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Chemistry—A European Journal doi.org/10.1002/chem.202303658

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Surface-Enhanced Raman Scattering Using 2D Materials

Beatriz Pinto de Sousa,[a] Sara Fateixa,*[a] and Tito Trindade[a]

The use of surface-enhanced Raman scattering (SERS) as a this field, this concept article highlights the significance of
technique for detecting small amounts of (bio)chemical analytes understanding the chemical mechanism that underlies the
has become increasingly popular in various fields. While gold experimental Raman spectra of chemisorbed molecules onto
and silver nanostructures have been extensively studied as SERS 2D materials’ surfaces. Therefore, the article discusses recent
substrates, the availability of other types of substrates is advancements in fabricating substrates using 2D layered
currently expanding the applications of this spectroscopic materials and the synergic effects of using their metallic
method. Recently, researchers have begun exploring two- composites for SERS applications. Additionally, it provides a
dimensional (2D) materials (e. g., graphene-like nanostructures) new perspective on using Raman imaging in developing 2D
as substrates for SERS analysis. These materials offer unique materials as analytical platforms for Raman spectroscopy, an
optical properties, a well-defined structure, and the ability to exciting emerging research area with significant potential.
modify their surface chemistry. As a contribution to advance

Introduction size. The EM is the main contribution for observing enhanced

Raman signals (up to 1010-fold) of a molecular analyte on a
Raman spectroscopy is a vibrational tool used to characterise metal nanosurface. However, it does not consider the chemical
chemical compounds and materials, giving spectral information interaction between the molecule and the metal. In fact, in
about their structures and lattices based on their repective general terms, the EM does not consider the surface chemistry
vibrational modes.[1] This spectroscopy provides high selectivity, involved between the molecule and the metallic substrate,
easy operation and is sample non-destructive, with a relatively which is considered in the chemical mechanism (CM), by
quick spectral response that provides fingerprints of molecular placing the molecule under the spotlight to explain the SERS
vibrations, which very often complement information collected effect.[5,7] The CM comprises charge-transfer (CT) that might
from infrared absorption spectroscopy.[1] However, since its occur between the electronic ground state of the molecule and
discovery, Raman spectroscopy applied to analytical contexts the metal or photoinduced CT between the metal substrate and
has been hampered due to the low scattering cross-section the adsorbate; it might also include resonance Raman scattering
associated with trace detection of molecules and quantitative that arises due to resonance excitation involving electronic
analysis, leading to low sensitivity in practical analytical levels of a molecular adsorbate-metal complex. Overall, the CM
scenarios.[1] depends on the molecular-metal substrate interaction, which
The SERS effect has been explored as a tool to detect can enhance up to 104-fold the Raman signal of the adsorbed
vestigial amounts of molecules, even at the single-molecule molecule due to changes in polarizability. This means that the
level, using as substrates rough surfaces of metals or colloidal CM contributes significantly less to the SERS effect observed in
nanoparticles (NPs), typically of silver and gold.[2–4] molecules adsorbed on metal nanosurfaces. However, when
The mechanisms underlying the observation of SERS interpreting SERS using other substrates, like 2D layered
comprise electromagnetic and chemical contributions.[5,6] The materials, the CM is required by considering the above
electromagnetic mechanism (EM) is the dominant effect in the conceptual framework. Understanding this chemical aspect is
Raman scattering enhancement, involving the increase of the crucial for predicting future advancements in SERS substrates
local electromagnetic field in the metal nearby the molecules based on 2D materials.
due to resonance excitation of localised surface plasmons in the Research has focused on developing metallic surfaces with
metal.[6] Hence, the EM depends on the type of substrate, such nanoscale roughness to achieve efficient SERS substrates for
as the metal dielectric function and the particles’ shape and different molecules.[8–11] These surfaces create enhanced local
electromagnetic fields, or hotspots, found in nanojunctions
between closely spaced metallic NPs or in the apexes of
[a] B. Pinto de Sousa, Dr. S. Fateixa, Prof. T. Trindade
anisotropic nanostructures.[12–15] However, it is essential to
Department of Chemistry and CICECO – Aveiro Materials Institute
University of Aveiro develop new fabrication methods and novel materials for SERS
3810-193 Aveiro (Portugal) platforms aiming at the use of this analytical and detection
E-mail: [email protected] spectroscopic technique in diverse fields. An important research
© 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH line is the nanofabrication of sensitive and reproducible SERS
GmbH. This is an open access article under the terms of the Creative
substrates without having necessarily noble metals. This is quite
Commons Attribution Non-Commercial NoDerivs License, which permits use
and distribution in any medium, provided the original work is properly cited, challenging, considering that the strong Raman signal
the use is non-commercial and no modifications or adaptations are made. enhancement observed in such metal substrates is associated

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Chemistry—A European Journal doi.org/10.1002/chem.202303658

