Received: September 26, 2000

Final version: May 15, 2001

Fig. 3. Verification of complete exposure of Si substrate surface by CFL. The

Shipley electroless Cu deposition process was used for this purpose. In the process, copper grows only on the exposed surface. Considering the poor characteristics inherent to electroless deposition, remarkably good Cu lines form.

and G is the gravitational constant. From the meniscus seen in

the cross-sectional SEM image, the contact angle is estimated
to be about 85. When we insert into Equation 1 the surface
tension (~30 dyne/cm) and density (0.95 g/cm3) of SBS and L
of 300 nm, a maximum height of 1.87 m is obtained, which
indicates that the height of the patterned polymer can be
made quite large. In fact, we were able to fabricate polymer
structures with a step height as high as 5 lm for an 80 lm
line-and-space pattern. If we take into account the interaction
at the polymer/substrate interface and the solid-like properties of the polymer melt, the theoretical maximum height
would be reduced. For a more accurate model, further study
would be required.
The time it takes for the polymer melt to fill up the void
space between the mold and the polymer film can be estimated. If we neglect the effect of gravity, then the surface tension and viscosity of the polymer melt and the size of the
capillary determine the rate of flow such that the time is given
by[11]
t

2 z2

Rcpolymer=air cos 

(2)

where z is the length of capillary to be filled, t is the time, g is

the viscosity of the polymer melt, and R is the hydraulic radius
(the ratio of the volume of the liquid in the capillary section
to the area of the solid and liquid interface), which is approximately one half the width L. We observed that it took about
30 min for the SBS polymer to completely fill the void in the
mold with a step height of 600 nm and a width of 400 nm at
100 C. The viscosity of the SBS is about 106 [Pa s] from the
rheometrics spectroscopy (RMS) measurement at zero shear
stress. When we use these values in Equation 2, the time

Adv. Mater. 2001, 13, No. 18, September 14

[1] Y. Xia, J. A. Rogers, K. E. Paul, G. M. Whitesides, Chem. Rev. 1999, 99,

1823. Y. Xia, G. M. Whitesides, Angew. Chem. Int. Ed. 1998, 37, 550.
[2] R. D. Piner, J. Zhu, F. Xu, S. Hong, C. A. Mirkin, Science 1999, 283, 661.
[3] C. J. Drury, C. M. J. Mutsaers, C. M. Hart, M. Matters, D. M. de Leeuw,
Appl. Phys. Lett. 1998, 73, 108.
[4] S. Y. Chou, P. R. Krauss, P. J. Renstrom, Science 1996, 272, 85.
[5] Y. Xia, G. M. Whitesides, J. Am. Chem. Soc. 1995, 117, 3274.
[6] J. A. Rogers, M. Meier, A. Dodabalapur, Appl. Phys. Lett. 1998, 73, 1766.
[7] E. Schffer, T. Thurn-Albrecht, T. P. Russell, U. Steiner, Nature 2000, 403,
874.
[8] E. Kim, Y. Xia, G. M. Whitesides, Nature 1995, 376, 581.
[9] E. Kim, Y. Xia, X. M. Zhao, G. M. Whitesides, Adv. Mater. 1997, 9, 651.
[10] A. W. Adamson, A. P. Gast, Physical Chemistry of Surfaces, Wiley, New
York 1997, Ch. 1.
[11] D. Myers, Surfaces, Interfaces, and Colloids, VCH, New York 1991,
pp. 87109.

Seed-Mediated Growth Approach for ShapeControlled Synthesis of Spheroidal and Rod-like

Gold Nanoparticles Using a Surfactant
Template**
By Nikhil R. Jana,* Latha Gearheart, and
Catherine J. Murphy*
The size- and shape-controlled synthesis of metal nanoparticles is important in present day advanced materials, as
almost every property within the nanometer regime are size
and shape dependent.[1] Common methods for size control
employ capping agents,[2] such as surfactants, ligands, polymers, or dendrimers, to confine the growth in the nanometer
regime. These methods commonly produce spherical particles
due to the low surface energy associated with such particles.
However, the procedures for shape-controlled preparation of
monodispersed nanoparticles are limited. Occasionally capping agents allow shapes other than spheres.[3] The mechanism
of such shape control has recently been studied by El-Sayed
et al. and Reetz et al.[4] Structures other than spheres form as
a result of specific interaction of the capping agents with different growing faces of the particles.[4]

[*] Dr. N. R. Jana, L. Gearheart, Prof. C. J. Murphy

Department of Chemistry and Biochemistry
University of South Carolina
Columbia, SC 29208 (USA)
E-mail: murphy@mail.chem.sc.edu

[**] We thank the National Science Foundation and the Office of Naval
Research for funding.

