Materials Research Bulletin 41 (2006) 1407–1416

www.elsevier.com/locate/matresbu

Preparation of silica–silver heterogeneous nanocomposite

particles by one-pot preparation strategy using polyol
process: Size-controlled immobilization
of silver nanoparticles
Jong-Min Lee, Dae-Wook Kim, Young-Doo Jun, Seong-Geun Oh *
Department of Chemical Engineering, Hanyang University, 17 Haengdang-dong, Seongdong-ku, Seoul 133-791, Republic of Korea
Received 16 November 2005; received in revised form 4 January 2006; accepted 15 February 2006
Available online 9 March 2006

Abstract
The size-controlled immobilization of silver nanoparticles onto the silica surface was carried out through one-pot process
involving polyol process for the first time. Thiol groups were employed as a chemical protocol to make a binding bridge between
silver nanoparticle and silica surface. The size of immobilized silver nanoparticles was controlled by reaction temperature and time
at two different concentrations of silver nitrate: 1000 and 10,000 ppm. This one-pot process involving polyol process can simplify
the conventional complex reaction process to control the size of immobilized metal nanoparticles. Also, this research can contribute
to the immobilization of the other metals onto the inorganic supports and to the control of the size of immobilized metal particles.
# 2006 Elsevier Ltd. All rights reserved.

Keywords: A. Composite; A. Metals; B. Chemical synthesis; C. Electron microscopy; D. Optical properties

1. Introduction

In the past few years, many preparation routes [1–5], by which metal nanoparticles are deposited to the various
inorganic supports, have been developed by many scientists to expand the application area of nano-materials and to
control the morphology and the behavior. These composite materials have potential applications in various fields such
as surface-enhanced Raman scattering (SERS) [6], photonic crystals [7], catalysis [8] and biochemistry for chemical
sensors [9], etc. Moreover, these hybrid materials can prevent metal nanoparticles from agglomerating without the use
of a stabilizer and be easily retrieved owing to the relatively large size of support materials. As a result, they make it
easy to handle metal nanoparticles. Recently, novel preparation routes for composite materials have been proposed to
simplify the conventional complex reaction process or to obtain dense and uniform metal layers: sono-chemical
deposition [10], electroless plating [11] and electrostatic attraction [12] techniques. Also, in order to easily prepare
polymer–metal nanocomposite particles, novel method including polyol process has been suggested in our former
studies for the first time [13]. Polyol process is the chemical reduction method using the polyol such as ethylene glycol

* Corresponding author. Tel.: +82 2 2220 0485; fax: +82 2 2294 4568.
E-mail address: seongoh@hanyang.ac.kr (S.-G. Oh).

0025-5408/$ – see front matter # 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.materresbull.2006.02.010
1408 J.-M. Lee et al. / Materials Research Bulletin 41 (2006) 1407–1416

and diethylene glycol. In this process, polyol acts both as the solvent of the metallic precursor and as the reducing
agent [14–16].
In this study, as a continuation of our previous research regarding the preparation of the polystyrene–silver
nanocomposite particles by polyol process [13], silver nanoparticles are successfully immobilized onto the MPTMS-
functionalized silica particles by polyol process. Resulting composite particles are analyzed by field emission
scanning electron microscopy (FE-SEM), UV–vis spectrophotometer and X-ray diffractometer (XRD). On the basis
of the experimental results, it was demonstrated that it is possible to obtain extremely small silver particles and to
control the size of silver particles and the thickness of silver layer by control of reaction temperature and time.

2. Experimental

2.1. Materials

Tetraethyl orthosilicate (TEOS 98%, Aldrich), absolute ethanol (HPLC grade 99.9%, DUKSAN Pure Chemical
Company, Korea) and ammonia solution (NH4OH 25%, Wako Pure Chemical Industries, Japan) were used to prepare
silica particles. 3-Mercaptopropyltrimethoxysilane (MPTMS) was purchased from SIGMA and used as a chemical
protocol to make a binding between silica and silver particles. Silver nitrate (AgNO3 99.995%, Aldrich) was used as a
silver ion source. Ethylene glycol (Yakuri Pure Chemicals Company, Japan) and poly(vinylpyrrolidone) (PVP, K-15,
Mw 10,000, Junsei Chemical Company, Japan) were used to reduce silver ions by polyol process. All materials were
used as received. The water used in this study was deionized by Milli-Q Plus system (Millipore, France), having
18.2 MV electrical resistivity.

