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Colloids and Surfaces A: Physicochem. Eng.

Aspects 242 (2004) 175–179

The formation of monodisperse spherical silver particles
I.M. Yakutik, G.P. Shevchenko∗ , S.K. Rakhmanov
Psyk-Chem. Research Institute, Leningradskaya 14, Minsk 220050, Belarus
Received 3 November 2003; accepted 23 April 2004
Available online 20 June 2004

Abstract
The process of formation of monodisperse spherical silver particles in gelatin-stabilized ammonia-tartrate electroless deposition solution
has been investigated. The production of monodisperse spherical silver particles, 150–420 nm in size, was shown to be feasible, the particle
diameter depending on pH of the solution. The spherical silver particles, as evidenced by TEM, optical spectroscopy and X-ray diffraction
data, were comprised of 10–15 nm sized particles, and hence, were formed by the colloidal aggregation mechanism. The optical spectra of the
sols largely composed of monodisperse silver particles over 300 nm in size demonstrate the absorption band in the region of silver plasmon
absorption (λmax = 420 nm), which is characteristic of colloidal particles.
© 2004 Elsevier B.V. All rights reserved.
Keywords: Monodisperse colloid; Colloidal aggregation; Silver

1. Introduction
Monodisperse colloids containing the particles uniform in
their size and shape comprise a field of investigations which
resulted in numerous applications being of technological interest for the production of ceramics, pigments and catalysts
[1–3]. The early work on synthesizing monodisperse colloids
was based on LaMer theory assuming spontaneous nucleation followed by diffusion growth of the nuclei [4,5]. However, the experimental evidence amassed by now showed
that the mechanism of formation of monodisperse nanoparticles of different shapes and sizes is far more complicated
than had been originally suspected. It includes several steps:
nuclei forming, nuclei growing via diffusion mechanism to
give primary particles and the latter aggregating [6–10]. The
mechanism of the colloidal aggregation is not yet entirely
elucidated. The reason for the particle size and shape selection remains obscure, that is, there is no way of telling
what makes the forming colloidal systems monodisperse,
and when the colloidal aggregation is directed so as to yield
spheres, platelets, rods or ellipsoids [9–13].
Colloidal particles of noble metals, among them silver,
are of great interest due to their unique optical, electrical
and other properties which make possible their use in micro∗

Corresponding author.
E-mail address: shevchenk@bsu.by (G.P. Shevchenko).

0927-7757/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2004.04.069

electronics, non-linear optics and in the analytical method
of surface-enhanced Raman scattering (SERS) [14–19].
One-dimensional nanostructures of noble metals act as
components of nanoscale electronic devices [20,21]. The
ways to produce colloids of noble metals by reducing their
ions in solution with strong reductants, for instance, with
sodium borohydride, are widely covered in the literature,
but as a rule, they do not allow to produce metal particles
of specified sizes with narrow size distributions [22–26].
To synthesize colloids of noble metals with a narrow size
distribution, a two-step process is often used, involving
the formation of nuclei as the first step (forming a seeding
sol), and the subsequent overgrowth thereupon from rather
diluted solutions by the autocatalytic mechanism as the
second one [19,27]. Considerable recent attention has been
focused on using laser radiation to produce noble metal
nanoparticles of various shapes (nanodiscs, nanowires and
nanorods) [27–29], and not only to synthesize metal colloids with definitely shaped particles but also to modify the
shape of the particles as well as to control their dimensions
[30,31]. Until recently, it was the synthesis of fine particles
(<10 nm) that most of the investigations were aimed at because of the unique properties of the noble metal nanoparticles. However, larger particles (>100 nm) are required for
many applications, particularly, in electronics. Controlling
sizes and shapes of metal nanoparticles (among them silver
ones) remains a challenge. There are lots of papers de-

