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Fabrication of dense two-dimensional assemblies

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2014, 13, 82
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over vast areas comprising gold(core)–silver(shell)
nanoparticles and their surface-enhanced Raman
scattering properties†

Kosuke Sugawa,*a Yoshimasa Tanoue,a Takuji Ube,b Sayaka Yanagida,b

Takahiro Yamamuro,a Yasuyuki Kusaka,c Hirobumi Ushijimac and
Tsuyoshi Akiyama*d

Fabrication of dense two-dimensional assemblies consisting of gold(core)–silver(shell) nanoparticles and

Received 15th August 2013,
Accepted 25th October 2013
DOI: 10.1039/c3pp50281c
www.rsc.org/pps
the resulting peculiar surface-enhanced Raman scattering (SERS) activity are reported. The assemblies
were prepared via assembly at air–toluene interfaces by drop-casting toluene solutions containing the
nanoparticles protected with octadecylamine molecules onto glass plates. This simple process, which
does not require special apparatus or significant fabrication time, leads to uniform assemblies over vast
areas (∼34 cm2). In the SERS measurements, the high spatial reproducibility of the SERS signals from
p-aminothiophenol adsorbed on the assemblies over vast areas demonstrates that this method is useful
for the quantitative investigation of SERS mechanisms. Under 532 nm laser excitation, the difference in
the enhancement factors of the SERS signals at the a1 mode between assemblies consisting of gold,
silver, and core–shell nanoparticles can be explained by the degree of overlap of the excitation wave-
length with their plasmon coupling modes. In contrast, under 785 nm excitation, even though the
plasmon band of the core–shell nanoparticle assemblies does not significantly overlap with the excitation
wavelength as compared with that of gold nanoparticle assemblies, the enhancement factor from the
core–shell nanoparticle assemblies was stronger than those from the gold nanoparticle assemblies.
Therefore, we have demonstrated that the gold(core)–silver(shell) nanoparticle assemblies are excellent
SERS active materials, which have strong electromagnetic mechanism (EM) as well as chemical mecha-
nism (CM) effects due to the silver shells.

Introduction molecules immobilized on metal electrodes, in the 1970s,1

Since the first discovery of surface-enhanced Raman scattering
(SERS), which dramatically enhances the Raman signals from
a
College of Science and Technology, Nihon University, 1-8-14 Kanda Surugadai,
Chiyoda-ku, Tokyo 101-8308, Japan. E-mail: sugawa.kosuke@nihon-u.ac.jp
b
Department of Material Science and Technology, Tokyo University of Science,
6-3-1 Niijuku, Katsushika-ku, Tokyo 125-8585, Japan
c
Flexible Electronics Research Center, National Institute of Advanced Industrial
Science and Technology (AIST), Higashi 1-1-1, Tsukuba, Ibaraki 305-8565, Japan
d
Department of Materials Science, School of Engineering, The University of Shiga
Prefecture, 2500 Hassaka-cho, Hikone-City, Shiga 522-8533, Japan.
E-mail: akiyama.t@mat.usp.ac.jp
† Electronic supplementary information (ESI) available: Extinction spectra of
colloidal aqueous solution, normalized extinction spectra of colloidal toluene
solutions of metal nanoparticles after phase transfer, cross-sectional SEM
images of nanoparticle assemblies, and AFM images of the assemblies. See DOI:
10.1039/c3pp50281c
SERS has shown promise for applications such as ultrasensi-
tive sensor tips2 and single molecule spectroscopy.3–6 Although
the precise mechanism has been a matter of considerable
debate, it is accepted that two mechanisms contribute: CM
and EM effects.5–7 The CM is based on charge transfer
induced by mixing of the metal orbitals with the orbitals of a
molecule, while the EM is based on the interaction of the local
electric field generated by localized surface plasmon resonance
(SPR) on metal nanoparticles and nanostructures with the
transition moment of the adsorbed molecules. Because both
mechanisms usually coexist in the SERS spectra, uniform
metal nanostructures that have reproducible SERS spectral pat-
terns are needed for the quantitative investigation of these
mechanisms. In addition, in order to develop useful SERS-
active metal nanostructures, the reproducibility of the SERS
signals (i.e., site-by-site variations in the signal intensity)
along with high sensitivity become important.8–15 Therefore,