2.2. Preparation of silica particles functionalized with thiol groups

Spherical silica particles were prepared by sol–gel process on the basis of Stöber method. [17]. For the MPTMS-
functionalization of the surface of silica particles, a procedure similar to that described by Philipse and Vrij was
applied [18]. 10.6 g of 25% ammonia solution was mixed with 125 g of absolute ethanol under mild stirring. After
20 min, the sol–gel reaction for the formation of silica particles was initiated by adding 5 g of TEOS into the solution.
After 1 h, 1 g of MPTMS was added into the solution. Resulting solution was kept for 6 h under mild stirring. After the
reaction, the reactant was centrifuged at 3000 rpm for 30 min to separate silica particles functionalized with thiol
groups. The separated particles were washed with ethanol to remove un-reacted reagents. Then, the washed particles
were collected and dried at 40 8C for 1 day in an incubator.

2.3. Immobilization of silver nanoparticles onto the silica particles functionalized with thiol groups

To immobilize the silver nanoparticles onto the silica surface modified with thiol groups, polyol process was
applied. Typical process is as follows: silica particles functionalized with thiol groups was dispersed in ethylene glycol
using sonication and agitation. And then, PVP was dissolved in the mixture under mild stirring to prevent distortion of
polymer chain. The concentration of silica particles and PVP was fixed to 0.1 and 4 wt% throughout the experiments.
After 1 day, a given amount of AgNO3 was added into the solution and the solution was slowly stirred for 30 min in
order to completely dissolve AgNO3. And then, the solutions were heated with reflux at a given temperature and time.

2.4. Characterization

To investigate the formation and the morphological properties of silica–silver nanocomposite particles, field
emission scanning electron microscopy (FE-SEM, JEOL JSM-6700F) was operated at acceleration, voltage of 5.0 kV.
To obtain specimens for FE-SEM analysis, silica–silver nanocomposite colloidal solution treated as follows: after
adding required amount of ethanol into resulting colloid, centrifugal force (3000 rpm, 20 min) was applied to make
resulting composite particles to be separated. Separated particles were washed with ethanol two times. During the
washing process, centrifugal force (3000 rpm, 20 min) was applied to the particles to shorten the sedimentation time.
Obtained particles were dried at 40 8C for 1 day in vacuum drying oven. Finally, these particles for FE-SEM analysis
were coated with platinum by sputtering for 3 min at 10 kV.
 J.-M. Lee et al. / Materials Research Bulletin 41 (2006) 1407–1416 1409

The UV–vis absorption spectra of the silica–silver composite particles prepared at different conditions were
measured by the UV–vis spectrophotometer (Agilent 8435, Agilent Technologies). All the samples were diluted
with ethylene glycol for measurement of the absorption spectrum at a volume ratio of 270 (ethylene glycol) to 30
(sample). X-ray diffraction (XRD) was carried out on a Rigaku D/max-2500 X-ray diffractometer operating at
40 kV and 100 mA with the Cu Ka radiation (l = 0.15418 nm) at a scanning rate of 28 min 1 in 2u ranging from
108 to 808.

3. Results and discussion

3.1. Morphology of the silica particles functionalized with thiol groups

Spherical silica particles were prepared by sol–gel process on the basis of Stöber method [17]. Thiol groups tend
to interact with silver ions by the cleavage of an S–H bond and the spontaneous formation of an S–Ag bond [19,20].
As a result of unique behavior of thiol groups containing sulfur atom, chemicals containing thiol groups have been
widely used as chemical protocols to make various metal–metal oxide composites [20–23]. In present research,
thiol groups were introduced by graft reaction between surface silanol groups of silica and MPTMS [24]. The FE-
SEM photograph of silica particles functionalized with thiol groups is shown in Fig. 1. In this figure, mono-
dispersed silica particles with spherical shape and an average particles size of about 320 nm in diameter are
observed.

