Fabrication and characterization of ZnO branched nanorods and ZnO/NiO

heterojunction electrodes by chemical solution method

Yi-Mu Lee
n
, Wei-Ming Nung, Chun-Hung Lai
Department of Electronic Engineering, National United University, MiaoLi 36003, Taiwan
a r t i c l e i n f o
Article history:
Received 3 February 2010
Received in revised form
3 May 2010
Accepted 5 May 2010
Available online 13 May 2010
Keywords:
ZnO
Nanorod
Chemical bath deposition
Electrical properties
Heterojunction electrode
a b s t r a c t
High quality ZnO nanorod arrays were synthesized by a two-step chemical bath deposition (CBD) on an
ITO substrate. Our synthesis method is a two-step process: seeding and subsequent growth. The CBD
was carried out in zinc acetate solution at 95 1C for 1 h, followed by thermal treatment at different
temperatures. The structural and the optical properties of ZnO were investigated by X-ray diffraction,
the scanning electron microscopy, and the optical transmission spectroscopy. The XRD results showed
that the CBD ZnO nanorods have a hexagonal wurtzite structure with at-tops as seen in SEM
morphologies. The diameter of ZnO nanorods was found to be in the range 380450 nm and the length
was up to 1.3 mm depending on the thermal-treatment temperature. An average optical transmittance
of more than 90% was obtained in the wavelength range 400800 nm for the thermal temperature of
400 1C, where the length/diameter ratio reached a maximum value of 3.08. The ZnO branched nanorods
fabricated by this two-step CBD at low temperature exhibited great crystal quality, leading to excellent
electrical properties (r3.2 10
3
O cm) and high carrier mobility (m40.4 cm
2
/V sec). Moreover, the
currentvoltage (IV) characteristics of n-ZnO/p-NiO heterojunction electrode indicated that this
nanostructure was rectifying in nature with low turn-on voltage and great rectication slope.
& 2010 Elsevier B.V. All rights reserved.
1. Introduction
Zinc oxide (ZnO) is an attractive IIVI compound semiconduc-
tor because of its unique chemical and physical properties such as
wide and direct band gap (3.37 eV), large binding energy
(60 meV) [1,2], high electrical conductivity and transparency in
the visible region [3]. With the scaling down of electronic devices,
nanostructured ZnO materials have undergone intensive research
for optoelectronic applications in the following elds: diode-
based devices [47], photovoltaic cells [8] and thin-lm transis-
tors [9] and other nanodevices [10,11]. For a board range of
applications in electronic devices, the np junction plays a key
role in the structure and the electrical performance. It is well
known that ZnO prepared by different deposition technologies
provide lms of different morphologies. Thin lms of ZnO can be
produced by rf magnetron sputtering [12,13], pulsed laser
deposition (PLD) [14] and solgel process [3,15]. For nanorod
arrays of ZnO, the growth techniques include chemical bath
deposition [16], spray pyrolysis [17], vapor phase transport [18]
and hydrothermal method [19]. The solgel method can also be
employed to prepare ZnO nanorods; however, sintering tempera-
ture must be higher than 900 1C [20]. Among these techniques,
chemical bath deposition (CBD) is a simple, economical, large area
coating and low-temperature process, which is compatible with
plastic substrates for the fabrication of nanostructured ZnO.
However, to the best of our knowledge, ZnO prepared by either
CBD [21] or chemical solution method [22] shows a poor
reproducibility due to difculty in controlling the size and
uniform coverage on the substrate, which directly results in poor
electrical and optical properties of the ZnO nanostructures [22].
ZnO nanorod arrays by the CBD have been grown on Si [21]
and glass substrates [23]. The nanorods were well aligned with
orientation in the c-axis direction; the diameters were ranged
from 40 to 150 nm [16] and the lengths are about 400 nm [21]. It
is important that, before the CBD growth, the substrates must
receive pre-treatment in aqueous solutions followed by annealing
at high temperatures [16,21,24]. Nanostructured ZnO demon-