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methods for fabricating metal nanostructures with macro-
scopic and microscopic morphological uniformity are required
for both fundamental and applied science.
Some studies have focused on dense two-dimensional (2D)
assemblies comprising plasmonic metal nanoparticles to
fulfill the above demands.8–12 It has been suggested that dense
assemblies can provide the required large electric fields,
known as the “hot spots,”16–18 in the interstitial region due to
plasmon coupling between adjacent nanoparticles.10,11,19,20
Also, it is expected that elaborate 2D assemblies improve repro-
ducibility because of their morphological uniformity. Mean-
while, fabrication of 2D nanoparticle assemblies has been
achieved by various bottom-up approaches such as liquid–
liquid interface-mediated assembly,20,21 capillarity-assisted
assembly,8 the Langmuir–Blodgett method,22,23 the seed-
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growth method,24 utilization of electrostatic interactions,25
and so on; however, the development of simpler methods that
require less time and do not need special apparatus is desired.
Previously, we demonstrated that the evaporation of toluene
droplets containing gold and silver nanoparticles protected
with alkylamine molecules forms high-quality 2D nanoparticle
assemblies on glass plates via assembly at the air–toluene
interface; these assemblies showed appreciable SERS activity.26
Although the formation mechanism has not been fully eluci-
dated, both the evaporation kinetics and the amount of excess
protective agents have been proposed to be key factors.27 So
far, gold and silver nanoparticles have been mainly used for
the fabrication of 2D assemblies. In order to increase the SERS
activity of the assemblies, we believe that it is necessary to
improve the intrinsic optical functions of the metal nanoparti-
cles that comprise the assemblies.
In this study, we fabricated 2D assemblies comprising gold-
(core)–silver(shell) nanoparticles (Au/AgNPs) and evaluated
their SERS activity, as compared with those of assemblies of
gold and silver nanoparticles. Although it is known that gold
nanoparticles show a lower enhancement factor than silver
nanoparticles, they are easier to synthesize with a high degree
Fig. 1 Preparation of metal nanoparticle assemblies.
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of size homogeneity. Therefore, the gold(core)–silver(shell)
nanoparticles synthesized by depositing silver on as-syn-
thesized gold nanoparticles are expected to have Ag-like
optical properties with higher homogeneity than silver nano-
particles.28,29 Furthermore, although it has not yet been fully
elucidated, it has been reported that the electronic interactions
between gold-cores and silver-shells have the potential to
provide novel optical properties that further enhance the SERS
activity.30–32 It is expected that uniform 2D assemblies of Au/
AgNPs assist in the quantitative investigation of these effects.
Experimental
Reagents and chemicals
Milli-Q-grade water was used for all aqueous solutions. Hydro-
gen tetrachloroaurate(III) tetrahydrate (HAuCl4·4H2O; Nacalai
Tesque), silver nitrate (AgNO3; Wako Pure Chemicals), octa-
decylamine (ODA; Tokyo Chemical Industry), sodium tetrahy-
droborate (NaBH4; Wako), trisodium citrate dihydrate (Kanto
Chemical), disodium citrate sesquihydrate (Tokyo Chemical
Industry), ascorbic acid (Wako Pure Chemicals), sodium
hydroxide (NaOH, Kanto Chemical), and p-aminothiophenol
(PATP; Tokyo Chemical Industry) were used as received
without further purification. Deionized water (resistivity: 18.2
MΩ cm) was obtained from a Millipore water purification
system.
Preparation of gold, silver, and gold(core)–silver(shell)
nanoparticle assemblies
The preparation of assemblies consisting of gold nanoparticles
(AuNPs), silver nanoparticles (AgNPs), and Au/AgNPs is
described in Fig. 1. Firstly, colloidal aqueous solutions of
AuNPs,33 AgNPs,34 and Au/AgNPs35 were synthesized using
modified versions of previously reported procedures. In brief,
an aqueous solution of HAuCl4·4H2O (0.01 wt%, 100 mL) was
refluxed for 30 min. Next, an aqueous solution of disodium
Photochem. Photobiol. Sci., 2014, 13, 82–91 | 83

