Emr/Esr/Epr Spectroscopy For Characterization of Nanomaterials

Advanced Structured Materials
Ashutosh Kumar Shukla Editor
EMR/ESR/EPR
Spectroscopy for
Characterization
of Nanomaterials
Volume 62
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Ashutosh Kumar Shukla
Editor
EMR/ESR/EPR
Spectroscopy
for Characterization
of Nanomaterials
123
Editor
Ashutosh Kumar Shukla
Department of Physics
Ewing Christian College
Allahabad
India
ISSN 1869-8433 ISSN 1869-8441 (electronic)

ISBN 978-81-322-3653-5 ISBN 978-81-322-3655-9 (eBook)
DOI 10.1007/978-81-322-3655-9
Library of Congress Control Number: 2016950380
© Springer (India) Pvt. Ltd. 2017

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To my parents
Preface
Nanotechnology has opened up a new area of research in different fields.

Advantages are as many as to overcome disadvantages. The present collection
intends to describe the applications of electron paramagnetic resonance
(EPR) spectroscopy in the area of nanomaterial characterization. I have used all the
three names in the title of the book for the technique, viz, electron magnetic
resonance (EMR), electron paramagnetic resonance (EPR) and electron spin reso-
nance (ESR). Logically EMR includes the terms EPR and ESR. Most of the
available books on EPR generally involve mathematics and quantum mechanics. It
poses a hurdle before the scientists from other disciplines. I have tried to avoid these
mathematical details to make this collection more meaningful for readers from
different disciplines.
This book contains two parts. First part deals with nanomaterials and their
classification. Second part deals with EMR characterization of nanomaterials.
Chapter “Nanomaterials and their Classification” by Cristina Buzea and Ivan
Pacheco is an excellent attempt to acquaint the reader with the nanomaterials and
highlights their physico-chemical properties. Chapter “A Brief Manifestation of
Nanotechnology” by Sharda Sundaram Sanjay and Avinash C. Pandey comple-
ments Chapter “Nanomaterials and their Classification” and includes applications
based classification. A section on magnetization dynamics of nanomaterials which
is covered in this chapter provides a link to the second part on EMR characteri-
zation of nanomaterials. Chapter “An Overview on Advances in the NanoCarriers
Drug Delivery Systems” by Anjana Pandey gives an overview of the recent trends
of nanocarriers drug delivery systems which have attracted the attention of the
scientific community due to several advantages over the conventional drug delivery
systems.
Applications of EMR spectroscopy covered in second part of the book deal
basically with two different categories of nanomaterials—metallic nanoparticles and
metal oxide nanoparticles. Chapter “EMR of Metallic Nanoparticles” by Siavash
Iravani deals with EMR of metallic nanoparticles. Chapter “Electron Spin
Resonance Applied to Nanosized-Doped Oxides” by Cesare Oliva and Marco
Scavini covers the ESR of nanosized doped oxides. Chapter “EPR Studies of
vii
viii Preface
Cerium Dioxide Nanoparticles” by me and my co-author Rafail Rakhmatullin deals

with recent EPR applications in the characterization of ceria nanoparticles. Most of
this chapter is based on the research work of Rafail Rakhmatullin and co-workers.
Chapter “Synthesis and Characterization of Undoped and Doped (Mn, Cu, Co) ZnO
Nanoparticles: An EPR Study” by Seyda Colak and Cangul Akturk covers EPR of
zinc oxide nanoparticles.
I am grateful to Prof. Ram Kripal, Head, Department of Physics, University of
Allahabad who has introduced me to the language of EMR research. I sincerely
thank Swati Meherishi, Publishing Editor, Springer for giving me an opportunity to
present this book to the readers. My special thanks to Dr. Natalia Noginova
(Norfolk State University, Norfolk, VA), Dr. Emre Erdem (University of Freiburg,
Germany), Dr. Bernadeta Dobosz (Adam Mickiewicz University, Poland), and Dr.
Thomas Yeager (Victoria University, Melbourne, Australia) for taking their time to
go through the chapters and provide their valuable reviews. I would also like to
thank the authors for their contributions.
My sincere thanks to Prof. Raja Ram Yadav, Department of Physics, University
of Allahabad, Dr. M. Massey, Principal, Ewing Christian College, Allahabad and
my colleagues Dr. R.C. Mital, Dr. Anjani Kumar Singh, Dr. Mrs. Kusum Lata
Pandey, and Dr. Anil Kumar Singh for their constant encouraging remarks and
suggestions during the development of this book.
It is difficult to express my gratitude in words to my brother Dr. Arun K. Shukla,
Department of Biological Sciences and Bioengineering, Indian Institute of
Technology, Kanpur, who has always been there to help me. My special thanks are
also due to my wife Dr. Neelam Shukla.
In spite of our efforts, errors and omissions might have crept in. I request
esteemed readers to bring these mistakes to our notice.
Allahabad, India Ashutosh Kumar Shukla

December 2015
Contents
Part I Nanomaterials and their Classification

Nanomaterials and their Classification . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
Cristina Buzea and Ivan Pacheco
A Brief Manifestation of Nanotechnology . . . . . . . . . . . . . . . . . . . . . . . . . 47
Sharda Sundaram Sanjay and Avinash C. Pandey
An Overview on Advances in the Nanocarriers
Drug Delivery Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
Anjana Pandey
Part II EMR Characterization of Nanoparticles

EMR of Metallic Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
Siavash Iravani
Electron Spin Resonance Applied to Nanosized-Doped Oxides . . . . . . . . 91
Cesare Oliva and Marco Scavini
EPR Studies of Cerium Dioxide Nanoparticles . . . . . . . . . . . . . . . . . . . . . 135
Ashutosh Kumar Shukla and Rafail Rakhmatullin
Synthesis and Characterization of Undoped and Doped (Mn, Cu, Co)
ZnO Nanoparticles: An EPR Study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
Şeyda Çolak and Cangül Aktürk
ix
About the Editor
Dr. Ashutosh Kumar Shukla has obtained his B.Sc., M.Sc., and D.Phil. degrees
from the University of Allahabad.
His talks on science have been regularly broadcasted on the radio. He has been
working to popularize science among the masses through his published science
articles on issues of general interest. He has received many scholarships and fel-
lowships including National Scholarship, Scholarship of Ministry of Higher
Education, Government of UP, Research Fellowship of Council of Science and
Technology, Lucknow, UP, Research Fellowship of Council of Scientific and
Industrial Research, New Delhi and Indian National Science Academy-Bilateral
Exchange Fellowship.
During his doctoral work he focused on electron spin resonance spectroscopy
and optical absorption spectroscopy to investigate transition ion doped single
crystals. In addition to his exposure to the available CW-ESR spectrometers at
leading institutes of his own country like National Physical Laboratory, New Delhi,
Indian Institute of Technology, Bombay and Bhabha Atomic Research Center,
Bombay, he has hands-on experience with modern CW and pulsed ESR spec-
trometers at several leading international laboratories including the University of
Dundee, Scotland, University of St. Andrew’s, Scotland and Kazan State
University, Kazan. ESR characterization of rare earth manganites and nanomaterials
are his current interests.
xi
Part I
Nanomaterials and their Classification
Nanomaterials and their Classification
Cristina Buzea and Ivan Pacheco
Abstract In this chapter, we present a general classification of nanomaterials based

on their dimensionality, shape, and composition. According to their dimensionality,
nanomaterials include nanoparticles, nanotubes, and nanofilms. Nanomaterials can
be made of single elements, such as metals or carbon, or multiple elements, such as
metal oxides or composites. We review the most used types of nanomaterials up to
date showing examples of their morphologies. The physicochemical properties of a
material in nanoform can be very different from its bulk counterpart, depending not
only on the type of materials, but on its size, shape, and functionalization. We
discuss the most important physicochemical properties of nanomaterials, among
which are morphology, dispersability, crystalline phase, melting temperature, and
magnetic properties.

Keywords Nanomaterials classification Nanoparticles Nanomaterials physic-
ochemical properties
Magnetic properties of nanoparticles Toxicity of

nanoparticles Melting temperature of nanoparticles
C. Buzea (&)
IIPB Medicine Corporation, Owen Sound, ON N4K 6S5, Canada
e-mail: cristinabuzea@mdcorporation.ca
I. Pacheco
Department of Pathology, Grey Bruce Health Services, 1800 8th St East,
Owen Sound, ON N4K 6M9, Canada
e-mail: ipacheco@gbhs.on.ca; iblandin@uwo.ca
I. Pacheco
Department of Pathology and Laboratory Medicine, Schulich School of Medicine &
Dentistry, Western University, London, ON N6A 5C1, Canada
© Springer (India) Pvt. Ltd. 2017 3

A.K. Shukla (ed.), EMR/ESR/EPR Spectroscopy for Characterization
of Nanomaterials, Advanced Structured Materials 62,
DOI 10.1007/978-81-322-3655-9_1
4 C. Buzea and I. Pacheco
1 Nanomaterials Definition and Classification
1.1 Nanomaterials Definition
A nanomaterial can be defined as a material with external dimensions in the

nanoscale or with internal structure or surface structure in the nanoscale. According to
this definition, most of the materials around us would qualify as nanomaterials, as
their internal structure is modulated at the nanoscale (See for example Buzea et al.
[21]).
A nanoparticle is defined as a particle with at least one external dimension in
the nanoscale.
The term nanoscale should be defined as a size range from about 1 nm to
1000 nm. The upper limit overlaps with the definition of microparticles (whose
lower size limit is about 1 micron). While the lower limit of 1 nm is commonly
accepted, an upper limit of only 100 nm has been adopted by some authors,
however this limit has no scientific evidence to support the choice of this value, and
the use of a single limit might be too limiting for the classification of nanomaterials.
A differential approach for the term of “nanoparticle” was proposed in 2011 by
the European Commission [113]. The number size distribution should be taken into
account using the mean size and the standard deviation of the size to refine the
definition.
Nanoparticles consist usually of agglomeration of particles with sizes in a par-
ticular distribution, some larger and some smaller than 100 nm limit. The European
commission suggests that a nanomaterial should consist of 50 % or more of par-
ticles having a size between 1 and 100 nm [113].
The European Union agencies suggest that the following definition should apply
to the term “nanomaterial” [113]:
‘Nanomaterial’ means a natural, incidental or manufactured material containing particles, in
an unbound state or as an aggregate or as an agglomerate and where, for 50 % or more of
the particles in the number size distribution, one or more external dimensions is in the size
range 1–100 nm. In specific cases and where warranted by concerns for the environment,
health, safety or competitiveness the number size distribution threshold of 50 % may be
replaced by a threshold between 1 and 50 %. By derogation from the above statement,
fullerenes, graphene flakes and single wall carbon nanotubes with one or more external
dimensions below 1 nm should be considered as nanomaterials.
‘Particle’, ‘agglomerate’ and ‘aggregate’ are defined as follows:
(a) ‘particle’ means a minute piece of matter with defined physical boundaries;
(b) ‘agglomerate’ means a collection of weakly bound particles or aggregates where the
resulting external surface area is similar to the sum of the surface areas of the indi-
vidual components;
(c) ‘aggregate’ means a particle comprising of strongly bound or fused particles.
“Nano” should be considered a different state of aggregation of matter in

addition to the solid, liquid, gas, and plasma states. The reason for this is because
nanoparticles of a given material have quite different physical (optical, magnetic)
Nanomaterials and their Classification 5
Fig. 1 Calculated surface–

to-bulk ratios for solid metal
particles versus size. Adapted
from Klabunde et al. [73]
chemical, and mechanical properties than the same material in bulk form [91], [77].
Two main factors contribute to this: surface effects and quantum effects that appear
with decrease in size. Surface effects lead to a smooth scaling of physical properties
due to an increased fraction of the atoms at the particle surface compared to the
interior (Fig. 1) [73]. Surface effects result in increased chemical reactivity, reduced
melting point of nanoparticles compared to larger particles or bulk material.
Quantum-size effects involve the confinement of electrons within a very small
nanoparticle, or quantum dot which manifest in a quantized energy spectrum,
resulting in the appearance of magnetic moments, particularly in nanoparticles
made of nonmagnetic materials in bulk form such as gold, platinum, and palladium.
A nanoparticle can be thought as an aggregate composed of a relatively small
number of atoms. The smaller nanoparticles, sometimes called clusters, consist of
only a few atoms. The larger nanoparticles can have more than 105 atoms.
Nanoparticles are objects with intermediate size between the domain of atoms,
which must be described using quantum mechanics, and the bulk materials that can
be described by classical electrodynamics and solid-state physics [69]. Therefore,
nanoparticles are objects at mesoscopic scale between the microscopic and macro-
scopic worlds. (Mesoscopic scale means pertaining to a scale between microscopic
and macroscopic, or an intermediate scale.) Because of this some nanoparticles
exhibit a number of new phenomena that we will try to capture in this chapter.
1.2 Nanomaterials Classifications
1.2.1 Dimensionality
From the point of view of their dimensionality, nanomaterials can be classified as

nanomaterials with one, two, and three dimensions within the nanoscale, see Fig. 2
[21]. Materials with one dimension in the nanoscale are also called very thin films
or surface coatings attached on a substrate usually made from a different material.

Nanomaterials with two dimensions in the nanoscale are either nanoparticles
attached onto a substrate, porous thin films with pores in the nanoscale, or free long
aspect ratio nanoparticles, wires, or tubes. Finally, nanomaterials with three
dimensions within the nanoscale can be fixed small nanostructures on a substrate,
membranes with nanopores on a substrate, or nanoparticles. In this chapter one will
focus mainly on nanoparticles.
Examples of nanoparticles of various nanomaterials are illustrated in Figs. 3, 4,
and 5. Figure 3 shows transmission electron microscopy (TEM) images of various
metal oxide nanoparticles: Al, Sb, Bi, Co, Cr, Fe, In, La, Mn, Ni, Si, Sn, Ti, W, V,
Y, Zn, and Zr [38]. Each material shows a specific aggregation pattern of the
nanoparticles, with aggregation depending on their surface chemistry, some mate-
rials have crystalline nanoparticles, while others are polycrystalline.
Figure 4 shows TEM images of Ag nanoparticles of various size ranges together
with plots of nanoparticle distribution [2]. In general, the particle distribution fol-
lows a Gaussian bell.
Figure 5 illustrates microscopy images of different shaped silica nanoparticles
[57]. The same material can be shaped in different forms, spherical, oval, or
nanorod forms.
When we think of long aspect ratio nanoparticles, we think carbon nanotubes,
however, a wide range of materials can be synthesized as nanoparticles with long
aspect ratio. Figure 6 illustrates some examples of long aspect ratio nanoparticles:
Fig. 2 Classification of nanostructured materials according to their dimensionality, morphology,

composition, uniformity, and agglomeration state [21]
Fig. 3 Transmission electron microscopy images of various metal oxide nanoparticles (MeOx).
a aluminum, b antimony, c bismuth, d cobalt II, e chromium, f iron, g indium, h lanthanum,
i manganese, j nickel, k silicon, l tin, m titanium, n tungsten, o vanadium, p yttrium, q zinc,
r zirconium. Reprinted with permission from: “Towards understanding mechanisms governing
cytotoxicity of metal oxides nanoparticles: Hints from nano-QSAR studies,” Gajewicz et al.
Nanotoxicology, 2015 Taylor & Francis Ltd [38]
b Fig. 4 Field emission gun-transmission electron microscopy (FEG-TEM) images of silver

nanoparticles of various size ranges a 5 ± 0.7 nm; b 7 ± 1.3 nm; c 10 ± 2.0 nm;
d 15 ± 2.3 nm; e 20 ± 2.5 nm; f 30 ± 5.1 nm; g 50 ± 7.1; h 63 ± 7.6; i 85 ± 8.2;
j 100 ± 11.2 nm. For each image, the corresponding high-resolution (HRTEM) image and
lattice fringes (d-spacing) are shown. The histograms in the right lower side indicate the particle
size distribution. Reproduced from Agnihotri and Mukherji [2]
Fig. 5 a, c, e Transmission electron microscopy and b, d, f scanning electron microscopy images

of different shaped silica nanoparticles; a, b sphere-shaped nanoparticles, c, d rod-shaped
nanoparticles, e, f long rod-shaped nanoparticles. Reprinted from Biomaterials, Volume 31, Issue
3, Huang X et al., The effect of the shape of mesoporous silica nanoparticles on cellular uptake and
cell function, pp. 438–448, Copyright (2010), with permission from Elsevier [57]
b Fig. 6 a TEM (corresponding electron diffraction pattern inset, lower) and b–f SEM images of
long aspect ratio nanomaterials. Nanowires of a Au, b Ag, c Si attached on a substrate, d Pd, and
e nanotubes of Pd, and f multi-walled carbon nanotubes. Figure a reproduced from Das et al. [33]
with permission from John Wiley and Sons. Figure b reprinted from Journal of Hazardous
Materials, Volume 177, B. Cheng et al., Preparation and enhanced photocatalytic activity of
Ag@TiO2 core–shell nanocomposite nanowires, pp. 971–977, Copyright (2010), with permission
from Elsevier [25]. Figure c reprinted by permission from Macmillan Publishers Ltd: Scientific
Reports [56] copyright (2014). Figures d and e reprinted with permission from nanoletters,
Volume 11, issue 9, Liu et al. Wet-Chemical Synthesis of Palladium Nanosprings, pp. 3979–3982,
Copyright (2011) American Chemical Society [87]. Figure f reproduced from Ma-Hock et al. [93]
nanowires of Au, Ag, and Si, Pd, nanotubes, and multi-walled carbon nanotubes
(MWCNT) [25, 33, 56, 87, 93].
One must emphasize that while the nanomaterials fixed on a substrate or those
with nanopores do not pose a health risk, the free nanoparticles can become air-
borne and may be very toxic to human health [21].
1.2.2 Nanomaterials Morphology
A classification of nanomaterials according to their morphology divides them in

low- and high aspect ratio particles, see Fig. 2. The high aspect ratio nanoparticles
can have different shapes, such as nanowires, nanohelices, nanozigzags, nanopil-
lars, nanotubes, or nanobelts. The low aspect ratio nanoparticles can have many
shapes as well, such as spherical, helical, pillar-like, pyramidal, cubes, among
others. Most of the images in this chapter illustrate their morphology.
1.2.3 Nanomaterials Composition
According to their composition, nanoparticles can be made of a single material,

compact or hollow. Nanomaterials can also be comprised of two or more materials
that can be as coatings, encapsulated, barcode, or mixed. More details are given in
Sect. 1.1.3a.
1.2.4 Nanomaterials Uniformity and Agglomeration State
According to their uniformity, nanoparticles can be classified as isometric and

inhomogeneous. From the point of view of their agglomeration status, nanoparticles
can be dispersed or agglomerate. Their agglomeration state depends on their
electromagnetic properties, such as surface charge and magnetism. When in a
liquid, their agglomeration depends on their surface morphology and functional-
ization which can confer it either hydrophobicity or hydrophilicity.
1.3 Physicochemical Properties of Nanoparticles
The most important physicochemical aspects of nanoparticles are:

• Composition and surface composition
• Crystalline phase
• Particle size distribution
• Agglomeration/aggregation
• Shape
• Specific surface area
• Roughness/Porosity
• Water solubility/dispersability or hydrophobicity/hydrophilicity
• Zeta potential or surface charge
• Surface chemistry
• Catalytic/Photocatalytic activity
• Magnetic properties
• Optical properties
1.3.1 Composition and Surface Composition
Nanoparticles can be made of a single material or composite materials. Examples of

single materials nanoparticles are given in Fig. 3. Many nanoparticles will oxidize
in the presence of air and form a thin film at their surface.
Nowadays nanoparticles comprising different composite materials are easily
fabricated using a physical vapor deposition process at grazing incidence over a
nanoseeded pattern, involving the manipulation of substrate motion and temperature,
as demonstrated in Fig. 7 [97, 121]. This technique of deposition at a glancing angle
incidence can be used to manipulate the morphology of single materials as well [20].
Figure 7 shows Cu–Ti–Al2O3–Au nanohooks, Ag–Al2O3–Ag–Al2O3–Ag
nanobar-codes, Ni–Si–TiO2–Au nanozigzags [97].
Other examples of various composite nanomaterials are illustrated in
Figs. 8, 9, and 10.
Figure 8 shows nanocomposites with a spherical morphology. They are called
often encapsulated or core-shell nanoparticles. One can notice core-shells com-
posite nanoparticles: (a) Ni particle encapsulated by a graphite shell [11],
(b) graphene sheets encapsulated Si nanoparticle [92], (c), (d) polymer coated
cobalt nanoparticles [76], (e), (f) rattle-type Au/CdS composite nanoparticles [143].
Nanocomposites can be fabricated in the most unusual shapes, such as core-shell
nanocubes, as shown in Fig. 10. Image (a) shows Pd nanocubes while (b), and
(c) shows Pd–Cu core-shell cubes with different shell thickness. [63].
Fig. 7 Composite or hybrid nanoparticles with progressively lower symmetry. Columns from left
to right show: nano-barcodes, nanozigzags combining magnetic, semiconducting and insulating
materials, and nanohooks with defined chirality. First row, structure models; second row TEM
images. Reprinted by permission from Macmillan Publishers Ltd: Nature Materials [97], copyright
(2013)
Nanocomposites made of long aspect ratio materials together with spherical

small nanoparticles are shown in Fig. 9 where one can notice scanning and
transmission electron images of Ag–TiO2 core-shell nanocomposite nanowires [25].
1.3.2 Crystalline Structure
Crystalline structure is of paramount importance in deciding a nanoparticle’s

mechanical, chemical, and physical properties. The same material in a different
crystalline form can have very different properties and applications.
Examples of nanomaterials of different allotropes are shown in Figs. 11 and 12.
Figure 11 shows schematics of the crystalline structure of carbon allotropes: full-
erene C60, C70, C540, graphite, single-walled carbon nanotube (SWCNT),
amorphous carbon, and multi-walled carbon nanotubes (MWCNT) [15]. Figure 12
shows scanning electron microscopy images of multi-walled carbon nanotubes,
graphene, graphite nanoplatelets, and carbon black [93].
b Fig. 8 a HRTEM image of a Ni particle encapsulated by a graphite shell. The outermost graphene
layer represents the shape of the original Ni particle; b lithiation of a graphene sheets encapsulated
Si nanoparticle; c, d TEM images of polymer coated cobalt nanoparticles chains at different
magnifications. e, f Rattle-type Au/CdS composite nanoparticles. CdS shells nanostructures
encapsulate Au nanocores. Image a reprinted from Carbon, Volume 46, issue 4, R. Anton, On the
reaction kinetics of Ni with amorphous carbon, pp. 656–662, Copyright (2008), with permission
from Elsevier [11]. Image b reprinted by permission from Macmillan Publishers Ltd: Scientific
Reports, [92] copyright (2014). Images c and d adapted with permission from Korth et al. [76].
Copyright (2006) American Chemical Society. Images e and f reprinted from Xia and Tang [143]
with permission from John Wiley and Sons
Fig. 9 a TEM and b SEM image of Ag nanowire coated with TiO2 nanoparticles. Reprinted from
Journal of Hazardous Materials, Volume 177, B. Cheng et al., Preparation and enhanced
photocatalytic activity of Ag@TiO2 core–shell nanocomposite nanowires, pp. 971–977, Copyright
(2010), with permission from Elsevier [25]
Fig. 10 a TEM image of 18-nm Pd nanocubes that served as seeds for the deposition of Cu shells,
and b, c SEM images of Pd@Cu core-shell nanocubes prepared with different volumes of the seed
suspension at a concentration of 1.8 mg/mL: 1.5 and 0.5 mL. The edge lengths of the core-shell
nanocubes were approximately b 50 and c 100 nm, respectively. The insets show TEM images of
the samples, and the scale bars are 20 nm. Reprinted with permission from Jin et al., ACS Nano,
2012, 6 (3), pp. 2566–2573. Copyright (2012) American Chemical Society [63]
Fig. 11 Structure of various carbon allotropes in nanoform a fullerene C60, b C70, c C540,
d graphite, e single-walled carbon nanotube SWCNT, f amorphous carbon, g multi-walled carbon
nanotubes. Image a courtesy of James Hedberg, images b, c, d, e, and f courtesy of Michael Ströck,
g reproduced with permission from Balasubramanian and Burghard [15], John Wiley and Sons
1.3.3 Shape or Morphology
Nanoparticles can now be fabricated in almost any shape and containing various
combinations of composites materials. Some examples are seen in Fig. 13. Mark
et al. demonstrate nanoparticles with complex three-dimensional morphologies
comprising a variety of different functional materials [97]. Their fabrication method
combines a physical vapor deposition process at grazing incidence over a nano-
seeded pattern, involving the manipulation of substrate motion and temperature.
b Fig. 12 SEM images of carbon allotropes. In the left side one can notice the agglomerates while
in the right hand mode detailed nanostructures are noted at higher magnification; a, b multi-walled
carbon nanotubes, c, d graphene, e, f graphite nanoplatelets, g, h carbon black. Reproduced from
Ma-Hock et al. [93]
Fig. 13 a SEM, TEM images and drawing of Pd nanosprings; b TEM micrograph of gold
nanoplates. The inset shows triangular, truncated triangular, and hexagonal gold nanoplates;
c SEM image if gold nanostars; d field emission scanning electron microscope image of zinc oxide
raspberry- and plate-like nanostructures. Image a reprinted with permission from nanoletters,
Volume 11, issue 9, Liu et al., Wet-chemical synthesis of Palladium nanosprings, pp. 3979–3982,
Copyright (2011) American Chemical Society [87]. Image b reprinted from Xie et al. [144] with
permission from John Wiley and Sons. Image a reprinted with permission from J. Phys. Chem. C,
116 (2), Kedia and Kumar, pp. 1679–1686. Copyright (2012) American Chemical Society [65].
Image d reprinted from Journal of Inorganic Biochemistry, Volume 103, Issue 8, M. Z. Hussein,
Bacillus cereus as a biotemplating agent for the synthesis of zinc oxide with raspberry- and
plate-like structures, Copyright (2009), with permission from Elsevier [60]
Nanoparticles with different morphologies have been demonstrated, such as:

• Nanorods [120, 19, 97],
• nanozigzags [120, 97],
• nanohooks [97],
• nanostars [66, 65],
• nanocubes [63],
• nanohelices [120, 97, 65, 87, 139] and
• nanoplates [144, 60]
Various materials have been deposited in nanohelical: such as Pd [87], Au, Ag
[97], Ni/Ti [139]. To have an idea of the size and morphology of nanohelixes, in
reference [97] is described the fabrication of gold nanohelixes that have two turns, a
pitch of 34 nm and an overall height of 100 ± 8 nm.
Long aspect ratio nanoparticles encompass not only carbon nanotubes, but Si
nanowires [83], Ag nanowires [25], Pd nanotubes [87]. Some of them have already
been discussed, as seen in Fig. 6.
More complex morphologies are also attainable by different synthesis methods,
such as core-shell nanoparticles: spherical CdSe/CdS core-shell nanoparticles [143],
Ni encapsulated by a graphite shell [11], Pd–Cu core-shell cubes [63], hollow
BaTiO3 nanoparticles [85]. An example is given in Fig. 14 showing BaTiO3
supercages [85].
Fig. 14 BaTiO3 supercages a SEM images, b TEM images, d illustration. Scale bars 200 nm.
Adapted with permission from ACS Nano, vol. 9, issue 1, BaTiO3 Supercages: Unusual Oriented
Nanoparticle Aggregation and Continuous Ordering Transition in Morphology, Li, pp. 496–502.
Copyright (2015) American Chemical Society [85]
1.3.4 Surface Area
Particle size and surface area are important parameters that play a major role in
interaction of nanomaterials with the exterior. Decreasing the size of the
nanoparticle leads to an exponential increase in surface area relative to volume,
resulting in an enhanced reactivity. See Fig. 1 that shows the variation of number of
surface and bulk atoms with the nanoparticle size.
1.3.5 Water Solubility-Dispersability

or Hydrophobicity-Hydrophilicity
Nanoparticles can be insoluble or repelling water, also called hydrophobic.

