Chemical Physics Letters 401 (2005) 271–275

www.elsevier.com/locate/cplett

The study of deposited silver particulate films by simple method

for efficient SERS
Jinghuai Fang *, Chonggui Zhong, Renwang Mu
Department of Physics, Nantong University, Nantong 226007, China

Received 8 September 2004; in final form 14 October 2004

Available online 8 December 2004

Abstract

We present a study on the preparation of silver particulate films by simple depositing colloidal solution on mica and highly ori-
ented pyrolytic graphite (HOPG), respectively. The morphologies of the deposits were revealed by atomic force microscopic obser-
vations. It has been shown that the deposition can preserve the disperse state as well as aggregation feature existed in colloidal
solution. Both silver particulate films were shown to be more activity than corresponding colloidal system for surface enhanced
Raman scattering (SERS). Compared with that on mica, the silver film on HOPG not only represents excellent SERS activity,
but also gives uniform spatial distribution for SERS signal measurement.

2004 Elsevier B.V. All rights reserved.

1. Introduction Among the methods employed to obtain silver colloids,

Since the observation of a surface enhanced Raman
scattering (SERS) signal from pyridine adsorbed on
roughened silver electrodes, SERS has been observed
in many systems of various configurations [1–7]. In gen-
eral, the SERS effect emerges for three types of surface
systems: (1) electrodes in electrochemical cells, (2)
roughened metal films and (3) colloidal dispersions of
metal particles. It has been demonstrated that a surface
roughness on the scale of submicrometers is required for
obtaining an appreciable enhancement of Raman scat-
tering [8].
Silver is one of the best materials for making SERS
active surface. Colloidal dispersions of silver particles
are the most widely used SERS substrates in various re-
search works and represent the most favorable case. Be-
sides the simplicity of preparation and characterization,
these systems exhibit remarkably strong enhancement.
*
Corresponding author.
E-mail address: fjhuai@nttc.edu.cn (J. Fang).
the chemical reduction of silver nitrate with sodium cit-
rate or sodium borohydride is frequently applied prepa-
ration technique. SERS spectral measurements are
routinely carried out on silver colloids aggregated by
addition of an adsorbate or a pre-aggregating agent.
The aggregation of silver particles appears to be crucial
for strong SERS enhancement [9,10]. At the same time,
the tendency for colloidal particles to aggregate sponta-
neously upon addition of analytes leads to poor stability
of system and irreproducibility in the magnitude of
SERS signals. Especially, with respect to the applica-
tions of SERS, knowledge about the factors that domi-
nate the sensitivity, stability, and reproducibility of
SERS is still not sufficient. It is also not easy to control
the experimental conditions of SERS such as the condi-
tions for aggregation of silver colloid. Extensive efforts
have been made to aim toward higher enhancement
and greater reproducibility of SERS-active substrates.
The preparation of SERS-active colloids on a solid sup-
port becomes one of the focuses of the field [11–13].
Many new solid substrates based on colloidal metal film
have been developed which combines the advantages of

