Materials Letters 58 (2004) 2326 – 2330

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Synthesis of gold nanorods and nanowires by a microwave–polyol method

Masaharu Tsuji a,b,c,*, Masayuki Hashimoto b, Yuki Nishizawa b, Takeshi Tsuji a,b,c
a
Institute for Materials Chemistry and Engineering, Kyushu University, Kasuga, Fukuoka 816-8580, Japan
b
Department of Applied Science for Electronics and Materials, Graduate School of Engineering Sciences, Kyushu University, Kasuga,
Fukuoka 816-8580, Japan
c
CREST, Japanese Science and Technology, Kasuga, Fukuoka 816-8580, Japan
Received 11 December 2003; accepted 20 February 2004

Available online 17 April 2004

Abstract

HAuCl4 was reduced by ethylene glycol, in the presence of polyvinylpyrrolidone (PVP) under microwave (MW) heating in a continuous
wave (CW) mode for 2 min. Dominant products were polygonal nanoplates and close-to-spherical nanoparticles of gold. In addition, small
amounts of single crystalline gold nanorods and nanowires (0.5 – 3% of total number of products) with diameters of 20 – 100 nm and lengths
of 0.6 – 5 Am were produced. The diameter and length of gold nanorods and nanowires could be controlled by changing the HAuCl4
4H2O/
PVP ratio. The formation mechanism of anisotropic gold nanostructures was discussed.
D 2004 Elsevier B.V. All rights reserved.

Keywords: Gold nanowire; Polyol method; Microwave heating; TEM

1. Introduction
A variety of metallic nanostructures, including particles,
prisms, plates, rods, and wires, have generated significant
scientific and technological interest because of their
unique optical properties as well as their novel chemical
and catalytic properties. Among them, gold nanostructures
with well-defined dimensions represent a particular class
of interesting nanomaterials to synthesize and study be-
cause of their wide practical application. Compared with
extensive experimental studies on the synthesis of gold
nanoparticles and nanorods with well-defined dimensions
[1 –6], little work has been made for the synthesis of gold
nanowires. Here, we define nanorods and nanowires as
materials with aspect ratios of 220 and >20, respectively.
The most widely used method for generating metallic
nanowires is template-directed synthesis that involves
either chemical or electrochemical depositions [7 –9]. For
the formation of needle and rod/wire shapes of gold,
polycarbonate track-etched membranes [7], pores of alu-
* Corresponding author. Institute for Materials Chemistry and Engi-
neering, Kyushu University, Kasuga, Fukuoka 816-8580, Japan. Fax: +81-
92-583-7815.
E-mail address: tsuji@cm.kyushu-u.ac.jp (M. Tsuji).
mina membranes [8], and HTAC (25 –30 wt.%) [9] were
used as templates. The disadvantage of the template-
directed synthesis is that the templates must be removed
in order to recover the individual nanowires. To avoid the
step of template removal, a new convenient process must
be developed.
Microwave (MW) dielectric heating is a new promising
technique for preparation of size-controlled metallic nano-
structures due to its rapid heating and penetration. Gold
nanoparticles have recently been synthesized under MW
heating (480 –1100 W) by Tu and Liu [10], Jiang et al. [11],
Pastoriza-Santos and Liz-Marzán [12], and Liu et al. [13].
When HAuCl4
3H2O or HAuCl4 was reduced in methanol
[10], ethanol [11], N,N-dimethylformamide [12], or water
and sodium citrate [13] for 0.515 min, spherical nano-
particles with diameters below 85 nm were synthesized.
Malikova et al. [14] synthesized triangular and hexagonal
nanoplates of gold by reduction of HAuCl4
3H2O in N,N-
dimethylformamide with salicylic acid, while Gao et al. [15]
prepared them in aqueous solutions with the surfactant
cetyltrimethylammonium bromide under conventional oil-
bath heating. These triangular and hexagonal nanoplates
have also been synthesized more selectively by the photo-
reduction of NaAuCl4 and HAuCl4 in the presence of PVP
or polyvinylalcohol [16,17].

