical
usage. For example, the wrong antigen coalescence with the analyte may provide
a wrong response of change in the refractive index or intensity which may provide a
false-positive or false-negative result [66]. Moreover, the various volume of the fluid
sample consists of different amount of antigen which is why in case of a diverse
amount of sample may also provide. On top of that, other environmental phenomena
affect the output waveguide in the case of this sort of optical microfluidic sensors
[67]. In order to maintain the feasibility in their performance, highly expensive
optical characterizations are required which increases the commercial price of the
sensor [61]. Despite having POC microfluidic SPR-based sensors, they lack sensi-
tivity in most cases. In recent times, many other microfluidic flow sensors are
reported capable of detecting the flow rate at nL/min range, whereas SPR-based
microfluidic sensors are yet to be touched the milestone [14]. However, continuous
efforts are underway aiming to resolve these incompleteness in this sort of sensor.
4.3 Future Perspectives
To date, the mechanism and integration of the surface plasmon resonance-based

(SPR, LSPR, SERS, etc.) microfluidic sensors have been achieved. Moreover, the
optical characterization instruments required to analyze the sample for the sensor are
also quite developed and commercialized. Although, there are few aspects which
ought to be improvised in this kind of sensor to get flawless performance as well as
increased range of use. Further, research in favor of enhancing the sensitivity of the
already developed SPR-based microfluidic sensor is highly required. In addition,

real-time demonstration is needed rather than only lab-on-chip demonstrations for
their real-time usage. As recent technology is forwarding towards nano-dimension,
LSPR can be a reliable process in this type of microfluidic optical sensors in the
upcoming era. However, LSPR lacks different shortcomings compared to other SPR
mechanisms. Therefore, development in the implementation process of LSPR in
microfluidic sample analysis is another perspective in near future in this regard for
better reproducibility.
Another burning concern is cost minimization which is yet to be achieved in the
case of most of the developed SPR microfluidic sensors. To enhance the signal and
as a beneficial electrode, a gold thin layer is fabricated in SPR sensors. Because gold
costs are very high, it results in an expensive sensor. Thus, more research is
on-demand to find out a replacement of the metallic layer of gold to minimize the
overall cost of the sensor. Furthermore, a system can be developed without the
additional equipment which is now used for optical characterization for POC
detection. SPR microfluidic sensors which are capable of detecting the blood flow
rate or other biofluidic flow level are desired to be developed for POC applications.
They can be mobilized with a mobile phone for output result exhibition.
An immensely new alliance that can be combined is machine learning in SPR
microfluidic sensors. Nowadays, artificial intelligence (AI) is ruling out almost every
sector of technology and illustrating a groundbreaking outcome. Since an AI system
is capable of big data analysis, it can be included in this type of sensor for diverse
parametric analysis in the same system.
5 Conclusion
In summary, a brief scenario of plasmonic behavior in the microfluidic system and

their sensing mechanism, as well as applications, have been discussed. After ample
discussion regarding this topic, it can be concluded that at present there are a good
number of well-established SPR-based microfluidic sensors. However, the higher
sensitivity of SERS and LSPR and in some cases SPR microfluidic sensor is yet to be
developed. The plasmonic microfluidic sensors are facing growing demand over the
course of time because they are a label-free detection method and a simpler sensing
mechanism than other optical microfluidic sensors. Currently, besides developing
the idea of the working mechanism of different plasmonic sensors in microfluidic
devices, the improvisation in the sensitivity of the existing sensors which work on
this principle is under research. Plasmonic sensors with sufficient sensitivity can
surpass the biomedical fluid assessment in terms of POC on in situ applications.
Moreover, the plasmonic flow sensors which are simple, cost-effective, and a
handful to use will be beneficial in the detection of unwanted material or chemicals
in food, polluted sample, or any chemical sample. Since in the upcoming near future
nanotechnology is going to rule the technology, the LSPR microfluidic sensor ought
to be more rapidly improvised in case of their mechanism and sensitivity. The
collaboration of artificial intelligence with plasmonic microfluidic sensors will assist

to monitor the biomedical fluid flow, chemical low flow deposition and also upgrade
the sensitivity. All in all, it can be predicted that plasmonic flow sensors will be a
promising device for real-time very low fluidic flow analysis in the upcoming future
technology.
Acknowledgments The authors would like to acknowledge the partial financial support from the
Center of Excellence in Nanotechnology, Asian Institute of Technology, Thailand for this work.
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Polyoxometalate-Based Composite
Materials in Sensing Applications
Sukanya Maity, Kumari Sweta, Partha Pratim Das, and Sib Sankar Mal
Abstract Sensing is one of the significant topics in modern day research and
technology. We use various types of sensors in our everyday life. This chapter
deals with the recent progress made in the field of sensors (electrochemical, gas,
humidity, or temperature) using the redox-active metal-oxygen clusters
(polyoxometalates). The oxometalate’s unique physical and chemical properties
result in sensitive electrodes with excellent analytical performance in practical
applications. Polyoxometalates are a group of early transition metal oxide clusters
with an extensive reservoir of an electron that can undergo a fast and reversible redox
reactions. Furthermore, the deposition of these oxometalates on the solid-state
substrate has been discussed. Nevertheless, a detailed review describes the different
classes of polyoxometalate modified sensors alongside their characterization and
detection techniques in lab practice.
Key words Sensing · Oxometalates · Sensitive electrodes · Polyoxometalates ·

Transition metal oxide clusters · Reversible redox reaction · Sensors
1 Introduction
A paradigm shift in people’s socioeconomic status and living standards has been
noticeable due to rapid industrialization. The population and development simulta-
neously emitted different hazardous gases, effects climate change and global
warming [1, 2]. Our lifestyle is surrounded by sensing devices, from our mobile
phones, and home appliances to transportation vehicles. Although most sensing
S. Maity · K. Sweta · P. P. Das

Low Dimensional Physics Laboratory, Department of Physics, National Institute of Technology
Karnataka, Surathkal, Karnataka, India
S. S. Mal (*)
Materials and Catalysis Laboratory, Department of Chemistry, National Institute of Technology
Karnataka, Surathkal, Karnataka, India
e-mail: malss@nitk.edu.in
https://doi.org/10.1007/978-3-030-99491-4_18
456 S. Maity et al.
technology moves around to detect hazardous gas and chemical substance, another
analyte such as humidity, chemical reagents, and temperature sensors gets moderate
attention. Herein, the promising prospects of polyoxometalates (POMs) in the field
of sensing are discussed explaining their structures and properties. The different
deposition techniques to build up POM’s (or its composite) mono/multilayer were
also discussed in this chapter. Furthermore, POM-modified sensors in various fields
(electrochemical, gas, temperature, and humidity sensors) are generally reviewed.
POMs are a group of oxygen and early transition metal clusters (e.g., Mo, V, W,
Ta, Nb) at the highest oxidation state [3–6]. The metal oxide cage contains many
metal ions (tens to hundreds) in a single molecule creating a nanoparticle. The study
reveals the structure of the POMs could have primarily consisted of either a)
iso-polyanion or b) heteropolyanion. A variation of heteroatoms (e.g., Si, As, P,
Ge, Ni) were explored in POM structure in literature. The POMs are often synthe-
sized in an aqueous medium, but in some cases, the assembly process can arise in
nonaqueous medium or even in solid-state (e.g., minerals) [7]. In between different
structures, e.g., (i) Keggin and (ii) Dawson compounds leads to the configuration of
additional complex architecture. The arrangement of the Keggin configuration
consists of 12 addenda atoms (metals) around heteroatom, which is a tetrahedron
in geometry. The grouping of two lacunary Keggin monomers yields a dimer defined
as the Dawson structure. This architecture demonstrates two arrangements,
(1) di-metallic group (resulting from the two octahedra, where metal atoms are in
the centers and oxygen atoms are in vertices) and (2) trimetallic group (occurs from
the three octahedra, same as the Keggin structure). Not only the structural diversity,
the wide range of applications (catalysis, medicine, solid-state device, sensor, energy
storage, and material science) due to its exceptional physical, chemical, and biolog-
ical properties attracts the eye of the researchers [8–11]. Herein, the most important
property of POMs is the capability to accept and release a large numeral of electrons
without disrupting their structural arrangement. However, exceptional structural and
chemical behavior opens an extensive field in the application. It is highly soluble in
aqueous or polar solvents and behaves like a strong acid. Generally, the multistage
redox system is associated with it and is electrochemically fast, reversible, and
restrain physiochemical properties. The limitations of POMs can be optimized by
immobilizing the moieties on various solid-state substrates to improve the reactivity
and selectivity of the associated electrochemical reaction [12–16].
POM-based analytical sensor device consists of mono/multilayer on the solid
solid-state substrate and acts as a transducer. Immobilize POM layers will recognize
the analyte and catalyze them. The electrochemical reaction among the POM layer
and the analyte will be converted into an electrical signal (Fig. 1). The system will
further amplify that and finally be converted to display by a signal processing unit. In
contrast with other sensors, POM-modified electrodes provide better sensitivity,
selectivity, lower detection time, stability over a long period, and high linearity
range [7, 17–20].
Polyoxometalate-Based Composite Materials in Sensing Applications 457
Fig. 1 Schematic representation of POM-based sensors
2 Deposition Techniques for POMs
There are numerous numbers of ways to deposit POMs on the electrode as a

monolayer or multilayer. In this long list, chemical adsorption or chemisorption is
the simplest way to deposit POMs on the substrate. This process is based on covalent
bonds, yielding maximum deposition of the compounds on the substrate (e.g.,
carbon, platinum, gold, and even conducting polymers) [21, 22]. Alternative method
to immobilize POMs on the substrate is electrodeposition under a regulated current
or potential. Since the polyanions carry negative charges, they can be deposited on
an anode as mono/multilayer with or without the presence of any polymer
[23, 24]. The first layer of the POM compound took less potential or energy than
others due to the cooperatives with the substrate materials. The most common way to
immobilize POM is to use polymers or sol-gel matrices through encapsulation
[25, 26]. The studies have shown that the immobilized POMs can retain the structure
after encapsulation to the polymers or sol-gel. Yet, the primary drawback lies in the
operation of these electrodes at high pH for electrocatalysis and sensing applications
[27, 28].
In an early application in the electronics field, another important deposition
process, Langmuir-Blodgett (LB), was abducted to deposit POM or POM doped
hybrid films on the electrode surface [29, 30]. The film formation process is
restricted to a monolayer or multilayer by a long hydrocarbon chain containing
surfactant (hydrophilic or hydrophobic) attached to a solid-state substrate via
458 S. Maity et al.
Table 1 Different deposition techniques of POMs

