J. Phys. Chem.

C 2007, 111, 6281-6287 6281

New Insights on the Nanoparticle Growth Mechanism in the Citrate Reduction of Gold(III)
Salt: Formation of the Au Nanowire Intermediate and Its Nonlinear Optical Properties

Boon-Kin Pong,† Hendry I. Elim,‡ Jian-Xiong Chong,§ Wei Ji,‡ Bernhardt L. Trout,†,⊥ and
Jim-Yang Lee*,†,§
Department of Chemical and Biomolecular Engineering, National UniVersity of Singapore, 10 Kent Ridge
Crescent, Singapore 119260, Republic of Singapore, Department of Chemical Engineering, Massachusetts
Institute of Technology, 77 Massachusetts AVenue, Cambridge, Massachusetts 02139, Singapore-MIT Alliance,
4 Engineering DriVe 3, National UniVersity of Singapore, Singapore 117576, Republic of Singapore, and
Department of Physics, National UniVersity of Singapore, 2 Science DriVe 3, Singapore 117542,
Republic of Singapore
ReceiVed: December 17, 2006; In Final Form: March 8, 2007

The synthesis of gold nanospheres via the reduction of AuCl4- salt by sodium citrate has been revisited, with
focus on the mechanism of particle growth. In stark contrast to the widely accepted LaMer nucleation-growth
model, the initially formed nanoclusters of about 5 nm diameter self-assemble to form an extensive network
of nanowires. The diameter of the nanowires progressively increases in size, and at the same time the connected
network is fragmented into small segments before the final spherical particles are formed. We put forward a
modified nanocrystal growth mechanism, which is able to explain a number of other experimental observations.
By arresting the reduction process by rapid cooling, the 5 nm diameter nanowires could be isolated and were
found to be very stable. The nonlinear optical properties of the Au nanowires were investigated and discussed.
Highly connected, small diameter nanowires of highly conductive metals may be useful for future electronic
applications, e.g., conductive polymer-metal composites with low metal loading.

Introduction formation is chemical in nature and follows the LaMer growth

Gold nanospheres (AuNS) have become one of the most
commonly studied metallic nanoparticles for the development
of bioanalytic assays, particularly the detection of sequence-
specific DNA molecules. This is due in part to the relative ease
of synthesizing stable AuNS of controlled size with narrow size
distribution. Also, AuNS exhibit optical and electronic properties
that can be exploited in a variety of detection methodologies.
For a review of the synthesis, properties, and applications of
these gold nanoparticles, the readers may refer to an excellent
review article by Daniel and Astruc.1
The simplest and commonly employed method to synthesize
AuNS is the reduction of Au(III) salt (usually HAuCl4) by
sodium citrate in water. In this method pioneered by Turkevich
and co-workers2,3 in 1951 and later refined by Frens4 in the
1970s, sodium citrate plays a double role as a weak reducing
agent and a capping agent that stabilizes the nanoparticles. The
AuNS colloid exhibits excellent stability and a relatively narrow
size distribution for particles between 10 and 20 nm in diameter.
The particle size is controlled by the ratio of citrate to AuCl4-
ions; a larger amount of citrate leads to smaller particle size.
The average diameter and the character of the distribution
changed with preparative conditions (concentrations, ratio of
reactants, and temperature), indicating that the process of particle
* Address correspondence to this author. E-mail: cheleejy@nus.edu.sg.
Fax: +65 6779 1936. Phone: +65 6874 2899.
† Singapore-MIT Alliance, National University of Singapore.
‡ Department of Physics, National University of Singapore.
§ Department of Chemical and Biomolecular Engineering, National
University of Singapore.
⊥ Department of Chemical Engineering, Massachusetts Institute of
Technology.
10.1021/jp068666o CCC: $37.00 © 2007 American Chemical Society
Published on Web 04/12/2007
model.5,6 It is generally accepted that the AuCl4- ions are first
reduced to atomic Au, the concentration of which rises quickly
to the supersaturation level. Collision of the Au atoms leads to
a sudden burst of nuclei formation (nucleation step) upon which
most of the other gold atoms are attached (growth).