with their plasmonic properties, as mentioned above. Hence,

seminal SERS research on ultra-thin 2D crystalline lattices has
been reported lately.[16–20] Exfoliated layered materials are
examples of such 2D non-metallic substrates, which never-
theless can also be explored as nanocomposites comprising
plasmonic NPs.
Graphene is considered the quintessential example of a
SERS active 2D flat structure. It consists of a single-layer of sp2
carbon atoms bonded together in a honeycomb-like crystalline
lattice and shows distinctive electronic, mechanical, and optical
properties.[21,22] The application of graphene-based materials in
SERS has demonstrated several advantages: i) graphene has the
capability to support various functional NPs;[23] ii) by combining
graphene with metal NPs, a nanocomposite is created, generat-
ing a strong local electromagnetic field due to the metal NPs
and promoting CT between graphene‘s ground state and the
metal NPs;[18,22] iii) graphene quenches the fluorescence back-
ground, enabling the detection of fluorescent analytes using
Raman spectroscopy;[24,25] iv) molecules have a high affinity for
the graphene’s surface, ensuring reproducible Raman signals
due to extensive adsorption and homogeneous coverage;[26] v)
the honeycomb-like structure of graphene allows for interac-
Figure 1. Illustrative examples of 2D layered materials used as SERS
tions with aromatic molecules through π-π interactions.[27–29] The substrates.
recognition of these characteristics in graphene substrates
prompts the question of whether other 2D crystalline lattices
can be successfully applied for SERS applications. As illustrated
in Figure 1, these include transition metal dichalcogenides the article provides a perspective on the current research
(TMDs), boron nitride (BN), as well as carbides and nitrides of landscape, highlighting the potential for a new field of study
transition metals (MXenes), among others. that combines the design of SERS substrates by exploring the
The initial part of this work describes advancements in 2D chemistry of 2D materials, namely, assisted by Raman imaging
layered materials for SERS, focusing on the surface chemistry of methods.
the 2D layered materials associated with enhancing the
molecular probes’ Raman signal. Additionally, the article
explores the application of 2D layered structures as SERS
substrates and their use in detecting molecular species. Lastly,

Ms. Beatriz Pinto de Sousa is a research fellow and silver) and 2D layered materials (graphene
at the University of Aveiro and CICECO – and transition metal dichalcogenides), with
Aveiro Institute of Materials. She graduated in potential interest for bio-applications, sensors
Biotechnology (2018) and received a master’s and water quality monitoring by using Raman
degree in Molecular Biotechnology and Bio- spectroscopic methods (SERS, TERS and Ram-
engineering (2023) from the University of an imaging).
Aveiro. Her research interests combine the
Tito Trindade is Full Professor at the University
chemical surface modification of 2D nano-
of Aveiro (UA). He graduated in Chemistry (U.
materials and SERS analysis, namely by explor-
Coimbra, 1986), then moved to UA, where he
ing transition metal dichalcogenides as ana-
completed a Materials Engineering Master
lytical platforms for bio-applications.
(1992). Following his PhD at Imperial College
Dr Sara Fateixa is a Researcher at the Univer- London (1996) with studies on nanocrystalline
sity of Aveiro and CICECO- Aveiro Institute of semiconductors, he returned to UA, where he
Materials. She graduated in Industrial had a pivotal role in founding a research
Chemistry and Management (2006), com- group mainly focused on the chemistry of
pleted her Master’s degree in Analytical colloidal nanoparticles. He has been involved
Chemistry (2007) and obtained her PhD in collaborative research projects and interna-
degree in Nanoscience and Nanotechnology tional networks on topics related with inor-
(2013). She has been interested in new ganic nanomaterials and nanocomposites
strategies of synthesis, characterisation and studies, which includes substrates for SERS
surface modification of inorganic nanopar- analysis, among other applications.
ticles, such as plasmonic nanoparticles (gold

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2D Nanomaterials for SERS at the surface and sandwiched molybdenum atoms, with a
band gap in the visible range.[34] Bulk MoS2 has an indirect
Innovative GERS (graphene-enhanced Raman scattering) sub- bandgap of 1.2 eV, but the monolayered semiconductor shows
strates have been developed, but other 2D materials with a direct bandgap of 1.9 eV. Among these materials, graphene
potential for SERS have also been discovered. This family of showed the strongest Raman enhancement effect. A distinct