Deposition
techniques Important features Disadvantages References
Chemisorption Covalent bond-based process The process is often limited to [21, 22]
which yields maximum the formation of a monolayer
deposition with high stability
Electrodeposition Using POM’s negative Deposition can be possible to [23, 24]
charge mono/multilayer the anode only due to the
deposition under controlled charge of POMs
potential or current
Encapsulation Mixture of POM with poly- The drawbacks of redox [25, 26]
mers or sol-gel deposited in polymer such as degradation
the solid-state electrode is one over time and low ionic
of the simplest ways to exchange capacity restrict
immobilize POM their operation
Langmuir- The film is formed in mono or The process is restricted to the [29, 30]
Blodgett multilayer via deposition of long hydrocarbon chains
surfactant on a solids containing both hydrophilic
substrate and hydrophobic component
Layer by layer Most popular deposition Degradation of POM structure [31, 32]
technique describing simple, during absorption process due
high stable, and controlled to strong electrostatic forces
multilayer deposition acting between the layers
dip-coating technique. The physical forces associated with this process are mainly
like electrostatic force which arises due to dipole interaction. Cationic surfactants or
polyelectrolytes are mixed POMs to form layers on the water surface. A substitute
method to form multilayer is by using layer by layer (LBL) deposition [31, 32]. Com-
pared with the former one, the LBL process gives control over the thickness of the
film by varying the number of layers. Thus, it provides good mechanical strength,
uniform morphology, and high stability. In this process, oppositely charged poly-
electrolytes (e.g., surfactants, polymers) in diluted solutions are deposited in alter-
native layers. The easiness of the process and the good quality films make this
process best suitable for the deposition of organic, inorganic, or biochemical
nanoparticles (Table 1).
3 Application in Different Sensing Technology
3.1 Electrochemical Sensors
In early 2000, Liu et al. designed and fabricated POM-modified electrochemical

sensor for the selective detection of nitrogen monoxide (NO) [33]. Herein,
co-substituted POM clusters were immobilized by a polyelectrolyte matrix (pair of
polystyrene sulfonate and polyallylamine hydrochloride). A modified electrode
could electrocatalyst (reduction) NO, and the reduction current is proportional to
its concentration. The sensor exhibits a linear range of amperometric current for the
concentration range of 1 nM–10 μM. However, several interfering reagents could
disturb the sensing process (e.g., nitrite). Thus, the device’s sensitivity is controlled
by the number of multilayers and optimized to detect of the reduced NO ions. The
multilayer nanostructure needs no external electron transfer mediators for localized
NO detection in the water-based environment-friendly fabrication.
Sahraoui et al. [34] advanced an electrochemical sensor by incorporating multi-
layer POM on a glassy carbon electrode for nitrite detection. The sensor electrode is
mainly modified by alternative layer by layer assembly with mono-lacunary Keggin
anion [SiW11O39]8 and oppositely charged polyelectrolyte [polyallylamine hydro-
chloride]. Since the layer by layer self-assembly process is efficient in fabricat-
ing ultrathin films, the authors used alternate adsorption of oppositely charged
species from a dilute solution of each. The formation of thin films is primarily
attributed to the electrostatic and Van der Waals interaction. The modified sensor
displays a wide range of concentrations from 100 μM to 3.6 mM for electrocatalytic
reduction of the nitrite. The number of layers plays an important role in the
electrochemical behavior of modified electrodes. With the increase in layers, the
catalytic properties also increased. However, the response of the sensor electrode is
practically constant after the fifth layer. The maximum catalytic peak was found at
0.68 V and is maintained linearly over the nitrite concentration of 100 μM–3.6 mM
with a correlation coefficient of 0.99991. The stability of the sensor is also investi-
gated over 75 days at air and room temperature. No significant changes in the current
response were observed (<10%) under 3 mM of nitrite injection in the presence of
0.1 M H2SO4 (pH 1.2).
A Dawson nature POM (K7P2W17O61(FeOH2)8H2O, (P2W17Fe)] together with
palladium nanoparticles (PdNPs) are explored as electrochemical sensing film by
H. Ma et al. in 2012 [35]. The layer by layer (LBL) method was followed to fabricate
the film by alternating deposition of PdNPs and P2W17Fe. The intrinsic character-
ization indicated the exceptional electrocatalytic activity towards reducing hydrogen
peroxide (H2O2) alongside oxidization of hydrazine sulfate (N2H4SO4), and able to
sense them at a suitable potential. The H2O2 exhibits the sensitivity, detection limit,
and linear concentration in the extent of 66.7 μA mM1, 1 μM (S/N ¼ 3), 1.5 μM to
3.9 mM, respectively. Likewise, N2H4SO4 displays the same parameter in the range
of 0.2 μA mM1, 1.5 μM (S/N ¼ 3), 2 μM to 3.4 mM, respectively, with sensing
response time around 4 s. The fabrication of the film by LBL deposition is well
characterized (by UV-Vis and XPS) to find the PdNPs incorporation in the deposited
films. The cyclic voltammetry (CV) experiment was carried out in 0.2 M H2SO4
solution for {P2W17Fe/PdNPs}3 film in successive addition of 0.2 M N2H4SO4. The
electro-activations of N2H4SO4 occurred at 1 V due to the presence of PdNPs.
Likewise, the electrocatalytic and sensing properties of the film towards H2O2 was
carried in a pH 2.0 buffer solution containing H2O2 at different concentration. As the
concentration increased, the current increased linearly at the applied potential of
2.0 V, indicating the sensing capability of H2O2. The sensing response time for this
case is <3.5 sec. Furthermore, the film exhibits excellent stability reproducibility to
detect N2H4SO4 and H2O2 over 30 days with unchanged response parameters.
460 S. Maity et al.
Fig. 2 Layer by layer deposition of POM layer with alternative polyelectrolyte layer
In 2019, Wang et al. [36] fabricated a thin film of Dawson-type POM-based