During synthesis, the color of the reaction mixture changes
progressively in the following order: pale yellow (AuCl4-),
colorless (Au atoms), very dark blue, purple and finally ruby-
red (AuNS). The UV-visible absorption property of spherical
Au nanoparticles of different sizes has been well recognized.7
Particles larger than ∼2 nm in diameter exhibit the characteristic
surface plasmon band and such a colloid appears red. The
intensity of surface plasmon resonance decreases sharply when
the particle size is smaller than ∼2 nm, making such colloids
less intensely colored. The concept of nucleation-growth mech-
anism dictates that each nucleus increases its size progressively
until the final colloidal particle is formed. However, this particle
growth mechanism cannot account for the observed color
changes in the Turkevich reaction. In particular, the nature of
the transient dark coloration is not understood. In the present
study, we focused on the particle growth process in the citrate-
reduction method and found that the growth process differs
remarkably from the commonly accepted LaMer nucleation-
growth model. During the initial stage of the reaction, Au
nanoclusters of about 5 nm in diameter coalesce to form an
extensive network of nanowires, which later fragments into
spherical particles. These nanowires could be isolated and were
found to be very stable after rinsing with water.
6282 J. Phys. Chem. C, Vol. 111, No. 17, 2007 Pong et al.

Experimental Methods

AuNS synthesis, developed by Turkevich, was carried out

with commonly employed standard conditions for preparing 13
nm diameter particles. All glassware and the magnetic stir-bar
were washed thoroughly with aqua regia (3 parts concentrated
HCl and 1 part concentrated HNO3). Ultrapure water (18 MΩ,
prepared from Elga LabWater purification system) was used Figure 1. TEM images of the dark intermediate showing an extensive
throughout this work. In brief, 10 mL of 1 mM aqueous HAuCl4 network of gold nanowires. The orientations of the lattice fringes change
(Sigma-Aldrich, >99.5% purity) solution was brought to boiling along the nanowires at regular intervals, which indicate the polycrys-
talline nature of the nanostructure.
in a 100 mL round-bottom flask. Under vigorous stirring, 1 mL
of 38.8 mM aqueous sodium citrate (prepared from trisodium
citrate dihydrate, Merck, 99.0% purity) solution was added
quickly to the AuCl4- solution. The concentrations of AuCl4-
and citrate in the mixture were 0.91 and 3.53 mM, respectively.
After a defined reaction time, a 5 mL aliquot of the solution
was extracted and added quickly to an equal volume of ice
(prepared from ultrapure water) to quench the reaction. The
aliquot was then immediately centrifuged at 10 000 rpm
(equivalent to 11200 relative centrifugal force) for 10 min to
isolate the particles, which were washed twice with 5 mL of
water. The heavy residue was re-dispersed in water and spotted
on a carbon-filmed TEM copper grid, which was then vacuum-
dried at room temperature. This procedure was repeated and Figure 2. UV-visible absorption spectra of the treated and untreated
aliquots were sampled after different reaction times. TEM samples collected when the reaction solution appeared dark blue: (a)
microscopy was performed on a JEOL 2010 transmission treated sample that has been rapidly cooled and washed with water
electron microscope. UV-visible absorption spectroscopy was and (b) untreated sample.
performed with a Shimadzu UV-2450 spectrophotometer.
The nonlinear optical (NLO) activities of the Au nanowires
were investigated with femtosecond Z-scans and pump-probe
at a visible wavelength of 780 nm with a 150 fs laser pulsed at
1 kHz repetition rate. The laser pulses were generated by a
mode-locked Ti:sapphire laser (Quantronix, IMRA), which
seeded a Ti:sapphire regenerative amplifier (Quantronix, Titan).
The laser pulses were focused onto a 1 mm thick quartz cuvette
that contained the Au nanowires solution with a minimum beam
waist of ∼24 µm. The linear transmittance of the solution was
adjusted to ∼25% at 780 nm by dilution with water. The incident
and transmitted laser powers were monitored as the cuvette was
moved (or Z-scanned) along the propagation direction of the Figure 3. UV-visible absorption spectra of the colloidal solutions
laser pulses. obtained at different stages of AuNS synthesis by citrate reduction of
AuCl4-. The spectra and visual colors of the colloids as the reaction
progressed are (a) colorless, (b) dark blue, (c) dark purple, (d) purple,
Results and Discussions and (e) ruby-red.