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citrate (1 wt%, 12 mL) was injected into the solution, and the
mixture was refluxed for 60 min to produce an aqueous solu-
tion of citrate-capped AuNPs. For the synthesis of citrate-
capped AgNPs, an aqueous solution of AgNO3 (1 mM, 100 mL)
was added to an equivalent volume of aqueous solution con-
taining NaBH4 (0.2 mM) and trisodium citrate (5 mM) under
cooling in an ice bath. To synthesize Au/AgNPs, the as-pre-
pared gold colloidal aqueous solution (18 mL) and ascorbic
acid (0.1 M, 2.4 mL) were placed in a 50 mL vial and stirred
vigorously. Next, an aqueous solution of AgNO3 (1 mM, 6 mL)
was added dropwise to the solution at 15 s intervals. After the
synthesis, the pH of the solution was adjusted to 5 using an
aqueous solution of NaOH (0.05 M).
Next, colloidal toluene solutions of the metal nanoparticles
were prepared by phase-transfer of the as-synthesized nano-
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particles from the aqueous to toluene phase using ODA as a
phase-transfer catalyst via a modified version of a previously
reported procedure.36 Toluene (1.5 mL) containing 2.5 × 10−4
M ODA was added to an aqueous solution containing nano-
particles (AuNPs and AgNPs: 9 mL; Au/AgNPs: 13.2 mL), result-
ing in two immiscible layers. Initially, the lower aqueous phase
was colored and the upper organic phase was colorless. After
5 min of vigorous stirring, transfer of the nanoparticles from
the aqueous phase to the toluene phase was observed as move-
ment of color across the interface.
To prepare the substrate, a glass plate was sonicated with
acetone for 20 min followed by washing with toluene to
remove unnecessary dust and pollution. A certain amount of
each colloidal solution was drop-cast onto the surface of a
glass plate and then left to dry in air at room temperature
resulting in the formation of nanoparticle assembly films
physically-adsorbed on the glass surfaces. Finally, the obtained
assemblies were rinsed in pure methanol.
Sample preparation for the evaluation of the SERS activity
The obtained substrates containing the metal nanoparticle
assemblies were immersed in a methanol solution of PATP
(1 mM) for 12 h followed by rinsing with pure methanol to
ensure the desorption of non-specifically bonded molecules.
The well-known high chemical affinity of thiol groups to
metals leads to the formation of a monolayer of PATP mole-
cules on assemblies consisting of metal nanoparticles;37,38 this
occurs as PATP displaces ODA on the metal surface because
the metal–S bond is stronger than the metal–NH2 bond.
Measurements
UV-Vis spectral measurements were performed using a JASCO
V-630 spectrophotometer. Field-emission scanning electron
microscopy (FE-SEM) images were taken on a Hitachi
S-4500 microscope with an acceleration voltage of 15 kV. Trans-
mission electron microscopy (TEM) images were recorded on a
Hitachi HF-2000 with an acceleration voltage of 200 kV.
Elemental mapping images, a high-angle annular dark-field
scanning/transmission electron microscopy (HAADF-STEM)
image, and energy-dispersive X-ray spectra were taken on a
STEM (HD-2300C, Hitachi Ltd). Raman scattering spectra of
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PATP-modified nanostructure substrates and the reference
methanol solution of PATP (10 M) were obtained using a
micro-Raman spectrometer (NRS-5100, JASCO). The excitation
sources were 532 and 785 nm CW laser. The laser was focused
onto the sample by using an objective lens (×100). Raman
signals were obtained by one-shot measurements with 1 s of
sampling time on each measurement point.
Results and discussion
Optical and morphological characterization of the colloidal
solution of the metal nanoparticles
Normalized extinction spectra for aqueous solutions of the
synthesized metal nanoparticles are shown in Fig. 2 (the non-
normalized spectra are also shown in Fig. S1†). AuNPs and
AgNPs showed peaks at 525 and 393 nm, respectively, which
can be assigned to the plasmon mode of a single isolated
NP.25,39,40 In contrast, Au/AgNPs showed two types of collective
oscillation modes at 390 and 490 nm. The former extinction
peak can be ascribed to plasmon excitation of the silver shell
on the AuNP core, while the latter broad shoulder band can be
ascribed to plasmon excitation of the AuNP core. The appear-
ance of these two modes and the blue shift of the plasmon
band of the AuNP core to 490 nm from the AuNP value of
525 nm suggests that gold(core)–silver(shell) nanoparticles
were successfully formed.29,35
In the normalized transmission extinction spectra (Fig. S2†)
after phase transfer of the nanoparticles into toluene, the
plasmon peaks derived from AuNPs and AgNPs were red-
shifted by 8 and 20 nm, respectively. Similarly, the plasmon
peak from the Ag shells of Au/AgNPs with the broadened
shoulder around 500 nm in the toluene phase was red-shifted
by 27 nm. These wavelength changes are attributed mainly to
the increase in refractive index of the solvent (from 1.33 for
water to 1.47 for toluene), as previously reported.36,41 These
results suggest that the metal nanoparticles were successfully
transferred into the toluene phase from the aqueous phase
without any aggregation.
Fig. 2 Normalized extinction spectra of colloidal aqueous solutions of
(a) AuNPs, (b) AgNPs, and (c) Au/AgNPs.
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Fig. 3 TEM images of (a) AuNPs, (b) AgNPs, and (c) Au/AgNPs dispersed
in toluene solution.

