Journal of Nuclear and Related Technology Vol.

4, Special Edition 2007, 165-170

PHASE FORMATION STUDY OF CuAlO2 TRANSPARENT

CONDUCTIVE OXIDE THIN FILMS

Sabar D. Hutagalung*, Wu S. Woon, Khatijah A. Yaacob, Zainovia Lockman

School of Materials and Mineral Resources Engineering, Universiti Sains Malaysia, 14300
Nibong Tebal, Penang, Malaysia
*E-mail: mrsabar@eng.usm.my

ABSTRACT
P-type transparent conductive oxide of copper aluminum oxide (CuAlO2) thin films were prepared
by using sol-gel method with nitrate solutions as starting precursor. Copper nitrate and aluminum
nitrate were selected as raw materials that provide the copper and aluminum source. The CuAlO2
thin films were deposited on pre-cleaned silicon substrate by spin-coating technique. To study of
phase formation of CuAlO2, as prepared sample was dried and subjected to heat treatment at
various temperatures. The heat-treated samples were characterized by x-ray diffraction (XRD) and
energy dispersive x-ray (EDX). From XRD analysis result found that CuAlO2 phase was formed
after annealing at 1100 oC for 4 hrs. EDX result of annealed sample at 1100 oC shows composition
of Cu and Al that indicate the possibility of forming CuAlO2.

Keywords: Phase formation, copper aluminum oxide (CuAlO2), sol-gel method, spin coating, thin
films

INTRODUCTION
Transparent conducting oxides (TCOs) are of great value in infrared reflection coating and optical
displays such as active matrix liquid crystal display (Robertson et al., 2002). The oxides must have
a band gap over 3.0 eV to be transparent. The development of transparent optoelectronic devices is
increasing and has been advancing for the past few years especially in the application of flat panel
display, architectural applications and any p-n junction-based oxide devices such as diodes,
transistors and light-emitting diodes (LED). One of the key to enable this technology is by
developing of the TCOs as basic material including improving or modifying the features of the TCO
so that the desired and required characteristic can be obtained.
The majority of TCOs are n-type conductors such as indium tin oxide (ITO), fluorine-doped tin
oxide (SnO2:F) and zinc oxide (ZnO). The conductivity of TCO materials can be controlled across a
wide range such that they can behave as insulators, semiconductors or metals. However, the most
TCO are n-type conductors. To achieve p-type semiconductors is still a major topic of research
works. The quests of finding suitable dopant processing techniques have only recently received
intense investigation. However, by using a thin film of copper(I) oxides one could easily obtained a
p-type semiconductor which as exciting optical properties as that of indium tin oxide (ITO). The
discovery of p-type conduction properties in thin film of the copper(I) oxides: CuAlO2 and SrCu2O2
by Kawazoe et al. (1997) have opened many possibilities of p-type TCOs.
P-type TCOs have potential applications in photovoltaic, transparent electronics and organic
optoelectronics. Realization of good TCOs could significantly affect a new generation of

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transparent electrical contact for p-type semiconductors and in conjunction with n-type, TCOs will
finally lead to a next generation of transparent electronics.
There are many techniques that can be used for preparation of CAO thin films including spray
pyrolysis (Bouzidi et al., 2005), dc-sputtering (Tsuboi et al., 2003, Banerjee and Chattopadhyay,
2004 and Banerjee et al., 2005) and spin-on technique (Gao et al., 2003). One way of producing
CuAlO2 (CAO) is by a wet chemical route of sol-gel (Tonooka et al., 2002). Sol-gel method was
known to be able to produce materials from solution either in bulk, coating films, fibers or powders.
This method can be performed at low temperature and hence it is simpler than the physical
processes and inherently cheaper. This technology has dramatically grown for the past decades and
has proven to be one of the fabrication techniques of choice to make functional devices in various
field including optoelectronics, magnetic, biomedical and biotechnology. A chemical route also can
be used to produce nanocomposite of Cu-Al2O3 through their nitrates by two processes namely: (1)
addition of CuO to aqueous solution of aluminum nitrate, and (2) dissolution of the nitrates of
copper and aluminum in water, followed by decomposition to their oxides and then preferential
hydrogen reduction of CuO for both processes (Jena et al., 2004).
Since the method is simple and straight forward, in this work, a chemical sol-gel route was applied
to prepare CAO. Thin films were deposited by spin coating of the precursors solution of CAO on
pre-cleaned Si substrate.