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2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cplett.2004.11.055
272 J. Fang et al. / Chemical Physics Letters 401 (2005) 271–275
the intense SERS effect of colloidal system and good sta-
bility of solid substrate.
In this Letter, we report simple procedures to fab-
ricate stable colloidal silver films on the surface of
mica and highly oriented pyrolytic graphite (HOPG).
The surface morphology of prepared colloidal films
were investigated by tapping mode atomic force
microscope (AFM) that is useful in the study of
weakly attached deposit on substrate surfaces. The
SERS activity of obtained thin films were tested by
measuring the SERS intensity when using crystal vio-
let as a probe, which is known to yield a high SERS
factor when adsorbed on silver colloids. The experi-
mental results have shown that colloidal silver films
prepared in such method not only preserve the neces-
sary aggregation state produced in silver colloidal
solution, but also possess the stability needed in prac-
tical application. Meanwhile, these silver colloidal
films show excellent SERS activity compared with
SERS exhibited by silver colloid.
2. Experiment
2.1. Materials
Silver nitrate and trisodium citrate were purchased
from Aldrich and used as received without further puri-
fication. All the other chemical reagents employed in the
experiments were of analytical grade. Doubly distilled
deionized water was used throughout the present
experiment.
2.2. Preparation of silver colloid
The silver colloid was prepared by using the chem-
ical reduction method according to the description of
Lee and Meisel [14]. The preparative procedure was
briefly described here. A stock 10 3 M AgNO3 aque-
ous solution and a stock 1% trisodium citrate solu-
tion were prepared first. 500 ml of AgNO3 aqueous
solution was headed to boiling, and to this solution
10 ml of trisodium citrate solution was added drop
by drop with vigorous magnetic stirring. Heading
and stirring were continued for 30 min, Green–gray
silver sol was ready for use upon cooling. Dye-coated
silver colloidal nanoparticles were prepared by
adsorbing crystal violet molecules, the molecular for-
mula of which was given in Fig. 1, on the surface
of metal nanoparticles. This was performed simply
by mixing the colloidal solution and crystal violet
aqueous solution. Before use, a 1 · 10 4 mol/L aque-
ous solution of crystal violet was prepared. Ten
microliters of the dye solution added to 1 ml of silver
colloidal solutions to yield effective concentration of
10 6 M.
Fig. 1. The structure of crystal violet.
2.3. Fabrication of silver colloid deposited films
Silver particulate films were prepared under the fol-
lowing procedure. A drop of silver colloidal solution
and dye-coated silver colloidal solution were directly ap-
plied to the basal plan of a freshly cleaved mica and
HOPG, respectively. Then, these dropped colloidal solu-
tions were allowed to evaporate naturally in the air to
form corresponding colloidal particulate films deposited
on the surfaces of mica and HOPG.
2.4. Apparatus and measurements
The Morphology of the silver colloidal films were
examined with an AFM ( DICO, NanoScope 3). Raman
scattering spectra were measured by a confocal micro-
Raman spectrometer (Super LabRam II system, Dilor,
France). The excitation line is 632.8 nm radiation from
a 10 mW He–Ne laser. The signal integration was set
at 1 s for measurement.
3. Results and discussion
3.1. Morphologies of silver particulate films
The morphologies of silver particulate films on the
surface of mica and HOPG on the nanometer scale were
presented by the tapping mode atomic force microscopic
(AFM) observations. The AFM image in Fig. 2a shows
a surface morphology of silver colloid dried naturally on
the surface of mica, which exhibits that the silver parti-
cles on the surface of mica are mostly spatially isolated,
single nanoparticles with a broad distribution of sphe-
roidal particles sizes in the range of diameter from 80
to 120 nm. Fig. 2b shows the AFM picture of silver col-
loid on the surface of HOPG. The main feature of the
morphology is the coexistence of large and small silver
islands that are in contact with each other. Compared
with the image shown in Fig. 2a, there exists a clear dif-
ference between the coverage of silver particles depos-
ited on mica and HOPG. In consideration of the
better hydrophilicity of mica, when a drop of silver col-
loidal solution is applied onto the surface of mica, it can
spread fully on the surface. This process significantly
 J. Fang et al. / Chemical Physics Letters 401 (2005) 271–275 273

Fig. 2. AFM pictures of silver nanoparticles deposited on (a) mica, and (b) HOPG.

reduces the particle density on the mica surface, and
particles are randomly bound to the surface to form
low-coverage silver colloid submonolayer. In contrast
to the hydrophilicity of mica, HOPG takes on the
hydrophobic feature. The dropping silver colloid solu-
tion keeps the form of bead and has a very little contact
interface with HOPG. With the natural evaporation of
solution, silver nanoparticles can be gravitationally
deposited on the surface, and form a high particle cov-
erage submonolayer. Further, we study the pattern of
crystal violet coated silver nanoparticles deposited on
the surface of mica. Large scale AFM observation
shows that some silver clusters in a few micrometers ap-
pear separated each other. Because crystal violet is a po-
sitive charge dye, while silver, which is surrounded by a
layer of negative charge of citrate, usually has negative
potential [15]. The surface-adsorbed citrate causes the
silver particles to be highly charged and the resulting
electric repulsive interaction between the particles makes
the sol very stable against aggregation. Aggregation is
initiated by the addition of crystal violet to the silver col-
loidal solution. The effective adsorption of crystal violet
on the surface of silver particles arising from the electro-
static interactions of silver particles with crystal violet
increases proton concentration at the surface which de-
creases the effective electric charge existing on colloid
particles, reducing the repulsive interaction between
the colloidal particles, and finally allowing them to ap-
proach each other and stick to form aggregates when
they collide. As a result, the single silver particles disap-
pear from the colloidal solution and have been replaced
by the silver aggregates induced by the adsorption of the
crystal violet. With the spreading and volatilizing of the
dropping colloidal solution on the surface of mica, those
aggregates existing in the dropping colloidal solution are
deposited on substrate in a separated pattern. Fig. 3a
displays the representative AFM image of such silver
colloidal aggregate. The aggregate is integrated by

