Effect of low substrate deposition temperature on the optical

and electrical properties of Al2 O3 doped ZnO films fabricated

by ion beam sputter deposition
J. W. Seonga)
P & I Corp., Shinnae-Techotown #405, 485, Sangbong-Dong, Jungrang-Gu, Seoul 131-221, Korea
and Department of Ceramic Engineering, Yonsei University, Sudaemun-Gu, Shinchon-Dong 134,
Seoul 120-749, Korea

K. H. Kim, Y. W. Beag, and S. K. Koh

P & I Corp., Shinnae-Techotown #405, 485, Sangbong-Dong, Jungrang-Gu, Seoul 131-221, Korea

K. H. Yoon
Department of Ceramic Engineering, Yonsei University, Sudaemun-Gu, Shinchon-Dong 134,
Seoul 120-749, Korea

Received 19 September 2003; accepted 14 March 2004; published 15 June 2004

Aluminum 2 wt % doped zinc oxide AZO films are prepared by ion beam sputtering method on
glass substrates with very low substrate deposition temperature below 150 C. The results of Hall
effect measurements showed the decrease in resistivity (2.6103 7.3104 cm) came from
an increase in mobility and carrier concentration as substrate deposition temperature increased. We
confirmed the decrease of resistivity, which resulted from the formation of oxygen deficiency
(ZnO1x ) as substrate deposition temperature increased. The increase of Hall mobility and carrier
concentration was also influenced by increases in crystallinity and grain growth of AZO films as
substrate deposition temperature increased. The optical transmission of AZO increased from 70% to
80% with increasing substrate deposition temperature. The surface morphology analysis by atomic
force microscopy showed the decrease of surface roughness might be related to the development of
optical properties. 2004 American Vacuum Society. DOI: 10.1116/1.1738654

I. INTRODUCTION
Extensive research directed on deposition techniques development and investigation of zinc oxide ZnO thin films
properties was performed during the last two decades. Dc
and rf magnetron sputtering in different modifications, pulse
laser deposition as well as electron beam evaporation were
used for ZnO films preparations on glass substrates.13 This
growing interest originated first of all from the circumstance
that ZnO is now considered a prospective material alternative to indium tin oxide ITO in display manufacturing. ITO
is well known to be one of the most expensive coating materials in the thin film market.
It was shown that ZnO films with good optical and electrical properties could be deposited on glass substrates at
room temperature by dual-ion-beam sputtering.4 It was also
found that the electrical resistivity of polycrystalline films
ranged depending on the oxygen percentage in the assistance
ion beam from 103 to 105 cm.
Later, Al, Ga, F, or B doping was used to improve sheet
resistance and transmittance for visible light.5 8 The resistivity of Al doped ZnO AZO films studied on a large scale
have been found to be 2104 to 5104 cm which is
comparable to that of ITO films. However, these results were
obtained under relatively high deposition temperatures from
150 to 250 C.
a

Author to whom all correspondence should be addressed; also at: Shinnae

Techotown #405, 485, Sangbong-Dong, Jungrang-Gu, Seoul 131-221, Korea; electronic mail: cermetal@yonsei.ac.kr

1139

J. Vac. Sci. Technol. A 224, JulAug 2004

Rf magnetron sputtering in usual mode9 and off-axis

one10 were used for AZO film fabrication. It was found in
this research that properties of the films are strongly dependent on Ar working pressure, deposition chamber, and substrate location with respect to target. Note in accordance with
this that ion beam sputter deposition IBSD could be realized at the better vacuum conditions. Consequently higher
arrival energy particles coming to substrate could be
achieved. Thus, the further improvement of AZO films properties fabricated by using IBSD could be expected.
In this study AZO films were fabricated on glass substrates by using Ar ion beam sputtering of the high purity
ZnO target doped with Al2 O3 . The effect of substrate heating on the electrical, crystalline, and optical properties of the
films has been investigated.

