Journal of the Australian Ceramic Society Volume 49[1], 2013, 15 20

15

Effective doping of Al in ZnO films by multi-target reactive

sputtering for near-infrared reflection
Y. Okuhara1*, H. Matsubara1, C. Numako2 and M. Takata3
1) Materials Research and Development Laboratory, Japan Fine Ceramics Center, Japan
2) Graduate School of Science, Chiba University, Japan
3) Department of Electrical Engineering, Nagaoka University of Technology, Japan
E-mail : okuhara@jfcc.or.jp
Available Online at: www.austceram.com/ACS-Journal

Abstract
Thin films of aluminium-doped zinc oxide (ZnO:Al) as heat reflective coatings were prepared by multi-target
reactive sputtering using metallic Zn and Al targets. To control the surface oxidation of each target during sputtering,
emission intensity of Zn plasma and current-voltage characteristics for the Al target were monitored. This technique
allowed to reduce ambient oxygen content to the lower limit of the ZnO:Al formation. The lowering oxygen content
in addition to the optimizing Al content achieved the carrier concentration Ne of 11.01020 cm-3 and the Hall mobility
of 25.0 cm2/Vs. The highest Ne provided the shortest plasma wavelength p of 1375 nm, which shifted the nearinfrared reflectance spectrum closer to the visible region. The high p reduced the optical absorption and enhanced
the reflectance. The local structure and the carrier generation behaviour of the doped Al were evaluated by X-ray
absorption fine structure (XAFS) measurements.
Keywords: Aluminium-doped zinc oxide, Transparent conductive oxides, Near-infrared reflection, Sputtering
process, Transition mode

INTRODUCTION
Heat reflective coatings to control the incoming solar
spectrum have been utilized for energy conservation.
Near-infrared rays (NIR) with high solar energy just
above the visible region should be shielded for
effective thermal insulation. Transparent conductive
oxides (TCOs) with a high concentration of free
electrons are one of the candidates for heat reflective
coatings [1, 2]. Thin films of aluminium-doped zinc
oxide (ZnO:Al) are expected as alternative TCOs in
place of expensive indium-containing films [2]. Tindoped indium oxide (In2O3:Sn) films indicated the
reflection commenced at plasma wavelengths p of
shorter than 1400 nm [2], whereas the NIR
reflectance for the ZnO:Al films was low because the
p placed at higher wavelength [3].
Most of the previously reported ZnO:Al films were
sputtered using Zn/Al alloy or ZnO including Al2O3
as a single target, so it was difficult to adjust the
Al/Zn ratio during the sputtering and to control the
doping condition of Al. In this study, the ZnO:Al
films were prepared by individual-control of Zn and
Al targets in a reactive sputtering process, in order to

adequately dope Al as active donors for enhancing the

NIR reflection. The multi-target sputtering system
was also applied to periodic doping of Al for
providing a high reflectance zone just above the
visible region. Moreover, this study aimed to
investigate the local structure of the doped-Al by Xray absorption fine structure (XAFS), and to clarify
the influence of the local structure on the carrier
generation behaviour.

METHODS AND PROCEDURES

A metallic Zn target (99.999%>) and an Al target
(99.999%>) were placed in the magnetron sputtering
sources. The O2 gas flow rate, f(O2), was varied from
0.0 to 3.7 sccm, and the Ar gas flow rate was
compensated so as to keep the total flow rate of 20
sccm. The total pressure was set at 0.4 Pa. A quartz
glass substrate was heated to 170C and rotated at 15
rpm during the sputtering. An AC power of 60 W
with a radio frequency of 13.56 MHz was applied to
the Zn target. In contrast, the Al target was sputtered
using DC voltage, VDC(Al), from 0 to 350 V. To
investigate the surface condition of each targets,

Okuhara et al.