Structural and Spectral Evolutions of Gold Nanoparticles.
When citrate reduction of AuCl4- was carried out under boiling
conditions, the color of the solution changed rapidly in the
following sequence: pale yellow, colorless, very dark blue,
purple, and finally ruby-red. Aliquots of the reaction solutions
were extracted and rapidly cooled with ice to quench the
reaction. After washing with water, the colloid samples were
studied by using UV-visible absorption spectroscopy and
transmission electron microcopy (TEM). The treatments of rapid
cooling and washings with water were to “freeze” the gold
nanostructures so that they could be isolated and studied with
TEM. Our first interest was to determine the nature of the dark
blue intermediate, which was found to be an extensive network
of Au nanowires of approximately 5 nm diameter (shown in
Figure 1). As an assurance against structural alterations by these
treatments, we compared the UV-visible absorption spectra of
the treated and untreated samples shown in Figure 2. The
spectral profile of the gold colloid remained essentially un-
changed after the treatment with ice and two rounds of washing
with water. The slightly higher absorbance in the untreated (and
hence unquenched) sample may be attributed to the fact that
the reaction was still occurring even as the spectrum was being
collected.
To understand the particle growth process, aliquots of the
reactions at different times were extracted and studied. Figure
3 shows the UV-visible absorption spectra of the colloids
collected when the reaction solution appeared colorless, dark
blue, dark purple, purple, and finally ruby-red. As expected,
the samples with dark appearances have relatively flat absorption
profiles, indicating that photons of all energies were absorbed
at the same extent. The surface plasmon band began to appear
when the solution turned dark purple. As the reaction progressed,
the plasmon band increased in intensity until an intense peak
at 520 nm, characteristic of spherical gold nanoparticles, was
formed at the end of the reaction.
The size and morphological evolutions of the gold nanopar-
ticles were determined by TEM. Shortly after the addition of
sodium citrate, the solution contained spherical Au nanoclusters
3-5 nm in diameter and some irregularly shaped chain-like
segments (Figure 4a, 5 s into the reaction). The short chain-
Citrate Reduction of Gold(III) Salt
Figure 4. TEM micrographs of heavy sediments obtained at different
reaction stages of AuNS synthesis by citrate reduction of AuCl4-. Refer
to Figure 3 for the corresponding UV-visible absorption spectra of
these samples of gold nanostructures. (a) The colorless solution formed
shortly after addition of citrate contained nanoclusters 3-5 nm in
diameter and some irregularly shaped chain-like segments. (b) As the
solution turned dark blue, an extensive network of Au nanowires of 5
nm diameter was formed. (c) In the dark purple stage, small sections
of the nanowire network, with diameter approximately 8 nm, were
formed as the extensive network broke up. (d) Spherical particles
between 10 and 13 nm in diameter began to “cleave” off from the
nanowires when the color of the reaction turned purple. (e) Constriction
and cleavage of spherical particles from the nanowires. (f) Well-defined
spherical particles of diameter 13-15 nm were finally formed in the
ruby-red solution.
like segments apparently increased in length as the solution
darkened, forming an extensive network of Au nanowires, whose
diameter was approximately 5 nm (Figure 4b, 30 s). As the
reaction progressed, the nanowires increased in diameter to about
8 nm, and at the same time the network fractured into smaller
segments (Figure 4c, 90 s). As the color of the reaction solution
started to lighten to purple, spherical particles between 10 and
13 nm in diameter began to “cleave” off from the nanowires
(Figure 4d, 120 s). The constriction and final cleavage of
spherical particles from the nanowires are depicted in Figure
4e. Finally, when the solution had turned to a ruby-red color,
well-defined spherical particles of diameter 13-15 nm were
formed (Figure 4f, 15 min).
We noted that Chow and Zukoski had made a similar study
but under different reaction conditions.8 Their reactions were
performed at lower temperatures (50-80 °C) and they used
different amounts of citrate (1.6 mM) and AuCl4- (0.24 mM).