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needed to fill the void in the mold is calculated to be 1377 s

(~23 min), which is a little shorter than the observed value.
Capillary force lithography presented here is a simple and
yet robust method for large-area patterning. With further
development the technique could become a strong candidate
for an alternative to photolithography in fabricating largescale integrated circuits.

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Controlling shape of nanoparticles has been most successfully achieved using a template. Templates provide a constrained environment during the nanoparticle growth and thus
shapes are tuned according to the template. Commonly used
templates are porous alumina,[5] polycarbonate membranes,[6]
carbon nanotubes,[7] and micelles.[8] In practice, the presence
of templates does not produce 100 % shape monodispersity;
rather, a significant fraction of thermodynamically favorable
spheres are also formed. In addition, soft templates such as
micelles may not be stable under the experimental conditions
(e.g., boiling), and thus the template may not function.[9] A
common reason for the failure of the template mechanism is
the change in template microstructures by reactants. We propose that the mechanism of conventional nanoparticle synthesis, which proceeds through successive nucleation and growth
steps (the two steps tend to overlap with each other), also has
direct consequence on the template mechanism. During nanoparticle synthesis, nucleation and successive growth are extremely sensitive to physical and chemical parameters.[2] In
some of the solution-phase metal nanoparticle synthesis procedures, the control of nucleation and growth steps are done
by the changing the reducing agent or stabilizer concentration. In doing so, the size and shape of nanoparticles can be
controlled.[2a,j,k,4] Similarly the control of nucleation and
growth can produce different sizes and shapes of semiconductors (CdSe).[10] For solution-phase Au nanoparticle synthesis,
we have observed an initial slow nucleation followed by a
nucleation burst associated with autocatalytic surface
growth.[11] We have controlled the nucleation and growth
steps to prepare different sized spherical particles through a
seed-mediated growth approach. Others have successfully employed a similar method for nanoparticle size control.[12]
Herein we used this same growth strategy in the presence of a
rod-shaped micelle[13] for template-mediated shape control.
The same template was used earlier to prepare gold nanorods
by an electrochemical approach.[14] Earlier attempts using
photochemical reduction of a gold salt in the presence of the
micellar template produced a mixture of nanorods and nanowires in addition to a significant fraction of small spheres.[15]
A possible reason for the polydispersity in shape is the difficulty in controlling nucleation and growth and due to continuous nucleation occurring throughout the entire growth process. Pileni et al. reported successful shape control of copper
nanorods by using a reverse micellar template.[8b] A similar
template was also used for the preparation of barium sulfate,[9c] barium carbonate,[8c] and calcium sulfate nanowires.[9d]
The basic principle for our method of shape-controlled synthesis involves two steps: First, the preparation of small size
spherical gold nanoparticles, and second, growth of the prepared spherical particle in rod-like micellar environment. Initial addition of preformed seeds has two advantages: first, it
increases the overall reaction rate, and hence the growth rate;
second, the particle size is controlled by varying the ratio of
metal salt to seed, thus restricting the particle size to the
nanometer regime. We employed ascorbic acid as the reducing agent of AuIII salts in the growth stage. Ascorbic acid is a

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WILEY-VCH Verlag GmbH, D-69469 Weinheim, 2001

mild reducing agent and cannot reduce the gold salt in the
presence of the micelle without the presence of seed. Consequently, minimal additional nucleation occurs during particle
growth.
We prepared roughly spherical borohydride-reduced gold
nanoparticle seeds with a mean diameter between 3 and 4 nm
and mixed them with a growth solution containing gold salt, a
rod-shaped miceller template, ascorbic acid (as the reducing
agent), and small amount of silver ions (for shape induction).
The importance of silver ions in the preparation of gold rods
was observed earlier in the electrochemical synthesis of gold
rods, where increasing silver ion concentration increased the
aspect ratio of the gold rods.[14] Our results show successful
production of spheroidal or rod-like gold particles exhibiting
aspect ratios (varied from 1 to 10) that are dependent on the
gold seed to gold salt ratio.
Figure 1ah shows the ultraviolet-visible (UV-vis) spectra
of rod-shaped gold particles with varied seed concentrations.
A single peak around 530 nm appears for solutions containing
relatively high seed concentrations (a and b). For sets ch,