Water-soluble nanoparticles are called hydrophilic.
Many of the engineered nanoparticles are hydrophobic and do not form stable
suspensions in aqueous media. They are nanoparticles made of metals and their
compounds (such as titanium dioxide or quantum dots), nonmetals (carbon-based
nanoparticles including fullerenes C60, carbon nanotubes, carbon soot, and
silicon-based nanoparticles).
In order to improve their dispersability via electrostatic repulsion, nanoparticles
can be coated with different substances. For example, gold nanoparticles can be
functionalized with citrate groups, while multi-walled carbon nanotubes are usually
functionalized via a selective breaking of C = C bonds achieved through oxidation
[112].
The soluble or biodegradable nanoparticles may convert into molecular com-
ponents as a result of biological and/or photochemical decomposition.
1.3.6 Catalytic/Photocatalytic Activity
Nanoparticles that have surface facets sufficiently large will have catalytic prop-
erties that approximate those of their bulk counterparts with crystalline surfaces [9].
With decreasing size, usually smaller than 3 nm, a nanoparticle catalytic activity
starts to deviate from its bulk behavior due to the increasing contribution of the
corner and edge atoms of the nanoparticle. Spherical nanoparticles with a size of
about 3 nm have half of their atoms on the surface. In the case of nanoparticles with
sizes between *1 and 2 nm, even slights changes in its structure, the deletion or
addition of a few atoms, can have an important impact on its catalytic properties.
Nanoparticles with such small size are usually hard to characterize experimentally
due to the fact that their structure may be altered during catalytic reactions [9].
Furthermore, for a given crystalline structure, the different crystalline surface
may show a different reactivity toward the same reaction. It has been shown that
different crystal surfaces of Pt have very different electronic structures and atomic
arrangements, consequently having a different reactivity toward the same reaction
[111].
1.3.7 Magnetic Properties of Nanoparticles
There are two types of materials that exhibit magnetism in nanoform. There are
magnetic nanomaterials that are magnetic in bulk form and nanoparticles that show
magnetic behavior only in nanoform, while in bulk are nonmagnetic. Below we will
discuss the two classes of magnetic nanomaterials.
Magnetic properties of nanoparticles that are magnetic in bulk form
Magnetic materials are defined as materials that change their magnetic behavior as a
result of an external magnetic field. There are five main types of magnetic materials:
ferromagnetic, paramagnetic, diamagnetic, antiferromagnetic, and ferromagnetic, as
shown in Fig. 15a [61].
In ferromagnetic materials (such as Fe, Ni, Co) the magnetism arises due to
atomic net magnetic moments as a result of unpaired electrons [59]. The material
has domains containing large numbers of atoms with parallel magnetic moments,
each domain having a net magnetic moment pointing in a specific direction [61].
Due to the random orientation of the magnetic moments of the domains, the net
magnetic moment of the material is zero. In an external magnetic field, the domains
of the ferromagnetic material align along the direction of the applied magnetic field,
resulting in a large net magnetic moment. After the removal of the external field
there is a residual magnetic moment left.
In paramagnetic materials (Gd, Mg, Li, Ta) magnetic domains are absent even
though atoms have net magnetic moment due to unpaired electrons [61]. After the
application of an external magnetic field, the atoms align along the direction of the
field resulting in a weak net magnetic moment. After the removal of the field, the
paramagnetic materials do not have a remanent magnetization.
Diamagnetic materials (bulk Cu, Ag, Au, and most of the rest of the elements)
have atoms with no unpaired electrons and show a zero net magnetic moment [61].
Their magnetic response in an external magnetic field is very weak and after the
removal of the field they do not retain any magnetic moment.
Antiferromagnetic materials (MnO, CoO, NiO) have two different atom types
occupying different lattice positions [61]. The two types of atoms have opposite
magnetic moments, resulting in zero net magnetic moment.
Ferrimagnetic materials (magnetite-Fe3O4) have also different atoms types
occupying different lattice sites with antiparallel magnetic moments, but different
magnitudes. Hence the magnetic moments do not cancel out, which results in a net
b Fig. 15 a The behavior of magnetic dipoles in the absence and presence of external magnetic
fields. According to their behavior they can be classified as diamagnetic, paramagnetic,
ferromagnetic, ferrimagnetic, antiferromagnetic [62]. b, c, d The magnetization of ferromagnetic
and superparamagnetic nanoparticles under an external magnetic field; a under an external
magnetic field the domains of a ferromagnetic nanoparticle align with the applied field and the
magnetic moment of single domain superparamagnetic nanoparticle aligns with the applied field;
b In the absence of an external field the ferromagnetic nanoparticles will have a net magnetization
and superparamagnetic nanoparticles will have no net magnetization due to rapid reversal of the
magnetic moment; c schematic illustration of the coercivity-size relations of small particles.
Reprinted from Akbarzadeh et al. [5]
spontaneous magnetic moment. In an external magnetic field, both antiferromag-

netic and ferrimagnetic materials behave similarly to ferromagnetic materials.
Magnetic nanoparticles are usually classified depending on their magnetic
response in an external magnetic field (Fig. 15a). According to this, nanoparticles
can be either ferrimagnetic, ferromagnetic, or superparamagnetic particles (a special
case of ferro- or ferrimagnetic particles) [74, 62]. Examples of magnetic nanopar-
ticles are Co, Ni, Fe3O4, CoFe2O4, HoMnO3, MnFe2O4, FePt [74].
Below a specific critical diameter, magnetic nanoparticles show magnetic
responses similar to paramagnetic materials, i.e., in the absence of an external
magnetic field show a zero average magnetic moment, while in an external field
increasing magnetic moments [74]. This phenomenon occurs due to comparable or
larger thermal fluctuations than the energy barrier for moment reversal. When the
magnetization of nanoparticles in the absence of an external field is zero, then these
nanoparticles are called superparamagnetic. Superparamagnetic nanoparticles are
used in applications such as drug delivery or magnetic resonance imaging.
Figure 15b, c shows the magnetization of ferromagnetic and superparamagnetic
nanoparticles under an external magnetic field. Under an external magnetic field the
domains of a ferromagnetic nanoparticle align with the applied field and the
magnetic moment of single domain superparamagnetic nanoparticle aligns with the
applied field. In the absence of an external field, the ferromagnetic nanoparticles
will have a net magnetization and superparamagnetic nanoparticles will have no net
magnetization due to rapid reversal of the magnetic moment [5].
Magnetic properties of nanoparticles that are not magnetic in bulk form
In addition to the above-discussed magnetic nanoparticles, some nanoparticles of
materials which are not magnetic in the bulk form exhibit a magnetic behavior in
nanoform, for nanoparticle size smaller than a few nanometers:
• Au [54, 55, 145, 94, 84, 104],
• Pt [124],
• Pd [54, 130],
• HfO2 [146].
Magnetism has also been observed not only in Au nanoparticles, but in thin films
of Au with 27 nm thickness deposited on Pyrex glass [119].
Magnetic behavior can be tuned by surface coatings or ligands [80, 31]. The
magnetic anisotropy of Pt nanoparticles is tunable via the modification of surface
conditions (thiol coatings) [124].
While at some point it was believed that the surface coatings or impurities were
responsible for the observed magnetism of these noble metals nanoparticles [145],
subsequently it was shown that also noble metal nanoparticles prepared under high
vacuum conditions and with high purity show magnetic behavior [126, 130].
In addition, it has been shown that ligand-stabilized Au nanoparticles exhibit
different magnetic behaviors: diamagnetic, paramagnetic, or ferromagnetic, as
shown in Fig. 16 [80]. Clusters with the same core size of about 25 atoms but
different ligands show two different magnetic behaviors. Mixed ligand-stabilized
and thiol-stabilized clusters of 25 and 38 Au atoms are diamagnetic while clusters
with 55 atoms are ferromagnetic.
While it could be argued that the influence of a substrate might influence the
magnetism of nanoparticles, it was shown that freestanding Pd nanoparticles with
clean surface exhibit ferromagnetism [130]. The ferromagnetic behavior is due to
the ferromagnetic ordering in a few topmost surface layers, while the rest of the
nanoparticle stays paramagnetic, similar to Pd bulk [130]. Consequently, the origin
of the ferromagnetism Pd small clusters can be associated with the two-dimensional
character of the particle surface.
Similarly, it has been observed that the surface atoms of Au nanoparticles are
ferromagnetic while the core is paramagnetic [145].
While in the bulk form Au is chemically stable and with diamagnetic properties,
at the nanoscale below a threshold size, gold nanoparticles exhibit ferromagnetism
[55]. The curve of the magnetization versus nanoparticle diameter exhibits a peak
for a nanoparticle size of around 3 nm [55]. The magnetism reverts back to the one
of bulk for nanoparticles larger than 4 nm. The magnetization peak can be
Fig. 16 Ligand-stabilized atomically precise gold clusters (APGCs) with their experimentally
observed magnetic behavior. Reproduced with permission from Krishna et al. [80], John Wiley
and Sons
explained by the decrease in surface magnetism and increase in spin-polarized

electron number with the nanoparticle diameter.
Some authors explain the observed magnetism of Au nanoparticles (and possibly
other metals) in the existence of self-sustained persistent currents having an orbital
origin [46].
The combination of quantum-size and Coulomb-charging effects cause the
properties of small metallic particles to depend on whether they have an odd or even
number of electrons [141]. However, some authors suggest that this mechanism
cannot explain the observed magnetization of Pd and Au nanoparticles with a
diameter of 3 nm, which shows an unexpectedly large magnetic moment of about
20 spins per particle [54]. They suggest that their results might be explained by the
existence of some common and characteristic spin correlation mechanism in the
nanoparticles [54]. At a critical size of about 3 nm diameter, there is a transition
from an atomic spin correlation region to a metallic spin correlation region.
1.3.8 Optical Properties
The optical properties of nanoparticles vary with their composition, morphology,

and size [69, 97, 99, 128].
Optical properties of nanoparticles pertain to the way that they interact with
light. If one exposes matter to light, several processes can occur [58]:
• Absorption of light
• Scattering of light at the same frequency as the incoming light (Mie or Rayleigh
scattering)
• Reemission of the absorbed light (fluorescence)
• Enhancing of the local electromagnetic field of the incoming light, thus
enhancing spectroscopic signals from molecules at the material surface.
Au nanoparticles exhibit an enhancement of all the above-mentioned processes
due to a unique interaction of the nanoparticle-free electrons and light [58]. When a
gold nanoparticle is exposed to an external optical field, the electrical component of
the light acts upon the conduction-band electrons and displaces them, creating
uncompensated charges at the nanoparticle surface [58, 69]. Because the polar-
ization occurs at the nanoparticle surface, these oscillations are called surface
plasmons. Plasmons are defined as collective excitations of conductive electrons in
metals [69]. There are several types of plasmons: bulk plasmons (or 3D plasma),
surface propagating plasmons polaritons (in 2D films), and surface localized
plasmons (in nanoparticles).
The surface plasmons have a well-defined resonance frequency, the coherent
oscillations of the nanoparticle electrons in resonance with the electromagnetic field
is called surface plasmon resonance (SPR).
In the case of Au nanospheres, the surface plasmon resonance is in the visible
spectrum at around 520 nm, hence the red color of solutions of spherical Au
nanoparticles, as shown in Fig. 17 [58, 117]. The resonance of gold nanorods is
Fig. 17 TEM images of cetyltrimethylammonium bromide-coated Au nanoparticles with different

aspect ratio (E) representative UV-Vis-NIR absorption spectra. (F) The relationship between
longitudinal plasmonic maximum LPM and calculated aspect ratios. The inset is the photograph of
the Au NRs suspensions. Adapted from Qiu et al. [117]. Adapted from Biomaterials, Volume 31,
issue 30, Qiu et al. Surface chemistry and aspect ratio mediated cellular uptake of Au nanorods,
pp. 7606–7619, Copyright (2010), with permission from Elsevier
created by oscillations along both the long and short axis, resulting in a stronger band
in the near-infrared region and a smaller band in the visible region, respectively.
These properties make Au attracting in biomedical applications [58]. For
example, biological tissue labeled with gold nanoparticles can be visualized clearly
by the surface plasmon resonance scattering of the Au nanoparticles under
monochromatic light from a laser. The light scattering from Au nanoparticles can be
105 stronger than the light scattering from a fluorescein molecule, widely used as a
fluorescent tracer [58]. For highly scattering tissue, the fluorescence of Au nanorods
can be used for imaging. The fluorescence of Au nanorods is about 6–7 times
higher than that of bulk Au, and it is attributed to the excitation of the longitudinal
plasmon [58]. The luminescence of Au nanorods with a length of more than
200 nm can be seen with the naked eye.
Quantum dots are also used for their photoluminescence properties. The pho-
toluminescence of a quantum dots can be manipulated to specific wavelengths by
controlling particle diameter as shown in Fig. 18a, b [133]. Examples of images of
quantum dots are shown in Fig. 18d, e, and f [148, 149].
Quantum dots are semiconducting nanocrystals of approximately spherical shape
with a typical diameter between 2 and 8 nm, encompassing between 200 and
10,000 atoms [7]. In a bulk semiconductor the valence electrons can be excited to a
b Fig. 18 (Color online) a The fluorescence spectra variation with the size of CdSe quantum dots,
b illustration of the relative particle sizes, c in vivo tumor imaging with quantum dots.
Fluorescence image of a live mouse with QD-tagged cancer cells injected into its right flank,
showing an orange glow (Courtesy of Dr Xiaohu Gao, Emory University). d, e, f Transmission
electron microscope images of quantum dots. d CdS-rich quantum dots (scale bar, 25 nm),
e ZnSe-rich quantum dots. f CdSe/CdS/ZnS quantum dots after phospholipid
micelle-encapsulation. Images a, b, c are adapted from Smith and Nie [133] with permission of
The Royal Society of Chemistry. Images d and e adapted by permission from Macmillan
Publishers Ltd: Nature Photonics [148], copyright (2015). Image f adapted by permission from
Macmillan Publishers Ltd: Nature Nanotechnology, [149], copyright (2012)
Fig. 19 (Color online) a Schematics of Au nanohelix with two turns showing critical dimensions,
b chiro-optical response of solutions of Au nanohelices; normalized circular dichroism
(CD) spectra of left-handed and right-handed helices. Inset TEM images of grown structures
with left (top) and right (bottom) chirality (image dimensions: 85 nm 120 nm). Reprinted by
permission from Macmillan Publishers Ltd: Nature Materials [97], copyright (2013)
higher energy conduction band, the difference in this energy being called the band
gap energy of the semiconductor [133]. After the emission of a photon with energy
equal to the bang gap energy, an excited electron may relax to its ground state. The
band gap of a semiconducting nanoparticle is dependent on nanoparticle size,
increasing with the nanoparticle size [133]. As a result the emitted light has shorter
wavelengths. Biological applications of quantum dots are dictated by the fact that
their size-tunable properties occur at the same size regime as biological molecules
such as proteins and nucleic acids.
Optical properties of nanoparticles can also be modified as a result of their
chirality or handnesness [97]. Figure 19 illustrates the tuning of the chiro-optical
response with the change in nanoparticles morphology. The long-wavelength cir-
cular dichroism spectra of the nanohelices with right-handed chirality show a
positive elllipticity, while for left-handed ones they exhibit a negative one. The
spectral peak position is a function of the radius of the helix.
Fig. 20 a The melting point, Tm, versus particle size for Ag [13], Sn [82], and Pb [116];
b sequence of TEM images exhibiting melting and vaporization of Ag nanoparticles. Image b
reprinted with permission from Cambridge University Press [13]
1.3.9 Mechanical Properties—Melting Temperature
Melting temperature of nanoparticles

Large cluster nanoparticles
The melting temperature decrease with decreasing particle size is a thermodynamic
consequence of the change in the surface-to-volume ratio that is confirmed
experimentally [3, 13, 30, 82, 116, 150]. For example, the melting temperature of
gold nanoparticles with a diameter of 3.8 nm (approximately 1,700 atoms) is about
1000 K, while for 2.5 nm nanoparticles (about 500 atoms) is around 500 K, and the
bulk melting point is 1,337 K [3].
As illustrated in Fig. 20, the melting point decreases smoothly with particle size
[3, 13, 82, 116].
Small clusters nanoparticles
Lowering further the particle size, in the cluster-size regime (tens to several hun-
dreds of atoms), the simple addition or removal of a single atom can drastically
change the physical properties of the cluster [115]. While the decrease of melting
temperature with size is true for large particles, when lowering the particle size
below a certain threshold, the melting temperature starts showing size-dependent
fluctuations [3]. This behavior is illustrated in Figs. 21 and 22. The measurements
of the melting temperature for Na clusters with n = 55–360 atoms show a fluctu-
ating dependence with cluster size. The melting temperatures are depressed by
almost 40 % compared to the Na bulk, and the average trend is for the melting
temperature to decrease with increasing cluster size (Adapted from Aguado and
Fig. 21 Normalized melting temperatures measured for Na clusters as a function of the inverse
cluster radius, N−1/3. The normalized melting temperature is the cluster melting temperature
normalized to the bulk melting temperature. The smaller size clusters have an icosahedral packing
(ico). At an unknown critical size must be a transition toward bulk-like (bcc) structures. Adapted
from Aguado and Jarrold [3] and references therein
Fig. 22 (color online). Upper panel: Na clusters of icosahedral growth pattern. Lower panel Size
dependence of the melting temperature (black), the latent heat of fusion per atom (q, red), and the
entropy change upon melting per atom (Ds, blue). The three data have their maxima around the
same N. The cluster sizes are indicated for some peaks. Melting temperatures of Na clusters exhibit
size-dependent fluctuations that correlate with geometrical shell closings. (Adapted from reference
Haberland et al. [49]). Reprinted image with permission from Haberland et al. Physical Review
Letters 94, 035701, 2005, Copyright (2005) by the American Physical Society, http://link.aps.org/
doi/10.1103/PhysRevLett.94.035701
Fig. 23 A selection of Na cluster global-minimum structures that have enhanced stabilities. The
structures are labeled by their size and point group symmetry. Adapted from Noya et al. [107].
With kind permission from Springer Science + Business Media: European Physical Journal D,
Geometric magic numbers of sodium clusters: Interpretation of the melting behavior, 43, 2007,
57–60, Noya et al. Copyright EDP Sciences, Societa Italiana di Fisica, Springer-Verlag 2007
Jarrold [3]). For clusters with larger size, having between 1,000 and 10,000 atoms
the melting temperature is depressed by only 20 % compared to the bulk, and there
is no clear extrapolation trend to the bulk value. The small sizes clusters are based
on Na icosahedral packing (ico), while the larger ones are Na bulk-like
(bcc) structures. The size-dependent fluctuations in the melting temperatures of
Na clusters correlate with geometrical shell closings (see Fig. 22) [49]. Clusters that
are more compact melt at a higher temperature [3, 4]. Figure 23 shows a selection
of Na cluster structures that have enhanced stabilities.
Calorimetric measurements of the heat capacity versus temperature of metallic
clusters show a peak in the heat capacity due to latent heat, which indicates the
value of the melting temperature of the clusters, as shown in Fig. 24a [115]. The
deduced melting temperature for these metals shows size-dependent fluctuations, as
illustrated in Fig. 24b [115]. One can notice large fluctuations (several 100°) can
occur just by simply adding or removing a single atom. For some clusters, the heat
capacities have extra features (an additional peak or a dip) that are related to a more
complex behavior than simple melting. For small clusters the influence of the
substrate might perturb their properties, and also for unsupported clusters it is
difficult to determine when they melt. Three main causes can lead to a second
feature in the heat capacity versus cluster size: partial melting when a part of the
Fig. 24 a The heat capacity versus temperature for very small Ga clusters with various number of
ions: 61, 80, 92, 94. Here 3 N = 3n − 6 + 3/2, where n is the number of atoms in the cluster, and
kB is the Boltzmann constant. b Melting temperatures determined from the fits to the peaks in the
heat capacities versus the number of atoms in each cluster. Reprinted with permission from Pyfer
et al. [115]. Copyright (2014) American Chemical Society
cluster melts at a lower temperature than the rest, the existence of two structural
isomers with different melting temperatures, and a solid-to-solid transition followed
by melting [3].
In this size regime, it is possible that the melting temperature of very small
clusters to be higher than the melting temperature of bulk, due to the fact that the
structure of the clusters is different than the structure of the bulk [131]. It has been
shown that Sn nanoparticles (cluster ions) with 10–30 atoms have remained solid at
555 K, which is 50 K above the melting point of bulk Sn [131].
The exact mechanism by which the melting points become elevated is still under
research. Some authors calculated by using first principles parallel tempering
molecular dynamics in the microcanonical ensemble that a strong charge segre-
gation between the internal and surface atoms might be responsible for a greater
than bulk melting temperature for Al clusters composed of 20 atoms [108]. The
clusters show negatively charged internal atoms and positive charge at the surface.
Other authors suggested that there is a marked shortening and stiffening of atomic
bonds with decreasing the number in the atomic clusters [114]. The stiffness of
bonds scales as the inverse tenth power of length [114].
1.4 Biologically Synthesized Nanoparticle
Nanoparticles can be synthesized by traditional physical and chemical methods,

such as laser ablation, chemical vapor deposition, ion sputtering, chemical reduc-
tion, sol-gel synthesis, etc. In addition to these methods, which we will not discuss
here for the sake of brevity, are biosynthesized nanoparticles.
The synthesis of metal nanoparticles via chemical and physical methods is often
expensive and may involve the toxic and hazardous chemicals. In order to mitigate
these facts, green synthesis is increasingly being explored. The basic requirements
for green synthesis are an ecofriendly solvent system and availability of biocom-
patible reducing and capping agents [81].
Metallic nanoparticles can be synthesized using biological agents, such as
bacteria, yeast, fungi, plants, algae [103, 118]. The exact mechanism of biosyn-
thesis is still unknown, except the fact that it involves proteins and/or enzymes
[118].
Some bacteria developed defense mechanism to mitigate toxicity of high metal
ions concentrations, such as Pseudomonas stutzeri that can live in soil rich in silver.
Some bacteria are able to synthesize inorganic materials, such as magnetite, as in
the case of the magnetotactic bacteria. A large number of bacterial species have
been used to synthesize metallic NPs, some of them being listed in Table 1 [103].
Some bacteria can reduce metal ions and form them as nanoparticles inside the
cells, other nanoparticles are able to synthesize them as nanoparticles both
intra- and extracellularly [118].
Table 1 List of microorganisms and synthesized metal nanoparticles

Microorganisms Products Size (nm) Shape
Sargassum wightii Au 8–12 Planar
Rhodococcus sp. Au 5–15 Spherical
Shewanella oneidensis Au 12 ± 5 Spherical
Plectonema boryanum Au <10–25 Cubic
Plectonema boryanum 485 Au 10 nm–6 lm Octahedral
Candida utilis Au – –
V. luteoalbum Au – –
Escherichia coli Au 20–30 Triangles,
Hexagons
Yarrowia lipolytica Au 15 Triangles
Pseudomonas aeruginosa Au 15–30 –
Rhodopseudomonas capsulate Au 10–20 Spherical
Shewanella algae Au 10–20 –
Brevibacterium casei Au, Ag 10–50 Spherical
Trichoderma viride Ag 5–40 Spherical
Phaenerochaete Ag 50–200 Pyramidal
chrysosporium
Bacillus licheniformis Ag 50 –
Escherichia coli Ag 50 –
Corynebacterium glutamicum Ag 5–50 Irregular
Trichoderma viride Ag 2–4 –
Ureibacillus thermosphaericus Au 50–70 –
Bacillus cereus Ag 4–5 Spherical
Aspergillus flavus Ag 8.92 ± 1.61 Spherical
Aspergillus fumigatus Ag 5–25 Spherical
Verticillium sp. Ag 25 ± 8 Spherical
Fusarium oxysporum Ag 5–50 Spherical
Neurospora crassa Au, Au/Ag 32, 20–50 Spherical
Shewanella algae Pt 5 –
Enterobacter sp. Hg 2–5 Spherical
Shewanella sp. Se 181 ± 40 Spherical
Escherichiacoli Cd/Te 2.0–3.2 Spherical
Yeast Au/Ag 9–25 Irregular polygonal
Fusarium oxysporum Au–Ag alloy 8–14 Spherical
Pyrobaculum Islandicum U, Tc, Cr, Co, Mn – Spherical
Desulfovibrio desulfuricans Pd 50 Spherical
Reprinted from Environmental Toxicology and Pharmacology, Vol 36, issue 3, D. Nath and
P. Banerjee, Green nanotechnology—A new hope for medical biology, pp. 997–1014, Copyright
Table 2 List of selected plants and synthesized nanoparticles

Plants Nanoparticles Shape Size (nm)
Alfalfa plant (Medicago Au and Ag Spherical and 20–40
sativa) triangular
Avena sativa Au Spherical 25–85
Azadirachta indica Ag, Au Spherical 50–100
Aloe vera Ag Spherical 15–15.6
Emblica officinalis Ag and Au Mainly spherical 10–20 and 15–
25
Cinnamomum camphora Au and Ag Mainly spherical 55–80
Tamarind leaf extract Au Mainly spherical 20–40
Capsicum annum Ag Mainly spherical 16–40
Medicago sativa Ti/Ni Mainly spherical 2–6
Medicago sativa Zn Spherical 2–5.6
Reprinted from Environmental Toxicology and Pharmacology, Vol 36, issue 3, D. Nath and
P. Banerjee, Green nanotechnology—A new hope for medical biology, pp. 997–1014, Copyright
Fig. 25 TEM images of biosynthesized Au nanoparticles with different shapes under different
reaction conditions (interaction of chloroauric acid and cell-free extract of the fungal strain
Rhizopus oryzae); a mixed morphologies: nanoplates with triangle, hexagon, pentagon, star,
shapes; b triangle; c hexagon; d pentagon. The upper and lower portions of each right-hand image
show high-resolution single-crystalline nanoplates and their SAED patterns, respectively.
Reproduced from Das et al. [33] with permission from John Wiley and Sons
A wide variety of metals nanoparticles, including semiconducting (Cd, Se, Zn,

Te), alkali-earth (Cs, Sr), magnetic (Fe, Co, Ni, Mn), and noble (Au, Ag) metals and
rare-earth fluorides (Pr, Gd) were synthesized using E. Coli [110].
The control of nanoparticles size and shape can be achieved by varying the
temperature, pH, incubation time, and/or metal precursor concentration [33]. The
variation in pH results in modifications in size and number of nanoparticles, while
temperature changes can affect the morphology of nanoparticles and their size. The
incubation time for forming nanoparticles can vary from seconds to several days
[118].
Plants and plant extracts can also be used to produce metallic nanostructures, see
Table 2 [103]. Plant extract is the most commonly used agent to produce metallic
nanoparticles, however, some live plants are able to absorb metals from the outside
and accumulate them as nanoparticles in their tissues [118].
An example of morphology and sizes of biosynthesized nanoparticles are shown
in Fig. 25 [33].
1.5 Nanoparticles Applications
Nanoparticles have a multitude of applications. The antimicrobial properties of

nanoparticles with different composition, such as silver [98], zinc oxide [125],
palladium [1], carbon [95], have antimicrobial properties against a variety of
microorganisms, such as Staphylococcus aureus and Escherichia coli [1, 129].
There are numerous applications of nanoparticles, among which are industrial
applications [135], in the construction industry in cement, coatings, paints, and
insulating materials [109], as electrocatalysts [9], for advanced energy conversion
and storage [32, 152], in functionalized textiles [10], in food contact material [52],
in cosmeceutical treatments for conditions such as photoaging, hyperpigmentation,
and wrinkles [90].
Theranostic nanoparticles are nanoparticles used in individualized therapies for
various diseases that combine diagnostic and therapeutic capabilities into a single
agent [28]. Magnetic nanoparticles might be used as potential theranostics to detect
and treat Alzheimer’s disease [18] while gold nanoparticles can be used as
oncotheranostics [140]. There are other various biomedical applications of
nanoparticles [22, 53, 106]. Some can be used for drug delivery to specific cells [12,
26, 64, 71, 96, 151], some for imaging [29, 45, 70, 86, 134, 136], some for
photothermal ablation of cancer cells [48].
While an increasing number of applications use nanoparticles and our knowl-
edge on nanoparticle toxicity progresses, the need for special legislature regarding
nanoparticles emerges [44].
As the toxicity of nanoparticles depends on their physicochemical characteris-
tics, it is difficult to predict which nanoparticles are toxic and to what extent. The
screening and prediction of toxicity of various nanoparticles should be performed

before the application of the nanoparticles in various industries. Screening tools and
predictive toxicological approaches are currently emerging [88, 89, 100, 105, 138].
1.6 Toxicity of Nanoparticles
When nanoparticles interact with organic matter they interact with biomolecules
which form a corona and will dictate the way they interact with cells [34–36, 47,
101, 122, 123] and their biodistribution within the body and tissue accumulation
within the organs [6, 68, 147].
Particle size plays an important role in the translocation of nanoparticles via the
air–blood barrier in the respiratory system [17, 78, 79, 102, 132] biodistribution to
organs [8, 43, 75], lung retention, and toxicity [14, 67, 137].
Oral exposure (ingestion) to some nanoparticles has shown to be associated with
toxic effects and diseases [16, 23, 24, 37, 50, 51, 72]. For example, nanoparticles of
various materials have been found in biopsies of patients with colon cancer [39].
Inhaled nanoparticles can enter the circulatory system and interact with blood
cells [41, 42, 142]. Patients with blood diseases have been shown to have
nanoparticles collected from explanted vena cava filters [40].
Epidemiologic studies show that nanoparticle exposure may lead to increased
blood pressure [27]. Experiments on rats show that titanium dioxide nanoparticles
promote arythmia by a direct interaction with cardiac tissue [127].
In conclusion, many nanoparticles have been found to be toxic to living
organisms, their toxicity depending on various physicochemical characteristics
whose relative importance is still unknown. Nanoparticles are associated to a wide
range of diseases that can manifest immediately following exposure or many years
later. It is impossible to extrapolate the toxicity of a nanomaterial from the prop-
erties of the bulk material, therefore a case-by-case approach is required in order to
identify hazardous nanomaterials. Therefore, care must be taken while handling and
using nanoparticles in applications.
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A Brief Manifestation of Nanotechnology
Sharda Sundaram Sanjay and Avinash C. Pandey
Abstract Nanotechnology is basically focused on the fabrication of nanomaterials

based on the manipulation, control, and integration of atoms and molecules at
nanometer scale, due to which there develops sudden change in the size-dependent
properties and functions. We have to integrate chemistry, physics and biology to
form materials, structures, components, devices, and systems at the nanoscale level.
In the metric system, prefix “nano-” refers to one-billionth (0.000 000 001 = 10−9)
of the base unit. In the nanoscale, at least one of the particle’s dimensions (height,
width, or depth) should be at less than 100 nm. At this level, the chemical reactivity
changes dramatically due to the reduction of particle size. This change occurs as a
function of the structure and the density of electrons in the outermost electronic
energy levels. Along with the physical properties such as optical, electrical, and
thermal properties, magnetic characteristics may also change which in-turn depend
on the distribution of electrons in the outermost energy levels, leads to the novel
optical, electrical, magnetic behaviors and changes in the surface dependent
properties. Because of the increase in the surface-to-volume ratio at the nanoscale
level the properties of the material become strongly dependent (controllable) on the
surface of the materials. The nanomaterials may be classified in number of ways,
viz., based on: (i) dimensionality (ii) surface morphology (iii) crystalline forms
(iv) chemical nature (v) chemical composition (vi) magnetic behavior (vii) func-
tionalization or (viii) applications. But none of these classifications can be con-
sidered as absolute one. They are usually composites or hybrid in nature because in
majority of cases organic compounds are used to stabilize them through capping or
functionalization during synthesis. Magnetic nanomaterials have giant spins, which
S.S. Sanjay (&)

Chemistry Department, Ewing Christian College, Allahabad, India
e-mail: sharda100@redifmail.com
A.C. Pandey
Nanotechnology Application Centre, University of Allahabad, Allahabad, India

DOI 10.1007/978-81-322-3655-9_2
48 S.S. Sanjay and A.C. Pandey
may be described as a single magnetic domain having uniaxial anisotropy, their

EMR signals can be exploited for various biomedical and many other applications.
Number of biomedical applications of nanoparticles is becoming possible because
of their specific physicochemical properties and controllable dimensions which
range from a few nanometers to nearly tens of nanometer, due to which they come
in the size range smaller than that of a plant or animal cells having submicron size
domain.

