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Silver Nano-Dendrite-Plated Porous Silicon Substrates Formed by

Single-Step Electrochemical Synthesis for Surface-Enhanced Raman
Scattering
Daohan Ge,* Jinxiu Wei, Jie Ding, Jin Zhang, Chao Ma, Minchang Wang, Liqiang Zhang,*
and Shining Zhu

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ABSTRACT: Nanostructured layers composed of porous silicon

(PSi)-based silver (Ag) nanodendrites have been formed by a simple
single-step electrochemical anodic oxidation process on p-type silicon
substrate. A mixture of hydrofluoric acid (HF), silver nitrate
(AgNO3), and dimethylformamide (DMF) solution was used as the
electrolyte to form PSi and nanoscaled Ag structures simultaneously
in a few minutes without any post treatment. We studied the
influence of the anodization parameters on the morphologies of Ag-
PSi structures. The results show that the metallic Ag attached to PSi
surfaces completed the conversion from nanoparticles to nano-
dendrites with the increase of AgNO3 concentrations, along with the
increase of the number, size, and the area they covered of dendrites.
The sensitivity and stability of the Ag dendrites-coated PSi substrate were evaluated using Rhodamine 6G (R6G) as probe molecule.
This Ag-PSi substrate exhibits high surface-enhanced Raman scattering (SERS) response, good reproducibility, and outstanding
long-time stability with a detection limit of R6G as low as 10−11 M. This single-step systhesis technique provides a simple method for
preparation of SERS-active substrates with high sensitivity and stability, representing a promising SERS platform for chemical and
biomolecule detections.
KEYWORDS: porous silicon, Silver dendrite, SERS, single-step synthesis, electrochemical etching

■ INTRODUCTION
Porous silicon (PSi) is a sponge-like structure with nanosilica
clusters as the skeleton, first discovered in 1956 when Uhlir
electropolished silicon in hydrofluoric acid (HF) acid.1 Due to
its visible light luminescence of Psi and strong light emission in
the near-infrared and visible light regions,2,3 Psi has attracted
great attention. Moreover, PSi has a large number of favorable
properties, such as the extremely large surface area, good size-
exclusion effect, and tunable optical properties,4−7 which make it
an attractive and suitable material for biosensing applications.8,9
A large number of studies have reported successful
applications of PSi as biosensors with various types of sensing
principles10−17 in the past decade. Among them, sensing via
surface enhanced-Raman scattering (SERS) has key advantages
over other optical platforms and has been widely used in PSi-
based biosensors, benefiting from the huge internal surface area
and its large open porous structures. Usually, noble metal
nanostructures with unique plasmonic properties are incorpo-
rated into PSi substrates to achieve strong enhancement of
Raman scattering for detection of biomolecules with high
sensitivity.18−24 Thus, development of high SERS-active
substrates based on metallic nanostructures-decorated PSi
remains an active area of research. A number of different
techniques have been developed to synthesize plasmonic silver
(Ag) or gold (Au) nanostructures (nanoparticles,25−27 nano-
plates,28,29 and nanodendrites30−32) on PSi, such as thermal
decomposition,33−35 wet chemical deposition,36 physical vapor
deposition,37 and immersion plating.31,35,38−40 However, every
method is met with issues: immersion plating takes a long time
and has low efficiency, whereas the other techniques require the
use of tedious preparations, sophisticated equipmental environ-
ment, and conditions. More importantly, in all of these
techniques, a PSi substrate needs to be fabricated before metal
nanostructures are deposited on it. This makes the whole
process long and complicated.
