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Scripta Materialia 58 (2008) 862–865

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Preparation of Au–Ag, Ag–Au core–shell bimetallic

nanoparticles for surface-enhanced Raman scattering
Yong Yang,a,b,* Jianlin Shi,a Go Kawamurab and Masayuki Nogamib
a
School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China
b
Department of Materials Science and Engineering, Nagoya Institute of Technology, Showa, Nagoya 466-8555, Japan
Received 17 October 2007; revised 5 December 2007; accepted 2 January 2008
Available online 16 January 2008

Surface-enhanced Raman scattering (SERS) integrates high levels of sensitivity with spectroscopic precision and has tremendous
potential for chemical and biomolecular sensing. The key to the wider application of Raman spectroscopy using roughened metallic
surfaces is the development of highly enhancing substrates for analytical purposes. Here, gold-coated silver and silver-coated gold
composite nanoparticles are prepared by a seeding growth method to study their SERS-active properties.
Ó 2008 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: Self-organization; Nanostructure; Optical absorbance; Surface Raman spectroscopy

Surface-enhanced Raman scattering (SERS) inte-
grates high levels of sensitivity with spectroscopic preci-
sion and thus has tremendous potential for chemical and
biomolecular sensing [1–4]. Localized surface plasmon
resonance (SPR) excitation in silver and gold nanoparti-
cles produces strong extinction and scattering spectra
that in recent years have been used for important SERS
enhancement. The SERS signal, normally a very weak
effect, has been found to be enhanced by the order of
1014 in the presence of nanometer-sized Ag ‘‘hot parti-
cles”, which allows the possibility of studying Raman
scattering even at the single-molecule level [5,6]. The
key to the wider application of Raman spectroscopy
using roughened metallic surfaces is to develop repro-
ducible and highly enhancing practical substrates for
analytical purposes, i.e., for better detection sensitivity
of trace contaminants and pollutants. Bimetallic com-
posite nanoparticles, composed of two different metal
elements, are of greater interest than monometallic
nanoparticles from both scientific and technological
viewpoints. The structure of bimetallic nanoparticles is
defined by the distribution modes of the two elements
and can be oriented in random alloy, alloy with an inter-
metallic compound, cluster-in-cluster and core–shell
structures. In particular, bimetallic nanoparticles with
* Corresponding author. Address: School of Materials Science and
Engineering, East China University of Science and Technology,
Shanghai, 200237, China; e-mail: yangdare@hotmail.com
a core–shell structure often exhibit improved physical
and chemical properties [7–11] over their single-compo-
nent counterparts due to the electric field enhancement,
which is responsible for SERS enhancement.
Controlled methods for preparing nano-structured
metal substrates may provide more useful correlations
between surface structure and signal enhancement [11].
A variety of metallic structures have been fabricated
and investigated as SERS substrates, including Ag
prisms [12], silver nanowires [13], spherical gold nano-
shells [8] and gold nanoparticle arrays [14]. Here, we pre-
pare bimetallic Au-core/Ag-shell and Ag-core/Au-shell
composite nanoparticles and self-assemble those com-
posite nanoparticles on glass substrates for sensitive
SERS substrates. The surface plasmon bands can be
tuned over an extended wavelength range by controlling
the molar ratio of Ag/Au, and this provides the oppor-
tunity to study the function of local field enhancement
with the SERS enhancement.
Briefly, gold colloids were prepared by the Na(cit)3
thermal reduction method [15]. Gold colloid was pre-
pared by adding 1 ml of 1 wt.% HAuCl4 aqueous solu-
tion and 2 ml of 38.8 mM sodium citrate aqueous
solution to 90 ml of boiling water. After the solution
had turned purple-red within 30 s, it was cooled quickly
in an ice bath. Silver colloids were prepared by the same
method: 0.018 g AgNO3 and 2 ml of 38.8 mM sodium
citrate aqueous solution were added to 100 ml of water
at 70 °C. After the solution had turned light yellow, it
was cooled quickly in the ice bath.

