Nanoscale

View Article Online

REVIEW View Journal

Recent advances and perspectives in photo-

Published on 23 April 2021. Downloaded by University of Connecticut on 5/16/2021 8:17:10 AM.

Cite this: DOI: 10.1039/d1nr01255j

induced enhanced Raman spectroscopy
Jingtian Zhao, a,b Ziyun Wang,a,b Jinshen Lan,a,b Imran Khan,a,b Xiaofang Ye,a,b
Jing Wan,a,b Yuchen Fei,a,b Shengli Huang, *a,b Shuping Lia and Junyong Kanga

Phototreatment is at the leading edge of a research hot topic as a driving force for structural transform-
ation, spectral and electromagnetism improvements, and the functional performance of nanomaterials.
Light irradiation can excite surface plasmons in noble metal nanoparticles, create electron–hole pairs,
and produce charge transfer in semiconductor substrates, which have led to it being widely used in
surface-enhanced Raman spectroscopy (SERS) for life sciences, environmental protection, and biological
analysis. Photo-induced enhanced Raman spectroscopy (PIERS) is a new technology developed on the
basis of traditional SERS and has proven to be an efficient way to resolve several critical challenges thanks
to its incomparable superiority for incontiguous operation, efficient charge separation and enrichment,
and a large signal enhancement for a wide range of biomolecules at the trace level. This makes PIERS a
powerful technique with very appealing and promising applications in various branches of analytical
science. In this review, the enhancement mechanisms of PIERS are analyzed in comparison with SERS.
Received 25th February 2021, Afterward, the parameters influencing the enhancement of PIERS, including the substrate, light irradiation,
Accepted 17th April 2021
and relaxation are discussed in detail. Finally, some perspectives on further developments of PIERS are
DOI: 10.1039/d1nr01255j exemplified. The PIERS technique will continue to evolve and grow with new developments and its suc-
rsc.li/nanoscale cessful application in bioanalysis and life sciences.

1. Introduction
In the past decades, phototreatment has become a hot topic in
medicine and nanoscience. It can not only serve as a medical
a
Engineering Research Center of Micro-nano Optoelectronic Materials and Devices, procedure for virus elimination and patient treatment,1 but
Ministry of Education, Fujian Key Laboratory of Semiconductor Materials and
can also provide a driving force for structural transformation,
Applications, CI Center for OSED, Department of Physics, Jiujiang Research Institute,
Xiamen University, Xiamen 361005, China. E-mail: huangsl@xmu.edu.cn spectral and electromagnetism improvement, and the func-
b
Shenzhen Research Institute of Xiamen University, Shenzhen 518057, China tional performance of nanomaterials (see Fig. 1).2–12 As a dis-

Jingtian Zhao is a master’s Ziyun Wang is a master’s student in the College of Physical
student in the College of Physical Science and Technology, Xiamen University, China. Her research
Science and Technology, Xiamen interests include Raman spectroscopy and surface plasmon reso-
University, China. His research nance.
interest focuses on functional
nanomaterials.

Jingtian Zhao

This journal is © The Royal Society of Chemistry 2021 Nanoscale

 View Article Online

Review Nanoscale
Published on 23 April 2021. Downloaded by University of Connecticut on 5/16/2021 8:17:10 AM.

Fig. 1 Phototreatment as a driving force for the structural transformation, spectral and electromagnetism improvement, and functional perform-
ance of nanomaterials (reproduced with permission from ref. 3. Copyright 2010, Elsevier publishing. Reproduced with permission from ref. 4.
Copyright 2021, AIP publishing. Reproduced with permission from ref. 5. Copyright 2006, ACS publishing. Reproduced with permission from ref. 6.
Copyright 2013, ACS publishing. Reproduced with permission from ref. 7. Copyright 2016, ACS publishing. Reproduced with permission from ref. 9.
Copyright 2016, Springer Nature Publishing. Reproduced with permission from ref. 10. Copyright 2018, Springer Nature Publishing. Reproduced with
permission from ref. 11. Copyright 2011, Elsevier Publishing).

contiguous and non-destructive method, light irradiation can widely used in surface-enhanced Raman spectroscopy (SERS)
excite surface plasmons in noble metal nanoparticles (NPs), as a powerful analytical technique.13,14 Nevertheless, as
create electron–hole pairs, and induce charge transfer (CT) in restricted by the strong intensity and low photon energy of the
semiconductors at the nanoscale, which have led to it being Raman laser, the electron–hole pairs of the semiconductors

Jinshen Lan received the master’s degree in physics from the Imran Khan received his master’s degrees in physics from the
College of Physical Science and Technology, Xiamen University, Department of Physics, University of Engineering and Technology,
China in 2020. He is working toward his Ph.D. degree in the same Lahore, Pakistan in 2005 and Department of Physics, The Islamia
lab. His research interest focuses on semiconductor nano- University of Bahawal-Pur, Pakistan in 2010, and Ph.D. degree in
materials. condensed matter physics from the College of Physical Science and
Technology, Xiamen University, China in 2018. He is currently an
assistant professor at the Department of Physics, University of
Okara, Renala Khurd, Pakistan. His research interest focuses on
the in situ TEM study of nanomaterials.

Nanoscale This journal is © The Royal Society of Chemistry 2021

 View Article Online

Nanoscale Review

are rarely excited, which leads to a slight or no enhancement not restricted to the hybrid Ag (and Au) NPs-TiO2 nanofilm,
of the SERS signals. and noble metal NPs-decorated semiconductor substrates,
In May 2016, Parkin’s group9 reported that the Raman including transition metal oxides,9,18 transition metal dichal-
signal of target molecules on a Ag (and Au) NPs-TiO2 substrate cogenides,19 niobates,20 organic semiconductors,10 hetero-
was enhanced significantly when the substrate was pre-irra- structures,25 and even NPs-decorated insulator substrates9 and
diated by ultraviolet (UV) light for a period of time. This single semiconductors20 have been found to show an obvious
phenomenon was termed as photo-induced enhanced Raman enhancement in PIERS. The technology may be a superior sup-
spectroscopy (PIERS). The PIERS technique just introduces plement for SERS analysis. However, as a novel technique, a
light irradiation without any other manipulation, which keeps large space is still available for PIERS development, such as
Published on 23 April 2021. Downloaded by University of Connecticut on 5/16/2021 8:17:10 AM.

the substrate incontiguous and is convenient for operation. substrate preparation, light choice, bioanalysis specificity, and
The magnification of PIERS can be increased several times to so on.
dozens over SERS. Although these values may seem an insuffi- To better understand the research progress in PIERS and to
cient focus, if the multiple is increased to the limit, even if it shed a light on future research, a critical review is presented
is doubled, the sensitivity will be greatly improved, which is of here. We first analyze the enhancement mechanisms of PIERS
importance for life sciences, environmental protection, and in comparison with SERS. Afterward, we discuss in detail the
biological analysis applications.9,15–17 Therefore, much work critical parameters influencing the enhancement of PIERS,
has been done to prepare various substrates and huge progress including the substrate, light irradiation, and relaxation.
has been made to apply them in PIERS. Up to now, there are Finally, we consider the future developments of PIERS.
three kinds of procedure for the PIERS operation. First, the
substrate is irradiated by the incident light for a period of
time, followed by deposition of the analyte sample and Raman 2. Raman-enhancement
analysis.9,16,18–20 This can be called substrate irradiation. mechanisms
Second, the substrate is deposited by the analyte sample, fol-
lowed by light irradiation for a period of time and Raman 2.1. Enhancement mechanisms of SERS
analysis,15,20,21 which can be called sample irradiation. Both The enhancement mechanisms for SERS include an electro-
these methods are ex situ as the analyte deposition and Raman magnetic mechanism (EM) and chemical mechanism
detection are performed at different locations. There can be (CM).26–28 The EM derives from the surface plasmon resonance
in situ operation as the third procedure, where the substrate is (SPR) in the metal surface with nanostructures.29,30 The con-
irradiated by incident light while doing Raman detection. The duction electrons in the plasmon-active metals can be coher-
light source may be a light-emitting diode (LED), which is ently excited by the incident light at a specific frequency and
placed near the Raman laser and both work at the same time collectively oscillate at the metal–dielectric interfaces, which
during the Raman detection.21 It was found that besides the results in the electromagnetic fields being highly focused to
advantages of SERS, the PIERS system has a better detection the nanoscale volume, known as hot-spot regions (see
universality, such as for explosives, pollutants, biomolecules, Fig. 2(a)).31 The hot-spot regions can both enhance the
and organic dyes at trace levels.9,21,22 It also has a wider detec- effective local incident field on the Raman analyte and
tion range for small molecules, such as those with a typical enhance the re-emitted Raman scattering, normally by an
low Raman cross-section.10 The light is not limited in the deep enhancement factor (EF) of >106.32,33
UV range, and blue light23 and visible light24 can also be The CM results from the chemical interaction between
applied as the light source. Moreover, the active substrate is molecules and the substrate surface. However, its origin is not