II. EXPERIMENTAL DETAILS

Experiments were carried out using high vacuum system,
which consisted of a stainless steel chamber, cold hollow ion
source, target, and substrate holders and auxiliary devices.
The AZO target Cerac Co., Ltd. was 6-in.-diam and 0.3-in.thick sintered oxide ceramic disk 98 wt % ZnO and 2 wt %
Al2O3, 99.99% purity mounted on a water-cooled holder.
The chamber was evacuated by a turbo pump to a base pressure of 1106 Torr. A 1 keV Ar ion beam with a diameter about 50 mm was used for film deposition. Angle of
incidence of bombarding ions was fixed at 50 from nor-

0734-2101200422411397$19.00

2004 American Vacuum Society

1139

1140

Seong et al.: Effect of low substrate deposition temperature

mal to substrate. Movable Faraday cup was used to measure

parameters of Ar ion beam. The pressure was raised to 1
104 Torr during film deposition.
Films were deposited on commercial glass slides Corning 2948, Corning Corp.. The substrate holder equipped
with a heater was placed parallel to the target surface. The
distance between target and substrate holders was 15 cm.
During a film deposition substrates temperature could be
kept in the range from 20 to 120 C within an accuracy of
2 C. Substrate temperature was measured by a thermocouple attached to a substrate surface. A quartz crystal oscillator placed near the substrates monitored in situ deposition
rate. The deposition rate was about 20 nm/min and films with
a thickness of about 150 nm were fabricated. The films thickness homogeneity was within 5%. The conductance and the
carrier concentration of fabricated films were determined by
using four-point probe resistance and Hall effect measurements.
To examine a crystal structure of the films the x-ray diffraction XRD peaks were recorded in 2 geometry by
Siemens Diffractometer D5000. A Ni-filtered Cu K
1.5418 source was used and the scanning range was
between 220 to 80 in these experiments. The films surface morphology and microstructure were investigated in
scanning electron microscope SEM, S-4200FE, Hitachi Co.
and by using atomic force microscopy AFM, SFM-BD2,
Park Scientific Instruments. The film composition analysis
was conducted by x-ray photoelectron spectroscopy XPS
by using ESCA LAB 220-XL, VG Scientific. The XPS spectra were obtained with monochromatic Al K x-ray h
1486.6 eV. The position of the C 1s peak was taken as a
standard 284.5 eV of binding energy. The films optical
transmittance was characterized by UV-visible spectrometer
Hewlett Packard.
III. RESULTS AND DISCUSSION
A. Crystallinity, microstructure and surface
morphology of AZO thin films

Figure 1 shows the XRD spectra of Al doped ZnO films

deposited at different substrate temperatures. The distinct
peak at 233.8 is seen in all spectra indicating that AZO
films have c-axis orientation of the hexagonal phase. The
above similar crystal structure was observed earlier for ZnO
films.6 However, the only AZO films deposited at 120 C
revealed a strong textured growth along c-axis.
It is also seen from Fig. 1 that at all temperatures, the
002 AZO peak position shifts lower angles as compared
with the normal ZnO powder value of 34.47. Shifting the
peak about 0.4 towards larger 2 value observed for films
fabricated by rf magnetron sputtering of ZnO target doped
with 3 wt % Al2 O3 and the shift value was found to depend
on the dopant concentration.1219 Authors suggested that if
all Al atoms were substituted in Zn sites, the lengths of the
c-axis should be shorter. However, increasing the AZO lattice parameters a and c with respect to ZnO was found
contrary to these results when the films were prepared by
spray pyrolysis at different dopant concentrations.9 Because
J. Vac. Sci. Technol. A, Vol. 22, No. 4, JulAug 2004

1140

FIG. 1. X-ray diffraction spectra of AZO films prepared at different substrate

temperatures.