Received: February 2, 2020
Accepted: February 12, 2020
Published: February 12, 2020

© 2020 American Chemical Society https://dx.doi.org/10.1021/acsanm.0c00296

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Scheme 1. Ag-Nanodendrites Coated PSi Substrates Formed by Single-Step Electrochemical Synthesis in the HF-Containing
Electrolyte Modified with AgNO3 and DMF
Here, we demonstrate the ability to produce a SERS-active Ag
nanodendrites-coated PSi substrate by a simple single-step
anodization method with no need of any post treatment and
rigorous equipment. In our experiments, p-type silicon wafers
were electrochemically etched in the HF-containing electrolyte
modified with silver nitrate (AgNO3) and dimethylformamide
(DMF) solutions to obtain the PSi layers and Ag nanostructures
simultaneously, as shown in Scheme 1. The morphologies of Ag
nanostructures on PSi, transformed from nanoparticles to
dendrites, were systematically investigated by modifying the
etching parameters. The SERS activity and sensitivity of the Ag-
PSi substrates were evaluated using Rhodamine 6G (R6G) dye
as the target molecule at different concentrations, and the crucial
parameters for the formation of the SERS-active substrates were
thoroughly discussed.
■ EXPERIMENTAL SECTION
P-type silicon wafers (10−20 Ω·cm, 500 μm-thick, CZ-grown, (1 0 0)-
oriented and single-sided polished) were used in our experiments. The
wafers were cut into squares of 16 × 16 mm2, followed by a standard
RCA cleaning step.6 The electrolytes used for one-step electrochemical
anodization were based on a mixture of 48 wt % aqueous HF, DMF, and
AgNO3 solution. A set of AgNO3 solutions with different concen-
trations were prepared by dissolving 0.01, 0.02, 0.03, 0.04, and 0.05 g of
AgNO3 crystals in 8 mL of deionized water in our experiments, and the
corresponding samples formed were marked as Samples 1, 2, 3, 4, and 5,
respectively. All samples were prepared in the dark on an electro-
chemical etching platform in a standard decontamination chamber at
room temperature (18 ± 1 °C), with the etching area of 1 cm2. A
platinum plate was used as the counter electrode. Galvanostatic current
density of 40 mAcm−2 was applied from a power source (Agilent
E3645A) for 5 min to synthesis Ag-coated PSi structures.
R6G was dissolved in laboratory deionized water to prepare R6G
solution with various concentrations (10−6−10−12 M). Then, the Ag-
coated PSi substrates were immersed in R6G solution for 2 h and dried
with nitrogen to study the SERS functionality of Ag-PSi. The volume of
the rhodamine solution used in this experiment is 5 mL.
The morphologies and sizes of the Ag-coated PSi structures
produced were observed by a field-emission scanning electron
microscopy (JSM-7800F), and the composition of the samples were
analyzed by XRD-6100 X-ray diffractometer (XRD; Shimadzu Corp.,
Kyoto, Japan). The SERS spectra of Ag-PSi substrates were recorded at
room temperature with a diode laser of 532 nm as excitation source in
the wavelength range of 200−4000 cm−1 using a DXR laser Raman
spectrometer (Thermo Fisher Scientific Inc., Waltham, MA). The laser
power is 2 mW and the integration time is 1 s.
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■ RESULTS AND DISCUSSION
Ag nanostructures on PSi with high SERS properties were
prepared by electrochemical anodization in one step (Scheme
1). The principle involved was the same as that of the previously
mentioned immersion method,33 which used a Ag+ solution of
AgNO3 to generate a redox reaction with the hydride generated
during etching of the silicon wafer,23 with the redox reaction in
this process expressed by the equation
4Ag + + Si + 6HF → 4Ag + H 2SiF6 + 4H+ (1)
Compared with the immersion method, this method was
superior in that PSi and Ag nanoparticles or nanodendrites were
simultaneously formed. The formation of PSi provided a large
number of nucleation sites for Ag ion crystallization.41 It was
observed that, after the Si was hydrogenated by HF, the Ag+ in
solution immediately reacted with the hydride. The morphology
of Ag ions crystallization depended on the electrolyte AgNO3
concentration and the time allowed for anodic corrosion
oxidation.28 In this experiment, the time of anodic corrosion
oxidation was constant, and it was found that Ag crystals grew
with increased electrolyte AgNO3 concentration, as shown in
Scheme 1.
