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Spectrochimica Acta Part A 70 (2008) 780784

Synthesis, characterization and SERS activity of AuAg nanorods

Daizy Philip a, , K.G. Gopchandran b , C. Unni b , K.M. Nissamudeen b
a Department of Physics, Mar Ivanios College, Thiruvananthapuram 695015, India
b Department of Optoelectronics, University of Kerala, Kariavattom 695581, India
Received 5 July 2007; received in revised form 31 August 2007; accepted 17 September 2007

Abstract
The formation mechanism and morphology of AuAg bimetallic colloidal nanoparticles depend on the composition. Ag coated Au colloidal
nanoparticles have been prepared by deposition of Ag through chemical reduction on performed Au colloid. The composition of the Au100x Agx
particles was varied from x = 0 to 50. The obtained colloids were characterized by UVvis spectroscopy and transmission electron microscopy
(TEM). The Au80 Ag20 colloid consists of alloy nanorods with dimension of 25 nm 100 nm. The activity of these nanorods in surface enhanced
Raman spectroscopy (SERS) was checked by using sodium salicylate as an adsorbate probe. Intense SERS bands are observed indicating its
usefulness as a SERS substrate in near infrared (NIR) laser excitation.
2007 Elsevier B.V. All rights reserved.

Keywords: Gold nanoparticles; Mixed AuAg nanoparticles; AuAg alloy nanorods; UVvis spectra; TEM; SERS; NIR laser excitation; Sodium salicylate

1. Introduction alytic and surface enhanced Raman scattering (SERS) properties

The wet chemical synthesis of inorganic nanoparticles of
various shapes made from metals, semiconductor, magnetic
materials or insulators has made significant progress in recent
years [1,2]. The unique optical, electromagnetic and thermo-
dynamic properties of metal nanoparticles have made them
useful in a variety of applications including biomedical sen-
sors, probing devices, drug administration, optical data storage
and electronic and semiconductor devices [24]. However, for
metal nanoparticles to be applied effectively to technological
advances something must be known of their material properties,
which can vary significantly from that of their bulk counter-
parts. New lithographic techniques as well as improvements to
classical wet chemistry methods have made it possible to syn-
thesize noble metal nanoparticles with a wide range of sizes,
shapes and dielectric environments [57]. Among the differ-
ent methods [812], the procedure developed by Jana et al.
[10] has attracted a great deal of attention since it provides an
easy way to obtain well controlled gold nanorods. Nanocom-
posites, i.e. alloy and corehell particles, is an attractive
subject because of their composition dependent optical, cat-
Corresponding author.
E-mail address: daizyp@rediffmail.com (D. Philip).
[1325].
AuAg alloy [20] and Agclad Au spherical nanoparticles
have been used in the SERS studies and it is reported [22] that
the SERS behaviour depends upon Ag:Au ratio. The depen-
dence of the SERS intensity on the number of gold nanorods
and the nanorods spacing on silica surface [23] were investi-
gated using a near infrared (NIR) excitation source (1064 nm).
Silver colloids usually have a higher SERS activity for excita-
tion wavelengths in the visible region whereas Au ones are more
active in the red but their activity highly decreases in the NIR
region. The preparation of AgAu mixed colloids allows for the
combination of the SERS activity of both metals in a broader
interval of the electromagnetic spectrum. On the addition of ana-
lyte, the aggregated colloids show new absorption bands which
appear towards the red region: 500600 nm for Ag colloids and
700900 nm for Au colloids. The new absorption bands are due
to the plasmon excitation in aggregated particles that govern the
SERS excitation profile [20]. Enhancement is large when the
exciting radiation is coincident with the plasmon absorbance
[22]. To achieve this in Au colloids at NIR laser excitation,
AuAg alloy nanorods can be used. Also, the surface plasmon
resonance (SPR) properties of AuAg alloy nanoparticles are
continuously tunable because of the possibility of composition
changes. So far, there is no report on AuAg alloy nanorods. In
this work we report the synthesis of alloy nanorods of AuAg

1386-1425/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.saa.2007.09.016
 D. Philip et al. / Spectrochimica Acta Part A 70 (2008) 780784 781

by a seed mediated method and its usefulness as a SERS

substrate.