the c/a ratio was found to be the same for both doped and
virgin ZnO films,3 it was concluded that the sites available
for Al in the ZnO lattice are probably very limited. In addition, Al, Al3 , or Al2 O3 segregates at the grain boundaries.
The peak position revealed in our measurements is very near
to ones found for the films fabricated by dc magnetron reactive sputtering 34.02 at 20 C11 and by dual ion beam
deposition 33.5020 on quartz glass and glass substrates,
correspondingly. Note also that similar to our measurements,
the peak position was observed to be nearly independent on
a substrate temperature change from 20 to 200 C,11 while
the peak intensity increasing was found to be seven times
when the temperature changed from 20 to 120 C. Compared
to our data, other studies show a low increase of peak intensity such as 1.4 and 1.5 times.2,11
To derive the film stress film parallel to the film surface,
the following formula has been used, which is valid for a
hexagonal lattice:23

film233 Gpa the strain c filmc bulk /c bulk ,

which is the tensile stress ( film) along the c-axis and would
draw the c-axis out. Figure 2 appears that the full width at
half maximum FWHM decreased as the substrate temperature increased and the stress decreased significantly from
36.4 Gpa at 20 C to 0.37 Gpa at 120 C. It is likely to be of
intrinsic, rather than of thermal origin. This suggests that the
stress should be generated during deposition due to the freezing of structural defects at low temperatures.11
It was concluded that the peak shifting could occur due to
the tensile stress along the c-axis.4,11,20 From these facts, we
will summarize that the stress value may be obviously dependent on such parameters as a deposition rate, gas capture
or release, film thickness, etc., which could defer for different substrate temperatures and for various deposition techniques. Thus, additional experiments are needed to clarify
reasons of the peak shifting.

1141

Seong et al.: Effect of low substrate deposition temperature

FIG. 2. FWHM a and the residual stress b of AZO in dependence of the

substrate temperature.

1141

were used for SEM it was suggested that the larger grains are
formed via the aggregation of small grains or grain boundary
movement.
Figure 5 demonstrates the AFM images of the AZO film
deposited on glass substrates at different temperatures. The
surface of the films deposited at 20 C appeared steep with a
rough topography, while the films grown at 120 C showed
round and uniform grains and a rather smooth surface.
The change of root mean square rms roughness of the
AZO films as a function of substrate temperature can be seen
in Fig. 6. The rms roughness decreased to the value about 0.5
nm as substrate temperature increased up to 120 C. The effect of substrate heating on rms roughness was observed for
AZO films deposited on Si and glass substrates.15 The value
of rms roughness was found in both studies to decrease by
9.35 and 1.5 nm, correspondingly, with the increase of substrate temperature up to 300 C. However, the highest Hall
mobility and consequently the lowest resistivity of the films
were measured at the deposition temperature about 150 C,
when the rms roughness was 3.4 nm.15
The improvement of surface roughness and quality of
AZO thin films was attributed to the increment of substrate
temperature. The substrate heating leads to increasing of mobility or surface migration of condensed atoms. In the case of
ion beam deposition, sputtered atoms were deposited on substrate surface with higher energy when compared with conventional deposition techniques such as vapor, spray pyrolysis, or rf and dc magnetron deposition. Thus, sputtered atoms
due to ion beam bombardment provide an additional energy
of surface atoms enhancing their surface mobility. Therefore,
as it is seen from our results, the better AZO film properties
can be achieved at relatively low substrate temperature.
B. Composition of the AZO films

