Journal of the Ceramic Society of Japan 117 [5] 703-705 2009 Paper

Preparation and properties for aluminum-doped zinc oxide

powders with the coprecipitation method
Anze SHUI†, Shumei WANG,* Hui WANG and Xiaosu CHENG
College of Materials Science and Engineering, South China University of Technology, Guangzhou 510640, China
*
Hunan Institute of Humanities, Science and Technology, Lou di 417001, China

Zinc oxide powders of different Al doping contents (AZO) were prepared with the coprecipitation method from zinc nitrate
solution and aluminum nitrate solution in this study. The effects of process parameters such as the Al doping content, calcina-
tion temperature and calcination time etc. on electric conductivity were examined quantificationally. The AZO powders had
good electric conductivity than that of zinc oxide powders. The resistivity of the AZO powders significantly depended on the
Al doping content, calcination temperature and calcination time. The minimum resistivity 179.2 Ω·cm was obtained from the
2 mol% Al doped powders in this work, which were prepared at the calcination temperature 1300°C for 2 h. The AZO pow-
ders were also characterized with the X-ray diffraction (XRD) and scanning electron microscopy (SEM). The experimental
results show that when the Al doping content is less than 2 mol%, the Al3+ enters into the ZnO lattice to form the solid solu-
tion, and causes the current carrier increase and the resistivity drop, but the excessive Al3+ doping brings the ZnAl2O4 spinel
phase generate, resulting in the resistivity increase.
©2009 The Ceramic Society of Japan. All rights reserved.

Key-words : Zinc oxide, Aluminum, Dopant, Conductive property, Coprecipitation method

[Received December 22, 2008; Accepted February 19, 2009]

good homogeneity, although the electric property may not be bet-

1. Introduction
There are metal, carbon black, carbon fiber and metal oxide
etc. in electric conductive materials. But the metal material is
expensive, and easily oxidized, resulting in the conductivity
drop. The carbon black and carbon fiber are high cost of, and
easily makes the product brittle. Otherwise, the metal oxides
such as SnO2:Sb, In2O3:Sn, and CdO:Sn etc. are toxic, and also
expensive.
On the other hand, zinc oxide has attracted great interest from
material researchers for its unique electrical and optical proper-
ties, low cost, and non-toxicity. It can be applied to various fields,
such as transparent oxide electrode1) varistor,2) gas sensor,3),4)
surface acoustic wave (SAW) device,5) solar cell,6) blue/UV light
emitting device,7) and coating material and additive etc..8),9) It is
important that produce electric conductive zinc oxide powder to
expand the application scope.
Zinc oxide is II–VI n-type semiconductor with a wide band
gap of about 3.3 eV at room temperature, and has a hexagonal
wurtzite structure. Its electric conductivity can be easily
improved by injecting the current carrier into the zinc oxide with
dopant, and the conductivity should depend on the dopant type
and doping content.10)–12) Zinc oxide is generally doped by group
III, IV and V elements (Al, Ga, In, Sn and Sb etc.).13)–16) In prac-
tice, Al doped zinc oxide (AZO) is the most desirable in the
group III element dopants from the cost and effectivity.17),18)
AZO powder can be prepared with a variety of techniques,
such as the solid reaction process,7),18) sol–gel method,15) copre-
cipitation method,4) hydrothermal method,16) plasma pyrolysis
method19) and CVD20) etc. The coprecipitation method is the
most inexpensive and simple in the techniques, and will have a
great potential to prepare the AZO powder due to low cost and
†
Corresponding author: A. Shui; E-mail: shuianze@scut.edu.cn
ter than that of the other methods. With the coprecipitation method,
the AZO powder of high-performance and homogeneity should be
prepared by optimizing the processing parameters such as the Al
doping content, calcination temperature and calcination time etc.
However, there have been few papers reported them in detail.
Zinc oxide powders of different Al doping contents (AZO)
were prepared with the coprecipitation method from zinc nitrate
solution and aluminum nitrate solution in this study. The effects
of process parameters on electric conductivity were examined in
detail. The AZO powders were also characterized with the X-ray
diffraction (XRD) and scanning electron microscopy (SEM).
2. Experimental procedure
All chemicals used in this work are the AR grade of. 1 M zinc
nitrate solution, and 1 M ammonium acid carbonate solution
were prepared from Zn(NO3)2·6H2O (Tianjin Rgent Chemicals
Co., Ltd., China), and NH4HCO3 (Guangzhou Chemical Reagent
Factory, China), respectively. Polyethylene glycol 2000 (Tianjin
Yongda Chemical Reagent Factory, China) as a dispersant was
added to the 1 M zinc nitrate solution, and the solution was
stirred for 10 min. Then Al(NO3)3·9H2O (Tianjin Rgent Chemi-
cals Co., Ltd., China) was added to this solution to obtain 0.5–
8 mol% Al concentration (i.e. [Al]/([Al]+[Zn])) of solution. The
ammonium acid carbonate solution was dropped to the solution
at constant temperature 70°C with stirring. The mixing solution
was stirred for 40 min, and was filtered after precipitating for 2 h.
The precipitate was washed with distilled water for above 5 times,
and followed by drying 24 h in an electric oven at 100°C and cal-
cining in an electric furnace at 900–1400°C for 1–3 h. Disk shape
of specimens in thickness 1–2 mm were made by uniaxial pressing
in a stainless steel die (diameter 15 mm) at 30 MPa, then the
specimens were covered by Ag electrodes (Sino-Platinum Metals
Co., Ltd., China), the resistance was measured for the specimens.

