Electrochemical surface-enhanced Raman

spectroscopy of nanostructures

Kari Iltanen
kari.iltanen@mbnet.fi
Salo 3.11.2021

This work is licensed under a Creative Commons “Attribution-ShareAlike 4.0 Inter-

national” license.
Contents

1 Introduction 1

2 Method 2

2.1 Raman spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . 2

2.2 SERS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

2.3 Electrochemical SERS . . . . . . . . . . . . . . . . . . . . . . . . . . 6

2.4 Limitations/advantages of EC-SERS . . . . . . . . . . . . . . . . . . 8

3 Applications 10

3.1 Use cases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

3.2 Examples from literature . . . . . . . . . . . . . . . . . . . . . . . . . 11

4 Summary 16

References 17
 1

1 Introduction

Electrochemical surface-enhanced Raman spectroscopy (EC-SERS) is one of many

spectroelectrochemical methods, some others are based on UV/VIS/IR spectroscopy,

photoluminescence and nuclear magnetic resonance. Spectroelectrochemistry is the

simultaneous electrochemical and spectroscopic investigation of the system allowing

one to collect more information than either method separately. [1]

Spectroelectrochemistry can acquire information about quantitative, thermody-

namic, molecular and mechanistic aspects of the system, which provide information

about electrode processes. It has an extreme rare capability to acquire information

from the electrode/solution interface without disturbing electrode processes. [1]

In UV/VIS/IR absorbance spectroelectrochemistry, absorption spectrum is mea-

sured from the electrochemical cell, so an optical path though the cell is required

which complicates the setup. Also, selectivity improves as different molecules with

similar absorption spectrum mostly have different electrochemical behavior. [1]

In electrochemical photoluminescence, the goal is to observe fluorescence from

the electrode surface and small distance around it. It is extremely sensitive and

requires good fluorescence from target which is uncommon, also the interference of

ambient light can be an issue. The main weakness is in quantitative analysis. The

measurement setup is more complex than in UV/VIS spectroelectrochemistry. [1]

EC-SERS is often favored due its sensitivity and ease of sample preparation

associated with Raman spectroscopy in general. SERS is one answer to the low

sensitivity of normal Raman spectroscopy and in EC-SERS it requires SERS enabled

electrodes. Ability to investigate water solutions is also major advantage. [1]

This work focuses on EC-SERS of nanostructures and is divided into methods

and applications sections. Methods section provides a short description of Raman

spectroscopy, SERS, EC-SERS and main strengths and weaknesses of latter. In

applications section, potential applications and some examples are discussed.

©2021 Kari Iltanen CC BY-SA 4.0 1

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2 Method

This section seeks to describe how Raman spectroscopy and especially its EC-SERS

variant works and what kind of equipment is required, before looking into its ad-

vantages and disadvantages.

2.1 Raman spectroscopy

In Raman spectroscopy electrons are excited with a laser to virtual energy states

above vibrational energy states but below the first electronic excited state. The

inelastic scattering of photons is known Raman scattering. Relaxation back to

ground state can happen in three possible ways that are known as Rayleigh, Stokes,

and anti-Stokes scattering (Figure 1). [2–4]

Virtual
energy
states

Vibrational
energy states
4
3
2
1
0
Infrared Rayleigh Stokes Anti-Stokes
absorption scattering Raman Raman
scattering scattering

Figure 1. Diagram of Raman scattering process on left. Source: Moxfyre, based

on work of User:Pavlina2.0 CC BY-SA 3.0, via Wikimedia Commons. On right
diagram of dispersive Raman spectrometer. Modification: blue path shortened.
Source: Smith et al. [5], CC BY 3.0.

In Rayleigh scattering electron relaxes directly to the same state that it was

excited from and a photon with the same energy that was used in excitation is

emitted. In Stokes scattering electron returns to the first excited vibrational state

and emitted photon has less energy than incoming photon. In anti-Stokes scattering

electron is excited from the first excited vibrational state to the virtual level and

©2021 Kari Iltanen CC BY-SA 4.0 2

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relaxes to the vibrational ground state emitting photon with higher energy than

incoming photon. [2–4]

The weakness of Raman spectroscopy is caused by rarity (∼ 1/108 ) of inelastic

scattering, thus the intensity of Rayleigh peak is many orders of magnitude larger

than Stokes peak, which is the next largest peak by intensity as the molecule is much

more likely to be in the ground state than in the excited state thus anti-Stokes peak

has the lowest intensity. Note that order of intensities of Stokes and anti-Stokes

peaks is not always the same. [2–4]

