© Copyright 2000 by the American Chemical Society VOLUME 104, NUMBER 35, SEPTEMBER 7, 2000

ARTICLES

Structure and Stability of Silver Nanoparticles in Aqueous Solution Produced by Laser

Ablation
Fumitaka Mafuné, Jun-ya Kohno, Yoshihiro Takeda, and Tamotsu Kondow*
Cluster Research Laboratory, Toyota Technological Institute, and East Tokyo Laboratory,
Genesis Research Institute, Inc., 717-86 Futamata, Ichikawa, Chiba 272-0001, Japan
Hisahiro Sawabe
Central Technical Research Laboratory, Nippon Mitsubishi Oil Corporation, 8 Chidori-cho,
Naka-ku, Yokohama 231-0815, Japan
ReceiVed: May 17, 2000; In Final Form: June 26, 2000

Silver nanoparticles were produced by laser ablation of a metal silver plate in aqueous solutions of surfactants,
CnH2n+1SO4Na (n ) 8, 10, 12, 16). The nanoparticles thus produced were characterized by electron microscopy
and UV-visible absorption spectroscopy. The abundances of the nanoparticles before and after centrifugation
were measured as a function of the surfactant concentration. The concentration dependence of the abundance
implies that the surfactant coverage and the charge state on the nanoparticle surface are closely related to the
stability of the nanoparticles in the solutions. The nanoparticles tend to be aggregated when the coverage is
less than unity, while they are very stable when the surface is covered with a double layer of the surfactant
molecules.

1. Introduction co-workers have prepared subnanometer-sized silver particles,

Intensive investigations on metal nanoparticles suspended in
solutions have been undertaken extensively because of their size-
dependent characteristic properties.1-5 In these studies, one of
the key issues is to develop a practical method for preparation
of nanoparticles suspended in liquid. Pileni and co-workers have
synthesized metal nanoparticles in reversed micelles by chemical
reduction of metal ions in them.6,7 The size of the nanoparticles
thus produced is controlled by the volume of the reversed
micelles, because the volume depends critically on the molar
ratio of the surfactant to water inside the reversed micelles. El-
Sayed and co-workers have reported a reductive synthesis of
platinum nanoparticles in a solution containing platinum ions
and capping polymer molecules. They have shown that the shape
of platinum nanoparticles can be varied by changing the molar
fraction of the capping polymer in the solution.8,9 Tichelaar and
* Corresponding author. E-mail: kondow@mail.cluster-unet.ocn.ne.jp.
10.1021/jp001803b CCC: $19.00 © 2000 American Chemical Society
Published on Web 08/17/2000
which is free of any stabilizing polymer, by anodic dispersion
of a silver electrode in an aqueous NaOH solution.10
Apart from these chemical syntheses, new methodology has
been developed to produce nanoparticles by laser ablation of a
metal plate in a solution by Henglein et al.11,12 and others.13-15
We have shown that the size distribution of the silver nano-
particles produced by laser ablation in an aqueous solution
containing sodium dodecyl sulfate (SDS) as a surfactant is
determined by particle growth in a plume by the laser ablation
and its termination by SDS coating.16 Evidently, SDS plays an
important role in determining stability and size of the nanopar-
ticles, because the termination of the nanoparticle growth is
controlled by the diffusion and the attachment rates of SDS on
the nanoparticle. It is expected, therefore, that the size distribu-
tion and the stability of the nanoparticles depend critically on
the properties of the surfactant employed.
In the present study, we examined nanoparticle formation in
8334 J. Phys. Chem. B, Vol. 104, No. 35, 2000
Figure 1. Electron micrograph (panel a) and an absorption spectrum
(panel b) of silver nanoparticles produced by 532 nm laser ablation of
a silver metal plate in a 0.01 M aqueous solution of SDS.
solutions containing surfactants, CnH2n+1SO4Na, with different
lengths of the hydrocarbon chain. The size and the stability of
the nanoparticles produced in the different solutions were
observed by electron microscopy and optical absorption spec-
troscopy, in combination with a centrifugal precipitation method.
2. Experimental Section
Silver nanoparticles were produced by laser ablation of a
silver metal plate in an aqueous solution of a different surfactant;
CnH2n+1SO4Na with n ) 8, 10 (Kanto Chemical Co., Inc.), that
with n ) 12 (Nacalai Tesque, Inc. >95%; denoted as SDS
hereafter), and that with n ) 14 (Tokyo Kasei Kogyo Co., Ltd.
containing ca. 40% sodium stearyl sulfate). The metal plate
(>99.99 in purity) was placed on the bottom of a glass vessel
filled with a 10 mL aqueous solution of a surfactant and was
irradiated with the second harmonic (532 nm) output of a
Quanta-ray GCR-170 Nd:YAG laser focused by a lens having
the focal length of 250 mm. A typical pulse width and a
repetition rate were ∼10 ns and 10 Hz, respectively. A spot
size of the laser beam was adjusted within 1-3 mm in diameter
by changing the distance between the lens and the metal plate.
