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Photoluminescence and photosensitive properties of ZnO strands self-twined by nanowires

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2004 Nanotechnology 15 559

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INSTITUTE OF PHYSICS PUBLISHING NANOTECHNOLOGY
Nanotechnology 15 (2004) 559–561 PII: S0957-4484(04)69044-1

Photoluminescence and photosensitive

properties of ZnO strands self-twined by
nanowires
Q Wan1,2,3, Z T Song1 , W L Liu1 , C L Lin1 and T H Wang2
1
The Research Centre of Semiconductor Functional Film Engineering Technology,
Shanghai Institute of Microsystem and Information Technology, Chinese Academy of
Sciences, Shanghai, People’s Republic of China
2
Institute of Physics, Chinese Academy of Sciences, Beijing, People’s Republic of China

E-mail: wanqing7686@sina.com

Received 11 September 2003

Published 26 February 2004
Online at stacks.iop.org/Nano/15/559 (DOI: 10.1088/0957-4484/15/5/027)

Abstract
Using argon as the transporting gas, freestanding macroscopic ZnO strands
have been synthesized by evaporating metal zinc pellets at 900 ◦ C in a quartz
tube. Scanning electron microscopy images show that the macroscopic ZnO
strands are self-twined by ZnO nanowires with a diameter in the range of
20–30 nm. A ZnO strand synthesized under larger argon flux contains more
oxygen vacancy, which will result in a stronger green emission at 2.43 eV.
Under illumination with a power of 10 W, the photosensitivity of the ZnO
strand is found to be about 800 at the bias voltage of 20 V. It is also
experimentally demonstrated that the recovery time of the ZnO strand is
relatively long due to the dominating surface process.

1. Introduction evaporation method. Our studies show that these macroscopic

One-dimensional (1D) nanostructures, such as carbon
nanotubes [1], Si nanowires [2], GaN nanorods [3] and ZnO
nanobelts [4], have become the focus of intensive research
owing to their unique applications in mesoscopic physics and
nanoscale quantum devices [5]. Among these one-dimensional
nanostructures, ZnO has been recognized as a promising
material for short-wavelength light emitting, and gas sensing
applications.
Several methods have been reported for synthesizing
ZnO 1D nanostructures. Using a porous alumina template,
polycrystalline ZnO nanowires were fabricated [6]. Randomly
distributed ZnO nanowires on a silicon substrate [7] and
aligned ZnO nanowires on a sapphire substrate were
synthesized using Au nanocrystals as the catalyst in a vapour
phase transport process [8]. In our previous report, tetrapod-
like ZnO nanostructures were successfully synthesized by the
evaporation of Zn in ambient air, and they show promising
applications for vacuum electron field emission [9].
In this report, long freestanding ZnO strands with different
amounts of oxygen vacancy were synthesized by a thermal
3 Author to whom any correspondence should be addressed.
ZnO strands are self-twined by ZnO nanowires with a diameter
in the range of 20–30 nm. Photoluminescence spectra are used
to study the optical properties of the synthesized ZnO strands.
The influence of light illumination on the electrical properties
of the synthesized ZnO strand was also investigated.
2. Experimental details
Our method is based on the direct thermal evaporation of
metallic zinc. In contrast to conventional thermal evaporation,
neither a catalyst nor a graphite/carbon additive is needed. A
similar process can be found in our previous report [10]. First,
high purity (99.99%) zinc pellets were loaded in a quartz boat
and positioned at the centre of a quartz tube that was inserted in
a horizontal tube furnace. Then, two samples (sample 1: argon
flux of 1 l min−1 , and sample 2: argon flux of 5 l min−1 ) were
synthesized at 900 ◦ C. After the system had cooled down to
room temperature, massive white cotton-like [10] and strand-
like products are observed at the low temperature port of the
tube. These strand-like products are very loose and can easily
hike up with the aid of the Ar flow. The morphology and crystal
structure of the strand-like products were characterized by

0957-4484/04/050559+03$30.00 © 2004 IOP Publishing Ltd Printed in the UK 559

Q Wan et al

(a)
(a)

1000
(101)
(b) a----sample 1
(100)
800 b----sample 2
Intensity (a.u.)