Raman activity requires that vibration leads polarizability changes in the molecule,

in contrast of IR spectroscopy that requires that dipole moment changes during vi-

bration. One major group of Raman active vibration are symmetric vibrations, also

generally covalent bonds lead to strong Raman vibrations. [2–4]

Raman spectrometer can be either dispersive (Figure 1) or a Fourier transform

device, which use 1064 nm laser and are nowadays used for routine measurements

only. Both consist of excitation source, a system to illuminate the sample and

collect scattered light, a filter unit, spectrometer, detector, control electronics, and

a computer for data capture and operating the equipment. The excitation source

is currently almost always a laser that are available from UV though visible to IR

wavelengths. [6, 7]

The role of sample optics is to focus the laser as small spot in millimeter range

and then collect the scattered light. If the Rayleigh scattered light is not blocked

with the bandstop filter it would saturate the detector preventing the detection of

Raman scattered light. The spectrometer uses a diffraction grating to disperse the

scattered light to reveal spectrum, which is then digitized usually with CCD camera.

[6, 7]

Laser wavelength selection is important part of Raman spectroscopy as it has

major impact on spectrum quality and spatial resolution. Some compounds are

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fluorescent, which leads high intensity fluorescent peak drowning low intensity Ra-

man peaks if the excitation laser corresponds to electronic transition. The signal

strength of Raman peaks decreases with increasing wavelength as the scattering

efficiency is proportional to 1/λ4 . The laser spot size increases with wavelength

decreasing spatial resolution. [3, 6, 7]

Many Raman spectroscopy variants have been developed to enhance response or

to address some other disadvantages, one of these methods is SERS enhances re-

sponse. In the resonance Raman variant the excitation wavelength is chosen so that

scattering happens from real electron eigenstates enhancing signal several orders of

magnitude. Enhancing the signal is required for the detection of low concentrations.

[3, 6, 7]

2.2 SERS

SERS enhances Raman signal though electromagnetic and chemical mechanism.

The enhancement can be 6-10 orders of magnitude of which the electromagnetic

enhancement is responsible most. In the electromagnetic mechanism light interacts

with surface plasmon resonances (SPR) exciting them on the surface of metallic

nanostructures, which have to be much smaller than the wavelength of incoming

light. [3, 8]

The excited SPR induces a strong electromagnetic field on the nanostructure

surface, which enhances the intensity Raman scattered light as its intensity is pro-

portional to intensity of incoming light that increases in interaction. Also, SPR and

inelastically scattered photon overlap, which provides further enhancement. [3, 8]

The chemical enhancement provides enhancement up to three orders of mag-

nitude and is the sum of various mechanisms: ground-state enhancement due in-

teraction between nanoparticle and molecule, excitation change transfer processes

between metallic surface and molecule, and the resonance Raman enhancement.

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This can be viewed as surface-induced resonance Raman effect due chemisorption

of a molecule on the metal surface disturbing the electronic structure of the sub-

strate. This allows the surface-induced electronically excited charge-transfer state

to be resonantly excited. [3, 8, 9]

Raman spectrum and SERS spectrum of the same compound can differ from each

other and enhancement varies between between different Raman modes. Surface

selection rules cause is this as according to them the modes parallel to the surface

are not enhanced at all or only very weakly while modes perpendicular to the surface

are enhanced. [3]

Good SERS substrates are non-toxic, chemically compatible with the sample,

temporally stable, reproducible, and preferably be both easily prepared and low cost.

Substrate changes during experiment could lead enhancement alterations reducing

reproducibility and repeatability. The highest enhancement is achieved with silver,

gold, and copper although other metals are possible but their enhancement factor is

usually at most a few hundred. Some possibilities are electrochemically roughened

electrode surfaces, colloids, and nanostructures. [8, 10, 11]

If nanoparticles are used their shape and size distribution affects greatly the

enhancement and the plasmon resonance frequency setting significant demands for

control of the fabrication process. Some substrates can be reused. Impurities on

surface of the SERS substrate can overwhelm the spectrum of the target compound

especially in low concentrations, or if metal absorbs target only weakly, or one is

looking at unknown sample. Often the SERS substrate has to be prepared just

before experiment though some commercial products exist. [8, 10, 11]