The output of the 532 nm laser (<90 mJ/pulse) was monitored
by a Scientech power meter.
The solution became colored under irradiation of the laser.
A small amount of the solution was extracted from the glass
vessel by a pipet, and half of it was preserved in a reservoir
without centrifugation, while the other half was distributed
among several 1 mL Eppendorf tubes, which were centrifuged
at 15 000 rpm in a TOMY MX-150 microcentrifuge for ∼10
min. After the centrifugation, a clear portion of the solution on
the top of the tubes was carefully extracted by a micropipet.
The absorption spectrum of the clear portion was measured
Mafuné et al.
repeatedly at least five times by a Shimadzu UV-1200 spec-
trometer, and the spectra obtained by these different runs were
accumulated in an NEC computer so as to obtain the spectrum
with a good signal-to-noise ratio.
An electron micrograph was observed by a transmission
electron microscope (JEOL JEM-100S ×50000). A drop of the
clear portion was placed on a copper grid, which was coated
with collodion and subsequently hydrophilic-sputtered in ad-
vance, and was dried by heating to 320 K. After this procedure
was repeated three times, the grid was washed in water in order
to remove free surfactant molecules. The size distributions of
the nanoparticles produced were obtained by measuring the
diameter of more than 1000 particles viewed in the micrographs.
3. Results
Figure 1 shows an electron micrograph (panel a) and an
absorption spectrum (panel b) of silver nanoparticles produced
by 532 nm laser ablation of a silver metal plate in a 0.01 M
aqueous solution of SDS. The micrograph demonstrates that
the silver nanoparticles are nearly spherical with a diameter of
∼10 nm. The absorption spectrum of the solution containing
the silver nanoparticles exhibits an intense peak at 400 nm and
a tail part of a broad band in the UV region (<320 nm). The
absorption spectrum is identical with that of silver nanoparticles
prepared chemically by reduction of silver ions in reversed
micelles and has been well reproduced by theory.17-26 The
spectral feature of the broad band in the UV region does not
change significantly with the size of the nanoparticle.6,7 This
fact allows us to adopt the absorbance at 250 nm as a measure
of the abundance of the silver nanoparticles in the solution.
Parts a-c of Figure 2 represent absorption spectra of silver
nanoparticles produced in 0.003, 0.01, and 0.1 M aqueous
solutions of SDS, respectively. The spectral features such as
the peak at 400 nm and the broad band in the UV region do
not change significantly, while the absorbance depends strongly
on the SDS concentration. In each spectrum, also shown is an
absorption spectrum of a clear portion of the solution on the
top of an Eppendorf tube after the centrifugation (dotted line
in the spectrum). The centrifugation causes no effect on the
spectral shape, but does cause a drastic reduction in the
absorbance for the 0.003 and 0.1 M solutions, and only a slight
reduction for the 0.01 M solution.
Figure 3 illustrates the abundance of the silver nanoparticles
before (solid circle) and after the centrifugation (open circle)
as a function of the SDS concentration. The abundances before
and after the centrifugation are denoted as I0 and Icentrifugation,
respectively. As shown in Figure 3, I0 increases up to 0.03 M
and then decreases with an increase in the SDS concentration,
while Icentrifugation exhibits similar but not identical concentration
dependence. To clarify the difference in their concentration
dependence, the ratio of precipitation by the centrifugation,
Rprecipitation, defined by
Rprecipitation ) (I0 - Icentrifugation)/I0 (1)
is plotted also in Figure 3 (shown as solid squares). As the SDS
concentration increases, Rprecipitation decreases up to 0.01 M and
then increases. The electron micrographs show that the size
distribution is influenced only slightly by the centrifugation.
The sharp rise of Rprecipitation above 0.01 M is ascribable partly
to the salting-out effect, as described in section 4.2. To evaluate
the contribution of the salting-out effect, stable nanoparticles
were prepared in advance at the concentration of 0.01 M, at
which the most stable nanoparticles are produced. Then, 0.026
Silver Nanoparticles in Aqueous Solution
Figure 2. Absorption spectra of silver nanoparticles produced in 0.003, 0.01, and 0.1 M aqueous solutions of SDS before (solid line) and after
(dotted line) the centrifugation.