©2009 The Ceramic Society of Japan 703

JCS-Japan Shui et al.: Preparation and properties for aluminum-doped zinc oxide powders with the coprecipitation method

The X-ray diffraction (XRD) results for the AZO powders
were determined with a Philips PW–1710 model X-ray diffracto-
meter by using Cu Kα . Scanning electron microscopy (SEM, Phil-
ips L30FEG) was also used to characterize the AZO powders.
3. Results and discussion
3.1 The XRD analysis and microstructure
Figure 1 is the XRD patterns for the AZO powders calcined
at 1200°C for 1 h. The crystal structures for all samples were the
wurtzite type of. Non diffraction peaks of aluminum oxide were
detected in the samples of the low Al doping contents
(< 2 mol%), these indicate that the Al ion enters into the ZnO
lattice to displace the Zn ion and form the solid solution in the AZO
powders. But when the Al doping content exceeded 2 mol%, the
diffraction peaks of ZnAl2O4 spinel phase appeared at 31.358° and
36.774°, the peak intensities of ZnAl2O4 spinel phase enhanced
with increasing the Al doping content. These results indicate that
the excessive Al doping causes the ZnAl2O4 spinel phase generate.
Table 1 shows the lattice parameters for the AZO powders cal-
cined at 1200°C for 1 h. The parameters gradually diminished
from the standard ZnO parameters (a = 3.2507 Å , c = 5.2075 Å)
with increasing the Al doping content. These results were similar
to study of Paraguay.21) They can be explained by the following
theory. The ionic radius is 0.6 Å and 0.39 Å , for Zn2+ and Al3+,
respectively, the former is larger than latter. When the Al3+ enters
into the ZnO lattice to substitute the Zn2+, forms the solid solu-
tion, and the ZnO unit cell will shrink, the lattice parameters will
diminish.
Figure 2 is SEM micrographs of the AZO powders calcined
at 1200°C for 1 h. Most of powders were hexagonal prism shape
of, and had smooth surface. But the surface smoothness was
appeared to minish with increasing the Al doping content. A
small number of impurity existed on the surface of powders,
when the Al content exceeded 2 mol%. The impurity was more
for the 4 mol% doped powders than that for the 2.5 mol% doped
powders. These are in reasonable agreement with the results of
Fig. 1. The impurity may be the above ZnAl2O4 spinel phase.
3.2 The effect of Al doping content on the resistivity
Figure 3 is the effect of Al doping content on the resistivity
for the samples calcined at 1200°C for 1 h. Clearly, the resistivity
significantly depended on the Al doping content. It decreased
with increasing the doping content when the doping content was
less than 2 mol%, and reached a minimum value at 2 mol%.
Then the resistivity augmented with increasing the doping
content when it exceeded 2 mol%. These were corresponding to
the above results. These results can be explained by the
following theory. When ZnO is doped by Al, a part of the Zn ions
in ZnO lattices are replaced by the Al ions, resulting in the
conductive electrons occur. A continuous dropping in the
resistivity is observed until the Al doping content equals 2 mol%,
but the excessive doping makes the superfluous Al3+ ions can not
be solved in the ZnO lattices, and causes the ZnAl2O4 spinel
phase generate and the current carrier loss, resulting in the resis-
tivity increase.