They also found that the color evolution from dark blue to red
was associated with a decrease in particle size. However, under
their reaction conditions, the large transitory particles were
spherical (100-200 nm in diameter) and composed of smaller
and defined subunits of spherical Au particles 5-15 nm in
diameter. That the intermediate they observed differs from ours
suggests that the assembly of small nanoclusters in the early
stage of particle growth may be sensitive to the reaction
conditions. To determine the pervasiveness of nanowires forma-
tion, we extended our study to lower reaction temperatures and
different molar ratios of AuCl4-/citrate. At 50 °C (keeping
AuCl4- and citrate concentrations at 0.91 and 3.53 mM
respectively), we found that similar nanowires were formed
(Figure 5a), although the shape of the final Au particles was
not well-defined (data not shown). At 100 °C and with the
amount of citrate increased to 4.55 mM (AuCl4- kept at 0.91
mM), similar nanowire networks were also formed (Figure 5b).
Interestingly, the diameter of the nanowires formed in both of
these reactions was also about 5 nm. On the other hand, a
reduced amount of citrate (1.82 mM citrate to 0.91 mM AuCl4-)
led to formation of a poorly defined network of nanowires
(Figure 5c) and final Au particles (data not shown). Hence the
J. Phys. Chem. C, Vol. 111, No. 17, 2007 6283
Figure 5. TEM micrographs of gold nanowires produced under
different reaction conditions: (a) reaction temperature at 50 °C, with
concentrations of AuCl4- and sodium citrate at 0.91 and 3.53 mM,
respectively; (b and c) reaction temperature at 100 °C, with sodium
citrate concentrations varied to 4.55 and 1.82 mM, respectively (AuCl4-
concentration kept at 0.91 mM).
SCHEME 1: Modified Growth Mechanism of
Nanospherical Gold Particles Synthesized by Reduction
of Aqueous AuCl4- by Sodium Citratea
a Key: (a) Gold ions reduced by citrate at elevated temperature
produced small gold nanoclusters smaller than 5 nm in diameter. (b
and c) The small nanoclusters self-assemble to form an extensive
network of nanowires which have diameter of about 5 nm. (d) The
diameter of the nanowires increases, which is accompanied by
fragmentation of the network to form small segments. (e and f)
Fragmentation continues along the segments until spherical-like particles
are cleaved and undergo ripening, e.g., Ostwald ripening.
formation of transient Au nanowires occurs under a wide variety
of conditions.
Modified Mechanism of Au Nanocrystal Growth. The
above observations call for modifications of the commonly
accepted LaMer model of nucleation-growth mechanism leading
to the sol formation of monodispersed, spherical Au nanopar-
ticles. Reduction of AuCl4- to Au atoms is followed by
nucleation leading to the formation of small nanoclusters about
5 nm in diameter. Contrary to common understanding, these
small Au nanoclusters assemble in a linear-like fashion into an
extensiVe network of nanowires. As more Au atoms are formed,
they adsorb onto the nanowires and the diameter of the latter
increases. Apparently, the increase in diameter destabilizes the
nanowires, which fragment and cleave into sphere-like particles.
Further aging and Ostwald ripening then lead to the formation
of well-defined spherical particles. The modified growth mech-
anism is depicted in Scheme 1.
The formation of nanowire intermediates in the course of
AuNS synthesis is not restricted to the citrate-reduction method.
Reduction by the strong reducing agent sodium borohydride has
been used to produce AuNS smaller than 10 nm in diameter.9,10
When freshly prepared sodium borohydride (100 mM, Sigma-
Aldrich 98% purity) was added dropwise to a 10 mL mixture
of HAuCl4 (1 mM) and sodium citrate (3.8 mM) at room
temperature and under vigorous stirring to synthesize 5 nm
diameter AuNS, we observed that a dark solution was also
transiently formed. We isolated the particulate intermediate
while the solution was dark by high-speed centrifugation at
10 000 rpm. The dark residue was washed twice with water
before spotting on the TEM sample grid. The TEM micrograph
6284 J. Phys. Chem. C, Vol. 111, No. 17, 2007
Figure 6. TEM micrographs of a small cluster and a linear chain of
Au nanowires obtained from the transient dark solution during the
reduction of AuCl4- by NaBH4. Sodium citrate was used as the capping
agent.