Xiaofang Ye is a master’s student in the College of Physical Jing Wan is a master’s student in the College of Physical Science
Science and Technology, Xiamen University, China. Her research and Technology, Xiamen University, China. Her research interest
interest focuses on nonlinear dynamics in optical devices and focuses on heterogeneous semiconductor nanomaterials.
optical systems.

This journal is © The Royal Society of Chemistry 2021 Nanoscale

 View Article Online

Review Nanoscale

as clear as EM. Several models have been proposed in different depending on the specific system under study. Parkin’s group
systems, including the CT process,34–36 polarizability modu- reported the basis of the PIERS phenomena arising from surface
lation,37 Fermi level modification,38 adatom,39 bias-voltage oxygen vacancy states in noble metal metal–oxide substrates.9,18,25
enhanced Raman in molecular junctions,40 and the resonant As shown in Fig. 3(a),17 under pre-irradiation with UV light,
or resonance-like Raman process.41,42 By contrast, the CT oxygen vacancies are created on the metal–oxide semiconductor
between the substrate and analyte molecules is widely surface as mediated by the photoreaction with adsorbed O2 and
accepted in the CE, which is illuminated in Fig. 2(b).34 In the H2O,18,21,22,46 and their number increases with the irradiation
close contact system of the analyte molecule–semiconductor time. This generates electron donor states below the conduction
substrate, the electrons in the valence band of a semiconductor band edge. Such a doping enables electrons to jump from the
Published on 23 April 2021. Downloaded by University of Connecticut on 5/16/2021 8:17:10 AM.

are likely to be photoexcited to the conduction band or a hot oxygen vacancy states to the conduction band when the laser
state, which then transfer to the matching energy level of the source of Raman is turned on, and then they can be injected into
lowest unoccupied molecular orbital (LUMO) level of the mole- the energy levels of the metal NPs.18 The injected charges lead to
cule through resonant tunneling and enhances the molecular a shift in the Fermi level of the NPs and increases their electro-
polarizability tensor via the vibronic coupling. The electrons in magnetic field.47 Raman scattering from molecules positioned in
the meta-stable state return to the initial state. The released these hot spots is significantly enhanced. In the hybrid substrate,
energy absorbed by the molecule increases its vibrational energy the plasmonic nature of the NPs provides an additional electro-
and it radiates Stokes photons with an amplified Raman scatter- magnetic enhancement. Moreover, the metal–semiconductor
ing cross-section of the probed molecule. Likewise, electrons in interface helps to stabilize the formation of oxygen vacancies,
the highest occupied molecular orbital (HOMO) level of the reduce the vacancy formation energy, prolong the carrier life-
molecule are photoexcited to the LUMO level, which then trans- times, and enhance the photocatalytic potential of the metal–
fer to the matching energy band of a hot state of the semi- oxide semiconductor.9,18,19,48
conductor and transit back to their initial state. During de-exci- The creation of oxygen vacancies is universal to explaining
tation, the energy absorbed by the molecule liberates extra PIERS in the literature.9,15,17,18,21,22,35,49 Nevertheless, in lots of
Stokes photons, which can effectively increase the molecular semiconductors, such as organic semiconductor diphenylala-
polarizability and Raman scattering cross-section. nine peptide and lithium niobate, it is difficult for oxygen
The CM generally creates an EF of <103,33,43 lower than those atoms to be expelled by the UV photons. In the systems of
reported for EM. However, recent reports using semiconducting these semiconductors decorated with Ag NPs, Rice et al.10 and
nanomaterials have shown comparable CM to EM Baghban et al.20,46 suggested that PIERS might come from the
enhancements.34,44 Therefore, the concomitant use of the two charge separation and migration in the semiconductors. As
mechanisms by both the metallic NPs and semiconducting nano- displayed in Fig. 3(b),46 upon light radiation of the specimens
materials is generally applied to improve the sensitivity of SERS in the UV range with an energy equal to or larger than the
(see Fig. 2(c)),45 allowing detection down to a single molecule. bandgap of the semiconductors, free electrons are excited
from the valence band to the conduction band and then trans-
2.2. Enhancement mechanisms of PIERS fer to the Ag NPs present at the semiconductor surface, which
Just as in CM in SERS, the enhancement mechanisms of PIERS in turn results in a further enhancement of the Raman scatter-
are still under debate. Several models have been put forward ing signal of the analyte in contact with the NPs.

Yuchen Fei is a master’s student in the College of Physical Science Shengli Huang received his Ph.D.
and Technology, Xiamen University, China. His research interest degree in condensed matter
focuses on nonlinear dynamics in optical devices and optical physics from the University of
systems. Science and Technology of
China, Hefei, China, in 2007. He
was then a research fellow with
the Department of Mathematical
and Physical Sciences, Nanyang
Technological University,
Singapore, and a visiting scholar
with the Department of
Biochemistry, University of
Shengli Huang Arkansas, USA. He is currently
an associate professor in the
College of Physical Science and Technology, Xiamen University,
China. His research interest focuses on functional nanomaterials
and nanodevices.

Nanoscale This journal is © The Royal Society of Chemistry 2021

 View Article Online

Nanoscale Review

In the hybrid Au/WS2 nanosheets, Maalej et al.19 also irradiation. For example, the absorption spectrum9,16 and
observed PIERS, but the extra enhancement was attributed to extinction spectrum49 of the hybrid templates will blue shift
the CT from the Au NPs to WS2 nanosheets, contrary to the and become broadened if the electron density increases on the
previous models. Fig. 3(c) presents a sketch of the model.19 particles after light irradiation (see Fig. 4(a and b)), where the
The photo-irradiation with UV light bombards the localized injected electrons can be estimated following the expression
surface plasmon resonance (LSPR) of the Au NPs, which determined in the work of Mulvaney et al.55 The photo-
creates hot spots as well as produces the CT from the Au NPs luminescence spectrum shows a decreasing intensity for the
to the WS2, thereby injecting additional electrons into mole- reduced electron transition in the semiconductor with
cules adsorbed on the WS2 surface through its conduction prolonging the irradiation (see Fig. 4(c)).10 In addition, the
Published on 23 April 2021. Downloaded by University of Connecticut on 5/16/2021 8:17:10 AM.

