Materials Chemistry and Physics 106 (2007) 5862

Hydrothermal synthesis of ZnO nanowires and nanobelts on a large scale

Hanmei Hu a,b, , Xianhuai Huang c , Chonghai Deng d , Xiangying Chen b , Yitai Qian b
a

Department of Material Science and Engineering, Anhui Institute of Architecture and Industry, Hefei, Anhui 230022, Peoples Republic of China
b Structure Research Laboratory and Department of Chemistry, University of Science and Technology of China,
Hefei, Anhui 230026, Peoples Republic of China
c Department of Environment Engineering, Anhui Institute of Architecture and Industry, Hefei, Anhui 230022, Peoples Republic of China
d Hefei University, Hefei, Anhui 230022, Peoples Republic of China
Received 28 August 2006; received in revised form 30 April 2007; accepted 6 May 2007

Abstract
ZnO nanowires (60%) and nanobelts (40%) have been fabricated on a large scale via a low temperature one-pot hydrothermal technique.
Na2 CO3 was introduced not only as alkaline source but also as a controllable reagent for the crystal growth of ZnO. The comparison experiment
results indicate that the adding amount of Na2 CO3 greatly affect the length/diameter aspect ratios of 1D ZnO nanocrystals. In addition, the
introduction of surfactant SDSN was indispensable in controlling the growth of belt-like ZnO. Room temperature photoluminescence spectrum
showed a weak UV band emission at 379 nm and a strong broad yellow emission around 564 nm. A possible mechanism on the formation of the
ZnO nanowires was proposed.
2007 Elsevier B.V. All rights reserved.
Keywords: Nanostructures; Chemical synthesis; Electron microscopy; Optical properties

1. Introduction
Nanorods and nanowires represent a class of one-dimensional
(1D) nanostructures, in which the carrier motion is restricted in
two directions such that they usually show interesting properties that differ from those of the bulk or spherical nanoparticles
of the same chemical composition [1,2]. These nanostructures
have potential applications as important components and interconnects in nanodevices [3,4].
ZnO is one of the most promising materials for optoelectronic
applications due to its wide band gap of 3.37 eV and large exciton
binding energy of 60 meV [5]. It has been recognized as one of
the promising nanomaterials in a broad range of high-technology
applications, such as photodetector [6], light-emitting diode [7],
gas sensor [8], solar cell [9], optical modulator waveguide [10],
and surface acoustic wave devices [11], etc.
In recent years, various methods have been used to synthesis 1D ZnO nanostructures, such as thermal evaporation
process [1214], chemical vapor deposition [15,16], metalor Corresponding author at: Department of Material Science and Engineering,
Anhui Institute of Architecture and Industry, Hefei, Anhui 230022, Peoples
Republic of China. Tel.: +86 551 3526891.
E-mail address: hmhu@ustc.edu (H. Hu).

0254-0584/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2007.05.016

ganic vapor-phase epitaxy [17], microwave plasma deposition

[18], pyrolysis [19], hydrothermal method [20,21], and etc. The
hydrothermal method is a promising one for fabricating ideal
nanomaterial with special morphology because of the low cost,
low temperature, high yield, scalable process. In the present
work, ZnO nanowires (60%) and nanobelts (40%) have
been produced in large quantities, using ZnCl2 as zinc source,
Na2 CO3 as mineralizer, and sodium dodecyl sulfonate (SDSN)
as morphology controller agent, via a low temperature one-pot
hydrothermal technique.
2. Experimental procedure
All chemicals (analytical grade reagents) were purchased from Shanghai
Chemical Reagents Co. and used without further purification. In a typical experimental procedure, 0.2 g ZnCl2 , 1.5 g SDSN and 20 g Na2 CO3 (4.72 M) were
successively added into a 50 mL Telfon-lined stainless steel autoclave, which
was then filled with distilled water up to 90% of the total volume. The obtained
reaction mixture was stirred for an additional 30 min. The autoclave was sealed
and maintained at 140 C for 12 h. After the reaction was completed, the resulting white products were filtered off, washed with ethanol and hot distilled water
for several times, and then finally dried in a vacuum at 60 C for 4 h.
The phase purity of the as-synthesized products was examined by X-ray
diffraction (XRD) using a Philips XPert PRO SUPER X-ray diffractometer

equipped with graphite monochromatized Cu K radiation ( = 1.541874 A).

The morphology and size of the obtained ZnO products were further observed by

H. Hu et al. / Materials Chemistry and Physics 106 (2007) 5862

59

transmission electron microscope (TEM) and field-emission scanning electron

microscope (FESEM), which were taken on a Hitachi model H-800 (200 kV)
and a field-emission microscope (JEOL-JSM-6700F 15 kV), respectively. The
HRTEM image was taken with a JEOL-2010 transmission electron microscope
with an accelerating voltage of 200 kV. SEM images were taken on an X-650
scanning electronic microanalyzer. The photoluminescence (PL) spectrum was
recorded on a Steady-state/Lifetime Spectrofluorometer (FluoRoloG-3-TAU).