strated different optical and structural properties depending on
the preparing conditions. It has been reported that the optical
transmittance is 8090% and 90% for the solgel ZnO [3,15] and
the CBD ZnO [23], respectively. We have found a few works
reporting the structural studies of ZnO thin lms and nanorods
[15,16,21,22]. Results showed that ZnO is a hexagonal structure
with different shapes and dimensions [15,16]. The resistivity of
the solgel ZnO is in a wide range of 510
2
5.910
2
O cm
depending on the preparing conditions [3,25], and the Hall
mobility of 9.8 cm
2
/V sec was obtained [26]. However, a few
studies on the electrical properties of ZnO and its oxide junctions
ARTICLE IN PRESS
Contents lists available at ScienceDirect
journal homepage: www.elsevier.com/locate/physe
Physica E
1386-9477/$ - see front matter & 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.physe.2010.05.004
n
Corresponding author. Tel.: +886 37 381532; fax: +886 37 362809.
E-mail address: [email protected] (Y.-M. Lee).
Physica E 42 (2010) 22892294
ARTICLE IN PRESS
by the CBD have been reported so far. So the fabrication of ZnO
and doped-ZnO with high mobility and low resistivity is still a
challenge [26].
In this study, we present a two-step CBD method to grow high-
transparency and low-resistivity ZnO branched nanorods on the
ITO substrate. The effects of growth conditions on the morphology
and crystallinity of ZnO were investigated in detail. The surface
dimension of ZnO nanorods was carefully controlled by thermal
treatment at a wide temperature range to improve the resistivity
and the carrier mobility. The dependence of the optical and
electrical properties on the thermal-treatment temperatures was
discussed. Moreover, we report the formation and IV character-
istics of the n-ZnO/p-NiO heterojunction electrode.
2. Experimental
Indium tin oxide (ITO) coated glass (AUO Co., Ltd.) was used as
a transparent conducting substrate with the sheet resistance of
7 O/&. The ITO glasses received wet chemical cleaning as
reported in detail in our previous studies [27]. The chemical bath
deposition (CBD) process of ZnO nanorods contains two steps, i.e.
seeding process and the CBD growth. All the aqueous solutions
were prepared using distilled water. First ITO substrates were
dipped in 500 ml aqueous solution containing 0.05 M zinc acetate
(99% purity, Showa) mixed with hexamethylenetetramine
(C
6
H
12
N
4
, HMTA, 99.5% purity, Riedel-de Haen) for 5 sec. The role
of HMTA is to provide hydroxide ions (OH
-
) and ammonia (NH
3
)
in the solution [21]. The above process was repeated twice, and
then the materials were dried in an oven at 1001C for 10min to
grow a ZnO seed layer. The drying process of initial deposit is
critical. Without this thermal treatment, the ZnO seed layer would
dissolve into the subsequent aqueous solution. In the following,
the seeded substrates were then immersed into the same zinc
acetate solution with pH value of7.5. Through the CBD reaction,
NH
3
OH was added into the reaction bath to maintain the pH
value. The reaction temperature was kept at 95 1C for 1 h. After
the CBD growth, all samples received thermal treatment in air at
varied temperatures of 200, 300, 400, 500 and 600 1C for 10 min
using an electronic furnace. This thermal treatment can crystallize
the deposit and make it to be stable [22]. The synthesized
material shows a white-grayish color. Finally, the samples were
rinsed with deionized water and then dried at room temperature
to remove any residuals and organic materials.
The surface morphology and cross-section views of the
nanostructures were examined by a eld emission scanning
electron microscopy (SEM, JEOL JSM-6700 F, 10 kV). The X-ray
diffraction (XRD) was employed to characterize the crystalline
structure of the synthesized ZnO in the 2y range of 20801.
Photoluminescene (PL) experiments were performed at room
temperature using a deep UV laser of 248 nm as the excitation
source. UVvis spectra were obtained from the PerkinElmer
Lambda 20 UV/vis/NIR spectrometer. In addition, the electrical
properties of the synthesized ZnO nanorod arrays were measured