Optical reflectance and transmittance spectra were

measured by a spectrometer with a 150 mm
integrating sphere. The film thickness d, refractive
indices n and extinction coefficients k were evaluated
by an ellipsometer. Electrical properties, such as
resistivity , carrier concentration Ne and Hall
mobility H, were measured by the van-der-Pauw
method and the Hall electromotive method.
Zn K-edge XAFS spectra for the ZnO:Al films were
measured at the BL-9A and 7C station of the KEK PF
rings in fluorescence yield mode using a Lytle
detector. Al and oxygen K-edge X-ray absorption
near edge structure (XANES) spectra were acquired
at the BL-11A station in total electron yield mode in a
vacuum ambient (<10-5 Pa).

exceeded the oxidization reaction. A possible

explanation for the behaviour is that the Al target
surface partially changed from oxide to metallic
mode. There were drops in current under f(O2) of 1.8
sccm. As the voltage closed to these critical points, an
increase in sputtering rate of Al enhanced ambient
oxygen consumption, and hence the coexisting Zn
plasma changed from oxide to metallic mode.
Therefore, transparent conductive films were
obtained below the critical voltages at each f(O2).

Normalized Zn emission

emission intensity of Zn plasma at 307.4 nm and

current-voltage characteristics (I-V curves) for the Al
target were monitored. The deposition time was set at
1 hour. Periodic doping of Al was carried out by the
intermittent opening and closing of a shutter for the
Al target, for which the thickness for each layer was
adjusted by controlling the deposition time.

16

1.0

Metallic surface
0.8
sccm

1.7 sccm
1.8 sccm

0.6

0.4

0.0

0.5

1.5

2.0

2.5

3.0

3.5

4.0

Fig. 1 Emission intensity of Zn plasma with

decreasing and increasing f(O2).

Discharge current of Al / A

The I-V curves for the Al plasma are shown in Fig. 2

[4]. The dashed line indicates the I-V curve in
oxidation atmosphere at f(O2) of 3.7 sccm, while the
dashed-dotted line denotes the I-V curve in inert Ar
atmosphere. The oxidized Al surface had higher
current than the metallic one, because the oxidized
surface emits more secondary electrons. The solid
lines with closed circles show the V-I curves of the Al
plasma coexisting with the Zn plasma at various
f(O2). On these curves the discharge current increased
with increasing voltage similar to the dashed line in
the oxide mode, but the V-I characteristics deviated
from the curve over the certain voltage, and the
discharge current kept almost constant. Over the
deflection points, the oxide surface on the Al target
was unsustainable because the sputtering rate

1.0

O2 flow rate / sccm

RESULTS AND DISCUSSION

Effective doping of Al in ZnO films
Figure 1 shows the emission intensity of the Zn
plasma as a function of f(O2) [4]. The emission
dropped at 1.8 sccm with increasing f(O2), implying
that the transition from metallic to oxide mode
appeared at the surface of the Zn target. By contrast,
the decrease in f(O2) caused the inverse transition at
1.6 sccm. This result suggests that, after oxidizing the
surface of the Zn target at high f(O2), the oxide-mode
was maintained at lower f(O2). The lower f(O2) is
preferable to depositing conductive ZnO with more
native defects.

Oxide surface

f (O2)=1.6

0.15

Oxide
surface
f (O2)=2.0 sccm
1.9 sccm
1.8 sccm

0.10

1.7 sccm
1.6 sccm

0.05

Metallic
surface
0.00
150

200

250

300

350

Sputtering voltage of Al / V

Figure 2. Relationships between sputtering voltage,

VDC(Al), and discharge current for the Al plasma.
Because higher VDC(Al) induced higher Al content in
the film, the Ne also increased as shown in Fig. 3 [4].
The maximum Ne at f(O2) of 1.7 and 1.8 sccm were
11.01020 and 9.91020 cm-3, whereas the Al contents
of each ZnO:Al film were 4.0% and 5.8%,

Journal of the Australian Ceramic Society Volume 49[1], 2013, 15 20

35
f (O2)=1.6 sccm
f (O2)=1.7 sccm 30
f (O2)=1.8 sccm
25

20

10

19

10

20
15

18

10

10
0

210

220

230

240

250

260

270

-1

40

-1

45

21

10

Hall mobility / cm V s

Carrier concentration / cm

-3

respectively. This result means that free electron

carriers were generated more effectively in the
ZnO:Al film deposited at lower f(O2).