Keywords Nanomaterials Classification Dimensionality Surface morphology
Chemical nature
1 Introduction
It will not be an exaggeration to call Nobel Prize winner physicist of the year 1965,
Sir Richard Feynman as “Father of nanotechnology,” as he came up with his
historical thought of nano by uttering these words, “there is plenty of room at the
bottom” in his historic lecture at a conference held by American Physical Society in
1959, though the term nanotechnology was first given by Norio Taniguchi [1] at the
University of Tokyo in 1974. Feynman introduced the idea of manipulating the
very small, even down to the level of individual atoms for technological purposes.
Within the span of a half century nanotechnology industry has taken over.
Nanotechnology generally means building things from the bottom level, with
atomic precision. Today, nanotechnology is meant for the science of making,
synthesizing, designing, producing things which have at least at one dimensions of
100 nm or less and using it for various devices. It means that purposeful engi-
neering of matter by manipulation, control, and integration of atoms and molecules
at scales of 100 nm or less forms the basis of nanotechnology to achieve
size-dependent properties and functions. This integrates chemistry, physics and
biology to form materials, structures, components, devices, and systems to play at
nanoscale level especially for industrial and commercial objectives.
Due to their peculiar size and physicochemical properties, nanomaterials offers
major advantages. The development of unique nanoscale structures has revolu-
tionized the industry. In the realm of nanotechnology the scientists, chemists,
physicist and engineers have started working at the molecular and cellular levels to
make important advances (Fig. 1) in various fields such as fabrication, modeling,
life sciences, medicine, magnets and healthcare, electronics, smart materials and
sensors, nanoscale biostructures, energy capture and storage devices, and consumer
products.
A Brief Manifestation of Nanotechnology 49
Fig. 1 Materials with nanotechnology
2 Classification
Each and every material is made up of peculiar arrangement of particular atoms in a

specific way which defines its properties and behavior. Nanomaterials can be pre-
pared by cutting, chipping, pounding, extruding, ball milling, precipitating and many
more top–down and bottom–up methods. The main difference in the structure of
nanomaterials arises on how they are prepared. Their formation requires knowledge
of new types of synthetic methods and new understanding of the formation of
materials at nanoscale. In the case of nanomaterials, the atoms align themselves in
space in such a different way which is not found in the bulk form of the same
material and there is significant variation in their properties also. According to the
difference in certain criteria, nanomaterials may be classified in number of ways.
Classifications based on some important criterions are given below
2.1 Classification Based on Dimensionality
Nanomaterials can be created with various modulation dimensionalities. Siegel [2]

classified these nanostructured materials accordingly into four categories based on
their dimensionality as
(i) Zero dimensional (0D)—Having three dimensions in the nanometeric range

(by a dimensionality limited to 50 nm), e.g., atomic clusters, filaments and
cluster assemblies, fullerenes, etc.
(ii) One dimensional (1D)—Having two dimensions in the nanometeric range,
e.g., multilayers, nanotubes, nanorodes, nanowires, nanofibers manifest more
advanced and promising properties as being the 1D quantum wires nano-
scopic in diameter but microscopic in length.
(iii) Two dimensional (2D)—These have one dimension in nanometeric range,
e.g., ultrafine-grained over-layers or buried layers, heterostructures, and
nanodisks.
(iv) Three dimensional (3D)—Such nanophase materials which consist of
equiaxed nanometer sized grains. For example, thin films with atomic-scale
porosity, colloidal and different nanoparticles having various structures and
morphologies.
Classification based on dimensionality is pictorially represented in Fig. 2.
Fig. 2 Classification of nanomaterials based on dimensionality

2.2 Classification Based on Surface Morphology
As a reflection of templation or mode of synthesis different types of morphologies or

shapes arise spontaneously. The properties and usage of a particular nanoparticles
depends on its morphology provides the basic key for their mode of utilization in
several advancing technologies. There are nanospheres that are spherical, nanoreefs,
nanoboxes, nanoclusters, nanotubes, nanoflowers, etc. They may be classified on the
basis of morphology considering their flatness, sphericity and aspect ratio. Aspect
ratio is attributed to the proportional relationship between the widths of a structure
with its height. Nanoparticles can be classified according to their aspect ratios also as
(i) Nanoparticles in which diameter varies with length have generally high aspect
ratio. For example, nanotubes, nanorods, and nanowires having various shapes
as helices, zigzags, nanobelts, etc.
(ii) Collections of many particles that exist as powders, suspension, or colloids
have generally small-aspect ratio. For example, nanoparticles having that
spherical-, oval-, cubic-, prism-, helical-, or pillar-shaped morphologies.
2.3 Classification Based on Crystalline Forms
The basic difference between crystalline nanostructures and amorphous nanopar-

ticles lies in the way how the atoms are arranged around each other in the
nanocrystalline systems besides their size. Thus on the basis of crystallinity, solids
generally appear in three forms (Fig. 3)
(i) Amorphous—It does not have long range order, e.g., as glasses. They have
some short range order at the atomic length scale depending on the nature of
chemical bonding.
(ii) Polycrystalline—They have multiple domains of varying size and orienta-
tion. Their orientation may not have any preferred directions. Therefore, they
may say to have random texture. These crystallite domains are sometime also
referred to as grains.
(iii) Crystalline—A single extended domain have high long range order, properly
arranged domains.
Fig. 3 Different types of crystalline forms

2.4 Classification Based on Chemical Nature
We know that all the materials are basically formed with the chemicals which may
be inorganic, organic, or mixture of these two. Classification of nanomaterials based
on the chemical nature is pictorially depicted in Fig. 4.
2.5 Classification Based on Chemical Composition
Chemical composition can be referred to the type of arrangement of atoms

according to the ratio of the size of atoms in molecules of a particular material.
Upon the addition and subtraction of chemical reagents, chemical composition of
the particular substance changes. The properties of a substance are established
according to its chemical composition.
According to Gleiter [3] the one-, two-, or three-dimensional nanostructures may
be further classified on the basis of their chemical composition too, into four
families (Fig. 5).
(i) First family—In the most simple case in which all the constituents are dis-
tributed homogenously through out the region having same chemical com-
position, e.g., semicrystalline polymers or multilayers of thin film crystallites
which are separated by an amorphous layer, etc. [4]
Fig. 4 Classification of nanomaterials based on chemical nature

Fig. 5 Classification of nanomaterials based on chemical composition [3]
(ii) Second family—Those substances in which materials have different chemical

composition of constituents, e.g., quantum well structures.
(iii) Third family—Those materials in which they a different chemical compo-
sition or having materials of mixed component system, e.g., alumina ceramic
with Ga in its interface [5].
(iv) The fourth family—All those nanomaterials which are formed by
nanometer-sized particles (layers, rods or equiaxed crystallites) dispersed in
such a matrix having different chemical composition, e.g., hardened alloys
precipitation.
2.6 Classification Based on Magnetic Behavior
All the materials do not respond similarly with the externally applied magnetic
field. Thus, on the basis of their response to any externally applied magnetic field,
nanoparticles may be classified into five categories, namely, diamagnetic, param-
agnetic, ferromagnetic, antiferromagnetic, and ferrimagnetic [6]. Orientations of the
magnetic moments in a material place them in the above categories accordingly. At
nanolevel also, the particles exhibits magnetic properties only in the presence of an
external magnet and changes to a nonmagnetic state again when the external
magnetic field is removed. At this state, many factors play their role in determining
the magnetic properties of nanomaterial, such as the, particle size, shape, mor-
phology, their chemical composition and interaction with the surrounding matrix
and the neighboring particles. The magnetic behavior of any material can be con-
trolled by altering any of these factors to a certain limiting extent. For example,
spontaneous magnetisation occurs below TC when the particle size is 1 µm. For
single-domain magnetic particles with particle size equal to 1–30 nm, at Tb < TC,
the orientation of the magnetic moment of a particle remains same in space, but the
particle ensemble shows a magnetic hysteresis. At higher temperature above to Tb,
the particle attains superparamagnetic state. Usual paramagnetic properties are
retained by a single atom (ion) with particle size equal to *0.2 nm. At the range of
the quantum dots, high field irreversibility type of new phenomena, superparam-
agnetism or extra anisotropy contributions, are observed by the magnetic
nanoparticles. The magnetic behavior of individual nanoparticles develops such
phenomena due to its small and finite-size and surface effects [7]. In a superpara-
magnetic material, spins are substituted by small ferromagnetic domains. Generally,
when the particle comes in a state of uniform magnetization at any field, it should
have only a single magnetic domain. As a result of magnetic anisotropy, such type
of superparamagnetism arises. It means that the spins are aligned along a preferred
crystallographic direction at this state [8]. In the presence of an external magnetic
field, the aligned domains generate a strong attractive interaction. Once the external
magnetic field is removed, thermal agitation cancels residual magnetization.
Despite of the great importance of the morphology of nanoparticles, in magnetic
devices for storing or processing information, where well-defined magnetization
axes and switching fields are required, and the alignment of domains play its
important role.
2.7 Classification Based on Functionalization
With the advancement in the nanomaterial-based applications, the development of

functionalized nanoparticles gained specific recognition especially in the field of
biomedical and life sciences. Clinical results have shown that functionalized
nanoparticles with different functional groups or can say multifunctional nanopar-
ticles yielded enhanced efficacy with minimal side effects [9]. For stabilization
purposes and to avoid agglomeration, nanoparticles surface modification/coating is
done by some capping or functionalizing agents. Thus, the on the basis of
coating/functionalization, nanoparticles can also be classified as
(i) Bare nanoparticles—without any coating
(ii) Capped Nanoparticles—to avoid agglomeration
(iii) Functionalized nanoparticles—to perform certain specific task. Function-

alization may be of two types
(a) Post Functionalization—When the functionalization of nanoparticle is
done by capping or grafting organic groups onto the active surface of
nanomaterials after the synthesis is known as post functionalization [10].
(b) In situ Functionalization—When during the synthetic process only
functionalization and modification of nanomaterials is carried by organic
compounds, then it is said to be in situ functionalization [11, 12]
2.8 Classification Based on Applications
Jack et al. have well said in their book “The Next Big Thing Is Really Small” [13]
that how the future of our business will be changed by nanotechnology, i.e., nan-
otechnology has a wide horizon of its applicatory attributes. Perhaps not a single
sphere of application is left without nanotechnology. Its broad applicatory scenario
may be broadly classified as mentioned in Fig. 6.
Fig. 6 Classification of nanomaterials based on applications

3 Reason for the Peculiarity in the Properties
As the sizes of a substance begins to move towards the nanoscale, its properties
become unique and dramatically different from the same substances in the bulk
form. For doing nanotechnology, scientists work at the nanoscale level to enable
them to utilize this unique different properties, viz., physical, chemical, mechanical,
and optical properties of materials that naturally occur at this scale. Properties such
as melting point, fluorescence, electrical conductivity, magnetic permeability,
chemical reactivity, etc., changes as a function of the size of the particle. The reason
for the dramatic change in the properties of nanomaterials can be attributed to the
following two facts.
3.1 Discretness of Energy Level
When we go from the macroscopic to the microscopic to nanoscopic to atomic

dimension, we move from classical mechanics to quantum mechanics. Quantum
mechanics gives a complete version to the world of nanometric scale, which is
absolutely different from the classical Newtonian mechanics, which governs
operations of everyday objects involving properties that are size-dependent. But
quantum mechanics governs the interactions of very small things that range from
micro-molecules to nano to atomic and subatomic particles. Nobel laureate Max
Planck (won Prize for Physics in 1918), show in his famous quantum mechanics,
that the particle of energy that is exchanged between matter and radiation is called
quanta, a discontinuous quantity. E. Schrödinger and P. Dirac (Nobel Prize winners
for Physics in 1933) have developed wave mechanical concept by incorporating
physicist Louis de Broglie’s matter wave concept and quantum mechanics which
has driven a “revolution” in this field. Wolfgang Pauli’s exclusion principle des-
ignated the states of particles, which has given highest degree of accuracy in the
atomic world though this world resides on probabilities and uncertainties.
A molecule is formed by the overlapping of atomic orbitals (the space where the
probability of finding electron is highest), i.e., representation of electrons at discrete
energy levels, can only be attained as a simulation.
The electron’s energy levels in quatum dots are discrete and quantified as in an
atom or in a molecule and not as in the case of an ordinary semi-conductor where
electrons are spread out in energy bands (Fig. 7). The distribution of energy on
these levels occurs according to the particle size of the crystal.
Thus, in nanocrystals, the electronic energy levels are discrete having finite
density of states, because of the confinement of the electronic wave function to the
physical dimensions of the particles and not continuous band as in the bulk. This
phenomenon is known as Quantum confinement. Due to the quantum confinement,
there occurs change in electrical properties of the material. Some materials that
show conductivity in the bulk form may become semiconductors or poor
Fig. 7 Representation of the comparison of band gap energy between bulk, nano, and atom
conductors at the stage of nanometer level. Some materials that were semicon-
ductors may become conductors or superconductors. However, the atoms at the
surface experience different surrounding than those present at the center of the
particle because of the presence of unsatisfied free electrons or dangling bonds. The
presence of dangling bonds onto the surface of a material can change its conducting
properties.
Optical properties are also size-dependent at the nanoscale level. As said above,
confinement leads to a transition from continuous to discrete energy levels (Fig. 7).
Due to the discreteness of energy levels, the excitonic band gap increases which
restrict the movement of electrons. It cannot move about as freely. Therefore, the
quantum confinement of the electrons changes the optical properties of a substance,
i.e., it reacts differently to light. As the band gap increases, those substances which
are usually opaque in bulk becomes transparent to light at nanolevel. For example,
at the macro scale gold appears yellow in bulk but the color changes to red at
nanosized scale. Similarly, large-sized zinc oxide particles are used for sun screen
because it scatters visible light and appear white but at nanolevel zinc oxide par-
ticles do not scatter visible light and becomes transparent to sunlight. With the
decreasing particle size, quantum dots changes the appearance of a substance by
creating different phosphor and fluorescent colors.
It was found that magnetic nanoparticle can often be described as a single
magnetic domain with the uniaxial anisotropy (which comes from the shape of the
particle and effect of surface spins) even in materials with other type of anisotropy
(such as cubic). The orientation of its magnetic moment points may be either up or
down in the absence of magnetic field. During the synthesis of a crystal, there may
develop several types of defects on the surface as well as in the core, such as atomic
vacancies, changes in the atomic coordination, dangling bonds or lattice disorder.
Due to these defects some electronic spins remain uncompensated which leads to
the surface magnetization (ferromagnetism or antiferromagnetism) and again, it
depends on the size of the particle and on the extent degree of disorder at the
surface [14, 15]. Small particles can have very high magnetic susceptibility with
permanent magnetic dipole. Small clusters consisting of a single ferromagnetic
domain that follow the applied field freely are placed in the category of super
paramagnetism. The magnetic susceptibility of superparamagnetic particles is in

orders of magnitude larger than bulk paramagnetic materials.
The deciding factor of the properties of materials such as conductivity, mag-
netism, and reactivity is the electrons possessed by the materials. Electromagnetic
force is unaffected by mass, as it is a function of charge and distance. This becomes
even more stronger at the nanosize level. Since electromagnetic forces operate
between protons and electrons, therefore as the distance between these charged
particles decreases, they experience stronger electromagnetic attraction between
them and vice versa. The forces that act on atoms can be attractive or be repulsive.
It means that it is these columbic attractive forces that helps an atom in giving its
shape and size which in-turn reflects the ability of an atom to form chemical bonds
that depends on the attractive forces acting on the outermost valence electronic
energy level of an atom. An atom that has incomplete outer energy level attains
stability by the rearrangement of valence shell electrons by transfer or sharing of
electrons with any other atom. During these rearrangements, potential energy for a
chemical bond develops which is responsible for the interactions between atoms
and molecules. Therefore, it is very important for the development of nanotech-
nology. Covalent and ionic bonds are much stronger than hydrogen bond and van
der Waals forces. At the nanoscale, van der Waals forces become very prominent.
Due to which materials become sticky. That is why nanofibre can be very effective
in attracting and trapping small particles. This makes nanofibres excellent materials
for use in filtration.
3.1.1 Increased Surface-to-Volume Ratio
We know that as the size of particle decreases, the surface area and therefore,
surface-to-volume ratio also increases. This increased surface area of nanoparticles
is responsible for the development of peculiar properties of a substance at the
nanoscale level (Fig. 8). Due to large surface area there occurs change in the
reaction time of a substance. As the particle size decreases, the percentage of atoms
on their surface increases [16]. This accounts for the increase in the
surface-to-volume ratio. The higher surface-to-volume ratio increase the rate of
reaction due to the drastic increase in the amount of exposed surface area at the
nanoscale level causing the increase in the reaction rate for a chemical reaction.
Nanomaterials are inherently unstable due to high surface energy. Atoms exist at
the surface or interface are different from the same atoms exist in the interior of a
material. At surface due to free dangling bonds nanomaterial acquires high surface
energy which make them highly unstable causing agglomeration.
The properties such as melting point, rate of reaction, capillarity and adhesion,
etc., are controlled by their surface area. For example, Gold at the macro scale, has
melting point of 1064 °C [18]. Its melting point radically drops about 100 °C as its
particle size reduces from 100 to 10 nm diameter. On the further size reduction to
Fig. 8 Representation of increasing area as the particle size decreases [17]
about 2 nm the melting temperature reduces to about half of the melting temper-
ature at the macro scales level. At this level gold will no longer be able to conduct
electricity.
4 Magnetization Dynamics of Nanomaterials
In order to study magnetic properties and magnetization dynamics, electron mag-

netic resonance (EMR) or electron spin resonance (ESR) spectroscopy is preferred.
Earlier a conventional ferromagnetic approach, where dynamics of the magneti-
zation was defined as ferromagnetic resonance (FMR) with the help of
Landau-Lifshits equation, considering strong thermal fluctuations have been used to
study EMR of nanoparticles [19, 20]. The behavior of nanomagnetic objects lie at
the boundary line between quantum dynamics and classical thermodynamics.
Considering magnetic nanoparticle as a giant spin, Noginova et al. [21] have
assumed that the EMR signals are resulted as a collective contributions of quantum
transitions that occurred between energy levels developed due to the projections of
the giant spin onto the direction of the magnetic field. Such nanoparticles gives
peculiar features in EMR signals that are common in quantum systems, as the
variations in narrow spectral component and multiple-quantum transitions with
temperature. As the particle size increases, the relative intensity of such EMR
signals decreases significantly. This suggests a route of a gradual transition from a
purely quantum system applied to sub atomic state to a classical behavior of
comparatively large systems, where such effects diminishes. Noginova and
co-workers [22] have also explored the effects of the particle size and magnetization
dynamics, with EMR studies of magnetic nanoparticles to determine their potential
to use them as building blocks for tunable microwave metamaterials.
5 Biological Importance
Molecular or cellular parts of biological systems lie in the submicron size domain,
As the size of the nanoparticles lie within these dimensions, they viable to have
number of biomedical applications, such as they can be exploited as a very small
probes to spy within the cellular machinery without disturbing or interfering their
working conditions. They can be easily capped with biological molecules, such as
DNA, RNA, proteins or carbohydrates, to enable them to interact with or bind to a
biological moieties, i.e., by “tagging’’ or “addressing” they can provide a con-
trollable means of delivering drug of in diagnostic applications. By changing gra-
dient of external magnetic field, magnetic nanoparticles can be taken and assembled
to the desired target. Since human tissues have intrinsic penetrability to the mag-
netic fields, with such type of external control mechanism operating from an
optimum distance, opens up many applications which involves transportation and
immobilization of these magnetic nanoparticles, or magnetically tagged biological
species. In such cases, the external magnetic field assists the injected magnetic
nanoparticles along with the tagged drug to the desired site within the body acting
as a site-specific drug delivery busses. Magnetic nanoparticles such as gadolium
may be used as contrast agents in magnetic resonance imaging (MRI). On sub-
jecting to an external magnetic AC field, the temperature around the effected sites
can be raised up to 40 °C as a hyperthermic cancer treatment destroying the
cancerous tissues and tumors [23].
Since magnetic nanocomposites have shown to have fluorescent, radio-opaque
and paramagnetic properties, they may be utilized in confining and concentrating the
target analytes in a very small minute volume for in situ optical detections.
Therefore, magnetic nano particles functionalized or tagged with biomolecules such
as DNA, proteins, peptides or antibodies significantly improves the selectivity and
sensitivity of the system serving as bio- and chemo-sensors [24, 25]. Corr et al. have
utilized electrostatic interactions to develop new fluorescent-magnetic nanocom-
posites. They have prepared fluorescent magnetite-porphyrin nanocomposites by
interacting core nanoparticle, the spacer group and the fluorophore. Intracellular
fragmentation of the above said nanocomposite have shown their utility as subcel-
lular imaging contrast agents and in targeted drug delivery systems [26].
Magnetic iron oxide nanoparticles have thus shown a very wide spectrum of
applications in various clinical, diagnostics and therapeutic fields such as, cancer,
cardiovascular, neurological disorders, hyperthermia, magnetic separation of cells,
proteins, DNA/RNA, and in other biomolecular probes. Although they have been
found to be very useful in various biomedical and in vitro applications but because
of the agglomeration and necessity of fast detection via immune cells in physio-
logical medium, their clinical use are mired [27–31]. In order to use nanoparticles in
biological systems, its water-dispersibility in bio-systems is very important and it
should be bio-compatible. The colloidal stability of nanoparticle suspension should
also be maintained in the bio-physiological conditions, with a wide range of pH [9].
6 Conclusion
Physicist Richard Feynman ignited the torch of revolution called nanotechnology

and it has illuminated the minds all over the world. Now it has developed number of
tentacles. Nanomaterials accordingly classified in number of ways and its appli-
cations in many fields are discussed. At the nanoscale level, quantum mechanics
plays very important role in determining the properties and characteristics of a
material which leads to change in its optical, electrical and magnetic behaviors. The
properties of the material become more or less surface dependent. Due to the
increase in the surface-to-volume ratio at the nanoscale many surface-dependent
properties show changes in many folds. When nanomaterials are engineered in the
right way, they not only become electrifying in terms of applications, but also
become very significant in current and fast growing field of nanotechnology.
Acknowledgments We gratefully thank “Nanotechnology application center” for facilitating us

to work and for literature survey. We acknowledge the valuable suggestions and encouragement
given by Dr. Lalit Eusebius, Head, Department of Chemistry, Ewing Christian College, Allahabad.
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An Overview on Advances
in the Nanocarriers Drug Delivery Systems
Anjana Pandey
Abstract The unceasing efforts and improvement of drug delivery systems (DDSs)
have been broadly researched to maximize therapeutic efficacy while curtailing
undesirable side effects. Nanoparticle technology was recently shown to hold great
promise for drug delivery applications in nanomedicine due to its favorable prop-
erties, such as better encapsulation, bioavailability, control release, and lower toxic
effects. Regardless of the great progress in nanomedicine, there remain many
limitations prior to widely being accepted for medical application. To overcome
these limitations, advanced nanoparticles for drug delivery have been developed to
enable the spatially and temporally controlled release of drugs in response to
specific stimuli at disease sites. An ideal drug delivery system should be able to
localize a drug specifically and directly to its target. This is particularly important
when drugs made by traditional manufacturing methods are hydrophobic and their
solvents are toxic. Nanotechnology promises to improve drug delivery system
design and targeting. Nanostructured drugs or delivery carriers allow the continuous
and controlled release of therapeutic drugs to maintain drug levels to a desired
extent. The size of nanoparticles ranges from 10 to 200 nm, about the size of a
protein. Because of their small size, nanoparticles can readily interact with bio-
molecules on the cell surface or inside cell allowing these nanoparticles to penetrate
tissues in depth with a high level of specificity. This chapter discusses an overview
of nanoparticulate systems that can be used as a potential drug delivery carriers and
focuses on the potential applications of nanoparticles in various biomedical fields
for improving human health care.
Keywords Drug delivery Nanoparticles Biomolecules
A. Pandey (&)
Department of Biotechnology, Motilal Nehru National Institute of Technology (MNNIT),
Allahabad, UP 211004, India
e-mail: anjanap@mnnit.ac.in

DOI 10.1007/978-81-322-3655-9_3
66 A. Pandey
1 Introduction
An upcoming area of nanotechnology is “nanomedicine,” which employs molecular

understanding of a drug and its binding surface to address medical problems.
Nanotechnology deals with the design, synthesis, characterization, and application
of materials and devices at the nanoscale (1–100 nm) [5, 15] which show novel
properties from their bulk materials [16]. The scope of nanomedicine ranges from
in vivo imaging and diagnosis to therapeutics such as drug delivery and gene
therapy. Nanotechnology has immense potential in diversified areas of
health-related areas, for example, nanoparticle (NP)-based assay devices have been
demonstrated to be able to detect proteins in the attomolar concentration range
(protein biomarkers, toxins etc.), a magnitude of six orders lower than concentra-
tions detected by ELISA [14]. Various materials (e.g., polymer, inorganic precur-
sors, silica, noble metal, and carbon) could be used for the fabrication of
nanoparticles which have the ability to load a wide range of bioactive components,
including small molecular chemotherapeutics, proteins, nucleic acid, and diagnos-
tics, for biomedical application [12]. Besides that functional groups (such as –OH, –
COOH, –NH2, etc.) of the nanoparticles make them suitable for conjugation of
drugs, genes, antibody, and aptamer allowing them for targeted imaging and
treatment of various diseases [8]. Nanoparticles are taken up by cells more effi-
ciently by diffusion or through receptor mediated than larger micron-sized mole-
cules and therefore, could be used as effective transport and delivery systems. For,
therapeutic applications, drugs can either be integrated in the matrix of the particle
or attached to the particle surface. A drug targeting system should be able to control
the fate of a drug entering the biological environment. Nanosystems with different
compositions and biological properties have been extensively investigated for drug
and gene delivery applications [9, 19, 39, 48, 50]. An effective approach for
achieving efficient drug delivery would be to rationally develop nanosystems based
on the understanding of their interactions with the biological environment, target
cell population, target cell surface receptors [17, 27, 37], changes in cell receptors
that occur with progression of disease, mechanism, and site of drug action, drug
retention, multiple drug administration, molecular mechanisms, and pathobiology
of the disease under consideration. It is also important to understand the barriers to
effective drug delivery such as stability of therapeutic agents in the living cell
environment. Reduced drug efficacy could be due to instability of drug inside the
cell, unavailability due to targeting multiple locations or chemical properties of the
delivery molecules, alterations in genetic makeup of cell surface receptors,
over-expression of efflux pumps, changes in signaling pathways with the pro-
gression of disease, or drug degradation. For example, excessive DNA methylation
with the progression of cancer [18] causes failure of several anti-neoplastic agents
like doxorubicin and cisplatin. A better understanding of the mechanism of uptake,
intracellular trafficking, retention, and protection from degradation inside a cell are
required for enhancing efficacy of the encapsulated therapeutic agent.
An Overview on Advances in the Nanocarriers Drug Delivery Systems 67
This improvement will allow early detection of many diseases such as cancer,
genetic disorders, cardiovascular diseases, infectious diseases, etc., and may save
millions of lives through the prevention and early treatment of these diseases.
Synthesis of nanodrug and/or gene delivery system provides superior potential for
many applications, including antitumor therapy by targeted delivery of therapeutic
agents to tumors. Treatment of cancer represents an enormous biomedical challenge
for drug delivery. A nanoparticle-mediated drug delivery system can significantly
eliminate drug or drug carrier side effects. Targeted drug delivery creates better
therapeutic effect than that of conventional drug dosing method with minimized
side effects because of reduced dosage required at target site. An ideal drug delivery
system should be able to localize a drug specifically and directly to its target. This is
principally important when drugs made by conventional manufacturing methods
that are hydrophobic and their solvents are toxic. Nanotechnology promises to
improve drug delivery system design and targeting because of biodegradability,
target site uptake, increased surface area, and stimuli responsive drug release.
Nanostructured drugs or delivery carriers allow the continuous and controlled
release of therapeutic drugs to maintain drug levels within a desired level in
response to various stimuli like pH, light, magnetic field, redox potential, ultra-
sound waves, temperature, ionic strength, enzyme, and substrate concentration.
Other advantages of nanostructured drugs include localizing and specifically tar-
geting the drugs to their intended tissues and cells, thereby decreasing drug doses
and improving patient compliance because of minimized side effects of drug. In this
chapter, we will describe a variety of possible nanodrug carriers.
2 Types of Nanoparticles Used in Drug Delivery
Nanoparticles applied as drug delivery vehicles are generally less than 100 nm in at
least one dimension. These nanocarriers may consist of different biodegradable
materials such as natural or synthetic polymers, lipids, metal oxides, or metals.
2.1 Polymer-Based Drug Carriers
Depending on the method of preparation, the drug is either physically entrapped in

or covalently bound to the polymer matrix [44]. The resulting compounds may have
the structure of capsules (polymeric nanoparticles), amphiphilic core/shell (poly-
meric micelles), or dendrimers (Fig. 1a, b, d). Polymers used as drug conjugates can
be divided into two groups of natural and synthetic polymers. Polymers such as
albumin, chitosan, and heparin occur naturally and are nontoxic polysaccharide
polymers [32]. These are also biodegradable and biocompatible and hence been the
materials of choice for the delivery of oligonucleotides, DNA, protein as well as the
drugs. Biodegradable polymeric nanoparticles, mainly consisting of polylactic acid
68 A. Pandey
(a) (b) (c)
Polymeric micelle Polymeric Nanoparticle Liposomes
(d) (e) (f)
Dendrimers Viral Nanoparticles Carbon Nanotube
Fig. 1 Types of nanocarriers for drug delivery. a Polymeric micelle: The hydrophobic core region
encapsulates the hydrophobic drug while hydrophilic shell renders the micelle water soluble.
b Polymeric nanoparticles: Drugs are conjugated to or encapsulated in polymers. c Liposomes:
Lipid bilayer spherical structure with central aqueous region for encapsulation. d Dendrimers:
Highly branched synthetic polymeric macromolecule of nanometer dimension. e Viral nanopar-
ticles: protein cages which are multivalent self-assembling structure. f Carbon nanotube: carbon
cylinders comprised of benzene rings
(PLA), polyglycolic acid (PGA), polylactic-glycolic acid (PLA-PGA), and poly

(methyl methacrylate) (PMMA) have been used for both gene and drug delivery
[58].
2.2 Liposomes
Liposomes are spherical self-assembling lipid particles in which an outer lipid

bilayer encloses a core aqueous space (Fig. 1c). The lipid layers of liposome in fact
protect and entrap the drug until the liposome binds to the outer membrane of target
cells. Nanocarriers made with liposomes have a long circulation time, reduced
systemic toxicity, increased uptake into tumors, and steady release of their payloads
[41, 59]. Liposomes are one of the first nanoparticle-based drug delivery platforms
to be applied in medicine [6]. The best example of a clinical liposome formulation
is liposomal doxorubicin (Doxil™). The encapsulation of doxorubicin in liposomes
shielded by polyethylene glycol (PEG) prolongs systemic drug circulation,
improves the therapeutic efficacy, and minimizes off target effects relative to the
free drug [3, 24].
2.3 Dendrimers
Dendrimers are synthetic polymeric macromolecule of nanometer dimension

(Fig. 1d). They are made up of different types of polymers such as poly(L-glutamic
acid) (PGA), polyamidoamine (PAMAM), poly(ethylene glycol) (PEG), and
polyethylenimine (PEI) that emerge radially from the central core using either
convergent or divergent step growth polymerization [1]. The dendrimer is hydro-
philic and so can preferably be used as a coating agent for drug delivery. The
process of preparation of dendrimers is quite easy and its terminal can be modified
for targeted drug delivery and selective imaging of different tissues such as tumors
[42, 43].
2.4 Viral Nanoparticles
Some viruses (canine parvovirus, cowpea chlorotic mottle virus, cowpea mosaic
virus, and bacteriophages) have been developed for biomedical and nanotechnology
applications like tissue targeting and drug delivery (Fig. 1e) [31]. A number of
functional targeting molecules and peptides can be displayed on the virus capsid
using chemical or genetic engineering. Several antibodies, ligands (transferrin and
folic acid) have been conjugated to viruses for specific tumor targeting in vivo [45].
2.5 Superparamagnetic Nanoparticles
In recent years magnetic inorganic nanomaterials have gathered considerable

attention because of their potential for biomedical applications such as targeted drug
delivery [28, 53] including cancer diagnosis and treatments [25]. The magnetic
properties of nanometer sized iron oxide powders such as a-Fe2O3, c-Fe2O3, and
Fe3O4 have been extensively studied [20, 61] and compared with their bulk
counterparts. Because of their high tissue permeability and colloidal stability,
applications of these magnetic nanoparticles as drug carriers and for controlled drug
release within the target cells, are enormous. Furthermore, these oxide materials
exhibit better chemical stability and biocompatibility in comparison to many
metallic magnetic materials [25]. In addition, superparamagnetic nanoparticles of
iron oxides do not retain magnetization before and after exposure to an external
magnetic field, which reduces the possibility of aggregation of particles in a
magnetic dispersion.
70 A. Pandey
2.6 Gold Nanoparticles
Gold nanoparticles have emerged as nontoxic drug carriers for selective delivery of
drugs into their targets. PEGylation is a common method to increase stability and
robustness of these nanoparticles. The release of the encapsulated therapeutic agent
could be triggered by internal (e.g., glutathione or pH) or external (e.g., light)
stimuli. Gold nanoparticles exploit their unique chemical and physical properties
for transporting and releasing the pharmaceuticals [57]. First, the gold core is
essentially inert and nontoxic. The second advantage is their easy synthesis pro-
cedure with monodisperse nanoparticles formation. Further, these nanoparticles are
versatile because of their functionalization through a thiol linkage.
2.7 Carbon Nanotubes
Carbon nanotubes are carbon cylinders composed of six membered rings (Fig. 1f)
that can be used as sensors, diagnostic devices, and carriers to deliver drugs. Carbon
nanotubes are completely insoluble in all solvents, generating some health concerns
and toxicity problems. Introduction of functional groups to carbon nanotubes can
make them water soluble and functionalized so that the active molecules like
peptides, proteins, nucleic acids, and drugs can be linked to it [7]. Methotrexate, an
Table 1 Types of nanocarriers for drug delivery

Particle type therapeutic Materials Size (nm) Toxicity
application
Magnetic nanoparticles Iron oxide 5–100 Low
diagnosis, disease
treatment and drug
delivery
Gold nanoparticles drug Chloroauric acid sodium citrate 30 Low
delivery nm–1.6 lm
Dendrimers drug/gene Branched polymers 5–50 Polymer and
delivery cell type
dependent,
low
Polymeric nanoparticles Polylactic acid, polyglycolic acid, 50–2,000 Low
drug/gene delivery polylactic-glycolic acid (PLGA),
chitosan and poly (methyl
methacrylate) (PMMA)
Liposomes drug/gene Lipid mixtures 30–200 Low
delivery
Viral particles gene Protein cage 30–100 High
delivery
Carbon nanotube Carbon cylinders of benzene ring 100–500 High
drug/gene delivery
anticancer drug, has been linked covalently to carbon nanotube with fluorescein
isothiocyante (FITC). Therefore, FITC-linked drug-carbon nanotubes were shown
to be more effectively internalized through folate receptors into cells in comparison
to the free drug [38] (Table 1).
3 Size and Functionalization of Nanoparticles
For effective delivery of drug to the target tissue, nanoparticles should have the
ability to remain in the blood stream for a substantial time (6–10 h) without being
eliminated. The injected nanoparticles are usually trapped in the circulation by the
reticuloendothelial system, such as the liver and the spleen, depending on their size
and surface characteristics [34].
3.1 Size
The size of nanoparticles used in a drug delivery system should be large enough to
prevent their rapid leakage into blood capillaries but small enough to escape capture
by fixed macrophages that are lodged in the reticuloendothelial system, such as the
liver and spleen. The size of the sinusoid in the spleen and fenestra of the Kuffer
cells in the liver are in the range of 150–200 nm [60] and the size of gap junction
between endothelial cells of the leaky tumor vascular system lies between 100 and
600 nm [62]. As a result, the size of nanoparticles should be up to maximum of
100 nm (in exception to carbon nanotubes which are larger than 100 nm) to reach
tissues by passing through these two particular vascular structures.
3.2 Surface Functionalization
The surface property of nanoparticle is an important factor which decides the life
span and fate during circulation. Nanoparticles should ideally have a hydrophilic
surface to escape macrophage capture [33]. This can be achieved by two ways:
coating the surface of nanoparticles with a hydrophilic polymer, such as PEG and
its derivatives, protects them from opsonization by repelling plasma proteins; on the
other hand, nanoparticles can be synthesized from copolymers with hydrophilic and
hydrophobic domains [2, 23].
For successful nanoparticle-mediated drug delivery, nanoparticles should be able
to target specific cells or tissues. Therefore, it is critical to modify the surface
properties of nanoparticles to achieve targeted drug delivery [29, 51]. Specific
ligands such as monoclonal antibodies, folic acid and peptides can be utilized as
suitable target molecule for targeted drug delivery in cancer therapy [11, 21, 22, 52].
72 A. Pandey
These ligands can specifically interact with tumor-associated antigens or receptors.