First, a set of electrochemical synthesis experiments were
performed at different AgNO3 concentrations to form Ag-PSi
samples. SEM micrographs of PSi and Ag-PSi nanoparticle
substrates prepared under different concentrations of electrolyte
are shown in Figure 1. The micrographs in the right column
show the high magnification views of the regions shown in the
left column. At a ratio of HF:DMF = 16 mL: 9 mL, the
macroporous silicon produced by passing a 40 mA cm−2 current
density for 5 min in the electrolyte had pore diameters of more
than 1 μm (Figure 1a and b). Samples shown in Figure 1c and d
were synthesized with the same anodized current density and
time as that in Figure 1a, except that the electrolyte was HF:
DMF: AgNO3 solution = 16 mL: 9 mL: 8 mL, with a AgNO3
solution including 0.01 g of AgNO3 (Sample 1), resulting in
0.007 M AgNO3. Here, Ag was only formed by reduction
reactions to adhere into PSi and the Ag nanoparticle diameters
are at ∼100 nm (Figure 1d).
SEM micrographs of Figure 2 show Ag nanodendrites-coated
PSi structures obtained under different AgNO3 electrolyte
concentrations. The micrographs in the right column show the
high magnification views of the regions shown in the left column.
The anodiazation time of all samples was 5 min with the current
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Figure 1. SEM micrographs of PSi and PSi-Ag nanoparticle substrates
prepared under different electrolytes: (a and b) HF: DMF = 16:9; (c
and d) HF: DMF: AgNO3 solution = 16:9:8.
Figure 2. SEM micrographs of PSi-Ag nanodendrite substrates
prepared under electrolyte HF: DMF: AgNO3 solution = 16:9:8 with
different AgNO3 concentrations: (a and b) 0.014 M (Sample 2), (c and
d) 0.022 M (Sample 3), (e and f) 0.30 M (Sample 4), (g and h) 0.37 M
(Sample 5).
density at 40 mA cm−2. A 0.014 M AgNO3 solution with 0.02 g
of AgNO3 crystals (Sample 2) produced Ag particles gathered
together to form a large number of regular dendrites (Figure 2a
and b). There were some nanoparticles on the dendrite trunks
that had failed to react to form dendrites. The products from a
AgNO3 concentration of 0.022 M (Sample 3) (Figure 2c and d)
showed the dendrite trunks to be much longer than the
backbone produced from 0.014 M AgNO3. There were still
some Ag nanoparticles on the trunk and the PSi surface between
the dendrite gaps. These remaining nanoparticles were too
sparse to cluster into dendrites. With 0.30 M AgNO3 (Sample
4), the Ag dendrite clusters increased tightly and some Ag
nanoparticles accumulated in the Ag branches (Figure 2e and f).
The bifurcation points of the crystals further enlarged the
number and branching of the dendrites. At 0.37 M AgNO3
(Sample 5), the time was sufficient to produce a large amount of
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coarse dendrites and, under the action of current, the
preferential corrosion area of the PSi was completely covered
by Ag dendrites (Figure 2g and h). There was a tendency for
dendrites to gradually cover the entire PSi surface with the
increase of AgNO3 concentration. At this time, the Ag dendrites
were much coarser than those formed with lower AgNO3
concentrations and the Ag nanoparticles were not densely
present.