Fig. 1. Extinction spectra of Au nanorods with increasing aspect ratios formed

by decreasing the amount of added seed. The volume of seed (250 lM in terms
of Au atoms) added to 10 mL of growth solution (having 250 lM HAuCl4) in
(ah) was as follows: 1.0, 0.5, 0.25, 0.125, 0.09, 0.06, 0.03, and 0.015 mL. Other
solution conditions are given in the experimental section. The gold rod solutions corresponding to spectra (g) and (h) contain D2O instead of H2O in order
to avoid interference from water in the NIR.

two peaks appear for the gold surface plasmon band. One
appears around 530 nm and is a conventional plasmon band
for spherical particles. A separate plasmon band appears in
the longer wavelength region, and its position depends on the
aspect ratio of the rod. This band appearing, around 600
1600 nm, corresponds to the longitudinal plasmon resonance
characteristic of rod-shaped particles.[1a,g,5b,14] As the amount
of seed was decreased, the aspect ratio increased, and this
longer wavelength plasmon band gradually red-shifted and
broadened. The seed performs a crucial role in the growth
process. With increasing amount of seed, the rate of particle
formation also increases. In the absence of seed, particle formation rate is very slow, no solution color change is observed,
and a gray precipitate forms after approximately 24 h.

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Adv. Mater. 2001, 13, No. 18, September 14

stand the fate of the silver ions added for shape control. After
adding silver salt to a solution mixture of gold seed, cetyl-trimethyl ammonium bromide (CTAB), and ascorbic acid, we
did not observe the characteristic silver plasmon band at
400 nm. We propose that the Ag+ forms AgBr (Br from the
CTAB), and because ascorbate is a weak reducing agent, it
cannot reduce the silver ion. However, when the pH of the
solution was increased by adding NaOH, the reducing power
of ascorbate also increased.[16] As a result, silver ions reduced
to form silver nanoparticles as judged by a plasmon band
occurring around 400 nm. This result confirms that silver ions
are not reduced under our experimental (lower pH) reaction
conditions. The mechanism by which Ag+ assists in controlling
metal particle shape is not completely understood; however,
we observed a decrease in particle formation rate in the presence of silver salt. We hypothesize that Ag+ adsorbs at the Au
particle surface in the form of AgBr and restricts growth. The
adsorption of AgBr at the Au particle surface appears to stabilize the spheroids and rods. In absence of Ag+ the spheroids
formed, but due to their instability, converted to spheres. The
higher aspect ratio rods were more stable and formed even in
the absence of Ag+. By using larger amounts of silver ions we
were able to prepare u shaped particles, which appear as
hybrids between spheres and rods (Fig. 3).
In the previous electrochemical synthesis, cyclohexane was
used in the preparation of gold rods.[14] The role of the cyclohexane was to elongate the micellar structure to form a more
rod-like template.[13] We have seen that rods are formed in
the absence of cyclohexane, but addition of cyclohexane
increases the aspect ratio. If we consider that additional nucleation does not appear, and only autocatalytic surface growth

Fig. 2. Representative electron micrographs of Au nanoparticles and nanorods corresponding to the spectra ah in Figure 1. Considering only the spheroids and
rods, the average aspect ratios of the particles are 1.5, 2.4, 6.1, 8.0, and 10.0 for sets c, d, f, g, and h, respectively. The particles in sets a and b are nearly spherical and
have aspect ratios very close to 1.0.

Adv. Mater. 2001, 13, No. 18, September 14

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Figure 2 shows the transmission electron microscopy