Figure 3. Abundance of the silver nanoparticles before (solid circles)
and after the centrifugation (open circles) as a function of the SDS
concentration. The ratio of precipitation (see text for definition) is
plotted by solid square.
g of SDS was added to a 1 mL SDS solution containing the
most stable nanoparticles; the mixture should have a SDS
concentration of 0.1 M. The Rprecipitation value attributable to the
salting-out effect was obtained to be 0.19 ( 0.03. The rest
should be attributed to a different cause (see section 4.2). Most
of the precipitants by the centrifugation were dispersed again
in the solution by stirring with addition of water, whereas those
resulting from the centrifugation of the nanoparticles produced
in a lower concentration than 0.01 M were not dispersed again
at all.
Figure 4 shows the concentration dependences of the nano-
particles in aqueous solutions of CnH2n+1SO4Na (n ) 8, 10,
12, 16). The concentration dependence for each sample before
the centrifugation (shown as solid circles) exhibits commonly
a concentration-independent portion in the <10-6 M range, and
a concentration-dependent portion in the >10-6 M range. Note
that silver nanoparticles were produced even in pure water by
the laser ablation. The open circles in each panel show the
abundance of the silver nanoparticles after the centrifugation.
The nanoparticles produced in the low concentration range are
precipitated completely by the centrifugation, but those in the
high concentration range remain in the solution. There is a
general tendency in all the surfactant solutions that the silver
J. Phys. Chem. B, Vol. 104, No. 35, 2000 8335
nanoparticles produced in the higher concentration range are
more abundant in the solution of a surfactant with a longer
hydrocarbon chain (larger n).
4. Discussion
4.1. Formation of Silver Nanoparticles in Solution. As
shown in the electron micrograph of Figure 1a, nearly spherical
silver nanoparticles with ∼10 nm in diameter were produced
by the laser ablation of the silver metal plate in the aqueous
solution of SDS. Even in a nonaqueous solution such as a
heptane solution of dodecanetiol, silver nanoparticles with 5-30
nm in diameter are produced, although their abundance is very
low.27 The laser ablation of silver is contrasted to that of gold,
by which smaller gold nanoparticles with 1-5 nm in diameter
are generated in an almost identical experimental condition, as
shown in our preliminary experiment.28
The optical absorption spectrum shown in Figure 1b exhibits
the characteristic spectral features of the silver nanoparticles,
which have been recognized so far by other groups;6,7 a peak
at 400 nm and a tail part of a broad band in the UV region,
which originate from surface-plasmon excitation and interband
transition, respectively.17-26 The prominent single peak at 400
nm is consistent with the fact that the nanoparticles present in
the solution are spherical in nature, as observed by electron
microscopy.29
The absorption spectrum is explained in terms of the Mie
theory in which the dipole term is assumed to contribute to the
optical absorption.17-26 The theory predicts that the surface
plasmon peak of a larger nanoparticle is more narrowed; intrinsic
size effect.18 In silver nanoparticles coated by sodium bis(2-
ethylhexyl) sulfosuccinate (AOT) in an alkane solution, for
instance, the width of the plasmon peak increases linearly with
the reciprocal of the particle diameter (1-10 nm).6 On the other
hand, the peak width increases with a further increase in the
diameter of the nanoparticle (>20 nm), because of the more
inhomogeneous polarization of the larger nanoparticle in the
electromagnetic field of the incoming light and resulting
excitation of a higher number of different multipole modes;
extrinsic size effect.18 In the present study, the produced silver
nanoparticles (10-20 nm in diameter) are shown to have peak
widths of typically ∼75 nm in the full width at the half-
maximum (fwhm) regardless of their diameters, probably
because of competition between the intrinsic and the extrinsic
8336 J. Phys. Chem. B, Vol. 104, No. 35, 2000
Figure 4. Concentration dependences of the abundance of silver
nanoparticles before (solid circles) and after (open circles) the
centrifugation in aqueous solutions of several surfactants, CnH2n+1SO4-
Na (n ) 8, 10, 12, 16).
size effects. Note that the size of the nanoparticles was controlled
in the range of 7-15 nm in diameter by changing the surfactant
concentration in the solution. The competition between the two
size effects is actually observed in gold nanoparticles.29,30
4.2. Formation and Structure of Nanoparticles. The
Mafuné et al.