The average diameters (D) of AuNPs, AgNPs, and Au/AgNPs

after phase transfer were estimated to be 10.4 ± 0.7, 9.6 ± 2.8,
and 13.9 ± 1.3 nm, respectively, from TEM images (Fig. 3).
Note that the diameters of AuNPs and AgNPs were almost the
same and the thickness of the Ag shells in Au/AgNPs was
calculated to be approximately 1.8 nm using the following
formula: [(D of Au/AgNPs) − (D of AuNPs)]/2. Au/AgNPs
showed prominent contrast with the core being darker than
the shells, as shown in the inset of Fig. 3(c); the lighter regions
are invariably a feature of silver. Furthermore, we have con-
firmed that the obtained Au/AgNPs formed gold(core)–silver-
(shell) structures utilizing the energy dispersive X-ray spectro-
scopy (EDS) mapping analysis, the HAADF-STEM image, and
the EDS spectra measurements as shown in Fig. 4. EDS
mapping analysis was conducted to investigate the relative
positions of silver and gold within Au/AgNPs (Fig. 4A). From
the mapping images of the Au M edge and the Ag L edge, it
was confirmed that silver exists over all of the surfaces of the Fig. 4 (A) (a) Bright field (BF)-STEM image and EDS elemental mapping
gold nanoparticles. In order to further investigate their morpho- images of Au/AgNPs; (b) Au M edge and (c) Ag L edge. (B) (a) BF-STEM
logical characterization, a HAADF image of the Au/AgNPs is image and (b) HAADF-STEM image of Au/AgNPs. (C) EDS spectra in the
shown in Fig. 4B. The outside shell region is darker, as com- regions of (a) the center and (b) the periphery of the Au/AgNP. (Inset)
Atomic composition ratio of the Au M edge and the Ag L edge.
pared with the core region, which indicates the presence of a
high-Z element at the cores and a low-Z element at the shells. In
this study, it is gold and silver, respectively. In addition, EDS
spectra were measured at the center and periphery regions of spectra of the assemblies after immobilization of PATP as a
the nanoparticle, as shown in Fig. 4C. As a result, it is shown probe molecule for the SERS measurements are shown in
that a majority of the gold exists at the center of the nanoparti- Fig. 5. Unlike those of the colloidal toluene solutions, the
cle. On the other hand, silver heavily exists at the periphery spectra of the assemblies of AuNPs and AgNPs showed broad
region. Thus, we confirmed that Au/AgNPs formed gold(core)– peaks at ∼71010,39 and ∼600 nm,25,40 respectively, which can
silver(shell) nanoparticles. be ascribed to the longitudinal plasmon mode of the coupling
of multiple nanoparticles. In addition, the AgNP assembly
Optical and morphological characterization of assemblies of showed a weak band at ∼380 nm, which is ascribed to isolated
metal nanoparticles AgNPs. In contrast, it was confirmed that the assembly consist-
Metal nanoparticle assemblies were fabricated via assembly at ing of Au/AgNPs showed an appreciable broad peak corres-
air–toluene interfaces by drop-casting colloidal toluene solu- ponding to the coupling mode at 680 nm, which is
tions onto glass surfaces.26,27 The transmission extinction intermediate between those of AuNPs and AgNPs.