substrates includes single- and few-layered materials that can Raman enhancement mechanism has been proposed for each
be obtained through exfoliation of the three-dimensional 2D material: CT for graphene, strong dipole-dipole coupling for
counterparts or by bottom-up approaches. In this concept h-BN and both CT and dipole-dipole coupling, though weaker
article, we will emphasise the importance of the surface in magnitude, for MoS2.
chemistry of such 2D layered materials for the observation of In GERS, the EM is negligible because graphene’s surface
Raman signals of molecular adsorbates, namely in the pure plasmon resonances (SPR) lie in the terahertz region (infrared to
phases. In fact, if an enhancement mechanism is to be present radio-wave frequencies), while the excitation laser wavelength
in such cases, it should be of a chemical nature rather than used for the Raman measurements on molecular samples are
relying on plasmonic properties, as it happens in Au and Ag typically in the visible range and near-infrared (NIR).[35] Thus,
surfaces. Furthermore, as the following discussion will clarify, graphene-based materials have been regarded as a prototypical
other factors, such as fluorescence quenching and adsorption 2D nanomaterial for studying the CM between adsorbate-
efficiency due to the flat surface, may also play a crucial role in substrate.[30,36–38] On the other hand, MXenes are formed by
observing Raman spectra of adsorbates on such 2D materials.[30] transition metal carbides and nitrides combined with surface-
Although strictly speaking, these materials are not truly flat terminated chemical groups. They are commonly represented
surfaces, because they contain wrinkles and folded regions, this by the formula Mn + 1XnTx, where n + 1 (n = 1–3) layers, M is a
term has been extensively used in the reported literature to transition metal (e. g., Ti, V, Cr, Mo, W), X is carbon or nitrogen,
identify such materials. Here, we restrict the use of this and Tx represents the surface terminations (e. g., O, F, OH, Cl),
designation to emphasise a molecular configuration that results which are bonded to the outer M layers. Distinct from
from the chemical interaction between the substrate and the graphene, there are some MXenes, such as single or few-layered
molecular probe, which, in most cases, are aromatic molecules. Ti3C2Tx (Tx = F or OH) flakes, that exhibit metallic character-
istics, namely intense surface plasmons due to the intra- and
inter-band transition at the nanometer scale.[39,40] However, the
2D Materials-Based Substrates plasmonic behaviour in these MXenes decreases with the
increase in the width of the layers.
An earlier observation of the enhancement of the Raman signal SERS using 2D layered materials depends on several factors
of a molecular adsorbate (rhodamine 6G, R6G) on graphene that can be divided into the three following categories: i)
was made by Xie et al.[25] The authors reported the occurrence analyte (molecule concentration, molecule-layered 2D material
of photoluminescence quenching of the R6G adsorbed on the distance, molecule orientation, and type of molecule); ii)
surface of graphene, attributing this phenomenon to electron substrate (thickness, Fermi level, and 2D materials derivatives);
and energy transfer between graphene and R6G molecules. and iii) excitation laser energy. Figure 2 illustrates the main
One year later, Ling and co-workers demonstrated the characteristics of SERS using 2D layered materials, as also briefly
enhancement of Raman bands of R6G adsorbed onto single-
layer graphene (SLG).[31] Comparative studies using R6G depos-
ited on SiO2(300 nm)/Si substrate displayed solely fluorescence
background. The observed Raman signal enhancement of R6G
was attributed to CT betweengraphene and the molecules,
leading to a limit of detection (LOD) lower than 8×10 8 M. Since
then, the enhancement of the Raman scattering effect observed
on graphene surfaces has been termed GERS, which is a
particular case of SERS.
The discovery of GERS unlocked the development of several
2D materials with flat surfaces but distinct characteristics as
SERS substrates, including h-BN, MXenes, and TMDs. Ling and
co-workers have compared the Raman signal of copper
phthalocyanine (CuPc) adsorbates using graphene, h-BN and
TMDs (MoS2) as SERS substrates.[32] As graphene, h-BN and MoS2
are 2D layered materials, but with distinct electronic and
chemical properties. Namely, h-BN has a hexagonal lattice
constituted by alternate boron and nitrogen atoms, is highly
polar and insulating, and is resistant to high temperatures with
Figure 2. An overview of the main characteristics of SERS using graphene
a wide band gap around 6.0 eV;[33] MoS2 is a semiconductor structures as an example. Adapted with permission from.[37] Copyright 2023
with a three-layered atomic structure composed by sulfur atoms American Chemical Society.