band. The photo-induced CT in the semiconductor–molecule photocurrent will be improved for the increasing charge car-
system increases the molecular polarizability tensor and mag- riers under light radiation (see Fig. 4(d)).11
nifies the Raman signals by the Herzberg–Teller coupling.50,51
This principle is the same as those under radiation by visible
light (see Fig. 3(d)) or even the Raman laser.24,35,52–54 3. Substrate effect
The above effects are based on the hybrid substrate of a
plasmonic NPs–semiconductor. In the heterogeneous TiO2-Ag The choice of a suitable substrate is vitally important for
hybrid nanowire arrays, the PIERS effect with a larger EF was effective PIERS, as it restricts the enhancement contribution of
observed by Liu’s group.25 The heterojunction interface could the CM and EM under photo-irradiation in a fixed wavelength
effectively separate electrons and holes in space. As displayed and duration. The substrates mentioned here are not necess-
in Fig. 3(e), the electrons in the valence band of both the arily simple hybrid nanomaterials of noble metal NPs–metal–
anatase and rutile TiO2 are excited to the conduction band by oxide semiconductors. They may also be transition metal
the UV light. Because the conduction band of rutile TiO2 dichalcogenides,19 niobates,20 organic semiconductors,10 het-
(bandgap of 3.0 eV) is lower than that of anatase TiO2 erostructural metal–oxide semiconductors,25 and insulators.9
(bandgap of 3.2 eV), the rutile TiO2 will act as an electron In order to increase the EF, the substrates are usually designed
absorber to accept photogenerated electrons from the anatase in a specific nanostructure with a large surface area and easy
conduction band. As a result, a significantly increased electron CT pathway. Table 1 lists the maximum enhancement of
density will be formed on the rutile TiO2 surface, and different substrates for PIERS as studied up to now, which can
additional PIERS enhancement will be hopefully obtained in be divided into three groups according to their constituents.
the mixed phase TiO2-metal hybrid. The first group are hybrid noble metal–semiconductors. The
In view of these different models, we can see that the noble metals are mainly gold and silver, as they possess SPR in
enhancement consists of two parts, one is CM from the CT the visible wavelength range. The metal@TiO2
between the semiconductor and the metal NPs, and the other substrates9,15,16,24 possess a distinct PIERS effect for the inci-
is EM from the electron aggregation or release in the NPs. dent light with different wavelengths, but generally, incident
Therefore, both CM and EM are produced at the same time for light with a shorter wavelength and longer irradiation creates a
PIERS. The CT interaction between the semiconductor and the much larger EF (this will be discussed in detail in the next
metal NPs plays a vital role in the enhancement, no matter section). The Raman signal was enhanced 34.79 times for
from the photo-active semiconductor to the plasmonic metal, glucose on the Au@TiO2 thin film when irradiated by 254 nm
or reverse. This process can be demonstrated by measuring light for 4 h, which is the largest EF reported so far. However,
some physicochemical parameters before and after light the enhancement varies for different Raman bands and

Shuping Li received his Ph.D. degree in condensed matter physics Junyong Kang received his Ph.D. degree from Xiamen University.
from Xiamen University. He is currently a professor in the College He is a professor at the Department of Physics in Xiamen
of Physical Science and Technology, Xiamen University, China. University, visiting professor at the Center for Interdisciplinary
His research interest focuses on the theoretical and experimental Research and International Frontier Center for Advanced
study of semiconductor optoelectronic materials and devices. Materials in Tohoku University of Japan, and member of the
Global COE Program “Photonics Integration-Core Electronics” in
Tokyo Institute of Technology of Japan. Now he is in charge of the
Engineering Research Center for Micro-nano Optoelectronic
Materials & Devices of State Education Ministry, and Key
Laboratory of Semiconductors & Applications of Fujian Province in
Xiamen University.

This journal is © The Royal Society of Chemistry 2021 Nanoscale

 View Article Online

Review Nanoscale
Published on 23 April 2021. Downloaded by University of Connecticut on 5/16/2021 8:17:10 AM.

Fig. 2 Schematic illustration of the proposed mechanisms for SERS: (a) electromagnetic field enhancement for surface plasmons of the metal NPs
and nanofilm (reproduced with permission from ref. 31. Copyright 2017, ACS publishing); (b) chemical enhancement for the charge transfer between
the semiconductor substrate and the analyte molecules (reproduced with permission from ref. 34. Copyright 2011, ACS publishing); (c) combining
the electromagnetic mechanism and chemical mechanism in a system (reproduced with permission from ref. 45. Copyright 2018, Elsevier
publishing).

analyte molecules. For example, the EF changed to 8.73 and the analyte molecule with respect to the metal–semiconductor
10.20, respectively for the bands at 997 and 1425 cm−1 instead interface, the ideal distribution of Au NPs, and the effective
of 34.79 at 1071 cm−1, and it only achieves 4.19 for rhodamine surface vacancy states within the hot-spot regions. In the sub-
6G (R6G) on the substrate.9 In the substrate of the Au@WO3 strates of Au@WO3,18,21 Au@ZnO,18,49 and Ag@LiNbO3,20,46
film,21 a strong effect of the NP size on PIERS enhancements the EF of the sample irradiation was larger than the substrate
was observed, which was ascribed primarily to the position of irradiation, which may result from instant charge migration

Nanoscale This journal is © The Royal Society of Chemistry 2021

 View Article Online

Nanoscale Review
Published on 23 April 2021. Downloaded by University of Connecticut on 5/16/2021 8:17:10 AM.

Fig. 3 Schematic illustration of the proposed mechanisms for PIERS: (a) photo-induced oxygen vacancy in the semiconductor by UV light and
charge transfer in the metal–semiconductor contact (reproduced with permission from ref. 17. copyright 2017, Springer Nature Publishing); (b)
photogenerated carriers at the semiconductor surface by UV light transferring to the metal NPs (reproduced with permission from the author of ref.
46); (c) photoexcited electrons at the metal surface by UV light transferring to the semiconductor (reproduced with permission from ref. 19.
Copyright 2020, ACS publishing); (d) photogenerated carriers at the semiconductor heterostructure by UV light transferring to the metal NPs (repro-
duced with permission from ref. 24. Copyright 2020, ACS publishing); (e) photoexcited electrons at the metal surface by visible light transferring to
the semiconductor (reproduced with permission from ref. 25. Copyright 2019, ACS Publishing).

and interaction between the substrate and analyte molecules strate, the Raman signal enhancement further depends on the
in the sample irradiation. This suggests that the experimental surface facets and substrate properties. A template of aligned
sequence also plays an important role in the PIERS effect. diphenylalanine peptide nanotubes (DPN) coated with plasmo-
Moreover, in Ag@LiNbO3,20 Al-Shammari et al. found that the nic NPs also displayed an obvious Raman signal enhancement
z-cut periodically proton-exchanged lithium niobate possessed with 254 nm light irradiation, allowing the detection of a wide
a stronger signal intensity than the unetched y-cut lithium range of small molecules and low Raman cross-section mole-
niobate on an insulator, although both were weaker than the cules at concentrations as low as 10−13 mol L−1.10 The photo-
x-cut lithium niobate on the insulator. The last sample was degradation-free enhanced SERS signals of the organic semi-
fabricated by ion implantation and ion beam slicing and conductor with its biocompatibility may lead to a wide range
further exposed to reactive ion etching. This processing of applications in bioscience. Nevertheless, under 365 nm
changed the roughness and the optical properties and intro- light irradiation, the specimen did not present any signal
duced a number of defects, which could have been significant enhancement compared to the normal SERS, just as observed
in enhancing the PIERS. Therefore, even for the same sub- in the hybrid Ag@LiNbO3,20 which was because of the rare

This journal is © The Royal Society of Chemistry 2021 Nanoscale

 View Article Online

Review Nanoscale
Published on 23 April 2021. Downloaded by University of Connecticut on 5/16/2021 8:17:10 AM.

