Highly transparent and conductive ZnO:Al thin films prepared

by vacuum arc plasma evaporation

Toshihiro Miyata,a) Youhei Minamino, Satoshi Ida, and Tadatsugu Minami
Optoelectronic Device System R&D Center, Kanazawa Institute of Technology, 7-1 Ohgigaoka, Nonoichi,
Ishikawa 921-8501, Japan

Received 3 November 2003; accepted 12 April 2004; published 22 July 2004

A vacuum arc plasma evaporation VAPE method using both oxide fragments and gas sources as
the source materials is demonstrated to be very effective for the preparation of multicomponent
oxide thin films. Highly transparent and conductive Al-doped ZnO AZO thin films were prepared
by the VAPE method using a ZnO fragment target and a gas source Al dopant, aluminum
acethylacetonate (AlC5 H7 O2 ) 3 ) contained in a stainless steel vessel. The Al content in the AZO
films was altered by controlling the partial pressure or flow rate of the Al dopant gas. High
deposition rates as well as uniform distributions of resistivity and thickness on the substrate surface
were obtained on large area glass substrates. A low resistivity on the order of 104 cm and an
average transmittance above 80% in the visible range were obtained in AZO thin films deposited on
glass substrates. 2004 American Vacuum Society. DOI: 10.1116/1.1759351
I. INTRODUCTION

II. EXPERIMENT

Transparent conducting indiumtinoxide ITO thin

films deposited by magnetron sputtering are in practical use
for most optoelectronic applications. Nevertheless, impuritydoped ZnO, such as Al- or Ga-doped ZnO AZO or GZO,
has recently gained much attention as an alternative material
for ITO thin films,1 because In, the principal ingredient, is a
very expensive and scarce material. The use of magnetron
sputtering for the deposition of transparent conducting ZnO
films, however, results in a severe problem of spatial resistivity distribution across the substrate surface.2 6 This is
mainly ascribed to spatial distributions, corresponding to the
erosion pattern on the target surface, in the amount and activity of oxygen reaching the substrate surface. In particular,
the effect is marked in ZnO films deposited on substrates at a
low temperature. Because of this spatial distribution problem, a vacuum arc plasma evaporation VAPE method providing uniform-resistivity ZnO film preparations on large
area substrates with a high deposition rate has been
developed.710 Recently, we reported the high rate deposition
of undoped and impurity-doped ZnO thin films on large area
substrates by the VAPE method using an oxide fragment target as a low-cost source material. In comparison with conventional magnetron sputtering, the VAPE method offers a
great advantage due to its potential for lower cost deposition
of highly transparent conducting ZnO thin films resulting
from factors such as low target processing costs. We have
demonstrated resistivities as low as 2104 cm in Gadoped and Ga- and F-codoped ZnO thin films deposited by
the VAPE method.8 10 Up to now, however, the preparation
of low resistivity AZO films by the VAPE method had not
been reported.
In this article, we describe the preparation of highly transparent conducting AZO thin films by the VAPE method using
a ZnO fragment target and a gas source Al dopant.

The AZO thin films were deposited by VAPE using either

an AZO fragment target or a nondoped ZnO fragment target
with a gas source Al dopant, as shown in Fig. 1. The film
depositions were carried out under the following conditions:
substrate temperature, room temperature to 450 C; target,
sintered ZnOAl2 O3 AZO or ZnO fragments; pressure,
0.08 1 Pa; Ar and O2 gas flow rates, 20 and 020 sccm; and
cathode plasma power, 3.510 kW. Aluminum acethylacetonate (AlC5 H7 O2 ) 3 ), contained in a stainless steel vessel,
was used as the Al dopant source. The Al content in the AZO
films was altered by controlling the vapor pressure or flow
rate of the Al dopant gas by varying the tank temperature.
The thin films were deposited on large area glass substrates
OA-2, Nippon Electric Glass Co. Ltd.. The AZO or ZnO
fragments, consisting of a mixture of ZnO and Al2 O3 powders or ZnO powder, respectively, were pressed and then
sintered at 1400 C for 5 h in air. The surface temperature of
the substrate could not be directly measured during the deposition because the substrate holder was rotating, the temperature was monitored at a position near the glass substrate. The
temperature of the substrate surface was determined to be
approximately the same as the monitored temperature. The
following deposition conditions remained constant in this
work: a substrate rotation of 14 rpm and a substrate
evaporation source distance of about 58 cm. Four glass substrates 100 mm100 mm were set on the 300 mm diam
substrate holder.
Electrical resistivity and Hall mobility were measured at
room temperature by the van der Pauw method. The optical
transmission through the films deposited on the glass substrates was measured in the range from 300 to 800 nm. The
crystallinity of the ZnO thin films was investigated by x-ray
diffraction XRD using a conventional x-ray unit with a
copper anode. The Al content Al/AlZn atomic ratio in
the deposited AZO thin films was measured by x-ray photoelectron spectroscopy XPS.