3. Results and discussions

Fig. 1(a) shows the typical XRD pattern of the as-prepared
ZnO products. All the reflections can be indexed to wurtzite
and
structure of ZnO with lattice parameters a = 3.247 A

c = 5.20 A, in good agreement with the reported data for ZnO

c = 5.205 A,
JCPDS File, 5-664). No character(a = 3.249 A,
istic peaks were detected for the other impurities such as
Zn(OH)2 , ZnCO3 . Fig. 1(b) and (c), respectively, shows the
low-magnification and high-magnification FESEM image of the
obtained sample, which indicates that the as-synthesized ZnO
products were composed of wire-like (ratio: 60%) and beltlike (ratio: 40%, indicated by the black arrow in Fig. 1(c))
nanostructures, and their lengths are up to 20 m. The diameters of ZnO nanowires are about 20100 nm and the widths of
ZnO nanobelts are in the range of 80250 nm.
Further structural characterizations of the ZnO
nanowires/belts were performed by TEM and HRTEM.
Fig. 2(a) shows the low-magnification TEM image of the ZnO
nanowires. With increasing the TEM magnification, belt-like
ZnO nanostructures are apparently observed (Fig. 2(b)).
Fig. 2(c) shows the TEM image of a well-developed single
crystal ZnO nanobelt with width of 220 nm. The SAED pattern
of the nanobelt (inserted at the upper left corner of Fig. 2(c))
indicates its single crystal nature and its growth direction along
c-axis. The typical HRTEM image, recorded from a certain
nanowire, is shown in Fig. 2(d). The crystal lattice fringes are
clearly observed and average distance between the adjacent
lattice planes is 0.52 nm, corresponding to the (0 0 0 1) plane
lattice distance of hexagonal-structured ZnO, which further
proves that ZnO nanowires/belts prepared in the present system
grow along [0 0 0 1] direction.
In the present reaction system, the possible formation process
for hexagonal ZnO phase under hydrothermal condition can be
expressed as follows:
CO3 2 + H2 O HCO3 + OH

(1)

HCO3 + H2 O H2 CO3 + OH

(2)

Zn2+ + 4OH Zn(OH)4 2

Zn(OH)4

ZnO + H2 O + 2OH

(3)

(4)

A suitable hydrothermal system may be helpful for the nucleation and subsequent 1D preferential growth of ZnO crystals. It
was interestingly found that the amount of mineralizer Na2 CO3
play a critical role in the control growth of ZnO nanowires. A
series of comparison experiments were performed by changing the adding amount of Na2 CO3 without using SDSN in the
reaction system. Fig. 3(a) shows the TEM images of the prepared ZnO products when the adding amount of Na2 CO3 was

Fig. 1. (a) XRD pattern of the as-prepared ZnO products. (b) Low-magnification.
(c) High-magnification FESEM images of the ZnO products.

5 g (1.05 M), which take on bowknot-like morphologies. These

bowknots are built from several to tens of bipyramidal ZnO
twinned crystals with average diameters of 810 nm and lengths
of 1020 m. The inset figure clearly shows the details of an
individual bowknot-like microcrystalline. When 10 g Na2 CO3

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H. Hu et al. / Materials Chemistry and Physics 106 (2007) 5862

Fig. 2. (a and b) TEM images of the as-prepared ZnO products, indicating the coexistence of wire-like and belt-like nanostructure. (c) The TEM image of an individual
ZnO nanobelt and corresponding SAED pattern (inserted at the upper left corner). (d) HRTEM image taken from an individual ZnO nanowire.

(2.10 M) was added into the reaction system, a great deal of

dumbbell-like ZnO twinned crystals with average diameters of
550 nm and lengths of 812 m were obtained (Fig. 3(b)). In
addition, another novel structure coexisting with themhollow
hexagonal prism with one closed end (see the enlarged part
inserted in the lower right of Fig. 3(b)) was observed. Most
of them assembled to forming flower-like aggregates. It is suggested that the growth mechanism for this novel structure should
be similar to that for the reported Te nanotubes [22,23]. In
this case, secondary nucleation and growth would preferentially occur at the circumferential edges of the hexagonal prism

because these sites had relatively higher free energies than other
sites on its surface. After a period of rapid growth, the concentration of Zn(OH)4 2 was decreased, which could not satisfy the
growth of rod. Thus, the hollow prism would be formed because
of no mass transportation to the inner region. When the adding
amount of Na2 CO3 was increased to 15 g (3.54 M), some
wire-like ZnO nanocrystals with average diameters of 180 nm
and lengths up to 15 m appeared in the synthesized products
(Fig. 3(c)). Large quantities of ZnO nanowires with average
diameters of 80 nm and lengths up to 20 m were produced when
the adding amount of Na2 CO3 was 20 g (4.72 M), and only