For instance, nanoparticles conjugated with aptamer have shown a very high
specificity for drug delivery in prostate cancer therapy. The A 10 2′-fluoropyrimidine
RNA aptamer recognizes the extracellular domain of the prostate-specific membrane
antigen (PSMA), an antigen expressed on the surface of prostate cancer cells. These
surface-functionalized nanoparticles can selectively deliver the docetazel (Dtxl)
(anti-prostate cancer drug), to prostate cancer cells through the interaction between
the nanoparticles-conjugated aptamers and PSMA. The drug Dtx1 was encapsulated
in PLGA-PEG copolymer nanoparticles, and the carboxylic acid group present at the
terminal end of PEG provides negative charge used for conjugating
amine-functionalized A 10 PSMA aptamer using carbodiimide coupling chemistry
[10, 13].
In order to further increase the selectivity of therapeutic nanoparticles, a
two-ligand approach has been worked out. This approach has been tested in the
human KB cell lines (Keratin forming tumor cell line HeLa), which overexpress
both epidermal growth factor receptor (EGFR) and folate receptor (FR).
Liposome-based nanoparticles bearing folic acid and a monoclonal antibody against
EGFR were designed to selectively deliver doxorubicin to tumor cells [46].
Another method selectively targeted drug delivery can be achieved by the drug
entrapped polymeric micelles formed by conjugates of soluble copolymers with
lipids for example, the poly(ethylene glycol)-phosphatidyl ethanolamine conjugate
(PEG-PE). These can spontaneously target those parts of the body area which have
the compromised vasculature (tumors, infarcts) via the enhanced permeability and
sustainability of the system [54]. In addition, micelles formed by lipid core and
positively charged lipids are capable of escaping endosome capture and delivering
drugs directly into a cellular cytoplasm [56].
Biocompatible and biodegradable polylactic-glycolic acid (PLGA) has been the
most widely investigated biomaterial for making nanoparticles for controlled
release and sustainable drug delivery [26, 47]. PLGA undergoes biodegradation
upon implantation into the body by the citric acid cycle [40]. Furthermore, the
degradation rate of PLGA can be controlled by changing block copolymer (unit
polymer) composition and molecular weight which accordingly regulates the
release rate of encapsulated drugs [30]. The controlled drug release from
biodegradable polymer nanoparticles can be further improved by using a “nanocell”
delivery system, comprised of nuclear nanoparticles (core of the nanocell) made
from PLGA to which drug can be conjugated and coated with a nanoscale
PEGylated phospholipid block-copolymer envelop to form a “nanocell” structure
[49]. This type of “nanocell” nanoparticles is an effective drug delivery system for
treatment of tumors. Furthermore, the combination of two drugs can also be
delivered using “nanocells” is an exciting new advance in suppressing tumor
growth. For example, trastuzumab (Herceptin) and rituximab (Rituxane) have been
linked to poly(lactic acid) nanoparticles resulting in composites that exhibit sixfold
enhanced nanoparticles uptake compared without targeting molecules [35, 36].
At last but not the least, another significant advantage of nanoparticle in drug
delivery is the treatment of age-related neurodegenerative disorders because of
unique capability of nanoparticles to transport across the blood–brain barrier

(BBB) by passive diffusion or carrier-mediated transcytosis pathways [4, 55].
4 Conclusion
Nanoparticles mediated drug delivery has emerged as a promising field of

biomedical applications of nanoparticles. Their unique properties like high surface
area, tunable stability, functionality, and low inherent toxicity make them materials
of choice to deliver drugs effectively at the target site. Development of multi-
functional nanoparticles remains to be explored for medical applications along with
toxicological issues before being applied to humans.
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Part II
EMR Characterization of Nanoparticles
EMR of Metallic Nanoparticles
Siavash Iravani
Abstract In this chapter, current trends and future prospects about the important
applications of electron magnetic resonance (EMR) spectroscopy for characteriza-
tion of metallic nanoparticles are discussed.
Keywords Electron magnetic resonance EMR ESR EPR Metallic

nanoparticles
1 Introduction
Nanoscience and nanotechnology have a particular field for research and devel-
opment. Metal and metal oxide nanoparticles (NPs) show unique size and
shape-dependent properties which are of interest for electronic, optoelectronic,
biological, medical, biomedical, pharmaceutical, cosmetic, wireless electronic logic
and catalytic structural applications [8, 16, 76]. Furthermore, metallic NPs have
many important applications in different scientific fields, such as medical imaging,
photocatalysts, nanocomposites, magnetic resonance imaging (MRI) contrast
agents, filters, drug delivery systems, biosensor materials, composite fibers, elec-
troconductive coatings, cryogenic superconducting materials, cosmetic products,
electronic components, thermal spray coatings, quantum optical devices, hyper-
thermia of tumors, cancer therapy and diagnosis, and solar cells [65, 40, 53, 50].
Generally, electron magnetic resonance (EMR), also known as electron spin
resonance (ESR), is a suitable analysis method to study magnetic properties and
magnetization dynamics. EMR spectroscopy deals with microwave region of
electromagnetic radiation, and it is based on the interaction between electronic
magnetic moments and magnetic field. Electron Paramagnetic/Spin Resonance
(EPR/ESR) is one of the most important magnetic resonance techniques, and it can
S. Iravani (&)
Faculty of Pharmacy and Pharmaceutical Sciences,
Isfahan University of Medical Sciences, Isfahan, Iran
e-mail: siavashira@gmail.com

DOI 10.1007/978-81-322-3655-9_4
80 S. Iravani
be performed on any sample which has unpaired electron spins. Actually, EPR is
the resonance absorption of electromagnetic radiation by paramagnetic substances
in constant and variable magnetic fields. It measures the energy difference between
energy levels for the unpaired electron in the magnetic field and gives a single line
spectrum at the energy level DE. EPR is an analysis technique which allows
researchers to study species possessing electrons with unpaired spins. Actually,
EPR/ESR has proven an essential tool for study of impurity states, molecular
clusters, antiferromagnetic, ferromagnetic and thin film compounds, natural or
induced radicals, electron spin-based quantum information devices, optically
excited paramagnetic states, and transition-metal based catalysts. Moreover, it can
be applied in structural and dynamical studies of metallo-proteins, spin-labeled
proteins and other complex biomolecules and their synthetic models. In summary,
EMR spectra are usually characterized by the spin Hamiltonian parameters, and
therefore rigorous EMR analysis requires quantum mechanical concepts. In addi-
tion, EMR can be used in order to analysis of the samples with paramagnetic
centers which are the sites with unpaired electrons. Important parameters of EMR
spectrum including intensity, line width, g value, and hyperfine splitting constant
provide researchers different information about the paramagnetic specimen [59].
EMR can also provide spectroscopic information on unpaired electronic spin states
at both the atomic (conventional EMR) and the nanoscale (ferromagnetic reso-
nance), and data obtained from EMR spectrum depends upon the nature and form of
specimen [61]. Among many researches on magnetic NPs, there are a considerable
number of studies performed by means of EMR [47, 56, 71]. In this chapter, current
trends and future prospects about the important applications of EMR spectroscopy
for characterization of metallic NPs are briefly discussed.
2 Nanomaterial Properties and EMR
Nanostructured materials are defined as materials with primary particles less than
100 nm in length in at least one dimension. Nanomaterials can have size-dependent
properties which result in unique behavior relative to materials composed of larger
particles. Actually, on the nanoscale, electronic, optical and magnetic properties can
be size dependent. Moreover, as particle size decreases, the surface/volume ratio of
a material increases. Nanostructures can have high surface/volume ratios, with a
large percent of total atoms present as surface atoms. Therefore, thermodynamic
stability is size dependent, with surface free energy becoming an increasingly
significant contribution to the total free energy as particle size decreases. The
primary particle size of a material can influence surface properties, including sur-
face area, arrangement of surface atoms, surface electronic structure, surface
composition and functionality, as well as bulk properties, including shape, size,
phase, electronic structure and crystallinity.
Nowadays, different properties obtained from nanomaterials lead to their tech-
nological importance, and therefore, the preparation and characterization of them
EMR of Metallic Nanoparticles 81
are very important for scientific researches. The magnetic properties observed on a
macroscopic scale are due to a very large number of atoms and, therefore, are
inexistent or very different on a microscopic scale for a single atom or molecule or
for a cluster of a few atoms. When fine magnetically ordered NPs are dispersed in a
diamagnetic matrix, a specific type of magnetic behavior, called superparamag-
netism is observed. EMR of NPs in ferrofluids, glasses, and other superparamag-
netic systems has been widely studied by researchers [28, 46, 61, 27, 59].
Consequently, comprehending this phenomenon made a very important contribu-
tion to the fundamentals of magnetism and laid the foundation for the development
of new materials for high-density information storage [35]. The physical properties
of magnetic NPs are determined by both magnetic nature and morphologies (size
and shape). A variety of experimental techniques including static magnetic, optical,
magneto optical, rheological measurements, Mössbauer spectroscopy, electron
microscopy, X-ray diffraction, small-angle neutron scattering have been used for
determination of the magnetic characteristics of these NPs in different superpara-
magnetic systems and to evaluate their size distribution [35]. A tailored value of l,
even of negative l, is obtained using magnetic resonance. Structural magnetic
resonance with split-ring resonators, which are made of a nonmagnetic metal such
as Cu, is a well-known technique to achieve negative l in microwave regions [52,
62]. Moreover, an alternative route using intrinsic magnetic resonance of ferro-
magnetic metals, e.g., Fe, Co and Ni, has been plotted [15]. Using EMR in the
metals, negative l is obtained around an EMR frequency [13]. The resonance
frequency tunability with an external magnetic field is expected to be a significant
advantage of this route. It is, however, necessary to miniaturize the ferromagnetic
metals, i.e., prepare ferromagnetic-metal nanoparticle systems, in order to suppress
the eddy current losses. Magnetic interactions between NPs strongly affect the
position and linewidth of the EMR spectra [9, 20, 32, 68]. Actually, in nanoparticle
systems, two kinds of interactions have been considered: long range magnetic
dipole interactions and short range direct/indirect exchange interactions [5, 4, 39].
The relative importance of each to EMR depends on the particle diameter (d) and
center-to-center interparticle separation (r). Therefore, from an experimental point
of view, NPs with independently controlled d and r are necessary to study EMR in
an interacting nanoparticle system [30, 54].
3 EMR of Metallic NPs
3.1 Gold NPs
Gold NPs have found potential applications in many fields such as drug and gene
delivery, biological detection of pathogens, catalysis of oxidation reactions, low
temperature oxidation of carbon monoxide (CO), gene delivery and drug delivery
systems, fluorescent biological label, animal viruses transport with gold templates,
82 S. Iravani
sensors (saccharides sensor and glucose oxidation), cancer therapy and diagnosis,
and probing of DNA structure [2, 3, 6, 7]. Oligonucleotide-capped gold NPs have
been applied for polynucleotide or protein detection using various detection and
characterization techniques, such as atomic force microscopy (AFM), gel elec-
trophoresis, scanometric assay, surface plasmon resonance imaging, amplified
voltammetric detection, chronocoulometry, and Raman spectroscopy [10, 63].
Furthermore, gold NPs have been employed in immunoassay [43], protein assay
[66], cancer nanotechnology [45], and capillary electrophoresis [70]. After cellular
uptake, gold NPs can act as precise and powerful heaters (thermal scalpels) to kill
cancer, and also they can be used as useful markers for biological screening tests
[21, 57]. These NPs are capable of inducing apoptosis in b cell-chronic lymphocytic
leukemia [48].
Many scientific studies have been done to monitor nanostructures and NPs for
possible toxic and/or carcinogenic effects, as well as to ascertain the mechanisms of
their biotoxicity. Even materials previously considered to be biologically inert
should be retested when their particulate size approaches the nanoscale. In one
study, the effects of particle size distribution, concentration, and agglomeration
have been evaluated. Gold, which is regarded as one of the most chemically inert
elements, can become catalytically active when employed in a nanoparticulate
form. In one study, Ionita et al. [27] reported the air-oxidation of organic substrates
containing active hydrogen atoms (e.g., amines and phosphine oxides) by phos-
phine and amine protected gold NPs, whereas NPs protected by more strongly
bound ligands (for example, thiols) were inactive in these reactions. Overall, it was
concluded that the mechanisms of such reactions could be best studied with EPR
spectroscopy and available spin trapping methods [27]. Moreover, in one study,
Ionita et al. [28] reported characterization of ligand dynamics attached to gold NPs.
As a result, EMR spectra of a series of spin-labeled NPs at variable temperature and
at different frequencies were recorded. Series of gold NPs protected by a monolayer
of organic ligands and labeled them with disulfide functionalized nitroxides. The
chain length of the spin labels and the surrounding ligands was systematically
varied. Authors of this study found that the rotational diffusion rate of the spin
labels increased with the length of the linker connecting the nitroxide unit to the
gold surface.
3.2 Silver NPs
Silver NPs are important because of their extensive applications in integrated cir-
cuits [37], sensors [12], biolabeling [12], filters [12], antimicrobial deodorant fibers
[75], cell electrodes [34], low-cost paper batteries (silver nanowires) (Hu et al.
2009) and antimicrobials [14]. These NPs can be used in dental materials, burn
treatments, coating stainless steel materials, textile fabrics, cosmetics and sunscreen
lotions [19]. Furthermore, silver NPs have been used in different fields of medicine,
various industries, animal husbandry, packaging, accessories, cosmetics, health and
military because of their unique antimicrobial properties [58, 19, 55, 64]. Silver
NPs provide potential antimicrobial effects against infectious organisms, including
Escherichia coli, Bacillus subtilis, Vibria cholera, Pseudomonas aeruginosa,
Syphilis typhus, and S. aureus [14], and they were applied in disinfecting medical
devices and home appliances to water treatment [29, 42, 58, 19]. For instance,
plastic catheters which were coated with silver NPs had significant antimicrobial
effects against E. coli, Enterococcus, S. aureus, C. albicans, Staphylococci, and
P. aeruginosa [55]. These can be very useful for reducing the risk of infectious
complications in patients with indwelling catheters. Furthermore, silver NPs/clay
was reported to have significant antimicrobial effects against dermal pathogens,
including S. aureus, P. aeruginosa, and Streptococcus pyrogens, as well as the
methicillin- and oxacillin-resistant S. aureus [64].
In one EPR study, silver NPs were prepared by the sol-gel technique in amor-
phous SiO2 and crystalline TiO2 matrices [46]. The spin-lattice relaxation
(SLR) times were investigated by pulsed electron paramagnetic resonance
(EPR) spectroscopy in a temperature range between 4 and 300 K. As a result, the
spin echo recoveries were slow enough, and demonstrated a biexponential char-
acter. This investigation demonstrated that for metallic silver NPs in the SiO2
matrix, the temperature dependence of T1 can be described by the relation
(1/T1) / Tn, where 0.4 < n < 1. Contrary to this behavior, the temperature
dependence of T1 has a Raman-type character (1/T1 / T2) for silver NPs in the
TiO2 matrix. Because of the amorphous phase of the SiO2 matrix, the SiO2 samples
showed unusual behaviors.
3.3 Nickel NPs
Nickel NPs show unique properties (e.g., temperature and size dependence proper-
ties), and have potential applications as anode of solid oxide fuel cells or conductive
electrolytic layer of proton exchange membrane fuel cells, magnetic fluid and cata-
lyst, propellant and sintering additive, automotive catalytic converters, and super-
capacitor electrode material. Moreover, these NPs are applied in coatings, plastics,
nanowires, nanofibers and textiles materials [69, 26, 23, 33, 65, 44, 72, 73, 31].
EPR investigations on nickel NPs have been mostly conducted for nickel oxide
and supported nickel, but its application to unsupported nickel NPs is not
well-documented [1]. In one study, EMR in ferromagnetic-metal nanoparticle
systems has been studied. Nickel NPs (approximately 8 nm) were inserted in
polymer films. Interestingly, the EMR signal shifted and broadened, when the
average distance between the NPs was decreased. Theoretical analyses based on
micromagnetics simulation demonstrated that the shift of the signal was traced back
to an increase in the magnetic dipole field in the nanoparticle systems due to the
decrease in interparticle distance. Furthermore, the simulation showed that the
perpendicular component of the dipolar field caused the broadening of the signal.
84 S. Iravani
As a result, this investigation demonstrated that a dynamic analysis of the mag-

netization, with an explicit treatment of the magnetic dipole interactions, is essential
for complete understanding of the EMR and magnetic permeability of interacting
nanoparticle systems [47]. Furthermore, Alonso et al. [1] reported the characteri-
zation of the nickel NPs, utilized in transfer hydrogenation reactions with iso-
propanol as the hydrogen donor, as well as a series of catalytic and kinetic
experiments. Presence of nickel NPs in the zero-valence state had been confirmed
by EMR experiments. In another study, researches on spin dynamics in nickel NPs
(3.8, 11.7, 15 and 21 nm) embedded in an amorphous SiO2 matrix of composition
15/85 (Ni/SiO2) were described using EMR spectroscopy at 9.28 GHz. As a result,
three resonance lines were observed that EMR parameters (linewidth (DH), reso-
nance field (Hr) and intensity (Io)) were measured carefully from 5 to 300 K. Line 1
with temperature-independent DH = 50 Oe and g 2, and intensity varying as 1/
T, was shown to result from paramagnetic defects in the SiO2 matrix. Lines 2 and 3,
with g 2.2 and 8, respectively, and temperature-dependent EMR parameters were
assigned to nickel NPs. While line 2 with g 2.2 was due to the majority of nickel
NPs, the source of line 3 was discussed in terms of two possibilities including large
clusters of blocked nickel NPs, and the inherent part of the composite asymmetric
line made up of lines 2 and 3 predicted by the Raikher–Stepanov (RS) model for
dispersed ferromagnets. The temperature dependence of DH (full width at
half-maximum) of the composite line obtained by integration of the EMR spectra
decreased with the increase in temperature, reaching a minimum near 300 K in
agreement with the RS model. The observed decreasing asymmetry of the com-
posite absorption spectra with increasing temperature was also in agreement with
the predictions of the RS model, therefore providing a satisfactory explanation for
the observed temperature dependence of the EMR spectra of nickel NPs [60].
3.4 Palladium NPs
Because of high surface-to-volume ratio and high surface energy of palladium NPs,
they have applications both in heterogeneous and homogeneous catalysis. In gen-
eral, most important applications of palladium NPs are: (1) Catalysts or electro-
catalysts, (2) Polymer membranes, (3) Sensor design application, (4) Coatings,
plastics, nanofibers and textiles, and (5) Fuel cells [38, 22, 24]. In one ESR analysis,
electronic structures of monodispersed palladium (Pd) NPs with the mean diameters
of 25 Å corresponding to the “magic atom number” of 561 atoms (five-shell
nanoparticle) and smaller than 25 Å (22 and 23 Å) was investigated. Authors of
this study reported that two broad absorption peaks corresponding to DS = 1 and 2
and a sharp one with DS = 1 were observed in their ESR spectra. The broad and
strongest spectrum with DS = 1 might obtained from the spin on the large orbital
moment state of the NPs. The relatively strong second harmonic spectrum with
DS = 2 was characteristic of the NPs, and its low-field shift compared with bulk
palladium implied the existence of the effective field from the orbital moment of the
electron. Moreover, the sharp ESR signal with DS = 1 might be derived from the
NPs which have the electronic structure with one s-state electron outside the closed
electron shell core with the “magic atom number” [67].
3.5 Cerium and Gadolinium Doped Nickel Ferrite NPs
Gadolinium (Gd) NPs can be used in MRI for detection of early stage cancer
(especially breast cancer order) and in order to increase the speed and capacity of
computer memory. These NPs acts as hosts for X-ray cassettes and in scintillator
materials for computer tomography. Furthermore, Gd NPs applied in neutron
capture therapy and for MRI contrast enhancement. NPs of gadolinium oxide can
be used in different areas including fluorescent materials, special optical glass,
electric industry, as additives, catalysts, and dopants, neutron converters,
cathode-ray tubes and UV detectors, high resolution X-ray medical imaging, fer-
roelectric memory, electroluminescent devices, field emission displays and plasma
display panels, luminescence, scintillators and sintering aids, and solid oxide fuel
cells [11, 18, 36, 51]. Cerium (Ce) oxide and free ceria salts have a number of
different industrial roles. Free cerium is used in glass polishing, cracking in pet-
roleum, fertilizers and oxygen sensors. Cerium oxide has found a number of
industrial uses, especially in automotive exhausts where it has been shown to
effectively reduce the amount of pollutants released from exhaust fumes [74, 49].
In one study, the EPR spectra of cerium and gadolinium doped nickel ferrite NPs
were recorded from 120 to 300 K. As a result, doping with cerium and gadolinium
reduced the line width and g value in comparison to that of pure nickel ferrite.
Cerium doped samples have the lowest values of both these parameters at room
temperature. This indicates that cerium doped samples show lowest loss and is
suitable for high frequency devices. EPR spin numbers are reduced while the spin
relaxation time is increased after doping with rare earth ions. Gadolinium doped
samples have higher values of relaxation time and lower spin numbers in com-
parison to that of cerium doped samples [17].
4 Conclusion
In conclusion, characterization of nanostructures and analysis of their properties

using appropriate techniques are important issues in nanotechnology, and therefore
in order to have precise knowledge on the characteristics and properties of
nanostructured materials, it is critical to fabricate monodispersed ones with a per-
fectly controlled size (sample uniformity in terms of size, morphology, internal
structure, and surface chemistry).
86 S. Iravani
Magnetic effects as one of the size-dependent physical properties show great

attractive for a broad range of biomedical and pharmaceutical applications (for
example, cancer diagnosis and therapy). Actually, the EMR in combination with
other experimental techniques provides a powerful tool of studying the physical
properties of magnetic NPs owing to its sensitivity to both the magnetic state and
the morphological characteristics. The EMR in ferromagnetic-metal nanoparticle
systems is not well-understood. Notably, the magnetic behavior and dynamics of
magnetization in nanoparticle systems are dependent both on single-particle prop-
erties (such as magneto-crystalline or shape anisotropies of a particle) and on
interparticle interactions. For magnetically isolated particles with negligible inter-
action, only single-particle properties need to be considered. In contrast, in the case
of strongly interacting particle systems, an explicit treatment of the interactions is
essential.
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Electron Spin Resonance Applied
to Nanosized-Doped Oxides
Cesare Oliva and Marco Scavini
Abstract The electron spin resonance (ESR or EPR) is a spectroscopic technique

particularly suited to investigate solid paramagnetic samples like powders com-
posed of nanosized paramagnetic particles. In this chapter we review ESR inves-
tigations on samples of this kind. The effects of doping oxidic nanoparticles by
metal cations or by nonmetal species are shown in the first paragraph. ESR can
provide information on the energy of the unpaired electron and on the crystal field
around it. When two or more unpaired electrons are present on a paramagnetic
system, their reciprocal interactions supply important information on nature and
distribution of dopant magnetic ions. Moreover, compositional fluctuations at the
nanometric scale can induce the formation of extended clusters of magnetic ions.
Systems of this kind are discussed in the second and third paragraph of the chapter.
Keywords ESR
Nanomaterials
Smart materials Oxides Doping

Superparamagnetism Ferromagnetism
1 Introduction
One of a more interesting parameter measurable by electron spin resonance (ESR or

EPR) is the spin–spin relaxation time T2, which is affected by many important
physical phenomena and is easily evaluated being inversely proportional to the
peak-to-peak width of the first-derivative EPR line. The magnetic interaction
between the unpaired electron S spin and the external magnetic field B is aniso-
tropic in a solid matrix, so that the resonance field depends on a g “tensor,”
C. Oliva (&) M. Scavini

Dipartimento di Chimica dell’Università degli Studi di Milano, Milan, Italy
e-mail: cesare.oliva@unimi.it
C. Oliva M. Scavini
CNR-Istituto Scienza e Tecnologie Molecolari, Milan, Italy
C. Oliva
Accademia Nazionale di Scienze Lettere ed Arti (Modena), Modena, Italy

DOI 10.1007/978-81-322-3655-9_5
92 C. Oliva and M. Scavini
reducing to a vector in a proper reference frame. g provides information on the

unpaired electron energy of a paramagnetic dopant and on the crystal field around
it. These data add to the information obtainable from the a hyperfine electron spin–
nuclear spin coupling constant which also has a tensorial character in the solids and
in general reduces to a vector in the same reference frame which diagonalizes
g. These will be the main topics of the first paragraph of this Chapter. In particular,
the effects of doping diamagnetic nanoparticles of TiO2 by metal cations or by
nonmetal species, or by both these kinds of dopants, will be reported, together with
other interesting examples.
When two or more unpaired electrons are present on the same paramagnetic
system, their reciprocal interaction can be accounted for by adding suitable spin
Hamiltonian contributions, containing both the exchange J (scalar) and the dipolar
D (tensorial) electron spin–electron spin interaction terms. Sometimes, D is con-
veniently represented by its “diagonal” elements D and E as in the case of the Fe3+
(S = 5/2) ions reported in the second paragraph of this Chapter.
A different situation occurs when the paramagnetic particles do not contain
isolated groups of reciprocally interacting unpaired electrons set at fixed reciprocal
distances but, instead, a stochastic distribution of unpaired electrons spread
everywhere and all interacting to each other. In this case, a unique unresolved EPR
feature is detected, which can have a Gaussian or a Lorentzian shape, depending on
the prevailing of the dipolar or of the exchange interactions, respectively. Systems
of this kind are discussed in the paragraphs 2 and 3. In particular, the exchange
phenomena observed with chains formed of paramagnetic metal ions alternated to
oxygen ions will be discussed in the third paragraph. At low temperature these
systems can become diamagnetic or ferromagnetic, with the consequent decrease or
increase of the spectral intensity. In the latter case, a ferromagnetic resonance
(FMR) spectrum is obtained, as those reported in the paragraph 2 with clusters of
Sm2+ and of Gd3+ ions. Nanosized magnetic particles can contain a single FM
domain. Then, the magnetic behavior is more similar to that of a paramagnetic
sample, and a superparamagnetic (SPM) system is obtained, as discussed with
nanosized clusters of Fe or Gd ions.
2 Isolated Paramagnetic Ions Doping Diamagnetic

Nanoparticles
2.1 Doped Titanium Dioxide
TiO2 has been the subject of extensive research due to its relevant photochemical
and photo-physical properties combined with its natural abundance, low cost, and
high chemical- and photo-stability. Applications of nano-crystalline TiO2 particles
are quite numerous and span from photo-catalysis, self-cleaning, and antifogging
devices, to solar energy conversion and photo-electrochemical water splitting [1–3].
Electron Spin Resonance Applied to Nanosized-Doped Oxides 93
However, the TiO2 photo-activity is restricted to the UV region, which repre-

sents only a few percent of the energy of solar spectrum. This limitation is due to
the wide band gap (>3 eV) characterizing this oxide. Several approaches have been
developed to reduce this energy gap, aiming at utilizing also the visible light
(k > 400 nm). Two main different possibilities of doping have been proposed
depending on the final application: either by metal cations or by p-block nonmetal
species (N, C, S, P, etc.).
2.1.1 Doping Titanium Dioxide by Metal Cations
Several metals of the first transition series have been proposed as dopant of TiO2.
However, the enhanced absorption in the visible region has not always been
accompanied by a significant improvement of the material photocatalytic perfor-
mance. Rather, even detrimental effects were observed in some cases [4]. The
doping effects are somehow different in the case of TiO2 doped with high valence
Sb(V) (d10) or Nb(V) (d0) ions, the latter being able to promote both photocatalytic
activity and water splitting processes [5], even combined with other lower valence
transition cations [6]. Furthermore, Nb–TiO2 shows an electronic conductivity
comparable to that of the classic transparent conductive systems (ITO, FTO), while
maintaining optimal visible transparency [7] and is employed for the development
of highly efficient photo-anodes in dye-sensitized solar cells showing a reduced
recombination loss and increased electron injection [8, 9].
A significant band gap reduction has been observed also with Cu-doped TiO2
nanoparticles [10].
The EPR spectroscopy is an important tool to determine the valence state of a
Cu-dopant ion, as only Cu2+ is paramagnetic. Furthermore, the EPR spectrum
provides g values which are very sensitive to the coordination environment of the
host framework, through the equations
k
g== ¼ ge þ 8 ð1Þ
D2
k
g? ¼ ge þ 2 ð2Þ
D1
valid for tetragonally distorted octahedral crystal field, or other analogous equations
reported in literature for other kinds of crystal fields [11]. The EPR spectrum of a
Cu-doped TiO2 is like that reported in Fig. 1. This is composed of two rather
well-resolved spectral regions centered at g// = 2.33 and g⊥ = 2.08, respectively,
further split into four lines, well resolved in the g// region only, due to the hyperfine
coupling between unpaired electron and Cu nucleus (which has spin I = 3/2). The
spectrum of Fig. 1 is perfectly compatible with Eqs. (1) and (2), i.e., with a Cu2+
ion in an octahedral (tetragonally distorted) field as that of Fig. 2b. Therefore, the
Cu2+ is substituted for a Ti4+ on the lattice site, being placed in the octahedral
Fig. 1 Room temperature

