J. Phys. Chem.

B 2000, 104, 9111-9117

9111

Formation and Size Control of Silver Nanoparticles by Laser Ablation in Aqueous Solution
Fumitaka Mafune , 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: April 6, 2000; In Final Form: June 26, 2000

Silver nanoparticles were produced by laser ablation of a metal silver plate in an aqueous solution of sodium
dodecyl sulfate, C12H25OSO3Na. The absorption spectrum of the silver nanoparticles is found to be essentially
the same as that of silver nanoparticles chemically prepared in a solution. The size distribution of the
nanoparticles measured by an electron microscope shifts to a smaller size with increase in the concentration
of sodium dodecyl sulfate and with a decrease in the irradiation laser power. These findings are explained by
a scheme that the nanoparticles are formed via rapid formation of an embryonic silver particle and a consecutive
slow particle growth in competition with termination of the growth due to SDS coating on the particle.

1. Introduction
Nanoparticles suspended in a solution have attracted much
attention because of their size-dependent optical properties,
magnetic properties, catalytic properties, etc.1-5 For instance,
gold nanoparticles show intense photoluminescence only when
their sizes are much smaller than a certain value (ca. less than
5 nm in diameter).1 One of the most important tasks is to develop
a simple and versatile method to prepare nanoparticles in
solutions in a size-selected and -controlled manner.6-12 Chemical
reduction of metal ions is most commonly employed in the
preparation of metal nanoparticles in solutions. Specifically, a
metal salt dissolved in water is confined inside reversed micelles
in a nonpolar solvent, and metal nanoparticles are formed in
the reversed micelles by chemical reduction. The size of the
metal particles is determined by that of the reversed micelles,
which is controlled by changing the amount of water inside the
reversed micelles with changing a molar ratio of water to the
nonpolar solvent.10-12 More recently, an electrochemical method
has been developed for generating stabilized metal nanoparticles
for a wide variety of metals.13
Alternatively, ablation of a metal surface immersed in a liquid
could produce nanoparticles of the metal in the liquid.14-17 In
fact, gas-phase metal clusters are most conveniently prepared
by laser ablation.18,19 Metal atoms with a less amount of small
metal clusters are ablated from a metal rod by laser irradiation
and are aggregated into metal clusters with a sufficiently larger
sizes. Self-aggregation of the nanoparticles suspended in the
liquid should be prevented by hindering direct contact of the
nanoparticles. For example, Takami and co-workers have
prepared small metal clusters by laser ablation of a metal plate
in liquid helium,20-22 where the clusters are encapsulated in
helium bubbles.
In the present paper, we described a method to prepare stable
nanoparticles in a solution containing a surfactant by use of
* Corresponding author. E-mail: kondow@mail.cluster-unet.ocn.ne.jp.

Figure 1. Schematic diagram of the experimental apparatus.

laser ablation on a metal plate immersed in the solution. The

surfactant which surrounds each nanoparticles prevents direct
contact of the nanoparticles. As a benchmark experiment, the
laser ablation against a silver plate was performed in an aqueous
solution of sodium dodecyl sulfate, C12H25SO4Na (denoted as
SDS hereafter). The formation mechanism of silver nanoparticles
in the solution was examined by changing the concentration of
SDS and the power of the ablation laser.
2. Experimental Section
Silver nanoparticles were produced by laser ablation of a
metal silver plate in an aqueous solution of SDS. As shown in
Figure 1, the metal plate (>99.99%) was placed on the bottom
of a glass vessel which was filled with a 10-mL aqueous solution
of SDS. The metal plate was irradiated by the focused output
of the second harmonic (532 nm) of Quanta-Ray GCR-170
Nd:YAG laser operating at 10 Hz with a lens having a focal
length of 250 mm. The spot size of the laser beam on the surface
of the metal plate was varied in the range of 1-3 mm in