Author to whom correspondence should be addressed; electronic mail:

tmiyata@neptune.kanazawa-it.ac.jp

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0734-2101200422417115$19.00

2004 American Vacuum Society

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Miyata et al.: Highly transparent and conductive ZnO:Al thin films

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FIG. 3. XRD patterns of films deposited using AZO targets with various
Al2 O3 contents.
FIG. 1. Schematic diagram of the VAPE system.

III. RESULTS AND DISCUSSION

A. Deposition using AZO fragment targets

Highly transparent and conductive thin films, consisting

of multicomponent ZnOIn2 O3 10 and impurity-doped ZnO
such as GZO and F-doped ZnO,8,9 could be prepared by
VAPE using various oxide targets. We initially found that
low resistivity could not be obtained in films deposited by
VAPE when using an AZO fragment target.9 Therefore, a
more detailed investigation of AZO thin film preparation by
VAPE using an AZO fragment target was conducted. It was
found that the resistivity gradually decreased as the Al2 O3
content in the AZO fragments used as the target was increased up to 10 wt %. The measured carrier concentration as
a function of the Al2 O3 content is shown in Fig. 2 for AZO
films deposited by VAPE using AZO fragments sintered with
various Al2 O3 contents. The films, with thickness in the

FIG. 2. Relationship between carrier concentration and Al2 O3 content of

films deposited using AZO targets with various Al2 O3 contents.
J. Vac. Sci. Technol. A, Vol. 22, No. 4, JulAug 2004

range from 150 to 440 nm, were deposited with a cathode

plasma power of 4.5 kW at a substrate temperature of
250 C. It should be noted that the carrier concentration increased in proportion to the Al content. The obtained carrier
concentration of AZO thin film prepared with an Al2 O3 content of 10 wt % was approximately 3.01019 cm3 . Since
the Al content in AZO fragments with an Al2 O3 content of
10 wt % is approximately 61021 cm3 , either the Al impurity was not effectively doped into the film, or the doped Al
did not act as an effective donor. Figure 3 shows the Al2 O3
content dependence of XRD patterns for the AZO films
shown in Fig. 2. The intensity of the XRD patterns shown in
this figure was normalized by dividing by the film thickness.
All deposited AZO thin films exhibited a strong c-axis orientation perpendicular to the substrate surface, regardless of
the Al2 O3 content. It is known that the crystallinty of AZO
thin films, estimated by the intensity and half width of the
0002 XRD peak, degrades as the Al content doped into the
films is increased.11 However, the crystallinity of the deposited AZO films did not show a tendency to degrade, as evidenced in Fig. 3.
The Al content in the films was lower than the minimum
level observable by the XPS measurement. This low Al content and the carrier concentration on the order of 1019 cm3
in the deposited films suggested that an insufficient amount
of the Al impurity was doped into the ZnO films. The photographs in Fig. 4 show the surface of the AZO targets before
a and after b the deposition. It should be noted that a

FIG. 4. Photographs of AZO target surfaces before and after deposition.

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Miyata et al.: Highly transparent and conductive ZnO:Al thin films

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FIG. 5. XRD patterns of spherical objects produced on AZO target surfaces.

FIG. 6. Electrical properties as functions of tank temperature for AZO films
deposited using the Al gas source.

number of small spherical objects were always found scattered across the surface of the target after the film deposition,
as seen in Fig. 4b. XRD measurements identified these objects as -Al2 O3 , as shown in Fig. 5. These facts suggest
that ZnO was evaporating through sublimantion prior to
melting, but Al2 O3 did not evaporate even though it was
melting. As a result, it can be concluded that with VAPE
depositions using an AZO target, doping Al into ZnO films is
difficult because of the large difference in decomposition energy vapor pressure between Al2 O3 and ZnO.
B. Deposition using Alacac 3 gas source

The above problem could be avoided by using a multisource deposition technique with each evaporation source
derived from different materials. However, it was not easy to
use such a technique with a VAPE deposition of films on
large area substrates at a high deposition rate. We proposed a
way for doping Al impurity in the preparation of transparent
conducting AZO thin films by VAPE: the introduction of a
metalorganic gas such as alkylmetal compounds or alkyoxide
onto the substrate surface during a ZnO film deposition with
an evaporation source using a ZnO fragment target. As an
example, we note AZO film preparation by VAPE using, as
the Al doping source, Al acethylacetonate (Alacac) 3 ) which
was low in cost and easy to handle and was previously reported to be useful as an Al gas source.12,13 The amount of
Alacac) 3 gas introduced into the reactor was controlled by
altering the temperature of the Alacac) 3 vessel and the timing of the two valves in the Alacac) 3 gas introduction system, as shown in Fig. 1.
Figure 6 shows resistivity, carrier concentration, and Hall
mobility as functions of the Alacac) 3 vessel temperature for
AZO films prepared by VAPE using a ZnO fragment target
and the Alacac) 3 gas source. The film deposition was carried out with a cathode plasma power of 4 kW, a substrate
temperature of 250 C, and a pressure of 0.3 Pa. The films
were deposited with a thickness of 160350 nm and a depoJVST A - Vacuum, Surfaces, and Films

sition rate of approximately 100 nm/min; the two valves in

the Alacac) 3 gas introduction system were completely open
during the deposition. It should be noted that a low resistivity
of 7.6104 cm and a maximum carrier concentration of
41020 cm3 were obtained in AZO thin films deposited by
VAPE using the Al doping system. As can be seen in Fig. 6,
the resistivity first decreased as the vessel temperature was
increased from room temperature, reaching a minimum at
about 140 C, and then increased with a further increase of
the temperature. The decrease in resistivity was associated
with both an increase in carrier concentration and a decrease
in Hall mobility.
C. Al doping effects