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TEM images. These results suggest that each nanoparticle

formed two-dimensional assemblies. The coverage of the
assemblies consisting of AuNPs, AgNPs, and Au/AgNPs, as
calculated using Image J, was 69, 75, and 63%, respectively.
These results suggest that the longitudinal plasmon coupling
modes of the assemblies observed in the extinction spectra
(Fig. 5) are caused by dense packing of the nanoparticles. In
addition, a picture of the assemblies prepared by drop-casting
3 mL of the colloidal toluene solution of Au/AgNPs is shown in
Fig. 6(B). Although there is little color heterogeneity, nearly
uniform nanoparticle assemblies were formed. Note that the
simple procedure of drop-casting a colloidal toluene solution
onto glass surfaces followed by air-drying for ∼15 min provides
assemblies with areas of ∼34 cm2 without any special appar-
Fig. 5 Extinction spectra of assemblies of (a) AuNPs, (b) AgNPs, and (c)
atus. Therefore, this air–toluene-interface-mediated procedure
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Au/AgNPs fabricated via the air–toluene interface-mediated process.

Dashed lines indicate the excitation source wavelengths (532 nm and is easier, less time-consuming, and less expensive for the fabri-
785 nm) in Raman scattering measurements. cation of dense nanoparticle assemblies over vast areas than
commonly used techniques such as the Langmuir–Blodgett
method22,23 and utilization of a layer-by-layer method.42

SERS properties on the metal nanoparticle assemblies

To evaluate the SERS activity of the metal nanoparticle
assemblies, Raman scattering spectra were measured using
PATP as a SERS probe molecule37,43 immobilized on the

Fig. 6 (A) SEM images of assemblies of (a) AuNPs, (b) AgNPs, and (c)
Au/AgNPs and (B) a picture of Au/AgNP assembly.

SEM images of the metal nanoparticle assemblies are

shown in Fig. 6(A). It was confirmed that all of the nanoparticles
formed 2D, high-density assemblies, although there are several
defects. In order to further verify this, the thicknesses of the
nanoparticle assemblies were estimated from their cross-sec-
tional SEM images and their atomic force microscope (AFM)
measurements, as shown in Fig. S3 and S4,† respectively. The
average thicknesses of the nanoparticle assemblies consisting
of AuNPs, AgNPs, and Au/AgNPs were calculated to be 12, 13,
and 13 nm, respectively, from the cross-sectional SEM images.
And the average thicknesses of the AuNP, AgNP, and Au/AgNP
assemblies were calculated to be 12, 9, and 10 nm, respectively, Fig. 7 SERS spectra of PATP immobilized on assemblies of (a) AuNPs,
from the AFM images. These thicknesses were nearly identical (b) AgNPs, and (c) Au/AgNPs measured with (A) 532 nm and (B) 785 nm
with the diameters of the nanoparticles calculated from their excitation.

