nanomaterials

Article
Graphene Oxide-Coated Metal–Insulator–Metal SERS
Substrates for Trace Melamine Detection
Zhenming Wang 1 , Jianxun Liu 1, *, Jiawei Wang 1 , Zongjun Ma 1 , Delai Kong 1 , Shouzhen Jiang 2 , Dan Luo 1
and Yan Jun Liu 1, *

1 Department of Electrical and Electronic Engineering, Southern University of Science and Technology,
Shenzhen 518055, China; [email protected] (Z.W.); [email protected] (J.W.);
[email protected] (Z.M.); [email protected] (D.K.); [email protected] (D.L.)
2 Provincial Key Laboratory of Optics and Photonic Device, School of Physics and Electronics,
Shandong Normal University, Jinan 250014, China; [email protected]
* Correspondence: [email protected] (J.L.); [email protected] (Y.J.L.);
Tel.: +86-134-2989-8590 (J.L.); +86-755-8801-8520 (Y.J.L.)

Abstract: Surface-enhanced Raman spectroscopy (SERS) has long been an ultrasensitive technique
for trace molecule detection. However, the development of a sensitive, stable, and reproducible
SERS substrate is still a challenge for practical applications. Here, we demonstrate a cost-effective,
centimeter-sized, and highly reproducible SERS substrate using the nanosphere lithography technique.
It consists of a hexagonally packed Ag metasurface on a SiO2 /Au/Si substrate. A seconds-lasting
etching process of a self-assembled nanosphere mask manipulates the geometry of the deposited
Ag metasurface on the SiO2 /Au/Si substrate, which attains the wavelength matching between
the optical absorbance of the Ag/SiO2 /Au/Si substrate and the excitation laser wavelength as





 well as the enhancement of Raman signals. By spin-coating a thin layer of graphene oxide on
Citation: Wang, Z.; Liu, J.; Wang, J.;
the substrate, a SERS performance with 1.1 × 105 analytical enhancement factor and a limit of
Ma, Z.; Kong, D.; Jiang, S.; Luo, D.; detection of 10−9 M for melamine is achieved. Experimental results reveal that our proposed strategy
Liu, Y.J. Graphene Oxide-Coated could provide a promising platform for SERS-based rapid trace detection in food safety control and
Metal–Insulator–Metal SERS environmental monitoring.
Substrates for Trace Melamine
Detection. Nanomaterials 2022, 12, Keywords: SERS; self-assembly; metasurface; surface plasmon; hot spot; sensitivity
1202. https://doi.org/10.3390/
nano12071202

Academic Editors: Isabel Pastoriza-

Santos and Maria Losurdo
1. Introduction
In recent years, the surface-enhanced Raman spectroscopy (SERS) technique for the
Received: 17 February 2022
detection of dangerous substances in small volumes and extremely low concentrations has
Accepted: 31 March 2022
attracted extensive interest [1–4]. As known, SERS can provide single-molecular sensitiv-
Published: 3 April 2022
ity [5–10], label-free detection [11–13], and high-throughput screening of a huge number of
Publisher’s Note: MDPI stays neutral samples [14,15], which is well suited for on-site trace detection and identification [16–18].
with regard to jurisdictional claims in Among numerous theoretical and experimental reports on SERS substrates [16–23], there
published maps and institutional affil- are three main strategies to enhance the Raman signal intensity and decrease the detection
iations. limit, including enhancing the absorption of incident light [19–22], amplifying the far-field
radiation of Raman scattering signals [23,24], and increasing the attachment of the targeted
substances [25,26]. A universal approach to enhancing absorption of the excitation laser and
Raman signals is to construct a substrate composed of dense metal nanostructures [27–29].
Copyright: © 2022 by the authors.
These nanostructures have not only large optical absorption cross sections but also numer-
Licensee MDPI, Basel, Switzerland.
This article is an open access article
ous “hot spots” produced by the localized surface plasmon resonance (LSPR) to enhance
distributed under the terms and
the far-field radiation. Large Raman signal enhancement has been achieved in some SERS
conditions of the Creative Commons substrates with randomly dispersed metal nanostructures [21,30]. However, how to in-
Attribution (CC BY) license (https:// crease the absorption of the excitation laser has yet been received enough attention. A good
creativecommons.org/licenses/by/ way to achieve a SERS substrate with specific wavelength absorption is to artificially design
4.0/).

Nanomaterials 2022, 12, 1202. https://doi.org/10.3390/nano12071202 https://www.mdpi.com/journal/nanomaterials

Nanomaterials 2022, 12, 1202 2 of 13

plasmonic metasurfaces [22,29,31,32], which are a periodic arrangement of subwavelength