EPR spectrum of Cu-2 %-
doped TiO2 nanoparticles.
Adapted from Ref. [10]
coordination of TiO2. Each of these substitutions was generating an oxygen

vacancy (Fig. 2a) and was creating a distortion of the octahedral field. Furthermore,
the spectral lines are rather broad, suggesting that the Cu2+ ions are dipolarly
interacting to each other. This could be associated with formation of copper-based
nano-clusters, since bulk copper clusters were not noticed in the diffraction patterns.
Therefore, charge transitions from the valence band of TiO2 to the Cu2+
nano-clusters attached to TiO2 were hypothesized. These electron transitions would
add to the d–d ones of the Cu2+ ions present in the crystalline environment of TiO2.
2.1.2 Doping Titanium Oxide by Nonmetal Species
N has been probably the more deeply investigated among the nonmetal dopants of
TiO2 and many EPR studies have been published on this subject [3, 12–30].
The chemical nature of the TiO2-doping nitrogen species has been discussed by
Livraghi et al. [16] and by Di Valentin et al. [17] and represented as in Figs. 3 and 4.
Nitrogen atoms can be substitutional of an oxygen atom (a) or belonging to an
interstitial NO molecule (b) (Fig. 3). In both these cases N doping creates localized
intra-gap electronic levels (Fig. 4). Therefore, the “collective” Nb symbol was
proposed [19] for these bulk nitrogen species, further labeled by “i” or by “s” in the
cases in which they are unequivocally “interstial” or “substitutional.” It has been
reported that different sample preparation procedures and N sources lead to samples
characterized by different activities and durabilities [3, 18, 29].
This matter has been reviewed in part by Nick Serpone [20] and by Emeline
et al. [24], who added some interesting considerations on possible light-absorbing
mechanisms, competitive to that above mentioned for the N doping (Fig. 5d) but,
instead, attributable to the formation of Ti3+ and to color centers F+ (Fig. 5e), not
able to excite electrons up to the conduction band of the sample. F+ centers could be
formed through the process
Fig. 2 a Distortion of the TiO6 octahedra on doping Cu2+ for Ti4+ in a lattice site. An oxygen
vacancy VO (white ball) is generated nearby Cu2+. Adapted from Ref. [10]. b The 3d9 electron
energy levels of Cu2+ in an octahedral (tetragonally distorted) field. The reported example is the
extreme one of square planar fields, in which dz 2 is at a very low-energy value. All the represented
levels are doubly occupied, with the exception of dx 2 y 2, which is singly occupied
Fig. 3 N (a) and ON (b), substitutionally and interstitially doping TiO2. Reprinted with
permission from Ref. [17]. Copyright (2005) American Chemical Society
Fig. 4 Intra-gap electron levels introduced by N (a) and by ON (b), respectively, substitutionally
and interstitially doping TiO2. Reprinted with permission from Ref. [24]
Fig. 5 Various schemes illustrating the possible changes that might occur to the electron energy
band gap of anatase TiO2 on doping with various nonmetals: (a) band gap of pristine TiO2; (b)
doped TiO2 with localized dopant levels near the VB and the CB; (c) band gap narrowing resulting
from broadening of the VB; (d) localized dopant levels and electronic transitions to the CB; and
(e) electronic transitions from localized levels near the VB to their corresponding excited states for
Ti3+ and F+ centers. Reprinted with permission from Ref. [20]. Copyright (2006) American
Chemical Society
Fig. 6 EPR spectra of N–

TiO2. Initial N/Ti atomic
ratio: 0.10, experimental (1);
0.10, simulated with
gx = 2.0066; gy = 2.0054;
gz = 0 2.0040; Ax ≅ Ay ≅ 0;
Az ≅ 32.2 G (2); 0.20
experimental (3); difference
track 3 minus track 2 (4),
resulting in a
Lorentzian-shaped line
attributed to F+ defects.
Adapted with permission
from Ref. [26]
VO þ 1e ! F þ ð3Þ
in which VO indicates an electron pair-deficient oxygen vacancy (sometimes

indicated also as F++ center) becoming F+ when trapping an electron.
The EPR line of the paramagnetic F+ defects is observable even at room tem-
perature at enough great amounts of N doping, as shown in Fig. 6 (line F).
The concentration of the F+ defects seems connected to the loss of activity
occurring during sample irradiation. The intensity of the F line increases also with
the aging of the sample and decreases with its regeneration by oxidation [26].
Preparation procedures and N sources control also the material microstructure
[31], which in turn determines the concentration and nature of both extrinsic and
intrinsic point defects. As for the latter, it has been hypothesized that a F+ center
might provide its electron to a neighboring Ti4+ ion to reduce it to Ti3+ and
determine the formation of new gap states just below the conduction band (CB) [15,
24, 32].
2.1.3 Co-doping Titanium Oxide by Nonmetal and Metal Species
Donor mid-gap states are usually quite deep within the gap, and they may be
responsible for a faster electron–hole recombination time [33]. Compensating
titania with nonmetals and transition metals is a highly promising way to obtain
second-generation photo-catalysts, where the apparent band gap decrease occurs
without increasing the electron–hole recombination rate [34–38]. Marquez studied
the structural and electronic properties of W–N codoped titania observing enhanced
photocatalytic properties [39]. Significant results have been reported also in the case
of V–N and Fe–N titania systems [40, 41].
Fig. 7 Representing
substitutional Nb providing
an electron to substitutional
N. Reprinted with permission
from Ref. [30]. Copyright
(2014) American Chemical
Society
The co-doping of titania by N–Nb species has been recently discussed in a

theoretical study with respect to its photo-electrochemical properties [33].
On the experimental side, Breault and Bartlett [42, 43] discussed heavily doped
TiO2 systems. Keller et al. [44] prepared N–Nb codoped titania nanotube arrays
which show relevant visible light photo-electrochemical activity due to contents up
to 15 % of Nb in the near-surface region. Lim et al. [45] carried out a work relative
to a conventionally N–Nb codoped TiO2 system, finding synergistic photocatalytic
effects both for oxidation and for reduction of water pollutants when using
SG-prepared samples with 0.001 < Nb/Ti molar ratio <0.03.
A possible electronic mechanism has been proposed [30] to explain this
evidence.
Indeed, it has been reported that substitutional Nb in anatase can transfer an
electron to the low-energy valence state of the co-dopant N, located near the
valence band (Fig. 7).
This intrinsic charge compensation mechanism was substantiated by EPR, which
showed a reduced EPR spectral intensity of Nb (labeled by * in Fig. 8) in the
presence of Nb co-dopant.
However, we must outline that no quantitative evaluation of the amount of Nb is
allowed by these EPR results. On the other hand, previous studies have shown that
the actual nitrogen content in TiO2 lattice is generally much lower than the nominal
amount [26, 46]. Therefore, nitrogen bulk quantification remains a quite chal-
lenging task [31]. Bartlett and coauthors [42] reported the absence of any Ti3+ in
XPS measurements, whereas the C to E lines of Fig. 8 were attributed to this
species. The last attribution is also supported by the fact that these features cannot
be detected at room temperature. Indeed, De Trizio et al. [47] reported that Ti3+
signals cannot be observed above 100 K due to the occurrence of carrier
detrapping.
Fig. 8 EPR spectra collected at 77 K. (*) Nb (gx = 2.066, gy = 2.0054, gz = 2.004, Ax ≅ Ay ≅ 0,
Az ≅ 32.2 G); A, B (gx = 2.0082, gy = 2.0118, gz = 2.0285) might be related to paramagnetic
radical oxygen species, while the lines C (g1 = 1.98), D (g2 = 1.93), and E (g3 = 1.96) can be
attributed to Ti3+ in different environments. The F line could be attributed to F+ color centers. A to
F lines are not detectable at room temperature. Adapted with permission from Ref. [30]. Copyright
(2014) American Chemical Society
However, these features decrease or completely disappear in all the N–Nb

codoped samples, supporting the occurrence of charge compensation between Nb
(acting as electron donor), involving also Nb (which would become diamagnetic
Nb ), as predicted by calculations [30, 33].
At last, only the A and B lines due to oxygen radical and the C to E lines due to
Ti3+ species were appreciable in the Nb-doped sample at 77 K (private commu-
nication), in agreement with the presence of Ti3+ species in the bulk of these
systems reported elsewhere [30, 47], as well as with calculations [30, 33].
2.2 Surface Oxygen Species Adsorbed on K-Doped SrTiO3–d
Transition metal oxide mixtures with perovskite-like structure are well known as
catalysts for the flameless combustion (CFC) of methane. Thermal stability and
high surface area of these materials can be achieved by preparing them as nanosized
particles, calcined at very high temperature [54]. Nanosized SrTi03±d particles
prepared by flame hydrolysis (FH) and partially substituted with potassium
(KFH) or with gadolinium (GFH) for strontium have been investigated [55, 56].
A different ionic charge of potassium (1+) and gadolinium (3+) with respect to
strontium (2+) was inducing a nonstoichiometric oxygen composition, which could
affect the catalytic activity. Only the former case will be taken into consideration in
this paragraph.
The X-band EPR spectrum of the Sr0.9K0.1TiO3±d (KFH) sample was detected
both with X-band and with Q-band EPR. It was composed of a very narrow
Lorentzian-shaped line at g ≅ 2.008, with a temperature-independent peak-to-peak
width DHpp of 1.6 G (X-band) and of 3.4 G (Q-band) (Fig. 9).
Fig. 9 X-band (upper) and

Q-band (lower) EPR spectra
of KFH sample, recorded at
290 K. The thinner lines are
Lorentzian-shaped
simulations. Reprinted with
permission from Ref. [55]
The partial substitution of K+ for Sr2+ could be counterbalanced by a partial

oxidation of Ti3+ to Ti4+. Indeed, it was the case with the Sr0.9K0.1TiO3±d
(KFH) sample. The single line at g ≅ 2.008 was then attributed to Ti4+/O 3 in which
a Ti4+ ion would interact with an ozonide radical, as already reported in analogous
literature cases [57–63]. Surface O
3 is characterized by high mobility (“suprafacial”
a oxygen) showing a “motional narrowed” Lorentzian-shaped spectrum. An
exchange frequency exceeding 17 MHz, provided by the thermal energy of ca.
10−21 J at 100 K, was evaluated in this case to mix the spectral anisotropies and
produce a Lorentzian-shaped line.
Furthermore, this line was disappearing after catalytic use further supporting its
attribution to surface species involved in the catalytic reaction, whereas the bulk
species formed when Gd3+ ion was doping SrTiO3±d (see below) seemed not much
involved in the CFC of methane, even causing a worsening of the catalytic activity.
By concluding, it was reported that the partial substitution of K+ for Sr2+ in
SrTiO3 caused an improvement of the catalytic activity, though only at T < 550 °C.
Indeed, the oxidation of Ti3+ to Ti4+, forced by the partial substitution with the
single valence K+ ion, was favoring the formation of the oxidant species Ti4+/O3−.
The O3− ions were almost free to move on the KFH surface (“supra-facial” oxygen
species) as indicated by their narrowed Lorentzian-shaped EPR line.
2.3 The Strange Case of Doped Nanoparticles of Cuprates
Cu2+ is a regular component of La1−x MxCuO4 (M-doped) cuprates. Therefore, it is

surprising that in many cases these systems show the EPR spectrum typical of
diluted Cu2+, i.e., with a resolved Zeeman and hyperfine structure, instead of dis-
playing a single EMR band due to spin–spin coupling among adjacent Cu2+ ions (as
shown later in the next paragraph for few cases of doped cuprates), or even showing
no-EPR spectrum at all, as expected for antiferromagnetic systems, due to adjacent
Cu2+ ions interacting with each other by superexchange through O bridges. EPR
patterns like that above shown in Fig. 1 would arise only from Cu2+ ions which are
Fig. 10 The EPR spectrum

of fresh La1.8Sm0.2CuO4
detected at 120 K. g// = 2.35;
g⊥ = 2.06; A// = 144 G.
Reprinted with permission
from Ref. [50]
isolated. Indeed, this was the case of the EPR spectrum which was accompanying
the formation of solid solutions of La2O3 in CeO2 (molar ratio 1:2) to which CuO
was added (La:Cu ratio 10:1) [48] An analogous pattern was detected also with
(CeO2)1−y(La2CuO4)y (y = 0.25; 0.43) [49]. In both those cases it has been
demonstrated that the EPR spectrum was coming from Cu2+ ions inserted into the
crystal framework.
A similar situation was observed also with 20–40 nm nanoparticles of La1.8
M0.2CuO4 (M = Pr3+, Sm3+, or Tb3+ [50] (Fig. 10).
Unfortunately, in the last case the Cu2+ EPR spectra were characterized by poor
intensity and resolution, so that they were not able to report any significant dif-
ference between distortions occurring in the Cu2+ neighbors because of the different
ionic radii of the Pr3+, Sm3+, or Tb3+ substituting for La3+.
Pr3+, Sm3+, and Tb3+ are paramagnetic ions [51]. However, their spin–lattice
relaxation rate is generally so high that their contribution to the EPR pattern is not
expected at temperature higher than 20 K. Indeed, only lanthanide ions in the
S-state (L = 0; 4f7), i.e., Eu2+, Gd3+, and Tb4+, can show an EPR spectrum at higher
temperature [52, 53]. However, no Tb4+ was noticed in the La1.8 Tb0.2CuO4,
indicating that Tb3+ only was present in it.
A broad band was added to the EPR spectrum shown in Fig. 10. This pattern
was not attributable to isolated paramagnetic ions but, instead, to the formation of
ferromagnetic domains. Therefore, it will be discussed in the next paragraph.
3 Nanosized-Doped Particle Systems and Collective

Phenomena
3.1 Ferromagnetic Domains of Sm2+ Ions in Nanosized

Sm-Doped Particles
When analyzing the EPR spectrum of La1.8Sm0.2CuO4 in a magnetic field range

wider than that of Fig. 10, a new very intense feature adds to that there shown. This
Fig. 11 The
temperature-dependent FM
band observed with
La1.8Sm0.2CuO4 attributed to
ferromagnetic resonance.
from Ref. [50]
broad band, labeled by FM in Fig. 11, is not attributable to Sm3+ ions. Furthermore,
it has been reported [50] that it undergoes hysteresis effect, so that it is not attri-
butable to any EPR resonance at all but, instead, to ferromagnetic resonance
(FMR) [64].
This means that FM domains form in this sample, generating an internal field Bi
and, therefore, a spectral shift toward lower fields [65]. Such systems should not be
distributed uniformly throughout the bulk, as suggested by the dependence of their
spectrum on sample orientation. FM clusters have been reported also with other
Sm-containing perovskites, namely with Sm0.2Ca0.8Mn1−xRuxO3 [66], and attrib-
uted to the formation of “Bound Magnetic Polarons” (BMP), also indicated as
“Ferrons” [67]. These systems should form in the presence of electrons concen-
trated enough to form local FM “droplets,” growing up in the vicinity of electron
donors, like Sm2+ ions. The last would be created through reactions like
10 La1:8 Sm0:2 CuO4 ! 9 La2 O3 þ 10 CuO þ Sm2 O3 ð4Þ
1
Sm32 þ O2
3 ! 2 Sm
2 þ 2
O þ O2 ð5Þ
2
Sm2+ are diamagnetic (J = 0) 4f6 ions in their fundamental state. However, the
energy necessary to excite one of their electrons so to obtain a J = 1 state is less
than 300 cm−1, i.e., comparable with the room temperature energy (*200 cm−1).
This value is very low if compared to that required by the other rare-earth ions,
which generally amounts to some thousands cm−1. This facility to obtain parallel
electron spins with Sm2+ ions can account for the formation of ferromagnetic
systems when some ions of this kind cluster together.
The FM bands were no more detected after sample calcination at 800 °C. On the
other hand, XRD patterns revealed that La2O3 was no more present in these cuprate
samples after such a treatment. This was in line with the above-reported attribution
of the FM band to systems forming only when reactions (4) and (5) occur.
3.2 Superparamagnetic Nanoparticles with Fe-Doped

Zeolites and Silicalites
3.2.1 Isolated Fe3+ Ions and Their Clusters in Fe-Doped Zeolites

and Silicalites
Iron-containing zeolites with MFI structure have attracted considerable interest

since 1988, when three groups of researchers [68–70] independently found that
these materials are effective catalysts in the one-step hydroxylation of benzene to
phenol by N2O, a process much less expensive and less troublesome than some
previously adopted ones [71]. Fe(III) is a fundamental constituent of the catalyst
[71–74], so that these systems have been widely investigated by EPR spectroscopy
[72, 73, 75–93].
Their EPR spectrum is due to the high-spin (S = 5/2) Fe(III) ions. It can be
described by the Hamiltonian

^ ¼ gb S B0 þ D S2z 1 SðS þ 1Þ þ E S2x S2y
H ð6Þ
3
where g ≅ ge since high-spin Fe(III) is a 6S ion, B0 is the static magnetic field

vector, D = 3 Dz/2, E = (Dx − Dy)/2, and Di (i = x, y, z) are the principal values of
the zero-field splitting (ZFS) interaction, which are ordered so that |D| |E/3| and
DE 0 [94]. For future convenience we also define the dimensionless parameter
k = 3 |E/D|, 0 k 1.
The ZFS interactions for a high-spin Fe3+ d5 ion are sensitive to its environment
because of their dependence on the ligand field [95]. The X-band EPR spectrum of
iron-doped zeolites and silicalites usually comprises several lines. A group of them is
observed at low resonance field, i.e., at geff 4 with a prominent peak at geff = 4.3
and several other ones down to geff ≅ 9. Two major broad lines are found at
geff ≅ 2.0 and 2.3, the two peaks being largely superimposed. Other minor features
are observed, including a peak very close to zero field (geff 10). Spectra of this
kind obtained with Fe–silicalite crystals of 0.5–1.0 lm [96] are reported in Fig. 12.
The conventional attribution of the lines of Fig. 12 was as follows [73, 75, 78, 80,
84–86, 88, 90–92]: the geff 4 group was attributed to isolated Fe(III) ions in the
zeolitic framework, undergoing various degrees of distortion and the geff ≅ 2.0 and
2.3 lines were attributed to oxidic iron clusters and particles where Fe(III) ions were
strongly interacting with each other (earlier interpretations [73, 75, 77] attributed the
geff ≅ 2.0 to extra-framework ions in octahedral symmetry). However, this inter-
pretation often was not in agreement with data from other techniques [79].
Therefore, it was later assumed [76, 77, 79, 89] that both framework and
extra-framework Fe(III), either as isolated ions or as aggregates (oligo-nuclear
clusters, oxidic particles), were contributing to each of the above spectral features.
Indeed, the ZFS interactions of Fe(III) ions in MFI zeolitic catalysts are largely
inhomogeneous in nature. Therefore, good spectral simulations were obtained for
Fig. 12 EPR spectra of

Fe-doped silicalite, detected at
110, 150, 200, 295 K ((a)–
(d)). Adapted with permission
from Ref. [96]
the EPR spectra of Fe(III)-doped MFI Zeolites by adopting a distribution of the

ZFS interaction parameters [93, 97, 98]. Many different intra- and extra-lattice sites
are possible for Fe(III) ions. The latter include both sites within the channels and on
the external surface of the crystallites, either as isolated ions or as oxidic aggregates.
Aiming at a better evaluation of the contributions of Fe(III) ions in extra-lattice
sites, these samples underwent a steaming process, i.e., a treatment in a flow of
75 mol% steam and 25 mol% nitrogen at 773 K for 6 h. Indeed, after this treatment
of the Fe-doped silicalite and of the MFI Zeolite samples, new FMR features were
observed at magnetic field values lower than ca. 2000 G and attributed to oxidic
aggregates [96, 99] (see, for the former sample, Fig. 13). These lines were further
affected by the following calcination process (see Fig. 14).
The g ≅ 2 line (detected at a magnetic field of ca. 3000 G) will be discussed
below.
3.2.2 Superparamagnetism of Nanosized Fe-Containing Clusters
The above-mentioned steaming process was setting a large fraction of iron into
extra-lattice sites. Those ions were organizing into nanometric superparamagnetic
particles. Indeed, the g ≅ 2 signal of Figs. 13 and 14 was approximately Lorentzian
at room temperature, but it became broader and more asymmetric with decreasing
temperature. This behavior is typical of single-domain superparamagnetic particles
[100], as reported for silicate glasses containing nanosized clusters of magnetite
[101], for c-Fe2O3 [102], for iron-doped borate glasses [103], and for nanosized
perovskites [104]. Superparamagnetic particles are single-domain nanosized mag-
netic systems. They form when the single-domain state is preferred to a
multi-domain one, because the energy required to the formation of the former is

Fe-doped silicalite after
steaming. Detection
temperature 110, 150, 200,
295 K ((a)–(d)). Narrow lines
in (a) indicate the presence of
physisorbed molecular O2.
from Ref. [96]

sample steaming followed by
recalcining. Detection
temperature 110, 150, 200,
295 K ((a)–(d)). Adapted
with permission from
Ref. [96]
smaller than that which would be needed to form the latter with its domain walls.
Such particles can exhibit superparamagnetic behavior above a certain critical
temperature, below which they are in the normal (anti)ferromagnetic state [100].
The resonance condition for an isotropic superparamagnet is
xc ¼ c B ð7Þ
where c is the magnetogyric ratio and xc 2pmc. On the other hand, for aniso-
tropic superparamagnetic particles, assuming that the anisotropy energy is smaller
than the coupling to the external field, the resonance condition is
xc ¼ c½B þ Ba P2 ½cosðwÞL2 ðnÞ=LðnÞ ð8Þ
where Ba is the anisotropic magnetic field, w is the angle between the anisotropy
axis and the external field, P2 is the second degree Legendre polynomial,
n = MnrVBa/kT, Mnr is the non-relaxing magnetization, V is the particle volume, L
(n) is the Langevin function, and L2(n) = 1 − 3 L(n). Equation (8) shows that
thermal fluctuations lead to a decrease of the effective anisotropy field (in addition
to any actual temperature dependence of the anisotropy constant), which can be
written as
Ba;eff ¼ Ba L2 ðnÞ=LðnÞ ð9Þ
It follows, from asymptotic behavior for n < 1, that Ba,eff decreases with
increasing temperature, being Ba,eff / n / 1/T. Therefore, from Eq. (8) the effect
of increasing temperature on EPR spectra is that the resonance field approaches the
isotropic value xc = cB. For an actual fine-particle system, with distribution of
particle volume and easy-axis orientation, the dependence of the resonance con-
dition upon the direction of the anisotropy axes results in an asymmetric lineshape
at low temperature, accompanied by a shift of the resonant field. With increasing
temperature, the linewidth reduces and the line tends to a Lorentzian shape with
isotropic resonance field Br = xc/c, as thermal fluctuations average to zero the
anisotropy field. With decreasing temperature, the linewidth increases and the shape
becomes more and more distorted, whereas the narrow line tends to vanish.
The narrow superparamagnetic line at g ≅ 2 is exhibited by those particles for
which ssp < sL. ssp is the superparamagnetic relaxation time, due to the thermal
fluctuations of the direction of magnetic moment in single-domain particles smaller
than a “critical size.” sL is the Larmor precession time in the magnetic resonance
field Ho. For these very small particles, when the anisotropy energy is much smaller
than kT, the following relations hold [105]:
ssp ffi MS V=ðc0 kB TÞ c0 ¼ 2p=ðsL H0 Þ ð10Þ
where MS is the saturation magnetisation (expressed in A m−1), V is the volume of

the particle undergoing the fast relaxation process, c0 is the gyromagnetic ratio, and
kB is the Boltzmann’s constant. The magnetic anisotropies are “motionally” aver-
aged out at temperature high enough to make ssp < sL. In this case, the EPR line
narrows by the temperature-dependent factor:
f ffi ssp =sL ffi Ms V H0 =ð2p kB TÞ ð11Þ

In real systems a distribution of particles volume occurs around a mean value

<V>, the particle diameter ranging between that of a single-domain particle (<15–
20 nm) and that of a superparamagnetic assembly of atoms (≅1 nm).
A co-existence of ferrimagnetic and superparamagnetic systems is expected [106],
the former causing a broader EPR feature, and the latter a motionally narrowed one.
The equilibrium between these two species depends also on the sample preparation
method [107]. The peak-to-peak linewidth DHpp of the narrowed line decreases at
high temperature, following Eq. (11). Therefore, in the regime of “motional” nar-
rowing, the EPR linewidth should be expressed by
D H ¼ D Ho þ DHo c V=T ð12Þ
where DHo is the linewidth for T ! ∞. In Eq. (12) DH = Hx,y − Hz, where
Hi = hm/gilB (i = x, y or z), h is the Planck’s constant, m is the instrument fre-
quency, and lB is the Bohr’s magneton and
c ¼ MS Ho =ð2p lo kB Þ ð13Þ
where MS is the saturation magnetisation value, Ho is the resonance magnetic field

(in tesla) and lo = 4p 10−7 (weber A−1m−1) is the vacuum permeability. lo must be
introduced if MS is expressed in tesla (as usual) instead of in (A m−1), as it should be.
For example, a value MS = 0.048 T is reported in literature [108] for Fe3O4.
Equation (12) can be compared with the experimentally determined straight line
D H ¼ a þ b=T ð14Þ
leading to
V ¼ b=ðacÞ ð15Þ
and hence to a qualitative evaluation of the particle diameter d.

In the above-mentioned examples, extra-framework nanosized superparamag-
netic particles were forming upon micro-sized Fe-doped zeolites.
Extra-framework superparamagnetic particles of similar kind form also with ca.
20-nm nanosized Fe-doped silicalites [109]. An even more detailed analysis was
carried out in that case on the nature of these superparamagnetic particles, by
comparing EPR to temperature-programmed reduction (TPR) results. After sample
steaming, two different kinds of extra-framework Fe3+ ions were singled out by the
latter technique. One of them (reducing to Fe2+ at 643 K) was attributed Fe2O3
entities, whereas the latter (reducing to Fe2+ at 823 K) was attributed to
charge-compensating Fe3+ ions.
The EPR spectra were collected before and after reducing the sample in a
40 cm3/min stream of 10 % H2 in He, while increasing temperature by 10 K/min
up to either 673 or 873 K, then maintained for 5 min, before cooling down to room
temperature in pure flowing He.

steaming: a as prepared,
b after reduction up to 673 K,
c after reduction up to 873 K.
(The inset shows an EPR line
attributed to traces of organic
radicals.) Reprinted with

steaming: a as prepared, as in
Fig. 15a, b after reduction up
to 673 K as in Fig. 15b, but
reported to the same intensity
of (a). c Difference between
(b) and (a). d Computer
simulation of spectrum in 16
(c), with g = 2.04,
peak-to-peak linewidth
=110 G, Lorentzian shape.
from Ref. [109]
The spectrum of the original, unreduced, sample was formed, as expected, of

two main features, at g > 4 and at g ≅ 2, respectively (Fig. 15a). After reduction of
the catalyst up to 673 K, the intensity of the whole pattern decreased by ca. 80 %
and a better resolution was obtained in the low-field region, which resulted com-
posed of two main lines, at g = 8.2 and 5.56, respectively (Fig. 15b). The spectral
intensity further decreased (by ca. 92 %, with respect to the unreduced sample)
after reduction of the sample up to 873 K (Fig. 15c).
Then, the authors compared the shape of the spectral profile before and after TPR,
by renormalizing the spectra of Fig. 15a, b, as shown in Fig. 16a, b, and subtracting
the former from the latter. The spectrum of Fig. 16c was so obtained, which resulted
a 110 G broad Lorentzian line, centered at g ≅ 2 (Fig. 16d). After reduction up to
873 K this Lorentzian-shaped line disappeared, indicating that it was due to species
no more present at T > 823 K. Therefore, it was possible to conclude that the
superparamagnetic particles were due to the extra-framework Fe2O3 entities in

which the Fe3+ ions were reducing to Fe2+ at 643 K, as established by TPR.
3.3 Gd3+ Nanosized Ferromagnetic and Superparamagnetic

Clusters in Gd-Doped SrTiO3–d
Nanosized SrTi03±d particles prepared by flame hydrolysis (FH) and partially

substituted with gadolinium for strontium (GFH samples) have been investigated
[54, 55]. The different ionic charges of gadolinium (3+) with respect to strontium
(2+) were inducing a nonstoichiometric composition, which could affect the
catalytic activity.
The X-band EPR spectrum of the (GFH) Sr0.9Gd0.1TiO3±d sample showed a
high-intensity, nearly symmetric band at room temperature, typical of ferromagnetic
(FM) resonance of Gd3+ ion domains (Fig. 17) which was about 100 times broader
than the EPR narrow line observed with K+-doped samples (see paragraph. 1.2).
With decreasing temperature, this pattern broadened and its intensity increased,
though less than how expected on the base of the Curie’s law, indicating that the
single ions are indeed reciprocally interacted in a ferromagnetic way. Furthermore,
at lower temperature the presence of bumps like B on the left part of the spectrum
was becoming more evident (Fig. 18), indicating the presence of internal magnetic
fields in FM systems with positive axial anisotropy [110].
The EPR spectrum of this sample was even more symmetric when analyzed at
the Q microwave band and, in that case, it was almost perfectly fitting the sum of
two Lorentzian lines at g = 1.991 and 2.020, width of 604 G and of 1600 G,
respectively, broadening with decreasing temperature and with integral area ratio of
Fig. 17 X-band (thinner track) and Q-band EPR room temperature spectra of the GFH sample.
L1 and L2 (dotted tracks) are two Lorentzian-shaped lines simulating the Q-band EPR line. Two
different microwave frequencies are employed to detect the X-band and Q-band spectra, so that
they have been both shifted to zero to be compared to each other. Reprinted with permission from
Ref. [55]
Fig. 18 X-band EPR spectra of GFH sample, recorded at 140 K (thicker track) and 290 K (dotted
track, multiplication factor 1.75). Reprinted with permission from Ref. [55]
4:1 at room temperature (Fig. 17) and of 1.5:1 at 100 K. The presence of bumps
like B in the X-band spectrum, and not in the Q-band one, was further confirming
their attribution to FM systems with magnetic anisotropy DHa |H// – H⊥|. Indeed,
the following equation holds [110]:
D Ha ¼ a0 f½mQ D Hpp ðXÞ mX D Hpp ðQÞ=ðmQ mX Þg ð16Þ
where a′ = 1.732 for Lorentzian shape. Since DHa 0, Eq. (16) requires
DHpp(X) 1/3 DHpp(Q), as in this case, where DHpp(X) > DHpp(Q). However,
no reliable quantitative evaluation of the magnetic anisotropy DHa(GFH) can be
obtained, due to the low spectral resolution (Fig. 17).
Different preparation methods were producing particles of different sizes, so
markedly affecting their EPR spectra. Indeed, the above-mentioned GFH sample
(prepared by FH procedure) was 56 nm in diameter, whereas a GSG sample with
the same chemical composition but prepared by sol–gel procedure was by far
smaller having a mean diameter of 24 nm only.
As a consequence, both X-band and Q-band EPR spectra of the latter sample
were composed, at room temperature, of a single nearly symmetric feature at
g = 1.991, with a peak-to-peak width of ca. 40 G (Fig. 19), i.e., less than 1/10 that
observed with the former (Fig. 17).
Furthermore, with decreasing temperature the intensity of these GSG spectra
decreased a bit, instead of increasing as expected on the base of the Curie’s law,
while a second broader overlapping feature was appearing both in the Q-band
(Fig. 20) and in the X-band spectra.
This behavior was in accordance with the particle nanometric size of the
(GSG) Sr0.9Gd0.1TiO3±d sample. In fact, it has been reported [110] that with small
(single-domain) particles (as in this case) at high temperature, when kT overcomes
the small anisotropy energy of these particles, the FM resonance bands narrow and
merge into a Lorentzian-shaped (Superparamagnetic, SPM) line like those shown in
Fig. 19 and similar to the symmetric narrow feature at RT shown in Fig. 20. At
Fig. 19 Room temperature Q-band (thicker track) and X-band (dotted track) EPR spectra of GSG
sample. Reprinted with permission from Ref. [55]
Fig. 20 Q-band EPR spectra

of GSG sample, recorded at
two different temperatures.
from Ref. [55]
intermediate temperatures an intermediate regime must occur in these systems, in

which a “two-line pattern” as that of GSG at 100 K (Fig. 20) appears, formed of a
broad feature overlapping a narrower one [111–114]. The relative intensity of these
two spectral contributions depends on particle size and shape distribution function,
as well as on the magnitude of the magnetic anisotropy.
3.4 Polarons and Polaritons Propagation with Nanosized