Also, some variants have been developed, one possibility is use silica coated

metallic nanoparticles, in tip-enhanced Raman spectroscopy (TERS) the enhance-

ment happens due strong electromagnetic field at metallic scanning probe micro-

scope (SPM) tip. TERS, while providing very high spatial resolution, requires

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modified equipment including modified SPM tip, so laser can be focused on the

tip/sample interface (Figure 2). Resonance effect applied to SERS is often referred

as surface-enhanced resonance Raman scattering (SERRS). SERS has also been used

in spectroelectrochemistry and then the method is known as EC-SERS. [10, 11]

2.3 Electrochemical SERS

Figure 2. Diagram of TERS illumination configurations on left. Source: Kumar

et al. [12] CC BY 4.0. On right Examples of EC-SERS sprectrum, note intensity
changes and shifts in peak position. Source: Hinuang and Hsiao [13], CC BY 4.0.

For electrochemical surface enhanced Raman scattering (EC-SERS) one requires

an electrochemical cell that can be placed under Raman spectroscope and control for

cell electrode potentials. This kind of setup usually requires long working distance

objectives, in some cases water immersion objectives can be used. [9, 11]

The electrochemical side of the measurement is often handled with potentiostat.

Reactions happen close to the electrode surface, so depending on electrode structure

reaction of interest might happen somewhere else than in area spectrum is measured

from. [9, 11]

From the electrochemical side a cyclic voltammetry is usually measured. Raman

spectra is often measured at constant potential with potential change between mea-

surements, but in some cases spectrum has been measured while potential changes

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continuously. [9, 11]

The cell design is critical part of experimental setup as it has to enable a strong

SERS response and ability to control the electrochemical experiment precisely. In-

tegrating optically transparent window that tolerates operating conditions into the

cell can be challencing. Connections to allow gas/liquid flow though the cell are also

usually part of the design. [9, 11]

Three electrodes are typically used, which are working electrode (WE), common

electrode (CE), and reference electrode (RE). To get SERS active WE one has

to either make the electrode surface active or use the electrode as substrate for

nanoparticles. [9, 11]

The reactions of interest happen at WE and its potential is monitored though

RE, which is chosen so that its electrode potential remains stable. CE is used to

remove excess current away from system to protect the RE. Typically CE is noble

metal electrode that remains inert under reaction conditions. [14]

With EC-SERS the electronic excitation of nanomaterials and target molecules

on SERS substrates can be investigated though SERS intensity as the molecular

selectivity of SERS depends on electrochemical potential. [9, 11]

The metal Fermi-level moves upwards closer to vacuum level as electrode poten-

tial becomes more negative and vice versa. As energy levels of the molecule remain

unchanged at some potential value energy difference between Fermi-level and lowest

unoccupied level in the molecule match the excitation energy allowing charge eas-

ily move between metal and molecule. This phenomena is equivalent to resonance

Raman mechanism. Intensity decreases as electrode potential changes from value

corresponding with peak intensity. [9, 11]

The plasmon frequency (ωp ) is dependent on electrode potential though free elec-
√︂
tron density (n) which increases with more negative potential (ωp = 4π ne2
me ϵ0
). A

band centered at ωp has the largest enhancement. The electrolyte choice affects the

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system properties, such as plasmon frequency and electrolyte refractive index. Elec-

trochemical reactions of the solvent containing both target molecule and electrolyte

has to be taken into account along with the possibility of the solvent spectrum

having much higher intensity than target. [9, 11, 15]

Multiple methods of fabricating SERS substrate required have been proposed,

which can be divided into a few main categories that are according Wu et al.

electrochemical oxidation and reduction cycles, metallic nanoparticle deposition to

electrically conductive substrate, core-shell nanoparticle deposition on conductive

substrate, and templated SERS substrates. The last one is the most interesting

as it provides more control over nanoparticle positions resulting ordered arrays of

nanoparticles. [15]

2.4 Limitations/advantages of EC-SERS

One of the largest issues in EC-SERS is the fabrication of the nanostructured elec-

trode that provides relatively uniform SERS enhancement over its whole surface

area that remains stable during the experiment. The fast development of nanofabri-

cation techniques can solve the electrode issue at least partially. EC-SERS setup is

also more complex than plain SERS setup, which can limit its usability somewhat.