meta-atoms with special shapes, such as nanodisks, nanopillars, nanogrids, etc. [33–38].
Among numerous kinds of plasmonic nanostructures, nanobowties have been demon-
strated to achieve relatively large Raman signal enhancement [34]. In addition, the choice of
metal materials will also affect the Raman enhancement. For the case of 532 nm excitation
laser, silver nanostructures have a smaller photothermal effect than gold ones, leading
to a larger enhancement factor [35,38]. Besides silver, other materials such as aluminum,
lead, and platinum are also good choices, but silver could be the best choice with a much
easier fabrication process [39–42]. A detection limit down to 10−16 M for Rhodamine 6G
has been reported by silver metasurfaces formatted with nanobowties [35]. Additionally,
it is worth noting that the reduced photothermal effect could help avoid damage to the
analytes during the measurement process [43].
As a well-known poisoning additive, melamine is sometimes illegally adulterated with
food products in order to increase the apparent protein content. Ingestion of melamine may
cause reproductive damage, kidney stones/failures, and bladder cancer. In adulterated
milk products, melamine concentrations could be as high as ~3300 ppm, far exceeding
the safety limit of 1 ppm (~7.9 × 10−6 M), hence posing an extreme danger to consumers.
Therefore, rapid and unambiguous detection of trace amounts of melamine in food products
is of paramount importance. To counteract the adverse effects of melamine, various
analytical techniques based on SERS for detecting it in dairy and food products have been
developed [44–47]. For example, in 2016, Dong et al. [44] used polythymine aptamer-
modified Au nanoparticles to decrease the limit of detection down to 8 × 10−12 M for
melamine with the SERS effect. Li and co-workers [45] synthesized a monolayer film
with Ag nanoparticles to realize a SERS effect on melamine with a limit of detection near
3 × 10−13 M. Such SERS substrates are characterized by the formation of a sufficient
number of hot spots near or between nanoparticles to achieve the strong SERS effect.
Huang and co-workers [46] demonstrated the low limit of detection of 1×10−16 M by
using Ag nanoparticles decorated with Zinc oxide/Silicon heterostructured nanomace
arrays as a SERS substrate. The large-area detection for extremely low concentration is
realized; however, the SERS substrate fabrication process is very complicated and time-
consuming. Kundan et al. [47] fabricated an Au nanorod array with a focused ion beam
(FIB) and achieved the detection limit of 1 × 10−12 M for melamine. Although the low
limit of detection for melamine is also achieved in a large area, the preparation processes
are greatly dependent on precision nanofabrication techniques, such as electron beam
lithography (EBL) and FIB, leading to complicated and costly fabrication. Therefore, it
is still in high demand to develop large-area, uniform SERS substrate with a simple and
cost-effective fabrication technique. More importantly, there is no artificially designed
structure to purposely investigate the effect of the characteristic absorption of excitation
light on SERS signal enhancement.
Self-assembly-based nanosphere lithography (NSL) is a simple, cost-effective approach
compared with EBL and FIB. Nanospheres as tiny as 200 nm can be used for monolayer
self-assembly that can be further used as a templated mask [48]. Dai et al. fabricated Au
triangular nanoarrays covered by Au nanoparticles by NSL to achieve the detection limit of
1 × 10−7 M for melamine [49]. In our previous reports, we have devised a slightly modified
self-assembly process to achieve a large-area, high-quality polystyrene (PS) nanosphere
monolayer [50,51]. In this work, we fabricate a hexagonally packed Ag metasurface on
SiO2 -Au-coated silicon (Ag/SiO2 /Au/Si) substrate based on the NSL technique, forming
a metal–insulator–metal (MIM) SERS substrate. By etching the PS nanosphere of the
template mask with the inductively coupled plasma (ICP), strong plasmonic coupling at
the wavelength of 532nm is achieved between the tips of nanotriangles in the metasurface
and the Ag metasurface with strong absorption for the excitation laser wavelength of
532 nm is fabricated purposely. By introducing the MIM (Ag/SiO2 /Au/) structure, the
characteristic absorption for the excitation laser wavelength of 532 nm can be further
enhanced. To additionally improve the SERS effect, a very thin layer of graphene oxide (GO)
Nanomaterials 2022, 12, 1202 3 of 13

is spin coated on the Ag/SiO2 /Au/Si structure to increase the number of target molecules
adsorbed on the structure. An analytical enhancement factor (AEF) of 1.1 × 105 and a
detection limit down to 8 × 10−9 M for melamine are achieved in the GO/Ag/SiO2 /Au/Si
SERS substrate. The experiment results reveal that our proposed MIM substrates exhibit
a highly sensitive and reproducible SERS activity. They also feature a simple, low-cost,
and large-area fabrication process. These advantageous features make our proposed MIM
SERS substrates promising for efficient and rapid detection in food safety control and
environmental monitoring.

2. Materials and Methods

2.1. Materials Preparation
Melamine (99.0% purity), GO aqueous solution (0.15 mg/mL, 2–5 layers dispersion
in water), and PS latex nanosphere solution in diameter of 400 nm (2.5 wt.% dispersion in
water) were purchased from Shanghai Aladdin Bio-Chem Technology Co., Ltd. (Shang-
hai, China). The silicon substrates were purchased from HWOTECH (Shenzhen, China).
Various molar concentrations of aqueous melamine solutions from 10−9 to 10−2 M were
prepared for SERS experiments.

2.2. SERS Substrates Preparation

Interventional studies involving animals or humans, and other studies that require
ethical approval, must list the authority that provided approval and the corresponding
ethical approval code. To prepare the templated masks, a cleaned Si substrate was treated
for 15 min with a UV-O3 cleaner (BZS250GF-TC, HWOTECH, Shenzhen, China). A 100 nm
Au layer and a 100 nm SiO2 layer were subsequently deposited on another cleaned Si
substrate. The templated mask was then prepared with an improved self-assembly method
that was described in detail in our previous report [50]. When the SiO2 /Au/Si substrate
was ready, the templated mask was finally transferred onto the SiO2 /Au/Si substrate for
the silver metasurface fabrication before the water was fully evaporated. Upon transferring
the templated mask onto the SiO2 /Au/Si substrate, the PS nanospheres were etched by O2
plasma via ICP (GSE200Plus, Northern Microelectronics, Gateshead, England) technique.
A flow of 50 sccm O2 was used with ICP power 100 W and bias power 20 W to etch the
nanospheres for 17, 19, 21, and 23 s, respectively, at a pressure of 8 mTorr. After etching, a
3 nm Cr layer was deposited onto the etched templated mask as an adhesion layer, and a
100 nm Ag layer was deposited subsequently by an electron-beam evaporator (EBE, TF500,
British HHV, Crawley, England). During the deposition process, a vacuum of 5 × 10−6 Torr
was maintained within the evaporator chamber. The evaporation rates were controlled
to be ~0.1 Å/s for Cr and ~0.8 Å/s for Ag. After deposition, the Ag-coated templated
masks were immersed in deionized water, and the PS nanospheres were removed using
ultrasonic cleaning. The removing process was 1 min under an ultrasonic power of 80 W.
To further enhance the sensitivity, a GO solution (0.15 mg/mL, Shanghai Aladdin Bio-
Chem Technology Co., Ltd., Shanghai, China) was diluted 10 times, and then a 40 µL
GO suspension was spin coated on the Ag metasurface at 2000 rpm for 2 min. Finally, a
GO/Ag/SiO2 /Au/Si substrate was ready for SERS testing.