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discussed below. It should be noted that a material used for by Zhang and colleagues demonstrated a higher enhancement
supporting (single- or multi-layered) 2D materials can also play factor (EF) for CuPc molecules adsorbed in a planar orientation
a role in enhancing the Raman signal. Hence, Ling et al. have on exfoliated graphene due to π-π interactions between CuPc
reported an interference phenomenon in SERS using SiO2/Si and graphene, compared to molecules adsorbed in a perpen-
supports with SiO2 layers of distinct thicknesses.[41] In this work, dicular orientation mode.[47] These findings highlight the
CuPc and protoporphyrin IX (PPP) molecules adsorbed on importance of molecular orientation induced by the flat
monolayer graphene showed optimal Raman signal when a structure of graphene in achieving enhanced Raman signals. Li
300 nm SiO2 layer was beneath it. Wang and co-workers have et al. have demonstrated that by modifying the surfaces of Ti3C2
demonstrated that the underlying support for ReS2 films plays sheets with Al-oxyanion groups, the molecular probes adopted
an important role in the photoluminescence quenching of R6G a flat conformation while closely interacting with the Al-
molecules adsorbed on the TMD films.[42] They have observed oxyanion surface, leading to the rare observation of highly
higher photoluminescence quenching of R6G molecules for sensitive but nonselective enhancement.[49]
monolayer ReS2 deposited on synthetic mica (fluorphlogopite) The coupling strength between molecule and substrate
than for SiO2 supports, which was attributed to the inert surface determines the CT efficiency, which depends on the Fermi level
of mica. of the latter.[48,50,51] Moreover, the EF in SERS using 2D layered
Analyte: 2D layered materials demonstrate remarkable substrates is promoted when the 2D materials’ Fermi level is in
stability against laser power and light exposure time. These between the adsorbates’ energy levels (highest occupied
substrates allow uniform distribution of molecular adsorbates molecular orbital (HOMO) – lowest unoccupied molecular
across their surfaces at the nanoscale. These characteristics orbital (LUMO)). For example, graphene is a zero-gap
enhance the substrate’s sensitivity and ensure the reproduci- semiconductor[48] whose Fermi level can be modulated by
bility of the Raman signal.[43] Additionally, fluorescent dyes like applying a gate voltage via surface functionalisation or chemical
R6G, when adsorbed on 2D layered materials, exhibit high doping. Xu and co-workers have shown that the graphene‘s
sensitivity, achieving a LOD comparable to metal NPs com- Fermi level changes due to an applied voltage, resulting in
monly employed in conventional SERS. Combining a monolayer differences in the Raman signal‘s intensity of metal phthalocya-
of aromatic molecules on 2D materials promotes the concen- nine (MPc, M: Mn, Fe, Co, Ni, Cu, Zn) molecules adsorbed on
tration of molecules on the surface, leading to the dye graphene.[50] They observed that the Fermi level of graphene
photoluminescence quenching. In a study by Ling et al., they shifted downwards when a negative gate bias was applied and
achieved a LOD as low as 8×10 8 M for R6G and 2×10 8 M for upwards when a positive gate bias was applied. The Raman
PPP using pristine exfoliated single-layer graphene supported signal of the MPc molecules increased when a negative gate
on SiO2/Si.[31] Brus et al. have studied the optical behaviour of voltage (downshifted Fermi level) was applied but decreased
R6G molecules adsorbed onto bilayered pristine graphene at when a positive gate voltage (upshifted Fermi level) was
resonant excitation and have obtained a cross-section of applied. Compared to graphene, TMD substrates have a density
5.1×10 24 cm2·molecule 1 for the 1650 cm 1 R6G mode due to of states (DOS) near the Femi level, and the three-layered
photoluminescence quenching.[30] This interpretation considers atomic structures offer rich surface sites for the chemisorption
that photoluminescence quenching is related to R6G/graphene of organic molecules and provide significant Raman
complexes formation, leading to photo-induced electron trans- enhancement under the CM. Yang et al. have achieved a LOD of
fer from R6G to graphene. TMDs, including 1T’-W(Mo)Te2 and 10 7 M for R6G using MoS2 grown on mica substrate because
WS2, have also shown photoluminescence quenching for R6G the Fermi level of MoS2 is in between the LUMO (-3.28 eV) and
molecules, leading to a LOD of 4×10 12 M.[44] the HOMO (-5.35 eV) energy levels of R6G molecules, promoting
CM enhancement relies on a short-range effect, also known CT between the R6G and MoS2 substrate.[52] An increased DOS
as the first-layer effect in SERS, in which the molecular at the Fermi level of MXenes would also facilitate the CT
adsorbate chemically interacts with the underlying surface.[45] processes, contributing to the enhanced Raman signals. Nitride-
The enhancement of Raman signals depends strongly on the based MXenes (e. g., Ti2NTx) have larger DOS at the fermi level,
distance between the adsorbate and the surface. Research by achieving a high EF of 1012 for R6G detection.[53] The Raman
Ling and Zhang on the application of the Langmuir-Blodgett signal enhancement of the dye molecules was ascribed to the
method to assemble successive monolayers of PPP molecules high electron density distribution on the N atoms, as a result of
on graphene surfaces has shown that the highest enhancement transfer of electrons from the Ti atom.
occurred for the first layer of PPP. In contrast, subsequent layers Substrate: The GERS effect is dependent on the number of
had little to no effect, further supporting the influence of the graphene layers, influencing the distribution of charge carriers
first layer on the SERS effect using 2D layered materials as and, consequently, the enhancement properties of graphene.
substrates.[46] Ling et al. observed that the enhancement of Raman signals
Moreover, the molecular orientation of the adsorbate on ascribed to CuPc molecules varied depending on the number of
the 2D materials’ surface plays a crucial role in observing Raman graphene layers (ranging from one to six layers), with SLG
enhancement. Studies on the molecular orientation and vibra- exhibiting the highest EF.[43] The SERS effect of TMDs and
tional modes of molecules adsorbed on 2D materials have MXenes is also layer-dependent, as observed for graphene. For
shown that a flat structure is significant in controlling the example, Meng et al. synthesised CVD-grown WS2 films span-
orientation of the molecular probe.[47,48] For instance, research ning from monolayer to bulk.[54] They showed that the Raman