composite on an indium tin oxide (ITO) electrode, which acts as a neurotransmitter
to detect dopamine (Fig. 2). The composite is developed by a layer by layer
deposition and self-assembly of α2-K7P2W17VO62.18H2O (P2W17V) and cationic
chitosan (CS). The modified electrode exhibits linear characteristics in the range of
1.25 108 M–3.04 104 M, demonstrating excellent electrochemical catalytic
activity towards dopamine. The composite film has a selective response with a low
detection limit of 0.18 μM (S/N ¼ 3) and elevated selectivity of 0.23 μAμM1 to
dopamine. The prepared films with six bilayers are noble metal-free, low cost, easy
to prepare, had the highest catalytic efficiency (response time 2.2 s). Furthermore,
the P2W17V containing composite represents a potential candidate for amperometric
sensors for future applications.
Suma et al. [37] developed a modified electrochemical sensor electrode by
combining reduced graphene oxide (rGO), polyaniline (PAni), and arsenomolybdate
for the detection of nitrite in food and environment. The preparation of the composite
was executed by clean hydrothermal method, and an as-prepared hybrid
was anchored to the polished (using alumina powder) bare glassy carbon electrode
in different volumes (2, 5, 10, 15 μL) by a drop coating method. The composite
modified glassy carbon electrode exhibited a high oxidative current and lowered the
potential for the electrochemical oxidation of nitrile compared with the bare glassy
carbon electrode. The improved sensing electrode show linearity over the concen-
tration range 25–7500 μM of nitrite. In addition, the proposed sensor has a limit of
detection of 10.71 μM with a sensitivity of 0.803 μA μM1 cm2. The addition of
arsenomolybdate prevents the agglomeration of the reduced graphene sheets and
contributes large pseudocapacitance alongside polyaniline. The high capacitive
current (from reduced graphene oxide) with elevated faradic current gives total
current in the oxidation of the nitrite. Thus, it increases the conductivity, which
can be explored as the catalytic property for the oxidation of nitrite.
Apostu et al. [38] constructed a selective membrane sensor with ion-selective
electrodes to determine ranitidine and nizatidine using silicotungstic acid (having
high molecular weight) ionophores. Ion complexes are often constructed with some
organic cations having large lipophilicity. In this study, these complexes are used as
ionophores with PVC (vinyl polychloride) matrix membranes with active recogni-
tion functions. Both the sensors exhibit a linear response range 101 to 105 M,
alongside the quantification limit of 2.83 106 and 3.43 106 M for ranitidine
and nizatidine, respectively, at 0.1 ionic strength. The response time for both cases is
below 50 sec. The electrochemical behavior of the electrode depends on the pH of
the electrolyte solution. In this case, it is fixed at 3.0 with buffer solution. The
electrode’s service life is investigated over 35 2 days. The ionophore regeneration
was produced by hydration (from the outer membrane gel layer), immersing the
exhausted electrode in 5% silicotungstate acid solution for 24 h, followed by
immersion in 1 M solution of ranitidine or nizatidine for 2–3 h. These prepared
sensors are further practically applied to detect ranitidine and nizatidine in pharma-
ceutical products. The method proposed for modified electrodes was low cost,
simple, and fast as a potentiometric sensor.
Xin et al. [39] found a convenient and effective method to find the heavy metal
chromium (VI) ion. They advanced a susceptible electrochemical sensor by devel-
oping two reductive crystalline materials coupling with POMs, mainly the com-
pounds with the formula of A. (H2bpp)2[Na4Fe(H2O)7][Fe(P4Mo6O31H6)2].2H2O
and B. (H2bpp)6(bpp)2[Fe(P4Mo6O31H6)2].13H2O (bpp stands for 1,3-bi(4-pyridyl)
propane). Structural analysis reveals that compound A is a three-dimensional porous
inorganic skeleton, whereas compound B displays a zero-dimensional polyanionic
cluster structure. Both crystal A and B modified electrodes show a broad linear range
over the concentration of 2–2610 μM for the detection of chromium. However,
crystal A superior sensitivity with a lower detection limit at 0.174 μM (lower than the
level set by WHO) compared to compound B (about 0.33 μM). Furthermore,
compound A modified sensor electrode can detect the chromium in the existence
of other heavy metal ions alongside exhibiting effective reproducibility even in a real
water sample.
3.2 Gas Sensors
The gas sensors in general work as the reducing toxic gas reacts with the absorbed
oxygen of clean air and breaks their covalent bonds, releasing free electrons. The
free electrons in the initial position of the sensing electrode result in electric flow
through the circuit. The conduction of electrons is proportional to the number of free
electrons. Therefore, highly toxic gas will deliver more charge to the circuit (Fig. 3).
In 2012, Ivanova et al. [40] developed nanostructured SiOX film with doping
Dawson-type heteropolyanion to detect ammonia gas in an air medium. The forma-
tion conditions and composition affect the sensitivity of ammonia. Herein, nano-
structured doped films were formed by the hydrolytic polycondensation method
from tetraethyl orthosilicate solutions (TEOS). TOES was blended thoroughly with
water and alcohol, and various HPCs were used to polymerize the TEOS into a sol
462 S. Maity et al.
Fig. 3 Mechanistic aspect of gas sensing process
solution. Composite films were built up on the 15.0 5.0 mm test structures. The
modified structures were then added with a system of interdigital metal electrodes
formed at their surface as an active zone of the sensor (4.0 4.0 mm). The addition
of formulated polyoxometalates into SiOX films results in high sensitivity and
selectivity to NH3. Furthermore, heteropolyanion composition and cation type
significantly impact the sensor behavior of modified films. The intramolecular
redox reaction sharply changes the electrophysical properties of polyoxometalate,
thereby modifying sensitive film’s characteristics. The composition with 30–50% of
the weight content of doping additive in silica matrix enables a maximum sensitivity
to measure gas. The temperature increase stabilization of the film. Therefore,
temperature treatment and decreasing environment humidity lead to the acceleration
of hydrolytic polycondensation of solutions and stabilizing sensitive films at accu-
rate conditions. The minimum threshold sensitivity to NH3 is found to be about
0.5–1.0 ppm for SiOX/(NH4)9P2W3Mo15O62 sensor alongside the linear range of
concentration of 1–100 ppm with a response time of 20 s.
Sun et al. [41] fabricated a photoconductive device made up of the POMs-TiO2
composite materials, where phosphotungstic acid (H3PW12O40) is used as the
faradaic component for the detection of acetone gas (Fig. 4). Compared to pristine
TiO2, the H3PW12O40-TiO2 composite displayed a higher photocurrent response due
to the reduced electron-hole recombination rate, increasing free carrier density.
Fig. 4 (a) Schematics of

the device structure, (b)
energy levels and the
electron transfer processes
3.3 Humidity and Temperature Sensors
Miao et al. [42] designed and fabricated proton-conducting POM

(polyoxomolybdate, PMo12)/polypyrrole thin films for the humidity sensing appli-
cation. The hybrid polymer films were prepared by co-electrodeposition with free
pyrrole monomer with the metal-oxygen clusters. The as-prepared hybrid film’s
thickness was standardized for the resistive type performance. Protonated
polypyrrole was chosen for its relatively large size and hydrophobicity. The
improved electrode (indium tin oxide, ITO) exhibits a response time of 1.9 s and a
recovery time of 1.1 s for the film’s thickness of 59 nm in the presence of 98%
relative humidity. The pyrrole’s polymerization and the deposition of the POM are
competitive processes. This process enhances the conductance and selectivity of the
hybrid, which eventually improves the humidity sensitivity. The sensor shows the
sensing regime for the relative humidity of 11–98%. The synergic effect between
the proton acid doping structure and the oxidation doping structure results in
exceptional sensing behavior. The reproducibility and the stability were repeatable
after 2 months.
Salomon et al. [43] demonstrated multifunctional POM-based hybrid chemical
probe electrodes for temperature sensing applications. Luminescent europium-based
POM [EuW10O36]9 is doped with a luminescent, highly porous zirconium metal-
organic framework (MOF) using a direct synthesis approach. EDX approach reveals
the europium is only 0.25% in the hybrid and the POM clusters reside inside the
octahedral cavities of the MOF (UiO-67) instead of on the surface. The EuW10/UiO-
67 hybrid is the solid-state sensing device to detect amino acids and metallic cations
(highly sensitive towards Fe+3) in water and other heterogeneous solutions. Further-
more, the double luminescence materials exhibit self-calibrated-ratiometric lumines-
cent thermometers in the physiological region (Table 2).
464 S. Maity et al.
Table 2 Various POM-based composites in different sensing applications

POM-based Deposition
composite Type of sensor technique Significant result References
[SiW11O39]8 Electrochemi- Layer by layer The maximum catalytic [34]
anion and cal nitrite peak at 0.68 V and show
polyallylamine sensor linearity over
hydrochloride 100 μM-3.6 mM
Dawson-type Electrochemi- Layer by layer Selective response of [36]
P2W17V and cat- cal dopamine and self- 0.18 μM (S/N ¼ 3) and high
ionic chitosan sensor assembly selectivity of 0.23 μAμM1
to dopamine
Silicotungstic acid Membrane Ionophore Linear response range for [38]
with vinyl sensor to regeneration ranitidine and nizatidine is
polychloride ranitidine and was produced 101 to 105 M and
matrix membranes nizatidine by hydration 3.43 106 M, respectively
at 0.1 ionic strength
SiOX/ Ammonia gas Hydrolytic Threshold sensitivity to [40]
(NH4)9P2W3Mo15- sensor polycondensa- NH3 is 0.5–1.0 ppm with
O62 tion method linear range of 1–100 ppm
Thin films and a response time of 20 s
PMo12/polypyrrole Humidity Co-electrode- Response time is 1.9 s for [42]
thin film sensors position with the 59 nm film thickness in
free pyrrole the presence of 98% relative
monomer humidity
[EuW10O36]9 is Temperature Direct synthe- Self-calibrated ratiometric [43]
doped with zirco- sensors sis approach luminescent thermometers
nium MOF
4 Conclusion
In summary, technological advancements allowed the design and fabrication of a

wide range of POM-modified sensors with various applications. The synthesis of
different types of nanomaterials with proper chemical functions and morphology
was explored for the electrochemical oxidation/reduction of the analyte. POM plays
a vital role in this sensing field of application due to its rich structure and tunable
properties. The immobilization process of POMs on various solid-state substrates
ware extensively explored. It is shown that various deposition methods have their
own perks and limitations. Furthermore, POM-based sensors demonstrate faster,
effective determination and detection of a diverse environment, analytical and
pharmaceutical applications. Although the study gives a great potential for POMs
in sensing applications, understanding the mechanism of the sensing pathways is still
underdeveloped. Next-generation POM-based sensors should be designed and fab-
ricated depending on the compatibility and stability of the microstructure for the
detection of analytes.
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Plasmonic Random Lasers
Pooja Naik, Al Ameen Abdul Nazar, and Junaid Masud Laskar
Abstract The initial research, on the prospect of building miniaturized high energy
efficient lasers, has focused on active random media consisting of dielectric or
semiconductor materials. However, research advancements exploiting metallic
nanoparticles and nanostructures have found a wide range of applications in laser
science from plasmonic random lasers to spasers, owing to their distinctive optical
properties. The use of plasmonic nanosystems has tremendously aided in improving
the quality factor (Q-factor), by harnessing surface plasmon resonances thereby
making them promising candidates for high energy efficient random nanolasers.
This chapter discusses and summarizes the research and development efforts done to
realize compact, high-power lasers using plasmonic nanostructures. It systematically
covers the fundamental ideas of both conventional and random lasing, focusing on
plasmonics and the reliance of the performance of plasmonic random lasers on
electromagnetic wave scattering parameters including scatterer (plasmonic nanopar-
ticle) concentration, scatterer spacing, size and metal nanoparticle-fluorophore
distance.
P. Naik
Nanophotonics Laboratory, Department of Physics and Nanotechnology, SRM Institute of
Science and Technology, Chennai, Tamil Nadu, India
Department of Physics and Astronomy, University of Sheffield, Sheffield, United Kingdom
A. A. A. Nazar
Department of Applied Physics and Photonics (TONA), Brussels Photonics (BPHOT), Vrije
Universiteit Brussel, Brussel, Belgium
J. M. Laskar (*)
e-mail: junaidmb@srmist.edu.in
https://doi.org/10.1007/978-3-030-99491-4_19
468 P. Naik et al.
Key words Lasers · Random active media · Multiple scattering · Plasmonics ·