2.3. Characterization and Measurement

A field emission scanning electron microscopy (FESEM, Merlin, Zeiss, Jena, Germany)
was used to examine the surface morphologies of the Ag metasurface. A UV-Vis-NIR
microspectrophotometer (CRAIC Technologies Inc., Altadena, California, United States)
was used to investigate the optical properties of the fabricated MIM substrate. For the
Raman spectra measurement, we used a 100× objective lens with a numerical aperture
of 0.8 to focus the 532 nm laser beam onto the samples and collected the Raman signal
with the spectrometer in a confocal Raman system (Alpha300, WITec, Ulm, Germany). The
power of the excitation laser was 160 µW/µm2 , and the acquisition time was 10 s for each
spectrum. For the Raman mapping, we used a 100× objective lens to focus the excitation
 each spectrum. For the Raman mapping, we used a 100× objective lens to focus th
tion laser onto the GO/Ag/SiO2/Au/Si substrate with the melamine concentration
Nanomaterials 2022, 12, 1202 4 of 13
M. The power of the laser beam was 160 µ W/µ m2, and the integrating time was
each point.
laser onto the GO/Ag/SiO2 /Au/Si substrate with the melamine concentration of 10−5 M.
3. Results
The power of the laser beam was 160 µW/µm2 , and the integrating time was 0.1 s for
each point.
Figure 1 shows the schematic for trace melamine measurement us
GO/Ag/SiO
3. Results 2/Au/Si SERS substrate. The MIM structure consists of a 100 nm Au la

nm Figure
SiO2 layer,
1 showsand
the 100 nm Ag
schematic metasurface
for trace layer, respectively,
melamine measurement using the from the bottom
GO/Ag/SiO 2/ to
The coated
Au/Si GO layer
SERS substrate. Thehas
MIMa structure
thickness of ~2ofnm.
consists a 100The inset
nm Au in 100
layer, Figure
nm SiO1 illustrates
2 layer, the
and 100 nm Ag metasurface layer, respectively, from the bottom to the
ular structure of melamine, whose Raman signals mainly come from two vibrationtop. The coated GO
layer has a thickness of ~2 nm. The inset in Figure 1 illustrates the molecular structure of
[47]. One mode is that the three C atoms in the central ring are stretched out-of-
melamine, whose Raman signals mainly come from two vibration modes [47]. One mode
form
is that a scissor
the three Coscillation,
atoms in thewhich
centraldrives
ring arethe three amino
stretched groups
out-of-plane to move
to form together;
a scissor
other onewhich
oscillation, is that thethe
drives three
threeN atoms
amino of the
groups central
to move ringand
together; oscillate
the otherout-of-plane
one is that inste
the three N atoms of the central ring oscillate out-of-plane instead of C
atoms, with which there is no oscillation for the three amino groups. Corresponatoms, with which
there is no oscillation for the three amino groups. Correspondingly, under the 532 nm laser
under the 532 nm laser excitation, two major peaks on the SERS spectrum can be
excitation, two major peaks on the SERS spectrum can be clearly observed, which will be
observed,
discussed which will be discussed later.
later.

NH2
532 nm Laser NH2
N

N N
Raman signal
NH2

Melamine
GO
Ag
SiO2
Au
Si

Figure1.1.Schematic
Figure Schematic illustration
illustration of melamine
of trace trace melamine measurement
measurement using the GO/Ag/SiO
using the GO/Ag/SiO 2 /Au/Si 2/Au

substrate.
SERS TheThe
substrate. gray
grayspheres
spheresrepresent themelamine
represent the melamine molecules.
molecules. The top
The right right top illustrates
illustrates the the
lar structure
molecular of melamine.
structure of melamine.

In the MIM structure, the Au layer serves as a reflection mirror. To calculate the
In thewe
absorbance, MIM structure,
can directly use Athe
= 1Au
− Rlayer serves
since there as light
is no a reflection mirror.the
passing through ToAucalculate
sorbance,
layer. In the we can directly
beginning, we firstuse A = 1-Rthe
optimized since theregap
insulator is no light passing
to achieve relativelythrough
strong the A
In the beginning,
absorption. Figure 2awe
showsfirsttheoptimized the insulator
schematic fabrication gap for
processes to achieve relatively strong
the Ag metasurfaces
without ICP etching. With the fixed Ag metasurface, we measured the
tion. Figure 2a shows the schematic fabrication processes for the Ag metasurfaces reflection spectra
with different insulator (i.e., SiO2 ) gaps, as shown in Figure 2b. It can be seen from Figure 2b
ICP etching. With the fixed Ag metasurface, we measured the reflection spectra w
that as the SiO2 gap increases, the overall reflectance of the MIM structure decreases,
ferent insulator
indicating increased(i.e., SiO2) gaps,
absorption. as shown
Given the excitationinlaser
Figure 2b. It can
wavelength benm,
of 532 seen
we from
have Figure
as the aSiO
chosen gap increases,
1002 nm-thick SiO2 layertheasoverall reflectance
the insulator gap. of the MIM structure decreases, in
increased absorption. Given the excitation laser wavelength of 532 nm, we have c
100 nm-thick SiO2 layer as the insulator gap.
x FOR PEER REVIEW 5 of 13
Nanomaterials 2022, 12, 1202 5 of 13

Self-assembled
(a) template mask (b) 80
60 nm
70 nm
80 nm
60 90 nm

Reflectance (%)
100 nm

40
Metal
deposition
Nanosphere
removal
20

0
400 600 800 1000
Wavelength (nm)

Figure 2. (a) Schematic fabrication

Figure processes
2. (a) Schematic for the
fabrication Ag metasurfaces
processes withoutwithout
for the Ag metasurfaces ICP etching. (b) Meas-
ICP etching. (b) Mea-
sured reflection spectra with different
ured reflection spectra with different insulator gaps. insulator gaps.