with the Hall measurement system (Ecopia HMS-3000) at room
temperature using the van der Pauws method. For the prepara-
tion of a heterojunction electrode, n-type ZnO oxide was rst
grown on an ITO substrate and then p-type NiO was spin coated
onto the n-ZnO/ITO by a spin coater. The coated NiO thin lms
were dried at 100 1C and then received thermal treatment at
450 1C [27]. As an upper electrode, gold was deposited by sputter-
ing. The active area of the devices was adjusted to 1.01.5 cm
2
.
The currentvoltage characteristics of the electrodes were
recorded at room temperature using an electrochemical work-
station (Jiehan 5000) with scan rate of 50 mV/s.
3. Results and discussion
3.1. Characterization of ZnO nanorods
The complete chemical reaction of ZnO growth in the solution
can be expressed as follows: [28,29]:
C
6
H
12
N
4
+6H
2
O-6CH
2
O+4NH
3
NH
3
+H
2
O-NH
4
+
+OH
-
Zn
2+
+2OH
-
-Zn(OH)
2
Zn(OH)
2
-ZnO+H
2
O
According to the above reaction, zinc hydroxides precipitates
and ZnO is formed after the CBD. Fig. 1 shows the XRD patterns of
the commercial ZnO powder (Showa, purity 99%) and the ZnO
prepared at different thermal-treatment temperatures. It can be
seen that the ZnO thermal-treated at low temperature (200 1C)
with Zn(OH)
2
remained as seen by the observation of supple-
mentary peaks in a range of 20 to 301. Zn(OH)
2
was converted into
ZnO after thermal-treated at higher temperature (300600 1C). No
signicant differences were observed for the synthesized ZnO
treated at 400600 1C; diffraction peaks (1 0 0), (0 0 2) and (1 0 1)
can be indexed to the wurtzite structure [22]. The diffraction
peaks with less intensity over a range from 40 to 801 are approved
of randomly oriented ZnO nanorods.
Typical SEM images of the ZnO seeding layer are shown in
Fig. 2. The overall morphology of the seeded layer with oriented
nanorod arrays and few individual nanorods can be seen. The
thickness of the seeded layer is around 170 nm as unambiguously
observed from the cross-section of the SEM micrographs
(Fig. 2(b)). The role of the seed layer is to provide good
adhesion between the ITO substrate and the ZnO branched
nanorods. Besides, the degree of the (0 0 2) crystallization and
the optical properties can be improved by a good-quality ZnO
seed layer [30]. It has been shown that 8085% (0 0 2) preferred
orientation was obtained for a 100200 nm seed layer [31]. Fig. 3
shows the SEM morphologies of the CBD synthesized ZnO
nanorods treated at different thermal temperatures. The lengths
and diameters of the ZnO nanorods increased with an increase in
2 (degree)
20
I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
(100)
(002)
(101)
(102)
(110)
(103)
(112)
600 C
500 C
400 C
300 C
200 C
ZnO
30 40 50 60 70 80
Fig. 1. The XRD patterns of the synthesized ZnO as a function of thermal-
treatment temperatures. Commercial ZnO powder (Showa, purity 99%) without
thermal treatment used for comparison.
Y.-M. Lee et al. / Physica E 42 (2010) 22892294 2290
ARTICLE IN PRESS
annealing temperature up to 600 1C as summarized in Table 1. It
can be seen that the length/diameter (L/D) ratio is increased with
increase in thermal-treatment temperatures up to 400 1C (with
L/D ratio of 3.08). However, the dependence of the L/D ratio on the
annealing temperatures is not strong ranging from 400 to 600 1C.
All the top surfaces of the synthesized nanorods are hexagonal in
shape, which conrms that the obtained ZnO possess a very stable
structure [29]. Also, the ZnO nanorods with at-tops were formed,
revealing that the concentration of the solution is uniform from
the roots to the top of the nanorods [19]. Similar results have
been reported for the ZnO nanorod array prepared by a combi-
nation of chemical solution method and electric eld assisted
nucleation [22].
The PL spectra of the ZnO nanorods received various thermal-
treatment temperatures as shown in Fig. 4. It is well known that
the visible emission ranged from 440 to 600 nm is due to oxygen
vacancies, while the UV peak is associated with the recombination
of photo-generated electrons and holes [32]. The strong band-
edge emission with negligible deep level emission of various ZnO