10.1021/jp001336y CCC: $19.00 2000 American Chemical Society

Published on Web 09/07/2000

9112 J. Phys. Chem. B, Vol. 104, No. 39, 2000

Mafune et al.
A transmission electron microscope (JEOL JEM-100S 50000)
was employed to take the electron micrographs of the solutions
studied. Practically, a drop of the sample solution of interest
was placed on a copper mesh coated with collodion and
sputtered by gold ions in advance. The drop on the copper mesh
was dried by heating to 320 K. After repeating this procedure
three times, the mesh was washed with water to remove free
SDS. Each size distribution was obtained by measuring the
diameters of more than 1000 particles in sight on the given
micrograph.
3. Results

Figure 2. Absorption spectrum of the silver nanoparticles produced

by laser ablation of a silver metal plate in a 0.01 M aqueous solution
of SDS (solid line). The dotted line shows the absorption spectrum
calculated on the basis of Drude model.

diameter by changing the distance between the focusing lens

and the metal plate. A Scientech power meter monitored the
output of the 532 nm laser with the maximum output of about
90 mJ/pulse. Upon irradiation of the laser beam, the solution
gradually turns brownish- yellow. The absorption spectrum of
the solution was measured by a Shimadzu UV-1200 spectrometer. At least five different runs were accumulated on an NEC
computer to obtain one spectrum.

Figure 2 shows an absorption spectrum of a 0.01 M aqueous

solution of SDS in which a silver plate was irradiated with the
532-nm laser having the output power of 40 mJ/pulse. The
spectrum exhibits a characteristic peak at 400 nm and a tail of
a broad band extending toward the UV wavelength range. The
absorption spectrum is essentially the same as that for silver
nanoparticles prepared chemically by reduction of a silver salt
in the reversed micelles.10-12 The agreement of the two spectra
shows that silver nanoparticles are formed by the laser ablation
in the solution. The formation of the silver nanoparticles in the
solution is also verified by the electron micrograph of a
specimen prepared from the solution as described above. Figure
3 shows electron micrographs and corresponding size distributions of silver nanoparticles produced by laser ablation (the
wavelength of 532 nm and 90 mJ/pulse) of a silver plate
immersed in aqueous solutions of SDS having different SDS
concentrations. The nanoparticles thus produced were calculated

Figure 3. Electron micrographs and size distributions of the silver nanoparticles produced by laser ablation at 90 mJ/pulse in a SDS aqueous
solution at the various SDS concentrations. The concentrations of the solution in panels a-c are 0.003, 0.01, and 0.05 M, respectively. The average
size decreases with an increase in the SDS concentration.

Formation and Size Control of Silver Nanoparticles

J. Phys. Chem. B, Vol. 104, No. 39, 2000 9113

Figure 4. Electron micrographs and size distributions of the silver nanoparticles produced by laser ablation in a 0.01 M SDS aqueous solution at
the various laser powers. The laser powers in panels (a)-(c) are 40, 55, and 70 mJ/pulse, respectively. The average size increases and the distribution
broadens with an increase in the laser power.

to have the average diameters of 16.2 ( 4.0, 14.9 ( 8.4, and

11.7 ( 5.3 nm in the 0.003, 0.01, and 0.05 M solutions,
respectively. The result shows that the average diameter
decreases with an increase in the SDS concentration. A similar
measurement was performed in a 0.01 M solution with changing
the laser power (see Figure 4). The average diameters of the
nanoparticles were obtained to be 7.9 ( 3.3, 10.7 ( 5.8, and
12.8 ( 4.1 nm for runs with the laser powers of 40, 55, and 70
mJ/pulse, respectively. Figure 5 shows the change in the average
diameter of the nanoparticles as functions of the SDS concentration (panel a) and the laser power (panel b), where the error
bars represent one standard deviation of the average diameters
determined from several runs of measurements.
In the absorption spectrum of silver nanoparticles, the broad
band in the UV region originates from an interband transition
of the silver nanoparticles. Its line shape does not change
appreciably with the particle size, but its intensity is proportional
to the number of silver atoms contained in the nanoparticle.10
In other words, the absorbance of the solution at the wavelength
of the interband transition (250 nm) is proportional to the
number of silver atoms in the solution. It follows that the number
density of the nanoparticles can be derived from the absorbance
if the size distribution of the nanoparticles is known. In reality,
all the size distributions of the nanoparticles produced under
the various conditions are not known. In this regards, let us
adopt relative abundance of the nanoparticles from the
absorbance at 250 nm. Evidently, the abundance is approximately proportional to the number density of the silver
nanoparticle as far as the size distribution does not change
significantly. Figure 6a shows the relative abundance of the