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intensity of R6G molecules is strongest in single-layer WS2, in the interaction with the molecules and, consequently, on the
decreasing as the number of layers increases due to the indirect SERS effect, some caution should be present in these types of
relaxation process. The SERS activity of Ti3C2TX nanosheets was studies due to different extent of surface functionalisation in
investigated concerning sheet thickness using methylene blue GO samples of variable thickness. This is an important aspect
(MB) as a probe molecule, as reported by Limbu et al.[55] The considering the reproducibility of SERS spectra acquired on
study revealed a strong dependence of the MB Raman signal molecules adsorbed on GO substrates. Nair et al. have used
on sheet thickness in thinner sheet regimes, specifically below reduced graphene oxide (rGO) fabricated by laser writing,
0.8 μm, and under 532 nm laser excitation. On the contrary, the where the GO’s functional groups have been removed, to
CM of h-BN remains unaffected by its thickness because the detect R6G molecules, in this case, leading to better results
dipole-dipole mechanism in h-BN operates at the single-layer than using the non-reduced GO sample.[63] Reduced Ti3C3Tx
level.[32,56] Basu et al. have conducted a comprehensive study MXene nanosheets (r-Ti3C3Tx) were also demonstrated to have
exploring the relationship between h-BN thickness (ranging higher Raman enhancement for R6G molecules (EF = 107) than
from 1.5 to 36 nm) and its impact on enhancing the Raman the analogous pristine Ti3C3Tx.[64] The reduction with L-ascorbic
signal of MB molecules. The authors determined an EF of acid removes the Tx terminations (up to 50 %), improving the
1.5×10 4 for the h-BN film with a thickness of 1.5 nm and interaction and CT between the r-Ti3C3Tx nanosheets and the
1.0×10 4 for the film with a thickness of 36 nm. These findings R6G molecules.
highlight the almost negligible influence of the BN film thick- Excitation laser energy dependence, resonance effect and
ness on its performance.[56] Besides this layer dependency, 2D Raman excitation profile: The resonance Raman effect is a
few- and multi-layered materials have also been explored in particular case of Raman scattering taking place when the
SERS studies. Yaghobian et al. explored the potential of multi- frequency of the exciting line is in resonance with the electronic
layer graphene as an active Raman platform for detecting 4- absorption of the sample: the vibrations involved in the
mercaptobenzoic acid (4-MBA).[57] A Ti3C2Tx multi-layered struc- electronic transition are then strongly enhanced.[65,66] For
ture of 300 nm thickness has shown remarkable activity in instance, the Raman modes of TMD materials exhibit a strong
selectively detecting probe molecules, such as R6G. It exhibited dependence on the laser excitation frequency, impacting both
a SERS enhancement ranging from 105–106, highlighting its on the Raman shifts and band’s intensities. Specifically, when
exceptional sensitivity and performance in molecular the laser excitation energy aligns with the exciton energy, a
detection.[40] These studies indicate that SERS applications using resonance Raman effect occurs, leading to significant
2D materials as substrates are not limited to monolayers. enhancement in the intensity of specific Raman modes. For
The redox chemistry and doping of 2D layered materials instance, in the case of monolayer MoS2 with an exciton energy
have been reported to enhance the Raman scattering effect of approximately 1.8 eV, using a 633 nm laser source (1.96 eV),
significantly. Consequently, doped graphene can enhance SERS induces a stronger Raman intensity compared to other common
sensitivity through modifications in pristine graphene‘s elec- laser sources, such as green (532 nm) or near-infrared (785 nm)
tronic structure, achieved via atom doping, such as nitrogen lasers.[67] In addition, Berkdemir et al. conducted Raman spectro-
incorporation[58,59] Feng et al. have shown that the Raman signal scopy on single- and few-layered WS2, employing laser
enhancement of Rhodamine B (RhB) is higher in N-doped excitation sources at 488, 514, and 647 nm.[68] They observed
graphene compared to pristine graphene. This enhanced effect that only first-order Raman bands are detected under non-
is due to the closer proximity of the dye’s LUMO level to the resonant conditions with 488 nm laser excitation. However,
Fermi level of N-doped graphene, allowing a remarkable LOD of under resonant conditions with 514 nm laser excitation, several
10 11 M.[59] The Zheng group successfully introduced an optimal second-order bands emerged, exhibiting stronger intensities
amount of oxygen into the MoS2 lattice using hydrothermal than those observed in bulk WS2. Note that the Raman features
synthesis.[60] They elucidated the enhancement of SERS perform- of the 2D materials, either in resonance or out of resonance, will
ance for detecting R6G molecules, comparing it with pristine appear in the SERS spectrum but because the SERS effect of the
MoS2. This improvement was attributed to the increase of the molecular probes is typically higher, their Raman features will
DOS near the Fermi level following oxygen incorporation. This stand out until a certain limit is reached. In the case of the
phenomenon facilitates exciton resonance, providing an addi- TMDs, their Raman features do not match the region of
tional contribution to SERS. common interest for analysing tmolecular analytes.
Graphene oxide (GO), an oxidised form of graphene, has On the Raman excitation profile, the CM introduces two
also been used in SERS analysis because the oxygen-active distinct CT models: the excited-state CT, which involves the
functional groups on its surface (core and edges), such as formation of a CT complex through chemical bonding, and the
carboxyl ( COOH), epoxide (C O C), hydroxyl ( OH), and ground-state CT, where a CT complex is not essential for Raman
carbonyl (C O) groups can interact with aromatic molecules by enhancement.[69,70] In the first case, the maximum enhancement
electrostatic interactions, enhancing their Raman signal.[61] The is associated with the transition energy to the CT resonance
SERS detection of RhB using a GO substrate has been confirmed state, depending on the electronic structure of both the
by Berrellez-Reyes and Alvarez-Garcia.[62] Their study demon- molecule and the substrate. In the latter case, CT takes place
strated the quenching of RhB fluorescence due to a photo- when the substrate and the molecule are in the ground state
induced CT process from RhB to the surface of GO. However, without the assistance of light radiation. Thus, this process
because the oxygen-active functional groups play a crucial role depends upon the electronic structure of the molecule but not