3.2. Formation of the silica–silver composite particles

3.2.1. The role of PVP

In this study, polyol process was applied to form and immobilize silver nanoparticles onto the silica surface
functionalized with thiol groups. Generally, PVP acts not only as a nucleation-promoting agent for silver ions but also
as a stabilizer for silver nanoparticles in polyol process. This role of PVP is clearly shown in Fig. 2(A and B). When
ethylene glycol solution containing 1000 ppm silver ions and silica particles functionalized with thiol groups was
heated with reflux at 120 8C for 4 h in the absence of PVP, few particles were formed and immobilized onto the silica
surface as shown in Fig. 2(A). On the contrary, when the same reaction proceeded in the presence of PVP, silver
nanoparticles were successfully formed and immobilized onto the surface of silica particles as shown in Fig. 2(B).
Similar result has been observed in our previous research [13], which means that the reduction potential of this system
consisting of AgNO3, silica particles and ethylene glycol is insufficient to reduce AgNO3 at a given reaction
temperature in the absence of PVP.

Fig. 1. FE-SEM image of the MPTMS-functionalized silica particles synthesized by modified Stöber Method.
1410 J.-M. Lee et al. / Materials Research Bulletin 41 (2006) 1407–1416

Fig. 2. FE-SEM images of the silica–silver composite particles prepared by polyol process at 120 8C for 4 h with silver concentration of 1000 ppm
(A) in the absence of PVP and (B) in the presence of PVP.

UV–vis absorption spectra also show the same result as shown in Fig. 3. In this figure, curve A and B indicate the
UV–vis absorption spectra of resulting composite particles prepared in the absence of PVP and in the presence of PVP,
respectively. Curve A shows very weak absorption intensity, whereas curve B shows a broad absorption band about
520 nm, red-shifted compared to the general absorbance band of silver nanoparticles observed at about 400 nm.
Generally, absorption and scattering of light by the particles depend on its chemical composition, size, shape,
surrounding dielectric medium and coupling of the colloids and adsorbed solutes [25]. Especially, in the case of
composite particles consisting of dielectric core and metal layer such as shell or particles, when the thickness and
coverage of silver layer are increased, the plasmon peak broadens, red-shifts, and depresses the scattering peak greatly
[12]. These variation trends of the plasmon peak can be explained by Mie scattering theory [26,27]. From these facts, it
is thought that red-shift and broadening of plasmon peak were attributed to the high degree of silver coverage on the
silica surface, which means that the silver nanoparticles were completely immobilized onto the silica particles with a
high degree of coverage. This result shows good correspondence with FE-SEM observation result. Therefore, it is
obviously concluded that PVP molecules successfully promoted the formation of silver nanoparticles without
interference of formation of combined structure between silver nanoparticles and silica surface.

3.2.2. The effect of reaction temperature and time

On the other hand, it is worth to notice that though the degree of apparent silver coverage is high, actually, a small
number of silver particles with a large size and a wide size distribution are immobilized onto the silica surface. It is

Fig. 3. UV–vis absorption spectra of the silica–silver composite particles prepared by polyol process at 120 8C for 4 h with silver concentration of
1000 ppm in the absence of PVP and in the presence of PVP.
 J.-M. Lee et al. / Materials Research Bulletin 41 (2006) 1407–1416 1411

Fig. 4. FE-SEM images of the silica–silver composite particles prepared by polyol process with silver concentration of 1000 ppm; (A) at 25 8C for
12 h and (B) after additional growth for 7 h with increasing reaction temperature.