silver nanoparticles as a function of the laser power under

different focusing conditions. When the laser is tightly focused
with its spot diameter, a, of 1.2 mm, the relative abundance
increases up to the laser power of 40 mJ/pulse and then levels
off, as the laser power increases. At the conditions with
a ) 1.6 and 2.4 mm, the relative abundance starts to increase
at a threshold laser power, and then levels off, as the laser power
increases. To examine the influence of the spot diameter on
the relative abundance of the silver nanoparticles, the relative
abundance was measured at different laser-spot diameters under
the same laser fluence; the laser power increased linearly with
the laser-spot area. The quadratic increase in the relative
abundance with the spot diameter shows that formation of each
silver nanoparticle takes places in a sufficiently smaller region
than the laser spot, and hence, the number of sites for
nanoparticle formation increases linearly with the laser-spot area.
Figure 7 shows the relative abundance as a function of the
number of the laser shots. The abundance increases almost
linearly with the laser shots in the initial stage, and its slope is
reduced above a laser shot of about 50000.
Laser ablation of the silver metal plate was performed in a
dodecanethiol solution in heptane, which turned to be slightly
brown after 10 h. The electron micrograph showed that silver
nanoparticles with 5-30 nm in diameter were produced. The
comparison of the present absorption spectrum with that of the
nanoparticles produced in the dodecanethiol solution in heptane
shows that a much less amount of silver nanoparticles are
produced in the heptane solution than that in the aqueous
solution. In conclusion, the relative abundance of silver nano-

9114 J. Phys. Chem. B, Vol. 104, No. 39, 2000

Mafune et al.

Figure 5. Average radius of the nanoparticles (solid circle) and average

dispersion of the radius distribution (open circle) are plotted as a
function of the concentration of SDS in panel (a) and as a function of
the laser power in panel (b). The error bars represent one standard
deviation determined from several runs of measurements. The solid
curves in panel (a) show the calculated radius on the basis of the
dynamic formation model (see in Section 4).

particles depends on the concentration of a surfactant and

naturally on the properties of the surfactant and the solvent
employed.

Figure 6. (a) Relative abundance of the silver nanoparticles as a

function of the laser power under the various focusing conditions. The
spot sizes of the laser were 1.2 nm (solid circle), 1.6 nm (open circle),
and 2.4 mm (solid square) in diameter, respectively. The solid curves
show the eye guide. (b) Relative abundance of the silver nanoparticles
at different diameters of the laser spot on the metal surface under the
same laser fluence.

4. Discussion
4.1. Optical Absorption of Silver Nanoparticles Produced
in Solution. The absorption spectrum of the silver nanoparticles
exhibits the surface plasmon peak at 400 nm on the broad
band due to an interband transition (see Section 3 for interband
transition).23-33 The presence of the single surface-plasmon peak
implies that the silver nanoparticles are spherical. Note that
ellipsoidal particles would have two plasmon peaks in the
absorption spectrum.10,33
An optical absorption of particles having diameters much
smaller than the wavelength of incoming light is well reproduced
by the calculation based on the Mie theory.23-33 When N
particles of volume V are suspended in a medium with the
dielectric constant, 0, the extinction coefficient, , of the
particles is given by

) 18NV03/22/[(1 + 20)2 + 22]