In our design, the purpose is to achieve strong absorption of the excitation laser as
In our design,well
theaspurpose is to achieve
the enhancement of Raman strong absorption
signals. Therefore, the of the excitation laser
Ag metasurfaces have toasbe
well as the enhancement
deliberatelyof Raman
designed signals. Therefore,
and fabricated the Agresonances,
with plasmonic metasurfaces have the
well suiting to laser
be
deliberately designed and fabricated with plasmonic resonances, well suiting the laserto
wavelength and enhancing the Raman signals. Various strategies have been developed
modify the nanostructures based on the NSL technique [52–60]. However, the main strategy
wavelength and enhancing
of these worksthe mainly
Ramanfocuses
signals. Various strategies
on generating the hot spots,have and thebeen developed
plasmonic to
couplings
modify the nanostructures based on the
inside the metasurface haveNSL technique
not been sufficiently[52–60]. However,
investigated. The proposedthe main strat-
strategy in our
work is to slightly dwindle the nanosphere via ICP etching,
egy of these works mainly focuses on generating the hot spots, and the plasmonic cou- producing the desired nanogaps
between the nanotriangles to realize plasmon coupling and achieve strong absorption of
plings inside the metasurface have not been sufficiently investigated. The proposed strat-
excitation laser with the operating wavelength of 532 nm. The experimental results show
egy in our work is to
thatslightly
compared dwindle the nanosphere
to non-etched template masks, viatheICP etching,
achieved MIMproducing
structures from theetched
de-
sired nanogaps between the nanotriangles to realize plasmon coupling and achieve strong
template ones can provide much stronger optical absorption as well as deliberately tuned
absorption
absorption of excitation laserpeakwith matching the excitation
the operating laser wavelength
wavelength of 532[61–63].
nm. The experimental
Figure 3a shows the schematic fabrication processes for the Ag metasurfaces with ICP
results show that compared to non-etched template masks, the achieved MIM structures
etching. Figure 3b–g show the fabricated Ag metasurfaces without and with ICP etching,
from etched template ones can
respectively. Weprovide much
can see from stronger
Figure optical
3a that for absorption
the non-etched as well
templated mask, asevery
delib-
two
erately tuned absorption peak matching the excitation laser wavelength [61–63].
adjacent PS nanospheres will stick together, and all the nanospheres form a close-packed
array (see the SEM image in Figure 3a). As a result, when depositing the Ag film, the
Figure 3a shows the schematic fabrication processes for the Ag metasurfaces with
entrance area is small, forming a metasurface with isolated nanotriangles in Figure 3b.
ICP etching. FigureThe
3b–ggapshow
between thethefabricated Ag metasurfaces
tips of the isolated nanotriangles without
is too far to and
form with
strongICP etch-
plasmonic
ing, respectively. We can seeWhile
couplings. fromforFigure 3a that
the etched for the
templated non-etched
mask, we can reduce templated
the size of mask, every
nanospheres via
ICP etching. With precise control, a thin bond can be
two adjacent PS nanospheres will stick together, and all the nanospheres form a close-formed between every two adjacent
nanospheres, which is named as “neck”, as shown in the SEM image of Figure 3a. As the
packed array (see the SEM image in Figure 3a). As a result, when depositing the Ag film,
etching time increases, the size of the nanospheres further decreases, and the neck becomes
the entrance area islonger
small,and forming a metasurface
thinner. Therefore, with isolated
we can adjust the size and nanotriangles
the gap distancein Figure
between the3b.
tips
The gap between the tips of the isolated nanotriangles is too far to form strong plasmonican
of the deposited Ag nanotriangles, as shown in Figure 3c–f. It is worth noting that for
couplings. While foretching
the time
etched of 25templated
s, nanotriangles in thewe
mask, metasurface
can reduce will connect
the size to form a holey array, as
of nanospheres
shown in Figure 3g.
via ICP etching. With precise control, a thin bond can be formed between every two adja-
cent nanospheres, which is named as “neck”, as shown in the SEM image of Figure 3a. As
the etching time increases, the size of the nanospheres further decreases, and the neck
becomes longer and thinner. Therefore, we can adjust the size and the gap distance be-
tween the tips of the deposited Ag nanotriangles, as shown in Figure 3c–f. It is worth
noting that for an etching time of 25 s, nanotriangles in the metasurface will connect to
form a holey array, as shown in Figure 3g.
2, x FOR PEER REVIEW 6 of 13
Nanomaterials 2022, 12, 1202 6 of 13

(a) Neck
Self-assembled ICP Metal Nanosphere
template mask Etching deposition removal

Non-etching 17 s etching 19 s etching

(b) (c) (d)

400 nm 400 nm 400 nm

21 s etching 23 s etching 25 s etching
(e) (f) (g)