thought that nucleation period was not enough and nucleation and growth steps occurred simultaneously during the
formation of silver particles. In order to obtain small particles having a narrow size distribution, nucleation and growth
steps are completely separated [28]. In addition, it is more advantageous to perform the preparation procedure in steps
during the preparation of composite particles consisting of dielectric core and metallic shell to prevent the formation of
large aggregates or particles [29].
To immobilize silver nanoparticles with small size and narrow size distribution onto the surface of silica
particles, the reaction proceeded at a low temperature for a relatively long time; the ethylene glycol solution
containing silica particles, AgNO3, and PVP was kept at 25 8C for 12 h under mild stirring. Fig. 4(A) shows FE-
SEM image of the resulting composite particles. In this photograph, it can be clearly observed that a large number
of silver particles with a small size are immobilized onto the silica surface, which means the size of silver particles
immobilized onto the silica surface greatly depend on the reaction temperate in the present system. Subsequently,
reaction temperature was increased up to 120 8C by stages as follows: temperature was kept at 40 8C for 4 h and 60,
90 and 120 8C for 1 h during the reaction, respectively. Fig. 4(B) shows the FE-SEM image of the resulting
composite particles. In this figure, it was observed that the size of silver particles was homogeneously increased
with relatively narrow size distribution. The UV–vis absorption spectra of the silica–silver composite particles at
different stages of immobilization process are shown in Fig. 5. In curve A, a broad absorption peak appears
about 490 nm, which indicates that very small silver nanoparticles are immobilized onto the silica surface.

Fig. 5. UV–vis absorption spectra of the silica–silver composite particles prepared by polyol process with silver concentration of 1000 ppm; at 25 8C
for 12 h and after additional growth for 7 h with increasing reaction temperature.
1412 J.-M. Lee et al. / Materials Research Bulletin 41 (2006) 1407–1416

After additional growth of silver particles, much higher and broader peak was observed as shown in Fig. 5. This
means that small silver particles grow to larger ones. Moreover, it is thought that the thickness of silver layer
increased after additional growth process. This result shows a good agreement with the FE-SEM observation results
in Fig. 4(A and B).
Therefore, it can be concluded that when polyol process is applied for the immobilization of silver nanoparticles
onto the large supports, it is possible to obtain extremely small silver particles and to control the size of silver particles
and the thickness of silver layer by control of reaction temperature and time. This size-controlled immobilization
route is explained by following two steps: (1) small silver particles are firstly formed on the silica surface and (2) these
small silver particles homogeneously grow to larger ones. These two steps are completely conducted in one-pot by
polyol process, which is attributed to the slower and more easily controllable reaction rate of the polyol reduction
method than that of general chemical reduction method using reducing agent such as hydrazine or sodium
borohydride. Especially, first step is more easily conducted by polyol process in the present system; extremely small
silver particles are easily immobilized onto the supports by polyol process at a low reaction temperature for a
relatively long reaction time.

3.2.3. The effect of concentration of silver precursor

At higher concentration of AgNO3 (10,000 ppm), this trend was more clearly proven. When the reaction proceeded
at 120 8C for 4 h, few silver particles with extremely large size were immobilized on the surface of silica particles as
shown in Fig. 6(A), whereas when the reaction was conducted at 25 8C for 12 h to give a sufficient nucleation time, as
we had expected, many small silver particles are immobilized onto the silica surface as shown in Fig. 6(B). As a result,
it is obvious that small silver particles with narrow size distribution are easily formed on the silica surface at a low
reaction temperature. Subsequently, additional growth step proceeded with increasing reaction temperature up to

Fig. 6. FE-SEM images of the silica–silver composite particles prepared by polyol process with the silver concentration of 10,000 ppm at (A) 120 8C
for 4 h, (B) 25 8C for 12 h and (C) after additional growth for 7 h with increasing reaction temperature.
 J.-M. Lee et al. / Materials Research Bulletin 41 (2006) 1407–1416 1413