Localized surface plasmon resonance · Nanoparticles · Mie resonance
1 Introduction
Laser technology research has expanded over the years as a result of its broad
spectrum of applications in the biotechnology industry, office spaces, aviation,
industries, surveillance, sensors, and other advanced technologies such as 3D imag-
ing and fluorescence microscopy [1–10]. Laser is regarded as one of the twentieth
century’s most innovative innovations due to its unique properties such as
(a) monochromaticity, (b) coherence, (c) directionality, and (d) brightness
[11, 12]. Einstein investigated Max Planck’s deduced relationship between energy
and radiation frequency, and the resulting postulated theory of energy absorption and
emission in discrete quanta of light, i.e., photons, led to the development of the
concept and theory of stimulated light emission [13]. The theory of stimulated
emission of radiation paved the foundations for the development of the first practical
laser. The most fundamental process for laser action is stimulated emission of
radiation [14]. When an electron is excited from its ground state to its excited state
by an external source of radiation, a spontaneously emitted photon forces the excited
electron to a lower energy state. When an electron returns to a lower energy level, it
releases energy in the form of a photon. The process of photon emission precipitated
by electron relaxation in an atom or molecule is referred to as “stimulated emission
of radiation” [15, 16]. A laser is composed of three essential components that work
together to produce lasing action via stimulated emission: (1) a pump source, (2) an
active medium, and (3) an optical resonator. The pump energy source stimulates the
atoms or molecules in the active medium, causing them to spontaneously emit
radiation. The photons generated by spontaneous emission are trapped within the
system by an optical resonator, resulting in stimulated radiation emission. Based on
the theoretical work by Charles Townes and Arthur Leonard Schalow [17],
Theodore H. Maiman created the first practical laser in 1960 by coating the ends
of a ruby rod (aluminum oxide doped with chromium) with silver to make it
reflective and serve as a resonator [18]. Since then, crystals, gases (argon, carbon
dioxide, helium-neon, carbon monoxide, etc.), glasses (silicate or phosphate glasses)
doped with lasing media, semiconductors (gallium nitride, gallium arsenide, etc.),
and liquid dyes have all been introduced as potential active lasing media [19]. None-
theless, despite its significance, the development of this powerful device was both
complex and costly. As the number of applications increased, so did the demand for
small-volume, compact, high-power, and high-efficiency lasers, prompting research
into the development of smaller high-power lasers.
The idea of simulating and building small-volume lasers gave rise to the concept
of nanolasers [20, 21]. Nanolasers operate on the same principle as the conventional
lasers: stimulated emission of radiation [21, 22]. The dimensions of the lasing
system distinguish a nanolaser from a conventional laser. The remarkable ability
of nanolasers to confine light on a scale approaching the diffraction limit is due to
Plasmonic Random Lasers 469
their small size [20, 23]. The construction of a smaller lasing system was made
possible by shrinking the laser dimension, but managing coherence remained a
challenge. As a result, a new strategy for controlling coherence while also reducing
the size of the laser system was required. When monochromatic coherent laser
emission was observed, it was discovered that an optical resonator is required to
maintain the laser emission’s directionality and monochromaticity [12, 19]. In a
traditional laser setup, the resonator, which consists of an active medium sandwiched
between two mirrors, is responsible for the lasing system’s bulkiness along with
being an important laser component. The removal of the optical resonator from a
laser was considered to be a means to lower the system’s overall size. A laser without
an optical resonator is known as a “random laser.” Because of the spatial inhomo-
geneity of the medium, random lasers do not require an optical cavity to generate
disorder-induced light scattering. The elimination of optical resonators from a laser
system not only reduced manufacturing costs but also simplified the laser’s design.
In 1967, Letokhov proposed the idea of producing laser-like emission using scatter-
ing particles with negative absorption [24]. Random lasing capabilities have since
been demonstrated in a wide range of materials, including semiconductors, dielec-
trics, biological samples, and metal nanoparticles. Although, most dielectric-based
random lasing cavities have experimentally recommended random lasers with a high
threshold and a low-quality factor (Q-factor). Metal nanoparticles have recently been
investigated to improve the performance of random lasers by integrating them into
the active media, to overcome these disadvantages of high threshold low Q-factor
random lasers [25, 26].
In this chapter, we explore plasmonic random lasing systems and their possible
applications in addition to contemporary research developments in the field of
random lasers. We also answer the following questions: (1) How does including
metallic nanoparticles into a random lasing system improve random lasing emission
despite metal-induced losses? (2) How can plasmons boost dye molecule fluores-
cence in random lasing media? (3) Why does a plasmonic-based random lasing
media have a low threshold for lasing action?
2 Theoretical Background
2.1 Laser Fundamentals
A laser is a type of light source that generates an intense beam of coherent

monochromatic light by optically amplifying photons released by excited atoms or
molecules inside an active medium [12, 16, 19]. The three fundamental processes for
laser action are (a) Absorption of radiation, (b) spontaneous emission, and
(c) stimulated emission (Fig. 1).
When an incoming photon from an external energy source (pump source)
matches the precise energy of the atomic system in the ground state, it excites the
electron in the lower energy state (E1) to a higher energy level (E2). The process of
470 P. Naik et al.
Fig. 1 Illustration of three fundamental processes for laser action—stimulated absorption, sponta-
neous emission, and stimulated emission
excitation of an electron from lower to higher energy state is termed as “absorption

of radiation.” The number of electrons in the excited state (N2) must be greater than
the number of electrons in the lower energy state (N1) for stimulated emission to
occur [11, 27]. The condition in which N2 exceeds N1 is known as population
inversion. Radiation absorption contributes to an increase in the number of electrons
in the excited state. The difference in energy between electrons in lower and higher
energy states (E2 – E1) determines the amount of incident radiation absorbed.
Because the electron has a finite lifetime, once excited to a higher energy level, it
will relax back to its lower energy state and emit the energy in the form of a photon.
The process of photon generation as a result of relaxation of an electron in the higher
energy state to lower energy state is termed as “fluorescence” or “spontaneous
emission.” As a result, spontaneous emission can be defined as a statistical phenom-
enon involving time, space, and an excited electron’s lifetime. The most important
process of the three mechanisms leading to laser action is stimulated emission. When
a photon interacts with an electron in an excited state, the electron is compelled to
return to a lower energy level and emits a photon. The stimulated generation of the
photon is proportional to the energy density of external radiation [12, 16]. The
photon released as a result of stimulated emission has the same direction and
phase as the photon that triggered it. These three critical steps—absorption of
radiation, spontaneous emission, and stimulated emission, enable a laser to generate
amplified coherent light.
2.2 Conventional Lasers
Lasers are recognized as a device that generate and amplify the monochromatic
coherent light via stimulated emission of radiation. What are the individual compo-
nents of a system that initiate the process of stimulated emission, and how does
lasing occur? The three fundamental components of a laser are shown in Fig. 2.
(i) gain medium, (ii) pump energy source, and (iii) optical resonator.
Fig. 2 Schematic of a conventional lasing system
(i) Active lasing media: The active lasing medium also known as gain media is a
component of the lasing system that amplifies electromagnetic radiation to
induce lasing action. The lasing media is contained within the optical resonator.
The active lasing media generates optical gain by emission via molecular or
electronic transitions of electrons from a higher to a lower energy state. It can be
any material such as liquid dyes, semiconductors, crystals, and gases with
quantum properties that amplifies the laser beam. When the gain in the cavity
surpasses the loss, lasing occurs.
(ii) Pump energy source: The pump energy source is a type of external energy
source that is used to stimulate atoms or molecules into higher quantum
mechanical energy levels in order to induce population inversion in an active
medium. Pumping molecules in the active medium can be accomplished
through optical pumping, electrical pumping, chemical pumping, and gas
discharge pumping.
(iii) Resonator: Lasing cannot be ensured only through stimulated radiation emis-
sion. Instead, we will only acquire the enhanced signals. As a result, an optical
resonator is used to yield resonant eigenstates, which then lase as cavity modes.
The most well-known and commonly utilized optical cavity in conventional
lasing systems is the Fabry-Perot cavity (Fig. 2). It consists of two mirrors,
completely and partially reflecting, positioned opposite to one another that
bounce the generated radiation back and forth to create modes. As a result, an
optical cavity or optical resonator can be defined as a standing light wave
resonator and an important component surrounding the gain media, where
standing wave patterns can be indexed by their modes. The mode’s quality is
closely related to the cavity loss and can be evaluated using the Q-factor
[22]. The photons produced by stimulated emission bounce back and forth
within the resonator, generating temporal and spatial coherence.
472 P. Naik et al.
2.3 Random Lasers
2.3.1 Random Amplifying Media
After more than 60 years of growth in the direction of developing lasers with smaller
volumes, greater power, higher efficiency, and faster modulation speeds, laser
technology is rapidly advancing. As a result, research in the field of lasers has
been restricted to engineering and technological advancements, leaving some scien-
tific aspects of lasers untouched. Experimentally, controlling the monochromaticity
and directionality of laser output was shown to be successful. However, as previ-
ously stated, the question of coherence control remained unresolved. The concept of
resonator-less lasing arose as a result of concerns about coherence control. Random
lasers, first proposed theoretically by Lethokov in 1968, are now one of the most
intriguing and engaging areas of research in the field of laser technology. In his
research, Lethokov theoretically developed the concept of producing laser-like
emissions from scattering particles with negative absorption [24]. Following the
theoretical studies of random lasers, other reports of laser-like emission in powdered
luminophosphors emerged, introducing random lasing to the field of laser
technology.
Random lasers are mirrorless lasing systems that operate on the principle of
multiple light scattering (Fig. 3) [28]. Unlike conventional lasers, a random lasing
system employs highly scattering disordered material in which the incident light
undergoes recurrent scattering and is amplified before leaving the cavity. When the
scatterers doped with dye molecules are pumped externally, the spontaneously
produced photons are scattered. Photons have a long enough dwell time in the
medium due to scattering to enhance the resultant random lasing radiation. This
mechanism generates resonant structures with high-quality factors. Hence, we can
Fig. 3 Illustration of a conventional random lasing system