XRD patterns were obtained from five Ag-PSi composite
samples shown in Figure 1 and 2, with the scanning speed of 5
degrees/min (Figure 3). Using the phase retrieval function of
the Jade software, it was determined that the peak at 69.16°in
Figure 3a was the silicon (Si) peak and the peak of metallic Ag
which was at 38.1°was shown in Figure 3b. The intensity and
sharpness of the peaks reflected the state of the corresponding
substance. It was clearly seen from the change in the intensity of
each peak in Figure 3b that, as the concentration of the AgNO3
solution increased, the amount of metallic Ag adhering to the
sample increased significantly and the magnitude of the increase
also increased. However, the Si peak in Figure 3a did not have a
particularly obvious increase tendency as did Ag. It was noted
that, when the quantity of AgNO3 dissolved in 8 mL deionized
water was 0.03 g (Sample 3), the Si peak was surprisingly small,
only ∼650 as shown in Figure 3c, whereas the Si peak in the
other four samples were all more than 60,000.
Figure 4a−e are the XRD spectrum containing the silver peak
of five samples. The proportion of metallic Ag in the substrate is
shown in Figure 4f, calculated via the phase retrieval function of
the Jade software. The morphology of the samples shown in the
insets of Figure 4a−e and the proportion of metallic Ag in Figure
4f demonstrate that a large amount of Ag nanoparticles and
dendrites accumulated simultaneously on PSi substrates when
0.03g silver nitrate crystal was added in the electrolyte (Sample
3). The simultaneous existence of Ag nanoparticles and
dendrites greatly reduced the amount of silicon that could be
detected by XRD (Figure 3c). Moreover, the proportion of Ag in
this sample was the highest in this set of samples and far
exceeded that of other samples (Figure 4f).
A base SERS performance spectrum of the Ag dendrites-
coated PSi structures, measured with R6G as a probe molecule,
is shown in Figure 5, with the R6G concentration at 10−6 M. For
clarity, the spectra are offset along the y-axis. The spectral
characteristic peaks of R6G in Figure 5a were at 614, 764, and
1360 cm−1. These peak values changed with the change of the
AgNO3 concentrations, and the enhancement of the SERS effect
mainly due to enhancement of the local electromagnetic field
near the metal surface as local surface plasmon excitation. It can
be seen here that the signals of Sample 1 and 2 were very weak
and there was almost no SERS performance. When the AgNO3
amount was increased to 0.03 and 0.04g (Sample 3 and 4), the
Raman signal became very strong and the characteristic peaks of
R6G were clearly enhanced, which indicated that these two
samples were excellent SERS substrates. Here, the intensity of
the characteristic peak at 614 cm−1 exceeded 20,000, as the
dendrites and nanoparticles provided more hot spots than other
samples and made the surface rougher, resulting in the best
SERS performance (Figure 5a). However, when the AgNO3
amount was increased to 0.05 g (Sample 5), the signal intensity
of SERS sharply decreased, the reduced Ag accumulated to a
certain extent and gradually filled the gaps between the
dendrites, making the Ag dendrite layer tighter. The surface
appeared smoother, resulting in a reduction in the number of hot
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Figure 3. X-ray diffraction pattern of five Ag-PSi composite samples formed with different AgNO3 concentration: (a) enlarged view of Si peak, (b)
enlarged view of metallic Ag peak, (c) high magnification view of Si peak of Sample 3.

Figure 4. XRD spectrum containing Ag peak of five Ag-PSi composite samples formed with different AgNO3 concentrations: (a) 0.01, (b) 0.02, (c)
0.03, (d) 0.04, and (e) 0.05 g AgNO3 crystals dissolved in 8 mL of deionized water. (f) A graph of the mass fraction of metallic Ag relative to the Si
substrate.

spots on the sample surface, thus decreasing the SERS
performance.