SCHEME 2: Hypothesized Assembly of Primary Gold
Nanoparticles in a Linear-like Fashiona
a Coalescence on two adjacent facets is forbidden due to steric effects
arising from truncated octahedral geometry.
in Figure 6 shows that these heavy particles are similar to the
nanowires formed in the citrate-reduction method (compare
Figure 4c). It is likely that an extensive nanowire network similar
to those in Figure 4b was formed, but the fast kinetics of the
borohydride reduction reaction did not allow us to isolate them
from the reaction solution.
We have now gained a better understanding of the particle
growth process. It is intriguing that the initially formed
nanoclusters self-assemble into a linear-like fashion. Pei sug-
gested that under a limited amount of sodium citrate, adsorbed
AuCl4- on Au nanoclusters render them attractive toward one
another and lead to coalescence.11-13 However the preference
for a chain-like assembly, as opposed to a random one that
would have led to formation of large spherical agglomerates,8
is not understood. We attempt to put forward a mechanism for
the chain-like assembly based on our observations and general
understanding of small gold nanoparticles. Assuming the small
primary nanoclusters adopt a truncated octahedral geometry with
well-defined planar facets,14 we hypothesize that the linear-like
alignment arises from steric effects. The formation of Au
nanowires is a fusion process between Au nanoclusters, and it
is necessary for the nanoclusters to achieve planar contact
between their lattice facets. (Note that this is unlike flocculation
or aggregation, where the surface atoms of the agglomerated
particles do not come into contact.) However, the angular surface
of each particle forbids its coalescence on adjacent planes
because of steric constraints (Scheme 2). This forbiddance of
interparticle fusion on adjacent planes is likely to have driven
the assembly of the particles in a linear, albeit twisted, pattern.
Moreover, this mode of assembly allows each particle to fuse
with several others, which may account for the highly branched
Pong et al.
SCHEME 3: Proposed Scheme for Au Nanoparticle
Assembly and Subsequent Disintegration into Spherical
Particlesa
a
Key: (a) Adsorbed AuCl4- on the small primary nanoclusters
results in their coalescence in a linear-like manner. Newly formed Au
atoms deposit rapidly in a disordered, noncrystalline manner into the
concaved cavities between the particles. (b) Once the cavities are filled,
newly formed Au atoms deposit preferentially on the crystalline, thereby
creating constrictions along the nanowires. (c) A process similar to
Oswald ripening depletes the noncrystalline regions. (d) Citrate ions
become the dominant capping agent as the AuCl4- ions are depleted
and repulsive forces between the primary particles pushes them apart
to form the citrate-capped spherical particles in (e).
structure. Our hypothetical mechanism is mostly conjectural
based on limited data. The driving force for the assembly may
involve more complex processes such as electrostatic interac-
tions. In-depth structural examinations of the gold nanowires
(e.g., high-resolution TEM) may yield more information on the
phenomenon, which is beyond the scope of this work.
Even more captivating is the subsequent disintegration of the
nanowires as they transform into spherical particles. We found
that at different reaction temperatures of 50, 80, and 100 °C,
the nanowires initially formed all had the same diameter of ∼5
nm. The nanowires increased in thickness and began to fragment
when the diameter was about 8 nm. These observations suggest
that during the nanocrystal growth process, the nanowires
structure became unstable when the diameter reached the
threshold value of about 8 nm. The lattice fringes along the
nanowires, shown in Figure 1, indicate that the primary
nanoclusters are randomly orientated to one another with respect
to their lattice facets (i.e., they are polycrystalline).11 Because
of the random orientation, most of the planes where fusion occur
are actually plane defects, e.g., (111) fused with the (100) plane.