(TEM) graphs of gold nanoparticles (sets ah) that correspond to the absorption spectra shown in Figure 1. The particles are either spherical (a and b), spheroidal (c and d), or
rod-like (fh). The average aspect ratio of the particles increased with decreasing amount of seed as the spheroidal particles gradually grew into rod-like structures. Spherical side
products were also observed with the spheroidal and rod-like
particles. However, the relative percentage of side products
decreased considerably compared to previously reported solution synthetic methods where no seed was used.[15] This was
corroborated from the appearance of additional intense plasmon bands at longer wavelength region that correspond to
spheroids/rods. The average number of spherical side products ranged between 4050 % of the total particles, as determined from counting ~1000 particles in the TEM images.
The lower aspect ratio spheroids are unstable under our experimental conditions and gradually convert to spheres. This
was confirmed by their change in plasmon absorbance with
time. For example, the long wavelength plasmon band of
spheroidal particles in set c (aspect ratio ~1.5) gradually disappears within 24 h, leaving only one plasmon band at
~530 nm. However, all other spheroids and rods are stable for
at least one month.
The presence of AgNO3 is essential for producing and controlling the aspect ratio of spheroids/rods. In absence of Ag+,
fewer rods (~1020 % of the total particles) form and their
aspect ratios are higher and have a wide distribution, ranging
from ~515. The aspect ratio could not be controlled by varying the seed-to-metal salt ratio when silver ions were not present in solution. We performed separate experiments to under-

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Preparation of TEM Grid: The TEM graphs were taken after separating the
surfactant from the metal particles by centrifugation. Typically 1 mL of the
sample was centrifuged for 12 min at a speed of 14 000 r/min. The upper part of
the colorless solution was removed and the solid portion was redispersed in
1 mL of water. 2 lL of this redispersed particle suspension was placed on a carbon coated copper grid and dried at room temperature.
Received: July 28, 2000
Final version: October 10, 2000

Fig. 3. Electron micrographs of u shaped Au particles formed in the presence of

5 times excess AgNO3 (2.5 lM). Other conditions for preparation of the particles shown here in sets a and b correspond to sets f and g in Figure 2.

occurs at the preformed seed surface, then the final particle

size can be calculated for spherical particles from the following equation:
r = rs{([Ma] + [M0])/[M0]}1/3

(1)

where rs and r indicate particle radius for seed and larger

particle, and [M0] and [Ma] indicate metal concentrations in
seed and added ion.[11,12a] Our observations show that final particle sizes closely match the calculated value for spherical side
products and lower aspect ratio spheroids but were larger
(1.53.0 times) for rods. Faster growth rates along the nanorod
long axis possibly contributes to the larger size of the rods. The
role of micellar template is to direct the particle growth along
one dimension, and finally stabilize the rods. Thus a simple
seed-mediated growth approach is used to prepare gold spheroids and nanorods with different aspect ratios which can be
controlled by varying the ratio of seed to metal salt.

Experimental
Instrumentation: Absorption spectra of the prepared solutions were measured using a CARY 500 Scan UV-vis-near-infrared (UV-vis-NIR) spectrophotometer. TEM images were acquired with a JEOL JEM-100CXII electron
microscope.
Preparation of Growth Solution: First, 100 mL of 250 lM HAuCl4 aqueous
solution was prepared in a conical flask. Next 3.0 g of solid CTAB, 1.5 mL of
cyclohexane, and 2.0 mL of acetone were added to the gold salt solution. (The
role of acetone is to loosen the micellar framework, and cyclohexane is necessary for enhancing the rod-like micellar structure.) The solution was heated to
60 C while stirring to dissolve the CTAB. After allowing to cool to room temperature, the solution was used as the growth solution.
Preparation of 34 nm Au seeds: First, a 20 mL aqueous solution containing
0.25 mM HAuCl4 and 0.25 mM trisodium citrate was prepared (trisodium
citrate acts as a capping agent and thus restricts particle growth [17]). Next,
0.6 mL of a 0.01 M NaBH4 solution was added at once into the gold solution
under constant stirring. Stirring was continued for another 30 s. The solution
turned a wine red color indicating particle formation. The solution was used as
a stock gold seed solution 4 h after its preparation, allowing all the excess borohydride to degrade. The solution should be used within 24 h of its preparation.
Beyond this time a thin gold film forms at the water surface, indicating particle
aggregation.
Growth of Spheroids and Rods: Eight different sets of solutions were prepared each containing 10 mL of growth solution and varying amounts (1.00,
0.50, 0.25, 0.125, 0.09, 0.06, 0.03, and 0.015 mL) of Au seed solution. 5 lL of
10 mM AgNO3 was added to each set and mixed thoroughly. Finally, 0.50 mL
of freshly prepared ascorbic acid (10 mM) was mixed with each set. The color
of the solutions turned pink to violet within 10 min, depending upon the
amount of seed present.

