Trans. Mat. Res. Soc.

Japan 40[1] 11-13 (2015)

Catalyst-Free Synthesis of Zinc Oxide Nanowires

by Thermal Oxidation of Zinc Film

Xuyang Li, Naoki Kishi and Tetsuo Soga*

Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555
* Corresponding author: Fax: 81-52-735-5532, and/or e-mail: soga@nitech.ac.jp

 

Zinc oxide (ZnO) nanowires with high aspect ratio were successfully
synthesized by annealing the Zn films in the air prepared by electron beam evaporation.
The diameter and the length of nanowires are 500 - 100 nm and 5 - 10m, respectively.
Transmission electron microscopy analysis showed that ZnO nanowire is highly
crystalline in nature. The experimental results were explained by vapor -solid growth
model.
Key words: zinc oxide, nanowire, thermal oxidation

1. INTRODUCTION using ZnO tablet for comparison. The Zn film

Zinc oxide (ZnO) nanowires have
attracted attentions for various applications, such
as solar cells, photo catalyst, sensors, field
emitters, etc. Although the synthesis of ZnO
nanowire is relatively easy, the synthesis of
uniform ZnO nanowire with high aspect ratio
without using any sophysiticated equipment has
not been established yet.
ZnO nanowires are usually synthesized by
chemical vapor deposition [1], spray pyrolysis
deposition [2], sol-gel method [3],
electrochemical deposition [4], hydrothermal
method [5], etc. In most cases, metallic catalysts
are used for the synthesis. But if it is possible to
synthesize ZnO nanowires free from metals, it
becomes possible to produce high-purity
nanowires without containing any impurity
element, resulting in the improvement of device
properties.
Recently, catalyst-free synthesis has been
studied by using ZnO power, Zn powder, Zn
substrate. Dai et al reported the synthesis of
tetrapot-like ZnO nanorod, through the oxidation
of Zn powder [6]. Sekar et al reported the
synthesis of ZnO nanowire on Si substrate by the
oxidation of Zn powder [7]. More recently, Ren et
al reported the synthesis of ZnO nanowires by
thermal oxidation of Zn substrate [8].
In this letter, we report that ZnO nanowires
are synthesized by the oxidation of Zn films on
glasses by electron beam (e-beam) evaporation in
the air. It is shown that the ZnO nanowires with
the diameter of 50 – 100 nm and the length of 5 –
10 m are synthesized by the simple method.
2. EXPERIMENTAL
The Zn film was prepared on glass
substrate using Zn wire (99.9%) by e-beam
evaporation at room temperature. The thickness of
Zn film is about 500 nm. The ZnO film was
prepared on glass substrate by e-beam evaporation
and ZnO film on glass substrates were heated up
to 600 ºC for 3 hours in the quartz tube with
electric furnace. The diameter of quartz tube is 75
mm and the flow rate of dry air is 0.5 l/min. The
samples were characterized by X-ray diffraction
(XRD), scanning electron microscopy (SEM) and
transmission electron microscopy (TEM).
3. RESULTS AND DISCUSSION
Fig. 1(a) and 1(b) show the SEM images of
500 nm-thick as-deposited Zn and ZnO films
prepared on glass substrate by e-beam evaporation
at room temperature, respectively. In Fig. 1(a),
the grain of metallic Zn with the diameter of
around 400 – 500 nm are randomly observed. On
the other hand, ZnO film deposited by e-beam is
relatively smooth compared with Zn film as
shown in Fig. 1 (b).
The SEM images of Zn and ZnO films after
annealing at 600 ºC are shown in Fig. 2(a) and Fig.
2(b), respectively. Fig. 2(a) reveals that high
density of wire-like structures with the length of
5-10m are observed. On the other hand,
wire-like structures are not observed in Fig. 2 (b).
It means that wire-like structures are observed
after annealing the Zn film in the air. On the other
hand, the grain size is increased by the annealing
of ZnO film, without forming wire-like structures.
The cross-sectional SEM image shows that the
nanowires grow towards random orientation.
In order to evaluate the crystal structure of
the films, XRD measurement was performed in
both samples. Fig. 3 (a) and 3 (b) show the XRD
patterns taken from the Zn and ZnO films after
annealing at 600 ºC, respectively. All the peak
in Fig. 3(a) and 3 (b) are indexed as wurtzite ZnO
with lattice constant of a = b = 0.325 nm and c =
0.521 nm. No peak corresponding to Zn or other
compounds are observed. It means that not only
the films but also wire-like structures are ZnO.