We also observed that lattice fringes are periodically absent
along the nanowires, where fringed regions (∼8 nm long) are
flanked by nonfringed regions (∼4 nm long). The fringe-free
segments correspond to a highly disordered “amorphous” Au
structure. These observations led us to postulate that the
disintegration of the nanowires into particles arises from an
interplay of Oswald ripening and kinetic stabilization of
spherical colloid by citrate ions. Our proposed mechanism is
depicted in Scheme 3. In the early stages of the reaction,
preferential adsorption of AuCl4- ions on the small primary
nanoclusters results in an attractive interaction,11-13 leading to
coalescence in a linear-like manner. As the reduction process
continues, newly formed Au atoms are drawn into the concaved
cavities between the connected particles and deposited rapidly
based on the Kelvin equation of condensation.11 We postulate
that due to the fast deposition rate of Au atoms into the highly
concave cavities, the Au atoms assemble in a disordered
noncrystalline manner, producing an amorphous region as
observed by HRTEM. Once the cavities have been filled, the
nanowires present a smooth surface along its length. As more
Au atoms are formed through the reduction process, deposition
Citrate Reduction of Gold(III) Salt
Figure 7. Fused spherical-like gold particles were present in the final
solution when the reaction was terminated without the treatment of
extended reflux after the solution turned ruby-red.
is now thermodynamically preferred on the crystalline sites over
the noncrystalline ones, since sorption on the ordered surface
leads to tighter packing and hence stronger binding. The result
is localized growth of the nanowires, creating constrictions along
its length as observed in Figure 4e. Our TEM observations show
that the spherical particles are “cleaved” from the nanowires,
which suggest that the Au atoms in the noncrystalline regions
diffuse away, probably to the adjacent crystalline sites through
a process similar to Oswald ripening. By this time, AuCl4- ions
are depleted and citrate ions become the dominant capping agent
on the nanostructures. The citrate ions impart strong electrostatic
repulsive forces on the particles. Due to the shape of these
nanostructures at this stage, repulsion between adjoining
particles pushes them apart to form the citrate-capped spherical
particles.
In the light of this new fundamental understanding of Au
nanoparticle growth, a number of observations may now be
better understood. In the preparation of AuNS with the citrate
reduction of Au(III) salt, a common practice is to reflux the
solution for an additional 10-15 min after the apparent
completion of the reaction.15,16 We found that when this
“maturing” step is not carried out, some of the particles remained
fused, as shown in Figure 7. This maturing step may now be
understood as essential to the complete disintegration of the
nanowires to yield the final spherical particles. Also, most of
the gold nanoparticles produced in this method are not single
crystals, but are twinned.17 This twinning effect is likely to have
arisen from the assembly of small nanoclusters in the early stage
of the synthesis. When Kunitake and Yonezawa18 prepared
mercapto ligand-stablized Au nanoparticles by adding sodium
3-mercaptopropionate in the citrate-reduction reaction, nano-
particles smaller than 4 nm were produced. When we repeated
the synthesis in our laboratory, we observed that the solution
turned from pale yellow to colorless, and slowly developed into
a reddish solution without developing the typical dark solution.
The strong mercapto acid ligand is likely to have passivated
the nanoclusters in the early stage of the reaction and prevented
the assembly into nanowires and also stunned the growth of
these nanoclusters into larger particles. Such a method may be
useful for producing AuNSs that are free from twinning effects.
AuNSs are one of the most intensely researched metallic
nanoparticles for various types of applications.1 Although the
citrate-reduction method is routinely used in many laboratories
to prepare AuNS, fundamental understandings on the growth
process of these nanoparticles are limited. The method has been
revisited recently by Kimling et al., who examined in detail
the roles of various reaction conditions on the size and
morphology of the final products.19 The new understandings
gained from our present study can help refine the synthesis
process to enhance the control of nanoparticle shape and
polydispersity. Also, the new mechanistic insights on the particle
J. Phys. Chem. C, Vol. 111, No. 17, 2007 6285
Figure 8. UV-visible absorption spectra of solutions of the gold
nanowire network (solid line) and spherical gold nanoparticles ∼5 nm
in diameter (broken line).
growth may also help improve the quantitative nucleation-
growth model that has been reported recently.20 The nanowires
that can be isolated from the reaction, and stabilized by thorough
washings, may be useful in future electronic applications. For
instance, the metal loading in polymer-metal composites can
be reduced by the use of these small-diameter, electrically
conductive networks of nanowires. By using a low citrate-to-
gold ratio, Au nanowires with a diameter of approximately 43
nm can be made.11 Vasilev used a limiting amount of 2-mer-
captosuccinic acid to reduce AuCl4- and was able to synthesize
Au nanowires with a diameter of 15 nm. By arresting the citrate
reduction of AuCl4-, we are now able to prepare thin nanowires
of 5 nm diameter.