5. a bimodal size distribution of the spherical particles is . the Fig. K-Na-tartrate was chosen as the reductant because it reduces silver ions readily in the solution bulk. with the isoelectric point in the pH range 8.0 X-ray diffractometer using Co K␣ radiation. wgelatin = 1%. we know the paper by Goia and Matijevic about producing monodisperse spherical gold particles in the size range from 80 nm to 5 ␮m.176 I. hence. using not less than 100 particles for the calculation. pH of the solution was 8. 1): lots of fine silver particles. gelatin produced by the acidic technique was used. According to TEM evidence. but scanty.5–9. without any catalytic particles thereon [40]. yet there is.8 M ammonia aqueous solutions were added to the solution of the stabilizer (gelatin) and then a specified volume of 0. spherical silver particles of sizes 170 and 540 nm appear in the sol along with the fine ones. silver particles are almost immediately formed in the solution (Fig. information in the literature on the production of monodisperse metal nanoparticles of specified dimensions and shapes [38. The coloration becomes more intensive with time. Experimental To investigate the process of formation of monodisperse silver nanoparticles. Results and discussion When K-Na-tartrate solution is added to ammoniacontaining AgNO3 solution. CAgNO3 :CKNaTart = 1:1. Electron micrographs of silver particles in the sol produced by the colloidal aggregation method from the standard solution. 3.0 by adding 1 M H2 SO4 or 1 M NaOH to AgNO3 and K-Na-tartrate containing solutions. which are formed by the colloidal aggregation mechanism [38]. Aspects 242 (2004) 175–179 scribing the procedures of synthesizing monodisperse oxide and hydroxide colloids where uniformly sized particles of the disperse phase are formed by the colloidal aggregation mechanism [9. that is. In 5 min.5 M K-Na-tartrate aqueous solution was added to the mixture agitated vigorously by a magnetic stirrer. 10–30 nm in size. Silver concentration in the reaction mixture was varied from 5 × 10−5 to 10−2 M. To produce silver nanoparticles. / Colloids and Surfaces A: Physicochem. The particle size and shape were determined by TEM method with JEM-100 and EM-125 K instruments. This paper presents the results of the research into the possibility of formation of monodisperse spherical silver nanoparticles by the colloidal aggregation mechanism. The particle size distribution was derived from the TEM data.29–37]. and 15 min after the reductant has been added. sol has a deep red-brown colour. a colored silver sol is formed in 5–7 min. The process was carried out at 30 ± 2 ◦ C. i. specified volumes of 0. To stabilize the ultrafine silver particles formed. X-ray diffraction analysis of the colloidal particles was carried out with DRON-2. 2. a non-autocatalytic mechanism of the reaction prevails. In particular. Silver is precipitated by its colloidal particles coagulating on a substrate. that is. Eng. and pH was adjusted in the range between 1. t (min): 1 (a).e. Yakutik et al. are produced in the first 40–50 s of the reaction (Fig. 1. it can precipitate even on unactivated dielectric surfaces.2. “Specord M 40” spectrometer was employed to register the absorption spectra of the sols in 300–800 nm wavelength region.39].0 and 10. 1a). CAgNO3 :CNH3 = 1:2.1 M AgNO3 and of 13.M. the following formulation of the standard solution was used: CAgNO3 = 10−2 mol l−1 . 5 (b) and 15 (c).