11
12 Catalyst-Free Synthesis of Zinc Oxide Nanowires by Thermal Oxidation of Zinc Film

The difference of Fig. 3 (a) and 3 (b) is due to that
of crystallization process of ZnO.
The ZnO nanowires were analyzed by TEM
for the further investigation. Fig. 4 (a) and 4 (b)
show the TEM photograph and selected -area
diffraction pattern of ZnO nanowires synthesized
by annealing Zn film at 600 ºC for 3 hours in the
air, respectively. The diamener of ZnO nanowire
is determined to be around 80 nm and the ZnO
nanowire is single crystalline with hexagonal
structure. It means that the single crystalline ZnO
nanowires are synthesized by annealing the Zn
films deposited by e-beam evaporation in the air.
The TEM observation of several ZnO nanowires
indicates that the diameter is between 50 – 100
nm.

(a) 700

002
101
600

500

Intensity
400

Indensity

103
300

100

102

201
200

110
100

0
20 25 30 35 40 45 50 55 60 65 70 75
2 (degree)

2 (degree)
(b)
Fig. 1 SEM images of 500nm-thick Zn (a) (a)
and ZnO (b) films without annealing.
101

400

300
Indensity
Intensity

200
002

201

100
102

0
20 25 30 35 40 45 50 55 60 65 70 75
2 (degree)
2 (degree)
(a)
(b)
Fig. 3 XRD pattern of ZnO films with annealing
Zn film (a) and ZnO film (b) at 600 ºC in the air.

The vapor-liquid-solid (VLS) mechanism

(b)
Fig. 2 SEM images of the samplse with annealing
Zn film (a) and ZnO film (b) at 600 ºC in the air.
and vapor-solid (VS) mechanism have been
proposed for the growth of ZnO nanowires [9, 10].
But our results cannot be explained by VLS
mechanism because the metal catalysts are not
used in the synthesis.
Our results suggest the “self-catalytic VLS
mechanism” as follows. The Zn film deposited by
e-beam evaporation is composed of r andom grains
with the diameter of 400 – 600 nm. When the Zn
film is heated to 600 ºC, the Zn film is melted and
aggregated to form the Zn film since the melting
 Xuyang Li et al. Trans. Mat. Res. Soc. Japan 40[1] 11-13 (2015) 13

point of Zn is 420 ºC. At the same time, the ZnO x Zn (Solid)

(x < 1) is formed by the reaction of Zn and O 2 in
the air. As Zn becomes supersaturated, ZnO
Glass Room temp
with small size is formed on the surface, which
becomes the nuclei for the growth of nanowires
[7, 11] and the long ZnO nanowires with high
aspect ratio are formed via “self-catalyst”. The O2 O2 O2 O2
growth model is schematically shown in Fig. 5.
Zn Droplet
(Liquid)
Glass
600 ℃

O2 O2 O2 O2
ZnO nuclei

Glass
600 ℃

ZnO nanowire

Room temp
Glass
(a)

Fig. 5 Growth model.

(b)
Fig. 4 TEM image (a) and selected area
diffraction pattern (b) of ZnO nanowire
synthesized by annealing Zn film at 600 ºC in the
air.
4. SUMMARY
In summary, ZnO nanowires with wurtzite
crystal structure were successfully synthesized by
annealing the Zn films at 600 ºC in the air
prepared by e-beam evaporation. Nanowires of
high aspect ratio with the diameter of 50 – 100 nm
and the length of 5 – 10m were formed. This
is a very simple method to synthesize ZnO
nanowires without using any catalyst.
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(Received October 22, 2014; Accepted December 2, 2014)