samples indicates that these ZnO branched nanorods have high-
quality crystalline [33]. The sharp emission peak at 380 nm
corresponds to the recombination of delocalized electrons near
the conduction band with deeply trapped holes in the zinc
vacancies [34]. The decrease in the intensity of band-edge
emission reects a decrease in the crystal quality by an increase
in the nonradiative recombination from the defect states [26].
It is worth noticing that D51 meV redshift was observed with
increase in annealing temperatures in the room temperature PL
spectra, similar to the redshift (D52 meV) observed in ZnO
nanopencils prepared by the rf magnetron sputtering [33]. The
origin of redshift is associated with different contributions of
excitonic emission and their phonon replicas [33].
Optical transmittance spectra of various ZnO nanorods
received different thermal temperatures, which are presented in
Fig. 5. The interference fringes in 300380 nm indicate that all the
ZnO samples possess optically smooth surfaces and the interface
at the seed layer/ITO is also smooth [35]. For thermal treatment at
400 1C, the ZnO shows a very high UV transparency with an
average optical transmittance higher than 90% in the visible
range, which may be attributed to high crystalline quality [18,33]
and highest length/diameter ratio. It has been reported that light
trapping is enhanced in the ZnO nanorod with higher length/
diameter ratio for solar cell devices [17]. For thermal-treated at
500600 1C, the optical transmittance was dramatically decreased
(o40%), which is due to the pores segregation [25,27] and defect
complexes such as oxygen vacancies evidenced by the green band
emission in the PL spectra [36,37].
3.2. Electrical properties of ZnO nanorodsHall effect measurement
Another critical parameter required for the application of ZnO
as a transparent-conductive electrode is its excellent electrical
properties. Hence, emphasis was given to characterize the
electrical resistivity and the carrier mobility of the synthesized
ZnO nanorods. The dependence of carrier concentration (n),
mobility (m) and electrical resistivity (r) on various thermal-
treatment temperatures of CBD ZnO are shown in Fig. 6.
Interestingly, the trend is different from the results obtained in
polycrystalline ZnO thin lms. This is because of the conductivity
and the carrier concentration in the polycrystalline structures
correlated with grain size and defect formation at the grain
boundaries [38]. For our ZnO nanorods, the Hall mobility
increases from 200 to 400 1C, reaches the maximum
(m40.4 cm
2
/V sec) at the temperature of 400 1C and then
decreases. The carrier concentration was found to decrease with
increase in the thermal-treatment temperature. Also, the
resistivity of the CBD ZnO nanorods is slightly increased from
7.710
4
to 3.810
3
O cm. These resistivity values are much
lower than those reported in the literatures for the solgel ZnO
thin lms [3] and Al-doped ZnO nanorod arrays [25]. Generally,
the peak value and the full-width at half-maximum (FWHM)
value of the XRD patterns are regarded as an indicator of the
crystal of ZnO materials [13]. Thus the change in the crystallinity
and the crystal quality would greatly affect the change in the
resistivity and the mobility. It has also been reported that
the impurity scattering is a dominant factor on mobility, due to
the tightness of the lms deposited at high temperature [39]. Our
results show the ZnO nanorods received thermal-treated at 400 1C
demonstrate the highest Hall mobility, reecting that the most
ideal crystal quality [26] and tightness of the nanostructures are
achieved. Table 2 summarizes the Hall mobility of ZnO prepared
by different processes. From the table it can be seen that the Hall
mobility of the CBD ZnO (m40.4 cm
2
/V sec) is higher than the
AlZnO lms by sputtering (m15.6 cm
2
/V sec) [13] and PLD
(m27 cm
2
/V sec) [14], indicating that the electron transport is
enhanced in nanorods rather than in thin lms.
Fig. 2. The SEM images of the ZnO seeded layer: (a) surface morphology and
(b) cross-section morphology.
Y.-M. Lee et al. / Physica E 42 (2010) 22892294 2291