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61

Fig. 3. SEM or FESEM images of ZnO products prepared from different adding amount of NaCO3 under hydrothermal conditions in the absence of SDSN: (a) 5 g;
(b) 10 g; (c) 15 g; (d) 20 g.

several belt-like nanocrystals were also occasionally observed

(Fig. 3(d)). The above comparison experiments suggested that
the length/diameter of 1D structured ZnO strongly depend on the
amount of Na2 CO3 . When the solution changed from undersaturation (5 g Na2 CO3 ), lower saturation (10 g Na2 CO3 ), saturation
(15 g Na2 CO3 ) to high supersaturation (20 g Na2 CO3 ), the diameter of 1D ZnO crystallites was greatly reduced from micro to
nanosize.
Generally speaking, the morphology control of ZnO under
hydrothermal conditions should be determined by two main
factors: one is the internal crystal structure of ZnO, the other
is the selected external condition, such as reaction temperature,
reaction additive, mineralizer and so on. It is well known that
ZnO is a polar hexagonal and highly anisotropic crystal, and
its oriented growth direction is along the c-axis [24]. From a
kinetics point of view of ZnO crystal growth, Zn(OH)4 2 is
proposed to be the growth unit and is directly incorporated into
ZnO crystal lattice at the interface under given conditions [24].
In the process of operating comparison experiment, due to the

different amount of mineralizer Na2 CO3 , the concentration of

Zn(OH)4 2 is also different in the aqueous solution, which will
result in different nucleation (such as nuclei size) and crystal
growth and further affect the ratio of length/diameter of 1D ZnO
crystallites.
Based on the above analysis, we proposed that a higher supersaturation solution is the key driving force for the growth of
ZnO nanowires. A possible formation mechanism of the ZnO
nanowires may be described as follows: first, an supersaturate
Zn(OH)4 2 precursor solution is obtained under appropriately
higher concentration of Na2 CO3 (20 g). Then, in the initial stage
of hydrothermal decomposition, much smaller nuclei are produced through a short burst of homogeneous nucleation process
[25]. Moreover, the size of a nucleus will determine the lateral
dimension of an1D ZnO nanostructure. Finally, after the nucleation step, the growth units of Zn(OH)4 2 are subsequently
incorporated into these seeds along the c-axis of ZnO crystal
lattice[24]. With the prolongation of reaction time, ultra-long
ZnO nanowires can be fabricated.

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H. Hu et al. / Materials Chemistry and Physics 106 (2007) 5862

the formation of ZnO nanobelts. The present strategy of fabricating ZnO nanowires/belts is simple, reproducible, high yield,
easily operating and may be applied to scale up to industrial
production.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (Grant No. 20501002), the Education
Department of Anhui Province (Grant No. 2005KJ110), and
Anhui Provincial Young Teacher Sustentation Project of Anhui
(Grant No. 2005jq1147zd).
References
Fig. 4. Photoluminescence spectrum of ZnO nanowires and nanobelts measured
at room temperature.

With respect to the formation of ZnO nanobelts, the directing role of surfactant SDSN is undoubtedly significant. In the
absence of SDSN, the obtained ZnO products were mainly composed of nanowires, as well as occasionally several nanobelts.
We proposed that the possible function of SDSN is to kinetically control the growth rates of different crystalline faces of
ZnO crystals by interacting with these faces through adsorption and desorption under suitable kinetic growth condition, and
finally resulting in the formation of ZnO nanobelts. The exact
role of SDSN in the present system is still under investigation.
The room temperature PL spectrum of as-prepared ZnO
nanowires and nanobelts, shown in Fig. 4, was obtained with
an excitation wavelength of 325 nm. Two luminescence bands,
including a weak UV emission centered at 379 nm and a strong
broad yellow emission with peak located at 564 nm, were
observed. The UV emission band was attributed to the near-band
emission of the ZnO products, coming from the direct recombination of the conduction band electrons and the valence band
holes. The deep-level involved in the yellow luminescence was
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4. Conclusion
In summary, ZnO nanowires (60%) and nanobelts (40%)
have been synthesized on a large scale via a low temperature
one-pot hydrothermal technique. The experimental results reveal
that mineralizer Na2 CO3 was introduced not only as alkaline
source but also as a controllable reagent for the crystal growth of
ZnO. The adding amount of Na2 CO3 could affect the concentration of Zn(OH)4 2 precursor, and made the average diameters
of 1D ZnO decrease from 810 to 80 nm with the increase of
Na2 CO3 . In addition, the surfactant SDSN played an assisting
role in controlling the growth of belt-like ZnO. It is proposed
that the possible function of SDSN is to kinetically control the
growth rates of different crystalline faces of ZnO crystals by
interacting with these faces through adsorption and desorption
under suitable kinetic growth condition, and finally resulting in

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