Fig. 4 Determination of the charge transfer on the substrate by different methods: (a) absorption spectrum (reproduced with permission from ref.
9. Copyright 2016, Springer Nature Publishing); (b) extinction spectrum (reproduced with permission from ref. 49. Copyright 2020, PCCP publishing);
(c) photoluminescence spectrum (reproduced with permission from ref. 10. Copyright 2018, Springer Nature Publishing); (d) current–potential curve
(reproduced with permission from ref. 11. Copyright 2011, Elsevier Publishing).

charges as excited by the low energy photons. Liu et al. possess the ability to create oxygen vacancies in the surface of
achieved an EF of 27.8 in a heterostructured anatase/rutile the SiO2 thin film, though the photon energy is smaller than
TiO2-Ag.25 Though the EF value was smaller than that in rutile the bandgap of the insulator. Thereafter, the Raman
TiO2-Au,9 the enhancement of this kind of heterogeneous sub- laser expels the electrons from the vacancies and injects them
strate may be stronger than the others when they detected the into the energy levels of the Au NPs, which improves the
same molecules at the same condition. For instance, the EF of Raman signal. Nevertheless, Rice et al.20 found that the
R6G was 4.19 in the rutile TiO2-Au,9 while it was 14.9 in the Raman spectrum kept constant for a Ag NPs-SiO2 thin film
anatase/rutile TiO2-Ag.25 The giant Raman enhancement may when irradiated by 365 nm UV light, which might be due to
be ascribed to the highly efficient charge transfer from anatase the lower energy of the incident photons to create oxygen
to rutile and then to Ag as driven by the heterojunction vacancies or to expel the charge from the vacancies to the con-
between anatase and rutile. In the sample of a single element duction band.
semiconductor coated by Ag NPs,10 the Raman signal was also The last group is the single semiconductors. In a lithium
enhanced by 2.5 times compared to the normal SERS. niobate thin film, the intensity of the Raman signal increases
Therefore, the choice of a photo-active substrate is vital for the twice in sample irradiation.20 In other words, even if the noble
PIERS effect, and the Raman enhancement of a substrate is metal NPs are not coated, the Raman signal can be enhanced,
influenced by the wavelength of incident light, the irradiation but only by chemical enhancement. However in a TiO2 thin
duration, the experimental process, the analyte molecules, and film, there was no enhancement in substrate irradiation.9 The
the choice of the active Raman scattering band. difference may be assigned to the lifetime of the photoexcited
The second group is the hybrid noble metal–insulators. carriers, which is pico-to-microseconds in TiO2 and hundreds
Parkin et al.9 reported a 2-fold enhancement in a hybrid of milliseconds to tens of seconds in lithium niobate.56,57
system of Au NPs-SiO2 thin film when irradiated for 4 h under Therefore, it is desirable to improve the PIERS effect by
254 nm UV light. In the process, the incident light may also prolonging the lifetime of the electron–hole pairs, such as by

Nanoscale This journal is © The Royal Society of Chemistry 2021

 View Article Online

Nanoscale Review

Table 1 Maximum enhancement (IPIERS/ISERS) of different substrates for PIERS

Eg of the semi-
conductor and insula- Enhancement
Substrate tor (eV) Light irradiation (folds) Ref.

Noble metal NPs Au NPs on TiO2 thin film (rutile) 3.0 254 nm for 4 hours in 34.79 9
decorated substrate irradiation
semiconductor Au NPs connected with TiO2 ∼3.2 Xenon ozone-free arc lamp (λ 2.1 24
nanoparticles > 400 nm) for 10 min in
sample irradiation
Ag NPs on TiO2 thin film 3.2 365 nm for 30 min in sample 3 15
Published on 23 April 2021. Downloaded by University of Connecticut on 5/16/2021 8:17:10 AM.

(anatase) irradiation
Ag NPs on TiO2 thin film 3.0 254 nm for 4 hours in ∼3 9
substrate irradiation
Ag NPs on TiO2 nanorods 3.2 365 nm for 30 min in sample 1.5 15
(anatase) irradiation
Ag NPs on TiO2 nanopores 3.2 254 nm for 21 min in 8 16
(anatase) substrate irradiation
Au NPs on WO3 film ∼2.6 254 nm for 45 minutes in 9 21
sample irradiation
Au NPs on WO3 film ∼2.6 254 nm for 25 min in 1.5 18
substrate irradiation
Au NPs on WS2 nanosheet 1.0–2.1 254 nm in sample irradiation 4 19
Au NPs on ZnO film 3.37 254 nm for 30 minutes in 7.52 49
sample irradiation
Au NPs on ZnO film 3.37 254 nm for 15 min in 4 18
substrate irradiation
Ag NPs on ZnO nanowires 3.37 254 nm for 15 min in 2.5 33
substrate irradiation
Ag NPs on LiNbO3 thin film 3.78 254 nm for 150 min in 7 20
substrate irradiation and
46
Ag NPs on LiNbO3 thin film 3.78 254 nm for 27 min in sample 3 20
irradiation
Ag NPs on LiNbO3 thin film 3.78 365 nm irradiation 0 20
Ag NPs on diphenylalanine 4.6 254 nm for 45 min in sample 7 10
peptide nanotubes (organic irradiation
semiconductor)
Au NPs on diphenylalanine 4.6 254 nm for 45 min in sample ∼4.5 10
peptide nanotubes irradiation
Ag NPs on diphenylalanine 4.6 365 nm for 45 min in sample 0 10
peptide nanotubes irradiation
Ag NPs on anatase/rutile TiO2 3.2/3.0 UPB mercury lamp for 27.8 25
heterostructure (film/nanorods) 24 min in substrate
irradiation
Ag NPs on Si substrate 1.1 254 nm lamp for 25 min in 2.5 10
sample irradiation

Noble metal NPs Au NPs on SiO2 thin film 5.659 254 nm for 4 hours ∼2 9
decorated insulator Ag NPs on SiO2 thin film 5.659 365 nm UV irradiation 0 20

Single semiconductor LiNbO3 thin film 3.78 254 nm for 9 min in sample 2 20
irradiation
TiO2 thin film 3.0 254 nm for 4 hours in 0 9
substrate irradiation

applying a pure semiconducting nanomaterial with an intrin- lithium niobate may create specific plasmon-active nano-
sic long carrier lifetime, or a heterojunction, or a combination particle patterns as achieved by the ferroelectric lithography-
of a metal and semiconductor. In fact, besides the substrate based methods,59–61 which will induce different PIERS
ingredients, the PIERS effect is also associated with the mor- enhancements for different bands of the analytes and in
phology and structure of the substrate. In contrast to the different locations. Similarly, for the TiO2 crystal, there are
smooth lithium niobate film, the periodically poled lithium three kinds of structure, namely rutile, anatase, and brookite.
niobate presented a different Raman scattering intensity of the They all possess a different refractive index, surface energy,
transverse and longitudinal optical phonons,58 which was rela- band structure, total density of states, and other
tive to the mechanical stresses and partially screened depolar- properties,62–64 which means they may react differently under
ization fields. For the anisotropy, the periodically poled light irradiation.

This journal is © The Royal Society of Chemistry 2021 Nanoscale

 View Article Online

Review Nanoscale

4. Irradiation effect
Different wavelengths of incident light induce different effects
on PIERS, because the different wavelengths indicate different
photon energies. Generally, the energy of the incident photons
much be equal to or larger than the bandgap energy of the
semiconductor substrate, so as to separate the electron–hole
pairs and expel electrons to the states of the oxygen
vacancies or to the conduction band. In this situation, the
Published on 23 April 2021. Downloaded by University of Connecticut on 5/16/2021 8:17:10 AM.