0167-577X/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2004.02.020
 M. Tsuji et al. / Materials Letters 58 (2004) 2326–2330
More recently, we have prepared polygonal gold nano-
plates by reduction of HAuCl4
4H2O in ethylene glycol in
the presence of PVP under MW heating in a CW or pulse
mode [18 –20]. A mixture of triangular, square, hexagonal,
and close-to-spherical gold nanoplates was synthesized.
One reason for the lack of formation of polygonal nano-
plates in the previous MW – polyol methods [10 – 13] may
be lower reaction temperatures in methanol (b.p. 65 jC),
ethanol (78 jC), water (100 jC), and N,N-dimethylfolma-
mide (156 jC) than that in ethylene glycol (198 jC) used
in our study.
Sun et al. [21] have succeeded in the synthesis of
uniform silver nanowires by reducing AgNO3 with ethyl-
ene glycol in the presence of seeds and PVP under oil-
bath heating. They found that both morphology and
aspect ratios of these silver nanostructures could be varied
from nanoparticles and nanorods to long nanowires by
adjusting the reaction conditions, including the ratio of
PVP to silver nitrates. By analogy with their study for
silver, similar anisotropic nanostructures may be created in
the case of gold. In the present study, we have attempted
to synthesize gold nanorods and nanowires by a MW –
polyol method in a one pot. In addition to isotropic
polygonal nanoplates and close-to-spherical nanoparticles,
small amounts of anisotropic gold nanorods and nano-
wires could be synthesized under CW MW heating for
only 2 min. It was found that the diameter and length of
gold nanorods and nanowires can be controlled by chang-
ing the HAuCl4
4H2O/PVP ratio. To the best of our
knowledge, this is the first synthesis of gold nanorods
and nanowires by a MW – polyol method within a few
minutes. The great advantage of this technique is that
templates are unnecessary as well as a short crystallization
time.
2. Experimental
An MW oven was modified by installing a condenser and
thermocouple through holes of the ceiling and a magnetic
stirrer coated with Teflon at the bottom. A 100-ml glass flask
was placed in an MW oven and connected to a condenser. A
resolved solution of HAuCl4
4H2O (20 –160 mg: 0.048 –
0.384 mmol) in ethylene glycol (20 ml: 0.357 mol) contain-
ing PVP (average molecular weight: 40,000, 2.288 or 4.576
g: corresponding to 20.6 or 41.2 mmol in term of monomeric
units, respectively) was irradiated by MW in a CW mode
(Shikoku Keisoku: 400 W). PVP acts as a stabilizer of small
gold nanostructures. For the solution irradiated by CW MW,
the temperature increased linearly and abruptly with a fast
heating rate and reached 196 jC after 1 min. The solution
was kept at 196 jC for 1 min. Thus, the total irradiation time
of MW was only 2 min. Product particles were characterized
by using transmission electron microscopy (TEM: JEOL
JEM-200CX) and UV-visible absorption spectroscopy (Shi-
madzu UV-2450). Before measurements of TEM photo-
2327
graphs, PVP was separated from gold nanostructures by
centrifugation. In this case, the reaction mixtures was diluted
with water and centrifuged at 13,000 rpm for 60 min.
Obscure TEM photographs were obtained without this
procedure due to a heavy coverage of PVP.
3. Results and discussion
At first, gold nanostructures were synthesized without
adding PVP in order to examine the effects of PVP. Thus,
only large spherical gold particles with diameters of 100–
300 nm were produced in solution, as shown in TEM
photograph (Fig. 1). These large spherical gold particles
must be formed by aggregation of small particles due to
the lack of surfactant PVP. Fig. 2(a) – (d) shows TEM
photographs of products obtained at four different
HAuCl4
4H2O/PVP molar ratios at a constant PVP con-
centration of 1.03 mmol dm 3 . At the lowest
HAuCl4
4H2O/PVP ratio of 1.2103, a small triangular,
square, rhombic, hexagonal, and close-to-spherical particles
with diameters of about 20– 40 nm are produced [Fig.
2(a)]. It should be noted that a nanowire with a diameter of
10 nm and a length of 600 nm is produced. At an
HAuCl4
4H2O/PVP ratio of 4.7103 [Fig. 2(b)], larger
triangular, square, rhombic, hexagonal, and close-to-spher-
ical particles with diameters of 20 –100 nm were produced.
In addition, a few nanorods and nanowires with a diameter
of f20 nm and lengths of 0.3 –1.4 Am were obtained. At
an HAuCl4
4H2O/PVP ratio of 9.3103 [Fig. 2(c)],
besides larger triangular and hexagonal nanoplates and
spherical particles, larger nanorods and nanowires with
diameters of 40 –80 nm and lengths of 0.4 –2.0 Am are
observed. At the highest HAuCl4
4H2O/PVP ratio of
1.9102 [Fig. 2(d)], in addition to small and large nano-
plates and spherical nanoparticles, a long nanowire with a
Fig. 1. TEM photographs of gold nanoparticles obtained by pulse MW
heating after 2 min without adding PVP.
2328 M. Tsuji et al. / Materials Letters 58 (2004) 2326–2330