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on the excitation laser frequency.[38,71] The ground-state CT analyte molecules through π-π stacking or electrostatic inter-
process has been reported for several 2D layered-based actions and can also improve sensitivity, chemical stability,
materials and distinct molecular adsorbates.[20,38,71] For example, biocompatibility, reproducibility, and fluorescence quenching.[22]
Ling et al. have reported a ground-state CT mechanism in the Several parameters have been explored to achieve better SERS
CuPc – graphene system based on Raman excitation profiles performances using such composites, including the use of
(545–660 nm).[71] In addition, Muehlethaler et al. have reported distinct metallic NPs, as illustrated in the following examples.
an EF of 3.8×105 for 4-mercaptopyridine (4-MPY) adsorbed on a Ag/2D layered composites: Aqueous-based methods have
monolayered MoS2 substrate using the laser excitation at been extensively investigated to prepare nanocomposites as
488 nm.[72] The enhanced Raman signal of 4-MPY molecules was SERS substrates. Typically, these methods involve the chemical
attributed to the CT state formed at the interface of the MoS2 reduction of a Ag(I) salt in the presence of 2D layered materials,
and 4-MPY when the excitation source is in resonance with the using reducing agents such as amines, sodium borohydride,
CT state. The Raman excitation profile acquired by scanning the ascorbic acid, and sodium citrate.[87–90] Alternative methods
Raman spectra of the adsorbate under distinct laser wave- associate 2D materials and already prepared colloidal Ag NPs
lengths can also provide information about the type of CM that via spin coating,[91] electrostatic interactions,[92] self-assembly,[93]
takes place. magnetron sputtering.[94] Dutta et al. have employed wet
chemistry to fabricate Ag/rGO materials for detecting the uranyl
ion (UO22 +) at 10 nM level.[90] The authors have observed shift
Metal Nanoparticle-Decorated 2D Materials on the Raman band of the symmetric stretching mode of UO22 +,
when the pH was varied from 5 to 12. Such shift on the Raman
2D materials have also been used in SERS to investigate band was associated with a pronounced charge transfer effect,
surfaces and explore interfacial phenomena. These studies thus supporting the higher sensitivity of this method towards
benefit from the properties of the 2D materials, such as their UO22 + over other oxometallate ions, namely CrO22 , MoO42 ,
high efficiency in interacting with light and surface sites that VO2 + and WO42 . Mahar and co-workers have reported paper-
can be chemically modified through surface functionalisation, based AgNPs@V2CTx substrates using a self-assembly method to
for example, using plasmonic metal NPs.[33,73,74] Functionalisation deposit the Ag NPs on the V2CTx film.[93] These materials were
using other types of NPs, such as semiconductors, has been used to detect low vestigial amounts of the chemotherapy drug
explored, but originating less intense Raman signals than metal gemcitabine, achieving a LOD of 10 12 M. A composite based
nanosurfaces.[75] Also, surface chemical modifications using on MoS2 spin-coated with Ag NPs and Ag nanowires (NWs) was
metallic NPs not only modify its structural and optical proper- reported by Li et al.[91] The results show that these composites
ties but also introduce surface irregularities, affecting the overall are highly sensitive, reliable and reproducible in detecting
flatness of the 2D material sheets. The extent to which the organic dyes, such as R6G, showing a LOD of 10 11 M.
flatness is changed depends on several factors, including the Only a few reports were found on applying pure graphene
size, shape, and spacing of the plasmonic NPs, as well as the in the above context. Xu et al. have added Ag nanostructures to
thickness of the 2D material[76–79] For example, Bhanu et al. have single-layer graphene, creating a flexible substrate for SERS
observed an increase in the roughness of the Au-MoS2 hybrid detection of organic molecules such as R6G and CuPc.[95] Ying
films, which was measured by atomic force microscopy (AFM). and co-workers have reported the fabrication of a graphene-
The roughness of thermal evaporated Au films increased with shield SERS sensing spots array for the optical detection of
thethickness: root mean square (RMS) = 0.6 nm for 1.0 nm Au cyanine-3 labelled single-stranded DNA.[94] h-BN has also been
film and RMS = 1.6 nm for 2.0 nm Au film, as compared to used as a protective barrier and reusable coating for Ag
RMS = 0.37 nm for the pristine MoS2 film.[79] NPs.[96,97] Cai et al. have fabricated sensitive SERS substrates by
Here, we consider only the cases in which the observed covering Ag NPs with atomically thin BN nanosheets to detect
Raman signal was enhanced for molecules adsorbed on a 2D organic dyes such as RhB (LOD: 10 6 M). The BN nanosheets
material’s surface. As compared to the dimensions of metal NPs offer Ag NPs long-term protection from oxidation even at high
and the 2D substrate, the molecular adsorbates are very small temperatures in the air, providing excellent reproducibility and
and likely experience a flat surface, for example, through π-π reusability.[96]
interactions and, consequently, promoting a CM effect. The Au/2D layered composites: Biosensors made of 2D materials
resulting composite nanostructures have been prepared by a can work based on a SERS effect by integrating them with Au
variety of methods that include nanolithography,[80] magnetron NPs. Indeed, among the plasmonic metals known for their SERS
sputtering,[81] thermal evaporation,[82] self-assembly[83] in situ activity, Au NPs stand out for bioapplications due to their
growth wet-chemical processes[84] and CVD methods.[85] The biocompatibility, non-cytotoxicity, and enhanced chemical
presence of plasmonic NPs on crystalline surfaces can result in stability.[98,99] Examples on the use of Au/2D hybrid substrates as
substrates that show enhanced Raman signals of molecular biosensors include the detection of DNA,[100] biomolecules,[101]
probes adsorbed on the hybrid surface due to the conjugation IgG,[102] doxorubicin[103] and bacteria.[104] An and co-workers have
of the strong local EM field in the metallic NPs and the CT reported a hybrid material composed of Au NPs and GO that
mechanism of 2D materials.[21,22,86] This synergistic effect can simultaneously presents photothermal and SERS behaviour.[105]
enhance the SERS EF to another order of magnitude. In such Although the hybrid showed low cytotoxicity, after doxorubicin
hybrid materials, the 2D material is effective in adsorbing the hydrochloride loading, cell death was induced, and photo-