600 (110)
(002) (b)
(102)
400
a
200
b
0
20 25 30 35 40 45 50 55 60
2-Theta (degree)

Figure 1. (a) Photograph of the synthesized ZnO strand, and

(b) XRD pattern of the synthesized ZnO strand.

Table 1. The amounts of oxygen and zinc in the synthesized ZnO

strands. The results were obtained from EDX spectra.
Figure 2. SEM of the synthesized samples, (a) sample 1, and
Sample Element Wt% At.% (b) sample 2. Many interlaced nanowires are shown in both SEM
images (scaling bar: 100 nm).
1 Oxygen 18.48 48.09
Zinc 81.52 51.91
2 Oxygen 15.99 43.74 0.6 a----sample 1
Zinc 84.01 56.26 b----sample 2
0.5
PL intensity (a.u.)

0.4
b
scanning electron microscopy (SEM, JSM-6700F) and x-ray 0.3
powder diffraction (XRD, D/max 2550 V, Cu Kα radiation).
0.2
The photoluminescence (PL) spectra were obtained with a
He–Cd laser of wavelength 325 nm and measured at room 0.1 a
temperature. Electrical and photosensitive properties were
0.0
studied by a 4284 A precision LCR meter at room temperature 400 500 600 700
in ambient air. Wavelength (nm)

Figure 3. PL spectrum measured at room temperature. A sharp

3. Results and discussion
Figure 1(a) shows a typical picture of the strand-like sample of
length about 20 cm. XRD measurements were used to assess
the overall structure and phase purity of both samples. All
of the diffraction peaks in figure 1(b) can be indexed to a
hexagonal wurtzite structure of ZnO with cell constants of
a = 0.324 nm and c = 0.519 nm. No diffraction peaks
from Zn or other impurities were detected. Energy-dispersive
x-ray fluorescence (EDX) results indicate that the synthesized
strands are composed of Zn and O. As indicated in table 1, when
the argon flux is 1 l min−1 (sample 1), the at.% of oxygen is
48.09%; when the argon flux is 5 l min−1 (sample 2), the at.%
of oxygen decreases to 43.74%. So a larger argon flux can
cause more oxygen vacancy in ZnO strands.
Figure 2 shows typical SEM images of the two synthesized
samples. Interlaced nanowires are observed in both SEM
images. These connected nanowires are helpful to the
formation of a long macroscopic strand by a process of
ultraviolet peak (3.22 eV) and a broad green peak (2.43 eV) are
observed.
‘aggregation’. We also find that a steady argon flow is
the second condition for the formation of macroscopic ZnO
strands, because no macroscopic ZnO strands are obtained
without the argon flow.
PL spectra of the synthesized samples were measured at
room temperature. As is shown in figure 3, both samples show
a strong and sharp ultraviolet (UV) emission at about 380 nm
(3.26 eV), which is attributed to the near band edge emission of
the wide band gap ZnO. The difference is that sample 1 shows
a weak green emission at 510 nm (2.43 eV) while sample 2
shows a relatively strong green emission peak at 510 nm.
Over the past several decades, the green luminescence
mechanisms of ZnO have been studied, and various models
have been proposed. Vanheusden et al [11] proved that the
green emission was attributed to the singly ionized oxygen
vacancy in the ZnO and the emission results from the radiative

560
 Photoluminescence and photosensitive properties of ZnO strands self-twined by nanowires

80 This reduces the carrier concentration in the n-type ZnO

(a) Sample 1 strand and thus suppresses its conductivity. Under ultra-
60 a--In the dark violet light illumination, photogenerated holes migrate to
b--Under light b the surface and discharge the adsorbed oxygen ions through
Current (nA)

surface electron–hole recombination. At the same time,

40
photogenerated electrons destroy the depletion layer, and thus
significantly increase the conductivity of the ZnO. Secondly,
20 further illumination will generate more electron–hole pairs in
a the conduction and valence bands, and these photogenerated
0 carriers can significantly increase the conductance of the ZnO
0 5 10 15 20 strand. The oxygen absorption and desorption process on the
Voltage (V) surface is slow [14]. The ZnO strand was aggregated by the
100 nanowires, so a surface related process is significant and it is
(b) not a surprise to find that the recovery time is relatively long
80
in our experiment.
60
Current (nA)