120 8C according to the same schedule as already mentioned. Fig. 6(C) shows the FE-SEM image of the resulting
composite particles. After the additional reduction process, the size of individual silver particles immobilized onto the
surface of silica particles increased irregularly and the number of silver particles greatly decreased. This fact means
that despite slow reaction rate of the polyol process, the reaction rate of growth process is so fast that immobilized
small silver particles homogeneously grow to larger ones because too high concentration of silver precursor
accelerates the reaction rate. It is thought that they are finally detached from the surface of silica particles because they
are too large to be immobilized onto the surface by thiol groups. In addition, the glass reactor was coated with yellow
substance during the experiment. This phenomenon is generally attributed to the silver deposition on the inside wall of
glass reactor, which was not observed at the low concentration of silver precursor (1000 ppm). It is experimentally
well known that when silver nanoparticles are prepared by polyol process, large particles about over 50 nm in size are
more easily deposited on the surface of inside wall of glass reactor than small one. From these facts, it is obvious that
large particles growing over than about 50 nm during the growth process were detached from the silica surface and
deposited on the inside wall of glass reactor.
This can be more clearly explained by UV–vis absorption spectra of the samples shown in Fig. 6(B and C). In two
curves of Fig. 7, it was observed that the maximum peak intensity was decreased after growth process, which indicates
that the concentration of the silver particles in the solution decreased as a reaction proceeded. This result agrees with
the glass wall coating phenomenon and FE-SEM images in Fig. 6(B and C). As a result, it is clearly concluded that too
high silver precursor concentration interferes with the immobilization of well-defined silver nanoparticles due to the
fast reduction rate of silver precursor.

3.2.4. X-ray diffraction (XRD) measurement of the composite particles

The XRD patterns of samples prepared at silver concentration of 1000 ppm are shown in Fig. 8(A). In this figure,
the crystalline nature of silver nanoparticles prepared at 120 8C for 4 h (A-1) is well demonstrated by the diffraction
peaks that match a face-centered cubic (fcc) phase of silver. The peaks at 2u = 38.11, 44.35, 64.45 and 77.418 are
assigned as the (1 1 1), (2 0 0), (2 2 0) and (3 1 1) reflection lines, respectively, of fcc silver. The average crystallite
size of silver nanoparticles was also determined from the width of the reflection according to the Scherrer formula
D = 0.9l/(b cos u), where b is the full width at half-maximum (FWHM) of the peak, u the angle of diffraction and l is
the wavelength of the X-ray radiation (0.15418 nm) [30]. The crystallite size (value of D) calculated from the (1 1 1)
reflection of the cubic phase of silver was 8.4 nm.
For the sample prepared at 25 8C for 12 h (A-2), FWHMs of all peaks were broadened and peak intensities were
low, which suggest that their crystallite size was extremely small. After additional growth for 7 h with increasing
reaction temperature (A-3), the diffraction peaks clearly appeared and intensities were increased. This result indicates
that small silver particles grew to larger ones. The crystallite size of sample was similar to the result obtained at 120 8C
for 4 h (D = 8.4 nm).

Fig. 7. UV–vis absorption spectra for the silica–silver composite particles prepared by polyol process with the silver concentration of 10,000 ppm;
at 25 8C for 12 h reaction and after additional growth for 7 h with increasing reaction temperature.
1414 J.-M. Lee et al. / Materials Research Bulletin 41 (2006) 1407–1416

The XRD patterns of samples prepared at silver concentration of 10,000 ppm are shown in Fig. 8(B). The crystallite
nature of silver nanoparticles prepared at silver concentration of 10,000 ppm showed very similar trend to those of
samples prepared at silver concentration of 1000 ppm. The crystallite size of all samples, determined by Scherrer
equation using FWHMs, was calculated to about 8.4 nm.