Particles of Gd-Doped CeO2
Ce4+ ions in CeO2 are diamagnetic, so that no-EPR spectrum is expected from this
material, when undoped. In principle, oxygen-deficient CeO2 could contain some
Ce3+ ions. However, the last has an unpaired 4f electron with a short spin–lattice
relaxation time [115–121] so that its EPR spectrum could be expected at very low
temperature only. By contrast, nano-structured fluoritic Ce1−xGdxO(4−x)/2 have been
intensively studied, also by EPR, as solid electrolytes for solid oxide fuel cells
Fig. 21 EPR spectra of “as prepared” Ce1−xGdxO(4−x)/2. Left, T = 110 K ((a) x = 0.10;
(b) x = 0.20): keeping constant T, broader lines are detected at higher x values. Right, x = 0.20
((a) T = 110 K; (b) T = 380 K): keeping constant x, more intense lines are detected at lower T
values. Adapted with permission from Ref. [126]
(SOFCs) [122], being ion conductors even better and able to operate at lower (500–
700 °C) temperatures [123] than conventional yttria-stabilized zirconia. The
investigated nanosized Ce1−xGdxO(4−x)/2 samples were characterized by a very high
specific surface area, so that their thermodynamics and defect equilibria were quite
different from that of bulk materials [124, 125].
Some selected EPR spectra of these systems [126] are shown in Fig. 21. All of
them were composed of a single line at g ≅ 2.02. In any case, the spectral shape
was only approximately Lorentzian, because their left part was always a bit broader
than the right one. No successful simulation was obtained for them, though the
bump on their left side could have the same ferromagnetic origin as that observed
with a Sr0.9Gd0.1TiO3±d sample above discussed in the section devoted to
Gd-doped titanates (see Refs. [55, 127]).
At T = 110 K the spectral intensity I was 1.5 times larger with the x = 0.10 than
with the x = 0.20 sample (Fig. 21, left). Such a different spectral intensity was
connected to a different DHpp peak-to-peak linewidth which was broader at higher
x values, due to a shorter spin–spin relaxation time T2 caused by the stronger
interaction occurring among more concentrated Gd3+ ions. By contrast, the EPR
linewidth and shape were independent on the temperature (Fig. 21, right),
excluding the presence of temperature-dependent phenomena affecting T2.
The Curie’s law would hold for a system of non-interacting paramagnetic ions.
Therefore, only in that case the magnetic susceptivity v (and so the spectral
intensity I(T)) would vary with temperature following the trend:
I ðT Þ T ¼ I110 K ð17Þ
where I110 K indicates a spectral intensity kept as reference, which in [68] was that
measured at the lowest (110 K) temperature. Deviations from the Curie law could
be described by
I ðT Þ T ¼ I110 K T a ð18Þ
Values of a greater than 0 were attributed to magnetic interactions among

paramagnetic ions. In this case, I(T) T would increase with T [128].
A decrease of I(T) T versus T (i.e., a < 0) was attributed to thermally activated
electronic conductivity r due to small polarons, hopping between ions in different
valence states [129, 130], i.e., to conduction electrons propagating in a percolative
way between localized states randomly distributed in energy and position [131]. In
fact, any electronic contribution to conductivity would cause a skin depth on the
surface of a sample undergoing a microwave magnetic field, as when detecting an
EPR spectrum. In a percolative regime, r increases with increasing temperature.
Therefore, a thinner skin depth would arise at higher temperature, causing an EPR
signal intensity lower than expected on the basis of the Curie law only, so that the
product I(T) T would decrease with increasing T, instead of being constant as with
Eq. (17). This is the meaning of the a a < 0 value measured instead of a = 0
observed with the “as prepared” x = 0.10 sample, and perhaps also after its oxi-
dation at 473 K.
This percolative conduction regime can be accounted for by the local structural
disorder introduced by the Gadolinium doping [132, 133] and by the oxygen
vacancies created by the gas–solid equilibrium occurring with the sample. This
deviation from Curie’s law reduced or disappeared at all after thermal treatment of
the x = 0.10 sample with O2 and the parameter a became even positive after oxi-
dation of this sample at 773 K. At the contrary, the a parameter was always positive
with the x = 0.20 sample, independently from any annealing procedure. All the
EPR results were identical 1 year later, indicating a great stability of those systems.
Therefore, the chemical formula of the samples was more properly written as Ce1
−xGdxO2−x/2−d, where d was a function of x, T, and P(O2). The electronic con-
ductivity r was increasing with increasing conduction electron concentration, i.e.,
with decreasing oxygen partial pressure and/or gadolinium x concentration. All the
EPR experimental results, being related to r, were interpreted by defect equilibria.
The last, in turn, were depending not only on annealing conditions and x doping
level, but also on the sample size.
All the samples investigated in [126] were ca. 20 nm nano-crystalline.
Crystalline samples of Ce1−xGdxO2−x/2−d ca. 100 nm in size and with 0 < x < 1
were also investigated in [134].
On the local scale, Gd- and Ce-rich nanosized droplets (i.e., small regions,
namely some Ångstroms wide) were forming in those samples, exhibiting either a
C-type (Gd2O3) or a distorted fluorite (CeO2) structure in the whole compositional
range. For x 0.25, the Gd-rich droplets were building C-type nano-domains
embedded in the distorted fluorite (CeO2) matrix. At x

0.311 these C-type
nano-domains were percolating inside each crystallite and a structural phase
transformation occurred to a C*phase (up to x 0.433) and then to a C phase at
higher x values. At x
0.311 the peak-to-peak EPR linewidth DHpp (always
increasing with increasing T) showed a step-like broadening of ca. 800 G, attrib-
uted to the increased Gd–Gd dipolar interactions characterizing the new crystal
structure. This topic has been further investigated by other techniques confirming
this interpretation. All these results were further rationalized in the framework of a
percolation-driven phase transition [135].
An interpretation of the EPR spectral profile was attempted at x 0.5 only, i.e.,
when a single mechanism seemed to prevail to form it. However, the result was
rather problematic. Indeed, at these x values the EPR pattern was assuming the
shape of a single Dysonian line [134]. This spectral profile was not new in the EPR
literature, where it had been attributed in general to the electron mobility [136–141].
However, electrons in Ce1−xGdxO2−x/2 have scarce or null mobility at x 0.2
[142]. Therefore, combining ESR and atomic force microscopy
(AFM) measurements on selected samples, a different explanation was found for
this Dysonian profile. Indeed, this spectral shape was attributed to the formation of
surface polaritons. The last are propagating coupled electromagnetic–electric dipole
excitation modes, created by the diffraction of the microwave ESR field on the
surface roughness of the sample, and able to mix absorption and dispersion ESR
modes [143]. The formation of polaritons could be further favored by the high spin–
orbit interaction characterizing the surface-doping Gd ions. Indeed, AFM data
showed the presence of 1.11 nm corrugations on the sample surface when
x = 0.125, increasing to 1.81 nm with the x = 0.5 sample and up to 2.2 with
x = 0.875. Correspondingly, the Dysonian shape was fitting increasingly better the
experimental ESR spectrum of samples with increasing x, up to the perfect fits
reported for the spectrum of the x 0.5 samples.
4 Spin Exchange Along Nanosized Chains
4.1 Spin Exchange Along –O–Cu–O–Cu– Chains
We have above reported the case in which Cu2+ ions were paramagnetic isolated
defects doping nanosized diamagnetic particles (paragraph 2.1). Now we will take
into consideration micro-sized particles in which Cu–O chains form ordered
nanosized sub-systems.
REBa2Cu3O6+d (RE = Y and Lanthanides; 0 d 1) are antiferromagnetic
charge transfer (CT) insulators for d
0, while they show metallic-like conduction
and undergo a superconductive transition [144] at TC
90 K for d
1. Here, the
case of RE = Sm is considered. Oxidation in the O4 site (see Fig. 22) introduces
holes in the valence band(s), following equation
Fig. 22 The crystal structure of SmBa2Cu3−xAlxO6+d. On the left-hand side is shown the
tetragonal P4/mmm structure. O4 sites are only partially occupied. On the right-hand side the
orthorhombic Pmmm structure of SmBa2Cu3−xAlxO7 is shown. Squares in positions O5 indicate
oxygen vacancies
1 ! 00
O2 þ Vi Oi þ 2h ð19Þ
2
00
Oi (in the O4 site) is considered an interstitial atoms when the SmBa2Cu3O6
compound is taken as a reference.
The increased conductivity upon increasing d values is due to the charge transfer
(CT) of a fraction of the holes concentration from Cu1-O4 chains, where oxidation
occurs to the superconducting Cu2-O2/O3 planes [145] (labels following
Ref. [146] as in Fig. 22).
Oxidation causes a progressive ordering of Cu1-O4 ions along the crystallo-
graphic b direction, which in turn causes a structural phase transition from P4/mmm
space group to orthorhombic Pmmm space group. Moreover, internal pressure is
introduced by inter-atomic distance changes [147]. Thus, in order to understand the
charge transfer mechanism, a separation of the above effects was needed.
In order to highlight the specific role of Cu–O chains length and ordering on the
rising of superconductivity in SmBa2Cu3−xAlxO6+d compound, samples with the
same oxygen and with the same Al doping amounts, but different mean Cu–O
chains’ lengths, have been investigated [149]. In fact, aluminum substitutes copper
only at the Cu1 sites. Therefore, taking fixed the oxygen concentration d, Al doping
at the Cu1 site implies a decrease of the hole concentration in the compound
because of the different charges of the two ions.
b
O1 O4
VO Al
a
O4
VO
O1
Fig. 23 Black, blue and red circles represent Cu1, Al and O4 ions in reduced conditions; red
crosses stay for the O ions introduced by oxidation. The inset displays the tetrahedric environment
for Al
A further effect of Al substitution for Cu1 on the structure [148] is to cut the
Cu1-O4 chains. This is due to the Al tetrahedric coordination [148–150], con-
trasting the Cu1 square planar coordination (Fig. 23).
Two SmBa2Cu3−xAlxO6+d samples, A and B, with the same x and (almost) d
values, have been compared by EPR spectroscopy. In particular, d was slightly
larger for A than for B implying a larger hole concentration for the former sample.
Due to two different annealing routes, Al ions were more stochastically distributed
in the A sample and more clusterized in the B one. Clustering assists the formation
of Cu1-O4 chains longer in the latter than in the former.
This different chain mean length affects also the EPR spectra, as shown in
Fig. 24. At T = 280 K these patterns were rather similar for the two compared
samples, being composed of a Lorentzian-shaped line (L) at g ≅ 2, to which a
broad, low-intensity Gaussian-shaped line (G) added at lower magnetic field. At
lower temperature, however, G became more intense and broader, also moving
toward lower field values, these effects being more accentuated for A than for B.
Furthermore, L was markedly increasing at lower temperature only with the latter.
A Lorentzian shape was indicating the occurrence of a spin–spin exchange in
both samples. Indeed, units like
Fig. 24 EPR spectra corresponding to the A sample (left) and to the B sample (right) at different
temperatures. G and L refer to the Gaussian- and Lorentzian-type peaks, respectively (modulation
amplitude 4 gauss, microwave power 20.07 mW, gain 60 dB). Reprinted with permission from
Ref. [149]
are present in the Al-undoped oxidized SmBa2Cu3O7 sample, both in the

Cu1-O4 and in the Cu2-O2/3 planes. The three unpaired spins on the right in
Scheme I are coupled ferromagnetically with one other [151] owing to the
orthogonality of pp and d orbitals, occupied by the unpaired electrons in O and in
Cu holes, respectively. This ferromagnetic coupling overcomes always [152, 153]
the superexchange interaction occurring between the central and the left Cu ions in
Scheme I. Because of the hopping of an O-pp hole [151, 152], ferromagnetically
coupled Cu2+ ions swap continuously with those coupled antiferromagnetically,
giving rise to the narrowed L feature.
In the Cu1-O4 plane, Al doping would produce fragments like
which no more contribute to EPR. The dispersion of Al in the Cu1-O4 plane (as
with A) generates spin bags (SBs), i.e., disordered systems made up of different
spin-polarized clusters of O− holes with limited mobility [153, 154], generating the
ferromagnetic (FM) G pattern [110] shown in Fig. 24(left). The SB size decreases
with increasing temperature, causing a spectral drift toward the g ≅ 2 region
accompanied by lower intensity. However, Al clustering in B induces a pronounced
increase of the L/G ratio, indicating that a more ordered system forms, in which SBs
almost disappear while longer chains like those of Scheme I form. Therefore, mean
mobility of conduction holes and CT increases in B, in spite of the slightly higher
total amount of holes in A.
The DC zero-field-cooled and field-cooled susceptibility measurements showed

that Sample A was characterized by TC = 46.8 K, lower than for Sample B
(TC = 56.7 K) and by a limit of the Meissner fraction of *9 %, lower than for the
latter (*13 %).
In spite of the slightly higher total amount of holes in A with respect to B
(dA > dB), the CT to the Cu2-O2/3 superconducting planes improves in B by
increasing the mean chain length as well as TC and Meissner fraction. Therefore, it
was concluded that local Cu1-O4 ordering is fundamental in determining the
amount of CT and the superconducting properties in REBa2Cu3O6+d system.
4.2 Ferromagnetic and Antiferromagnetic Interactions

Along –O–Co–O–Co– Chains
Perovskitic samples of formula La1−xCexCoO3 are well known as quite active

catalysts for exhaust gas depollution [155, 156] as well as for the catalytic flameless
combustion (CFC) of methane [157, 158]. Indeed, samples of this kind, prepared by
the traditional sol-gel (SG) procedure, have been successfully tested for CO oxi-
dation with air [155] and NO reduction by CO [156].
The 3d6 Co3+ ions, in general, are stable in the low spin (S = 0, t62g, e0g) state
when octahedrally coordinated to six oxygen atoms in an ideal LaCoO3 structure
[159], so that no ESR spectrum was expected with these samples. However, a g ≅ 2
Lorentzian-shaped line (see Fig. 25) was revealed [158] by La1−xCexCoO3 with a
x = 0.05 sample prepared by calcinations of sol-gel citrate precursors (hereafter
CN) as well as with samples of composition x = 0.05 and 0.2 prepared from oxide
mixtures in molten ammonium nitrate (hereafter AN). Those ESR features were
broadening with increasing temperature.
The substitution of Ce4+ for La3+ would reduce some cobalt ions to Co2+. The
last can be either in the (S = ½) low spin state or in a (S = 3/2) high-spin state.
However, the latter is characterized by very fast relaxation times, giving [159] ESR
spectrum at temperature lower than *20 K only. Therefore, only the (S = ½) low
spin Co2+ ions are generally detectable. These ions, when octahedrally coordinated
to oxygen, could form –Co2+–O2−–Co2+–O2– chains in which the paramagnetic
Co2+ ions would be coupled antiferromagnetically to each other through superex-
change mediated by the O2− ions. The presence of oxygen vacancies interrupting
these chains could account for the observation of the Lorentzian-shaped line [156,
160]. However, the last was no more observed with the x = 0.2 CN sample which,
by the way, was the best catalyst for the CFC of methane. This ESR feature could
be attributed to the presence of Co3O4 phase impurities, though the XRD patterns
seemed to show this phase in the x = 0.2 samples of both A and C series [158].
Therefore, the attribution of this line can be considered rather controversial, on the
base of these data only.
Fig. 25 Some
Lorentzian-shaped EPR lines
detected at 140 K.
a x = 0.05 CN;
b x = 0.05 AN; and
c x = 0.2 AN.
DHpp = a 1580 G; b 1360 G,
c 1060 G. Adapted with
Therefore, La1−xCexCoO3 samples prepared by a different method (flame

hydrolysis, FH) were analyzed. They were characterized by a perfect perovskite
structure, though the last is not thermodynamically favored with respect to other Co
oxidic species. In addition, these FH samples did not show the above-mentioned
ESR spectrum [157]. Then, in a bit more recent investigation [161] a few further
La1−xCexCoO3 (x = 0.1) catalysts were prepared by the traditional sol-gel (SG) or
by flame pyrolysis (FP) [162] procedures and analyzed by ESR spectroscopy at
120 T 300 K. Small amounts of Co3O4 and CeO2 phases were noticed in the
x = 0.1 (SG1) catalyst, accompanied by La2O3. This sample gave a single very faint
ESR feature at g ≅ 2, Lorentzian shaped at 120 K and broadening with increasing
temperature, as in the previous cases. By contrast, the single-phase x = 0.1 (FP1)
sample did not give any ESR spectrum.
We can conclude that the pure mono-phasic perovskite-like La1−xCexCoO3
samples did not show any g ≅ 2 Lorentzian-shaped line, as indeed observed with
FP1 and with the samples prepared by the FH method [157], whereas this ESR
feature was attributed to (presumably nanosized) particles of Co3O4, when forming
in these systems. Indeed, a g ≅ 2 Lorentzian-shaped line, broadening with
increasing temperature, has been noticed since a long time with Co3O4 [160, 163,
164]. Narrower lines were obtained at higher preparation temperature, i.e., at lower
residual disorder. The magnetic structure of this cobalt oxide has been deeply
investigated [164]. Units like
have been hypothesized, in which two Co2+ (3d7, S = 3/2 or 1/2) ions, localized
in tetrahedral sites, would interact with each other through O2−–Co3+–O2− bridges,
Co3+ (3d6, S = 0) being localized in octahedral field. Two sets of units like that
outlined in Scheme III would form, characterized by antiferromagnetic (AFM) and
ferromagnetic (FM) coupling, respectively. The former would have multiplicity 12,
and the latter multiplicity 24. Other similar schemes have been elsewhere proposed
[160, 163]. In any case, a prevailing of FM over AFM interactions in SG1 was
suggested.
The line broadening with increasing temperature was interpreted on the base of
polaron propagation, i.e., of spin–phonon interactions.
It should be noted that in this case, a “negative” correlation between ESR signal
and catalytic activity was highlighted. ESR silent (active) were good (bad) catalysts.
In fact, the segregation of CeO2 (as well as of Co3O4 which generate the ESR
signal) hindered the formation of Co2+/Co3+ couples involved in the catalytic
process.
4.3 Polaron Mobility Along –O–Mn–O–Mn–O– Nanosized

Chains
La1−xMxMnO3+d (M = Ce, Sr) mixed oxides have been deeply investigated in the
recent past. Among the possible practical applications, there is the catalytic
flameless combustion (CFC) of hydrocarbons [165]. To this purpose, it is com-
pulsory to combine their thermal stability to their high specific surface area (SSA).
These and other properties of doped manganites strongly depend on the procedure
followed in their preparation [166]. In particular, the synthesis parameters affect the
incorporation degree of the ion M, substituting for La [167, 168].
The last parameter was particularly important because the partial substitution of
Sr2+ for La3+ was favoring the oxidation of some Mn3+ to Mn4+, increasing the
catalytic activity of the sample for the CFC of methane [169, 170] and giving rise to
a mixed valence compound which was displaying a variety of phenomena such as
electron conduction linked to double exchange interactions between Mn3+ and
Mn4+ species along chains like
[171, 172] and ferromagnetic transition due to ferromagnetic polarization arising

around the Mn4+ ions at low T [172–174].
A different case was that of Ce4+ substituting for La3+, in which some Mn3+
might reduce to Mn2+ ions [172], which contribute to the ESR pattern (Fig. 26a).
However, in the last cited paper, a single EPR line was observed also with the
undoped as-prepared sample. This fact was considered rather intriguing, as Mn3+ (if
not involved in a double exchange with Mn4+) is characterized by a very fast
relaxation time, so that its ESR spectrum is detectable at very low temperature only.
Indeed, in the undoped sample this line could be attributed to Mn3+ ions only, in the
presence of a strong coupling between lattice, electronic, and magnetic degrees of
freedom due to static Jahn–Teller (JT) effect. The last would distort the oxygen
octahedra of the cubic cell giving rise to an orthorhombic or monoclinic [175]
structure, so that the degeneracy would be removed by lowering the energy of the
occupied d3x2−r2 or d3y2−r2 orbital. Then, the Mn3+ ions would acquire a
zig-zag-type ordering of occupied orbitals in ab planes. In this situation, an ESR
line was expected at about gz ≅ 1.95 and gx = gy = 1.99, in agreement with
experimental literature data [159, 173]. No variation of the ESR peak-to-peak
linewidth was expected for this line at the detected temperatures, ranging between
280 and 550 K, because LaMnO3 remains JT distorted up to TJT = 750 K [176]. By
contrast, unexpectedly, the EPR line was broadening with increasing temperature in
[172]. Therefore, it was not possible to explain this effect by just invoking the static
JT effect. Some temperature-dependent spin–spin relaxation process might be also
hypothesized. This was singled out as the temperature-dependent interactions
between phonons and conduction electrons (i.e., to polarons formation) [172, 177].
Referring again to the catalytic properties, the materials described above, pre-
pared using the traditional sol-gel (SG) preparation, did not get sufficient thermal
resistance. Therefore, an alternative preparation procedure by flame pyrolysis
(FP) [162, 178, 179] was proposed for La1−xMxMnO3+d (x = 0, x ≅ 0.1 with
M = Ce; x ≅ 0.1 and ≅0.2 with M = Sr). The FP preparation of undoped and
Ce-doped samples was leading to nanoparticles with monoclinic structure, whereas
Sr-doped catalysts showed orthorhombic/rhombohedral symmetry. The observed
structural phases were connected to the concentration of Mn4+ present in the
Sr-doped samples, and to the fact that the undoped and the Ce-doped monoclinic
samples were almost Mn4+ free [136].
Samples prepared by this way have been compared to sample prepared by a
traditional SG process by examining their ESR spectra and X-ray powder diffrac-
tion patterns [136]. ESR measurements were carried out on samples (i) as prepared,
(ii) after activation, and (iii) after reaction. The single ESR line was observed also
with the undoped FP-prepared LaMnO3+d sample [136] (Fig. 26a). Its peak-to-peak
linewidth variation in the 250 T 420 K range is shown in Fig. 26b.
A marked ESR line narrowing was always observed after the activation treatment,
similar to that noticed with the same samples after their catalytic reaction (see for
example inset of Fig. 26a). We note that the spectrum of the as-prepared one
(dotted line in Fig. 26a) displays an exchange-narrowed ESR feature with a bit
asymmetric shape, well described by the Dysonian model. As above reported in the
paragraph 2.4, the Dysonian lineshape can be attributed to an a
dispersion-to-absorption contribution to the Lorentzian-shaped line. This effect
Fig. 26 ESR spectra of LaMnO3. a ESR spectra of as-prepared sample (dotted line), after
activation (solid line), after reaction (dashed line) at T = 290 K. (*) Mn2+ ESR contribution.
b ESR spectra of the as-prepared sample as a function of temperature; c ESR spectra of
as-prepared sample collected at T = 290 K (empty dots) fitted using a Dysonian (solid line) and
Lorentzian (dotted line) functions; d Comparison between the parameters obtained by the
Lorentzian model (DHpp) and the Dysonian parameter (D) (see text for details). Reprinted with
permission from Ref. [136]. Copyright (2012) American Chemical Society
occurs in samples in which the electron mobility is high enough to create the
so-called “skin effect” for the microwave field employed by the ESR spectrometer
[180, 181]. A a = 1 value would correspond to dispersion of the same strength of
absorption, in a sample larger than its skin depth. On the opposite, in any case a = 0
with samples smaller than their skin depth. The situation reported in [136] was an
intermediate one, with 0 < a < 1.
The Dysonian and the Lorentzian lineshape models for the ESR spectrum of
undoped FP-prepared LaMnO3 were compared (Fig. 26c). Only a little discrepancy
was noticed in the low-field part of the line, so that the T2 spin–spin relaxation time
values obtained through these two models were very close to each other (Fig. 26d).
Therefore, the peak-to-peak linewidth obtained by the Lorentzian model, being
DHpp = (2/√3)/T2, was retained valid in order to compare quantitatively the T2
values at different doping amounts and with samples prepared by the different SG
and FP procedures (see Fig. 27).
Fig. 27 Temperature dependences of peak-to-peak width (DHpp) of the g ≅ 2 ESR line observed.
The DHpp values refer to a La0.9Ce0.1MnO3 (full circles), LaMnO3 (full squares), La0.9Sr0.1MnO3
(empty circles) FP as-prepared samples; b LaMnO3–FP as-prepared (full circles) and used (empty
circles) samples and LaMnO3–SG as-prepared (full triangles) and used (empty triangles) samples;
c La0.9Ce0.1MnO3–FP as-prepared (full circles) and used (empty circles) samples and
La0.9Ce0.1MnO3–SG as-prepared (full triangles) and used (full triangles) samples;
d La0.9Sr0.1MnO3–FP as-prepared (full circles) and used (empty circles) samples and
La0.9Sr0.1MnO3–SG as-prepared (full triangles) and used (empty triangles) samples. Reprinted
with permission from Ref. [136]. Copyright (2012) American Chemical Society
The ESR line broadens with increasing temperature a bit more markedly with the
Ce-doped than with the undoped sample (Fig. 27a). This has been attributed to the
formation of some electron–hole (EH) pairs [182–184] composed of Mn2+–Mn4+
ions. Indeed, EH pairs have a very large fluctuating electrical dipole moment, able
to cause attractive electrostatic dipole–dipole interactions. Therefore, EH pairs can
group themselves into an EHBL (Bose Liquid) phase. The formation of the last
would subtract some Mn4+ ions from the DE, decreasing its ESR line-narrowing
efficiency. On the other hand, Mn3+ ions are by far more abundant than the Mn4+
ones, so that a decreased amount of the latter only would be sufficient to cause a
decreased DE.
By contrast, doping LaMnO3 by Sr2+ was increasing the amount of the Mn4+
ions present in the material. This was confirmed by the ESR lineshape, which was
by far narrower with the x = 0.1 Sr-doped sample than with the undoped and
Ce-doped ones (Fig. 27a). This strong narrowing could be attributed to an increased
Mn4+–O–Mn3+ DE, favored by the greater availability of Mn4+ ions [172, 174], as
well as by the smaller distortion of the Mn–O–Mn bond angle arising from the
substitution of Sr2+ for La3+ [185].
The undoped LaMnO3 sample showed an ESR line broader with FP-prepared
than with SG-prepared samples (see Fig. 27b, where the DHpp values obtained after
reaction are also reported, though discussed on the original paper, only) [172, 177].
We can generalize that the ESR line of the nanosized FP-prepared samples was
about 2–3 times (1.3 times with M = Sr) broader than those of the analogous
SG-prepared materials, at least in the range of *280 (380 with
M = Sr) < T < 420 K.
However, we must outline that ESR features broader than with SG samples were
already reported and discussed for flame hydrolysis (FH) prepared undoped La
manganite at room temperature [177]. The observed differences in ESR linewidth
can be related to different structural sample phases. Indeed, the undoped manganite
was rhombohedral when SG-prepared, orthorhombic when FH-prepared, and
monoclinic in the present FP-prepared sample [177].
In addition, the linewidth of undoped and of Ce-doped samples was continu-
ously increasing with increasing temperature when the samples were prepared by
the FP procedure (Fig. 27a), but not when they were prepared by the classical SG
method (full triangles in Fig. 27b, c). In the latter case, the linewidth versus tem-
perature revealed a relative minimum at T = Tmin, and a line broadening at T < Tmin
accompanied by increased spectral intensity, typical in the presence of a magnetic
transition to a ferromagnetic state [172]. Indeed, the undoped and Ce-doped
LaMnO3 samples were characterized by an abundance of Mn4+ ions lower when in
the monoclinic phase obtained by the FP procedure than when in the rhombohedral
phase obtained by the SG procedure. Therefore, a lower amount of free electrons
available to form FM domains was present in the former than in the latter case. The
complex relationship between crystallographic structure and ESR as a function of
dopant concentration and annealing conditions is described in term of Mn4+/Mn3+
ratio in [136].
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EPR Studies of Cerium Dioxide
Nanoparticles
Ashutosh Kumar Shukla and Rafail Rakhmatullin
Abstract This chapter intends to provide a review of EPR spectroscopic charac-

terization of ceria nanoparticles. It covers recent EPR applications to investigate the
synthesis, local structure, and distortion of ceria nanoparticles. Room temperature
ferromagnetism, toxicological screening, free radical scavenging properties, cat-
alytic effects, and some other properties of ceria nanoparticles as studied by EPR
are also included in this chapter.
1 Introduction
Cerium dioxideor ceria (CeO2) nanoparticles have found energy related techno-
logical applications such as solar cells and solid oxide fuel cells [1]. It has attracted
the attention due to its wide band gap and high dielectric constant [2]. Increasing
the catalytic activity of nanocrystalline ceria for applications in diesel particulate
filters for removal of soot from diesel and organic compounds from wastewater has
also attracted the researchers [3]. Ceria nanoparticles also have antioxidant prop-
erties. Their antioxidative ability lies in the ability of Ce ions to switch between
different valence states, i.e., from Ce3+ to Ce4+. This has opened up new dimen-
sions for application of ceria nanoparticles against radiation damage, oxidative
stress, and inflammation [4]. Toxicological screening of ceria nanoparticles has also
gained importance due to expected occupational exposure in the wide range of
applications. Enhancing the photoactivity of CeO2 in the visible range is another
area of interest which has led to the modifications like doping in CeO2. Electron
Paramagnetic Resonance spectroscopy has suitably been applied in the study of
undoped and doped ceria nanoparticles. The application of CW and pulsed EPR
A.K. Shukla (&)

Physics Department, Ewing Christian College, Allahabad 211003, UP, India
e-mail: drakshukla@gmail.com
R. Rakhmatullin
Institute of Physics, Kazan Federal University, Russian Federation, 420008 Kazan, Russia

DOI 10.1007/978-81-322-3655-9_6
136 A.K. Shukla and R. Rakhmatullin
techniques can provide new information that may lead to improvement in the
performance of ceria-based devices. We have therefore made an attempt to review
recent EPR studies of undoped and doped ceria nanoparticles in this chapter.
2 Synthesis, Local Structure, and Distortions
Araujo et al. (2012) have reported the synthesis of CeO2 nanoparticles by a

microwave-assisted hydrothermal method at different synthesis temperatures [5].
These nanoparticles were characterized by EPR spectroscopy. Figure 1 presents the
EPR spectra of the samples. Authors have reported that pure CeO2 revealed for-
mation of one type of paramagnetic species, A, due to Ce3+. Assumption of the
presence of Ce3+ ions and oxygen vacancies in the samples could be confirmed.
To improve the catalytic and oxygen storage properties of ceria, it is important to
know the distribution of oxygen vacancies and the crystal field change depending
on size of nanoparticles and dopant concentration. Such kind of information can be
obtained with the EPR technique using probe ions introduced in small concentra-
tion to ceria in the process of synthesis.
EPR of Gd3+ probe ions, to study yttrium doped ceria (YDC) with the formula
Ce1-x-yGdxYyO2-[0.5 (x+y)] (x = 0.0025, y = 0.10 and 0.25) with crystallite sizes
ranging from 600 nm down to 5 nm, is reported by Rakhmatullin et al. [6].
All YDC samples were synthesized via a co-precipitation method, where an
aqueous solution of NH4OH was added drop wise to an aqueous solution con-
taining the stoichiometric amounts of metal nitrates. The precipitated oxides were
collected by centrifugation and were washed with water; a 50 % vol. ethanol–water
solution and subsequently with pure ethanol. The resulting nanopowders were then
dried at 120 °C for 12 h, ground and finally annealed under air at temperatures
ranging between 450 and 650 °C for 1–2 h to obtain crystallites ranging
between *5 and 10 nm in diameter. Samples with larger grain size (600 ± 50 nm
in diameter) were obtained from the nanocrystalline powders that were pelletized
Fig. 1 EPR spectra of CeO2

samples synthesized at
different temperature.
A represents the formation of
paramagnetic species due to
Ce3+. Reproduced from Ref.
[5] with permission of The
Royal Society of Chemistry
EPR Studies of Cerium Dioxide Nanoparticles 137
via cold isostatic pressing at 276 MPa and subsequently sintered at 1400 °C for
12 h. X-ray diffraction (XRD) measurements of powder samples indicated that all
micro and nanocrystalline doped ceria samples studied may be characterized by the
cubic fluorite crystal structure. The crystallite size of the nanocrystalline samples
could be estimated from widths of the four strongest peaks in the XRD patterns
using the Williamson–Hall analysis. The particle size of the microcrystalline
samples was estimated from field emission scanning electron microscopy
(SEM) images. The Y contents were analyzed using energy dispersive x-ray
spectroscopy in an SEM and were found to be within ± 1 cation% of the nominal
composition in all cases. The unit cell dimension calculated from the XRD peak
positions was found to be independent of the crystallite size (within ±0.005 Å) and
decreased by *0.01 Å with increasing Y content from *10 to 25 cation%.
X-band CW EPR spectra of heavily Y-doped ceria samples were found to be
similar to those observed in oxide glasses rather than those characteristic of
Gd-doped CeO2. Q-band spectra are dominated by the central transition that is
located near about 12000 Gauss. X-band spectral line shapes were consistent with
the expected low symmetry of the crystal field around Gd3+ ions in YDC samples,
where the first coordination sphere of Gd would contain oxygen vacancies and a
fraction of the 12 Ce4+ next nearest neighbors is substituted by Y3+ ions. In both X
and Q-band spectra, the width of the central transition j1=2i $ j 1=2i near
g * 2.0 is found to decrease systematically with decreasing size of the crystal
(Figs. 2 and 3) as well as with decreasing Y content (Fig. 4) and with increasing the
temperature of measurement from *6 K to room temperature.
The broadening of the central transition results from a distribution of crystal field
parameters and in the case of a powder samples, also from a random distribution of
crystallite orientations relative to the applied field. The approximate estimate of line
width Dm from perturbation theory for both types of scatter is given by Dm * |
HCF|2/hm, where HCF is the crystal field potential. The observation in the EPR
spectra of progressive narrowing of the width of the central transition with
decreasing crystallite size (Figs. 3 and 4) can be explained by a concomitant
weakening of the crystal field around Gd3+ ions in the yttrium doped ceria lattice.
This hypothesis is consistent with the observed narrowing of the width of the
central transition with decreasing Y content and with increasing the temperature of
measurement from *6 K to room temperature. Both increasing temperature and
decreasing Y content are known to result in lattice expansion of yttrium doped
ceria, the former due to thermal expansion and the latter due to removal of oxygen
vacancies [7, 8]. Such expansion of the lattice is expected to weaken the crystal
field around Gd3+ ions in the YDC lattice resulting in a narrowing of the width of
the central transition. [Reproduced with permission from J. Chem. Phys. 131,
124515 (2009). Copyright 2009, AIP Publishing].
Authors could conclude that weakening of the average crystal field and nar-
rowing of the EPR line width result from a more random oxygen vacancy distri-
bution in the nanocrystals compared to their microcrystalline counterparts of same
composition.
Fig. 2 CW EPR spectra of micro and nanocrystals of 10 and 25 cation% Y-doped ceria samples
(co-doped with 0.25 % Gd) at X-band and liquid helium temperature (*6 K).The scale on the
abscissa corresponds to the bottom-most spectrum. The other spectra are shifted horizontally for
visual clarity. The topmost spectrum shows the simulation of the powder spectrum of Gd3+ in
Y-free CeO2. Reprinted with permission from J. Chem. Phys. 131, 124515 (2009). Copyright
2009, AIP Publishing LLC
Fig. 3 The line width of (−½