(1)

where is a wavelength of the incoming light in the medium,

and 1 and 2 represent the real and imaginary parts of the
dielectric function, , respectively ( ) 1 + i2). Suppose that

the Drude model is applicable to describe the dielectric function

of the silver particle, one obtains the real and imaginary parts
of the dielectric function. In addition, when the diameter of the
particle is smaller than the electron mean free path (52 nm in
a silver crystal), 1 and 2 become size dependent due to
additional electron scattering at the particle boundary.26
The optical absorption spectrum thus calculated reproduces
the experimental one, when the plasma frequency is reduced to
90% of the plasma frequency of a silver crystal, and the collision
frequency and the Fermi velocity of the silver crystal are
adopted. The reduction of the plasmon frequency may result
from attachment of surfactant on the silver nanoparticles (see
the dotted line in Figure 2).10 In the range of the particle radius
studied (5-7.5 nm), no appreciable change of the spectral
features (peak width and shift) with the particle radius was
observed, as expected from the theory. In this range, an intrinsic
size effect competes with an extrinsic size effect, which acts
toward the opposite direction.25,33 Actually, the surface plasmon
peak of silver nanoparticles with the radius of 1-5 nm is
reported to change its width and height as the radius changes,
and the width of the surface plasmon peak increases linearly

Formation and Size Control of Silver Nanoparticles

J. Phys. Chem. B, Vol. 104, No. 39, 2000 9115

rp ) (3NpVa/4)1/3

(2)

In the derivation of eq 2, the particle is regarded as spherical

because the absorption spectrum exhibits a single plasmon peak.
The cross section for attachment of a silver atom to the particle
should be proportional to the geometrical cross section of the
particle (rp2) (see eq 2). Suppose that a silver atom diffuses
toward the particle with a velocity of Va. Then, the rate of
increase in the particle volume is given by

Va dNp(t)/dt ) krp2VadaVa

Figure 7. Relative abundance of the silver nanoparticles as a function

of the laser shot. The abundance increases almost linearly with the
laser shot below 50000 shots.

with the reciprocal of the radius (intrinsic size effect).10 On the

other hand, the width of the surface plasmon peak increases
with increase in the radius in the range larger than >10 nm,
because of inhomogeneous polarization of the particles in the
electromagnetic field of the incoming light: Excitation of a
different multipole mode makes a peak in the spectrum at a
different energy (extrinsic size effect). The alternative explanation for the invariable peak width in the present study can be
given by the relatively broad size distribution of the nanoparticles. The change of the size dependence of the spectral profile
is observed in the optical absorption spectra of gold nanoparticles.33
4.2. Dynamic Formation Mechanism. Description of Dynamic Formation Mechanism. It is shown in the present
experiment that (1) the nanoparticles are produced above a
threshold laser power, (2) their number density increases
proportionally with the laser power, and (3) their average size
increases with an increase in the laser power and decreases with
increase in the SDS concentration. These findings are explained
in terms of rapid formation of an embryonic silver particle and
a consecutive particle growth in competition with termination
of the growth due to SDS coating on the particle. Let us consider
the particle formation in a chronological order. Immediately after
the laser ablation, a dense cloud of silver atoms is built over
the laser spot of the metal plate. As the interatomic interaction
is much stronger than the interaction between a silver atom and
a SDS molecule or a solvent molecule, silver atoms are
aggregated as much as silver atoms are supplied. This initial
rapid aggregation continues until silver atoms in the close
vicinity are consumed almost completely. As a result, an
embryonic silver particle forms in a region void of silver atoms
(cavity). However, the supply of silver atoms outside the region
through diffusion causes the particle to grow slowly even after
the rapid growth ceases. In competition, the slow growth tends
to be terminated by coating the particle surface with SDS
molecules, which diffuse through the solution toward the
particle.
Calculation of AVerage Particle Size. Let us define Np0 as
the number of silver atoms in an embryonic particle and Np(t)
as that at a time, t, after the slow growth started, and Va as the
effective volume of a silver atom. The radius of the particle,
rp, is then given by the particle volume, NpVa, as

(3)

where da is the number density of silver atoms in the cloud of

the silver atoms and krp2 is the attachment cross section. Let
us assume that da does not change appreciably in the time scale
of our interest for the first-order approximation, although da
might slightly decrease with time. Then, the volume and the
radius of the particle at a time t are given, respectively, by