3.3. Formation mechanism

Fig. 9 shows the schematic representation of the mechanism for the immobilization of the silver nanoparticles onto the
silica surface by polyol process. At the initial stage of the reaction, MPTMS-functionalized silica particles and PVP are
dissolved into the ethylene glycol. After complete dissolution of PVP, AgNO3 is added into the system. In this stage, silver
ions are bonded with thiol groups of the silica surface by the cleavage of an S–H bond and the spontaneous formation of an
S–Ag bond [19,20], and excess silver ions form complex with PVP by interaction between the hydrophilic pendant rings
of PVP and the silver ions [31,32]. In the second stage, Ag+ ions are reduced to Ag0 metal state by ethylene glycol and
PVP, and silver nuclei are formed on the surface of the MPTMS-functionalized silica particles; nuclei are created at the
silver ions bound to the thiol groups of the silica surface by the nucleation site role of Ag+ ions bound to thiol groups [12],
similar with the role of seed materials. Finally, silver nanoparticles are formed on the silica surface by growth of nuclei
[33]; reduced silver species such as silver atoms or clusters in the solution are deposited on the nuclei immobilized on the
silica surface [34], which is attributed to the slower reduction rate of polyol process than that of general chemical
reduction method using reducing agent such as hydrazine or sodium borohydride.

Fig. 8. XRD patterns of the silica–silver composite particles prepared by polyol process with silver concentration of (A) 1000 ppm and (B)
10,000 ppm; (A-1, B-1) at 120 8C for 4 h, (A-2, B-2) at 25 8C for 12 h, (A-3, B-3) at 25 8C for 12 h and additional growth for 7 h with increasing
reaction temperature.
 J.-M. Lee et al. / Materials Research Bulletin 41 (2006) 1407–1416 1415

Fig. 9. A schematic representation of the mechanism for the immobilization of the silver nanoparticles onto the silica surface by polyol process.

4. Conclusions

Silver nanoparticles were successfully immobilized onto the surface of silica particles by novel method involving
polyol process. Thiol groups at the surface of the silica particles were used as a chemical protocol to immobilize the
silver nanoparticles onto the surface of silica particles. On the basis of experimental results, it has been concluded that
when polyol process is applied for the immobilization of silver nanoparticles onto the large supports, it is possible to
obtain extremely small silver particles and to control the size of silver particles and the thickness of silver layer by
control of reaction temperature and time. This size-controlled immobilization route is explained by following two
steps: (1) small silver nanoparticles are firstly formed on the silica surface and (2) these small silver nanoparticles
homogeneously grow to larger ones. These two steps are completely conducted in one-pot by polyol process, which is
attributed to the slower and more easily controllable reaction rate of the polyol reduction method than that of general
chemical reduction method using reducing agent such as hydrazine or sodium borohydride. However, too high silver
precursor concentration, 10,000 ppm, interferes with the immobilization of the well-defined silver nanoparticles due
to the fast reduction rate of silver precursor.

Acknowledgement

This work was supported by Center for Ultramicrochemical Process Systems sponsored by KOSEF.

References

[1] D. Lawless, S. Kapoor, P. Kennepohl, D. Meisel, N. Serpone, J. Phys. Chem. 98 (1994) 9619.
[2] S.J. Oldenburg, R.D. Averitt, S.L. Westcott, N.J. Halas, Chem. Phys. Lett. 288 (1998) 243.
[3] Z.J. Jiang, C.Y. Liu, J. Phys. Chem. B 107 (2003) 12411.
[4] W. Wang, S.A. Asher, J. Am. Chem. Soc. 123 (2001) 12528.
[5] D. Wang, V. Salgueiriño-Maceira, L.M. Liz-Marzán, F. Caruso, Adv. Mater. 14 (2002) 908.
[6] S. Nie, S.R. Emory, Science 275 (1997) 1102.
[7] Z.L. Wang, C.T. Chan, W.Y. Zhang, Z. Chen, N.B. Ming, P. Sheng, Phys. Rev. B 64 (2001) 113108.
[8] C.W. Chen, T. Serizawa, M. Akashi, Chem. Mater. 11 (1999) 1381.
[9] S.A. Kalele, S.S. Ashtaputre, N.Y. Hebalkar, S.W. Gosavi, D.N. Deobagkar, D.D. Deobagkar, S.K. Kulkarni, Chem. Phys. Lett. 404 (2005) 136.
[10] V.G. Pol, A. Gedanken, J. Calderon-Moreno, Chem. Mater. 15 (2003) 1111.
[11] Y. Kobayashi, Y. Tadaki, D. Nagao, M. Konno, J. Colloid Interface Sci. 283 (2005) 601.
[12] J. Zhang, J. Liu, S. Wang, P. Zhan, Z. Wang, N. Ming, Adv. Funct. Mater. 14 (2004) 1089.
[13] J.M. Lee, D.W. Kim, Y.H. Lee, S.G. Oh, Chem. Lett. 34 (7) (2005) 928.
[14] F. Fievet, J.P. Lagier, B. Blin, B. Beaudoin, M. Figlarz, Solid State Ionics 32/33 (1989) 198.
[15] P.Y. Silvert, R. Herrera-Urbina, N. Duvauchelle, V. Vijayakrishnan, K. Tekaia-Elhsissen, J. Mater. Chem. 6 (4) (1996) 573.
[16] P.Y. Silvert, R. Herrera-Urbina, K. Tekaia-Elhsissen, J. Mater. Chem. 7 (2) (1997) 293.
[17] W. Stober, A. Fink, E. Bohn, J. Colloid Interface Sci. 26 (1968) 62.
[18] A. van Blaaderen, A. Vrij, in: H.E. Bergna (Ed.), The Colloid Chemistry of Silica, American Chemical Society, Washington, DC, 1994, p. 83
(Chapter 4).
1416 J.-M. Lee et al. / Materials Research Bulletin 41 (2006) 1407–1416

