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Fang 2005
Fang 2005
Fang 2005
www.elsevier.com/locate/cplett
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.
0009-2614/$ - see front matter 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 silver colloid was prepared by using the chem- 3.1. Morphologies of silver particulate films
ical reduction method according to the description of
Lee and Meisel [14]. The preparative procedure was The morphologies of silver particulate films on the
briefly described here. A stock 10 3 M AgNO3 aque- surface of mica and HOPG on the nanometer scale were
ous solution and a stock 1% trisodium citrate solu- presented by the tapping mode atomic force microscopic
tion were prepared first. 500 ml of AgNO3 aqueous (AFM) observations. The AFM image in Fig. 2a shows
solution was headed to boiling, and to this solution a surface morphology of silver colloid dried naturally on
10 ml of trisodium citrate solution was added drop the surface of mica, which exhibits that the silver parti-
by drop with vigorous magnetic stirring. Heading cles on the surface of mica are mostly spatially isolated,
and stirring were continued for 30 min, Green–gray single nanoparticles with a broad distribution of sphe-
silver sol was ready for use upon cooling. Dye-coated roidal particles sizes in the range of diameter from 80
silver colloidal nanoparticles were prepared by to 120 nm. Fig. 2b shows the AFM picture of silver col-
adsorbing crystal violet molecules, the molecular for- loid on the surface of HOPG. The main feature of the
mula of which was given in Fig. 1, on the surface morphology is the coexistence of large and small silver
of metal nanoparticles. This was performed simply islands that are in contact with each other. Compared
by mixing the colloidal solution and crystal violet with the image shown in Fig. 2a, there exists a clear dif-
aqueous solution. Before use, a 1 · 10 4 mol/L aque- ference between the coverage of silver particles depos-
ous solution of crystal violet was prepared. Ten ited on mica and HOPG. In consideration of the
microliters of the dye solution added to 1 ml of silver better hydrophilicity of mica, when a drop of silver col-
colloidal solutions to yield effective concentration of loidal solution is applied onto the surface of mica, it can
10 6 M. 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 the sol very stable against aggregation. Aggregation is
particles are randomly bound to the surface to form initiated by the addition of crystal violet to the silver col-
low-coverage silver colloid submonolayer. In contrast loidal solution. The effective adsorption of crystal violet
to the hydrophilicity of mica, HOPG takes on the on the surface of silver particles arising from the electro-
hydrophobic feature. The dropping silver colloid solu- static interactions of silver particles with crystal violet
tion keeps the form of bead and has a very little contact increases proton concentration at the surface which de-
interface with HOPG. With the natural evaporation of creases the effective electric charge existing on colloid
solution, silver nanoparticles can be gravitationally particles, reducing the repulsive interaction between
deposited on the surface, and form a high particle cov- the colloidal particles, and finally allowing them to ap-
erage submonolayer. Further, we study the pattern of proach each other and stick to form aggregates when
crystal violet coated silver nanoparticles deposited on they collide. As a result, the single silver particles disap-
the surface of mica. Large scale AFM observation pear from the colloidal solution and have been replaced
shows that some silver clusters in a few micrometers ap- by the silver aggregates induced by the adsorption of the
pear separated each other. Because crystal violet is a po- crystal violet. With the spreading and volatilizing of the
sitive charge dye, while silver, which is surrounded by a dropping colloidal solution on the surface of mica, those
layer of negative charge of citrate, usually has negative aggregates existing in the dropping colloidal solution are
potential [15]. The surface-adsorbed citrate causes the deposited on substrate in a separated pattern. Fig. 3a
silver particles to be highly charged and the resulting displays the representative AFM image of such silver
electric repulsive interaction between the particles makes 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
1619
visible feature in the AFM image of the aggregate is that
1175
1372
the silver nanoparticles touch each other to form some 50000
(a)
441
branch pattern. The branches have their main stems
Intensity (CPS)
420
which interconnect with many small chain-like silver 40000
913
802
particles clusters. The morphology of resulting aggre-
1296
1586
1443
gates suggests that the aggregate structure is characteris- 30000
765
1476
525
1530
726
tic of self-comparability tree-like fractal. Although the
978
558
663
20000
aggregates were originally formed in suspension in three
dimensions, their deposition on the two dimensions ba- (b)
10000
sal plan of support gives a structure that is very nearly
two-dimensional. This is apparent from the large (c)
0
amounts of open space and lack of overlapping among 400 800 1200 1600
the silver particles contacted each other. In the case of Raman shift/cm -1
clusters [16]. Therefore, the molecules involved in the the silver film on HOPG not only represents excellent
SERS effect are predominantly those adsorbed on aggre- SERS activity, but also gives uniform spatial distribu-
gates that are favorable for surface plasmon resonances. tion for SERS signal measurement. This study provides
Further, the dependence of SERS intensity on surface a framework of fabricating the colloidal particulate film
morphology is predicted by the electromagnetic by preserving the celebrated fractal structures that have
enhancement mechanism [17]. A resonant fractal theory peculiar enhancing properties produced in colloidal
about effect of the aggregate state on SERS activity solution to achieve the further improvement of SERS
shows that the surface Raman enhancement of a collec- activity.
tion of analyte-covered colloidal particles exhibiting
fractal properties will be greatly enhanced over the
equivalent number of analyte-covered spatially isolated References
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