infer that the gain medium is strongly dependent on the scattering strength as well as
the gain volume within such systems [29]. The scattering strength is quantified using
the scattering mean free path (ls), i.e., the distance travelled by a photon in between
two successive collisions. According to the Mie scattering theory put forth by
Gustav Mie, the scattering parameters (scattering mean free path ls ¼ ρσ1sca, transport
mean free path (lt), scattering cross sections (σ sca) , and Mie scattering coefficients)
are a function of size and shape of the scatterers and the refractive index contrast
[30]. The mathematical formulation of the scattering parameters implies that the
profile of the random lasing emission spectrum is influenced by the geometry of
individual scatterers in the active random lasing media as well as the refractive index
contrast between the scatterers and the surrounding media. As the scattering strength
of the active random medium increases, so does the optical path length, or the
transport mean free path of the emitted photon. Depending upon the optical path
length or the transport mean free path (lt), there are three regimes of multiple
scattering in a random media (L is the sample size, λ is the incident light wavelength)
[31],
(a) Localization regime (lt λ).
(b) Diffusive regime (λ < lt < L )
(c) Ballistic regime (lt L)
Furthermore, as illustrated in Fig. 4, two types of random lasing emission profiles
are identified based on the photon travel path within the active random media:
coherent emission and incoherent emission. In the case of incoherent emission, the
feedback provided by multiple light scattering does not return the photon to its place
of origin. Random lasers with coherent feedback, on the other hand, drive the photon
to return to its origin, resulting in a closed loop. The coherent emission spectra are
made up of several narrow spikes as a result of the interference created by the photon
closed loop generation. The profile of the emission spectra can be changed from
coherent to incoherent by altering the scatterer concentration in a random amplifying
medium.
Fig. 4 (a) Incoherent emission and (b) coherent emission random lasing profiles
474 P. Naik et al.
2.3.2 Types of Random Lasing Media
Dielectric Random Lasing System
Intriguing optical phenomena emerge when dye molecules or active centers are
introduced into a disordered media. The optical amplification of spontaneous radi-
ation emission caused by an increase in photon mean free path due to multiple light
scattering has particularly been the optical phenomena of interest to researchers.
Dielectrics are one of the most commonly used materials in active random lasing
media due to their ability to generate strong modes within individual scatterers or
resonators. As a result, the dielectric modes created by individual resonators com-
bine to greatly boost the Q-factor. Dye molecules combined with dielectric systems
can produce random lasing because dielectric resonators can provide efficient
scattering for optical feedback, which is vital for efficient lasing activity [26]. The
scatterer form (shape, size, dimension, aspect ratio) [32] and geometry (inter-
scatterer distance and positioning) [33] will determine the permissible modes gen-
erated within the individual dielectric resonators, as well as the mode coupling. The
coupling of dielectric-resonator modes (Mie mode, Fabry-Perot mode, Whisper
gallery mode, etc.) will increase the Q-factor depending on the phase difference
between the modes generated in the individual resonators, resulting in quantum
mechanical phenomena such as Fano resonance [34], supercavity mode, and bound
states in continuum (BIC) [32, 35]. Recently, a magnetic nanofluid was investigated
as a passive system with a Fano-like profile [36]. Fano resonance is a phenomenon
resulting in the appearance of asymmetric sharp-like shape because of the interfer-
ence between the resonator eigenmodes and the background disturbance in a system.
The dielectric medium in use exhibiting Fano-like profile in the emission spectra was
a magnetic nanofluid. The profile of the peak in the emission spectra changed as the
shape, size, and arrangement of the individual scatterers changed. The emission
spectra with change in the shape and size of the scatterers in the disordered media
exhibited Fano-like peaks implying that the dynamical changes within the passive
random system can be tuned and adjusted to result in a change in the emission
profile. The dynamics of the scatterers in the magnetic nanofluid were controlled
using an external magnetic stimulus [37]. A similar study using a magnetic nanofluid
doped with Rhodamine 6G was carried out to demonstrate random lasing phenom-
ena. The emission spectrum shown in Fig. 5 was recorded at a constant external
magnetic field of 100 Gauss as a function of varying time to observe the changes in
the emission light intensity with change in the scatterer configuration. Fano-like
emission profiles are observed at 573 nm and 579 nm wavelengths in the emission
spectrum suggesting interference between resonant states and background
disturbance.
Fig. 5 Random lasing emission spectra of an active magnetic nanofluid (unpublished)
Semiconductor Random Lasing Cavity
Stimulated emission in semiconductors was originally reported in 1981 using ZnO

powder [38], which was then investigated further by Cao et al. to determine if the
observed emission spectra were caused by an individual particle or an ensemble of
ZnO particles [39]. In the photonic examination of ZnO powder, the emission
spectra of 200–350 nm thick ZnO films composed of 50–150 nm sized particles
randomly organized over an amorphous fused silica substrate was studied. The ZnO
sample was pumped with 15 ps pulses at 355 nm using a frequency tripled Nd:YAG
laser. To explain the spikes in the random lasing peaks in the emission spectra, it was
stated that closed loops were created as a result of strong scattering. These loops can
hold the generated photon for long enough to operate as a laser light ring resonator,
allowing the frequencies of narrow stimulated emission lines to be identified.
Because different resonators have different losses and support varied oscillation
frequencies, discrete stimulated emission lines appear in the spectrum at variable
thresholds. Furthermore, as the size of a pump spot on the sample grows, so does the
number of ring cavities, resulting in a greater number of narrow emission lines in the
spectrum. Qualitatively similar emission properties were observed in various semi-
conductor systems predominantly in the commercially most available semiconductor
laser material GaAs [40].
476 P. Naik et al.
Biological Random Lasing Cavity
Various complex biological structures including bones, human tissues, organs,

nanoimprinted DNA, and a variety of animal biological membranes have been
systematically studied and modeled to realize that biological samples can serve as
scattering centers for random lasing purposes as well [41–45]. Coherent random
lasing was demonstrated in biological tissues infiltrated with laser dye using the
nanostructures on cicada wing as the scattering center [46]. Similarly, bone struc-
tures infused with dye molecules resulted in discrete peaks on optical excitation.
Since the random lasing cavities are strongly dependent upon the geometrical and
structural properties of the media in use, scattering in the biological samples have
been used as an advantage to study the structural properties of biological sample
from the obtained emission spectra [43, 45]. For instance, it is possible to identify the
abnormal tissues from the healthy ones since experimentally it has been observed
that the malignant human tissue in a gain medium yielded more laser lines when
compared to that of the healthy ones. Plant species have also been observed to
possess random lasing properties. Owing to that, recently, Li et al. have demon-
strated random laser based on lotus leaves from planar liquid waveguide wherein
they have achieved tunable random lasing for a wide wavelength range by changing
the pump position [47].
Metallic Random Lasing System
Light-induced nanoscale optical fields on metallic nanoparticles strongly enhance

optical intensities and have a wide range of applications. Recently, optical amplifi-
cation and laser action by metallic nanostructures were extensively studied owing to
their large charge density waves at nanoscale that resulted in some interesting optical
phenomena such as localized surface plasmon resonance (LSPR). The laser systems
exploiting this property of nanoscale metallic nanostructures are called plasmon
lasers [48–52].
Plasmon random lasers in contrast to conventional random lasing cavity
consisting of dielectric scatterers amplify light coupled to oscillating charge carriers
which adds momentum to the light enabling their physical size and mode volume to
shrink below the diffraction limit. The strong electromagnetic confinement in a
plasmonic cavity modifies the laser action by enhancing spontaneous emission
causing drastic spatial redistribution of spontaneous emission. Plasmons therefore
significantly reduce the pump conditions for the onset of laser action hence modi-
fying the threshold behavior. Initially, Dice et al. observed incoherent random lasing
enhanced by surface plasmons after suspending silver nanoparticles in a laser dye
solution [53]. Following the successful demonstration of incoherent plasmonic
random lasing Meng et al. experimentally illustrated coherent random lasing in
polymer films with silver nanoparticles. The metallic nanoparticles concentrate the
incident optical field on the nanoparticle surface generating localized surface
plasmons. From the observations, Meng suggested that the scattering systems
embodying metal nanoparticles provide stronger absorption of excitation light and a

larger amplification of fluorescence that the dielectric scatterers [54]. This happens
because of the enhancement in the localized electric field as well as the scattering
effect resulting from the large scattering cross section than the dielectric counterparts
at the same dimension. However, addition of metal nanoparticles not only increases
the scattering strength within a random lasing cavity because of its large scattering
cross section but also induces absorption losses hindering the overall performance of
random lasers.
2.3.3 Advantages of Random Lasers over Conventional Lasers
In case of conventional lasers, the construction of lasing system requires meticulous