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Fig. 8 Intensities of the SERS peak at ∼1070 cm−1 of PATP in 60 spots
on assemblies of (a) AuNPs, (b) AgNPs, and (c) Au/AgNPs measured at
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the 785 nm laser line.
assemblies.44–46 As shown in Fig. 7, a spectral SERS pattern
characteristic of PATP was observed from all of the assemblies.
Typically, the prominent peaks at 1428, 1384, and 1137 cm−1
are assigned to the non-totally symmetric b2 modes of the
PATP molecule, and the peaks at 1183 and ∼1070 cm−1 are
assigned to the totally symmetric a1 modes.
To obtain a reliable assessment of their utility as SERS sub-
strates, the development of uniform substrates with high
spatial reproducibility (i.e., site-by-site variations in signal
intensity) is strongly desirable. Thus, in order to evaluate the
reproducibility of the SERS intensity, the intensities of the
SERS signals at ∼1070 cm−1 under 785 nm excitation were
measured at 60 different points on assemblies of AuNPs,
AgNPs, and Au/AgNPs. Note that the measurements were not
performed in non-uniform regions observed macroscopically
such as reddish regions as seen in Fig. 6(B). As shown in
Fig. 8, the SERS signals obtained from all the assemblies
showed high reproducibility: the relative standard deviation
(RSD) of the SERS signals was ≤10% (AuNPs: 8%; AgNPs: 9%;
Au/AgNPs: 10%). These RSD values are low enough, as com-
pared with the SERS-active substrates reported
previously.8–10,12,14,15,47 Therefore, it has been demonstrated
that the air–toluene-interface-mediated assembly method is
useful for the quantitative investigation of SERS mechanisms
as well as the fabrication of practical SERS substrates.
To quantitatively evaluate the enhancement effect of the
obtained SERS signals, enhancement factor (EF) values were
estimated based on the following equation, which was
reported previously:48–50
EF ¼ ðI SERS =N surf Þ=ðI bulk =N bulk Þ
where ISERS is the intensity of a vibrational mode on the SERS
spectrum of PATP and Ibulk is the intensity of the same
vibrational mode on the normal Raman spectrum of the
methanol solution of PATP (10 M). In this study, the peak at
∼1070 cm−1 (a1 mode) was selected to calculate the EF
values because the a1 vibrational mode is largely associated
with the EM mechanism (SPR effect).43,44,51,52 In eqn (1), Nsurf
and Nbulk are the numbers of PATP molecules effectively
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excited by laser irradiation on the nanoparticle assemblies and
solutions, respectively. Nsurf can be calculated via the following
equation:
N surf ¼ RA=σ ð2Þ
where R is the roughness factor of the nanoparticle assemblies,
A is the area of the focal spot of the laser, and σ is the surface
area occupied by immobilized PATP molecules. The coverage
of PATP molecules immobilized on the nanoparticle surfaces
was assumed to be full monolayer coverage. The PATP molecule
occupies ∼0.20 nm2 on full coverage of gold and silver assum-
ing that PATP molecules are immobilized perpendicularly on
the metal surfaces via a metal–sulfur atom bonding. Therefore,
σ can be assumed to be ∼0.20 nm2 per molecule.50,53 In this
study, AuNPs, AgNPs, and Au/AgNPs formed almost 2D assem-
blies. Therefore, we have assumed that the obtained films
formed 2D assemblies with no multilayer. The roughness factor
(R) is calculated using the following equation:
R ¼ ðΓAsphere Þ=Apro ð3Þ
where Γ, Asphere, and Apro denote the surface coverage of the
nanoparticle, surface areas of the nanoparticles, and projected
surface areas of the nanoparticles on the glass surfaces (the
shape of the nanoparticles was assumed to be an ideal spheri-
cal form), respectively. The coverage (Γ) of the obtained nano-
particle assemblies consisting of AuNPs, AgNPs and Au/AgNPs
was calculated to be 69, 75, and 63%, respectively. Thus, Nsurf
can be expressed by the following equation:
N surf ¼ ðΓAAsphere Þ=ðσApro Þ ð4Þ
Next, Nbulk is calculated using the following equation: 48,49
N bulk ¼ AhcN A ð5Þ
where h is the height of the volume of the PATP solution con-
tributing to the Raman signal, c is the concentration of the
PATP solution (10 M), and NA is the Avogadro constant.
We determined h for the measurement configuration by
transferring a silicon (100) wafer across the focal plane of the
objective lens (×100) and recording the intensity of the Raman
signal at 520 cm−1 from the silicon. We calculated h = 6 μm
(532 nm) and 19 μm (785 nm) by integrating the intensity of
the Raman signal over distance and dividing the calculated
value by the largest observed Raman signal. Based on the
above results, we determined EF values at 532 nm and 785 nm
laser excitation.
ð1Þ Furthermore, the charge-transfer (CT) mechanism is not
only the main contributor to the enhancement of the Raman
signals, but is also important for the resolution of the enhance-
ment mechanisms. In this study, we calculated the degree of
CT ( pCT) in order to investigate the CT contribution to the
SERS signals. According to previous reports, the pCT(k) of the
k-band (the index “k” is used to identify individual molecular
lines in the SERS spectra) can be presented as follows:54–57
pCT ðkÞ ¼ ½I k ðCTÞ  I k ðSPRÞ=½I k ðCTÞ þ I 0 ðSPRÞ ð6Þ
Photochem. Photobiol. Sci., 2014, 13, 82–91 | 87