400 nm 400 nm 400 nm

Figure 3. (a) Schematic fabrication

Figure processes
3. (a) Schematic forprocesses
fabrication the Ag for
metasurfaces with ICP
the Ag metasurfaces with etching. Typical
ICP etching. TypicalSEM
SEM
images of the templated masks are comparatively illustrated before and after
images of the templated masks are comparatively illustrated before and after ICP etching. (b–g) ICP etching. (b–g) SEM
images of the fabricated Ag metasurfaces without and with ICP etching, respectively.
SEM images of the fabricated Ag metasurfaces without and with ICP etching, respectively.
To find the optimal etching time for the desired Ag metasurfaces, we measured the
To find the optimal
gaps between etching time nanotriangles
the adjacent for the desired when Ag metasurfaces,
the templated masks wereweetched
measured the
at different
times from 17 to 23 s, as shown in Figure 4a. As the etching
gaps between the adjacent nanotriangles when the templated masks were etched at different time increases, the gap decreases
almost linearly from ~70 to 26 nm. Correspondingly, we have simulated and measured
times from 17 to 23thes, reflection
as shown in Figure 4a. As the etching time increases, the gap decreases
spectra of the MIM substrate with different gaps, as shown in Figure 4b,c.
almost linearly from ~70 atosimilar
Overall, 26 nm. trendCorrespondingly,
can be observed from webothhave simulated
simulation andand measured
experimental the
results.
reflection spectra of
Wethecan MIM
see thatsubstrate
the reflection with
dipdifferent
within thegaps, as shown
near-infrared inbecomes
range Figure 4b,c.
shallowerOverall,
with
the size increase in the nanotriangles, indicating a gradually
a similar trend can be observed from both simulation and experimental results. We can see weak resonance. In contrast,
the reflection dip within the visible range becomes deeper, indicating a gradually strong
that the reflectionresonance.
dip within the
At the near-infrared
etching time of 17 s, range
there is abecomes
resonance shallower
at a wavelengthwith the nm
of ~581 sizefrom
in-
crease in the nanotriangles, indicatingAsa the
isolated nanotriangles. gradually weak
etching time resonance.
increases, In contrast,
the resultant resonancetheblueshifts,
reflection as
clearly shown from the absorbance spectra in Figure
dip within the visible range becomes deeper, indicating a gradually strong resonance. At4b,c. At the etching time of the 23 s, a
deep dip with only ~7% reflectance at the wavelength of 555 nm can be clearly observed
the etching time of 17 s, there is a resonance at a wavelength of ~581 nm from isolated na-
from the reflection spectrum. The measured absorbance spectra for MIM structures with
notriangles. As theAg etching
metasurfaces time increases,
fabricated the resultant
by different etching times resonance
are shownblueshifts,
in Figure 4d.as clearly
Therefore,
shown from the absorbance
one can tunespectra
the MIMin Figure 4b,c.
structure’s At the
absorption to etching
match thetime of thelaser
excitation 23 s, a deep dip
wavelength as
much as possible. It is worth mentioning that for the
with only ~7% reflectance at the wavelength of 555 nm can be clearly observed from the fabricated MIM structures without
ICP etching, there is only an LSPR centering at ~820 nm from the isolated nanotriangles,
reflection spectrum. The
while formeasured absorbance
the Ag metasurface spectra
with ICP etching,fora new
MIM structures
resonance with Ag
dip appears in metasur-
the visible
faces fabricated byrange,
different
which etching
is mainly times aretoshown
attributed in FigureLSPR
nanogap-induced 4d. Therefore,
coupling. one can tune
the MIM structure’s absorption to match the excitation laser wavelength as much as possi-
ble. It is worth mentioning that for the fabricated MIM structures without ICP etching, there
is only an LSPR centering at ~820 nm from the isolated nanotriangles, while for the Ag
metasurface with ICP etching, a new resonance dip appears in the visible range, which is
mainly attributed to nanogap-induced LSPR coupling.
Nanomaterials 2022, 12, x FOR PEER REVIEW
Nanomaterials 2022, 12, 1202 7 of 13

90
(a) Median line
(b)
80 80
Average value
70 69.7

Reflectance (%)
60

Gap (nm)
60
54.8
50
40
17 s
40 19 s
37.5
21 s
30 20
23 s
25.5
20
17 s 19 s 21 s 23 s 500 600 700 800 900 1000
Etching time (s) Wavelength (nm)
30
(c) 17 s (d) 532 nm 17 s
19 s 19 s
21 s 21 s
90 23 s

Absorbance (%)
23 s
Reflectance (%)

20

10
80

0
500 600 700 800 900 1000 520 540 560 580 600 620 640 660 680
Wavelength (nm) Wavelength (nm)

Figure
Figure 4. 4.
(a) (a) Measured
Measured the gapthe gap distances
distances between thebetween the adjacentat nanotriangles
adjacent nanotriangles different etching at diffe
times. (b,c) Simulated and measured reflection spectra of the MIM substrate
times. (b,c) Simulated and measured reflection spectra of the MIM substrate with different gaps.
with differ
(d) Measured absorbance spectra of the MIM substrate with different gaps.
Measured absorbance spectra of the MIM substrate with different gaps.
To further confirm that the coupling came into being during the etching process,
RamanTo further
spectra confirmforthat
measurement the coupling
melamine was carriedcame
out tointo being
see the duringbetween
relationship the etching p
the degree of etching and the intensity of the Raman signal. Figure
man spectra measurement for melamine was carried out to see the relationship 5a shows the SERS signal b
of 10−5 M melamine on Ag/SiO2 /Au/Si structures with different etching times from 19 s
degree of etching and the intensity of the Raman signal. Figure 5a shows the SE
to 23 s, respectively. We can see that for the same melamine concentration, the SERS signal
10−5 M melamine
increases on Ag/SiO
with the increase 2/Au/Si
in etching structures
time. The Ag/SiO2with/Au/Sidifferent
structures etching
with thetimes
23 s from
respectively. We can see that for the same melamine concentration, the SERS sign
etching time demonstrate the highest Raman intensity. As a control experiment, the Raman
signal of melamine was also collected for the bare Ag film. From the experimental results,
with the increase in etching time. The Ag/SiO2/Au/Si structures with the 23 s e
we can confirm that the SERS performance is highly related to the structural geometry in
demonstrate
addition to the Agthe highest
itself. Raman
To further intensity.
clarify the changeAsofathe
control
couplingexperiment,
between the thedipsRaman
of si
amine was
triangles duringalso collected
etching, for the
the electric bare
field Ag film.ofFrom
distributions the experimental
the nanostructure results, we
with different
etching times are shown in Figure 5b. In our simulation, the excitation
that the SERS performance is highly related to the structural geometry in laser wavelength is additio
532 nm, and the gap distances are retrieved from Figure 4a. Figure 5b clears shows that
itself. To further clarify the change of the coupling between the dips of triangles d
with the etching time increasing from 19 s to 23 s, the plasmonic coupling between gaps
ing,
of the the electric
triangles field distributions
gets stronger. of the nanostructure
Both the experimental and simulated resultswithconfirm
different
that etchin
shown in Figure 5b. In our simulation, the excitation laser wavelength is 532 n
the plasmonic resonances and couplings of the metasurfaces play a key role in the SERS
signal enhancement.
gap distances are retrieved from Figure 4a. Figure 5b clears shows that with the e
increasing from 19 s to 23 s, the plasmonic coupling between gaps of the tri
stronger. Both the experimental and simulated results confirm that the plasm
nances and couplings of the metasurfaces play a key role in the SERS signal enh
FOR PEER REVIEW 8 of 13