Raman signal will be enhanced with increasing the irradiation

time (see Fig. 5(a) and 6(a)).10 Nevertheless, when the photon
energy is smaller than the bandgap energy of the semi-
conductor substrate, or the substrate is photo-inactive, the
Raman signal will remain stable under light irradiation (see
Fig. 5(b)).10 Moreover, the intensity of the light source should
be restricted, as it may induce a degradation of the analyte
molecules.
The Raman enhancement does not merely increase with
prolonging the irradiation for the photo-active substrate. In
the Ag@TiO2 heterostructure, Liu et al.25 found that the
Raman signal was first intensified and then weakened after a
critical irradiation time (Tirr), as shown in Fig. 6(b). The Tirr for
the maximum enhancement is different for different chemical
substrates (see Table 2), the substrate in different nano-
structures (see Table 2), or different analyte molecules (see
Table 3). Besides the successful increase before Tirr and
decrease after Tirr in the hybrid TiO2 heterostructure-Ag NPs,
the band intensity of the analyte on the Au@TiO2 substrate
was found to decrease initially for about 3 min, then increase Fig. 6 Time-dependent Raman signal intensity following and after light
irradiation on different substrates: (a) aligned DPN/AGNP template
steadily for about 12 min to reach a maximum enhancement
(reproduced with permission from ref. 10. Copyright 2018, Springer
value, and then kept stable upon continuous irradiation (see Nature Publishing); (b) TiO2 heterostructure-AGNPS substrate (repro-
Fig. 6(c));18 while on the Au@WO3 substrate in Fig. 6(d),24 the duced with permission from ref. 25. Copyright 2019, ACS publishing); (c)
Raman signal increased steadily initially but then increased Au NP-TiO2 thin film; (d) Au NP-WO3 thin film; (e) au NP-ZnO thin film
rapidly after around 20 min.18 On the Au@ZnO substrate in (reproduced with permission from ref. 18); (f ) Ag NP-LiNbO3 substrate
with increasing irradiation time; (g) Ag NP-LiNbO3 substrate with
Fig. 6(e),18 except for an initial decrease due to the laser-
increasing relaxation time (reproduced with permission from ref. 20.
copyright 2012, ACS publishing).

induced degradation of the analyte molecules, the profile was

the same as that of the Ag@TiO2 heterostructure in Fig. 6(b),
but the variation took place in a shorter time. The violent
change may be relevant to the microstructure, crystallinity,
charge state, and Zn–O bond energy of the ZnO thin film.18
Different from other specimens, the Raman signal on the
Ag@LiNbO3 substrate displayed a sudden increase upon the
initial irradiation, then with an abrupt drop after Tirr (see
Fig. 6(f )).20 According to the model as suggested by Parkin’s
group,18 the time-dependent changes in the measured Raman
signal depend primarily on three factors: oxygen vacancy for-
mation, vacancy healing, and laser-induced bleaching of the
analyte molecules. The maximum enhancement under photo-
irradiation suggests an equilibrium between an enhancing
Fig. 5 Raman spectra of TMPyP on the aligned DPN/AGNP template
following light irradiation in different wavelength: (a) 254 nm; (b) 365 nm
and decay mechanism, i.e., an equilibrium among these
(reproduced with permission from ref. 10. Copyright 2018, Springer factors. The increasing enhancement before Tirr results from
Nature Publishing). vacancy formation overwhelming the vacancy healing and

Nanoscale This journal is © The Royal Society of Chemistry 2021

 View Article Online

Nanoscale Review

Table 2 Irradiation time (Tirr) for the maximum enhancement and environment.17,18 Even for a substrate with the same analyzing
relaxation time (Trel ) for the original signal level for different substrates techniques, the Trex will also vary in different Raman bands for
the same analyte.18,24 In order to extend the relaxation process
Tirr Trel
Substrate (min) (min) Ref. with a strong signal intensity, the substrates can be kept under
vacuum to stop the healing of the surface upon exposure to
Au NPs on TiO2 thin film (rutile) — 60 9
air.18
Au NPs on TiO2 thin film (rutile) — 33 21
Au NPs on TiO2 thin film (rutile) 20 15 18
Ag NPs on TiO2 thin film (anatase) — 60 15
Ag NPs on TiO2 nanopores (anatase) >21 30 16
Ag NPs on anatase/rutile TiO2 heterostructure 24 40 25 6. Summary and perspectives
Published on 23 April 2021. Downloaded by University of Connecticut on 5/16/2021 8:17:10 AM.

(film/nanorods)
Au NPs on ZnO film 15 25 18 In this review, the enhancement mechanisms of PIERS were
Au NPs on ZnO film >30 30 49
surveyed, in addition to the critical influential parameters of
Au NPs on WO3 film >30 >30 18
Ag NPs on LiNbO3 thin film (before analyte 150 600 20 the substrate, light irradiation, and relaxation. PIERS can be
coating) performed by substrate irradiation, sample irradiation, or
Ag NPs on LiNbO3 thin film (after analyte 30 40 20
in situ operation of the irradiation and analysis. Just like SERS,
coating)
Ag NPs on diphenylalanine peptide nanotubes 35 45 10 the contribution of PIERS in the noble metal–semiconductor
(bare) substrate is from both CM and EM, where the CM comes from
Ag NPs on diphenylalanine peptide nanotubes >45 60 10
the CT between the semiconductor and the metal NPs, and the
(with TMPyP)
Au NPs on diphenylalanine peptide nanotubes 40 — 10 EM arises from the electron aggregation or release in the NPs.
(with TMPyP) The active substrates in PIERS may be hybrid noble metal–
semiconductors, hybrid noble metal–insulators, and single
semiconductors. The substrate plays an important role for the
Table 3 Irradiation time (Tirr) for the maximum enhancement and enhancement as it restricts the CM and EM under photo-
relaxation time (Trel ) for the original signal level for the substrate Ag NPs irradiation in a fixed wavelength and duration. Generally, the
decorated diphenylalanine peptide nanotubes with different analytes
photon energy need to be equal to or larger than the bandgap
(ref. 10)
energy of the semiconductor substrate, so as to separate elec-
Analyte Tirr (min) Trel (min) tron–hole pairs and expel electrons to the states of the oxygen
vacancies or the conduction band. The Raman intensity will
Bare 35 45
TMPyP >45 60 become strong before Tirr and weaken after Tirr due to the
RhB 35 60 relaxation effect. Increasing the lifetime of the photoexcited
4-ABT 25 60 charge carriers in the substrates can extend the relaxation
Glucose >45 60
period. The PIERS technique will continue to evolve and grow
with new developments and successful applications in bioana-
lysis and life sciences. For example, the bacterium in the
analyte bleaching, while it is inverse for the decreasing human body can be detected by PIERS thanks to its non-
enhancement. contact and high sensitivity. The photo-active substances can
be fabricated in particles or flakes in small size, which can be
injected or swallowed into the body. In order to reduce relax-
5. Relaxation effect ation and achieve a strong signal intensity, the PIERS equip-
ment can be designed in a cavity structure, like for computed
As with the recombination of electrons and holes after the tomography, so as to irradiate, characterize, and analyze in the
removal of light irradiation, the intensity of the Raman signals same position.
decay to the original level for a period of time, which is termed Although great achievements have been made in PIERS
as the relaxation effect. As shown in Fig. 6, Tables 2, and 3, the technology, several issues should be addressed in future
relaxation time (Trex) for most substrates was not more than research: (1) Experiment optimization. The EFs of the sub-
60 min, while it was 600 min for Ag@LiNbO3.20 The various strates are seriously influenced by the experimental procedure.
durations may come from the diverse lifetime of the photo- In previous research, the EF of sample irradiation was much
excited charge carriers in the substrates, as the lifetime in larger than that of substrate irradiation,18,20,22,49 but these
most metal oxides is only in the pico- to microseconds, while studies were conducted with different irradiation durations for
it is in the hundreds of milliseconds to tens of seconds in only three substrates. Whether it is universal for any specimen
LiNbO3. That is to say, for different samples, although the requires further study at the same irradiation condition. The
mechanism of relaxation was the same, the probability of in situ operation of irradiation and analysis may be convenient
charge recombination was different, which was related to the with a strong signal intensity as it eliminates the relaxation.
composition and characteristics of the substrate. In fact, the However, due to the small cross-sectional area of the substrate,
Trex is also influenced by the light wavelength, irradiation how to set the Raman laser and the UV light sources and to
time, irradiation sequence, analyte molecules, and confine the light with designed intensity on the sample