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where Ik(CT) is the intensity of a band in which the CT reso-
nance contributes to the SERS signal and I0(SPR) is the inten-
sity of the totally symmetric band, which is enhanced only by
the EM mechanism of SPR. If the k-band is totally symmetric,
the contribution of the EM mechanism dominates the SERS
signal and I k(SPR) is equivalent to I0(SPR). On the other hand,
if the k-band is non-totally symmetric mode, the contribution
of the CT resonance dominates the SERS intensity. In this
case, because Ik(SPR) is often quite small, it can be approxi-
mated as zero. The pCT value is zero when there is no CT con-
tribution to the SERS signal, and approaches one when the CT
contributions dominate the spectrum. For example, if pCT is 1/
2, the surface plasmon and CT contributions are approxi-
mately equal. In this study, the strong SERS peak of the a1
mode at ∼1070 cm−1 was selected as I0(SPR) and those of the
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b2 mode at 1138 cm−1 with 532 nm excitation and at
1132 cm−1 with 785 nm excitation were selected as Ik(CT).
SERS spectra of PATP immobilized on the metal nanoparti-
cles measured with 532 nm excitation are shown in Fig. 7(A).
Only weak SERS signals were detected from the AuNP assem-
blies. In contrast, the signal at ∼1070 cm−1 (a1 mode) from the
assemblies consisting of AgNPs was 12 times stronger than
that from AuNPs (the detailed EF values are described in
Table 1). As shown by the extinction spectra (Fig. 5), the exci-
tation laser wavelength overlaps well with the plasmon band of
the longitudinal plasmon coupling from AgNP assemblies, but
does not overlap well with that of the AuNP assemblies. There-
fore, the appearance of stronger SERS signals from AgNP
assemblies is likely caused by the generation of strong local
electric fields (i.e., hot spots) at the interstitial region between
nanoparticles.10,17–19 Note that although the excitation wave-
length does not overlap well with the plasmon coupling band
of the Au/AgNP assemblies, the SERS signals at ∼1070 cm−1
were six times stronger than that of the AuNP assemblies, as
shown in Table 1. This result implies that the enhancement by
the Au/AgNP assemblies is caused by the strong SPR effect of
the silver shells that coat the AuNP cores.
Table 1 Enhancement factors of the SERS peak at ∼1070 cm−1 of PATP
on assemblies of AuNPs, AgNPs, and Au/AgNPs measured at the 532 and
785 nm laser lines
EF at 532 nm EF at 785 nm
AuNPs (2.7 ± 0.4) × 103 (2.5 ± 0.2) × 105
AgNPs (3.2 ± 0.2) × 104 (1.5 ± 0.1) × 105
Au/AgNPs (1.6 ± 0.3) × 104 (4.0 ± 0.4) × 105
Table 2 Degree of charge transfer ( pCT) of PATP on assemblies of
AuNPs, AgNPs, and Au/AgNPs measured at the 532 and 785 nm laser
lines
pCT at 532 nm pCT at 785 nm
AuNPs 0.33 ± 0.06 0.06 ± 0.006
AgNPs 0.66 ± 0.002 0.19 ± 0.03
Au/AgNPs 0.63 ± 0.009 0.14 ± 0.02
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As shown in Table 2, pCT calculated from the SERS spectra
of the AgNP assemblies was larger than that of the AuNP