alignment of resonators and accurate fabrication which makes the manufacturing of
conventional lasers both expensive and complicated. Additionally, conventional
lasers are subjected to the diffraction limit, wherein their size cannot be less than
half the wavelength restricting the miniaturization of lasers. In contrast, since the
resonant random lasing is enabled by randomly formed cavities of high refractive
index dielectric or metallic nanostructures inside a gain medium, it eliminates the
need for an optical resonator within the system permitting an easy and cheap
fabrication method making them extremely attractive for a manifold of potential
applications, starting from displays and lighting devices [55], to smart sensors [56–
58] and medical diagnostics [42, 44, 59]. The realization of this technology cata-
lyzed research towards demonstrating various materials exhibiting random lasing.
Many scattering systems including semiconductor materials [40, 60, 61], biological
samples [41–46, 62, 63], dielectric systems, metallic nanoparticles [25, 26, 54, 64–
70], liquid crystals [71, 72], polymer thin films, and many other materials have been
studied to demonstrate random lasing phenomena.
2.3.4 Drawbacks of Random Lasers
Random lasers have certain drawbacks such as control, tunability, and flexibility of
random lasing emission [64]. However, certain systems have been studied to control
the geometry of the scattering particles such as controlling the dynamics of scatterers
using external electric or magnetic field [36, 72]. Another limitation of random lasers
is that a high laser threshold is required to initiate lasing in disordered media. For
random lasing media that use dielectrics, the resonator cavity is observed to have a
low Q-factor, i.e., decreased lasing efficiency is observed in random and disordered
cavities. To maximize the available gain volume, it is essential to use scattering
particles that have large geometrical cross sections. It is a challenge to achieve such a
criterion with dielectric scatterers [53]. Therefore, the two main challenges in
random lasers are (a) high lasing threshold and (b) low laser efficiency and
Q-factor. To eliminate these issues one of the methods that has been extensively
adopted is to additionally introduce metal nanoparticles instead of using dielectric
478 P. Naik et al.
disordered systems alone. The ability of metal nanoparticles to confine light into the
subwavelength optical mode, due to their inherent property of localized surface
plasmon resonance (LSPR) can be exploited to overcome the abovementioned
shortcomings. In the following section, we discuss the theory of plasmonics in detail
and how it can be used to increase the efficiency of a random lasing system by
increasing its Q-factor and lowering the lasing threshold.
3 Theory of Plasmonics
Plasmonics research has gained increased attention over the last two decades
because of their unique optical properties. The pronounced interest in the application
of plasmonics is because of three major reasons:
(i) Plasmons, the collective oscillations of electrons, can resonate with light at a
particular frequency to a great degree of freedom.
(ii) Plasmons are capable of producing enormous enhancement in light intensity.
(iii) Plasmons have the ability to confine the photon energy in deep subwavelength
region.
3.1 Bulk Plasmons and Surface Plasmons (SPs)
Metals, rich with a sea of free electrons, which on being stimulated by an external
optical energy source are capable of inducing collective oscillation of these valence
electrons. The quantized radiation induced by collective electron oscillation in a
metallic system are known as plasmons [73–75]. In case of macro metallic systems,
the bulk plasmons are charge density oscillations which do not have the capability to
confine the electromagnetic radiation. Plasmons in a bulk metallic system oscillate
above a plasmon frequency (ωp) given as,
Ne2
ωp ¼ ð1Þ
mε0
where N is the valence electron density, e is the charge of the electron, m is the
effective mass of the electron, and ε0 is the dielectric constant of free space. The
incident electromagnetic wave propagates through the volume of the bulk metal and
induces collective oscillation of loosely bound valence electrons or conducting
electrons within the bulk metallic system. The bulk plasmon energy depends only
on the electron density of the metallic system (Eq. 1). In case of bulk metallic
systems, the plasmons cannot couple with the electromagnetic field and hence there
is no field confinement observed (Fig. 6).
Fig. 6 (a) Bulk plasmon (b) Surface plasmon induced in a metallic system
However, when an electromagnetic wave is incident on a metal-dielectric inter-

face, the wave travels through the surface of the material with a frequency value that
ω
is below the plasma frequency, ωsurface ¼ ppffiffi2. The electromagnetic radiation traveling
through the surface of the metal results in the formation of photo-induced plasmon
called “surface plasmon polariton (SPP).” In a metal-dielectric system, the electro-
magnetic field strongly couples with the electron plasma of the metal confining the
plasmons to the surface that induces photon-plasmon interaction to produce SPP
[73, 76, 77]. In summary, SPP are electromagnetic excitations propagating at the
metal-dielectric interface. “Surface plasmons” on the other hand are photo-induced
oscillations of charge carriers on the surface of the metallic system. Each collective
oscillation of surface plasmons or polaritons associated with different surface charge
distribution is known as surface plasmon resonance (SPR). SPR is exclusively
observed in metallic systems because of its high charge density. The point at
which the oscillation amplitude reaches a maximum at a particular incident radiation
wavelength is the SPR peak.
3.2 Localized Surface Plasmons (LSPs)
As the size of the metallic system is decreased, particularly size reduction along one
or two dimensions limits the movement of the charge carriers hence appearing to be
localized on the surface of the metallic nanosystem. As a result, localized surface
480 P. Naik et al.
Fig. 7 Illustration of localized surface plasmon resonance (LSPR)
plasmons are defined as the non-propagating excitations of the valence electrons of

metallic nanoparticles [73]. The resonance resulting from the oscillation of these
restricted electrons is called “Localized surface plasmon resonance (LSPR) [78, 79]
(Fig. 7).”
The oscillatory motion of the charge carriers or free electrons in metal
nanoparticles under the influence of the external electric field component of the
incident electromagnetic wave is given by the following equation:
d2 x dx
m þ mγ ¼ eE0 exp ðiεt Þ ð2Þ
dt 2 dt
where m, γ, ω, and E0 are the electron mass, damping constant, frequency, and
amplitude of the external electric field, respectively [80].
3.3 Factors Affecting Localized Surface Plasmon Resonance

(LSPR) Peak
The striking feature of metallic nanosystems is that the LSPR wavelength can be
significantly altered by tuning their shape, size, and dielectric constant contrast with
the surrounding media. The variation in the LSPR peak can be understood in detail
using the Mie scattering theory. The extinction cross section coefficient can quan-
titatively explain SPR for metal nanoparticles smaller than 20 nm, which is mathe-
matically given as follows,
24π 2 R3 ε3∕2 εi
C ext ¼ m
ð3Þ
λ ðεr þ εm Þ2 þ ε2i
where R is the radius of the metal nanoparticle, εm is the permittivity of the

surrounding media, and εr and εi are the real and imaginary parts of the permittivity
of the metal nanoparticle, respectively. The LSPR intensity and wavelength depend
upon various factors that affect the electron charge density on the particle surface
such as the type of metal, particle shape, size, composition and structure, and the
dielectric constants of both the metallic particles and the surrounding media. In case
of metal nanoparticles with size less than 20 nm, the extinction efficiency spectra are
mainly influenced by absorption efficiency, given that small metal particles absorb
large amounts of electromagnetic radiation. In contrast, when the size of the particle
exceeds 20 nm scattering is the dominant phenomena occurring in the system and
therefore governs the extinction output. The real part of the dielectric constant
determines the LSPR position and the imaginary part determines the resonance
peak width. The LSPR resonances occur when εr(ω) ¼ 2εm and the peak broadens
with an increase in the dielectric constant in the surrounding media. From the
expression of scattering cross section of a metallic sphere (Eq. 2), we can infer
that the LSPR phenomena are dependent mainly on the dielectric constants of both
the surrounding medium and the metal nanoparticle. The dielectric constants of the
metal nanosystems are much larger than the dielectric ones which is why metal
nanoparticles have a larger scattering cross section than dielectrics of the same
dimensions (Fig. 8).
Fig. 8 COMSOL Simulation of (a) dielectric nano-scatterer (b) metal nanoparticle

482 P. Naik et al.
Therefore, the various applications of plasmonic nanoparticles are associated

because of two important physical effects:
1. Optical extinction of the metallic nanoparticles has a maximum at visible near-
infrared wavelengths which is much larger than their geometrical size (because of
their large extinction cross section).
2. Localized enhancement of electromagnetic field near the particles.
Hence, metallic nanoparticles because of their unique optical properties are ideal
for being used as scattering centers in an active random lasing system. Both the
scattering and absorption cross sections will be greatly enhanced due to the resonant
surface plasmon response caused by the negative real part of the metal’s permittivity.
Plasmon-enhanced scattering is observed to be greatest for metallic nanoparticles
which when are incorporated in an active random media, result in optimization of
both the scattering strength as well as the gain volume of the random laser.
Additionally, confinement of electromagnetic radiation near the particle’s surface
will enhance the local field strength increasing the gain within the particle’s vicinity.
This gain is accessed by colocalization of the pump light and laser emission, whose
wavelengths fall within the surface plasmon resonance bandwidth.
3.4 Employing Metal Nanoparticles in Random Lasing
The study of the emerging field of nanophotonics now calls for lasing systems that
are unimpeded from diffraction limitations to extend its horizons towards investi-
gating the rich physics at the nanometer scale by developing high-performance
devices with new capabilities. The use of plasmonics due to its fascinating properties
as discussed in Sect. 3.2. allow us to break the diffraction limit reducing the size of
the bulky coherent light sources. It has been experimentally observed over distrib-
uted studies that the incorporation of metal nanoparticles predominantly gold and
silver with various configurations and dimensions in active random lasing media
offers low threshold lasing because of their good optical confinement and strong
plasmonic enhancement properties. Furthermore, the ability of plasmons to scatter
light more effectively and efficiently as compared to its dielectric or semiconductor
counterparts of similar dimensions and shape of higher refractive index allows us to
model lasers with high lasing efficiency. Metal scattering nanosystems provide
stronger absorption of excitation light and a larger amplification of fluorescence
than conventional dielectric scatterers owing to the enhancement of both the scat-
tering effect and the localized electric field. The use of metal nanoparticles also
offers greater amplification of weak physical and chemical light-matter interactions
at nanoscale.
Plasmonic random lasers consist of metallic nanostructures that support localized
surface plasmon modes [22]. The dye molecules coupled with the metallic
nanostructures and a resonant energy transfer can occur between stimulated emission
of the gain medium and EM fields of the surface plasmons, resulting in population
inversion. These plasmons undergo stimulated emission and result in plasmon laser
emission [81]. Consequently, the electromagnetic fields of the metal nanostructures
can enhance both the spontaneous and stimulated emission of the surrounding gain
media.
4 How Do Plasmons Enhance Random Lasing