Fig. 2. TEM photographs of gold nanostructures obtained by MW heating after 2 min. HAuCl4
4H2O/PVP molar ratios were (a) 1.2103, (b) 4.7103, (c)
9.3103, and (d) 1.9102 at a PVP concentration of 1.03 mmol dm3, and (e) 9.3103 at a PVP concentration of 2.06 mmol dm3. (f) Electron diffraction
pattern of the longest nanowire shown in panel (e).

diameter of 70 nm and a length of 3 Am is observed. These
results indicated that the size of particles and plates and the
diameter and length of nanorods and nanowires generally
increased with increasing the HAuCl4
4H2O/PVP ratio.
The relative number ratio of nanorods and nanowires to
the total number of products increased from about 0.5% to
2% with increasing the HAuCl4
4H2O/PVP molar ratio
from 1.2103 to 9.3103, then decreased to 1% at
the highest HAuCl4
4H2O/PVP ratio of 1.9102. As
shown later, the reduction of HAuCl4 was not completed
and a small amount of reagent remained in the solution at
the highest HAuCl4
4H2O/PVP ratio of 1.9102. When
more PVP was added, the reduction was completed. Fig.
2(e) shows the TEM photograph obtained at an
HAuCl4
4H2O/PVP ratio of 9.3103 under a higher
PVP concentration of 2.06 mmol dm3. Besides large
triangular and hexagonal nanoplates and spherical particles,
a few long nanowires with diameters of 60 –100 nm and
lengths of 2– 5 Am are produced. The relative number ratio
of nanorods and nanowires to the total number of products
was about 3%, which was larger than 1% under the
condition of Fig. 2(d).
The formation of anisotropic gold nanostructures proba-
bly starts by the following reactions according to reduction
mechanism of metallic ions in ethylene glycol proposed by
Fievet et al. [22]:
CH2 OH  CH2 OH ! CH3 CHO þ H2 O; ð1aÞ
6CH3 CHO þ 2AuðIIIÞ ! 2Au þ 6Hþ þ 3CH3 COCOCH3 :
ð1bÞ
As a result of the above reduction process, nucleation and
growth processes of gold yield a mixture of polygonal
plates and close-to-spherical nanoparticles. These nano-
plates and nanoparticles were well dispersed because of
the presence of a polymeric surfactant PVP that could
chemically adsorb onto the surfaces of gold solid probably
through an interaction between an N – C=O group and Au.
The surface energies of large particles are lower than those
of smaller ones. It is therefore expected that some small
nanoparticles are grown to larger ones via an Ostwald-
ripening process [23]. With the assistance of PVP, some of
the large nanoparticles were grown into anisotropic rod-
shaped and wire structures. PVP acts as a kinetically
controller of the growth rates of different crystalline faces
through adsorption and desorption. The PVP adsorbed on
specific crystalline surfaces could significantly decrease
 M. Tsuji et al. / Materials Letters 58 (2004) 2326–2330
their growth rates and lead to a highly anisotropic growth
[24]. Small gold nanoplates and nanoparticles were con-
sumed with increasing the reaction time, and then nano-
rods, nanowires, and more stable larger nanoparticles were
produced.
In the oil-bath heating, besides small amounts of short
nanorods with aspect ratios below 5 and nanoplates, large
spherical particles (>100 nm) were dominantly produced
[18 – 20]. No evidence for the formation of nanowires was
observed in the oil-bath heating. Particles and plates in the
oil-bath heating had less sharp edges than those formed
under CW MW heating due to lower crystallization. Size
and morphology of gold nanostructures obtained under MW
heating were different from those obtain by the oil-bath
heating. It was therefore concluded that irradiation effects of
MW such as MW dielectric heating of Au3+ and Au,
superheating, and/or nonthermal acceleration of chemical
reaction, contribute to the nucleation and growth of Au
nanostructures. Higher crystallization leading to single crys-
talline Au nanorods and nanowires under MW heating must
be induced by bursting nucleation due to rapid and homo-
geneous dielectric heating, which cannot be achieved by oil-
bath heating.
We found here that the HAuCl4
4H2O/PVP ratio plays an
important role in determining the morphologies of final