Nanomaterials 2022, 12, 1202 8 of 13

(a) 10−2 M on Ag film

(b) 17s 19s 7.2
200
10−5 M on 19s-etching Ag/SiO2/Au/Si E/E0
Raman Intensity (a.u.)

10−5 M on 21s-etching Ag/SiO2/Au/Si 0

10−5 M on 23s-etching Ag/SiO2/Au/Si
−200

600 (a.u.)
21s 23s
200

(Unit: nm)
0

−200
0
600 900 1200 1500 −200 0 200 −200 0 200
Raman shift (cm−1) (Unit: nm)

Figure 5. (a) Measured SERS spectra for the 10−5 M melamine on the Ag/SiO2 /Au/Si substrates with
Figure 5. (a) Measured different
SERS spectra for the 10−5 M melamine on the Ag/SiO2/Au/Si substrates with
etching times of 19 s, 21 s, 23 s, and 10−2 M melamine on the Ag film substrate, respectively.
different etching times of(b)19 s, 21field
Electric s, 23distributions
s, and 10−2onM themelamine on the
nanostructured Ag with
surface filmdifferent
substrate, respectively.
etching times. Scale bar:
(b) Electric field distributions
100 nm. on the nanostructured surface with different etching times. Scale bar:
100 nm.
As known, GO can help adsorb much more targeted molecules and hence chemically
enhance the SERS activity [64–66]. Therefore, GO-coated plasmonic SERS substrates could
As known, GO can havehelp
muchadsorb much more
higher sensitivity targeted
and lower molecules
detection and
limits due to ahence chemically
combination of chemical
enhance the SERS activity [64–66].
enhancement of Therefore,
GO and the number GO-coated of hot plasmonic SERS nanostructures.
spots of plasmonic substrates could Various
methods have been proposed to form thin GO
have much higher sensitivity and lower detection limits due to a combination of chemicalfilms on structures, such as dip coating,
enhancement of GO spin andcoating,
the number and electric-field-assisted coating [67–70]. For electric-field-assisted coating,
of hot spots of plasmonic nanostructures. Various
the Ag oxidation could be accelerated with the exposure to plasma or chemical solution
methods have been proposed
with electricto form Both
charges. thinspin GOcoating
films and
on structures,
dip coating are such
facile,asefficient
dip coating,
approaches.
spin coating, and electric-field-assisted
However, spin coating is coating
a favorite [67–70]. For
to achieve theelectric-field-assisted
large-area, uniform GO films. coating,
the Ag oxidation could be We,accelerated
therefore, furtherwith investigated
the exposurethe SERS toperformance
plasma orofchemical
the GO-coated MIM sub-
solution
strate. In the Raman spectrum of melamine under excitation of 532 nm laser, there are two
with electric charges.major
Bothpeaksspinlocated
coating and dip coating are facile, efficient approaches.
at 671 cm−1 and 981 cm−1 , as shown in Figure 6a, which correspond
However, spin coating is aring
to the favorite
breathing to vibration
achieve and thethelarge-area,
CNC + NCN uniform
bendingGO films.respectively [71].
vibration,
− 1
We, therefore, further
For theinvestigated
peak at 671 cmthe SERS
, the performance
corresponding of the GO-coated
wavelength of the excitedMIM Raman sub-
signals
is 552 nm, which is very close to the coupled resonance wavelength of 555 nm from the
strate. In the Raman spectrum of melamine under excitation of 532 nm laser, there are two
Ag/SiO2 /Au/Si substrate with the etching time of 23 s. Therefore, we can enhance the
major peaks located at 671 cm
Raman signalsand
−1 981 the
via both cmPurcell
−1, as shown in Figure 6a, which correspond to
effect [51,72–74] and the increased absorption efficiency
the ring breathing vibration and the
of the excitation CNC
light. + NCN
Figure bending
6b shows the SEM vibration, respectively
image of the GO-coated MIM [71].substrate.
For
The inset in
the peak at 671 cm , the corresponding
−1 Figure 6b illustrates the measured Raman spectrum
wavelength of the excited Raman signals is 552 with two clearly observed
peaks at 1356 cm−1 and 1601 cm−1 , corresponding to the D and G bands of GO, respec-
nm, which is very close to the coupled resonance wavelength of 555 nm from the
tively [65]. Figure 6a shows the SERS signal of 10−6 M melamine on the GO/Ag/SiO2 /Au
Ag/SiO2/Au/Si substrate withthe
substrate, theAg/SiO
etching time of 23 s. Therefore, we can enhance
2 /Au substrate, and the Raman signal of 10
the Ra-
−2 M melamine on the
man signals via bothSithe Purcell
substrate, effect [51,72–74]
respectively. We can seeand that the
withincreased absorption
the GO-coating, the Raman efficiency
signals can be
of the excitation light.greatly
Figure enhanced.
6b shows The analytical
the SEMenhancement
image of the factor (AEF) [70] MIM
GO-coated is calculated using the
substrate.
equation below to further quantify the enhanced distribution of the SERS substrate:
The inset in Figure 6b illustrates the measured Raman spectrum with two clearly observed
peaks at 1356 cm−1 and 1601 cm−1, corresponding AEF = (Ito the
SERS × CDREF
and G bands
)/(IREF × CSERSof) GO, respectively (1)
[65]. Figure 6a shows the SERS signal of 10 M melamine on the GO/Ag/SiO2/Au sub-
−6
where ISERS and IREF represent the peak intensity of the Raman signal from the GO/Ag/SiO2 /
strate, the Ag/SiO2/Au substrate,
Au/Si substrateand
and the Raman
the Raman signal
signal of 10from
obtained
−2 M melamine on the Si sub-
the Si substrate, respectively. CSERS
strate, respectively. We
andcan
CREFsee
arethat with the GO-coating,
the concentrations the Raman
of melamine solutions signals
dropped can
on the beand
SERS greatly
reference
substrates, respectively. The peak at 671 cm −1 is chosen to calculate the AEF.
enhanced. The analytical enhancement factor (AEF) [70] is calculated using the equation
below to further quantify the enhanced distribution of the SERS substrate:
AEF = (ISERS × CREF)/(IREF × CSERS) (1)