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Chemistry—A European Journal doi.org/10.1002/chem.202303658

thermal treatment further decreased cell viability. Wu et al. have passivation layer.[110,111] Hence, Yang et al. have reported the
developed a ratiometric aptasensor to detect Mycotoxin B1 in preparation of core-shell graphene@Cu NPs by CVD to detect
peanut samples based on AuNP/Ti3C2Tx dimers.[101] AuNPs/WS2 vestigial amounts of R6G.[110] In this case, the graphene shell not
hybrid nanostructures that can efficiently identify antibiotic- only assisted the Raman signal enhancement of R6G through
resistant pathogens, such as Salmonella strains, which are the CM but also limited the oxidation of Cu NPs. The use of GO
resistant and non-resistant to certain antibiotics, have been associated with Cu NPs has been successfully explored for
reported by Pramanik et al.[104] developing SERS sensors. Anh et al. have reported a colouri-
Although the Au/2D layered composites are essentially used metric and SERS sensing Cu@GO platform to detect amoxicillin
as biosensors, they have been proven helpful in other fields, in aqueous samples.[112] The authors demonstrated that electro-
namely in water quality monitoring. For example, Nguyen et al. chemically prepared Cu@GO nanocomposites show high sensi-
fabricated AuNPs/graphene composites to detect by SERS tivity to amoxicillin as colourimetric (1.71 μM) and SERS
selected pesticides, namely azinphos-methyl, carbaryl, and (0.0012 μM) substrates in comparison to Cu NPs (2.17 μM;
phosmet.[106] Shi et al. have developed a simple SERS-based 0.0152 μM, respectively) prepared by the same method.
“turn-off” sensor by self-assembling AuNPs coated with
cucurbit[7]uril onto GO sheets to detect Pb2 +.[107] Fateixa and
her team have been exploring hybrid materials containing GO
or MoS2 as the 2D layered material coated with Au NPs using Raman Imaging of 2D Materials and its
several methodologies to detect organic dyes, biomolecules Application in SERS
and pesticides (Figure 3). Recently, they have reported the
development of filter membranes based on GO and Au nano- Confocal Raman microscopy (CRM) has emerged as a powerful
stars for detecting several dyes. They achieved a higher tool for characterising diverse materials, including graphene,
enhancement for MB using the hybrid material as compared to TMDs and BN. The application of CRM for studying 2D materials
the use of GO and colloidal Au nanostars deposited on is expected to increase due to its potential for getting insights
polyamide filter membranes, attributing this result to the about their structure and bonding. The number of layers,[82,113,114]
synergistic effect of the plasmonic properties of the Au nano- density of charge,[115] crystal orientation/composition,[116,117]
stars and the ground-state CT from GO.[108] doping,[118,119] defects,[118,120,121] and strain[119,121,122] can be probed
Cu/2D layered composites: Copper NPs are a cheaper by monitoring the position, width, and integrated intensity of
alternative for fabricating SERS substrates instead of Au and Ag the Raman bands of 2D layered materials. Cong et al. have
NPs.[109,110] However, neat Cu NPs are easily oxidised, which is an reported a Raman imaging study of the edges of single-layer
essential issue for practical applications in ambient conditions. graphene, demonstrating that the G band can probe the edge
The combination of graphene-based materials and Cu NPs can orientation, in addition to the D mode.[116] They have observed
improve their oxidation resistance because graphene acts as a polarisation dependence in Raman images by monitoring the G
band at the edges of zig-zag and armchair conformations,
which were explained by the unequal interaction between LO
and TO phonons with electrons at the different types of edges.
Baillargeat and co-workers have systematically studied few-layer
MoS2 (< 5 layers) using CRM.[113] They have observed that the
layer number of ultrathin MoS2 flakes strongly influences the
Raman frequencies of E12g and A1g bands. Bera et al. have used
CRM to study the defects and strains of thin h-BN films
supported on sapphire during heat treatment.[121]
CRM has been used in bioimaging to investigate cell
targeting and to follow disease diagnosis and therapy.[123–126]
Because the Raman effect is caused by scattered light resulting
from molecular vibrational modes, incident light of lower
energy can be used to monitor biological samples as compared
to other techniques such as fluorescence,. These features have
been explored with graphene materials for drug delivery and
biotargeting purposes.[127] Sohová et al. have used Raman
imaging to study the cellular uptake pathways of GO nanoflakes
in cancer-living cells by tracking the GO presence through the
Raman features of GO.[128] They have observed that the GO
penetration in the cells occurs through the cell membrane and
Figure 3. 1. a) AFM image of GO/AuPd filter membranes and b) SERS spectra agglomerates in the lysosomes. Trindade and co-workers have
of MB (100 μM) using GO (a) and GO/AuPd (b) filter membrane as substrate; combined carbon nanomaterials (e. g. GO sheets) with porphyr-
2. a) transmission electron microscopy (TEM) image of MoS2/AuNPs and b)
SERS spectrum of 4-MBA (100 μM) using MoS2/AuNPs and MoS2 as ins and phthalocyanines to create nanosystems that detect
substrates. AFM image by courtesy of Dr. Gil Gonçalves (U. Aveiro) DNA G-quadruplex.[27,129,130] The Raman imaging analysis on the

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Chemistry—A European Journal doi.org/10.1002/chem.202303658