Fig. 3. AFM pictures of silver particles aggregates induced by the addition of crystal violet in silver colloidal solution deposited on (a) mica, and (b)
HOPG.
274 J. Fang et al. / Chemical Physics Letters 401 (2005) 271–275
particles of a size similar to original particles. A clearly
visible feature in the AFM image of the aggregate is that
the silver nanoparticles touch each other to form some
branch pattern. The branches have their main stems
which interconnect with many small chain-like silver
particles clusters. The morphology of resulting aggre-
gates suggests that the aggregate structure is characteris-
tic of self-comparability tree-like fractal. Although the
aggregates were originally formed in suspension in three
dimensions, their deposition on the two dimensions ba-
sal plan of support gives a structure that is very nearly
two-dimensional. This is apparent from the large
amounts of open space and lack of overlapping among
the silver particles contacted each other. In the case of
crystal violet coated silver particles deposited on the
HOPG, the examination of the image in Fig. 3b exhibits
that the silver particles touch each other to form some
dense clusters and small clusters are linked by the chains
of individual particles of silver to produce a large web-
like network of connected silver particles, behaving the
feature of fractal cluster–cluster aggregation. Compari-
son of these two crystal violet coated silver particulate
films reveals the clear differences in particle coverage.
Namely, silver particulate film deposited on mica con-
sists of small discrete segregated areas of aggregates with
low particle coverage. However, the film deposited on
HOPG represents a homogeneous particle aggregation
pattern concentrated on the contact interface of the
dropping colloidal solution and HOPG with high parti-
cle coverage.
3.2. SERS activity of silver colloid deposited films
Using crystal violet as a molecular probe, we checked
the SERS activity of the above silver colloidal films. For
the case of silver film consisted of small separated aggre-
gates with scale of a few micrometers on mica, we can
make use of the advantage of laser beam spot focusing
at the surface with scale of about 1 lm and optical
microscopy provided by confocal micro-Raman system
to focus the laser beam on the aggregate directly to ob-
tain a SERS spectrum from silver aggregates. This
means that the Raman signal and the AFM images are
correlated to a large extent. Fig. 4a and b are SERS
spectra of crystal violet obtained from the silver nano-
particles aggregates deposited on HOPG and mica,
respectively. For the sake of comparison, the SERS
spectrum of crystal violet from the corresponding silver
colloidal system is also given in Fig. 4c. The result re-
corded shows that the silver film on HOPG offer a high-
er SERS signal than that of silver film on mica and both
types of silver films are very active and exhibit strong
SERS effect compared with the silver colloidal system.
Considering that the aggregates are originally formed
in suspension in three dimensions, their deposition on
the surface of mica gives an aggregation structure in a
60000
1619
1175
1372
50000
(a)
441
Intensity (CPS)
420
40000
913
802
1296
1586
1443
30000
765
1476
525
1530
726
978
558
663
20000
(b)
10000
(c)
0
400 800 1200 1600
Raman shift/cm -1
Fig. 4. SERS spectra of crystal violet from (a) silver film on HOPG,
(b) silver film on mica and (c) silver sol.
very nearly two-dimensional form. Thus, compared with
the aggregate in the silver colloidal solution, a more
compact aggregate on mica can be obtained and the
number of crystal violet molecules in the probed volume
decided by confocal micro-Raman system is obviously
increased. Maybe, these two factors contribute to the
remarkably enhanced SERS effect observed from silver
aggregate on mica. Likewise, very large, high-density
fractal cluster–cluster weblike aggregation structure on
HOPG is responsible for the significantly improvement
of its SERS response relative to that on mica. In order
to test the spatial uniformity in signal intensity of depos-
ited silver particle film on the surface of HOPG, we mea-
sure SERS spectra at least five different locations at the
edges and in the center of the sample. The result exam-
ined indicates that the SERS signal intensity recorded at
different locations is almost same. We could reasonably
think from the above that the silver particle film ob-
tained by depositing aggregated silver colloids on
HOPG behaves better homogeneity on a larger scale
in space for SERS effect.
We further study the influence of silver particles
arrangement on SERS activity. A drop of crystal violet