1359-6462/$ - see front matter Ó 2008 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.scriptamat.2008.01.017
 Y. Yang et al. / Scripta Materialia 58 (2008) 862–865 863

Au-core/Ag-shell nanoparticles were prepared using

2 (a) Au seed
the following seed colloid technique. As-prepared Au
(c) (b) 0.4 mL
colloids (0.4, 1, 2, 5, 10, 20 and 40 ml) and 1 ml of (c) 1 mL
38.8 mM Na(cit)3 solution were added to 30 ml of water. (a) (d) 2 mL

Then 1.2 ml of 10 mM AgNO3 aqueous solution and
0.4 ml of 100 mM ascorbic acid aqueous solution were
added to the above solution while stirring. Ag-core/
Au-shell nanoparticles were prepared using the same
method. The related experimental conditions are listed
in Table 1. Finally, the Au, Ag, Au–Ag and Ag–Au films
were self-assembled on glass substrates as reported pre-
viously [16].
The interaction of small metal particles with an exter-
nal electromagnetic field induced by light results in
coherent oscillations of the conduction (free) electron
(mainly within the surface), called surface plasmon res-
onance (SPR). This surface plasmon resonance mainly
depends on the particle size and shape, and its surround-
ing environment. The evaluation of the surface plasmon
band for the core–shell bimetallic nanoparticles can be
described by considering the polarizability of a core–
shell particle with radius R as follows [17]:
ðes  em Þðec þ 2es Þ þ ð1  gÞðec  es Þð2es þ em Þ
a ¼ R3
ðes þ 2em Þðec þ 2es Þ þ ð1  gÞðec  es Þð2es  em Þ
g ¼ 1  R31 =R32
where em is the dielectric constant of the matrix, ec and es
are the dielectric functions of the core and shell materi-
als, respectively, and g is the volume fraction of the shell
layer. The radii of the total composite particle and its
core are R2 and R1, respectively.
Figure 1 shows ultraviolet (UV)–visible absorbance
spectra of Au and Ag-coated Au colloids. The gold col-
loids exhibit absorbance band at around 520 nm. When
the molar ratio (MR) of Ag/Au is around 1 (spectrum f),
two SPR bands, located at 390 and 500 nm, can be ob-
served, which indicates the partial coverage of gold by
silver nanoparticles or the formation of independent
particles [7]. With the continual decrease of the Au seed
volume, only a plasmon band appears between 400 and
460 nm. This can be exclusively attributed to plasmon
resonance of Ag particles. The appearance of only one
absorbance band corresponding to silver nanoparticles
indicates that homogeneously mixed colloidal particles
Table 1. The molar ratios and their SPR band positions of Au, Ag,
Au–Ag and Ag–Au colloids
Absorbance /a.u.
(e) 5 mL
(b) (f) 40 mL
(f)
(d)
(e)
0
300 400 500 600 700 800
Wavelength /nm
Figure 1. UV–vis absorbance spectra of (a) Au seed and (b–f) Au–Ag
composite nanoparticles prepared with different Au seed volumes: (b)
0.4 ml, (c) 1 ml, (d) 2 ml, (e) 5 ml and (f) 40 ml.
of the two metals are formed without significant forma-
tion of independent particles [7]. The plasmon band
gradually red-shifts as the seed concentration is de-
creased, suggesting the formation of composite particles
ð1Þ with larger diameter [7,18]. The changes of plasmon
band with seed volume are consistent with the calculated
ð2Þ tendency, according to Eq. (1), that the plasmon band
red-shifts with increasing thickness of the Ag shell.
From the UV–vis absorbance spectra, we can reason-
ably infer that the reduction of Ag salt alone occurs
on the preformed Au core surface rather than forming
more nucleation sites, and the core–shell structure of
Au–Ag composite nanoparticles is formed [18–20].
Thus, it is not surprising that the optical properties of
composite nanoparticles are dominated by the Ag shell,
and the plasmon band of the composite nanoparticles
red-shifts when the Ag shell gradually becomes thicker
as the seed concentration is decreased.
Figure 2 shows the absorbance spectra of Ag and Ag–
Au composite colloids. The Ag seed colloids exhibit one
SPR band around 410 nm. After the addition of
HAuCl4 solution, the colloid exhibits an Au-like SPR
band, which indicates that optical properties of compos-
0.5
(a) Ag seed
(b) 1 mL
0.4 (c) 4 mL
(d) 12 mL
Absorbance /a.u.