essential feature of the particle formation in a surfactant-
containing solution is explained by the dynamic formation
mechanism.16 Briefly, (I) a silver plume consisting of silver
atoms (and clusters) is produced by laser ablation, (II) embryonic
silver particles grow rapidly in the plume, and (III) the particles
further grow slowly with supplying silver atoms by diffusion
and practically cease to grow when the surfaces are covered
with the surfactant molecules. The surface coverage increases
with the surfactant concentration and at extreme the surface is
doubly covered. Evidently, the nanoparticles are resistant against
re-aggregation when the particle surfaces are sizably charged
and covered fully with the surfactant molecules; otherwise the
particles are vulnerable to aggregation. It follows that the
stability of the nanoparticle is characterized by the coverage or
more practically the surfactant concentration. 31
Let us examine, in particular, the concentration dependence
of the abundance of the silver nanoparticles produced in the
SDS solution (see Figure 4). As the SDS concentration increases,
the abundance remains unchanged in the concentration range
lower than 10-4 M but starts to decrease slightly in the vicinity
of 0.001 M. In this concentration range, positively charged silver
nanoparticles produced are dispersed even without SDS but are
aggregated into black precipitates within a day. This finding
implies that the nanoparticles are unstable because of insufficient
coverage of the particle surface. The slight decrease in
abundance at 0.001 M is considered to originate from formation
of a single layer of C12H25SO4- on the silver nanoparticles so
that the charge density of the particle surface is reduced and
the repulsive force among the nanoparticles is weakened.
Consistently, the centrifugation with 15 000 rpm precipitates
the nanoparticles produced in this concentration range. The
electron micrograph identified the precipitate as a cluster of the
nanoparticles.
On the other hand, in the narrow concentration range
centering at 0.01 M, the nanoparticles attain the maximum
abundance; namely, those are most stable. As expected, the
nanoparticles are found to be resistant against the centrifugation.
The nanoparticles can be preserved for 1 month under the
atmospheric condition and are found to exhibit no significant
change in the absorption spectrum. The nanoparticles produced
in this concentration range are negatively charged. Actually,
the silver nanoparticles were completely adsorbed on the surface
of a negative ion-exchange resin, and they were driven toward
the anode in the electrophoresis. It is well-known that the stable
nanoparticles are coated with a double layer of SDS.32
In the concentration range higher than 0.01 M, the abundance
in the solution is much lower and is further precipitated almost
completely by the centrifugation, although the precipitate can
be redissolved in the solution by adding pure water and stirring.
The tendency of the precipitation is explained by (1) weakening
of the repulsive force between the nanoparticles, because an
excess amount of SDS in the solution neutralizes the coating
C12H25SO4- through the equilibrium C12H25SO4Na S C12H25SO4-
+ Na+, in the solution (salting-out effect), and (2) binding of
several stabilized nanoparticles by SDS. Approximately 20%
of the precipitate is attributed to the salting-out effect, as
described in the previous section, and the rest is the particle
binding by SDS.
4.3. Surfactant Dependence. The concentration dependence
for the other surfactant solutions can be explained similarly to
the SDS solution (see Figure 4). The concentration dependence
exhibits a similar concentration-independent portion in the
<10-6 M range and a concentration-dependent portion in the
>10-6 M range. On the other hand, a large amount of stable
Silver Nanoparticles in Aqueous Solution
nanoparticles are produced in an aqueous solution of CnH2n+1-
SO4Na (n G 12), whereas a smaller amount is produced for n
E 10. This finding implies that a surfactant with n E 10 does
not sufficiently stabilize silver nanoparticles produced by the
laser ablation. As mentioned in the previous section, stable silver
nanoparticles are coated with a double layer of SDS; in the first
layer the SDS molecules orient with the hydrophilic -SO4-
end inward and with the hydrophobic -C12H25 end outward,
while they do oppositely in the second layer. The two layers
are bound by a hydrophobic interaction between SDS molecules.
Taking this fact into consideration, one can conclude that
nanoparticles produced by the laser ablation are stabilized at
the highest extent when their surfaces are coated with double
layers of surfactant molecules, CnH2n+1SO4Na and the hydro-
phobic interaction between CnH2n+1SO4Na (n G 12) is suf-
ficiently large to form a stable double layer on the nanoparticles.
5. Conclusions
We investigated the stability of silver nanoparticles produced
by laser ablation of a silver plate in aqueous solutions of various
surfactants, CnH2n+1SO4Na, in the framework of the dynamic
formation mechanism proposed in our previous paper. The
nanoparticles are suspended in the solutions by taking advantage
of the repulsive force exerted among the nanoparticles in the
solutions. The nanoparticles survive for a long time in the
solutions only when they are coated with a double layer of the
surfactant molecules. The tendency that a surfactant with a
longer hydrocarbon chain can stabilize the nanoparticles more
efficiently is explained in terms of a larger hydrophobic
interaction between them.
Acknowledgment. This work is financially supported by the
Special Cluster Research Project of Genesis Research Institute,
Inc.
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