To study the uniformity of the SERS substrates, we present
the Raman maps of four samples (Sample 1−4) in Figure 5b−e,
respectively, with the scanning area of 200× 200 μm2, step
length of 10 μm and excitation wavelength of 633 nm. As shown
in Figures 1 and 2, only the surface of Sample 1 is full of Ag
nanoparticles, and the other substrate surfaces are covered with
Ag nanodendrites. It can be seen from Figure 5b that the entire
area of Sample 1 appears dark red, except one point that appears
bright red, indicating that the SERS performance of the substrate
is stable and uniform throughout the whole region. While
AgNO3 crystals increased to 0.02 g, the entire area of Sample 2
appears relatively bright red with only a few points showing
bright red (Figure 5c). By further increasing the AgNO3
concentration (Sample 3), Figure 5d shows the high uniformity
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of enhancement with a high and uniform hot-spot density, owing
to the huge amount of silver nanoparticles and silver
nanodendrites covered on PSi substrate (Figure 2d). However,
the Raman map of Sample 4 shows a deep dark red color again. It
is due to the increased number of Ag dendrites, thicker branches
and reduced Ag nanoparticles compared to Sample 3.
Based on these experimental results, we can infer that when
the AgNO3 concentration was 0.022 M (Sample 3), the SERS
performance of the substrate was the best (Figure 5). Therefore,
this SERS-active substrate was used to further investigate the
detection limit of R6G. As a widely used efficient bioindicator,
R6G is usually used as the target molecule to evaluate the actual
SERS activity and sensitivity of the substrate. A set of R6G
aqueous solutions ranging between 10−7 and 10−12 M was used,
and the effects of R6G concentration on SERS performance are
shown in Figure 6. The R6G aqueous solution is usually scarlet,
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Figure 5. Raman analysis of five samples shown in Figure 4 using R6G (10−6 M) as the probe: (a) Raman spectra of Sample 1−5, (b) Raman map of
Sample 1, (c) Raman map of Sample 2, (d) Raman map of Sample 3, (e) Raman map of Sample 4.

Figure 6. Raman spectra of SERS-active substrates (Sample 3) exposed to different concentrations of R6G: (a)10−7 M, (b)10−8 M, (c)10−9 M,
(d)10−10 M, (e)10−11 M, (f)10−12 M.

but the concentration of R6G aqueous solution used in our
experiments was 10−7 or below, resulting in pale yellow color
shown in the inset of Figure 6a. As the concentration further
decreased, the color became lighter and faded until undetectable
as we can see in the insets of Figure 6a−f, which meant that the
sensitive detection of R6G in aqueous solution was very
necessary.
The laser focus was adjusted so that the intensity of the silicon
peak at ∼520 cm−1 was always to be 10 000. The results showed
that, when the concentration of R6G was 10−7 M, the R6G
aqueous solution was yellow and there was a prominent R6G
Raman peak at 614 and 764 cm−1, with the intensity of the peak
6000 and less than 3000, respectively (Figure 6a). When the
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R6G concentration deduced to 10−8 M, the peak intensity at 614
was reduced to around 3500 (Figure 6b), but there was a slight
increase in the peak at 764 cm−1. The 10−9−10−11 M R6G
solutions were colorless and clear. The Raman spectra measured
from these substrates showed only a weak peak signal at 614
cm−1 (Figure 6c−e). When the R6G concentration was reduced
to 10−12 M, the Raman peak intensity of R6G was too weak to be
seen. Therefore, from Figure 6a−f, we can conclude that the
detection limit for R6G by the Ag dendrite-plated PSi substrates
was as low as 10−11 M, which was a breakthrough in the low
detection limit reported for Ag-PSi substrates.23,26,30,33,34
SERS spectra of 10−6 M R6G were further collected using
three sets of Ag-PSi substrates (Samples 2, 3, 5) to evaluate the
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Figure 7. (a) Reproducible SERS spectra of 10−6 M R6G obtain from three sets of Ag-PSi substrates (Samples 2, 3, 5). Each set of samples were
fabricated under identical conditions. ((b) SERS spectra of 10−6 M R6G obtained from Ag-PSi substrate (Sample 3) after fabrication (blue line) and 6
months later (red line) . For clarity, the spectra are offset along the y-axis.
reproducibility of the SERS substrates (Figure 7a). In each set,
two different samples were fabricated under identical conditions.