(e) 24 mL
Sample Au3+ Au seed Ag+ Ag seed Molar ratio
0.3
(mmol) (ml) (mmol) (ml) of Ag/Au
SPR (nm)
Au 0.27 520 0.2
(a) (b) (c) (d) (e)
Au–Ag1 0.4 0.012 111 454
Au–Ag2 1 0.012 44.4 428
Au–Ag3 2 0.012 22 415 0.1
Au–Ag4 5 0.012 8.9 410
Au–Ag5 40 0.012 1.1 391, 500
300 400 500 600 700 800 900
Ag 424
Ag–Au1 0.27 1 0.037 524 Wavelength /nm
Ag–Au2 0.27 4 0.167 550
Figure 2. UV–vis absorbance spectra of (a) Ag seed and (b–e) Ag–Au
Ag–Au3 0.27 12 0.5 570
composite nanoparticles prepared with different Ag seed volumes: (b)
Ag–Au4 0.27 24 1 590
1 ml, (c) 4 ml, (d) 12 ml and (e) 24 ml.
864 Y. Yang et al. / Scripta Materialia 58 (2008) 862–865
ite nanoparticles are dominated by gold shell. With the
increase of Ag seed volume, their SPR bands red-shift.
From the UV–vis absorbance spectra, we can reason-
ably infer that the reduction of Au salt alone occurs
on the preformed Ag core surface rather than forming
more nucleation sites. If Au–Ag alloy nanoparticles or
individual Au and Ag mixed colloids were formed, the
SPR band would blue-shift with increasing Ag seed vol-
ume [21]. As a result, the core–shell structure of Au–Ag
composite nanoparticles is formed, which has also been
confirmed by comparing the experimental absorbance
spectra of Au–Ag core–shell nanoparticles with their
calculated spectra [10,20] according to the equation gi-
ven by Hao [10]. Thus, it is not surprising that the opti-
cal properties of composite nanoparticles are dominated
by the Au shell, and the plasmon band of the composite
nanoparticles red-shifts when the Au shell gradually be-
comes thinner as the seed concentration is increased.
One of the major goals of the present study is to pre-
pare SERS-active substrates that can be useful for inves-
tigating the molecules adsorbed on them. We prepared
four films for SERS substrates by immersing APTMS-
modified glass slides [16] into Au seeds, Ag seeds, Au–
Ag (MR: 44.4) and Ag–Au (MR: 0.037) solutions. The
packing structures and topographies of Au, Ag, Au–
Ag and Ag–Au films were investigated by dynamic
mode of atomic force microscopy (AFM). These parti-
cles are spherical and of good uniformity, as shown in
Figure 3. The average diameters of pure Au (Fig. 3a)
and Ag (Fig. 3b) nanoparticles are 15 and 20 nm, respec-
tively. The average diameter of Au–Ag composite nano-
particles (Fig. 3c) is 50 nm, which is larger than the
diameters of the pure Au and Ag nanoparticles, indicat-
ing that gold nanoparticles are coated by a silver shell.
Figure 3. AFM images of (a) pure Au, (b) pure Ag, (c) Au–Ag and (d)
Ag–Au monolayer.
1365
1538
1650
1575
+ R6G:
+ + +
1190
30000
+ (d)Au@Ag
Intensity /a.u.
(c)Ag
20000
(b)Ag@Au
10000 x10 (a)Au
1000 1200 1400 1600 1800 2000
Raman Shift /cm-1
Figure 4. SERS spectra of R6G adsorbed onto (a) Au monolayer, (b)
Ag–Au monolayer, (c) Ag monolayer and (d) Au–Ag monolayer.
The average diameter of Ag–Au composite nanoparti-
cles (Fig. 3d) is 45 nm, which is larger than those of pure
Au and Ag nanoparticles, also indicating that silver
