Colloids and Surfaces A: Physicochem. Eng.

Aspects 242 (2004) 175179

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, 150420 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 1015 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 (max = 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
[13]. 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 [610]. 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 [913].
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) [1419].
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 [2226].
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) [2729], 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-

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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 [9,2937], yet there is, but scanty, information
in the literature on the production of monodisperse metal
nanoparticles of specified dimensions and shapes [38,39].
In particular, we know the paper by Goia and Matijevic
about producing monodisperse spherical gold particles in
the size range from 80 nm to 5 m, which are formed by
the colloidal aggregation mechanism [38].
This paper presents the results of the research into the
possibility of formation of monodisperse spherical silver
nanoparticles by the colloidal aggregation mechanism.

2. Experimental
To investigate the process of formation of monodisperse silver nanoparticles, the following formulation of
the standard solution was used: CAgNO3 = 102 mol l1 ,
CAgNO3 :CKNaTart = 1:1, CAgNO3 :CNH3 = 1:2, wgelatin = 1%.
The process was carried out at 30 2 C, pH of the solution
was 8.5. K-Na-tartrate was chosen as the reductant because
it reduces silver ions readily in the solution bulk, that is, a
non-autocatalytic mechanism of the reaction prevails. Silver
is precipitated by its colloidal particles coagulating on a
substrate; hence, it can precipitate even on unactivated dielectric surfaces, i.e. without any catalytic particles thereon
[40]. To stabilize the ultrafine silver particles formed,
gelatin produced by the acidic technique was used, with the
isoelectric point in the pH range 8.59.2. To produce silver
nanoparticles, specified volumes of 0.1 M AgNO3 and of
13.8 M ammonia aqueous solutions were added to the solution of the stabilizer (gelatin) and then a specified volume
of 0.5 M K-Na-tartrate aqueous solution was added to the
mixture agitated vigorously by a magnetic stirrer. Silver
concentration in the reaction mixture was varied from 5
105 to 102 M, and pH was adjusted in the range between
1.0 and 10.0 by adding 1 M H2 SO4 or 1 M NaOH to AgNO3
and K-Na-tartrate containing solutions. The particle size
and shape were determined by TEM method with JEM-100
and EM-125 K instruments. The particle size distribution
was derived from the TEM data, using not less than 100
particles for the calculation. Specord M 40 spectrometer
was employed to register the absorption spectra of the sols
in 300800 nm wavelength region. X-ray diffraction analysis of the colloidal particles was carried out with DRON-2.0
X-ray diffractometer using Co K radiation.

3. Results and discussion

When K-Na-tartrate solution is added to ammoniacontaining AgNO3 solution, a colored silver sol is formed
in 57 min. The coloration becomes more intensive with
time, and 15 min after the reductant has been added, the

Fig. 1. Electron micrographs of silver particles in the sol produced by

the colloidal aggregation method from the standard solution, t (min): 1
(a); 5 (b) and 15 (c).

sol has a deep red-brown colour. According to TEM evidence, silver particles are almost immediately formed in
the solution (Fig. 1): lots of fine silver particles, 1030 nm
in size, are produced in the first 4050 s of the reaction
(Fig. 1a). In 5 min, spherical silver particles of sizes 170
and 540 nm appear in the sol along with the fine ones, that
is, a bimodal size distribution of the spherical particles is

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177

Fig. 2. Electron micrograph of a silver particle in the sol produced by

the colloidal aggregation method from the standard solution, t = 60 min.