EC-SERS can provide additional enhancement for signal intensity over plain SERS.

[16]

The lifetime of SERS substrate is one major issue, as typically used gold or

silver can dissolve during electrochemical reactions, some groups have used metal

nanoparticles with passivating coating to try to circumvent this problem. In catalysis

research combining SERS substrate with catalytic substance can cause issues. [17]

Gittleson et al. note that as Raman measurement can be also done with aqueous

electrolytes and during the electrochemical process directly from the electrochem-

ical cell, which are major advantages for battery research. Raman spectroscopy is

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preferred over Fourier transform infrared (FTIR) spectroscopy for in-situ measure-

ments of electrochemical cell due its more flexible setup and some species of interest

are not known be detectable in FTIR. [18]

EC-SERS can be used to study interactions between components on the com-

posite electrode surface as they can affect spectrum and especially can determine

how and what molecules can attach to the surface. [1]

There is risk that laser used in Raman spectroscopy, as tightly focused spot has

high power density on the sample surface even at milliwatt laser power levels, could

induce unwanted chemical reactions, such as the decomposition of surface species,

on target. This leads to unwanted signals, such as florescence and Raman signals

from decomposed species, which lower the signal-to-noise ratio. [16, 18]

Current materials for SERS substrate limit the usability of EC-SERS, but ex-

isting materials still improve and researchers are looking into totally new materials

for next generation SERS substrates, such as alloys. Microfluidic cells would enable

the investigation of continuous reactions, biological experiments and ease experi-

ment preparation, in EC-SERS this would require integrating electrodes and SERS

substrate into microfluidic channels. [16]

The highest sensitivity is achieved when the gap between adjacent metallic nanos-

tructures is in nanoscale (10 nm), these gaps are referred as "hot spots". [13]

As answer to the current weaknesses of EC-SERS researcher are constantly de-

veloping new, enhanced variants, such as EC-SERRS, EC-TERS, and time-resolved

EC-SERS. EC-TERS offers high spatial resolution and removes need for substrate

support for localized SPR, but on other hand setup is much more complex as illu-

mination and SPM within the electrochemical cell has to be fitted together. Illu-

mination depends on optics and cell structure, as transparent electrodes might be

needed. [19]

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3 Applications

This section seeks to provide some information about potential applications for EC-

SERS of nanostructures and application examples.

3.1 Use cases

Due the high sensitivity of EC-SERS it has multiple applications in basic research,

such as investigating reaction pathways and kinetics, biosciences. Absorption and

reactions of molecules on the metal surface is one potential application for EC-SERS.

Just by adjusting electrode potential sensitivity can be increased. Raman tags with

strong SERS signal can enable the detection of the target compound though indirect

detection with potential control. [16, 20]

Reaction pathway research allows the identification of intermediate steps, so one

knows what parts of reaction to pay most attention when looking to either en-

hance or block some reactions. Applications can be found for example in corrosion

protection, fuel cells, synthesis, and catalyst search. In biophysics, inter- and in-

tramolecular electron transfer reactions can be investigated with EC-SERS though

protein dynamics. [20]

EC-SERS and its variants can be used to investigate different charge transfer

reactions. In biochemistry, the behavior of DNA bases which could allow diagnos-

tic by identifying disease biomarkers. Also, other investigations reactions of DNA

and RNA with other molecules often use EC-SERS. Identifying bacteria was also

reported. EC-SERS as biosensor is potentially one major application for the tech-

nique. [21, 22]

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3.2 Examples from literature

Huang and Hsiao have developed an integrated EC-SERS chip (Figure 3) for uric

acid detection. The chip consists of printed circuit board (PCB) with three elec-

trodes, EC-SERS working electrode, and microfluidic reservoir. The goal is to use

the chip for rapid testing so good usability, small size, and small sample volume

were requirements. [13]

The WE was fabricated by using a nanostructured aluminum mold to create a

polycarbonate nanocone array by pressing the heated mold against polycarbonate

plate for several minutes. After cooling the substrate is released from the mold, and

then gold nanoshperes were formed at the tips of each nanocone with sputtering.

[13]

The chip was tested at first with NaCl electrolyte solution containing rodamine-

6G to measure EC-SERS response which shows the right potential level significantly

enhances signal. Using settings determined during testing detection of uric acid even

at 0,1 µmol/L concentration from artificial urine. Enhancement was up to 8,5 × 106 .