assemblies; this difference is most likely because of the differ-
ences in the work functions of gold (5.0 eV) and silver
(4.3 eV).57 Also, the pCT of the Au/AgNP assemblies was almost
the same as that of the AgNP assemblies. These results suggest
that the SERS properties of the Au/AgNP assemblies are very
similar to those of the AgNP assemblies.
In the SERS spectra (Fig. 7(B)) measured with 785 nm exci-
tation, the signal at ∼1070 cm−1 obtained on the AuNP assem-
blies was stronger than that of the AgNP assemblies (the
detailed EF values are shown in Table 1). As shown in Fig. 5,
the excitation wavelength matches the plasmon band of the
AuNP assemblies better than that of the AgNP assemblies,
which leads to the difference in the EF values. Interestingly,
despite having less overlap between the plasmon band of Au/
AgNP assemblies and the excitation wavelength than the AuNP
assemblies, the signal from the Au/AgNP assemblies was stron-
ger than that from the AuNP and AgNP assemblies. Also, the
pCT value of the Au/AgNPs was intermediate between those of
AuNPs and AgNPs, as shown in Table 2.
It has been reported that gold(core)–silver(shell) nanoparti-
cles produce peculiar SERS activity because of appreciable CT
effects31 and have characteristic Fermi levels that are different
from gold and silver nanoparticles.32 However, our results
showed that the CT effect of the Au/AgNP assemblies is
almost the same under 532 nm excitation and is less under
785 nm excitation than that of the AgNPs. Accordingly, it is unli-
kely that the Fermi level of the Au/AgNPs is significantly
different from that of the AgNPs. Although the mechanism is
unclear at this stage, more importantly, it should be noted
that the Au/AgNP assemblies showed an appreciable EM effect
due to the strong local electric fields as well as a strong CM
effect due to the silver shells at 785 nm excitation. Therefore, we
have demonstrated that the Au/AgNP assemblies are excellent
SERS active materials, which have strong EM and CM effects.
Conclusion
We successfully fabricated dense 2D assemblies consisting of
Au/AgNPs over vast areas. The assemblies were produced
simply by drop-casting colloidal toluene solutions onto glass
surfaces. The SERS signals from PATP immobilized on assem-
blies consisting of AuNPs, AgNPs, and Au/AgNPs showed excel-
lent spatial reproducibility. The SERS activity of the Au/AgNP
assemblies was investigated in detail using 532 and 785 nm
lasers. The Au/AgNP assemblies showed higher SERS activity
than those of AuNP and AgNP assemblies (strong CM and EM
effects). Thus, we demonstrated that bimetallic nanoparticles
can be used for highly SERS-active substrates. The nanoparti-
cles in this study were too small to generate strong local
electric fields; therefore optimization of the bimetallic nano-
particle size can provide much more highly SERS-active sub-
strates with large EF values. Research on this is currently
underway.
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Photochemical & Photobiological Sciences
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