For clarity, the spectra are offset along the y-axis. As can be seen
in Figure 7a, the SERS spectra taken at different substrates in
each set were found to overlap well to each other, and the
intensities of Raman peaks at 614 and 764 cm−1 are quite
resemble, indicating the good reproducibility of the SERS
substrate preparation.
Finally, a set of comparative experiments were carried out to
evaluate the stability of the SERS-active substrates. The SERS
spectra were obtained from the same Ag dendrites-coated-PSi
substrates (Sample 3) after fabrication and 6 months later with
10−6 M R6G, as shown in Figure 7b. The intensity of the R6G
SERS signals is still as high as 15 000 after the substrate WAS
stored in the air for 6 months, showing outstanding long-term
stability. These results demonstrate that the Ag dendrites-
coated-PSi substrates has great potential in practical SERS-based
sensing applications.
■ CONCLUSION
In summary, single-step electrochemical etching of p-typed
silicon substrates in HF-DMF-AgNO3 electrolyte was utilized to
produce heteronanostructured layers composed of Ag dendrite
and PSi. The morphology, composition, and SERS properties of
the samples were analyzed by means of SEM, XRD, and Raman
scattering. It was found that, with the increase of AgNO3
concentration, the Ag nanostructures changed from nano-
particles to nanodendrites. Besides, as the number of hot spots
on PSi surface increased, the Ag-PSi substrates showed superior
SERS performance. A detection limit as low as 10−11 M has been
achieved. Moreover, the uniformity, reproducibility, and
stability of the substrate were also tested, and a Ag-PSi sample
stored in air for 6 months still showed high sensitivity,
demonstrating its good long-time stability. Therefore, this
method provides a simple, efficient, low-cost, and high-yield way
for preparing SERS-active substrates with high sensitivity and
outstanding stability for implementing contaminant detection
and biodetection.
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■ AUTHOR INFORMATION
Corresponding Authors
Daohan Ge − Institute of Intelligent Flexible Mechatronics, Jiangsu
University, Zhenjiang 212013, PR China; National Laboratory
of Solid State Microstructures, School of Physics, Nanjing
University, Nanjing 210093, PR China; orcid.org/0000-
0002-7224-7518; Email: gedaohan@mail.ujs.edu.cn
Liqiang Zhang − Institute of Intelligent Flexible Mechatronics,
Jiangsu University, Zhenjiang 212013, PR China; Jiangsu
Collaborative Innovation Centre of Photovoltaic Science and
Engineering, Changzhou University, Changzhou 213164, PR
China; orcid.org/0000-0002-5722-8298;
Email: zhanglq4158@ujs.edu.cn
Authors
Jinxiu Wei − Institute of Intelligent Flexible Mechatronics, Jiangsu
University, Zhenjiang 212013, PR China
Jie Ding − Institute of Intelligent Flexible Mechatronics, Jiangsu
University, Zhenjiang 212013, PR China
Jin Zhang − National Key Laboratory of Microsystem Technology,
Shanghai Institute of Microsystem and Information Technology,
Chinese Academy of Sciences, Shanghai 200050, PR China
Chao Ma − Institute of Intelligent Flexible Mechatronics, Jiangsu
University, Zhenjiang 212013, PR China
Minchang Wang − Institute of Intelligent Flexible Mechatronics,
Jiangsu University, Zhenjiang 212013, PR China
Shining Zhu − National Laboratory of Solid State
Microstructures, School of Physics, Nanjing University, Nanjing
210093, PR China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsanm.0c00296
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
We are grateful for the financial support from Natural Science
Foundation of Jiangsu Province (Grant BK20180098) and
Open Research Fund of National Laboratory of Solid State
Microstructures (Grant M32045). L.Z. is grateful for the
financial support from the open fund for Jiangsu Key Laboratory
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ACS Appl. Nano Mater. 2020, 3, 3011−3018
ACS Applied Nano Materials
o f A d v a n c e d M a n u f a c t u r i n g T e c h n o l o g y (G r a n t
HGAMTL01702).
■
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