products. A heavy coverage of PVP on the surfaces of
nanoplates and nanoparticles results in an isotropic growth
for all different faces leading to small nanostructures. With
decreasing the coverage of PVP on the surfaces, the chance
for the formation of anisotropic rod and wire structures
increases. A decrease in coverage not only for the fast-
growing end faces, but also for the side surfaces of each
nanowire occurs at high HAuCl4
4H2O/PVP ratios. Thus,
thicker and longer nanowires are generally grown at high
HAuCl4
4H2O/PVP ratios.
Selected-area electron diffraction (ED) patterns of nano-
rods and nanowires were measured. A typical result
obtained for the longest wire in Fig. 2(e) is shown in Fig.
2(f). The ED spot array gave the hexagonal symmetry,
which was very similar to that reported previously for gold
nanoplates [14,16]. Similar ED patterns were obtained for
the other nanorods and nanowires. Based on these findings,
it was concluded that product nanorods and nanowires are
single crystals, and the incident electron beams are perpen-
dicular to (111) facets of the nanowires.
Fig. 3 shows UV-visible absorption spectra of reagent (a)
and products (b) –(f). The reactant spectrum is composed of
an absorption peak of AuCl4 at 328 nm. This peak either
becomes weak in spectrum (e) or disappears in spectra (b),
(c), (d), and (f). In the product spectra (b) – (f), broad surface
plasmon bands of gold nanostructures appear in the 500 –
800 nm region. The observation of a weak peak at 328 nm
in spectrum (e) indicates that the reduction of HAuCl4 was
not completed at a high HAuCl4
4H2O/PVP ratio. It is
known that a surface plasmon band of spherical gold nano-
particles appears in the 500600 nm region with a sharp
2329
Fig. 3. Absorption spectra of the original solution (a) and product solutions
(b) – (f) obtained by MW heating after 2 min. The HAuCl4
4H2O/PVP
molar ratios were (b) 1.2103, (c) 4.7103, (d) 9.3103, and (e)
1.9102, respectively, at a PVP concentration of 1.03 mmol dm3 and (f)
9.3103 at a PVP concentration of 2.06 mmol dm3. Sample solutions are
diluted by a factor of 50.
peak at about 520 nm [4,12,14], while plasmon bands of
gold polygonal plates are observed in the 550– 800 nm
region [18]. Thus, strong bands in the 500 – 600 nm region
observed in spectra (b) – (f) are ascribed to a surface plas-
mon band of spherical gold nanoparticles, while the longer-
wavelength bands above 600 nm are attributed to plasmon
bands of polygonal gold plates. The plasmon band of
polygonal gold plates increases and shifts to red from 610
to 680 nm with increasing the HAuCl4
4H2O/PVP ratio
from 1.2103 to 9.3103, as shown in spectra (b), (c),
and (d). Spectrum (e) is composed of a single peak at f570
nm, while spectrum (f) is composed of a broad band with a
peak at f620 nm. These observations are consistent with
the facts that dominant products in the former case are large
spherical particles [Fig. 2(d)], while those in the latter case
are large polygonal plates. It is known that gold nanorods
and nanowires give peaks above 700-nm region [5]. Be-
cause the relative number ratio of gold nanorods and nano-
wires to the total number of products was small (<3%), its
contribution to the observed absorption spectrum will be
small.
4. Conclusion
In summary, small amounts of single crystalline gold
nanorods and nanowires with lateral dimensions of 20 – 100
nm and 0.6 – 5 Am long were synthesized in a one pot under
CW MW heating (400 W) for only 2 min. The diameter and
length of nanorods and nanowires could be varied by
changing the HAuCl4
4H2O/PVP ratio. A further study is
in progress in order to enhance the yields of nanorods and
nanowires in the products.
2330 M. Tsuji et al. / Materials Letters 58 (2004) 2326–2330
Acknowledgements
This work was partially supported by a Grant-in-Aid for
Scientific Research No. 15651046 from the Japanese
Ministry of Education, Culture, Sports, Science, and
Technology. We thank the Research Laboratory for High
Voltage Electron Microscopy, Kyushu University for the use
of TEM.
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