Optical Activities of the Au Nanowire. The dark appearance
of the Au nanowire sol suggests that the extensive Au structure
has an active absorbance throughout the visible region of the
electromagnetic spectrum. Indeed, the absorption spectrum in
Figure 8 shows its broad absorbance from 320 to 800 nm. Note
the stepped increase of absorbance that plateaus off around 520
nm, which corresponds to the surface plasmon resonance (SPR)
peak of spherical Au nanoparticles 5-15 nm in diameter. In
general, the location of the SPR peak is dependent on the
dimensionality of the particles, red-shifting to longer wavelength
as particle size increases. Also, the SPR absorbance of noniso-
tropic particles may be resolved along the three principal axes.
For example, long Au nanorods with a traverse diameter of ∼10
nm have two SPR peaks: one peak around 520 nm corresponds
to the traverse diameter (10 nm), and another broader band
located between 600 and 1300 nm results from the longitudinal
dimension of the nanorods.21 The absorbance profile of the Au
nanowires may be approximately viewed as a heterogeneous
mixture of Au nanorods with various longitudinal lengths but
all having the same traverse diameter of ∼5 nm. Hence, the
location of the stepped increase in absorbance is indicative of
the diameter of these nanowires; larger diameter nanowires will
have the stepped increase red-shifted to longer wavelength.
The resonant surface plasmons are not only responsible for
the high absorption of metallic nanoparticles, but also give rise
to nonlinear optical (NLO) activity. The NLO activity of
spherical Au nanoparticles is strongly correlated to their
extinction coefficient of absorption.22 For spherical Au nano-
particles, the NLO activity is highest around the SPR peak
around 520 nm. Au nanorods exhibit NLO activity at longer
wavelengths because of the additional longitudinal SPR peak
around 800 nm.23 Since the Au nanowires have a very broad
and intense surface plasmon band spanning the whole visible
spectrum, their NLO activity will also span a wide range of
wavelengths.
The Z-scan technique can be used to determine nonlinear
optical absorption of colloidal metallic nanoparticles.24 Figure
6286 J. Phys. Chem. C, Vol. 111, No. 17, 2007
Figure 9. (a) Open-aperture Z-scans of a 1 mm thick solution of the
Au nanowires measured with 150 fs laser pulses of 780 nm wavelength.
The laser irradiance used is in the range from 8 to 98 GW/cm2. (b)
Experimental open-aperture Z-scan data and its theoretical fit of Au
nanowires at an excitation irradiance of 8 GW/cm2. The solid line is
the best-fit curve calculated by using the Z-scan theory reported in ref
20.
9a displays the typical open-aperture Z-scans with different
irradiances at the wavelength of 780 nm and shows the negative
signs of the absorptive nonlinearities of the gold nanowires at
irradiance lower than ∼52 GW/cm2. As the Au nanowires are
moved toward the focus of the laser, the increased laser intensity
induces bleaching of the ground-state plasmon absorption and
results in a transmittance increase. This saturable absorption
(SA) process occurs at relatively low laser irradiance <52.2
GW/cm2. As the laser intensity is increased to 98.1 GW/cm2,
the reverse saturable absorption (RSA) process becomes domi-
nant.
To quantitatively determine the SA properties of the Au
nanowires, we simulate the Z-scan data with the Z-scan theory,25
in which the nonlinear absorption is assumed to be R2I, where
I is the light irradiance and R2 is the nonlinear absorption
coefficient (which is proportional to the imaginary part of third-
order nonlinear susceptibility Im χ(3)). From the best-fit of the
Z-scan data at a low irradiance (Figure 9b) the extracted R2
was found to be -0.41 cm/GW or Im χ(3) ) -7.2 × 10-13 esu.