5
280

Sputtering voltage of Al / V
Fig. 3 Carrier concentration and Hall mobility for the
ZnO:Al films sputtered at various VDC(Al).
A possible reason for the effective doping is that the
concentration of inactive Al dopants was reduced at
lower f(O2), since the oxidation of Al on the target
surface and in the deposited film were suppressed.
Figure 3 also shows that lower f(O2) provided higher
for the ZnO:Al films. The is given by e m*,
where
m* is the effective
electron mass. As discussed later, the higher was
attributed to longer
centers. This result supports that the Al doped at
lower f(O2) tends to be active donors for free carrier
generation rather than inactive impurities acting as
scattering centers.
f (O2)=1.6 sccm
f (O2)=1.7 sccm
f (O2)=1.8 sccm

80

100

80

60

60

40

40

20

20

500

1000

1500

2000

Reflectance / %

Transmittance / %

100

0
2500

Wavelength / nm

Fig. 4 Optical transmittance and reflectance for the

ZnO:Al films sputtered by the best VDC(Al) at each
f(O2).

17

The optical transmittance and the reflectance of the

ZnO:Al films are shown in Fig. 4 [4]. They are the
best spectra with the highest NIR reflectance at each
f(O2). The Al content was limited under 1.1% at f(O2)
of 1.6 sccm, so the NIR reflectance was low. An
increase in f(O2) to 1.7 sccm allowed to raise the
VDC(Al) to 250V, and the higher Al content enhanced
the NIR reflectance. The reflectance for the ZnO:Al
sputtered at f(O2)of 1.8 sccm reduced again even at
the best VDC(Al) of 260 V.
The dependences of p on f(O2) are shown in Fig. 5 as
a function of VDC(Al) [4]. The p is defined as the
wavelength where n equals k. The p shortened with
increasing Ne, and reached 1375 and 1438 nm at f(O2)
of 1.7 and 1.8 sccm, respectively. The shorter p
caused a horizontal shift of the reflectance spectrum
toward the visible region in Fig. 4. Moreover, the
lower optical absorption due to the higher H shown
in Fig. 3 contributed to a vertical enhancement of the
NIR reflectance. The reason for the high H is
considered as follows. From the p in Fig. 5 and the
electrical properties shown in Fig. 3, the m* can be
calculated as the following equation,

2 c0
p
p

Nee2
0 opt m

e
m

(1)

where dielectric constant opt was set at 2.0. The

calculated m* as a function of Ne for the films
prepared at f(O2) of 1.7 and 1.8 sccm traced almost
similar line. This result supported that the higher at
f(O2
not smaller m*. Because higher reduces optical
absorption [5], the higher reflectance in Fig. 4 was
attributed to the longer Consequently, the
independent-control of the Al and the Zn targets
allowed the effective doping of Al as active donors,
which generated more carriers and suppressed the
formation of scattering centers. The high Ne balanced
with the hig
performance.
Local structure around the doped-Al
Although the doped Al were dilute (4 at.%) in the
highly conductive ZnO:Al films, the XANES spectra
for the Al K-edge were able to be observed. The Al
K-edge XANES spectra (1550 ~ 1670 eV) were
similar in shape to the spectra for the Zn K-edge
(9650 ~ 9670 eV) as shown in Fig. 6. This result
shows the local structure around the doped-Al was
analogous to the Zn site, suggesting most of the
doped Al substituted in the Zn sites.

can be due to oxidation of a part of the doped Al. This

result explains that the Al doped at higher f(O2)
tended to become inactive donors.