[13]

Figure 3. Diagram of EC-SERS cell developed by Huang et al.. Source: Huang et al.
[13] CC BY 4.0, via Wikimedia Commons. On right diagram of the nanoparticle-
RNA conjugate and its fabrication and use. Source: Lee et al. [23], CC BY 4.0.

Lee et al. have build a package consisting of a sephadex G-100 resin tagged

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RNA chain with a three-way junction to which biotin and Methylene Blue termi-

nated RNA chains were connected. This structure was then attached to streptavidin

coated gold nanoparticles with biotin (Figure 3). The nanoparticle-RNA conjugate

was then used as an EC-SERS biosensor to detect microRNA-155. ITO substrate

with electrodeposited gold nanoparticles on it was used as working electrode, and

phosphate buffered saline was used as the electrolyte. [23]

Nanoparticle and thiol termined head of RNA attached to substrate when small

positive electrode potential was applied with Methylene Blue, which provides the

SERS signal, termined head pointed upwards. After the microRNA-155 strand at-

taches itself to the junction, structure changes as the junction dissolved and Methy-

lene Blue swings towards surface attaching itself there. Comparison of Raman spec-

trum before and after microRNA-155 attachment showed a significantly higher in-

tensity of Methylene Blue peaks in the latter case. If the target RNA strand differs

from microRNA-155 even by single base Raman intensity drops significantly. This

type of setup was considered a potentially interesting starting point for the devel-

opment of general nucleic acid detection platforms. [23]

Vezvaie et al. have used a working electrode with silver nanocavities to study

lipid bilayers of dimyristoyl-phosphatidylcholine (DMPC), and hybrid bilayers con-

sisting of a hydrogenerated lipid layer and deuterium substituted DMPC molecule

layer with EC-SERS to see how potential changes affect these model membranes.

[24]

The nanocavities were fabricated on one or more monolayers of polystryrene mi-

crospheres on top of gold film on glass plate by electroplating silver on it, after this

template was dissolved. Lipid was then deposited to the cavities. Electrochemi-

cal and EC-SERS measurements show that bilayers can transition from the liquid

crystalline state to the mixed gel/liquid crystalline state at some potential values.

[24]

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Guo et al. have developed a way to electrochemically adjust SERS enhancement

of core-shell nanoparticles for nonelectroactive molecules. The working electrode

was a gold tip coated with a self-assembled monolayer of biphenyl-4-thiol with gold

nanoparticles on top. RE was Ag/AgCl wire. Then a few nanometers thick sil-

ver layer was electrochemically deposited on nanoparticles with AgNO3 electrolyte

solution. [25]

SERS intensity changes caused by potential variation were attributed to the

transformation of Ag shell to AgCl. The cause SERS intensity changes was at-

tributed changes in molecule-shell interaction causing chemical enhancement to

change. The setup can be used to investigate SERS enhancement mechanisms, and

help to apply EC-SERS at least to plasmonics, heterogeneous catalysis, molecular

electronics, biosensing, and electroanalysis. [25]

Kang et al. have investigated local heterogeneity in redox behavior on the elec-

trode surface at nanoscale with EC-SERS setup based on atomic force microscopy

(AFM). The electrode was polycrystalline indium tin oxide (ITO) substrate with

Au nanoplate on it and Nile Blue molecules absorbed on it as the target. Ag/AgCl

was used as the RE and Pt as the counter electrode, the electrolyte was mixture of

Tris buffer and NaCl. AFM tips were coated with Au. [26]

Nile Blue changes at reducing potential, which is visible in Raman spectrum as

an intensity drop. TERS intensity was mapped over area containing Au nanoplate

corner at different potential values. The intensity maps show higher intensity on

nanoplate than on ITO before the potential level where the reduction of the molecule

happens is reached. After reduction, no intensity differences were observed. Infor-

mation about the role of local electrode structure was acquired as spatial resolution

was about 40 nm. Potential applications are in electrocatalysis research as chemical

mechanisms at the molecular level can be investigated. [26]

Li et al. investigated electroreduction of RuO2 with EC-SERS by using AuRuOx

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core-shell nanoparticles. Working electrode was glassy carbon and the electrolyte

was a mixture of NaClO4 and NaOH in solution. Reduction of RuO2 was done at

pH levels 10 and 7, in latter case the electrolyte was NaClO4 solution. [27]