ARTICLE IN PRESS
3.3. Electrical performance of the ZnO/NiO heterojunction electrodes
The typical IV characteristics of the single ZnO layer and
the ZnO/NiO heterojunction are shown in Fig. 7(a) and (b),
respectively. For a single ZnO, the linear IV behavior indicates
that the ohmic contacts are formed between Au counter
electrodes and the ZnO. The IV characteristics of n-ZnO/p-NiO
and n-TiO
2
/p-NiO heterojunction electrodes are measured in the
dark, where the n-type TiO
2
and p-type NiO with thickness of
200 nm were prepared by the solgel process [27]. As seen in
Fig. 7(b), both n-ZnO/p-NiO and n-TiO
2
/p-NiO heterojunctions
exhibited typical rectifying IV characteristics; n-ZnO/p-NiO
has a low turn-on voltage of 1.2 V and the rectifying current
is 2.35 mA measured at 4 V. The rectication slope of
ZnO/NiO heterojunction is 1.25 mA/V, which is greater than that
(0.91 mA/V) of n-TiO
2
/p-NiO heterojunction and is greater by as
much as an order of magnitude compared to the ZnO-based
heterojunction device (slope0.17 mA/V) by the RF sputtering
method [40]. This is due to the fact that a p/n interface was
formed in the ZnO/NiO heterojunction with low lattice mismatch
[41,42], which facilitates electron transport through the interface.
Fig. 3. The SEM surface micrographs of the CBD synthesized ZnO nanorods received different thermal-treatment temperatures (200600 1C). Inset is the high magnication
of the FE-SEM image for ZnO nanostructures.
Table 1
Length and diameter of the ZnO nanorods received at different heat treatment
temperatures.
Heating temperature (1C) Length (mm) Diameter (mm) L/D ratio
200 0.98 0.38 2.57
300 1.12 0.39 2.87
400 1.27 0.41 3.08
500 1.28 0.43 2.97
600 1.32 0.45 2.94
Y.-M. Lee et al. / Physica E 42 (2010) 22892294 2292
ARTICLE IN PRESS
However, the TiO
2
/NiO heterojunction provided a p-i-n interface
by the formation of NiTiO
3
between TiO
2
and NiO layers [43]. This
interfacial layer retards transport of electrons through the
nanocrystalline TiO
2
thin lm via a hopping mechanism, which
enhances charge recombination and limits efcient charge
transfer [44].
4. Conclusion
We have synthesized highly transparent and low-resistivity
ZnO branched nanorods on ITO substrates by two-step CBD
method at low temperature. The effects of post-deposition
thermal treatments ranging from 300 to 600 1C on the structural,
optical and electrical characteristics of ZnO were investigated in
details. From the analysis of the XRD and the SEM, the ZnO
nanorods were formed with hexagonal wurtzite structure where
the thickness of the seed layer is around 170 nm. A structural
study revealed that the dimension of ZnO nanorods increases with
increase in thermal temperatures, and the decrease in crystal
quality is substantiated from the PL spectra. The nanorods were
observed in the range 380450 nm in diameter and 0.981.32 mm
in length. The average transmittance is higher than 90% in the
visible wavelength region (400800 nm) for ZnO thermal-treated
at 400 1C. The optical transmittance is dramatically reduced with
increase in thermal-treatment temperatures due to poorer crystal
quality and the increase in the defect states evidenced by the PL
measurements. The fabricated ZnO nanorods exhibit low resis-
tivity of the order of 10
3
O cm, high mobility (35.240.4
cm
2
/V sec) and high carrier concentration (4.421.410
19
cm
3
).
It is concluded that the thermal treatment of 400 1C is optimum
for ZnO branched nanorods to achieve great coverage, high optical
transmittance and excellent electrical resistivity by increasing
the aspect ratio. Furthermore, the dark IV characteristics of
n-ZnO/p-NiO heterojunction electrode reveal that this structure is
rectifying in nature with lower turn-on voltage (1.2 V) and
greater rectication slope (1.25 mA/V) as compared to the n-TiO
2
/
p-NiO electrode. Experimental data clearly revealed that the
electron transportation is signicantly enhanced in nanorod
structure rather than in the thin lms. The results of this work
show great promise for the ZnO nanorods by low-temperature
0
500
1000
1500
2000
2500
3000
3500
4000
300
300C
400C
500C
600C
P
L