This journal is © The Royal Society of Chemistry 2021 Nanoscale

 View Article Online

Review Nanoscale

surface can become elaborate. (2) Mechanism illustration. The funding acquisition, project administration, resources, super-
enhancement mechanisms of the PIERS mentioned above may vision, validation, visualization, writing – review & editing.
not be universal to every substrate. In the previous study, the Shuping Li: visualization, writing – review & editing. Junyong
PIERS effects were mainly attributed to the oxygen vacancies Kang: visualization, writing – review & editing.
as expelled by UV light.9,18 It is unclear whether the oxygen
vacancies will still occur for crystals that are not prone to pro-
ducing vacancies or crystals with relatively large band gaps. Conflicts of interest
Moreover, the current mechanisms describe the enhancement
of the CT effect and the separation of electron–hole pairs in There are no conflicts to declare.
Published on 23 April 2021. Downloaded by University of Connecticut on 5/16/2021 8:17:10 AM.

hybrid metal–semiconductors. If there are changes in other

factors, such as changes in the substrate structure or phonon
vibration,65–68 although the change is not obvious, it may also Acknowledgements
affect the Raman signal intensity. In order to highlight the This work was supported by the National Key Research and
Raman peak caused by the inherent parameters, the signal Development Program of China (2016YFB0400801,
change for the inessential factors should be excluded. (3) 2016YFB0400800), 863 program (2014AA032608), National
Substrate choice. It was found that different substrates have Natural Science Foundation of China (U1405253, 61974125,
different EFs, in addition to the differences in the enhance- 61227009, 90921002), Natural Science Foundation of
ment evolution with the light irradiation and relaxation. Guangdong Province of China (2018A0303130271), Natural
Seeking a sensitively photo-active substrate with a long lifetime Science Foundation of Jiangxi Province of China
of photoexcited charge carriers is needed for PIERS. (20192ACBL20049).
Nevertheless, the substrates may possess a photocatalytic
ability, which will degrade the analyte molecules under light
irradiation. In order to find the best substrate for PIERS, sub- References
strates with different components, organization, morphology,
and structure should be tested in the future. (4) Light source. 1 V. Wickenheisser, E. M. Zywot, E. Rabjohns, N. Orlova,
Previously, the UV light generated by a mercury lamp or xenon C. M. Marvin, S. Ding, D. S. Lawrence and T. K. Tarrant,
lamp was commonly used at the wavelength of 254 nm and Photo-released drugs: a targeted treatment approach for
365 nm, respectively, but such UV light may degrade analyte arthritis, Proc. SPIE, 2020, 11223, 112230R.
molecules and consumes much energy. For narrow bandgap 2 X. Hu, M. Zhou and Q. Zhou, Ambient water and visible-
semiconductors, visible light or other light sources may be light irradiation drive changes in graphene morphology,
used to obtain the desired results. (5) Signal evolution. The structure, surface chemistry, aggregation, and toxicity,
change of Raman signal intensity with the photo-irradiation Environ. Sci. Technol., 2015, 49, 3410–3418.
time or relaxation time is different for different substrates. As 3 P. Pu, H. Cachet and E. M. M. Sutter, Electrochemical
shown in Fig. 6, the signal intensity successfully increased impedance spectroscopy to study photo - induced effects
with the irradiation time for Au@TiO2 (as tested in a short on self-organized TiO2 nanotube arrays, Electrochim. Acta,
period), while it generally increased before Tirr and decreased 2010, 55, 5938–5946.
after Tirr for most samples, and it unexpectedly displayed a 4 Y. Muraoka, N. Takubo and Z. Hiroi, Photoinduced conduc-
valley or a platform for some samples. The optimal irradiation tivity in tin dioxide thin films, J. Appl. Phys., 2009, 105,
time is different for different substrates with different light 103702.
sources, which needs to be explored in the future. Likewise, 5 S.-i. Ohkoshi, H. Tokoro, T. Hozumi, Y. Zhang,
Trel varies for different system, which may change from dozens K. Hashimoto, C. Mathoniere, I. Bord, G. Rombaut,
of minutes to dozens of hours. The signal intensity may M. Verelst, C. C. dit Moulin and F. Villain, Photoinduced
decrease violently or smoothly. All these should be character- magnetization in copper octacyanomolybdate, J. Am. Chem.
ized in order to find a substrate with an intense and lasting Soc., 2006, 128, 270–277.
PIERS effect. 6 C. Liu, J. Tang, H. M. Chen, B. Liu and P. Yang, A fully inte-
grated nanosystem of semiconductor nanowires for direct
solar water splitting, Nano Lett., 2013, 13, 2989–2992.
Author contributions 7 Y. Chen, Y. Zhang, F. Pan, J. Liu, K. Wang, C. Zhang,
S. Cheng, L. Lu, W. Zhang, Z. Zhang, X. Zhi, Q. Zhang,
Jingtian Zhao: data curation, formal analysis, investigation, G. Alfranca, J. M. de la Fuente, D. Chen and D. Cui, Breath
methodology, writing – original draft. Ziyun Wang: data cura- analysis based on surface-enhanced Raman scattering
tion, investigation, methodology. Jinshen Lan: conceptualiz- sensors distinguishes early and advanced gastric cancer
ation, visualization. Imran Khan: formal analysis, investi- patients from healthy persons, ACS Nano, 2016, 10, 8169–
gation. Xiaofang Ye: investigation, methodology. Jing Wan: 8179.
investigation, methodology. Yuchen Fei: investigation, meth- 8 S. Eaton-Magaña, C. M. Breeding, A. C. Palke,
odology. Shengli Huang: conceptualization, formal analysis, A. Homkrajae, Z. Sun and G. McElhenny, Raman and

Nanoscale This journal is © The Royal Society of Chemistry 2021

 View Article Online

Nanoscale Review

photoluminescence mapping of gem materials, Minerals, Raman spectroscopy (PIERS): sensing atomic-defects,
2021, 11, 177. explosives and biomolecules, Proc. SPIE, 2019, 11010,
9 S. Ben-Jaber, W. J. Peveler, R. Quesada-Cabrera, E. Cortes, 110100D.
C. Sotelo-Vazquez, N. Abdul-Karim, S. A. Maier and 22 D. Glass, E. Cortés, W. J. Peveler, C. R. Howle, R. Quesada-
I. P. Parkin, Photo-induced enhanced Raman spectroscopy Cabrera, I. P. Parkin and S. A. Maier, Enhancing hybrid
for universal ultra-trace detection of explosives, pollutants metal-semiconductor systems beyond SERS with PIERS
and biomolecules, Nat. Commun., 2016, 7, 12189. (Photo-induced enhanced Raman scattering) for trace
10 S. Almohammed, F. Zhang, B. J. Rodriguez and J. H. Rice, analyte detection, Proc. SPIE, 2020, 11416, 1141602.
Photo-induced surface-enhanced Raman spectroscopy 23 L. Zhou, H. Fu, Z. Wang, L. Chen, G. Ren, T. Jiang, C. Gu,
Published on 23 April 2021. Downloaded by University of Connecticut on 5/16/2021 8:17:10 AM.