At both cases two-step reduction process was noted in SERS spectra recorded

at different potential levels, from Ru(IV) to Ru(II) (1,6–1,0 V) and then to metal-

lic Ru (0,8–0,3 V). Results indicate formation of OH species during reduction, and

therefore Li et al. believe that O from RuO2 reacts with water forming these species

which are later removed as H2 O. The same intermedies are produced during the sec-

ond step. The goal is to use these results to advance research into water electrolysis

and other catalytic reactions on RuO2 and Ru surfaces. [27]

Mahurin et al. have looked into interactions between room temperature ionic

liquid electrolytes and graphene electrode with EC-SERS. SERS enhancement was

provided by a roughened silver working electrode. The ionic liquid used consisted

of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. At first measure-

ments were done just with the silver electrode. [28]

Significant differences in SERS spectrum were visible when negative potential was

applied compared to the zero potential case. Differences were attributed to increased

cation concentration near WE and re-ordering of cations. Impact of densification of

ionic liquid was considered relatively small. [28]

Increase in applied potential caused higher overall intensity and changes in the

relative intensities of the peaks. The dominant interaction in imidazolium can be

located from intensity changes, and interaction strength of the cation determined.

Also, the relative intensities show the orientation of the molecule relative to the

surface. [28]

Graphene on the electrode caused some changes in spectrum, one effect was

supression of the graphene peaks likely caused by strong interaction between ionic

liquid and graphene. Some peak shifts were noticed at zero potential indicating

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stronger interaction with graphene than silver. Applied potential led additional

shifts caused by differences interaction strengths. The results indicate that EC-SERs

is a good method for studying interfacial interactions between electrode surfaces and

ionic liquid electrolytes. [28]

Lynk et al. have used EC-SERS to identify bacteria from their nucleotide break-

down products by comparing acquired spectra to a database containing spectra from

previously identified breakdown products. Motivation for EC-SERS usage was to

enhance the SERS signal and to take into surface charge differences between differ-

ent bacteria strains. The working electrode was a screen printed carbon electrode

coated with silver nanoparticles. Bacteria were placed at the electrode by incubating

electrode in concentrated bacteria solution. [22]

Compared to SERS EC-SERS spectra was shown to have clearer and more in-

tense peaks, with up five times higher enhancement. Reproducibility of signal inten-

sity was weak with likely cause indicated as nanoparticle coating being non-uniform

due the coating method used. Next development steps were stated to be improve-

ments to sample preparation to allow real-world samples and point-of-need screening.

[22]

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4 Summary

Spectroelectrochemistry provides more information from the target than either of

its components separately. SERS and its variants offer one solution to weak Ra-

man signal by using using surface plasmons to enhance the signal, which requires

nanoscale features on the metallic surface. In EC-SERS processes on and around

the working electrode are investigated, which requires nanostructured electrode or

nanostructures on the electrode to provide the enhancement. [1]

The enhancement is divided into chemical and electromagnetic parts, with latter

providing most of it. SERS spectrum can differ from the Raman spectrum of the

same compound. For the reproducibility substrates with similar enhancement fac-

tors is important and is realized though controlling the shape and size distribution

of nanostructures used as SERS substrate. EC-SERS can lead further enhancement

over SERS and enhancement can be controlled with applied potential. [3, 8, 9]

Rapidly evolving nanofabrication techniques can solve many issues with SERS

substrates, such as the stability, uniformity, lifetime, and use of non-plasmonic ma-

terials as the electrode. High power density of the laser spot on the surface could

induce unwanted chemical reactions that could lead unwanted signals. [16–18]

The application field for EC-SERS is extremely wide as it can be used to investi-

gate reaction pathways, bioscience, absorption on the surface, etc. Energy storage,

catalysis, and synthesis are some potential research targets with EC-SERS. Also,

biosensors could benefit from the sensitivity of EC-SERS and the ability to adjust it

with electrode potential, and are likely one of first applications outside lab. [20–22]

EC-SERS is a fast developing technique offering high sensitivity and flexibility.

Commercial SERS enabled electrodes would allow the much wider utilization of the

technique. EC-TERS combines SPM and EC-SERS for extremely high spatial reso-

lution. Integrating EC-SERS with microfluidics would combine nano/microstructures

and photonics within a single device opening many fascinating possibilities.

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