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[1] a) J. A. Creighton, D. G. Eadon, J. Chem. Soc., Faraday Trans. 1991, 87,

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SolGel Template Synthesis of an Array of Single

Crystal CdS Nanowires on a Porous Alumina
Template**
By Huaqiang Cao, Yan Xu, Jianming Hong, Huibiao Liu,
Gui Yin, Baolong Li, Chenyang Tie, and Zheng Xu*
The research field of one-dimensional nanostructured materials constitutes one of the most important frontiers in materials science.[1,2] These materials are of fundamental importance, e.g., nanowires and nanotubes have great potential for
testing and understanding fundamental concepts about the
roles of dimensionality and size on physical properties, and
they hold promise for a wide range of potential applications,
including chemistry, physics, electronics, optics, materials
science, and biomedical sciences. Many attempts have been
made to fabricate one-dimensional nanostructured materials.[36] However, it is still a challenge to produce an ordered,
monodisperse, single crystal nanowires array. The template
method is one of the most efficient methods for the synthesis
of well-distributed tubular and fibrillar nanostructures within
the pores of an alumina membrane or other nanoporous solid.
Alumina membranes have been used as an ideal template to
prepare cylindrical nanowires with a narrow diameter distribution, because they possess uniform and nearly parallel
porous structures. But the template method generally produces polycrystalline materials. With the solgel template
method we have fabricated arrays of single crystal C60[7] and
C70[8] nanowires.
Cadmium sulfide is an important semiconductor material,
and has received much interest.[919] Electrochemical deposi-

[*] Prof. Z. Xu, Dr. H. Q. Cao, Dr. Y. Xu, Dr. H. B. Liu, Dr. G. Yin,
Dr. B. L. Li, C. Y. Tie
Coordination Chemistry Institute
State Key Laboratory of Coordination Chemistry
Center of Nanometer Science and Technology
Nanjing University
Nanjing 210093 (P. R. China)
E-mail: profzxu@jlonline.com
J. M. Hong
Center for Materials Analysis
Nanjing University
Nanjing, 210093 (P.R. China)

[**] We are grateful to the National Natural Science Foundation of China for
the key project, Natural Science Foundation of Jiangsu Province, and to
the staff at Nanjing University for the analysis and measurement of SEM
and TEM, performed by the Center for Materials Analysis, Nanjing University.

Adv. Mater. 2001, 13, No. 18, September 14

tion of CdS nanowires in the pores of an alumina membrane

has been reported.[20,21] However, this method results in a lot
of stacking faults and twinned segments in these nanowires;
moreover, the alumina membrane is not stable in conventional aqueous acid electrolytes containing Cd2+ and sources
of colloidal sulfur. Recently, an aligned CdS single-crystal nanowire array was synthesized by electrochemical deposition.[21] Here we report a new way to fabricate an ordered array of single-crystal CdS nanowires in an alumina membrane
by the solgel method.
The array of CdS nanowires was obtained in the pores of
an alumina membrane with 100 nm diameter. The alumina
template was immersed in a Na2S solution containing mercapto ethanol (HSCH2CH2OH). It well known that alumina
is a Lewis acid with the acidity center on Al3+;[22] the S2 ions
will preferably attach to the alumina wall, at the reaction
sites with Cd2+, and induce the deposition of colloidal CdS
particles on the alumina wall. It is important to note that
deposition does not work when the alumina template is
immersed in the CdCl2 solution first, and the CdS mainly
precipitates on the surfaces of the alumina membrane.
HSCH2CH2OH is used as a protecting agent absorbed on
the surface of the CdS colloidal particles to make the CdS
particles very fine. Figure 1 shows scanning electron microscopy (SEM) images of the CdS nanowires arrays. The lengths
of the nanowires are ca. 60 lm, corresponding to the thickness of the alumina template.

Fig. 1. SEM images of CdS nanowires prepared by solgel template synthesis.

a) Aerial general view. b) Part-view.

Figure 2a shows a transmission electron microscopy (TEM)

image of the CdS nanowire obtained after removal of the alumina membrane by dissolution in 6 N NaOH. The electron
diffraction data are shown in Figure 2b. Analysis of the electron diffraction pattern proves that only crystals with a wurtzite structure are present. Furthermore, the CdS nanowires
synthesized here are single crystals, and the pattern can be
indexed as (102), (104), (203), and (105) with d = 2.421, 1.502,
1.439, and 1.244 , respectively. This matches well with the
hexagonal crystalline CdS (ASPDF 6-0314) structure with an
error <3 %.
The length of isolated nanowires is shorter than the thickness
of the alumina template, which may be disrupted when pol-

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