2. Experimental

AgNO3 , HAuCl4 3H2 O, trisodium citrate and sodium salicy-

late were of highest purity available from SigmaAldrich. The
aqueous solutions were prepared using deionized water. All glass
materials were cleaned by using aqua regia and rinsed several
times with deionized water.
The initial Au colloid was prepared according to Grabar et al.
[26] with slight modification. 500 mL of 1.4 103 M solution
of HAuCl4 3H2 O was brought to boil. To the boiling solution
50 mL of 1% sodium citrate was added drop by drop while stir-
ring. Boiling was continued for 30 min and then left to cool
to room temperature. The resulting solution was made up to
500 mL. This colloid is wine red in colour and has absorption
maximum at 526 nm. Fig. 1. Photograph of pattern formed on a Whatman filter paper.

2.1. Preparation of AuAg mixed colloids
6 104 M solution of AgNO3 was prepared. Aliquots of
this solution 20, 10, 6.7 and 5 mL were added drop by drop to
20 mL of preformed citrate reduced Au colloid with continuous
stirring to get 1:1, 2:1, 3:1 and 4:1 mixed colloid. Afterward, the
corresponding volume of the sodium citrate aqueous solution in
relation to the AgNO3 volume was added to induce the chemical
reduction of Ag and its deposition on Au particles [20]. The mix-
ture was kept boiling for 30 min. The resulting mixed colloids,
1:1, 2:1, 3:1 and 4:1, correspond to Au50 Ag50 , Au67 Ag33 ,
Au75 Ag25 and Au80 Ag20 , respectively. Of these four prepa-
rations, Au80 Ag20 does not show any precipitation and is very
stable. The other three colloids precipitated within 1 month after
the preparation.
The UVvis absorption spectra were recorded on a Jasco
V-550 UVvis spectrophotometer in a 1 cm optical path quartz
cuvette. The size of particles was analyzed by TEM using a JEOL
JEM 1011 transmission electron microscope operating at 80 kV.
The samples for TEM were prepared on a foamvar coated copper
grid by depositing and drying 10 L of the colloid. SERS spectra
were recorded using a Bruker RFS 100/S model spectropho-
tometer connected to a liquid nitrogen cooled Ge detector with
sample placed in a 1 cm path length glass cuvette. The 1064 nm
line provided by a Nd:YAG laser was used for excitation in
the NIR with 150 mW power output. Samples for SERS mea-
surements were prepared by adding 5 mL of 102 M aqueous
solution of sodium salicylate to 5 mL of the colloid.
3. Results and discussion
A novel evolution of pattern as shown in Fig. 1 is observed
within 20 s when a drop of the initial gold colloid is deposited
on a Whatman filter paper. At first water spreads out and a small
purple coloured sphere is formed at the centre which increases
in size with time and finally a ring is formed around it. This
pattern evolution may be due to the property of Au colloid to
self assemble into a dense layer [27] that excludes water. The

Fig. 2. Photograph of the colloids: (a) Au50 Ag50 , (b) Au67 Ag33 , (c) Au75 Ag25 , (d) Au80 Ag20 and (e) Au.
782 D. Philip et al. / Spectrochimica Acta Part A 70 (2008) 780784

Fig. 4. Dependence of plasmon absorbance maximum of (a) Au and (b) Ag on

Fig. 3. UVvis spectrum of the colloids: (a) Au50 Ag50 , (b) Au67 Ag33 , (c) the mole fraction of gold.
Au75 Ag25 , (d) Au80 Ag20 and (e) Au.