nanoparticles are coated by gold shell [22].
SERS measurements were performed by a Jasco
NFS-220 M scanning near-field optical microspectrome-
ter operated in the far-field mode with a 532.0 nm laser.
The laser power at the sample position was about 2 mW
for Rhodamine 6G (R6G) on the SERS substrates. All
the spectra reported here were the results of a single
3 s accumulation. All samples for SERS measurement
were prepared by casting 10 ll of 0.1 mM R6G in etha-
nol onto metallic nanoparticles monolayers and allow-
ing the solvent to evaporate [23,24]. Figure 4 shows
far-field SERS spectra of R6G on the monolayers of
Au, Ag, Au–Ag and Ag–Au nanoparticles excited at
532.0 nm. The observed Raman bands at 1650, 1575,
1538, 1365 and 1190 cm1 can be attributed to m(C–C)
stretching vibrations of R6G molecules and agree well
with values in the literature [6]. The Au nanoparticle
monolayer deposited on glass shows a very weak Raman
spectrum (spectrum a), indicating that Au nanoparticles
are a SERS-inactive substrate. The Ag nanoparticles
monolayer exhibits a strong Raman signal, indicating
that silver monometallic nanoparticles are a good
SERS-active substrate (spectrum c). We note that the
Au–Ag nanoparticles monolayer exhibits a much stron-
ger and better resolved spectrum than that from the
monometallic Au and Ag nanoparticle monolayers,
indicating that the Au–Ag film is more powerful than
pure Ag and Au film as a SERS-active substrate. The
enhancement can be attributed to the electronic ligand
effect in bimetallic nanoparticles and localized electric
field enhancement [25]. Because the Fermi level for gold
(about 5.0 eV) is lower than that for silver (about
4.6 eV), the gold atoms in the core can have a strong
electronic effect on the surface silver atoms by charge
transfer, causing the surface silver atoms neighboring
the gold core to become more active than the silver
atoms in monometallic silver nanoparticles. However,
the Ag–Au nanoparticle monolayer deposited on glass
shows a weak and poorly resolved Raman spectrum
(spectrum b), worse than that from silver monometallic
 Y. Yang et al. / Scripta Materialia 58 (2008) 862–865
nanoparticles but better than that from gold nanoparti-
cles [9]. Recently Ren et al. [8] studied the SERS activity
of Ag(100x)Aux (x = 3–30) core–shell nanoparticles
with some pinholes on the surface, and found the SERS
activity to be dependent on the Ag:Au ratio of the core–
shell composite nanoparticles; with increasing Au molar
fraction, the SERS activity is first enhanced and then
weakened, with the maximal intensity being 10 times
stronger than that of Ag colloids. The molar fraction
of Ag/Au (0.037) in our SERS sample is far less than
that in their samples, indicating that the Ag core is com-
pletely coated by a gold shell without pinholes and no
SERS enhancement is obtained by Ag nanoparticles
completely coated by gold shell without pinholes. In this
case of the Agcore–Aushell nanostructure without pin-
holes, gold shell will transfer electrons to the silver core,