f (O2)=1.6
sccm

2400

1.7 sccm

2200

1.8 sccm

2000
1800
1600
1400
1200
200

220

240

260

280

300

Sputtering voltage of Al / V

Fig. 5 Plasma wavelength as a function of VDC(Al) at

various f(O2).
Figure 7 depicts a comparison of Al K-edge XANES
spectra for the ZnO:Al prepared at f(O2) of 1.7 and
1.8 sccm. These spectra were normalized at their first
peak around 1560 eV. The XANES spectrum for the
Al doped at f(O2) of 1.7 sccm with higher carrier
generation efficiency was found to have the
absorption spectrum at higher energy. Increasing
valence or lowering electron density around the
intended ions shifts the XANES spectra to higher
energy [6]. The spectral shape for -Al2O3 drastically
changed as shown in Fig. 8. The shift in the Al Kedge absorption energy in Fig. 7 preserved similar
spectrum shape, implying that the low electron
density around the doped-Al ions is attributed to more
effective generation of free electrons rather than
oxidization of Al.
Normalized
absorbance

2.0

1.80 sccm
1.0

0.5

0.0
1550

1560

1570

1580

1590

1600

Energy / eV

Fig. 7 XANES spectra of the Al K-edge for the

ZnO:Al film sputtered by the best VDC(Al) at each
f(O2).
2.0

Al K-edge
1.5

Al in ZnO doped at
f(O2)=1.70 sccm

1.0

0.5

-Al2O3 powder
1560

1570

1580

1590

1600

Fig. 8 XANES spectra of the Al K-edge for the

ZnO:Al film sputtered at f(O2) of 1.7 sccm and Al2O3 powder.

1.0
0.5
1560

1580

1600

1620

1640

1660

Energy / eV
Normalized
absorbance

f(O2)=1.70 sccm

Energy / eV

(a) Al K-edge

1.5

1.5

(b) Zn K-edge

1.0
0.5
0.0

Al K-edge
1.5

0.0
1550

2.5

0.0

18

Normalized absorbance

2600

Normalized absorbance

Plasma wavelength / nm

Okuhara et al.

9660

9680

9700

9720

9740

9760

Energy / eV
Fig. 6 Typical XANES spectra of (a) the Al K-edge
and (b) Zn K-edge for the ZnO:Al films.
Moreover, in Fig. 7, the XANES spectrum for the Al
doped at f(O2) of 1.8 sccm had smaller second and
third peak of absorbance. As shown in Fig. 8,
oxidation of Al tended to decline the second peak at
1567 eV and to have no third peak at 1577 eV.
Therefore, the change in spectral shape at higher f(O2)

Periodic doping of Al in ZnO films

Comparing the best reflectance spectrum in Fig. 4
with the solar energy spectrum revealed that the solar
irradiance under the p of 1375 nm, which is out of
the reflective range, contains high energy. To shield
the high energy heat ray, ZnO:Al multilayers with
periodic Al doping have been proposed [7]. In the
sample preparation using a new Zn target, the best
sputtering condition changed slightly to f(O2) of 1.6
sccm and VDC(Al) of 245 V for the Al target. For
deposition of non-doped ZnO layers, the RF power
for the Zn target reduced from 60 to 30 W in order to
suppress the native defects and to ensure the visible
transmittance. The five layers of 200 nm-thick
ZnO:Al and the four layers of 150 nm-thick ZnO
were alternately stacked. The topmost and the bottom
layers were the ZnO:Al films. The cross-sectional
SEM (secondary electron microscope) image is
shown in Fig. 9.

Journal of the Australian Ceramic Society Volume 49[1], 2013, 15 20

ZnO:Al
ZnO
ZnO:Al
ZnO
ZnO:Al
ZnO
ZnO:Al
ZnO
ZnO:Al

Fig. 9 A Cross-sectional SEM image for the

periodically-Al doped ZnO multilayer.
2.5

2.0

2.0

1.5

1.5

1.0

1.0

0.5

0.5

2.5

0.0

500

1000

1500

0.0
2500

2000

Wavelength / nm

Fig. 10 Wavelength dependences of n and k for the

non-doped ZnO and the ZnO:Al.
The spectrum of refractive index n and extinction
coefficient k for the non-doped and Al-doped ZnO are
shown in Fig. 10. In contrast to the constant n and k
for the ZnO film, the ZnO:Al film showed a drop in n
and a rise in k above the NIR region. There was no
major difference in n around the visible region, while
the gap widened over the NIR region. Therefore,
periodic distribution of n for the multilayer in Fig. 9
is available only for the NIR reflection. The uniform
distribution of n in the visible region prevents
unnecessary high-order reflection, which is
advantageous to the high visible transmittance.