By taking the linear absorption ()13 cm-1) of the Au nanowires
into consideration, we find that the figure of merit |Im χ(3)/R|
is 6 × 10-13 esu cm, which is two times greater than that
reported by Schrof for spherical gold nanoparticles.22 The
preceding results for SA are obtained at a low excitation level
of 8.0 GW/cm2, which is far below the irradiances where RSA
becomes apparent at 98.1 GW/cm2. The transformation from
SA to RSA suggests that the RSA process becomes dominant
at high irradiances. Such an interesting effect has also been
observed in Au nanorods.23 The origin of the RSA is attributed
to free-carrier absorption and/or the formation of strong light
Pong et al.
Figure 10. Transient transmission measurements on the Au NWs
solution performed with 780 nm, 150 fs laser pulses for different pump
irradiances.
scattering centers due to the vaporization of the initial particles
induced by the laser pulse.23,26
To evaluate the recovery time of the observed nonlinearities
and to obtain an insight of the underlying mechanism, we
conducted a degenerate pump-probe experiment with 150 fs,
780 nm laser pulses. In these experiments, the pump irradiance
was gradually increased, thereby providing information on the
transformation of SA to RSA processes. Figure 10 displays the
transient absorption signals of the Au nanowires, which also
confirms the SA process measured in the Z-scan method. With
input irradiances below 29 GW/cm2, the relaxation time of the
photoexcited electron dynamics in the Au nanowires is less than
6 ps. This is much faster than that observed in Au nanorods.23
This indicates the absence of phonon-phonon interactions in
the nanowires at low excitation energies. At 29.2 GW/cm2, an
oscillation of the signal near the zero delay is observed. The
origin of this oscillation is attributed to interplay between the
SA and RSA processes. As the pump irradiance is increased
further to 33.5 GW/cm2, the oscillation disappears and the peak
at the zero delay decreases, which indicates that RSA is now
the dominant process. The RSA process continues until the
irradiance reaches 50.7 GW/cm2, where the signal shows a
shallow dip below the baseline followed by an abrupt rise. The
maximum rise over the baseline is clearly observed at irradiance
of 56.6 GW/cm2, followed by a slow response time. This RSA
process becomes dominant at irradiance greater than 56.6 GW/
cm2 as shown in Figure 10.
The relaxation of the RSA process can be attributed to three
processes: The excited electrons relax to the ground state
through electron-electron, electron-phonon, and phonon-
phonon interactions. These interactions further induce the
excitation of hot electrons around the surface plasmon peak.
Thus, the broadband transient absorption subsides in this
duration and gives way to the complete recovery of the bleached
spectrum. Such optical response is interpreted in terms of
frequency shift and broadening of the SPR, and is related to
the changes of the Au nanowires dielectric function induced
by fast perturbation of the electron distribution. It is interesting
to note that our measurements of the RSA process in the Au
nanowires are comparable to the relaxation times (τe-ph ) 3.9
ps and τph-ph ) 100 ps) reported for bleaching recovery at the
transverse SPR27 and longitudinal SPR of Au NRs.23
Conclusions
A close investigation of the citrate-reduction method for
producing colloidal Au has revealed new mechanistic informa-
tion that was not expected from the widely accepted nucleation-
Citrate Reduction of Gold(III) Salt
growth mechanism. At the initial stage of the reaction, Au
nanoclusters of about 5 nm in diameter assembled to form chain-
like nanowires interceded with branches, forming an extensive
nanowire network. As the reaction proceeds, these nanowires
increase in diameter and eventually fragment into spherical
particles. The nanowires were inherently unstable in the reaction
and quickly converted to the spherical particles, but can be
conveniently harvested by quenching the reaction with rapid
cooling. These fine nanowires of high aspect ratio, produced
by a simple one-step solution-phase approach, could potentially
reduce the metal load of polymer-metal composites for future
electronic applications. Nonlinear optical properties and their
relationships with the conduction-band electron dynamics of the
Au nanowires have been studied with high-sensitivity femto-
second pump-probe and Z-scan techniques. By focusing
nonlinear optical measurements in a position on the broad
surface plasmon band, the spectral dependence of saturable
absorption was determined with a recovery time of ∼6 ps at
low excitation irradiances. Due to further absorption of excited
electrons and/or nonlinear scattering, reverse saturable absorp-
tion occurs at high excitation levels (>55 GW/cm2).
Acknowledgment. We thank the Singapore-MIT Alliance
program for financial support.
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