Np(t)Va ) ((Np0Va)1/3 + (/48)1/3kVadaVat)3

(4)

rp(t) ) r0 + (1/4)kVadaVat

(5)

where r0 is the radius of the embryonic particle. As shown in

eq 5, the radius of the particle increases linearly with t. On the
other hand, the attachment cross section of a SDS molecule
should be proportional to krp2. Then, the rate of increase in
the number of the SDS molecules, Ns, which attaches to the
particle is

dNs(t)/dt ) krp2dsVs

(6)

where ds is a density, and Vs is a velocity of a surfactant molecule

in the solution. Then, Ns is given by

Ns(t) ) (4/3)(kdsVs/kVadaVa)[(r0 + (1/4)kVadaVat)3 - r03]

(7)
the total area that Ns SDS molecules occupy is NsS, when the
surface area occupied by one SDS molecule on the particle is
defined as S. The radius of the spherical particle, rs(t), which
has the same surface area as NsS is given by

rs(t) ) (NsS/4)1/2
) (S/3)1/2 (kdsVs/kVadaVa)1/2 [(r0 + (1/4)kVadaVat)3 - r03]1/2
(8)
In other words, rs(t) is the maximum radius of the spherical
particle that the Ns SDS molecules completely cover. Evidently,
the radius, rs(t), increases hyper-linearly with t. It should be
noted that the radius of the embryonic particle, r0, depends on
the number density of silver atoms (da) in the silver cloud. The
da-dependence of r0 is obtained on the assumption that the cavity
radius does not change with the silver concentration in the silver
cloud. This assumption is rationalized because an effective
region within which silver atoms attract strongly is determined
by the interatomic interaction, but not by the density of silver
atoms.
Figure 8 illustrates the change of the calculated particle radius
with a reduced time, kt, where Va is calculated to be 1.25
10-29 m3 from the atomic radius of a silver atom in a silver
crystal, and S of 6.2 1019 m2 is taken from a literature.34 In
addition, the number density of the SDS molecules, ds, is

9116 J. Phys. Chem. B, Vol. 104, No. 39, 2000

Figure 8. Time evolution of the particle radius, rp (solid line) and rs

(dotted line), calculated on the basis of the dynamic formation model.
The radius of the particle is calculated to be 7.6 nm when r0 ) 5.5 nm
and k/k ) 0.1.

obtained from the SDS concentration, on the assumption that

the SDS molecules are homogeneously distributed in the
solution. The number of the silver atoms liberated into the
solution per single laser shot is estimated to be 1011-1012 from
the absorbance of the silver nanoparticles in the region of the
interband transition. The number density of silver atoms in the
silver cloud, da, is estimated to be 1023-1024 m-3 on the
assumption that silver atoms ablated into the solution are
thermalized immediately within a 1 m diffusion length. The
velocities of a silver atom and an SDS molecule in the solution
are estimated from each diffusion constant, and the ratio, k/k,
is left as a variable parameter. As shown in Figure 8, the radius
of the particle (rp) increases linearly with the reduced time. On
the other hand, the maximum radius (rs) of the particle, which
can be fully covered by Ns SDS molecules, increases more
rapidly with the reduced time and exceeds at the reduced time
where the two lines crosses. This crossing point determines the
average radius of the nanoparticles observed.
4.3. Average Size of Nanoparticles. Dependence of AVerage
Size on SDS Concentration. The average size of nanoparticles
produced at different SDS concentrations by a given laser power
is obtained from the crossing point of the two lines given by
eqs 5 and 8 (see Figure 8). The calculation predicts that smaller
nanoparticles tend to be produced in a more highly concentrated
SDS solution because a slope of the rs - kt curve increases as
the SDS concentration increases and hence the crossing point
appears at an earlier reduced-time. Evidently, this prediction is
consistent with the observed concentration dependence of the
average particle size. The solid curve in Figure 5a depicts the
calculated average radius by using eqs 5 and 8 with k/k ) 0.1
and r0 ) 5.5 nm. This dynamic formation mechanism also
predicts that the embryonic particle continues to grow until it
consumes all of the available silver atoms without any effective
termination. Actually, the optical absorption spectrum shows
that particles produced in pure water continue to grow in the
absence of any surfactant and finally precipitate within a day.
Dependence of AVerage Size on Laser Power. The observed
laser-power dependence of the average size originates mainly
from the da dependence of r0 in the framework of this model;
both rp and rs similarly depend on da, and hence the average
size determined from the crossing point of the rs - kt and rp kt curves does not change with da, if r0 is constant. The behavior
accords well with the physical picture that the attachment rate