where ISERS and IREF represent the peak intensity of the Raman signal from the
Nanomaterials 2022, 12, x FOR PEER REVIEW 9 of 1

Nanomaterials 2022, 12, 1202 9 of 13

(a) 10−6 M on GO/Ag/SiO2/Au/Si (b)

Raman Intensity
1000 (a.u.) 10−6 M on Ag/SiO2/Au/Si

Raman Intensity (a.u.)

10−2 M on Si

1300 1400 1500 1600

Raman shift (cm−1)

2 mm
600 900 1200 1500
Raman shift (cm−1)
(c) 8×10−9 M (d)
2000 (a.u.) 10 a.u.
1×10−8 M
1×10−7 M
Raman Intensity (a.u.)

1×10−6 M 10,000

Raman Intensity
1×10−5 M
600 750

1,000 R2 = 0.978

100

X2
X2
10
600 800 1000 1200 10−8 10−7 10−6 10−5
−1 Concentration (M)
Raman shift (cm )

Figure 6. (a) Measured SERS spectra with 10−6 M melamine on the GO/Ag/SiO2 /Au/Si substrate,
Figure 6. (a) Measured SERS spectra with 10−6 M melamine on the GO/Ag/SiO2/Au/Si substrate, th
the Ag/SiO2 /Au substrate, and 10−2 M melamine on the Si substrate, respectively. (b) SEM image
Ag/SiO 2/Au substrate, and 10−2 M melamine on the Si substrate, respectively. (b) SEM image of GO
of GO-coated Ag metasurface. The inset shows the Raman spectrum of GO on the metasurface.
coated Ag metasurface.
(c) Measured SERS spectra Theforinset shows
melamine the
with Raman
different spectrum of
concentrations fromGO1×on10the
−5 M metasurface.
to 8 × 10−9 M(c) Meas
uredonSERS spectra for melamine with different concentrations from 1 × 10
the GO/Ag/SiO2 /Au/Si substrate. The inset illustrates the Raman peak of trace melamine with a
−5 M to 8 × 10−9 M on th

GO/Ag/SiO 2/Au/Si substrate.

concentration of 8 × 10−9 M atThe 671 inset
cm−1 .illustrates the Raman
(d) Raman intensity peak of at
of melamine trace melamine
671 cm with a concen
−1 as a function
tration of 8 × 10
of different
−9 M at 671 cm
concentrations
−1 . (d)
in log Raman intensity of melamine at 671 cm as a function of differen
scale.
−1

concentrations in log scale.

Herein, the measured ISERS and CSERS are 2450 and 10−6 M for melamine on the SERS
substrate,
Herein,and thethe measuredISERS
measured IREF and
and C SERSare
CREF are227 10−2 10
and and
2450 M −6forMthe
forreference
melamine substrate.
on the SERS
5
Thus, the calculated AEF is 1.1 × 10 , indicating a high level of SERS performance of the GO-
substrate, and the measured IREF and CREF are 227 and 10 M for the reference substrate −2
coated MIM substrate. We explored the sensitivity of the optimal SERS substrates further.
Thus, the 6c
Figure calculated
shows the AEF measuredis 1.1SERS× 10spectra
5, indicating a high level of SERS performance of th
with different melamine concentrations. We
GO-coated
can achieve the limit of detection (LOD) as low sensitivity
MIM substrate. We explored the as 8 × 10−9 M of for
thethe
optimal
melamine. SERS substrates
Figure 6d fur
ther. Figure
shows the6c shows of
intensity thethemeasured SERSpeak
typical Raman spectra with
at 671 − 1
cmdifferent melamine
as a function concentrations
of melamine
Weconcentration
can achieve on thea log scale,
limit demonstrating
of detection (LOD) excellent
as low linear
as 8dependency
× 10−9 M for withthea melamine.
correlation Figur
coefficient 2 ) of 0.978.
6d shows the(Rintensity of the typical Raman peak at 671 cm−1 as a function of melamin
For SERS-based molecular detection, in addition to the high sensitivity, uniformity is
concentration on a log scale, demonstrating excellent linear dependency with a correlation
another important factor for practical applications. We carried out a 10 × 10 µm2 Raman
coefficient (R 2) of 0.978.
mapping for uniformity evaluation of the modified SERS substrate surface. Figure 7a,b
For SERS-based
shows the Raman mapping molecularresultdetection,
and the measuredin addition to theofhigh
SERS spectra sensitivity,
melamine uniformity i
at 16 random
another important
positions within the factor
Raman for practical
mapping area.applications.
It is obvious thatWethecarried out
obtained a 10 ×of10
profiles µ m 2 Raman
spectra
are almost
mapping for identical,
uniformity withevaluation
neither a significant shift of the SERS
of the modified characteristic
substrateRaman peaks Figure
surface. nor 7a,b
the obvious change of the peak intensity, indicating excellent
shows the Raman mapping result and the measured SERS spectra of melamine at 16 ran uniformity of the fabricated
SERS substrate.
dom positions within the Raman mapping area. It is obvious that the obtained profiles o
spectra are almost identical, with neither a significant shift of the characteristic Raman
peaks nor the obvious change of the peak intensity, indicating excellent uniformity of th
fabricated SERS substrate.
, x FOR PEER REVIEW 10 of 13
Nanomaterials 2022, 12, 1202 10 of 13

(a) (b)

Raman Intensity (a.u.)