$ +½ transition) as a
function of crystallite size of
the sample with 25 cation% Y
at Q-band and liquid helium
temperature (6 K). The labels
1, 2, and 3 correspond to
crystallite sizes of *600, 10,
and 5 nm, respectively.
from J. Chem. Phys. 131,
124515 (2009). Copyright
EPR spectroscopy of Gd3+ probe ions to investigate size dependent lattice dis-
tortions in bulk and nanocrystalline CeO2 with crystallite sizes of 600 (bulk) and 10
(nano) nm, respectively, and doped with 0.5 and 1 cation% Y is reported by
Rakhmatullin et al. [9]. The studied samples were synthesized in the same way as
earlier [6], except lower content of yttrium. It was found that incorporation of Gd3+
ions at 0.25 % cation concentration level does not introduce by itself any
Fig. 4 The line width

dependence of (−½ $ +½
transition) on the crystallite
size of the sample at X (open
symbols) and Q-band (filled
symbols) and at liquid helium
temperature (6 K). Circles
and triangles correspond to
the samples with 25 and 10
cation% Y, respectively.
from J. Chem. Phys. 131,
124515 (2009). Copyright
measurable strain in the CeO2 lattice. EPR spectrum of the bulk sample with 0.5
cation% Y with simulation parameters of monocrystalline CeO2 (Fig. 5) indicates
the absence of any other significant contribution to the EPR line shape and suggests
a nearly perfect cubic structure of the lattice of this sample.
Introduction of 1.0 cation% Y in bulk ceria lead more vacancies and clear
distortions appear in the experimental spectrum. The simulation of the spectrum
(Fig. 6) then yields the result that *83 % of the Gd3+ sites have undistorted cubic
symmetry and *17 % of the Gd3+ sites are axially distorted from the presence of a
neighboring oxygen vacancy.
The nanocrystalline samples display a different line shape, where the fine
structure of Gd3+ is substantially broadened (Fig. 7). The simulations of EPR
spectra for both nanocrystalline samples reveal the presence of two types of axial
sites with rather different distortions that belong to the core and the surface regions
of the nanocrystals and solely originate from crystallite size effect as the ratio of
surface: bulk energy rapidly increases with decreasing size in nanocrystals. The
Fig. 5 The experimental

(black line) and simulated
(red line) EPR spectra of Gd3+
ions in the “bulk” ceria
sample co-doped with 0.5
cation% Y. Reprinted with
permission from [J. Appl.
Phys. 114, 203507 (2013)].
Copyright 2013, AIP
Publishing LLC
Fig. 6 Curves 1 and 2 represent experimental (black) and simulated (red) EPR spectra of Gd3+
ions in the “bulk” ceria sample co-doped with 1.0 cation% Y. Curve 3 (blue) represents simulated
contribution from cubic sites, Curve 4 (green) represents simulated contribution from the trigonal
sites. Reprinted with permission from [J. Appl. Phys. 114, 203507 (2013)]. Copyright 2013, AIP
Publishing LLC
Fig. 7 Curves 1 and 2 show experimental (black) and simulated (red) EPR spectra of Gd3+ ions in
the nanocrystalline ceria sample co-doped with 0.5 cation% Y, respectively. Curve 3 (blue) shows
simulated contribution from the core trigonal sites, Curve 4 (pink) shows simulated contribution
from the surface trigonal sites, Curve 5 (green) shows simulated contribution from surface
superoxide species. Reprinted with permission from [J. Appl. Phys. 114, 203507 (2013)].
Copyright 2013, AIP Publishing LLC
authors of this publication supposed that the size dependent lattice distortions may
be universal in nanomaterials.
EPR studies of Er3+ probe ions in ceria nanoparticles with grain sizes of about 22
and 300 nm are reported [10, 11]. Ceria samples contained nominal concentration
of 0.01 % of Er3+ ions in initial components. The nanocrystals synthesized via a
co-precipitation method had crystallite diameter of 22 ± 2 nm (Sample 1) and
300 ± 10 nm (Sample 2). The purpose of these studies is to find out the vacancy
distributions and the origin of unusual EPR lines with g-values around 14 and 20
Fig. 8 X-band EPR spectra at 10 K of Er-doped CeO2 single crystal (bottom) and nanocrystalline
powder samples 1 (top) and 2 (middle) with average crystallite diameters of *22 nm
and *300 nm, respectively. The line marked by C represents the cubic center with g = 6.76
along with arrows marking the spread of hyperfine lines from the odd isotope Er167. The weak
lines marked by A and B in the spectra of samples 1 and 2 are located near g *20 and 14,
respectively. [Reproduced with permission from Appl. Magn. Reson. 46, 741 (2015)]
detected in nanocrystalline CeO2.These lines are marked by A and B in the Fig. 8.

The most intensive EPR line of Fig. 8, marked by “C” corresponds to the cubic site
of Er3+ ions with g 6.75 due to the even isotopes and eight relatively weak lines
correspond to the hyperfine splitting from the odd isotope of Er3+ (Er167abundance
is 22.9 %) with nuclear spin I = 7/2. The line width values DBpp for the cubic
center were 5.4, 4.8, and 0.2 mT for sample 1, sample 2 and single crystal,
respectively. The larger widths of the EPR lines in the nanocrystals compared to
those in the single crystal assume larger degree of local structural disorder in the
former that increases with decreasing crystallite size. The concentration of the Er
cubic centers as estimated from the EPR spectra was *0.0050(5) at.% for sample 2
and *0.0020(2) at.% for the sample 1. These values are smaller than the nominal
concentration of Er of 0.01 at .% in these samples even taking into account the
experimental error. The latter consideration suggests the presence of low symmetry
Er sites in the nanocrystalline ceria samples along with the cubic site though the
observed EPR intensities of low symmetry sites are small as compared with cubic
sites. Thus, for the low concentration of Er3+ centers in studied nanosized and
single crystal samples, the coordination number of rare earth ions is mainly 8.
Authors concluded that vacancies are located mainly in the next nearest neighbor
positions. This finding is not consistent with the conclusion of recent works [12–14]
based on DFT calculations that rare earth ion dopants like Er3+ trap a vacancy in the
nearest neighbor position. It should be noted that at low-level doping it is necessary
to consider the impact of uncontrolled impurities from the precursor in cerium
Fig. 9 The EPR spectrum of

Sample 1 (crystallite
diameter *22 nm) collected
in parallel mode at X-band
(9.37 GHz) and 11 K. The
lines in the region marked by
C are hyperfine signals from
Er3+ odd isotopes in a cubic
environment. The lines
marked by A and B are the
same as those in Fig. 8.
[Reproduced with permission
from Appl. Magn. Reson. 46,
741 (2015)]
dioxide. [Text reproduced with permission from Phys. Status Solidi B 251, 1545
(2014)]
It was supposed that the weak lines A and B in the spectrum originated from the
formation of low-symmetry Er2+; Er4+centers in the lattice. In this case, Er2+ should
be isoelectronic to Tm3+ with the ground state 3H6 and a Landè factor K = 7/6, for
which the maximum possible g-value for non-Kramers doublet or two close singlets
is g∥ = 2K6 = 14. The EPR line with g * 20 (weak line A in Fig. 8) would be to a
non-Kramers Er4+ ion that is isoelectronic to Ho3+. The ground state of Ho3+ is 5I8,
with Lande factor K = 5/4 that results in a maximum possible g = 20 for the
non-Kramers doublet.
Additional experiments were carried out at X-band with magnetic field B0
parallel to the microwave magnetic field to demonstrate that the lines at g * 14
and *20 do not originate from Er3+ Kramers centers. In this relative geometric
configuration of the microwave and the static external magnetic fields the electronic
spin transitions are strictly forbidden for Kramers ions. The results for Sample 1 are
shown in (Fig. 9). It is clear that the main EPR line from Er3+ even isotopes in cubic
centers has almost completely disappeared while the hyperfine lines of Er3+ odd
isotope have become remarkably smaller compared to the lines at A and B, mea-
sured also in parallel mode.
3 Room Temperature Ferromagnetism
The recent discovery of room temperature ferromagnetism (RTFM) in oxide

nanoparticles such as CeO2, Al2O3, ZnO, In2O3, and SnO2 stimulated studies to
find out its origin [15]. They suggested exchange interactions of unpaired electrons
trapped in oxygen vacancies (F+-center) result in RTFM. EPR technique is espe-
cially important for studying F-centers in ferromagnetism formation. As applied to
ferromagnetism, EPR is most often called electron magnetic resonance, which is
successfully used to study magnetic nanoparticles [16–18]. EPR has been used to
Fig. 10 X-band EPR spectra

of the samples at 40 K with
grain size of *35 nm (1)
and *150 nm (2).
[Reproduced with permission
from Phys. Status Solidi B,
(2015). doi 10.1002/pssb.
201552542]
study the ferromagnetism in CeO2 nanocrystals doped with Ni (Ni content more
than 1 %) and Co (5 % Co) ion [19, 20]. Askrabic et al. [21] studied pure
nanocrystalline CeO2 synthesized by selfpropagating room temperature method
(S-CeO2 sample) and the precipitation method (P–CeO2 sample). It was shown that
F+centers with g = 1.99 and g = 1.9 dominated in the S–CeO2 sample, whereas F0
centers were the major defects in P–CeO2 sample. Based on observation of EPR
from F+ centers in the S–CeO2 sample, that exhibits RTFM, authors could conclude
about F+-center mediated ferromagnetism [22].
Studies of two ceria powder samples with grain sizes of *35 nm and *150 nm
containing small amount of manganese (0.1 at.%) and traces of iron are reported
[23–25]. The ferromagnetism in a CeO2 powder with a grain size of *150 nm was
found to be substantially weaker than in such a powder with a grain size of about
35 nm. EPR measurements revealed in both samples the lines with g *2.003 that
was assigned to F+ centers. The comparison of intensities of F+ center lines
(Fig. 10) that was considerably stronger in the sample exhibiting stronger ferro-
magnetism lead authors to the conclusion that ferromagnetism in studied samples
cannot be explained by exchange interacting F+-centers. The charged transfer fer-
romagnetism was found to be more suitable to explain experimental results.
4 Toxicological Screening of Ceria Nanoparticles
Cytotoxic effect of Cerium Oxide nanoparticles in several cancer and normal cell
lines and their potential to change intracellular redox status is reported [26]. Free
radicals related antioxidant capacity of the cells was studied by the reduction of
stable free radical TEMPONE radical in the HaCaT, 518 A2, and HT-29 cell lines,
untreated and treated with 100 or 200 lM cerium oxide nanoparticles using EPR
spectroscopy. The reduction was followed during 20 min since addition of
Fig. 11 Reduction of the

TEMPONE radical in the
HaCaT, 518 A2, and HT-29
cell lines, untreated and
treated with 100 or 200 lM
cerium oxide nanoparticles.
HaCaT cell line has more
preserved free radical
metabolism. [Reprinted from
Chemico-Biological
Interactions 232, 85 (2015),
with permission from
Elsevier]
TEMPONE to the cells. It could be concluded that HaCaT cell line had more
preserved free radical metabolism, and thus redox status, in comparison with the
two other cell lines (Fig. 11).
5 Free Radical Scavenging Properties of Ceria

Nanoparticles
Radical scavenging properties of ceria nanoparticles may be studied using EPR

spectroscopy. For detecting free radicals in chemical and biological system (due to
short time), spin-trapping techniques are being used.
EPR of gadolinium doped CeO2 nanoparticles has been used to assess super-
oxide radical scavenging using xanthine oxidase/xanthine reaction and spin trap
technique [27]. CeO2 with different dopant concentrations were found to show
(Fig. 12) significant scavenging properties. They could find that antioxidant
potential decreases with increasing doping. It could therefore be concluded that as
doping increases, thus subsequently increasing the Ce(3+)/Ce(4+) ratio, antioxidant
potential decreases, suggesting that differences in reactivity of CeO2 are due to the
ability of Ce to transition between the two valence states and the presence of
increased oxygen vacancies, rather than dependent on a specific valence state.
Babu et al. [28] used EPR in the presence of a spin trap (5,
5-dimethylpyrroline-N-oxide (DMPO)) to study oxygen free radical scavenging
properties of ceria nanoparticle, synthesized by chemical method. The EPR spectra
for DMPO-OH adduct and simulated spectra are shown in Fig. 13. Intensity of
hydroxyl spectra were plotted with respect to time with and without ceria
nanoparticles to find the effect of ceria nanoparticles. The hydroxyl radical
Fig. 12 a Superoxide radical scavenging assessed using xanthine oxidase/xanthine reaction and
spin trap technique. b The first, fourth fifth, and eighth peaks were used for superoxide radical
production. All three CeO2 particles show significant scavenging properties [27]. (Open Access)
Fig. 13 EPR spectra of DMPO-OH adduct. A represents experimental spectrum and B represents
simulated spectrum. Reprinted from Chem. Phys. Lett. 442, 405 (2007), with permission from
Elsevier
Fig. 14 Extinction plot for hydroxyl radical and hydroxyl radical in presence of 1 mM (a) and
10 lM (b) concentration of ceria nanoparticles. A corresponds to the intensity of DMPO-OH
adduct in the absence and in the presence of nanoparticles, respectively. Intensity of hydroxyl
radicals in the presence of ceria nanoparticles decreases very fast at low concentration and hence
indicates the possibility to use ceria nanoparticles as free radical scavenger. It also indicates toward
the agglomeration at higher concentrations Reprinted from Chem. Phys. Lett. 442, 405 (2007),
with permission from Elsevier
scavenging properties of ceria nanoparticles were found to vary with concentrations

(Fig. 14). It was concluded that catalytic effect was better at lower concentration.
They presumed that it may be due to the agglomeration at higher concentrations.

CeO2 sample (77 K) under
increasing O2 pressure [29].
(Open Access)
6 Catalytic Effects of Ceria Nanoparticles
EPR spectroscopy results for oxygen activation property of Gold–ceria (Au/CeO2)

and gold–ceria–alumina (Au/CeO2/Al2O3) catalysts are reported by Lakshmanan
et al. [29]. Nature and the location of the adsorbed oxygen species could be studied,
and they could find that the concentration of superoxo species was lower for
oxide-supported gold samples than for bare oxides. Increase in oxygen mobility due
to specific gold–ceria interaction is probably responsible for the higher catalytic
performance of Au/CeO2 and Au/CeO2/Al2O3 in oxidation reaction compared to
bare supports (Fig. 15).
7 Other EPR Applications
Investigation of the extent of ROS generation by different CeO2 nanoparticles

including one prepared by them using hydrothermal method (HT–CeO2) under
different illumination conditions is reported in literature by Lieung et al. [30]. EPR
spectra were recorded with DMPO spin trap in 0.9 % NaCl solution and in f2-Si
medium on different CeO2 nanoparticles. In f2-Si medium under UV illumination,
significant signals corresponding to hydroxyl radicals were observed. They also
further performed ESR measurements to investigate the impurities and suggested
that multiple peak signal may be attributed possibly to Gd impurities in CeO2 [31,
32].
Hernandez-Alonso et al. [33] used EPR spectroscopy to study the photoactivated

processes occurring due to UV illumination of CeO2 nanoparticles. Capability of
the samples for the trapping of photogenerated charge carriers has been investi-
gated. The photocatalytic activity of the samples is proposed to be related with the
efficiency in the charge separation processes, in accordance with EPR results of
oxygen photo adsorption.
EPR assisted by X-ray photoelectron spectroscopy (XPS) and UV-visible
analyses is reported which confirms the reactivity of nanoceria as superoxide dis-
mutase (SOD) mimetic [34]. It could be concluded that the surface oxidation state
of nanoceria plays an integral role in the SOD mimetic activity of nanoceria. The
ability of nanoceria to scavenge superoxide is found to be directly related to cerium
(III) concentrations at the surface of the particle.
8 Future Scope
Recent publications about observation of weak room temperature ferromagnetism

in pure ceria nanoparticles can give a new impetus to the study of magnetic res-
onance spectra and explanation of their features. These findings make ceria based
material a perspective for application in spintronics. Modifying CeO2 to enhance its
photoactivity in the visible range is another important area which needs further
efforts. Toxicological screening also needs attention due to potential applications
such as sun creams and outdoor paints leading to increased exposures of ceria
nanoparticles.
Acknowledgments We acknowledge publishers of repute for granting us permissions to reuse

text extracts and reproduce figures.
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Synthesis and Characterization
of Undoped and Doped (Mn, Cu, Co) ZnO
Nanoparticles: An EPR Study
Şeyda Çolak and Cangül Aktürk
Abstract Diluted Magnetic Semiconductors are obtained by introducing dilute

amount of transition metal ions into semiconductors and they are subjected to their
promising applications to spintronics. Zinc Oxide (ZnO) nanoparticles, which are
used in large scale both in research and technology, belong to dilute magnetic
semiconductors (DMS). In this study, structural, optical, and magnetic characteri-
zation of the synthesized undoped and Mn, Cu, and Co-doped (5 %) ZnO
nanoparticles by Co-precipitation method were performed. Crystal sizes of the
synthesized unannealed ZnO nanoparticles have been determined to be *8 nm and
*90 nm by XRD and SEM analyses, respectively. AFM analysis is used for the
determination of the surface topographies of the synthesized samples. From the
results of UV-Vis studies, the absorbance peaks for the synthesized ZnO
nanoparticles have been appeared at *335 nm and the mean gap energy is cal-
culated to be 3.47 eV. Electron Paramagnetic Resonance (EPR) spectroscopy is
performed for the magnetic characterization of synthesized ZnO nanosamples
dominantly and Vibrating Sample Magnetometry (VSM) was also used as a
complementary technique. No EPR signal has been observed for undoped syn-
thesized ZnO nanoparticles where six resolved EPR resonance lines, four resolved
EPR resonance lines, and a broad, single unresolved EPR resonance line was
recorded for 5 % doped synthesized ZnO:Mn, ZnO:Cu, and ZnO:Co nanoparticles,
respectively. For UV-irradiated and annealed samples, some new EPR resonance
lines have also been arised originating from the defects and oxygen damage centers
involved in the crystal structure of ZnO. VSM results indicated that none of the
synthesized ZnO nanoparticles were purely in ferromagnetic character at room
temperature.

Keywords EPR Nanotechnology DMS ZnO ZnO:Mn ZnO:Cu ZnO:

Co VSM XRD SEM AFM UV-Vis
Ş. Çolak (&) C. Aktürk

Physics Engineering Department, Hacettepe University, Beytepe, 06800 Ankara, Turkey
e-mail: seyda@hacettepe.edu.tr

DOI 10.1007/978-81-322-3655-9_7
152 Ş. Çolak and C. Aktürk
1 Introduction
1.1 Nanoparticles
Nanoparticles are extremely small in size, which are in the dimension of 100 nm or
less. Nanotechnology is a broad and interdisciplinary research area that has been
growing fast worldwide nowadays [3, 24]. Nanotechnology is in relationship with
physics, chemistry, biology, computer, and material sciences integrated with
engineering.
Nanoparticles have a much greater surface area to their volume ratio which can
lead the material to greater chemical reactivity and affect its physical properties
when compared with their bulk form [3]. Nanoparticles have created high interest
by virtue of some their unusual properties on mechanical, electrical, optical, and
magnetic properties and their applications on these areas [3, 26, 45, 53].
Nanotubes, nanowires, and nanobelts are some of the basis of nanoscience and
nanotechnology [10] and for future electronic, optical, and optoelectronic nan-
odevices are aimed to use. Recent developments in nanotechnology and the results
of their quantum size effects for nanoscale particles are the indications that most of
the devices in the future will be really based on nanomaterials [8, 69]. Besides,
magnetic properties of the material can be controlled to an extent just by changing
the composition, size, shape, and structure of the nanoparticles [24].
Co-precipitation, sol-gel, thermal decomposition, microemulsion, grinding,
hydrothermal, laser ablation, hydrosis, combustion gas-phase reaction, chemical
vapor deposition, flame spray, etc, methods are some of the used synthesis
mechanisms of nanoparticles [27, 55, 66]. The physical and chemical specifications
of the magnetic nanoparticles are strongly depended on the synthesis method
preferred [1, 3, 52]. The synthesized ZnO nanoparticles can exhibit the mor-
phologies such as spheres, plates, rod-like, belt, wires, worms-like, tetra-pod, etc.)
[13].
1.2 Magnetic Nanoparticles
Magnetic nanoparticles commonly consist of elements such as iron, nickel, and

cobalt and their chemical compounds [1, 24]. Magnetic nanoparticles also exhibit
some new and interesting physical properties due to their quantum size effects in the
nanoscale dimensions, including magnetic interactions, electronic properties,
charge transfer, etc. [53].
Ferrite nanoparticles (iron oxide nanoparticles) are in maghemite or magnetite
crystal structure and have superparamagnetic character in nanoscale.
Superparamagnets exhibit magnetic behavior when an external magnetic field is
Synthesis and Characterization of Undoped and Doped … 153
applied on them. The surface of ferrite nanoparticles are preferred to be modified

generally by silica or polymers to increase their stability in solution. Magnetic
nanoparticles are used in medical diagnostics and cancer treatments (magnetic
hyperthermia), chemistry, biomedical imaging, electronics for storage of informa-
tion processes, memory applications, and also for a variety of genetics applications
[1, 12, 35, 70]. Identification of the magnetic behavior of the widely used
nanoparticles such as Zinc oxide is an important concept.
1.3 Dilute Magnetic Semiconductors (DMS)
Semiconductor nanoparticles have physical and chemical properties between

molecules and bulk solid semiconductors which are strongly size dependent [21].
Nanostructured semiconductors are known to show quantum size effects such as
surface and interface effects, enhanced optical nonlinearity, and excellent photo-
catalytic properties [8, 26, 69] so that this topic is accepted to be very important and
studied across the world [5]. Semiconductors and many other metals can also show
some changes in their optical properties depending on their particle sizes. It is
known that semiconducting nanoparticles can exhibit fluorescence showing blue
shift with the decreasing particle size [11].
Diluted magnetic semiconductors (DMS) obtained by introducing a dilute
amount of rare earth or transition metal ions into semiconductors in which the
transport and magnetic properties can be combined in a single substance. Thus,
DMSs have wide interest recently for their possible applications in generating and
manipulating spin-polarized currents [11, 17, 18, 38, 44]. DMSs are subjected to
their promising applications particularly to spintronics (spin + electronics) [1, 11,
14, 16, 47, 59]. DMSs have also several favorable properties such as ultraviolet
absorbance, piezoelectricity, luminescence at high temperatures, good transparency,
high electron mobility, etc. [8].
Recently, investigations on oxide diluted magnetic semiconductors such as
transition metal doped ZnO, TiO2, SnO2, etc., have been investigated due to their
promising magnetic properties [4, 14, 17, 37, 51, 58, 67]. Among the most studied
metal oxides nanoparticles, Zinc Oxide (ZnO) stands out due to its low cost and
ease of synthesis, extraordinary optoelectronical properties, environmentally
friendly, and highly versatile device fabrication [57]. Band gap of ZnO nanopar-
ticles demonstrate strong size dependency [19] so ZnO nanoparticles can have
broad applications for UV lasers, photodetectors, switches, bio-sensors, solar cells,
etc., [62]. ZnO is also a promising host material for ferromagnetic transition metal
ion dopants such as Mn, Co, Cu.
1.4 Room Temperature Ferromagnetism of ZnO

Nanoparticles
Spintronic technology aims to use the spin of the electron instead of its charge for
reading, writing, and transferring data in technology, at high temperatures, espe-
cially at room temperature [44]. Room temperature ferromagnetism has been
realized from the wide band gap of semiconductors [56]. Ferromagnetism in DMSs
is a very interesting problem in magnetism and it is also based on some theoretical
work for transition metal doped ZnO nanoparticles [16, 31].
ZnO-based DMSs are accepted to be the possible candidates for high tempera-
ture ferromagnetic semiconductors and promising host materials for ferromagnetic
doping [1, 6, 19]. Because ZnO-based DMSs have wide band gap (3.4 eV) and
large excitonic binding energy (60 meV) to the possibility of achieving room
temperature ferromagnetism [51] for the applications such as spin-based light
emitting diodes, sensors, and transistors [50].
Above room temperature, ferromagnetism has been predicted for several tran-
sition metals doped to ZnO [14] such as Co [4, 9, 61], Mn [19, 67], Fe [19], Cu [6],
etc. Although the mechanism responsible for ferromagnetism behavior at
high temperature is still not clear [65], it is known that the ferromagnetism of
the samples are very sensitive to their synthesization methods or their prepara-
tion conditions. So many controversial results, such as very low magnetic property
or even the absence of ferromagnetism have been also reported in the literature
[1, 11, 14].
1.5 Zinc Oxide (ZnO) Nanoparticles
Zinc oxide is an inorganic compound and it is accepted to be one of the most

important semiconductor materials, both with scientific and technological interest
[10, 11, 23].
ZnO is present in the Earth’s crust as a mineral zincite but mostly it is produced
synthetically. ZnO usually appears as a white powder which is nearly insoluble in
water and ZnO is used in large scale including plastics, ceramics, glass, paints,
pigments, foods (source of Zn nutrient), batteries, ferrites, etc. [8]. ZnO is a II–VI
semiconductor where zinc and oxygen belong to second and sixth groups of the
periodic table [8]. ZnO crystallizes in three forms such as hexagonal wurtzite, cubic
zincblende, and cubic rocksalt but it generally crystallizes in hexagonal wurtzite
form as this is the most stable form at ambient conditions. The chemical structure of
the ZnO is given in Fig. 1.
ZnO has a direct wide band gap energy 3.4 eV besides its high exciton binding
energy of 60 meV where the large exciton binding energy provides it more efficient
excitonic emission even at high temperatures [19, 54]. It is one of the few oxides
that show quantum confinement effects experimentally depending on its size range
Fig. 1 Chemical structure of