Fig. 2. SEM micrographs of the AZO powders calcined at 1200°C for 1 h.

Fig. 1. XRD patterns for the AZO powders calcined at 1200°C for
1 h.

Table 1. Lattice Parameters for the AZO Powders Cal-

cined at 1200°C for 1 h
Al doping content (mol%) a (Å) c (Å)
0 3.2507 5.2075
0.5 3.2498 5.2072
1.0 3.2494 5.2071
2.0 3.2493 5.2066
2.5 3.2486 5.2061
4.0 3.2496 5.2058
Fig. 3. Effect of Al doping content on the resistivity for the samples
8.0 3.2493 5.2053 calcined at 1200°C for 1 h.

704
Journal of the Ceramic Society of Japan 117 [5] 703-705 2009
Fig. 4. Effect of calcination temperature on the resistivity for the Fig. 5. Effect of calcination time on the resistivity for the 2 mol%
2 mol% doped samples in calcination time 1 h condition. doped samples at 1300°C.
3.3 The effect of calcination temperature on the Young Teachers Program of M0E China.
resistivity
Figure 4 is the effect of calcination temperature on the resistivity
for the 2 mol% doped samples in calcination time 1 h condition. 1)
The resistivity decreased with enhancing the calcination tempera-
ture, and reached a minimum value at 1300°C. It almost had not a
change when the calcination temperature exceeded 1300°C. 2)
The Al3+ entering into the ZnO lattice increases with enhanc-
ing the calcination temperature, and causes the current carrier 3)
augment, resulting in the resistivity drop. On the other hand, the
excessive calcination temperature may cause the ZnAl2O4 spinel
4)
phase generate, which makes the ratio Al3+/Zn2+ in the ZnO
lattice minish and the electron scattering occur.
5)
3.4 The effect of calcination time on the resistivity
Figure 5 is the effect of calcination time on the resistivity for
the 2 mol% doped samples at 1300°C. The resistivity firstly 6)
decreased with extending the calcination time, and reached a
minimum value (179.2 Ω·cm) at 2 h, then increased with extend- 7)
ing the calcination time when it exceeded 2 h.
The Al3+ entering into the ZnO lattice increases with extending
8)
the calcination time when it is less than 2 h. It needs the active
energy and diffusion time to the Al3+ enter into the ZnO lattice, 9)
an adequate calcination time can ensure the Al3+ to displace suf-
ficiently the Zn2+, but the excessive calcination time may also 10)
cause the ZnAl2O4 spinel phase generate, resulting in the resis-
tivity increase.15) 11)
4. Conclusions 12)
Conductive aluminum doped zinc oxide (AZO) powders have
been successfully prepared with the coprecipitation method from
13)
zinc nitrate solution and aluminum nitrate solution in this study.
The effects of process parameters such as the Al doping content, 14)
calcination temperature and calcination time etc. on electric con-
ductivity were examined in detail. The resistivity of the AZO 15)
powders significantly depended on the Al doping content,
calcination temperature and calcination time. The minimum resis-
tivity 179.2 Ω·cm was obtained from the 2 mol% Al doped pow- 16)
ders, which were prepared at the calcination temperature 1300°C
for 2 h. The AZO powders were also characterized with the X- 17)
ray diffraction (XRD) and scanning electron microscopy (SEM).
18)
The experimental results show that when the Al doping content
is less than 2 mol%, the Al3+ enters into the ZnO lattice to form 19)
the solid solution, and causes the current carrier increase and the
resistivity drop, but the excessive Al3+ doping brings the ZnAl2O4 20)
spinel phase generate, resulting in the resistivity increase.
21)
Acknowledgments This work was supported by the National
Natural Science Foundation of China (No.50872034) and the Excellent
JCS-Japan
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