MATERIALS AND EXPERIMENTAL METHOD

The precursor solution in this experiment consisted of acetic acid (40 mmol), de-ionized water (100
ml), copper nitrate (30 mmol) and aluminum nitrate (30 mmol). To facilitate better mixing of the
solution and reaction a small amount of ethanolamine (EA) was added to the solution. Si wafer
substrates (1 cm x 1 cm in size) were cleaned according to RCA cleaning procedure. CAO thin
films were prepared by spin-coating technique of the bath solution on Si substrate. The spin coater
machine-controlled equipment was set at 3000 rpm for 30 seconds to form homogeneous film on
substrate. Spin-coated films were left for drying for 10 minutes. After drying, the films were
annealed at different temperatures of 900 oC, 1000 oC and 1100 oC for 4 hours. All prepared films
were analyzed by x-ray diffraction (XRD) for phase identification. Scanning electron microscopy
(SEM) and energy dispersive x-ray (EDX) were used for examining the morphology and
composition. Thin films thickness was measured by Filmetrics F20.

RESULTS AND DISCUSSION

XRD was used for phase identification. Three samples were characterised by XRD. These samples
were made at different annealing temperatures of 900, 1000, and 1100 oC. Obviously, CuAlO2 was
the most desired phase. Nevertheless, SiO2, CuO, CuAl2O4 were also expected to co-exist as well.
Fig. 1 to 3 shows the XRD patterns for the samples made at 900, 1000 and 1100 oC, respectively.
From the XRD results, sample annealed at 900 oC (Fig. 1) did not show any existence of CuAlO2
peak significantly but intermediate material such as CuO and CuAl2O4 have been detected. Sample
annealed at 1000 oC (Fig. 2) and 1100 oC (Fig. 3) shown CuAlO2 formation. The annealed films at
1000 and 1100 oC present the crystalline structures with a strong peak at about 44o which is belong
to CuAlO2 (104) peak. The XRD patterns in Fig. 2 and Fig. 3 show that the intensity of CuAlO2
peak was increase with annealing temperature. SiO2, CuO peaks were also detected but CuAl2O4
peak disappeared. It is conclusive here that CuAlO2 phase formed at annealing temperature of 1100
o
C. The reason why SiO2 was detected intensively is because the use of Si substrate to support the
films.

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The main reaction that leads to the formation of CAO film can be defined as reaction (1) and (2)
(Kazuhiko et al., 2002),

CuO + Al2O3 o CuAl2O4 (1)

2CuAl2O4 + 2CuO o 4CuAlO2 + O2 (2)

Fig. 4 are SEM images of the CAO thin films. From Fig. 4, we can see that the CAO thin films have
been deposited homogeneously on Si substrate (Fig. 4 (a)). Even though a pore and inhomogeneous
films also been noticed on the other sample (Fig. 4 (b)). This defect is assumed due to the sol-gel
solution condition, which consisted of aqueous solution including water, EA and acetic acid. Some
of the additive solutions would evaporate during sintering process leaving a pore surface. The
shrinkage happened also caused the films become inhomogeneous. This is a disadvantage of sol-gel
process to produce continuous film. Overgrowth of some grains over the surface also being notice in
the Fig. 4 (c) due to the high sintering temperature of 1100 oC. A similar case of overgrowth grain
size was observed on the CAO films prepared by spray pyrolysis method at 525 oC or above
(Bouzidi et al., 2005).
Fig. 5 shows the EDX result of sample annealed at 1100 oC. The sample contains higher amount of
Si and O. This is due to the silicon wafer substrate was used. Besides that, composition of Cu and
Al have been notice showing that the formation of CAO in this sample.
Filmetrics measurement gave film thickness is increase with sintering temperature. The obtained
film thickness increases from 128.4 nm to 379.2 nm when annealing temperature increase from 900
to 1100 oC. This is due to the forming of CAO is not complete in lower sintering temperature.
Higher thickness obtained when grains growth and more CAO were being formed.


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Fig. 1. XRD pattern of sample annealed at 900 oC.

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JOURNAL Of NUCLEAR And Related TECHNOLOGIES, Volume 4, Special Edition, 2007


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Fig. 2. XRD pattern of sample annealed at 1000 oC.

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700

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Fig. 3. XRD pattern of sample annealed at 1100 oC.

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 JOURNAL Of NUCLEAR And Related TECHNOLOGIES, Volume 4, Special Edition, 2007

Pore

(a) (b)

Peeling off

(c)
Fig. 4. FESEM images of the selected samples of CAO thin films annealed at different
temperatures: (a) 900 oC, (b) 1000 oC and (c) 1100 oC.

Fig. 5. EDX result of sample annealed at 1100 oC.

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JOURNAL Of NUCLEAR And Related TECHNOLOGIES, Volume 4, Special Edition, 2007

CONCLUSION
In conclusion, thin film of CuAlO2 (CAO) was successfully synthesized by sol-gel technique. CAO
thin film was formed at 1100° for 4 h. However, the film contains other phases apart from CAO.
CuAl2O4 was among the phases formed in the film. The CAO thin films are rather homogeneous
and uniform. Overgrowth of some grains over the surface also can be seen due to the high sintering
temperature process.

ACKNOWLEDGMENTS
This work was supported by IRPA (MOSTI) Project No. 09-02-05-4086-SR0013/06-04 and
Nippon Sheet Glass Foundation Research Grant, Japan.

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