Peak A 407 cts. Peak A

s
int
Po
2 mm 0 cts. 600 700 800 900 1000 1100
Raman shift (cm−1)

Figure 7. (a) Raman mapping

Figure 7. of
(a) 10
−5 M melamine with
Raman mapping of 10−5 Mthe collected
melamine withsignal of peak
the collected A atof671
signal cm
peak A at. (b)
−1
671 cm−1 .
Collected Raman signals of 10 M
−5
(b) Collected melamine
Raman signals ofat1016 M
− 5 randomly selected
melamine at positions
16 randomly selectedwithin the
positions Raman
within the Raman
mapping area. mapping area.

4. Conclusions
4. Conclusions
In summary, we have demonstrated a facile, cost-effective strategy to achieve highly
In summary, we have demonstrated
sensitive and reproduciblea SERS
facile, cost-effective
substrates using astrategy
modified toNSLachieve highly
technique. Through
precise control of nanosphere etching time, we can tune
sensitive and reproducible SERS substrates using a modified NSL technique. Through pre- the MIM structure’s absorption
to match the excitation laser wavelength as much as possible so as to enhance the light-
cise control of nanosphere etching time, we can tune the MIM structure’s absorption to
MIM structure interactions. More importantly, we can precisely control the gap of the Ag
match the excitationnanotriangles
laser wavelength asplasmonic
to strong much as couplings
possible to sofurther
as to enhance theRaman
enhance the light-MIM
signals. We
structure interactions. More
have importantly,
achieved we can precisely
a high-performance control
SERS activity for the gap ofwith
melamine the the
AgAEFnanotri-
of 1.1×105
− 9
angles to strong plasmonic
and LOD ofcouplings
10 M within to further
a large areaenhance
under the the532Raman
nm lasersignals.
excitation.WeOurhave
proposed
strategy could enable highly sensitive and reproducible
achieved a high-performance SERS activity for melamine with the AEF of 1.1×105 and LOD SERS substrates with a simple,
low-cost, and large-area fabrication process, hence providing a promising platform for
of 10−9 M within a large area under the 532 nm laser excitation. Our proposed strategy
SERS-based rapid trace detection in food safety control and environmental monitoring.
could
enable highly sensitive and reproducible SERS substrates with a simple, low-cost, and large-
area fabrication process,
Authorhence providing
Contributions: a promisingZ.W.,
Conceptualization, platform
J.L. andfor SERS-based
Y.J.L.; methodology,rapid trace
Z.W., J.W. and J.L.;
software, Z.W. and D.K.; validation, J.L., Z.M., J.W. and Y.J.L.; formal analysis, Z.W.; investigation,
detection in food safety control and environmental monitoring.
Z.W. and J.L.; resources, Z.W., Z.M. and D.K.; data curation, Z.W.; discussion and advising, S.J., D.L.,
J.L. and Y.J.L.; writing—original draft preparation, Z.W.; writing—review and editing, all authors;
Author Contributions: Conceptualization,
visualization, Z.W.,
J.L. and Y.J.L.; J.L., andY.J.L.;
supervision, Y.J.L.; methodology,
project Z.W.,
administration, J.W.,
Y.J.L.; and acquisition,
funding J.L.;
software, Z.W. and D.K.;
Y.J.L.validation, J.L., read
All authors have Z.M.,andJ.W., and
agreed to Y.J.L.; formalversion
the published analysis,
of theZ.W.; investigation,
manuscript.
Z.W. and J.L.; resources, Z.W.,This
Funding: Z.M.,
workand D.K.; data
was supported curation,
in part Z.W.; Natural
by the National discussion and
Science advising,
Foundation S.J., (Grant
of China
D.L., J.L. and Y.J.L.; writing—original draft
No. 62075093), Natural preparation,
Science FoundationZ.W.; writing—review
of Guangdong and editing,all
Province (Grant au-
No. 2019A1515110864),
thors; visualization, J.L. and Y.J.L.; supervision, Y.J.L.; project administration, Y.J.L.; funding acqui- and
Guangdong Innovative and Entrepreneurial Research Team Program (Grant No. 2017ZT07C071),
Shenzhen
sition, Y.J.L. All authors Science
have read andagreed
and Technology Innovation
to the published Commission
version (Grant
of theNo. GJHZ20180928155207206).
manuscript.
Institutional Review Board Statement: Not applicable.
Funding: This work was supported in part by the National Natural Science Foundation of China
Informed
(Grant No. 62075093), Consent
Natural Statement:
Science Not applicable.
Foundation of Guangdong Province (Grant No.
2019A1515110864), Guangdong
Data Availability Statement: The data presented inResearch
Innovative and Entrepreneurial Team
this study are Program
available (Grant
on request from the
No. 2017ZT07C071), and Shenzhen
corresponding Science and Technology Innovation Commission (Grant No.
author.
GJHZ20180928155207206).
Acknowledgments: The authors acknowledge the assistance of SUSTech Core Research Facilities.

Institutional Review Conflicts

Board Statement: Notauthors
of Interest: The applicable.
declare no conflict of interest.

Informed Consent Statement: Not applicable.

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