Performance?
In case of random lasing systems using dielectric particles as scatterers, light

scattering is identified as the dominant phenomenon in the cavity. However, in the
case of random lasers consisting of metal nanoparticles, the lasing mechanism
becomes much more complicated given that plasmons not only scatter light but
also absorb some amount of light. Therefore, in the case of plasmonic random lasers,
the idea of tuning the lasing threshold and enhancing the random lasing output is
based on controlling (a) scattering, (b) absorption, and (c) local field enhancement.
4.1 Increasing Random Lasing Efficiency
Lasing efficiency can be enhanced via two mechanisms in a metallic active disor-
dered system,
(a) Enhancement of scattering strength.
(b) Enhancement of localized electromagnetic field in the vicinity of the metallic
scatterer.
4.1.1 Increasing Lasing Efficiency Via Enhancement of Scattering

Strength
In a random lasing system, the scattering strength is the decisive factor to enhance
random lasing output. Physically, the scattering mean free path describes the dis-
tance traveled by a photon in between the two successive collisions the photon
undergoes with the scattering centers. According to the Mie scattering theory,
scattering strength of a random laser is quantified using the scattering mean free
path (ls), which is given as [30],
1
ls ¼ ,
ρσ sca
where ρ and σ sca are the scatterer number density and scattering cross section of a
single scatterer, respectively (Fig. 9).
484 P. Naik et al.
Fig. 9 Illustration of
scattering mean free path (ls)
in a disordered system
Therefore, the scattering strength of a disordered system can be controlled by

either tuning the scatterer number density or by using scatterers with smaller
scattering cross section. The number of particles in an optical gain volume can
only be finite; therefore, the other method of increasing the scattering strength of a
random lasing media is increasing the scattering cross section of the scattering
particles. The scattering cross section of metal nanoparticle is larger than that of
dielectric particles for a given size thereby making metal nanoparticle systems a
better candidate to use in a random lasing media. In addition to controlling the
scattering strength, light absorption needs to be tuned which again is dependent upon
the cross section of the scatterers. Hence, metal nanoparticles have been widely
embodied in a random laser medium.
4.1.2 Plasmonics-Induced Enhancement of Localized Electromagnetic

Field
The spectral position of the plasmon resonance peak strongly depends on the
material type, shape, size, and surrounding environment of the plasmonic
nanoparticles. The variation in one or more of these parameters allows spectral
tuning of the plasmon resonance to overlap with the absorption and emission
spectrum of the active medium of interest. Plasmonic resonances change the local
density of optical states in the close proximity of the nanoparticles, resulting in
enhanced and highly confined optical fields close to the metal nanoparticle’s surface.
Thus, plasmonic nanoparticles modify the non-radiative and radiative decay rates of
nearby dye molecules by altering their electron decay lifetime and quantum yield.
When metallic nanoparticles are excited resonantly, they scatter the energy of the
emitters with enhanced scattering cross section therefore easily leading to spectral
narrowing of the resonance peak. The radiation from the dye molecules is strongly
scattered by metal nanoparticles due to the particle plasmon resonance. The enhance-
ment in the fluorescence occurs when there is a spectral and spatial overlap between
the metal particle plasmon resonance and the emission spectrum of the dye molecule
[82]. In summary, depending upon the distance between the fluorophore and the
metal nanoparticle the metal nanostructures have two main effects on the fluores-
cence of the dye molecule: (a) fluorescence enhancement and (b) fluorescence
quenching. Here, we discuss how the presence of metallic nanoparticles contributes
to increasing the dye molecule luminescence by affecting its radiative relaxation
rate. When the separation distance between the dye molecule and the metal nano-
structure is in the order of a few nanometers, a dramatic enhancement in fluorescence
is observed due to the influence of localized surface plasmons (LSPs) excited in the
metallic nanoparticles under the influence of external radiation. The fluorescence
enhancement is possible due to the interaction between the near fields generated by
LSPR and the fluorophores. The enhancement in the fluorescence of dye molecules
is maximum when the plasmon resonance spectrum overlaps the absorption of that
of the dye molecules. When the two spectra overlap, the pump radiation can be used
completely for inducing the electronic or molecular transitions within the
fluorophores, exciting a greater number of dye molecules thereby improving the
overall absorption of pump light. When the external electromagnetic radiation
induces electronic transitions within the dye molecules, the excited state
fluorophores polarize the metal by interacting with the free electrons of the metal
nanoparticle [83]. The LSPs generated as a result of the interaction, in turn, impose a
reactive field on the fluorophore causing constructive interference between the
molecular and metal nanoparticle dipole as shown in Fig. 10. Therefore, the metal
nanoparticles serve as a source of enhanced local fields and amplified excitation.
The presence of metal nanoparticle also increases the rate of energy transfer. The
increase in resonance energy transfer within a random lasing system inclusive of
plasmonic particles will increase the radiative decay rate. The fluorophore lifetime
(τN) will decrease with an increase in the radiative decay (τN ¼ Γ 1) [84]. As a result,
Fig. 10 Effect of localized surface plasmon resonance (LSPR) on fluorophore

486 P. Naik et al.
in the presence of metal nanoparticles within a lasing system, the light absorption
and scattering are enhanced by 5–6 times more than the emission of most strongly
emitting fluorescent molecules. In contrast, the direct contact between the dye
molecules and the metallic nanostructures when in close spatial proximity will
introduce additional losses into the lasing system [68]. However, due to the fluores-
cence enhancement caused due to the presence of plasmon resonance, the optical
gain can compensate for intrinsic losses in the metal nanocavities [85].
Since the metal nanoparticles scatter the energy of emitters with larger scattering
cross section when resonantly excited, they lead to spectral narrowing. The Q-factor
of the lasing cavity (Qc) is a function of the spectral width (Δλ) and the emission
wavelength (λ). Therefore, spectral narrowing corresponds to a high Q-factor. The
mathematical formulation of Q-factor of metal nanoparticles (QMNP) is given as
follows [85],
Re ½εðωÞ
QMNP ¼ ð4Þ
Im½εðωÞ
A higher Q-factor of the metal nanoparticles corresponds to stronger local field

enhancement. Similar to dielectric scattering centers, when metal nanoparticles are
spatially close to each other, a variety of enhanced optical modes are generated as a
function of the phase difference between the interfering modes. Depending upon the
type of interference, constructive or destructive interference, asymmetric LSPR
emission profiles can be observed in the resulting spectra which are known as
Fano resonance. In conclusion, we can use metal nanoparticles to not only intensify
the fluorescence but also increase the quality factor of the random lasing media for
constructing high-power lasers.
4.2 Lowering Random Lasing Threshold
According to the mathematical definition of lasing threshold, it is a ratio of total

cavity loss to spontaneous emission factor (β). The use of dielectric nanosystems for
random lasing required a comparatively high threshold to initiate lasing action. To
unravel the issue of high threshold random lasers, metal nanoparticles were tested in
an active disordered media since the emission factor of metal nanoparticles is high.
Metallic nanoparticles generate modes at discrete wavelengths. The most confined
modes in the metallic nanostructures exhibit faster emission coupling rates as
compared to less well confined modes, leading to preferential coupling of the most
confined modes. The spontaneous emission factor (β) is extremely important in the
threshold behavior of a laser. It is the proportion of emission that couples into a
single mode. The emission factor for metal nanoparticles can be as high as 0.8 [86]
suggesting low threshold lasing conditions in the presence of metallic nanoparticles.
For instance, in their work, Sebastian et al. used rhodamine 6G doped polymer
Fig. 11 Laser-induced emission from the fibers as a function of pump energy. The inset shows the
output intensity versus wavelength graph of all fibers R1, R2, R3, and R4 (different concentrations
of silver nanoparticles—refer to Sect. 4.2) at pump energy of 26 mJ. Reprinted with permission
from [54]. Copyright 2014, Institute of Physics
optical fibers as active media for random lasing. However, the sample showed no
signs of lasing in the sample containing only the active media doped polymer fibers,
i.e., in the absence of metal nanoparticles. As soon as the silver nanoparticles were
added to the sample, the sample began to lase randomly at an optimum concentration
of silver nanoparticles suggesting that the laser threshold can be significantly
reduced with addition of metal nanoparticles as shown in Fig. 11 [54]. In Fig.11,
R1, R2, R3, and R4 represent samples containing different concentrations of silver.
R1 contains only the dye molecules, i.e., Rhodamine 6G, R2, R3, and R4 contained
9 106 mol L1, 1.5 106 mol L1, and 4.5 106 mol L1 of Ag
nanoparticles, respectively.
We are aware that the addition of metallic nanosystems in random lasing media
can induce losses; therefore, often silver nanoparticles are recognized as the best
choice and are preferred over gold nanoparticles for random lasing purposes.
Furthermore, since losses dominate over gain due to feedback from multiple scat-
tering in case of gold nanoparticles, the local field enhancement is moderate as
compared to silver nanoparticles. Silver nanoparticles are the best choice to realize a
low threshold plasmon random laser because it has low surface plasmon loss in the
visible and near-infrared spectral range. However, gold nanoparticles feature much
lower chemical degradation and are hence more stable in ambient conditions.
488 P. Naik et al.
5 Plasmonic Systems Employed in Random Lasing
Reports of random lasers received considerable attention and inspired vigorous