80

80

60

60

40

40

20

20

modulation of n was found to provide a local

maximum and a local minimum from 900 to 1300 nm
in wavelength; the wavelength region was impossible
to be reflected by the ZnO:Al monolayer. By the high
reflectance zone, the solar heat gain coefficient of
0.69 for the ZnO:Al monolayer was reduced to 0.57
for the multilayer. There was no subsequent highorder reflection in the visible region because of the
similar n for each layer, which preserved the visible
transmittance above 79%.

CONCLUSION
This study proposed the independent control of multitargets for preparing highly reflective ZnO:Al, and
provided two advantages.
The first one was effective doping of Al by
controlling metal-oxide transition mode for the Zn
and Al targets. Monitoring of the transition mode
enabled us to reduce ambient oxygen content to the
lower limit during sputtering, which was crucial to
enhance the carrier generation efficiency and hence to
suppress inactive Al dopants acting as scattering
centers. As a result, increases in carrier concentration
and mobility reduced plasma wavelength and optical
absorption, and hence achieved high NIR reflectance.
XAFS measurements proved that most of the doped
Al substituted in the Zn sites. In addition, the dopedAl with higher carrier generation efficiency showed
Al K-edge absorption spectrum at higher energy,
which was consistent with low electron density
around the doped-Al.
The second benefit for multi-targets sputtering
process was periodic doping of Al. The periodic
structure provided a high reflectance zone around
1200 nm, which was shorter than the p of the
ZnO:Al monolayer. Because the periodic n
distribution was available only above NIR region,
transparency in the visible region was preserved.

100

500

1000

1500

2000

Reflectance / %

Transmittance / %

100

19

0
2500

ACKNOWNLEDGEMENTS
This work was supported by the New Energy and
Industrial Technology Development Organization
(NEDO) as The Project of Development of Multiceramic Films for New Thermal Insulators. The
XAFS measurements were performed under the
approval of the Photon Factory Program Advisory
Committee (Proposal No.2009G619).

Wavelength / nm

Fig. 11 Optical transmittance and reflectance for the

periodically-doped ZnO:Al multilayers.
The reflectance and the transmittance spectra for the
multilayer are shown in Fig. 11. The periodic

REFERENCES
1. H. L. Hartnagel, A. L. Dawer, A. K. Jain and C.
Jagadish, Semiconducting Transparent Thin Films,
Institute of Physics Publishing, Bristol, (1995).

Okuhara et al.
2. I. Hamberg and C. G. Granqvist, Evaporated Sndoped In2O3 Films: Basic Optical Properties and
Applications to Energy- efficient Windows, J.
Appl. Phys. Vol. [60], (1986), R123-R159.
3. Z.-C. Jin, I. Hamberg and C. G. Granqvist,
Optical Properties of Sputtered ZnO:Al Thin
Films, J. Appl. Phys., Vol. [64], (1988), 51175131.
4. Y. Okuhara, H. Matsubara and M. Takata, Nearinfrared Reflection from Al-doped ZnO Films
Prepared by Multi-target Reactive Sputtering,
Mater. Sci. Eng., accepted.
5. T. J. Coutts, D. L. Young and X. Li,
Characterization of Transparent Conducting

20

Oxides, MRS Bulletin, Vol. [25], (2000), 58-65.

6. N. M. D. Brown, J. B. McMonagle and G. N.
Greaves, An Absorption Edge and Extended Xray Absorption Fine Structure Study of a
Dispersed Manganese Dioxide Oxidation
Catalyst, J. Chem. Soc., Faraday Trans. 1, Vol.
[80], (1984), 589-597.
7. Y. Okuhara, T. Kato, H. Matsubara, N. Isu and M.
Takata,
Near-infrared
Reflection
from
Periodically Aluminium-doped Zinc Oxide Thin
Films, Thin Solid Films, Vol. [519], (2011) 22802286.