solution was drop coated on above pure silver particle
film prepared on mica and HOPG, respectively. The
concentrations of crystal violet used on the silver films
in this case are higher than that used on the deposited
crystal violet coated silver films. However, AFM analy-
sis indicates that morphologies of this kind crystal violet
modified silver films preserve the basic same as original
films. The SERS measurements show that high-density
silver film on HOPG exhibit a weaker SERS signal than
silver colloidal system, and no SERS spectrum was ob-
served from crystal violet on low-density colloidal film
on mica. It is known that the SERS activity depends
strongly on the geometry of the aggregates and the
strongest enhancement comes from the molecules situ-
ated between particles of the fractal colloidal silver
 J. Fang et al. / Chemical Physics Letters 401 (2005) 271–275
clusters [16]. Therefore, the molecules involved in the
SERS effect are predominantly those adsorbed on aggre-
gates that are favorable for surface plasmon resonances.
Further, the dependence of SERS intensity on surface
morphology is predicted by the electromagnetic
enhancement mechanism [17]. A resonant fractal theory
about effect of the aggregate state on SERS activity
shows that the surface Raman enhancement of a collec-
tion of analyte-covered colloidal particles exhibiting
fractal properties will be greatly enhanced over the
equivalent number of analyte-covered spatially isolated
colloidal particles [18]. Clearly, the SERS effects are clo-
sely related to the aggregate structure. Thus, variance
of the aggregate morphology, in principle, should lead
to the change of SERS intensity. We can conclude from
the above that the aggregation of colloidal particles is
crucial for strong SERS enhancement and the high-
density fractal weblike strcture on HOPG appears to
be the most favorable for SERS measurements.
4. Conclusion
We have shown that silver nanoparticles on mica and
HOPG can be prepared by dropping the colloidal silver
on above both surfaces. The different surface morpho-
logies of silver nanoparticles are formed with submono-
layer coverage and can be defined in a manner similar to
colloidal suspensions. The important advantage of this
preparation method is that the fabricated colloidal films
preserve the disperse state as well as aggregation feature
existed in colloidal solution. However, in contrast to
loose tridimensional aggregation structure in colloidal
solution, colloidal films posses more tightly bidimen-
sional structure arrangement. Stronger enhancement of
Raman scattering from thus-prepared silver nanopartic-
ulate films can be achieved in comparison of the SERS
signal exhibited by silver colloidal system. In addition,
275
the silver film on HOPG not only represents excellent
SERS activity, but also gives uniform spatial distribu-
tion for SERS signal measurement. This study provides
a framework of fabricating the colloidal particulate film
by preserving the celebrated fractal structures that have
peculiar enhancing properties produced in colloidal
solution to achieve the further improvement of SERS
activity.
References
[1] M. Fleischmann, P.J. Hendra, A.J. McQuillan, Chem. Phys. Lett.
26 (1974) 163.
[2] M.G. Albrecht, J.A. Creighton, J. Am. Chem. Soc. 99 (1977)
5215.
[3] J.A Creighton, C.G. Blatchford, M.G. Albright, J. Chem. Soc.,
Faraday Trans. 75 (1979) 790.
[4] M. Moskovits, Rev. Mod. Phys. 57 (1986) 783.
[5] A. Otto, I. Mrozek, H. Grabhorn, W. Akemann, J. Phys.:
Condens. Mater. 4 (1992) 1143.
[6] S.J. Oldenburg, S.L. Westcott, R.D. Averitt, N.J. Halas, J. Chem.
Phys. 11 (1999) 4729.
[7] P.M. Tessier, O.D. Velev, A.T. Kalambur, J.F. Rabolt, A.M.
Lenhoff, E.W. Kaler, J. Am. Chem. Soc. 122 (2000) 9554.
[8] S. Byahut, T.E. Furtak, Langmuir 7 (1991) 508.
[9] O. Siiman, H. Feilchenfeld, J. Phys. Chem. 92 (1988) 453.
[10] X. Dou, Y.M. Jung, Z. Cao, Y. Ozaki, Appl. Spectrosc. 53 (1999)
1440.
[11] R.G. Freeman, K.C. Grabar, K.J. Allison, R.M. Bright, J.A.
Davis, A.P. Guthrie, M.B. Hommer, M.A. Jackson, P.C. Smith,
D.G. Walter, M.J. Natan, Science 267 (1995) 1629.
[12] J. Schmitt, P. Mächtle, D. Eck, H. Möhwald, C.A. Helm,
Langmuir 15 (1999) 3256.
[13] K.C. Grabar, K.J. Allison, B.E. Baker, R.M. Bright, K.R.
Brown, R.G. Freeman, A.P. Fox, C.D. Keating, M.D. Musick,
M.J. Natan, Langmuir 12 (1996) 2353.
[14] P.C. Lee, D. Meisel, J. Phys. Chem. 86 (1982) 3391.
[15] Y.-S. Li, Y. Wang, J. Chang. Vib. Spectrosc. 27 (2001) 65.
[16] K. Kneipp, H. Kneipp, I. Itzkan, R.R. Dasari, M.S. Feld, Chem.
Rev. 99 (1999) 2957.
[17] M. Moskovits, Rev. Mod. Phys. 57 (1985) 783.
[18] M.I. Stockman, V.M. Shalaev, M. Moskovits, R. Botet, T.F.
George, Phys. Rev. B 46 (1992) 2821.