Fig. It should be emphasized that the fine unaggregated 10–30 nm sized particles are present at all the reaction stages. which quickly grow. there is a burst of nuclei. At pH below 8. 2 represents the TEM image of a spherical silver particle at high magnification. the nuclei produced early in the reaction grow up to give primary particles which then aggregate to form the spherical ones.5 and t = 60 min. Electron micrograph of silver particles in the sol produced by the colloidal aggregation method from the solution of the following formulation: CAgNO3 = 5 × 10−5 mol l−1 .M. 56 and 16% of the particles are the spherical ones and 390 and 625 nm sized. t = 60 min. Spherical silver particles were observed to form beginning from pH 2. Besides. when the sol comprised predominantly spheroidal silver particles 10–40 nm in size (Fig. No spherical silver particles are formed when there is less than 10−2 mol l−1 AgNO3 in the reaction mixture (with the same ratio of the solution components). With 10−3 mol l−1 of AgNO3 . at pH 7. 3. The silver sphere is seen to be made up of great many small spheroidal silver particles roughly uniform in size (10–15 nm). 10–70 nm in size (Fig. with a general increase in their diameter accompanied by their relative number growing. 1c).0 and 10. 2. Yakutik et al. / Colloids and Surfaces A: Physicochem. and accordingly. give primary particles and then aggregate into spheres.0. that is. still with a bimodal size distribution of the spherical particles. except for pH 1. but formed by the colloidal aggregation mechanism: the diffraction peaks of silver are weak and base-broadened (Fig. respectively (Fig. .0 and on. more than 70% of the particles are spherical (85% of the particles in the sol formed at pH 10. 1b). Fig. their amount continuously decreasing. the sol is composed of polydisperse particles 210–770 nm in diameter. and at pH 8. the respective particle diameters being 390 and 625 nm. the precipitation time being 60 min. Eng. 5a). To look into the possibility of producing monodisperse spherical silver particles of various sizes. respectively. 5d). CNH3 = 10−4 mol l−1 . If the solutions low in AgNO3 are used. In the sol.0. Electron micrograph of a silver particle in the sol produced by the colloidal aggregation method from the standard solution. the high surface charge together with the efficient protective action of gelatin considerably hinders the particle aggregation.5. the reduction rate is decreased with decreasing pH. we studied the effect of pH of solutions on the characteristics of the silver nanoparticles formed by the colloidal aggregation method. 3. a bimodal size distribuion is observed. less than 30% of the silver particles formed are spherical. Spherical silver particles can be produced of different sizes and size uniformity varying with pH: at pH 2.0. with the consequent aggregation of the primary particles. main body of the particles being the small ones (up to 30 nm).I. the TEM investigation showed that in the ammonia-tartrate solution rich in silver nitrate. The increase in the percentage of the monodisperse spherical particles with pH seems to be related to a decrease of the surface charge contribution to the system stability for pH approaching the isoelectric point of gelatin. With high AgNO3 levels. silver particles grow by LaMer mechanism. not larger than 220 nm. the sol is formed comprising particles of different shapes (triangled. X-ray diffraction data also evidence that the spherical particles are not compact.0. but their diameters become 390 and 625 nm and remain so on further aging (Fig. wgelatin = 1% at pH 8.0. 3). 380. six-angled and roundish ones). 4).0 are the spherical ones) (Fig. At pH below 8.0. the chemical reduction proceeds yielding spherical silver particles which are formed by the non-directional colloidal aggregation mechanism. Aspects 242 (2004) 175–179 177 Fig. monodisperse particles are formed with diameters 150.0. observed (Fig. The low trend of silver to aggregate at low AgNO3 levels seems to be due to low silver nuclei concentrations. CKNaTart = 5 × 10−5 mol l−1 . a sol is formed. At pH over 8. Spherical silver particles were found to be formed at all the pH values. 535 and 420 nm. Fig. With still lower AgNO3 concentration (5 × 10−5 mol l−1 ). 5b–d).0. In 15 min. the fine particles (up to 30 nm in size) constituting over 50% of the sol particles. spheroidal silver particles are formed. 5. hindering the growth of the particles by the colloidal aggregation mechanism. 5 shows TEM images of the silver particles in the sols produced at different solution pH. with concurrent crystallization processes. Thus. providing conditions for a slow particle growth by LaMer mechanism.

. Aspects 242 (2004) 175–179 .M. 5.0 (d). XRD data of silver particles in the sol produced by the colloidal aggregation method from the standard solution. / Colloids and Surfaces A: Physicochem. pH: 1.0 (c) and 10. Yakutik et al. The sols produced at pH 8. There is no ultraviolet absorption. have virtually the same spectra characterized by the absorption maximum in the visible region at 420 nm.0 (b). 5. Electron micrographs of silver particles in the sol produced by the colloidal aggregation method from the standard solution.0 and 10. Optical density of the sols is also observed to change nonlinearly with pH. t = 60 min. dropping to λ = 715 nm. t = 60 min. the reaction rate in this pH range can change non-monotonically with pH because of the possible Ag+ complexation with gelatin depending largely on pH of the solution [45].0 (a). Fig. The spectroscopy evidence as well as TEM data suggests the colloidal aggregation mechanism for the formation of monodisperse spherical silver particles. Second. these ions adsorb on silver particles causing the plasmon resonance band of the latter to red-shift. the reduction in the pH range from 1. with a shoulder at 400–450 nm. There may be several reasons for the peculiarities of the optical spectra of the sols. First. the sols contain Ag+ ions absorbing in ultraviolet region [44].0 have a substantial ultraviolet absorption. The sols formed at pH varied over the range from 1.0 to 7. Optical spectra of the silver sols produced at different pH are shown in Fig. Eng. Third.178 I. although differing in the size and distribution of the particles. 4.0. 3.0 to 7. The absorption band in the region of silver plasmon resonance (λmax = 420 nm) characteristic of colloidal particles [41–43] suggests that the spherical particles over 300 nm in size behave as silver nanoparticles not more than 20 nm in size.Ag 100 90 80 70 60 2Θ 50 40 30 Fig. with the optical density at λmax decreasing and the absorption band broadening [14].0 being slow. 6.

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