from a diphenylalanine peptide nanotube-metal nano- L. Liu, W. Zhang, W. Zhang, J. Zhou and J. Han,
particle template, Sci. Rep., 2018, 8, 3880. Isomerization behavior of p-aminoazobenzene directly
11 M. Shi, X. Pan, W. Qiu, D. Zheng, M. Xu and H. Chen, Si/ anchored on MoS2/graphene oxide nanocomposite, Appl.
ZnO core-shell nanowire arrays for photoelectrochemical Surf. Sci., 2020, 530, 147216.
water splitting, Int. J. Hydrogen Energy, 2011, 36, 15153– 24 Z.-Y. Ke, C.-J. Tsai, P.-H. Liao and K. V. Kong,
15159. Photoinduced enhanced Raman probe for use in highly
12 M. Nehra, N. Dilbaghi, G. Marrazza, A. Kaushik, specific and sensitive imaging for tyrosine dimerization in
R. Abolhassani, Y. K. Mishra, K. H. Kim and S. Kumar, 1D inflammatory cells, J. Phys. Chem. Lett., 2020, 11, 7443–
semiconductor nanowires for energy conversion, harvesting 7448.
and storage applications, Nano Energy, 2020, 76, 104991. 25 M. Zhang, H. Sun, X. Chen, J. Yang, L. Shi, T. Chen, Z. Bao,
13 S. Cong, Y. Yuan, Z. Chen, J. Hou, M. Yang, Y. Su, Y. Zhang, J. Liu and Y. Wu, Highly efficient photoinduced enhanced
L. Li, Q. Li, F. Geng and Z. Zhao, Noble metal-comparable Raman spectroscopy (PIERS) from plasmonic nanoparticles
SERS enhancement from semiconducting metal oxides by decorated 3D semiconductor arrays for ultrasensitive, por-
making oxygen vacancies, Nat. Commun., 2015, 6, 7800. table, and recyclable detection of organic pollutants, ACS
14 J. Lee, K. T. Crampton, N. Tallarida and V. A. Apkarian, Sens., 2019, 4, 1670–1681.
Visualizing vibrational normal modes of a single molecule 26 S. Nie and S. R. Emory, Probing single molecules and
with atomically confined light, Nature, 2019, 568, 78–82. single nanoparticles by surface-enhanced Raman scatter-
15 T. Man, W. Lai, M. Xiao, X. Wang, A. R. Chandrasekaran, ing, Science, 1997, 275, 1102.
H. Pei and L. Li, A versatile biomolecular detection plat- 27 W. Ji, L. Li, Y. Zhang, X. Wang and Y. Ozaki, Recent
form based on photo-induced enhanced Raman spec- advances in surface-enhanced Raman scattering-based
troscopy, Biosens. Bioelectron., 2020, 147, 111742. sensors for the detection of inorganic ions: Sensing mecha-
16 M. Zhang, T. Chen, Y. Liu, J. Zhu, J. Liu and Y. Wu, Three- nism and beyond, J. Raman Spectrosc., 2020, 2020, 1–14.
dimensional TiO2-Ag nanopore arrays for powerful photo- 28 B. Yang, S. Jin, S. Guo, Y. Park, L. Chen, B. Zhao and
induced enhanced Raman spectroscopy (PIERS) and versa- Y. M. Jung, Recent development of SERS technology:
tile detection of toxic organics, ChemNanoMat, 2019, 5, 55– Semiconductor-based study, ACS Omega, 2019, 4, 20101–
60. 20108.
17 W. J. Peveler, S. B. Jaber and I. P. Parkin, Nanoparticles in 29 J. F. Li, Y. F. Huang, Y. Ding, Z. L. Yang, S. Bo Li,
explosives detection – the state-of-the-art and future direc- X. S. Zhou, F. R. Fan, W. Zhang, Z. Y. Zhou, D. Y. Wu,
tions, Forensic Sci., Med., Pathol., 2017, 13, 490–494. B. Ren, Z. L. Wang and Z. Q. Tian, Shell-isolated nano-
18 D. Glass, E. Cortés, S. Ben-Jaber, T. Brick, W. J. Peveler, particle-enhanced Raman spectroscopy, Nature, 2010, 464,
C. S. Blackman, C. R. Howle, R. Quesada-Cabrera, 392–395.
I. P. Parkin and S. A. Maier, Dynamics of photo-induced 30 H. Minamimoto and K. Murakoshi, Surface-enhanced
surface oxygen vacancies in metal-oxide semiconductors Raman scattering as a probe for exotic electronic exci-
studied under ambient conditions, Adv. Sci., 2019, 6, tations induced by localized surface plasmons, Curr. Opin.
1901841. Electrochem., 2020, 22, 186–194.
19 K. Abid, N. H. Belkhir, S. B. Jaber, R. Zribi, M. G. Donato, 31 J.-F. Li, Y.-J. Zhang, S.-Y. Ding, R. Panneerselvam and
G. Di Marco, P. G. Gucciardi, G. Neri and R. Maalej, Z.-Q. Tian, Core–shell nanoparticle-enhanced Raman spec-
Photoinduced enhanced Raman spectroscopy with hybrid troscopy, Chem. Rev., 2017, 117, 5002–5069.
Au@WS2 nanosheets, J. Phys. Chem. C, 2020, 124, 20350– 32 A. Hardiansyah, A.-Y. Chen, H.-L. Liao, M.-C. Yang,
20358. T.-Y. Liu, T.-Y. Chan, H.-M. Tsou, C.-Y. Kuo, J.-K. Wang and
20 R. M. Al-Shammari, M. A. Baghban, N. Al-attar, A. Gowen, Y.-L. Wang, Core-shell of FePt@SiO2-Au magnetic nano-
K. Gallo, J. H. Rice and B. J. Rodriguez, Photoinduced particles for rapid SERS detection, Nanoscale Res. Lett.,
enhanced Raman from lithium niobate on insulator tem- 2015, 10, 412.
plate, ACS Appl. Mater. Interfaces, 2018, 10, 30871–30878. 33 A. Fularz, S. Almohammed and J. H. Rice, Oxygen incorpor-
21 D. Glass, E. Cortés, S. Ben-Jaber, T. Brick, R. Quesada- ation-induced SERS enhancement in silver nanoparticle-
Cabrera, W. J. Peveler, Y. Zhu, C. S. Blackman, C. R. Howle, decorated ZnO nanowires, ACS Appl. Nano Mater., 2020, 3,
I. P. Parkin and S. A. Maier, Photo-induced enhanced 1666–1673.

This journal is © The Royal Society of Chemistry 2021 Nanoscale

 View Article Online

Review Nanoscale

34 X. Wang, W. Shi, G. She and L. Mu, Using Si and Ge nano- 50 J. R. Lombardi and R. L. Birke, Theory of surface-enhanced
structures as substrates for surface-enhanced Raman scat- Raman scattering in semiconductors, J. Phys. Chem. C,
tering based on photoinduced charge transfer mechanism, 2017, 118, 11120–11130.
J. Am. Chem. Soc., 2011, 133, 16518–16523. 51 A. Li, J. Yu, J. Lin, M. Chen, X. Wang and L. Guo, Increased
35 L. Yang, X. Jiang, W. Ruan, J. Yang, B. Zhao, W. Xu and O 2p state density enabling significant photoinduced
J. R. Lombardi, Charge-transfer-induced surface-enhanced charge transfer for surface-enhanced Raman scattering of
Raman scattering on Ag-TiO2 nanocomposites, J. Phys. amorphous Zn(OH)2, J. Phys. Chem. Lett., 2020, 11, 1859–
Chem. C, 2009, 113, 16226–16231. 1866.
36 P. Kambhampati, O.-K. Song and A. Campion, Probing 52 S. Lei, C. Tao, J. Li, X. Zhao and W. Wang, Visible light-
Published on 23 April 2021. Downloaded by University of Connecticut on 5/16/2021 8:17:10 AM.