i
n
t
e
n
s
i
t
y

(
a
.
u
.
)
Wavelength (nm)
381.9 nm
376.0 nm
350 400 450 500 550
Fig. 4. Room temperature PL spectra of ZnO branched nanorods under different
thermal-treatment temperatures.
100
80
60
40
20
0
300 400 500 600 700 800 900
Wavelength (nm)
T
r
a
n
s
m
i
t
t
a
n
c
e

(
%
)
300
400
500
600
Fig. 5. Transmittance spectra of the synthesized ZnO nanorods received various
thermal-treatment temperatures. The substrate is ITO-glass.
0
110
20
210
20
310
20
410
20
510
20
30
35
40
45
200
c
a
r
r
i
e
r

c
o
n
c
e
n
t
r
a
t
i
o
n

(
c
m
-
3
)
H
a
l
l

m
o
b
i
l
i
t
y

(
c
m
2
/
V
-
s
e
c
)
Temperature (C)
0
0.002
0.004
0.006
0.008
0.01
200
resistivity
r
e
s
i
s
t
i
v
i
t
y

(
O
h
m
-
c
m
)
Temperature (C)
250 300 350 400 450 500 550 600
250 300 350 400 450 500 550 600
Fig. 6. The Hall measurement of the synthesized ZnO nanorods at room
temperature: (a) carrier concentration and Hall mobility and (b) resistivity.
Y.-M. Lee et al. / Physica E 42 (2010) 22892294 2293
ARTICLE IN PRESS
CBD for applications as transparent-conductive electrodes in
oxide electronics, especially in large-area fabrication technology.
Acknowledgments
This work was funded through the National Science Council,
Taiwan, ROC under grant number NSC97-2221-E-239-027. The
nancial support is gratefully acknowledged.
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Table 2
Electrical properties of ZnO and doped-ZnO prepared by various processes.
Structure Hall mobility (cm
2
/V sec) Lowest resistivity (O cm) Process
Thin lm 510
2
Solgel [3]
Thin lm 910
2
Solgel [15]
Thin lm 9.8 3.57 Solgel [26]
AlZnO lm 15.6 4.6210
4
Sputtering [13]
AlZnO lm 27 3.310
4
PLD [14]
Nanorod 40.4 7.710
4
CBD (this work)
0.1
0.05
0
-0.05
-0.1
-4 -2 0 2 4
Voltage (V)
I

(
A
)
I (A)
0.003
0.0025
0.002
0.0015
0.001
0.0005
0
-0.0005
-1.6 -0.8 0 0.8 1.6 2.4 3.2 4
Voltage (V)
I

(
A
)
ZnO/NiO
TiO2/NiO
Fig. 7. IV characteristics of (a) single ZnO layer and (b) ZnO/NiO and TiO
2
/NiO
heterojunction electrodes. Active electrode area is 1.01.5 cm
2
.
Y.-M. Lee et al. / Physica E 42 (2010) 22892294 2294