observed (Fig. 1b). In 15 min, a sol is formed, still with a

bimodal size distribution of the spherical particles, but their
diameters become 390 and 625 nm and remain so on further
aging (Fig. 1c). In the sol, 56 and 16% of the particles are
the spherical ones and 390 and 625 nm sized, respectively. It
should be emphasized that the fine unaggregated 1030 nm
sized particles are present at all the reaction stages, their
amount continuously decreasing. Fig. 2 represents the TEM
image of a spherical silver particle at high magnification.
The silver sphere is seen to be made up of great many
small spheroidal silver particles roughly uniform in size
(1015 nm).
No spherical silver particles are formed when there is less
than 102 mol l1 AgNO3 in the reaction mixture (with the
same ratio of the solution components). With 103 mol l1
of AgNO3 , spheroidal silver particles are formed, not larger
than 220 nm, the fine particles (up to 30 nm in size) constituting over 50% of the sol particles. With still lower AgNO3
concentration (5 105 mol l1 ), the sol is formed comprising particles of different shapes (triangled, six-angled and
roundish ones), 1070 nm in size (Fig. 3).
Thus, the TEM investigation showed that in the
ammonia-tartrate solution rich in silver nitrate, the chemical reduction proceeds yielding spherical silver particles
which are formed by the non-directional colloidal aggregation mechanism, that is, the nuclei produced early in the
reaction grow up to give primary particles which then aggregate to form the spherical ones. X-ray diffraction data
also evidence that the spherical particles are not compact,
but formed by the colloidal aggregation mechanism: the
diffraction peaks of silver are weak and base-broadened
(Fig. 4). If the solutions low in AgNO3 are used, silver
particles grow by LaMer mechanism, with concurrent crystallization processes. The low trend of silver to aggregate
at low AgNO3 levels seems to be due to low silver nuclei
concentrations. With high AgNO3 levels, there is a burst of
nuclei, which quickly grow, give primary particles and then
aggregate into spheres.

Fig. 3. Electron micrograph of silver particles in the sol produced by

the colloidal aggregation method from the solution of the following
formulation: CAgNO3 = 5 105 mol l1 , CNH3 = 104 mol l1 , CKNaTart
= 5 105 mol l1 , wgelatin = 1% at pH 8.5 and t = 60 min.

To look into the possibility of producing monodisperse

spherical silver particles of various sizes, we studied the
effect of pH of solutions on the characteristics of the silver
nanoparticles formed by the colloidal aggregation method.
Fig. 5 shows TEM images of the silver particles in the
sols produced at different solution pH, the precipitation
time being 60 min. Spherical silver particles were found to
be formed at all the pH values, except for pH 1.0, when
the sol comprised predominantly spheroidal silver particles
1040 nm in size (Fig. 5a). Spherical silver particles were
observed to form beginning from pH 2.0 and on, with a
general increase in their diameter accompanied by their
relative number growing. Spherical silver particles can be
produced of different sizes and size uniformity varying with
pH: at pH 2.0, 3.0, 5.0 and 10.0, monodisperse particles
are formed with diameters 150, 380, 535 and 420 nm, respectively (Fig. 5bd); at pH 7.0, the sol is composed of
polydisperse particles 210770 nm in diameter, and at pH
8.5, a bimodal size distribuion is observed, the respective
particle diameters being 390 and 625 nm. At pH below 8.0,
less than 30% of the silver particles formed are spherical,
main body of the particles being the small ones (up to
30 nm). At pH over 8.0, more than 70% of the particles are
spherical (85% of the particles in the sol formed at pH 10.0
are the spherical ones) (Fig. 5d).
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 the consequent aggregation of the primary particles. At pH below 8.0,
the high surface charge together with the efficient protective
action of gelatin considerably hinders the particle aggregation. Besides, the reduction rate is decreased with decreasing pH, providing conditions for a slow particle growth by
LaMer mechanism, and accordingly, hindering the growth
of the particles by the colloidal aggregation mechanism.

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- Ag

100

90

80

70

60

50

40

30

Fig. 4. XRD data of silver particles in the sol produced by the colloidal aggregation method from the standard solution, t = 60 min.