photoinduced charge transfer at atomically smooth metal induced charge transfer to improve sensitive surface-
surfaces using surface enhanced Raman scattering, Phys. enhanced Raman scattering of ZnO/Ag nanorod arrays,
Status Solidi A, 1999, 175, 233. Appl. Surf. Sci., 2018, 452, 148–154.
37 B. N. J. Persson, K. Zhao and Z. Zhang, Chemical contri- 53 Z. Mao, W. Song, L. Chen, W. Ji, X. Xue, W. Ruan, Z. Li,
bution to surface-enhanced Raman scattering, Phys. Rev. H. Mao, S. Ma and J. R. Lombardi, Metal-semiconductor
Lett., 2006, 96, 207401. contacts induce the charge-transfer mechanism of surface-
38 A. Das, D. Singh, C. P. Saini, R. Ahuja, A. Kaurc and enhanced Raman scattering, J. Phys. Chem. C, 2011, 115,
S. Aliukovd, Orbital hybridization-induced band offset 18378–18383.
phenomena in NixCd1−xO thin films, Nanoscale, 2020, 12, 54 S.-H. Seo, B.-M. Kim, A. Joe, H.-W. Han, X. Chen, Z. Cheng
669. and E.-S. Jang, NIR-light-induced surface-enhanced Raman
39 A. Otto, J. Timper, J. Billmann, G. Kovacs and I. Pockrand, scattering for detection and photothermal/photodynamic
Surface roughness induced electronic Raman scattering, therapy of cancer cells using methylene blue-embedded
Surf. Sci., 1980, 92, L55–L57. gold nanorod@SiO2 nanocomposites, Biomaterials, 2014,
40 M. Galperin, M. A. Ratner and A. Nitzan, Raman scattering 35, 3309–3318.
in current-carrying molecular junctions, J. Chem. Phys., 55 P. Mulvaney, J. Perez-Juste, M. Giersig, L. M. Liz-Marzan
2009, 130, 144109. and C. Pecharroman, Drastic surface plasmon mode shifts
41 L. Zhao, L. Jensen and G. C. Schatz, Pyridine-Ag20 cluster: A in gold nanorods due to electron charging, Plasmonics,
model system for studying surface-enhanced Raman scat- 2006, 1, 61–66.
tering, J. Am. Chem. Soc., 2006, 128, 2911–2919. 56 K. Ozawa, M. Emori, S. Yamamoto, R. Yukawa,
42 D. W. Silverstein and L. Jensen, Vibronic coupling simu- S. Yamamoto, R. Hobara, K. Fujikawa, H. Sakama and
lations for linear and nonlinear optical processes: Theory, I. Matsuda, Electron-hole recombination time at TiO2
J. Chem. Phys., 2012, 136, 064111. single-crystal surfaces: Influence of surface band bending,
43 I. Alessandri and J. R. Lombardi, Enhanced Raman scatter- J. Phys. Chem. Lett., 2014, 5, 1953–1957.
ing with dielectrics, Chem. Rev., 2016, 116, 14921–14981. 57 T. Volk and M. Wöhlecke, Lithium niobate defects, photore-
44 Y. Quan, J. Yao, Y. Sun, X. Qu, R. Su, M. Hu, L. Chen, fraction and ferroelectric switching, Springer-Verlag, Berlin
Y. Liu, M. Gao and J. Yang, Enhanced semiconductor Heidelberg, 2009.
charge-transfer resonance: Unprecedented oxygen bidirec- 58 R. Hammoum, M. D. Fontana, P. Bourson and
tional strategy, Sens. Actuators, B, 2021, 327, 128903. V. Y. Shur, Characterization of PPLN-microstructures by
45 S. Huang, B. He, X. Yan, I. Khan, J. Wang, M. Gao, J. Lan, means of Raman spectroscopy, Appl. Phys. A, 2008, 91,
S. Li and J. Kang, Hierarchical ZnO/Si nanowire arrays as 65–67.
an effective substrate for surface enhanced Raman scatter- 59 Y. Sun and R. J. Nemanich, Photoinduced Ag deposition on
ing application, Sens. Actuators, B, 2018, 273, 48–55. periodically poled lithium niobate: Wavelength and polariz-
46 M. A. Baghban, Integrated nanophotonic devices in lithium ation screening dependence, J. Appl. Phys., 2011, 109,
niobate, Thesis, KTH Royal Institute of Technology, 104302.
Stockholm, Sweden, 2018. 60 S. Damm, N. C. Carville, B. J. Rodriguez, M. Manzo,
47 L. Yang, X. Jiang, L. Chen, W. Ruan, W. Xu and B. Zhao, K. Gallo and J. H. Rice, Plasmon enhanced Raman from Ag
Relationship between photoluminescence performance nanopatterns made using periodically poled lithium
and SERS effect of TiO2 nanoparticles (in Chinese), niobate and periodically proton exchanged template
Chem. J. Chin. Univ., 2010, 31, 1019–1022. methods, J. Phys. Chem. C, 2012, 116, 26543–
48 A. R. Puigdollers, P. Schlexer, S. Tosoni and G. Pacchioni, 26550.
Increasing oxide reducibility: The role of metal/oxide inter- 61 G. McConnell and A. I. Ferguson, Simultaneous stimulated
faces in the formation of oxygen vacancies, ACS Catal., Raman scattering and second harmonic generation in
2017, 7, 6493–6513. periodically poled lithium niobate, Opt. Express, 2005, 13,
49 G. Barbillon, T. Noblet and C. Humbert, Highly crystalline 2099–2104.
ZnO film decorated with gold nanospheres for PIERS 62 N. Rahimi, R. A. Pax and E. M. Gray, Review of functional
chemical sensing, Phys. Chem. Chem. Phys., 2020, 22, titanium oxides. I: TiO2 and its modifications, Prog. Solid
21000–21004. State Chem., 2016, 44, 86–105.

Nanoscale This journal is © The Royal Society of Chemistry 2021

 View Article Online

Nanoscale Review

63 D. A. H. Hanaor and C. C. Sorrell, Review of the anatase to 66 R. M. Taha, H. A. Jawad, P. Parvin and M. Refahizadeh,
rutile phase transformation, J. Mater. Sci., 2011, 46, 855– Modification of CR39 surfaces by 193 nm ArF laser for bio-
874. material sensing, Mater. Today: Proc., 2021, 42, 2273–
64 J. Y. Hwang, G.-h. Moon, B. Kim, T. Tachikawa, T. Majima, 2276.
S. Hong, K. Cho, W. Kim and W. Choi, Crystal phase-depen- 67 J. Lin, J. Yu, O. U. Akakuru, X. Wang, B. Yuan, T. Chen,
dent generation of mobile OH radicals on TiO2: Revisiting L. Guo and A. Wu, Low temperature-boosted high
the photocatalytic oxidation mechanism of anatase and efficiency photo-induced charge transfer for remarkable
rutile, Appl. Catal., B, 2021, 286, 119905. SERS activity of ZnO nanosheets, Chem. Sci., 2020, 11,
65 R. Holomb, N. Mateleshko, V. Mitsa, P. Johansson, A. Matic 9414.
Published on 23 April 2021. Downloaded by University of Connecticut on 5/16/2021 8:17:10 AM.

and M. Veres, New evidence of light-induced structural 68 Z. Mao, W. Song, X. Xue, W. Ji, L. Chen, J. R. Lombardi and
changes detected in As–S glasses by photon energy depen- B. Zhao, Multiphonon resonant Raman scattering and
dent Raman spectroscopy, J. Non-Cryst. Solids, 2006, 352, photoinduced charge transfer effects at ZnO-molecule
1607–1611. interfaces, J. Phys. Chem. C, 2012, 116, 26908–26918.

This journal is © The Royal Society of Chemistry 2021 Nanoscale