[19] Y. Cao, Y.S. Li, J.L. Tseng, D.M. Desiderio, Apectrochim. Acta Part A 57 (2001) 27.
[20] P.N. Floriano, O. Schlieben, E.E. Doomes, I. Klein, J. Janssen, J. Hormes, E.D. Poliakoff, R.L. McCarley, Chem. Phys. Lett. 321 (2000) 175.
[21] A. Dokoutchaev, J.T. James, S.C. Koene, S. Pathak, G.K.S. Prakash, M.E. Thompson, Chem. Mater. 11 (1999) 2389.
[22] J.H. Park, S.G. Oh, B.W. Jo, Mater. Chem. Phys. 87 (2004) 301.
[23] J.H. Park, Y.G. Kim, C. Oh, S.I. Shin, Y.C. Kim, S.G. Oh, S.H. Kong, Mater. Res. Bull. 40 (2005) 271.
[24] R.D. Badley, W.T. Ford, J.J. McEnroe, R.A. Assink, Langmuir 6 (1990) 792.
[25] A. Slistan-Grijalva, R. Herrera-Urbina, J.F. Rivas-Silva, M. Ávalos-Borja, F.F. Castillón-Barraza, A. Posada-Amarillas, Physica E 27 (2005)
104.
[26] G. Mie, Ann. Phys. 25 (1908) 377.
[27] D.S. Wang, M. Kerker, H. Chew, Appl. Opt. 19 (1980) 2135.
[28] N. Toshima, in: T. Sugimoto (Ed.), first ed., Fine Particles: Synthesis, Characterization, and Mechanisms of Growth, vol. 92, Marcel Dekker
Inc., New York, 2000 , p. 461 (Chapter 9.2).
[29] M. Schierhorn, L.M. Liz-Marzán, Nano Lett. 2 (1) (2002) 13.
[30] C. Suryanarayana, M. Grant Norton, X-Ray Diffraction: A Practical Approach, Plenum Press, New York, 1998, p. 207.
[31] B. Yin, H. Ma, S. Wang, S. Chen, J. Phys. Chem. B 107 (2003) 8898.
[32] H.S. Shin, H.J. Yang, S.B. Kim, M.S. Lee, J. Colloid Interface Sci. 274 (2004) 89.
[33] F. Caruso, Adv. Mater. 1 (13) (2001) 11.
[34] N. Toshima, in: T. Sugimoto (Ed.), first ed., Fine Particles: Synthesis, Characterization, and Mechanisms of Growth, vol. 92, Marcel Dekker
Inc., New York, 2000 , p. 453 (Chapter 9.1).