colour change of the Au100x Agx colloid on varying the mole

fraction is evident from the photograph shown in Fig. 2.
Fig. 3 shows the UVvis spectra of the initial Au colloid
and the mixed AuAg colloids in the molar ratio 1:1, 2:1, 3:1
and 4:1 corresponding to Au50 Ag50, Au67 Ag33 , Au75 Ag25
and Au8 Ag20 , respectively. The 1:1, 2:1 and 3:1 composites
show two distinct SPR bands indicating individual existence of
Ag and Au nanoparticles having coreshell structure [14,16,20].
The relative intensities of the SPR band maxima depend on the
molar ratio. Table 1 gives the dependence of SPR maximum on
Au mole fraction. Fig. 4 shows a linear variation for SPR with
mole fraction up to 0.75 for Au100x Agx colloids. As Au mole
fraction increases the SPR of Au is red shifted and that of Ag
is blue shifted. A single plasmon band observed at 513 nm for
the composite colloid of molar ratio 4:1. Similar results were
reported [13,16,20,25,27,28] in mixed metallic colloids. The
appearance of only one absorption band indicates that homo-
Fig. 5. TEM image of Au colloid.
geneous mixed colloidal particles of both metals are formed
without significant formation of independent particles. In other
words, AuAg alloy nanoparticles are formed.
Fig. 5 shows TEM of initial Au colloid with nanoparticles
of size 30 nm. The TEM displays a more uniform distribution
of sizes and shapes and no rod-shaped particles are seen. TEM
image obtained for Au80 Ag20 colloid is shown in Fig. 6. It has a
novel feature compared to the previous reports [13,14,16,20] on
alloy nanoparticles. Large rod-shaped particles having average

Table 1
Dependence of SPR maximum on mole fraction
Mole fraction SPR maximum

Au (nm) Ag (nm)

0.50 493 405

0.67 500 387
0.75 504 375
0.80 513
1.00 526
Fig. 6. TEM image of Au80 Ag20 colloid.
 D. Philip et al. / Spectrochimica Acta Part A 70 (2008) 780784
Fig. 7. SERS spectrum of sodium salicylate in Au80 Ag20 colloid.
size of about 25 nm 100 nm with aspect ratio 4 and SPR max-
imum at 513 nm which is lower that that of the initial Au colloid
is observed. The absence of the band arising from the longitu-
dinal plasmon mode [23,2932] is due to the high aspect ratio.
The aspect ratio 4 for the rod-shaped alloy nanoparticles is
favourable for SERS activity using the NIR laser excitation as
the longitudinal plasmon mode can be partially excited [33].
We have checked the SERS activity of the Au, Au50 Ag50 ,
Au67 Ag33 , Au75 Ag25 and Au80 Ag20 colloids using sodium
salicylate as molecular probe. SERS spectrum could be obtained
only for the Au80 Ag20 colloid and the enhancement observed
may be attributed to the unique rod-like morphology exhibited
by it compared to other mixtures. The morphology change of Au
in the alloy form is supposed to increase its plasmon resonance
towards NIR region on the addition of the analyte which leads
to electromagnetic field enhancement.
SERS spectrum of sodium salicylate (102 M aqueous solu-
tion) in Au80 Ag20 colloid is shown in Fig. 7. The intense band
observed at 1370 cm1 is due to the carbonyl CO stretching,
(CO)c , mode [34,35]. Bands appearing below 250 cm1 cor-
respond to the metaloxygen stretching, AgAu O, mode
[3437]. The other prominent bands at 1233, 1003 and 448 cm1
are assigned to the (CO)h , CH and CC modes, respec-
tively. The CH and CC modes [34,37] appear at 849 cm1 and
1580 cm1 , respectively. However, the intensity distribution is
different from that observed for SERS of sodium salicylate in Ag
colloid [34]. This is due to the surface selectivity of SERS. The
results show that the use of AuAg alloy nanorods as a substrate
can expand the capabilities of SERS using NIR laser excitation.
4. Conclusion
The formation mechanism and morphology of colloidal
nanoparticles of Ag coated Au depend on the relative amount
783
of deposited Ag. The rod-shaped alloy nanoparticles are charac-
terized by optical absorption spectroscopy and TEM. The large
aspect ratio 4 of the particles is favourable for the use of these
alloy nanoparticles as a substrate for SERS in the NIR laser exci-
tation. The enhancement is evidenced using sodium salicylate
as a molecular probe.
Acknowledgements
This research has been sponsored by UGC under the Research
Award scheme granted to Daizy Philip. Excellent technical sup-
port for electron microscope was provided by Sanjai D, RGCB,
Thiruvananthapuram.
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