4. Conclusion
40
In conclusion, with the aid of argon flow, macroscopic ZnO
20 strands with different amounts of oxygen vacancy have been
synthesized by rapid thermal evaporation of metal Zn in a
0 quartz tube at 900 ◦ C. Our results show that the strand is
-100 0 100 200 300 400 500 600 700 self-assembled by ZnO nanowires by a process of aggregation
Time (s) with the aid of argon. A ZnO strand synthesized under larger
argon flux contains more oxygen vacancy, which will result
Figure 4. (a) Current–voltage characteristic of the synthesized ZnO in a stronger green emission at 2.43 eV. The ZnO strands
strand (sample 1). (Curve a: dark current, and curve b: also show a photosensitivity of 800 at a voltage of 20 V and
photocurrent.) (b) Current recovery characteristic of sample 1; the
bias voltage is 20 V. light power of 10 W. Due to the dominating surface process,
the recovery time is relatively long. These macroscopic ZnO
strands may find promising applications for gas/light sensors
recombination of a photogenerated hole with an electron
and photocatalysts.
occupying the oxygen vacancy. Since the ZnO strands are
synthesized in a relatively oxygen-deficient ambient in our
experiment, it is therefore reasonable to believe that the green Acknowledgments
emission is related to the oxygen vacancy. Based on the results
of EDX and PL spectra, it is proved that the more oxygen there The authors acknowledge support from the Special Funds
is, the stronger the green emission in ZnO nanowires. for Major State Basic Research Project No. G2001CB3095
Figure 4(a) shows the current–voltage (I –V ) characteris- of China and the National Natural Science Foundation of
tics of sample 1 with length about 2 cm in the dark and under China through Grant No 60201004, and also the support from
illumination. Without illumination, the current is only 0.1 nA Shanghai Nanotechnology Promotion Centre (No. 0252nm084
at the bias voltage of 20 V. Under illumination (light source: and No. 0359nm004).
ultra-violet light of 10 W), the current is measured to be about
80 nA at 20 V, indicating that the ZnO strand is very photo- References
sensitive. The photosensitivity is calculated to be about 800.
[1] Iijima S 1991 Nature 354 56
The photoresponse decay characteristic of the ZnO strand was
[2] Morales A M and Lieber C M 1998 Science 279 208
also studied under 20 V at room temperature. As shown in fig- [3] Kim H et al 2002 Appl. Phys. Lett. 81 2193
ure 3(b), the recovery time of the photoresponse is relatively [4] Li Y B et al 2002 Appl. Phys. Lett. 81 144
long. It takes about 100 s for the current to drop to 10% of its [5] Xia Y et al 2003 Adv. Mater. 15 353
maximum value. [6] Li Y, Meng G W and Zhang L D 2000 Appl. Phys. Lett. 76
2011
The physical principles underlying the photosensitivity
[7] Huang M et al 2001 Adv. Mater. 13 113
properties of semiconducting metal oxides have been explained [8] Huang M et al 2001 Science 292 1897
in many reports [12, 13]. We believe that two major [9] Wan Q et al 2003 Appl. Phys. Lett. 83 2253
mechanisms are active in the photoconductive ZnO strand. [10] Wan Q et al 2004 Appl. Phys. Lett. 84 124
First of all, because of the affinity between the electrons [11] Vanheusden K et al 1996 J. Appl. Phys. 79 7983
[12] Kind H et al 2002 Adv. Mater. 14 158
and the oxidizing O2 molecules, O2 can adsorb on the ZnO
[13] Xirouchaki C et al 1996 J. Appl. Phys. 79 9349
nanowire surface and combine with the nearby free electrons [14] Sharma P, Sreenivas K and Rao K V 2003 J. Appl. Phys. 93
to form an O− 2 layer once the nanowire is exposed to air. 3963

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