which results in the gold shell experiencing the effect of
nucleophiles and the subsequent weakening of the local
field enhancement.
In summary, we have employed a seeding growth
technique to prepare Ag–Au and Au–Ag films on glass
substrates for SERS-active substrates. The Au–Ag film
shows a much stronger SERS signal for R6G than those
from pure Au, Ag and Ag–Au films, indicating that the
Au–Ag film is more powerful than pure Ag and Au film
as SERS-active substrates.
This work was supported by the National Natural
Science Foundation of China (No. 50701018) and Re-
search Fund for the Docoral Program of Higher Educa-
tion of China (No. 20070251031).
[1] W.L. Barnes, A. Dereux, T.W. Ebbesen, Nature 424
(2003) 824.
[2] K. Kneipp, H. Kneipp, J. Kneipp, Acc. Chem. Res. 39
(2006) 443;
C.L. Haynes, A.D. McFarland, R.P. Van Duyne, Anal.
Chem. 77 (2005) 338.
[3] M.M. Maye, J. Luo, L. Han, C.J. Zhong, Nano Lett. 1
(2001) 575.
[4] A.M. Michaels, M. Nirmal, L.E. Brus, J. Am. Chem. Soc.
121 (1999) 9932.
865
[5] H.X. Xu, E.J. Bjerneld, M. Käll, L. Börjesson, Phys. Rev.
Lett. 83 (1999) 4357.
[6] S. Nie, S.R. Emory, Science 275 (1997) 1102.
[7] S. Pande, S.K. Ghosh, S. Praharaj, S. Panigrahi, S. Basu,
S. Jana, A. Pal, T. Tsukuda, T. Pal, J. Phys. Chem. C 111
(2007) 10806.
[8] Y. Cui, B. Ren, J. Yao, R.A. Gu, Z.Q. Tian, J. Phys.
Chem. B 110 (2006) 4002.
[9] L. Rivas, S. Sanchez-Cortes, J.V. Garcia-Ramos, G.
Morcillo, Langmuir 16 (2000) 9722.
[10] E. Hao, S. Li, R.C. Bailey, S. Zou, G.C. Schatz, J.T.
Hupp, J. Phys. Chem. B 108 (2004) 1224.
[11] Y. Yang, M. Nogami, J. Shi, H. Chen, G. Ma, S. Tang,
Appl. Phys. Lett. 88 (2006) 081110;
Y. Yang, M. Nogami, J. Shi, H. Chen, G. Ma, S. Tang,
J. Phys. Chem. B 109 (2005) 4865.
[12] A.J. Haes, S. Zou, G.C. Schatz, R.P. Van Duyne, J. Phys.
Chem. B 108 (2004) 6961;
Y. Yang, S. Matsubara, L. Xiong, T. Hayakawa, M.
Nogami, J. Phys. Chem. C 111 (2007) 9095.
[13] Y. Lu, G.L. Liu, L.P. Lee, Nano Lett. 5 (2005) 5.
[14] H. Wang, C.S. Levin, N.J. Halas, J. Am. Chem. Soc. 127
(2005) 14992.
[15] Y. Yang, S. Matsubara, M. Nogami, J. Shi, W. Huang,
Nanotechnology 17 (2006) 2821.
[16] Y. Yang, M. Hori, T. Hayakawa, M. Nogami, Surf. Sci.
579 (2005) 215.
[17] M. Moskovits, I.S. Sloufova, B. Vlckova, J. Chem. Phys.
116 (2002) 10435.
[18] L. Lu, H. Wang, Y. Zhao, S. Xi, H. Zhang, J. Hu, B.
Zhao, Chem. Commun. (2002) 144.
[19] N.R. Jana, L. Grearheart, C.J. Murphy, Chem. Mater. 13
(2001) 2313.
[20] E. Hao, G.C. Schatz, J. Chem. Phys. 120 (2004) 357.
[21] S.T. He, S.S. Xie, J.N. Yao, H.J. Gao, S.J. Pang, Appl.
Phys. Lett. 81 (2002) 150.
[22] Y. Sun, B.T. Mayers, Y.N. Xia, Nano Lett. 2 (2002) 481.
[23] S.B. Chaney, S. Shanmukh, R.A. Dluhy, Y.P. Zhao,
Appl. Phys. Lett. 87 (2005) 031908.
[24] Y. Yang, L. Xiong, J. Shi, M. Nogami, Nanotechnology
17 (2006) 2670;
Y. Yang, J. Shi, T. Tanaka, M. Nogami, Langmuir 23
(2007) 12042.
[25] G.V. Pavan Kumar, S. Shruthi, B. Vibha, B.A. Ashok
Reddy, T.K. Kundu, C. Narayana, J. Phys. Chem. C 111
(2007) 4388.