As shown in Fig. 6, the carrier concentration increased to

a level as high as 41020 cm3 as the vessel temperature
was increased. In addition to the carrier concentration, the Al
content in the deposited AZO films was also affected by the
Al doping, as evidenced by XPS. Figure 7 shows the relationship between the obtained carrier concentration and the
Al content in the AZO films deposited at various vessel temperatures. It should be noted that the carrier concentration
increased as the Al content was increased. The carrier concentration increase is also associated with the increase of Al
content in the AZO films. This fact suggests that the Al impurity doped in the AZO films is acting as an effective donor.
In addition, test evaluating usage at a high temperature in
various atmospheres showed that the stability of resistivity in
AZO films deposited by the VAPE method was approximately the same as that in films deposited by magnetron
sputtering.14,15 This also suggests that the Al in AZO films
acts as an effective donor.16
It was found that the Hall mobility decreased considerably
as the vessel temperature was increased above about 120 C,
as shown in Fig. 6. In order to investigate the origin of this

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FIG. 9. Al content dependencies of Hall mobility and normalized 0002

XRD peak intensity for AZO films.

FIG. 7. Relationship between carrier concentration and Al content of AZO

films.

Hall mobility decrease, the crystallinity of the deposited

AZO films was evaluated by XRD analyses. The Al content
dependence of XRD patterns is shown in Fig. 8 for the AZO
thin films shown in Fig. 6. The intensity was normalized by
dividing by the film thickness for the XRD patterns shown in
this figure. All the AZO films had their c axis strongly oriented perpendicular to the substrate surface. The intensity of
the 0002 XRD peak decreased considerably as the Al content was increased above 0.4 at. %. The Al content dependencies of the Hall mobility and the intensity of the 0002 XRD
peak shown in Fig. 8 are compared in Fig. 9 for the AZO
films shown in Fig. 6. The peak XRD intensity indicated in
Fig. 9 was also divided by the film thickness. The decrease
of the 0002 peak intensity is correlated to the decrease of
Hall mobility. In addition, the crystallinity of the AZO films
decreased considerably as the Al content increased above 0.4
at. %. Therefore, the decrease of Hall mobility may be as-

cribed to the degradation in crystallinity of the AZO films

that results from the effect of doping an Al impurity into a Zn
site of the ZnO lattice.
It was found that the carbon content C/CZn atomic
ratio in the AZO thin films increased from approximately
0.9 to 3.5 at. % as the Al content in the films increased from
0.2 to 1.1 at. %. Therefore, the observed degradation of crystallinity may be mainly caused by the introduction of carbon
into the AZO films, resulting from the decomposition of the
acetylacetonate used as the Al gas source. In particular, the
marked decrease of Hall mobility in AZO films deposited at
an Al content of 1.1 at. % may be ascribed to carbon contamination in the AZO film. Nevertheless, all the AZO thin
films deposited with an Al content up to 1.1 at. % exhibited
high optical transmittance in the visible range. Figure 10
shows the Al content dependence of the transmission spectra
through the AZO thin films, which were deposited on glass
substrates, shown in Fig. 6. A high average transmittance
above 80% in the visible range was obtained for the AZO
films, regardless of the Al content.

FIG. 8. XRD patterns as a function of the Al content of AZO films.

FIG. 10. Transmission spectra as a function of the Al content of AZO films.

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Miyata et al.: Highly transparent and conductive ZnO:Al thin films

IV. CONCLUSIONS
Highly transparent conducting Al-doped ZnO AZO thin
films were prepared by a VAPE method using ZnO fragments
and a gas source Al dopant. Aluminum acethylacetonate
(AlC5 H7 O2 ) 3 ) contained in a stainless tank was used as the
Al dopant source. The Al content in AZO films was altered
by controlling the temperature of the AlC5 H7 O2 ) 3 tank.
Film depositions at a rate of 100 nm/min were carried out on
large area glass substrates at a deposition temperature of
250 C, a pressure of 0.3 Pa, and a cathode plasma power of
4 kW. A low resistivity on the order of 104 cm and a high
average transmittance above 80% in the visible range were
obtained in AZO thin films deposited on glass substrates. It is
concluded that the VAPE method, which uses both an oxide
fragment target and a gas source as the source materials, is
very useful for the preparation of multicomponent oxide thin
films.
ACKNOWLEDGMENTS
The authors would like to thank J. Kitamura, S. Tsukada,
and S. Tanaka for their technical assistance in the experiments.

JVST A - Vacuum, Surfaces, and Films

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