Optical spectra of the silver sols produced at different pH

are shown in Fig. 6. The spectroscopy evidence as well as
TEM data suggests the colloidal aggregation mechanism for
the formation of monodisperse spherical silver particles. The
sols produced at pH 8.0 and 10.0, although differing in the
size and distribution of the particles, have virtually the same
spectra characterized by the absorption maximum in the visible region at 420 nm. There is no ultraviolet absorption.
The absorption band in the region of silver plasmon resonance (max = 420 nm) characteristic of colloidal particles
[4143] suggests that the spherical particles over 300 nm in
size behave as silver nanoparticles not more than 20 nm in
size. The sols formed at pH varied over the range from 1.0

to 7.0 have a substantial ultraviolet absorption, with a shoulder at 400450 nm, dropping to = 715 nm. Optical density
of the sols is also observed to change nonlinearly with pH.
There may be several reasons for the peculiarities of the optical spectra of the sols. First, the reduction in the pH range
from 1.0 to 7.0 being slow, the sols contain Ag+ ions absorbing in ultraviolet region [44]. Second, these ions adsorb on
silver particles causing the plasmon resonance band of the
latter to red-shift, with the optical density at max decreasing
and the absorption band broadening [14]. Third, 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].

Fig. 5. Electron micrographs of silver particles in the sol produced by the colloidal aggregation method from the standard solution, t = 60 min, pH: 1.0
(a), 3.0 (b), 5.0 (c) and 10.0 (d).

I.M. Yakutik et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 242 (2004) 175179

Absorption

2,0
1,6
1,2
0,8
0,4

3
2
4
5
1
7
6

0,0
400

500

600

700

800

, nm
Fig. 6. UVvis absorption spectra of the sols produced by the colloidal
aggregation method from the standard solution, t = 60 min, pH: 1 (1), 2
(2), 3 (3), 5 (4), 7 (5), 8.5 (6), 10 (7); (6) and (7), diluted a hundred times.

Thus, in this paper, we show the possibility to produce

monodisperse spherical silver particles using K-Na-tartrate
to reduce silver ions in the presence of gelatin. The spherical particles as evidenced by TEM, optical spectroscopy and
X-ray diffraction data are comprised of 1015 nm sized particles, and hence, have been formed by the colloidal aggregation mechanism. The diameter of the spherical particles
produced can be varied over a wide range between 159 and
700 nm by changing pH of the initial solutions. The most efficient colloidal aggregation was found to occur at pH 10.0,
when most of the particles (over 85%) were monodisperse
spheres, 420 nm in diameter. Note that the spherical silver
nanoparticles are tolerant to a short-term ultrasound exposure and can be separated as a solid phase by precipitating
them with organic solvents, such as acetone or ethanol. The
optical spectra of the sols comprising monodisperse spherical silver particles over 300 nm in size were found to demonstrate the absorption band in the region of silver plasmon
absorption (max = 420 nm), which is characteristic of colloidal particles.

References
[1]
[2]
[3]
[4]
[5]
[6]
[7]

E. Matijevic, Langmuir 10 (1994) 8.

E. Matijevic, Annu. Rev. Mater. Sci. 15 (1985) 483.
H.K. Bowen, Sci. Am. 47 (1986) 225.
V.K. LaMer, Ind. Eng. Chem. 44 (1952) 1270.
V.K. LaMer, R.H. Dinegar, J. Am. Chem. Soc. 72 (11) (1950) 4847.
H. Edelson, A.M. Glaeser, J. Am. Ceram. Soc. 71 (1988) 225.
M. Ocana, R. Rodriguez-Clementr, S.J. Serna, Adv. Mater. 7 (12)
(1995) 212.