efforts in research towards designing systems exhibiting random lasing. The sub-
stantial research in the field of random lasing included using dielectric particles,
semiconductors, biological samples, polymers and also metal nanoparticles, specif-
ically plasmonic nanoparticles [53, 64, 67, 70, 87, 88]. The incorporation of
plasmonic nanoparticles in laser dye medium has been of particular interest owing
to the extraordinary optical properties displayed by metal particles at nanoscale.
Most of the research using metal nanostructures focuses on reducing the laser
threshold by modifying the fluorescence yield of the gain molecules. The idea of
using metal nanosystems in random lasing was set in motion by Dice et al. by mixing
silver nanoparticles of diameter 55 nm to a dye solution of rhodamine 6G [53]. Spec-
tral narrowing in the random lasing emission spectra was observed at threshold
value. However, in this work, the plasmon resonance wavelength (~411 nm) weakly
overlapped with the emission maximum of rhodamine 6G. Popov et al. suggested
that for optimization of enhancement of random lasing using metal nanoparticles, a
strong spectral overlap between the plasmon resonance and emission of gain media
is a necessary condition [70]. This assertion was further backed by Popov by using a
sample of polymer film with dye molecules and dispersed spherical gold
nanoparticles. On examining the effect of metal nanoparticle size on the emission
spectra, it was observed that with increase in the size of the plasmonic particles, the
lasing threshold decreased thereby increasing the lasing efficiency. The optimum
enhancement of the random lasing system was obtained when the plasmon wave-
length overlapped with the emission of the dye molecule. Following these studies,
many active random lasing systems were introduced incorporating metal
nanoparticles coupled with various materials. For instance, Kang reported a silica
nanosphere coated with gold producing strong random lasing with a low power
continuous wave laser pump (200 mW) [87]. Coherent feedback random lasing from
polymer optical fibres doped with silver and rhodamine 6G was observed with
increased photostability of fluorophores and low threshold spectra narrowing was
reported for the first time [54]. With different morphologies of metal nanoparticles
tested to study the effect of varying size and dimension of metal nanoparticles on
random lasing output, Ziegler et al. reported gold nanostars to demonstrate the
enhanced performance of this configuration as compared to gold nanospheres and
nanorods. Gold nanostars produced multiple plasmon resonances that overlapped
with the emission spectra of the gain molecule (Rhodamine 6G) [65]. Studies
concerning the tunability of plasmonic random lasers have also been conducted.
One of the approaches that were used was mechanically tuning the polarization of
the random lasers by stretching the silver nanowires embedded on a flexible sub-
strate doped with Rhodamine 6G by Zhai et al. Using the mechanical tunability
approach, Zhai and group could tune the random lasing emission wavelength from
558 nm to 565 nm. The wavelength-tunability within the sample was a result of
narrowed plasmon resonance of silver nanowires on stretching the sample
[64]. Recently, another cross-sectional study with a change in shape and size of the
metal nanoparticle was carried out using gold nano-urchins in a dye doped polymer
sample for random lasing. The study showed that gold nano-urchins had a higher
scattering cross section as compared to gold nanospheres indicating two-fold local
field enhancement [67]. Various similar experiments coupling semiconductors and
dielectrics to metal nanoparticles are being carried out for testing enhanced random
lasing [25, 68, 89, 90].
6 Applications of Plasmonic Random Lasers
Plasmonics when incorporated into a random lasing system allow us to reduce the
size of the lasers increasing the laser efficacy which in turn could be integrated into
photonic circuits to increase the speed of the optical communications opening up
new applications in optics and spectroscopy. The potential applications for these
unique plasmon-driven lasers are displays [55], sensors [58, 91, 92], and tunable
narrowband coherent light sources [93]. Since the random lasing emission depends
upon the configurational and geometrical changes within the cavity, they can be used
in monitoring structural changes in biological samples [41]. For instance, random
lasing emission spectra can assist in examining the structural deformations and
material damage in bone structures [43, 45] allowing us to carry out detailed analysis
of bone composition at nanoscale. Furthermore, as discussed (Sect. 2.3.2.3), there
have been studies concentrated on using plasmonic random lasers for distinguishing
tumor cells from a system of mammalian cells by monitoring the changes in the
scattering pattern observed in the form of multiple spectral lines for cancerous cells
[42, 44]. The addition of metal nanoparticles to enhance the lasing effects in a
biological system has been of great interest, ranging from adding metal nanoparticles
predominately gold and silver nanoparticles to amplify the effects in photodynamic
and photothermal therapy [94, 95] to biological applications such as nanomedicine
and drug delivery [96, 97], biosensing [57, 98–100], imaging and spectral analysis
[57, 59, 101, 102]. Similarly, in order to increase the efficacy of tumor cell analysis
and structural deformation studies, one can incorporate plasmonics to amplify the
random lasing output simplifying analysis.
7 Conclusion and Future Scope
In this chapter, we have discussed a method of using plasmonic nanosystems for

random lasing applications by addressing concerns of high threshold and low
Q-factor that limited the significance and usefulness of random lasers till date. We
have highlighted all the elements of research directed towards overcoming the
shortcomings of random lasers by using metallic nanosystems that harness plasmon
resonance. Over a period of time, the field of plasmonic random lasers has grown and
490 P. Naik et al.
displayed unexpected futuristic applications and hence has now become a rich field
for investigation. High-efficiency lasers without cutoff sizes can be manufactured by
integrating plasmonic nanosystems in the random lasing media. Additionally, the
study of plasmonic nanosystems can be extended towards real-time tunable lasing
emission. There are many other possibilities of future work in plasmonic random
lasers such as the emission directionality control and also coherence studies for
determining the concentration of plasmonic nanoparticles to observe spatial and
temporal coherence [22]. The engineering studies to integrate plasmonic nanolasers
to model and construct powerful small volumed devices can open up a new branch of
technology for newfangled futuristic applications.
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Lecture Notes in Nanoscale Science and Technology 33

More information about this series at https://link.springer.com/bookseries/7544

ISSN 2195-2159 ISSN 2195-2167 (electronic)

Chapter “Aluminum: A Sustainable Universal Plasmonic Material” deals with the

Applications of Chiral Nanoparticles as Plasmonic Probes.” Two chapters

Tezpur, Assam, India Rajib Biswas

I am sincerely indebted to my mother, elder brother, and my spouse for their

Fundamentals of Plasma Oscillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

Improved Biosensor Device to Diagnose Malaria Based

Gazi A. Ahmed Department of Physics, Tezpur University, Tezpur, Assam, India

Tanujjal Bora Center of Excellence in Nanotechnology, School of Engineering

Katsumasa Fujita Department of Applied Physics, Osaka University, Osaka,

Ajeetkumar Patil Department of Atomic and Molecular Physics, Manipal Acad-

Abstract Plasma Oscillation is the most fundamental aspect of Plasma Physics. An

Key words Plasma oscillation · Plasmon · Particle-In-Cell (PIC) · Simulation ·

Plasma is considered as one of the primitive states of matter in the universe.

© The Author(s), under exclusive license to Springer Nature Switzerland AG 2022 1

The momentum equation is written as:

Linearizing the continuity equation (1), we get,

Thus, we write for Eq. (4),

Thus, simplifying we get,

ωn1 ¼ kn0 υ1 ð5Þ

Linearizing Eq. (2) we get,

This eventually gives,

Again, from the Poisson’s equation, we get,

which we may write as:

ikE0 E 1 ¼ ene1 ð7Þ

Total number of nodes present in the domain is:

ni ¼ Ion Slots Ion Spacing þ 1

ndi ¼ Plasma Density Ion Spacing

Fig. 2 Phase space plot of

Fig. 3 Time evolution of the position of the electron

It is important to note that the density of the plasma is considered to be

Appendix: The MATLAB Code for Plasma Oscillation

clc; clearvars; close all;

% Deﬁne the ﬁeld variables

nde = ones ();

% Number of electrons is same as the ions

% Memory space for electrons

% Set domain length

% open ﬁle to trace electrons

% open ﬁle for results

% Scatter particles to the mesh

nde(i+1) = nde(i+1) +spwt*(1-di);

% Divide by cell volume to get density

% Apply periodic boundary condition

% Compute the electric ﬁeld

%ef(1)=-(phi(2)-phi(1))/(DH); % Forward Difference

% Gather electric ﬁeld onto the particle position

% Rewind velocity by 0.5*DT

% Compute particle node position

% Gather electric ﬁeld onto particle position

% Take care of particle that left the domain

% Adjust position to get continuous trace of particle

% Periodically save results

Tonmoy Gogoi, Sita Chettri, Prankrishna Borgohain, and Ritupan Sarmah

Abstract Collective excitations of electrons at metal surfaces play a fundamental

Key word Collective behavior · Plasmons · Surface plasmon polariton · Localized

T. Gogoi · S. Chettri · P. Borgohain · R. Sarmah (*)

© The Author(s), under exclusive license to Springer Nature Switzerland AG 2022 15