Mafune et al.
of a silver atom to the particle should increase with da and
simultaneously that of a surfactant molecule also increases with
the geometrical cross section of the growing particle, resulting
in the formation of particles having the same radius. The radius
of the embryonic particle, r0, should increase linearly with da1/3,
as the radius of the cavity does not change with da. The solid
curve in Figure 5b is the prediction given by this mechanism,
where da is supposed to increase linearly with the laser power
above the threshold value (see Figure 6). The radius of the
cavity, in which an embryonic silver particle is present, is
estimated to be in the order of 100 nm.
Dependence of AVerage Size on Number of Laser Shots.
Figure 7 shows the relative abundance of the silver nanoparticles
as a function of the number of the laser shots. The abundance
increases almost linearly with the laser shots in the initial stage,
and its slope is slightly reduced above a laser shot of about
50000. The finding indicates that the nanoparticle formation
takes place within each laser shot. According to our preliminary
experiment on gold nanoparticles which has an appreciable
optical absorption at 532 nm, the abundance of the nanoparticles
by the laser ablation at 532 nm increases and then levels off
immediately as the number of the laser shot increases. This
immediate leveling off is considered to arise from absorption
of the incoming ablation laser by gold atom cloud over the metal
plate. It is highly likely that the gold nanoparticles are
dissociated into smaller particles by the ablation laser. Koda
and co-workers have reported that chemically prepared gold
nanoparticles in a solution are dissociated into smaller particles
(photoinduced reshaping) under irradiation of a 532 nm laser.35
Conversely, the linear increase in the abundance of the silver
nanoparticles with the laser shot implies that no appreciable
dissociation of the silver nanoparticles occurs under irradiation
of the ablation laser. The reduction of the slope above 50000
shots should originate from a weak absorption at 532 nm by
the silver nanoparticles which attenuate the laser beam penetrating through the solution above the metal plate and hence cause
a less efficient nanoparticle formation. Note that all the
experiments have been performed in a region where the relative
abundance increases linearly with the laser shot.
4.4. Average Size vs Static Properties of SDS. In a diluted
SDS solution whose SDS concentration is less than the critical
micelle concentration (CMC), SDS molecules are unimolecularly dissolved. On the other hand, the SDS molecules form
micelles at a concentration higher than CMC; 8.2 mM at 298
K.36 If the static properties of the SDS molecules govern the
average size of the nanoparticles in the solution, the average
size should change significantly at the CMC. Nevertheless, no
appreciable change in average size is observed at the CMC when
the SDS concentration is changed. It is concluded, therefore,
that the static dissolved form of the SDS molecules in the
solution has no direct influence on the determination of the
average size. This finding is consistent with the dynamic
formation mechanism proposed.
5. Conclusions
Laser ablation of a silver plate in an aqueous solution of
sodium dodecyl sulfate was employed to prepare size-selected
and size-controlled silver nanoparticles in the solution. We
characterized the nanoparticles by using optical absorption
spectroscopy and electron microscopy. We proposed a mechanism based on a rapid growth of an embryonic silver particle
and a consecutive slow growth in competition with termination
of the growth due to SDS coating on the particle. Seemingly,
this method is applicable to preparing metal nanoparticles of
any kind including multicomponent ones.

Formation and Size Control of Silver Nanoparticles

Acknowledgment. This work is financially supported by the
Special Cluster Research Project of Genesis Research Institute,
Inc.
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