179

[8] V. Privman, D.V. Goia, J. Park, E. Matijevic, J. Colloid Int. Sci. 213
(1999) 36.
[9] W.P. Hsu, L. Ronnquist, E. Matijevic, Langmuir 4 (1988) 31.
[10] T. Sugimoto, E. Matijevic, J. Colloid Int. Sci. 74 (1980) 227.
[11] A.V. Baaderen, J.V. Geest, J. Vrij, J. Colloid Int. Sci. 154 (1992)
481.
[12] P.J. Murphy, A.M. Posner, J.P. Quirk, J. Colloid Int. Sci. 56 (1976)
284.
[13] M. Andres-Verges, A. Mifsud, C.J. Serna, J. Chem. Soc. Faraday
Trans. 86 (1990) 959.
[14] P. Mulvaney, Langmuir 12 (1996) 788.
[15] A. Henglein, J. Phys. Chem. 97 (1993) 5457.
[16] G. Chumanov, K. Sokolov, B.V. Gregory, T.M. Cotton, J. Phys.
Chem. 99 (1995) 9466.
[17] I. Nabiev, G.D. Baranov, I. Chourpa, A. Beljebbar, G.D. Sockalingum, M. Manfait, J. Phys. Chem. 99 (1995) 1608.
[18] C.G. Blatchford, O. Silman, M. Karker, J. Phys. Chem. 87 (1983)
2503.
[19] S. Schneider, P. Halbig, H. Gray, U. Nickel, Photochem. Photobiol.
60 (6) (1994) 605.
[20] N. Prokes, K.L. Wang, MRS Bull. 24 (8) (1999) 13.
[21] Y. Gui, Q. Wei, H. Park, C.M. Lieber, Science 293 (2001) 1289.
[22] A. Henglein, Chem. Mater. 10 (1988) 444.
[23] A. Loginov, V. Gorbunov, T. Boitsova, Zh. Obshchei Khimii, J. Gen.
Chem. 67 (1997) 189 (in Russian).
[24] A. Henglein, Chem. Phys. Lett. 154 (1989) 473.
[25] T. Ung, M. Giersig, D. Dunstan, P. Mulvaney, Langmuir 13 (1997)
1773.
[26] J. Turkevich, P.C. Stevenson, J. Hillier, Disc. Faraday Sci. (1951) 55.
[27] N.R. Jana, L. Gearheart, C.J. Murphy, Chem. Comm. (2001) 617.
[28] A.V. Simakin, V.V. Voronov, G.A. Shafeev, R. Brayner, F.
Bozon-Verduraz, Chem Phys. Lett. 348 (2001) 182.
[29] V.M. Cepak, C.R. Martin, J. Phys. Chem. B 102 (1998) 9985.
[30] M.A. El-Sayed, Acc. Chem. Res. 34 (4) (2001) 257.
[31] R. Jin, Yu.W. Cao, Ch.A. Mirkin, K.L. Kelly, G.C. Schatz, J.G.
Zheng, Science 294 (2001) 1901.
[32] M. Ocana, W.P. Hsu, E. Matijevic, Langmuir 7 (1991) 2911.
[33] A. Garg, E. Matijevic, Langmuir 4 (1988) 38.
[34] T. Ishikava, E. Matijevic, Langmuir 4 (1988) 26.
[35] A. Chittofrati, E. Matijevic, Colloids Surf. A 48 (1990) 65.
[36] S-H. Lee, Y-S. Her, E. Matijevic, J. Colloid Int. Sci. 186 (1997)
193.
[37] M. Niederberger, F. Krumeich, K. Heteschweiler, R. Nesper, Chem.
Mater. 14 (2002) 78.
[38] D.V. Goia, E. Matijevic, Colloid Surf A. 146 (1999) 139.
[39] D.L. Hyning, Ch.F. Zukoski, Langmuir 14 (1998) 7034.
[40] V.V. Sviridov, T.N. Vorob, eva, T.V. Gaevskaya, L.I. Stepanova, in:
V.V. Sviridov (Ed.), Khimicheskoe osazhdenie metallov is vodnykh
rastvorov (Electroless metal deposition from water solutions), Universitetskoe Publishers, Minsk, 1987 (in Russian).
[41] E. Klein, H.J. Metz, J. Photogr. Sci. Eng. 5 (1961) 5.
[42] C.R. Berry, D.C. Skillman, J. Photogr. Sci. Eng. 17 (1969) 145.
[43] P.V. Ashrit, G. Bader, S. Badilescu, F.E. Girouard, L.Q. Nguyen,
V.V. Truong, J. Appl. Phys. 74 (1993) 602.
[44] B.G. Ershov, N.L. Suhov, Izvestiya Akademii Nauk, Ser. Chim. 6
(1996) 1429 (in Russian).
[45] H. Bixia, D. Yongping, Y. Jun, Z. Zhixia, J. Soc. Photogr. Sci.
Technol. Jpn. 65 (5) (2002) 319.