GO/porphyrin nanosystem has shown that the porphyrin

molecules are predominantly located at the edges of GO
through electrostatic attractions and at the core through van
der Waals and π-π stacking interactions.[27] The same analysis
after the spectrofluorimetric titrations of the GO/porphyrin with
DNA G-quadruplex led to fluorescence recovery because the
porphyrin molecules linked through electrostatic interactions
were detached from the surface of the nanosystem to interact
with the G-quadruplex. A multifunctional theranostic platform
composed of h-BN nanosheets conjugated with DNA oligonu-
cleotide and CuPc molecules has been developed by Liu
et al.[131] Here, the CuPc molecule played double key roles in
photodynamic therapy as well as in situ monitoring and Raman
imaging of MicroRNA-21, a biomarker involved in many types of
malignancies, including brain, lung, and breast cancer.
Plasmonic NPs have been combined with graphene-based
materials to enhance the Raman signal of graphene‘s bands.
This enables rapid Raman detection and spatial imaging of the Figure 4. A. Optical image (100x objective) of MoS2 deposited on Au wafer
(red circle marked the Raman imaging scan area); B. Plot of the Raman
analyte or molecular target, even under conditions of low laser intensity of the RhB band at 1645 cm 1 (100 μM) using Si wafer, Au wafer,
power (e. g. 0.1 mW) and short acquisition time.[75,132] Liu et al. MoS2/Si wafer and MoS2/Au wafer as SERS substrates; Raman images
have investigated GO materials decorated with AuNPs to detect obtained by monitoring the MoS2 Raman band (Ag1) at 405 cm 1 (C) and the
RhB Raman band at 1645 cm 1 (D).
GO directly in living cells.[133] They demonstrated that Au/GO
hybrids could be used for fast Raman imaging of HeLa cells by
monitoring the surface-enhanced Raman band at 1595 cm 1 (G
band of GO). In addition, Sutrová et al. have used Raman Conclusion and Outlook
imaging at varying excitation wavelength (532–830 nm) to
explore the mechanisms of SERS in composite systems. They The continuous innovation and development of 2D layered
probed annealed samples of Ag NPs on glass platforms materials are anticipated to position them as indispensable
sequentially coated with SLG and a monolayer of free-base tools for surface science research in the coming years. This
phthalocyanine (H2Pc) molecules. By comparing excitation paper aimed to provide insights into applying 2D layered
profiles through the determination of EF and the Fermi level of materials as substrates for observing the Raman signals of
SLG, the investigation established for the glass/AgNPs/SLG/H2Pc chemisorbed molecules. The significance of the chemical
composite the CM due to the 2D material and the EM due to interaction within the surface complex formed by the molecular
the AgNPs, but only CM was suggested for the glass/SLG/H2Pc probe on the 2D material was exemplified by several reports
system.[134] found in recent literature. The research indicates that such
Considering that a Raman enhancement effect has been interaction underlies the mechanism for observing enhanced
observed on the surface of other 2D materials, as pure Raman bands in 2D materials, a phenomenon that, in most
substrates or combined with metallic NPs, these systems practical scenarios, has involved aromatic molecules. Indeed,
constitute probes with great potential for Raman imaging. the examples provided clearly show that the research so far
However, the use of other 2D materials has been practically predominantly focused on graphene-based materials and in a
unexplored in this context. Our group has been interested in few selected aromatic molecular probes (e. g. R6G, CuPc). In
exploring the synergistic effect of TMDs and metallic NPs in these cases, the chemical mechanism might arise from charge
detecting specific biomarkers concerning food quality monitor- transfer and dipole-dipole interactions occurring between the
ing and healthcare applications. For instance, MoS2 deposited molecular adsorbate at the surface of the 2D material, which
on gold wafers (silicon wafer coated with Au NPs with a varies depending on the chemical nature of the complex
diameter of 50 nm) was proven to be sensitive to detect RhB by formed. Consequently, working the surface chemistry of 2D
using SERS imaging (Figure 4); RhB is a cancerogenic dye that materials provides tools for improving their SERS
has been reported as illegally used to impart a red colour to performance.[136]
chilli powder.[135] The Raman analysis showed a higher The research published so far suggests a conceptual frame-
enhancement of the RhB Raman signal for the MoS2/Au wafer work in which the SERS performance of 2D materials can be
concerning its counterpart (MoS2/Silicon wafer and Au wafer). improved through various parameters, including varying the
The Raman images monitoring the dye band (1645 cm 1) and number of layers, modulating the Fermi level of the substrates,
the MoS2 band (405 cm 1) indicate that the RhB molecules are and by considering the chemical composition of the 2D
adsorbed on the MoS2 sheets’ surface, and the enhancement material. However, it is necessary a deeper understanding of
effect is due to the combination of the TMD material and the the CM effect and the intricate interplay among distinct 2D
metallic film. materials, molecular analytes, and excitation laser energy.
Among other possibilities, Raman studies on van der Waals

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heterostructures can bring new fundamental insights. Although Acknowledgements

a few studies exist reporting Raman spectroscopy applied to
such heterostructures,[137,138] their use as Raman amplifiers has This work was developed within the scope of the project
been scarcely investigated.[139] Still, it offers the prospect of in- CICECO – Aveiro Institute of Materials, UIDB/50011/2020, UIDP/
depth investigations of 2D materials as Raman amplifiers, by 50011/2020 & LA/P/0006/2020, financed by national funds
addressing important issues such as chemical stability, substrate through the FCT/MCTES (PIDDAC) and when appropriate
composition, geometric configurations, tunnelling effects, and cofinanced by FEDER under the PT2020 Partnership Agreement.
materials’ thickness dependence, among others. Moreover, SF thanks FCT for her research contract (REF-069-88-ARH-2018),
within the chemical mechanism, the Raman signal observed not which is funded by national funds (OE) through FCT-Fundação
only relies on the nature of the substrate but also intrinsically para a Ciência e a Tecnologia, I.P., in the scope of the framework
depends on the characteristics of the chemisorbed molecule. As contract foreseen in the numbers 4, 5, and 6 of the article 23, of
previously mentioned, the focus of studies has predominantly the Decree-Law 57/2016, of August 29, changed by Law
been on aromatic molecules, which show high sensitivity (about 57/2017, of July 19.
10 8 M). Consequently, a promising research line emerges
through judicious chemical functionalisation of these aromatic
molecular probes. For instance, the presence of substituent Conflict of Interests
groups onto the aromatic ring, depending upon whether they
exhibit electron-withdrawing or electron-donating properties, The authors declare no conflict of interest.
provides an avenue to investigate electronic effects on the 2D
material-molecule complex.
Research on 2D materials as Raman signal amplifiers is still Data Availability Statement
in its early stages when considering their practical applications
in real-world scenarios like environmental chemical analysis, Research data are not shared.
food safety and biosensors. However, it is important to keep in
mind, that SERS using 2D materials become a game changer Keywords: 2D materials · surface chemistry · SERS · Raman
when certain characteristics are considered, therefore providing spectroscopy · nanostructures
an alternative to the application of substrates relying solely on
plasmonic nanostructures. Hence, 2D layered materials offer
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