ZnO
[41]. The quantum confinement of nanocrystalline ZnO particles can be illustrated

from the blueshift in their photoluminescence UV emission and the properties of the
ZnO nanocrystals depend closely on their particles size, morphology, and surface
area [27].
Because of the wide and direct band gap properties, ZnO nanopowders are
preferred to be investigated due to their applications in different optic, electronic,
spintronic, or magnetic devices [31, 32, 37]. ZnO is also widely preferred in
optoelectronic applications such as field effect transistor (FET), transparent elec-
tronics and UV light emitters, displays, sensors, ultraviolet and visible lasers, solar
cells components, in pharmaceutical and cosmetic industries, in thin film printing,
in transparent electronics, in information storage, etc., [5, 6, 8, 13, 18, 20, 22, 25,
39, 40, 42, 43, 45, 47, 49, 52, 54, 55, 59, 62].
1.6 Doped ZnO Nanoparticles
The magnetic properties of wide band gap semiconductors doped with transition
metals are another current and controversial topics [6]. Doping is generally used to
improve electrical, optical, and mechanical properties of a semiconductor com-
pound [54] and it is needed to use the well-chosen and suitable impurities. ZnO,
TiO2, CeO2, and SnO2 diluted magnetic oxides are doped with various transition
metals such as Co, Fe, Ni, and Mn and they are investigated both in theoretical and
in experimental so as to predict their magnetic properties [1, 6, 11, 20, 31, 44, 66].
It is known that the conductivity and optical properties of ZnO depend strongly on
the concentration of doped impurities [45]. As an example, ZnO which is trans-
parent to visible light can be made highly conductive by only doping process [20].
Thus, investigations on doped elements in ZnO host materials and the electrical,
optical, magnetic properties of these samples are also very important.
Mn-doped ZnO nanoparticle is very promising due to the wide band gap of
ZnO host material and high solubility of Mn atoms in ZnO matrix [14]. Having
similar charge state and ionic radius with the host Zn2+ cations, Mn2+ ions are
suitable for sensitive atomic probes in Zn-based compounds [63]. Mn-doped ZnO
semiconductors have also become a topic of current interest because of the possi-
bility of their room temperature ferromagnetism, thus Mn-doped ZnO can be a
promising material in spintronic applications. Thus, ZnO is one of the host oxide to
which addition of Mn causes paramagnetic or ferromagnetic depending on the
concentration of the doped Mn and the preparation methods [11, 14, 67]. It has been
also observed that doping concentration of Mn has also significant effect on the
optical properties of ZnO [31, 39]. For the low doping concentrations of Mn (<3 %
mol), the band gap of ZnO is reduced while it is increased for higher Mn doping
concentrations (>3 % mol). In addition, a much weaker blue-green peak is also
observed at 435 nm and the peak is accepted to be in relation with the surface
defects coming through the oxygen vacancies and/or zinc interstitials. As the
concentration of Mn increases, the blue emission significantly increased due to the
strong exchange interactions in the short range spin system [39].
Cu-doped ZnO nanoparticle is another important research area where metallic
Cu and Cu related oxides are nonferromagnetic materials. Some theoretical and
experimental studies have confirmed that Cu-doped ZnO nanoparticles can indicate
room temperature ferromagnetism depending on their synthesis procedure [6].
Co-doped ZnO nanoparticle has also been intensively studied in aiming to
observe the room temperature ferromagnetism in transition metal-doped semicon-
ductors [9]. Especially Co-doped ZnO is possible candidates for high temperature
ferromagnetic behavior and has attracted attention [1, 4]. But it is again very
sensitive to the synthesization method of the samples and depending on their
preparation conditions, thus many controversial results have also been reported.
1.7 Defect Types in ZnO Nanoparticles
The magnetically ordered doped or undoped semiconductors with wide band gaps
generally contain a specific amount of point defects. Electronic, magnetic, optical,
and structural properties of these semiconductors are very sensitive to the defects
where the defects can localize in the metastable energy levels of the wide band
gap. The nature of the defects strongly depends on the synthesis method and
dimension of the material.
It is evident from literature that various behaviors of ZnO are due to the presence
of native defects, such as oxygen vacancies, zinc vacancies, zinc interstitials, and
oxygen interstitials [54, 69]. In many cases, these defects act as shallow donors or
deep acceptors within the wide band gap of ZnO. Based on ESR and PL analyses, it
was concluded that VZn and Zni defects are the main cause of the room temperature
ferromagnetism of the ZnO nanostructures [42]. Oxygen vacancies on metal oxide
surfaces are found to be electrically and chemically active and responsible for the
increasing of the conductivity of the materials [8, 19]. ZnO nanowires are also
reported to show n-type semiconductor behavior attributed to intrinsic defects

involved in ZnO [19, 22].
These defect centres are also believed to be responsible for visible photolumi-
nescence for ZnO [8, 15] and the concentration of these defects in ZnO nanos-
tructures prepared at low temperatures are believed to be under control by annealing
[8]. The presence of OH groups attached to the surface was also accepted to be
responsible for the green emission of ZnO [46]. Hydrogen impurities absorbed by
ZnO from the air is also reported acting as shallow donors [22]. In another study,
core defects are assumed to be originated from the negatively charged zinc
vacancies on the crystalline region and shell defects are assumed to be originated
from positively charged oxygen vacancies on the surface of ZnO [18]. It is also
reported that above 800 °C annealing temperature, ZnO microcrystallites com-
pletely become bulk material and no defect centers could be observed [69].
Electron Paramagnetic Resonance (EPR) spectroscopy is a powerful analytical
method to monitor these defect centers found and/or created in the samples and can
be successfully applied for undoped and doped ZnO nanoparticles [55]. In this
study, EPR results for the ZnO nanostructures have also manifested that the Vo
centers are the predominant defects in the doped and undoped synthesized ZnO
nanoparticles confirming the literature [2].
1.8 Electron Paramagnetic Resonance (EPR) Spectroscopy
Electron Paramagnetic Resonance (EPR) is a very sensitive spectroscopic tech-

nique that can detect many types of transition metal ions, free radicals, biradicals,
and defect types, particularly for paramagnetic materials [14]. This method was first
discovered in 1944, in Kazan University by Zavoisky, on the investigations of
electromagnetic energy absorption by paramagnetic metal salts. This technique has
high resolution (*1012 spins), the measurement is easy, accurate, and harmless to
the analyzed sample [68]. EPR crosses multidisciplines including free radicals
observed in gaseous, liquid, and solid systems, the irradiated substances in organic
compounds, paramagnetic color centers, irradiated chloroplasts, conducting poly-
mers, free radical intermediates, chemical complexes with transition metals, for
dosimetric and sterilization purposes, for dating and for spin labeling studies [29].
EPR is also successfully being used for analysis of semiconductor microcrys-
tallites [69]. EPR is mostly playing a key role in the determination of point defects
found in bulk semiconductors, for more than 60 years. Thus for the analysis of
undoped and doped ZnO nanoparticles, sensitive EPR results are used to be a direct
method to monitor the presence of native defects, such as oxygen and zinc
vacancies [54, 58, 59].
EPR spectroscopy is based on the absorption of microwave electromagnetic
radiation by the unpaired electrons included in the investigated sample, when the
sample is placed in an external magnetic field (Fig. 2). When the unpaired electron
is placed within the applied magnetic field, H0, two possible spin states of the
Fig. 2 EPR spectrometer
Fig. 3 Energy levels in the

existence of external magnetic
field
electron will have different energies, by the result of the Zeeman effect. The lower
energy state occurs when the magnetic moment of the electron, l, is aligned with
the magnetic field and a higher energy state occurs where l is aligned against the
magnetic field (Fig. 3) [68].
If a second weaker alternating magnetic field H1 oscillating at a microwave
frequency (Fig. 2) is applied at right angles to the static field of H0, then the
electron will begin to precess in the axis of H1 and when the microwave frequency
will be equal to the precession frequency, the “resonance condition” will be sat-
isfied (Eq. 1). In the Eq. 1; m is the microwave radiation frequency, h is the Planck
constant, g is the spectroscopic splitting factor (g–factor) and b is “Bohr
magneton”.
ht ¼ gbH0 ð1Þ
The unpaired electron absorbs microwave energy in the resonance condition and
transitions between the energy states are observed, named as EPR signals. Free
radicals have values that are fairly close to g = 2.0023 which characterizes a free
electron. For crystalline samples, g-factor values corresponding to crystal orienta-
tion are designated as gxx, gyy, and gzz, respectively.
EPR signal represents the first-order derivative of absorption line so as to

increase the resolution of the recorded spectrum. The area under the line of
absorption is proportional to the concentration of paramagnetic centers contained in
the sample. The line width of the EPR spectrum gives information about the spin
system and the lattice interactions. EPR spectrum can also contains several lines
referring to hyperfine splitting relating with the electrons interacting with the
neighboring nuclear spins. The magnetic behavior of the electron is modified by its
surroundings, so EPR spectra of different samples will be different [68].
EPR provides information not only about the structure, but also the localization
of the dopants, particle size, and phases present in the nanostructures with a good
accuracy level [63]. It is a very sensitive method for also detecting ferromagnetic
ordering as well as the existence of other magnetic species [14, 31, 48, 65].
2 Experimental Results and Discussions
2.1 Synthesis of Undoped and Doped ZnO Nanoparticles
Chemical Co-precipitation Method was used in the synthesis of undoped and 5 %

content of Mn, Cu, and Co-doped samples. Chemical co-precipitation synthesis
method is cost effective, has lesser synthesis time, requires low temperature for
processing, and both low and homogeneous dimension of nano scale particles can
be produced. Chemical synthesis of ZnO nanoparticles has been tried in alcoholic
media as ethanol as the growth of oxide particles is slow and controllable in
alcoholic media [5].
For the synthesis process of undoped ZnO nano particles, 23 mmol of Zn
(CH3COO)22H2O and 100 mL methanol were stirred by a magnetic stirring for 2 h
at 50 °C with 250 rpm. Another solution of 70 mmol of NaOH and 100 ml
methanol were stirred for 2 h, at 50 °C. These two solutions were mixed and
centrifuged at three steps on the last solution. In the first step, the solution was
centrifuged at 8500 rpm for 30 min. For the second step, liquid phase of the
solution is separated, ethanol was added and centrifuge was again held at 4500 rpm
for 15 min. In the third step, liquid phase of the sample was again separated from
the solution, ethanol was again added and it was stirred at 4500 rpm for 5 min.
Finally, the liquid phase was separated from the stirred sample and nano sample in
solid phase was obtained.
For the synthesis of doped ZnO nano particles; Mn(CH3COO)24H2O, Cu
(CH3COO)2H2O, and Co(CH3COO)24H2O were added in 5 % content to the
prepared solution, for the synthesis of Mn, Cu, and C -doped ZnO nano samples,
respectively.
2.2 XRD Results
X-ray diffraction is a non-destructive analytical method for identification and

quantitative determination of various crystalline forms in powder and solid samples
[1, 4, 8, 27, 45, 66]. For the investigation of structural properties of undoped and
5 % Mn2+, Cu2+, and Co2+ doped ZnO samples, XRD studies were held.
Rigaku D Max-2200 (CuKa-40 kV, 40 mA, 200VAC, 3 phase) type of XRD
diffractometer was used in XRD experiments. Crystallite size of the samples were
found by using Scherer’s formula (Eq. 2) where in the equation t is the crystallite
size, k is wavelength (k = 1.5405 Å), b is the full maxima half width, h is
diffraction angle and k is a constant (k = 0.9).
kk
b cos h ¼ ð2Þ
t
XRD results indicated that Mn, Cu and Co ions in the ZnO nanoparticles only
substituted with Zn ions (Figs. 4 and 5). The synthesized undoped and doped ZnO
nano samples have the wurtzite structure and no secondary phases were detected
although some little amount of impurities were observed and these results are also
agree with the literature [1, 4, 27, 34, 38, 44, 45, 56, 64, 66].
Fig. 4 XRD results of

synthesized ZnO
nanoparticles (unannealed and
700 °C annealed undoped and
Zn:Mn doped (%5) samples)
Fig. 5 XRD results of

synthesized ZnO
nanoparticles (unannealed and
700 °C annealed Zn:Cu and
ZnO:Co-doped (%5) samples)
Annealing studies for the synthesized samples were held at 300 °C (1 h), 500 °C
(2 h) and 700 °C (2 h). For the annealing studies, MF 120 ash furnace with a Ni–
CrNi temperature controller [600–1200 °C (±2 °C)] has been used. The samples
were wet after the annealing procedure and white color of the samples were turned to
pink, gray, or black colors after annealing process. Thus, organoleptic properties of
the samples were changed after the annealing procedure which is also confirmed by
some of the data in the literature [7, 69].
Annealing procedure causes to decrease the defects found in the samples, thus
optical, electrical, and structural properties of the samples are expected to be cured
at high temperatures [17]. In this study; the particle dimensions of undoped and
doped ZnO nano samples have observed to be increased by the treatment of heat
and the broad peaks recorded for the unannealed samples became sharper for the
annealed samples (Figs. 4 and 5). The average of the particle size of the unannealed
samples were found to be *8 nm by using Scherer formula (Eq. 2) where the
average particle size was *60 nm for the samples annealed at 700 °C. These
dimensions are also in good agreement with SEM results.
2.3 Scanning Electron Microscope (SEM) Results
Scanning Electron Microscope (SEM) analyses were recorded by using an

Carl-Zeiss EVO-50 EP Scanning Microscope (W flaman-20 kV–10 pA, gain is
65,000–150,000). The dark shapes in the SEM results generally related with the
rich content of Zn and doped ions (oxygen content is low). It is observed that the
unannealed and annealed doped ZnO nano samples were nearly cylindrical in shape
with particle sizes of *90 and *200 nm, respectively (Fig. 6). Agglomerations
Fig. 6 SEM images of synthesized undoped and doped ZnO nanoparticles

have been also taken place for the 700 °C annealed doped ZnO nanoparticles which
is in agreement with the XRD results obtained. This result is also confirmed with
literature [10, 67].
2.4 Ultraviolet-Visible (UV-Vis) Spectroscopy Results
In Ultraviolet-Visible (UV-Vis) spectroscopy, high energy electromagnetic radia-

tion in the wavelength range of 100–700 nm is utilized to promote electrons to
higher energy orbitals. Since orbitals have quantized energy, only certain transitions
can occur in the UV-Vis energy range. The differences in the incident and trans-
mitted beam give us information about the frequencies which are absorbed by the
investigated samples. Basing on the absorbance data recorded, the chemical
structure of the investigated sample can be analyzed [12]. Among various spec-
troscopic methods, UV-Vis spectroscopy has been often used to characterize the
optical properties of the nanoparticles.
ZnO is accepted to be excellent promise for blue and ultraviolet optical devices
because of its wide band gap energy [20, 27] and the quantum confinement of
nanocrystalline ZnO particles is illustrated from the blueshift in its photolumines-
cence UV emission [27]. The band gap energy is also changed by doping type and
content to ZnO nanoparticles [14, 20, 39]. In this study, UV-Vis is used to get
information about the absorption curve of doped and undoped synthesized ZnO
nanoparticles, besides the calculation of the band gap energy of the samples.
For identification of the optical behavior of the synthesized undoped and doped
ZnO nanoparticles, a Hitachi U-1900 model of UV-Vis spectrometer has been used.
The synthesized samples that were handled before centrifuge process (in liquid
form) and stored at normal conditions (atmospheric pressure and moisture) in dark
were used for UV-Vis studies.
The strong UV absorbance peaks were appeared approximately at
kaverage = 335 nm and the mean gap energy was calculated to be Egap = 3.47 eV
Fig. 7 UV-Vis result of synthesized ZnO:Cu nanoparticle

by using Beer-Lambert’s law. These results are in consistent with also the literature
[5, 13, 40, 54]. UV-Vis result of ZnO:Cu sample is given in Fig. 7. It is observed
that with the decreasing of particles sizes, UV light absorbance of the ZnO
nanoparticles was increased. Thus, the optical properties get better with the
increasing of surface-to-volume ratio for Zinc oxide nanoparticles [43].
2.5 Atomic Force Microscope (AFM) Results
The surface topographies of the synthesized Mn-doped ZnO nano particles are
investigated before and after annealing process by AFM studies. Nanomagnetics
Instruments Ambiant (1 lm 1 lm area, 1 lm/s sweep velocity, 256 256 pixel
resolution, dynamic mode) AFM instrument was used in the experiments. Different
growing directions and the grain sizes were observed from AFM results for
unannealed and annealed ZnO:Mn nanoparticles (Fig. 8). Agglomerations have
also been observed from the AFM images of the samples which are in agreement
with the literature [34, 67].
2.6 Electron Paramagnetic Resonance (EPR) Results
Electron Paramagnetic Resonance (EPR) spectroscopy is a quick, nondestructive

analytical method for investigation of particulary the paramagnetic centers in the
samples. In this study, the magnetic characterization of synthesized ZnO nano
samples has been performed dominantly by using electron paramagnetic resonance
(EPR) spectroscopy. Vibrating sample magnetometry (VSM) was also used as a
complementary technique.
Fig. 8 AFM results of unannealed and 700 °C annealed ZnO:Mn nanoparticles

Bruker EMX-131 X-band (9.3 GHz) EPR spectrometer was used in the exper-
iments. Spectrometer operating conditions were as follows; central field:
348.5 mT; sweep field: 200 mT; microwave frequency: 9.84 GHz; microwave
power: 1 mW; modulation frequency: 100 kHz; modulation amplitude: 1 G;
receiver gain: 6.3 104; sweep time: 81.92 ms; time constant: 40.9 ms.
2.6.1 EPR Results for Undoped Synthesized ZnO Nanoparticles
The defect types found in nano scale ZnO is generally related with the oxygen
vacancies Vo+2 (O−2 superoxide ions, F centers) in the literature and this defect type
is accepted to be responsible from the EPR signal for the undoped ZnO nanopar-
ticles [7, 18, 28]. Vo+2 oxygen vacancy is not stable and appears from the shallow
part of the ZnO nanoparticles and it gives rise to the EPR resonance line with the
corresponding g-value of 2.0021 [30] which is very close to the g-value of the free
electron (gfree electron = 2.0023). Vo+2 oxygen vacancy can also be trapped by a
single electron (Vo+1) or by two electrons (Vo0). Vo+1 oxygen vacancy (O−1 ion) is
contributing from the deeper part of ZnO (core of ZnO) nanoparticle which is more
stabile and giving rise to the EPR resonance line with the corresponding g-value of
1.9588 [28]. Zn vacancies found in the structure of ZnO nanoparticles are also
accepted to be relatively stable defect type.
In this study, no EPR resonance signal was detected for the synthesized undoped
ZnO nanoparticles, indicating that undoped ZnO nanoparticle was in diamagnetic
nature. When the undoped ZnO nanoparticles were annealed at 300 °C for 1 h, a
single, broad, and unresolved EPR resonance line with spectral parameters of
g = 2.169 and DHpp = 6 mT was arised. Besides, two other resonance lines (Ia and
Ib), hardly distinguishable from noise, with corresponding g-values of ga = 2.009
and gb = 1.959 were also observed. Ia and Ib resonance lines are accepted to be
originating from Vo+2 and Vo+1 damage centers, respectively (Fig. 9). For the
samples annealed at 500 °C for 2 h, the intensities of Ia and Ib resonance lines
increased while the area calculated for the whole EPR spectrum recorded had been
decreased. For the annealed samples at 700 °C for 2 h, a dramatic decrease for the
whole spectrum, including Ia and Ib resonance lines, had been observed, indicating
the sharp decrease in the number of paramagnetic centers found in the sample. But
one of the new resonance line Ib (gb = 1.959) could be still distinguishable from the
noise. This result indicates that Ib resonance line was related with Vo+1 damage
center which has deeper (core) location in ZnO crystal structure and is relatively
stable [28].

unannealed and annealed
(300, 500, and 700 K)
synthesized undoped ZnO
nanoparticles
2.6.2 EPR Results for Mn-Doped Synthesized ZnO Nanoparticles
Mn+2 ion has 3d5 electronic configuration, electronic ground state of 6S5/2, and
spectroscopic splitting factor of g * 2.002 [68]. The variation of Mn concentration
(1, 2 and 5 %) have not changed the EPR spectrum pattern of the Mn-doped ZnO
nanoparticles but the EPR signal intensities have increased with increasing the Mn
content. For the 5 % Mn-doped ZnO nanoparticles, 6 resolved EPR resonance lines
were recorded and g-value related with the central EPR resonance line was cal-
culated to be 2.009. The recorded spectrum was spread over a 80 mT magnetic field
range and the average hyperfine splitting factor for ZnO:Mn nanoparticles was
calculated to be 8.0 mT (Fig. 10).
The baseline signal observed in the spectrum which is shown with dashed line is
related with the “ferromagnetic resonance behaviour” of ZnO:Mn nanoparticles,
where six resolved narrow ESR signals are related with the “paramagnetic char-
acter” of Mn+2 ions found in ZnO:Mn nanoparticles. Thus, for Mn-doped ZnO
nanoparticles, both paramagnetic and ferromagnetic characters are observed
Fig. 10 EPR spectrum of 5 % Mn-doped ZnO nanoparticle
together which is also confirmed by VSM results in this study. There are also
similar results appeared in the literature [14, 16, 36].
In annealing studies, no EPR spectrum pattern change had been observed for
Mn-doped ZnO nanoparticles but the average value of hyperfine splitting constants

(300, 500, and 700 K)
synthesized %5 Mn-doped
ZnO nanoparticles
calculated for the unannealed samples (8.0 mT) were decreased in small ratio
(7.9 mT) when the samples were annealed. The number of paramagnetic centers
contributing to Mn-doped ZnO nanoparticles annealed at 300 °C for 1 h was
calculated by double integration method and it is seen that the area of the spectrum
which is linearly proportional with the number of magnetic centers involved in the
sample had increased in the order of *10 %. Magnetic centers contributing to the
recorded EPR spectrum continued to increase for also the samples that were
annealed at 500 °C for 2 h and finally the number of magnetic centers calculated
for the annealed samples at 700 °C were calculated to be *10 times higher than the
case for unannealed samples showing that the magnetic unit content was increased
for the heat treated ZnO:Mn nanoparticles (Fig. 11). This result was also confirmed
by VSM data.
2.6.3 EPR Results for Cu-Doped Synthesized ZnO Nanoparticles
Cu+2 ion has 4s1 electronic configuration, electronic ground state of 2D5/2, and
spectroscopic splitting factor with g * 2.116 [68]. For the 5 % Cu-doped ZnO
nanoparticles, the g-value corresponding to the central resonance line of EPR
spectra was found to be 2.063 where four resolved EPR resonance lines were
observed. The hyperfine splitting factor was calculated to be A = 13.5 mT and the
spectrum was spread over 100 mT magnetic field range (Fig. 12).
Annealing process caused sharp decreases in the intensities of EPR resonance
lines recorded for the 5 % Cu-doped ZnO nanoparticles. This result indicates that
the number of magnetic centers found Cu-doped ZnO nanoparticles decreases under
Fig. 12 EPR spectrum for 5 % Cu-doped ZnO nanoparticle


(300, 500, and 700 K)
synthesized Cu-doped ZnO
nanoparticles
the influence of heat treatment (Fig. 13) and ZnO:Cu nanoparticles annealed at
700 °C were completely in diamagnetic character. This result was also confirmed
by VSM studies.
2.6.4 EPR Results for Co-Doped Synthesized ZnO Nanoparticles
Co+2 ion has 3d7 electronic configuration, electronic ground state of 4F9/2, and
spectroscopic splitting factor with g// * 2.2 and g⊥ * 4.6002 [51, 68]. A single,
unresolved, broad EPR resonance line was recorded for 5 % Co-doped ZnO
nanoparticle, and the spectral parameters such as g-value and peak-to-peak width
were calculated to be 2.119 and 77.3 mT, respectively (Fig. 14).
A smooth increase in the EPR signal intensity has been observed for Co-doped
ZnO nanoparticles which are annealed at 300 °C for 1 h. Besides, one more EPR
Fig. 14 EPR spectrum of 5 % Co-doped ZnO nanoparticle
resonance line (Ia) with ga value of 2.002, that is related with Vo+2 center, had also
been observed (Fig. 15). The whole spectrum area (double integration method is
used) recorded for the annealed sample at 500 °C for 2 h was found to increase in
the order of *%3 where the intensity of new appeared Ia resonance line was

(300, 500, and 700 K)
synthesized 5 % Co-doped
ZnO nanoparticles
increased *10 times compared with that of annealed at 300 °C. But a sharp
decrease has been observed for the annealed samples at 700 °C for 2 h and besides
Ia resonance peak had disappeared completely.
2.6.5 EPR Results of UV-Irradiated Undoped and Doped ZnO

Nanoparticles
To examine the effect of UV-irradiation on the synthesized undoped and doped

ZnO nanoparticles, the samples were exposed upon UV-irradiation with additive
dose method for predetermined irradiation times up to 200 min. The samples were
UV irradiated with a distance of 60 cm to irradiation source with using a Termo
Oriel-6295 model, 1000 W monochromatic Hg (Xe) arc lamp.
UV irradiation caused some organoleptic changes during the irradiation process,
such as darkening colors of the irradiated samples. This result is in agreement
with literature where such similar effects have also been obtained by Schneider
et al. [59].
No EPR signal was observed for UV irradiated undoped ZnO nano particles but
two new EPR resonance lines Ia and Ib with corresponding g-values of ga = 2.009
and gb = 1.959 have been arised in the EPR spectrum of UV-irradiated undoped
ZnO nanoparticles. These new resonance lines were probably causing from the
oxygen damage centers involved in the crystal structure of ZnO nanoparticles.
For the UV irradiated Cu-doped ZnO nanoparticles, a new EPR resonance line,
Ia, with ga = 2.003 had also been appeared for the UV-irradiated samples, at the
irradiation duration of 30 min. The intensity of this new resonance line was
increased linearly with increasing the irradiation time, up to 200 min. This Ia res-
onance line is accepted to be related with Vo+2 damage center and this result is also
in agreement with the literature [54].
For UV-irradiated Co-doped ZnO nanoparticles, another new EPR resonance
line, Ia, with ga = 2.001 had appeared after 5 min of UV-irradiation duration and
the line intensity of this new resonance line, which is related with Vo+2 damage
center, had increased slightly with the increasing UV-irradiation time. The varia-
tions of Ia resonance line with UV-irradiation time are not given.
Oxygen and zinc vacancies can exist in more than one charge state, and they are
often using to explain the optical properties of ZnO. Exposure of light can produce
new EPR resonance lines on the irradiated ZnO nanoparticles originating from
oxygen vacancies and/or impurities related with zinc vacancies [33]. It is observed
that irradiation at room temperature with high energy electrons (3 meV) can
also produce oxygen and zinc vacancies in the crystal structure of ZnO nanopar-
ticles [33].
The EPR spectrum area variations of the UV-irradiated Mn, Cu, and Co-doped
ZnO nanoparticles with UV-irradiation time is given in Fig. 16. It is seen from this
Fig. 16 EPR signal intensities of UV-irradiated 5 % doped ZnO nanoparticles for different
irradiation times. a Mn-doped ZnO, b Cu-doped ZnO, c Co-doped ZnO
figure that the area, relating with the magnetic units found in doped ZnO
nanoparticles, had decreased slightly with the increasing UV-irradiation time
(Fig. 16).
2.7 VSM Results
It is known that obtaining room temperature ferromagnetism will greatly advance

future research [49, 66]. Vibrating sample magnetometry (VSM) technique was
used as an alternating and complementary method for the magnetic characterization
of synthesized undoped and doped ZnO nanoparticles. For VSM analysis,
Cryogenic Limited PPMS, and ADE Magnetics VSM measurement systems were
used.
It was observed that the undoped and unannealed ZnO nanoparticles were in
diamagnetic character (Fig. 17). The VSM results obtained for undoped and
annealed at 700 °C (for 2 h) ZnO nanoparticles showed also diamagnetic behavior
Fig. 17 VSM results of undoped ZnO. a unannealed, b annealed at 700 °C
confirming the results of EPR studies. Similar results were also reported in the
literature depending on the preparation conditions of ZnO nanoparticles [30, 56].
VSM result for %5 Mn-doped unannealed ZnO nanoparticles showed that this
sample indicated both ferromagnetic and paramagnetic character together
(Fig. 18). But the annealed Mn-doped ZnO nanoparticles at 700 °C showed only
paramagnetic type of magnetic character. The same results were also observed by
EPR spectroscopy.
In the literature, some controversy types of magnetic characters for Mn-doped
ZnO nanoparticles have been observed [67]. Sharma et al. [60] have observed
ferromagnetism above room temperature for bulk and thin film forms of Mn-doped
ZnO. In another study, the ferromagnetism in Mn-doped ZnO nanoparticles have
appeared for low temperature annealed samples and disappeared in the samples
annealed at high temperatures [65]. But there are also some several reports on
Mn-doped ZnO samples that do not exhibit ferromagnetic properties. The ferro-
magnetism of such materials is accepted depending strongly on their synthesis
Fig. 18 VSM results of Mn-doped ZnO nanoparticles. a unannealed, b annealed at 700 °C

Fig. 19 VSM results of Cu doped ZnO nanoparticle. a unannealed, b annealed at 700 °C
procedures preferred [48]. The difference in the ferromagnetic properties of the

Mn-doped ZnO nanoparticles can be also attributed to the Mn content [11].
VSM result recorded for 5 % Cu-doped ZnO nanoparticles which was unan-
nealed and annealed at 700 °C indicated diamagnetic characters. It is well known
that this property is strongly dependent on the preparation conditions of the samples
and the type of synthesis method used (Fig. 19).
VSM result of 5 % Co-doped unannealed ZnO nanoparticles showed that this
sample had both ferromagnetic and paramagnetic type of magnetic property. The
annealed Co-doped ZnO nanoparticles at 700 °C were found to be in paramag-
netic character by using VSM studies (Fig. 20). These results were also confirmed
by the EPR data obtained for the same sample. Ferromagnetic character of ZnO:Co
nanoparticle at room temperature is observed in the literature [61].
Room temperature ferromagnetism in doped samples is also accepted to be
generated from the oxygen vacancies in the structure of ZnO [14]. There are some
studies in the literature indicating that doped ZnO nanoparticles with Co, Mn, Ni,
etc., can be ferromagnetic at room temperature [1, 17] but this character is still in
Fig. 20 VSM results of Co-doped ZnO nanoparticles. a unannealed, b annealed at 700 °C

debate [9] as the magnetic properties of doped ZnO are most likely dependent on
the preparation conditions [11, 14]. There are also some studies in the literature
where ZnO nanoparticles indicating bulk character after the annealing process [7,
30] as annealing process decreases the impurities of defect centers.
3 Conclusion
In this study; structural, optical, and magnetic properties of undoped and 5 %

content of Mn, Cu, and Co-doped ZnO nanoparticles were synthesized by chemical
co-precipitation method and have been investigated dominantly by EPR, and some
other complementary techniques such as XRD, SEM, AFM, UV-Vis, and VSM.
Crystal sizes of the synthesized ZnO nanoparticles have been determined to be
*8 nm by XRD analysis and particle sizes of the ZnO nanoparticles were found to
be *90 nm by SEM analysis. Annealing process increased the dimensions of the
synthesized nanoparticles. The surface topographies of the samples were recorded
by AFM. UV-Vis results indicated that for undoped and doped synthesized ZnO
nanoparticles, the absorbance peaks were appeared at about k = 335 nm and the
mean gap energy is calculated to be *3.47 eV. No EPR signal had been observed
for undoped ZnO nanoparticles. For ZnO:Mn; six resolved EPR resonance lines
have been recorded with gcentral = 2.0097, for ZnO:Cu; four resolved EPR reso-
nance lines have been recorded with gcentral = 2.0637 and for ZnO:Co; a single
broad resolved EPR signal have been recorded with g = 2.1199. UV irradiation and
annealing processes caused some organoleptic changes on the samples and some
new EPR resonance lines were also appeared in their EPR spectra with very low
intensities and corresponding g-values of ga = 2.0021 and gb = 1.9588, probably
causing from the oxygen vacancies (damage centers) involved in the crystal
structure of ZnO. VSM findings have indicated that, unannealed and annealed
undoped ZnO were diamagnetic, unannealed, and annealed Mn-doped ZnO
nanoparticles were paramagnetic + ferromagnetic and paramagnetic, unannealed
and annealed Cu-doped ZnO nanoparticles were diamagnetic and unannealed and
annealed Co-doped ZnO nanoparticles were in paramagnetic + ferromagnetic and
paramagnetic.
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Emr/Esr/Epr Spectroscopy For Characterization of Nanomaterials

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Advanced Structured Materials

ISSN 1869-8433 ISSN 1869-8441 (electronic)

© Springer (India) Pvt. Ltd. 2017

Printed on acid-free paper

This Springer imprint is published by Springer Nature

Nanotechnology has opened up a new area of research in different ﬁelds.

Cerium Dioxide Nanoparticles” by me and my co-author Rafail Rakhmatullin deals

Allahabad, India Ashutosh Kumar Shukla

Part I Nanomaterials and their Classiﬁcation

Part II EMR Characterization of Nanoparticles

Cristina Buzea and Ivan Pacheco

Abstract In this chapter, we present a general classiﬁcation of nanomaterials based

© Springer (India) Pvt. Ltd. 2017 3

1 Nanomaterials Deﬁnition and Classiﬁcation

1.1 Nanomaterials Deﬁnition

A nanomaterial can be deﬁned as a material with external dimensions in the

“Nano” should be considered a different state of aggregation of matter in

Fig. 1 Calculated surface–

1.2 Nanomaterials Classiﬁcations

From the point of view of their dimensionality, nanomaterials can be classiﬁed as

or surface coatings attached on a substrate usually made from a different material.

Fig. 2 Classiﬁcation of nanostructured materials according to their dimensionality, morphology,

b Fig. 4 Field emission gun-transmission electron microscopy (FEG-TEM) images of silver

Fig. 5 a, c, e Transmission electron microscopy and b, d, f scanning electron microscopy images

1.2.2 Nanomaterials Morphology

A classiﬁcation of nanomaterials according to their morphology divides them in

1.2.3 Nanomaterials Composition

According to their composition, nanoparticles can be made of a single material,

1.2.4 Nanomaterials Uniformity and Agglomeration State

According to their uniformity, nanoparticles can be classiﬁed as isometric and

1.3 Physicochemical Properties of Nanoparticles

The most important physicochemical aspects of nanoparticles are:

1.3.1 Composition and Surface Composition

Nanoparticles can be made of a single material or composite materials. Examples of

Nanocomposites made of long aspect ratio materials together with spherical

1.3.2 Crystalline Structure

Crystalline structure is of paramount importance in deciding a nanoparticle’s

1.3.3 Shape or Morphology

Nanoparticles with different morphologies have been demonstrated, such as:

1.3.4 Surface Area

1.3.5 Water Solubility-Dispersability

Nanoparticles can be insoluble or repelling water, also called hydrophobic.

1.3.6 Catalytic/Photocatalytic Activity

1.3.7 Magnetic Properties of Nanoparticles

spontaneous magnetic moment. In an external magnetic ﬁeld, both antiferromag-

explained by the decrease in surface magnetism and increase in spin-polarized

1.3.8 Optical Properties

The optical properties of nanoparticles vary with their composition, morphology,

Fig. 17 TEM images of cetyltrimethylammonium bromide-coated Au nanoparticles with different

1.3.9 Mechanical Properties—Melting Temperature

Melting temperature of nanoparticles

1.4 Biologically Synthesized Nanoparticle

Nanoparticles can be synthesized by traditional physical and chemical methods,

Table 1 List of microorganisms and synthesized metal nanoparticles

Table 2 List of selected plants and synthesized nanoparticles

A wide variety of metals nanoparticles, including semiconducting (Cd, Se, Zn,

1.5 Nanoparticles Applications

Nanoparticles have a multitude of applications. The antimicrobial properties of

screening and prediction of toxicity of various nanoparticles should be performed