Figure 3 shows SEM surface images of AZO films deposited at different substrate temperatures. The coalescence process of grains is seen from Fig. 3 to appear gradually with an
increasing of a substrate temperature. The grain size can be
deduced from x-ray diffraction by using Scherrer formula l
0.9 Cu K /cos (2) with l of grain size, Cu K
1.5418 , 2 of FWHM.7 The calculated dependence
of the grain size on the substrate deposition temperature is
shown in Fig. 4. The grain size of AZO films prepared in this
study at 20 C is about 12 nm and is very similar to 10, 12,
and 13 nm found for the films made by dual-ion-beam,20 by
rf-magnetron sputtering4 and by midfrequency reactive magnetron sputtering, respectively.15 Due to the crystallinity improvement of the films seen from Figs. 1 and 2 the grain size
grew 36 nm with substrate temperature increasing to 120 C.
The very similar values were estimated for AZO films deposited at 150 C about 31 nm15 and for the post-annealed
films deposited at 20 C from 20 to 45 nm with increasing
annealing temperature from 272 to 390 C.5 The grain size
of 150 nm AZO films was estimated about 33 nm from XRD
measurements, while the grain size revealed from SEM micrographs was about 20 times.12 Since thick films 3 m
JVST A - Vacuum, Surfaces, and Films

The deposited AZO films have been found from XPS

analysis to be free from contaminants other than oxygen and
carbon. These contaminants are adsorbed partly during the
deposition from a residual gas environment and additionally
due to an air exposition while the films were transferred to
the XPS chamber. Figure 7 shows the O 1s peak in XPS
spectrum of the films. It is seen from Fig. 6 that this peak can
be consistently fitted by Gaussian, centered at 530.150.15
and 531.250.20 eV, respectively. The first of the peaks
mentioned above corresponds to oxygen constituting the
AZO film.11 The intensity of the second peak, which appears
due to adsorbed oxygen decreases with increasing substrate
temperature. The second peak indicated the shoulder of O 1s
peak in XPS spectrum.
Ratios of oxygen-to-zinc concentrations in the ZAO films
(CO /CZn) were calculated as ratios of areas under Zn 2p
1024 eV and O 1s 530 eV peaks, respectively. A temperature dependence of the concentration ratio is shown in
Fig. 8a. As it is seen from Fig. 8a, above 70 C the ratio is
less than 1 and decreases slightly with an increasing of the
deposition temperature, indicating an oxygen deficiency in
the AZO films. It was found also from analysis of XPS
spectra that Al concentration in the films is about 3.9 at. %

1142

Seong et al.: Effect of low substrate deposition temperature

1142

FIG. 3. SEM micrographs of the AZO films prepared on a glass substrate: a 20 C, b 70 C, c 95 C, and d 120 C.

regardless of the substrate deposition temperature in Fig.

8b. Thus, it could be concluded from XPS analysis that the
composition of deposited films is a nearly stoichiometric ratio and coincides well with the target composition.

C. Electrical property of AZO thin films

Dependence of the resistivity, carrier concentration, and

Hall mobility of the AZO films versus the substrate temperature are shown in Fig. 9. It is seen that the resistivity of the
films decreases considerably exhibiting minimum resistivity
of about 4104 cm at 120 C. The similar minimum resistivity value and temperature behavior of resistivity and
Hall mobility was observed in earlier studies.12,15 Note that
the change of the resistivity with the sustrate temperature
was attributed to the escape of chemisorbed oxygen.15 It was
suggested that the formation of oxygen vacancies leads to the
decreasing of resistivity and increasing of carrier concentration and Hall mobility.21 These conclusions confirmed well
our results of the AZO films composition analysis.
In addition, the carrier concentration and Hall mobility
was shown to increase with the increase of substrate temperature. Such a behavior of carrier concentration was attributed to the increase of free electron concentration. The temperature dependence of Hall mobility was found to obey
Satos relation16

Lq 1/2 mkT 1/2 exp E b /kT ,

FIG. 4. Influence of substrate temperature on calculated grain size of AZO
films.
J. Vac. Sci. Technol. A, Vol. 22, No. 4, JulAug 2004

where L is the average grain size, q is the electron charge,

and m * denotes the effective mass of the electron assumed
to be 0.35 m e ), T and E b are temperature and the grain

1143

Seong et al.: Effect of low substrate deposition temperature

1143

FIG. 5. AFM of AZO films were deposited according to substrate deposition temperature: a 20 C, b 70 C, c 95 C, and d 120 C.

boundary potential barrier height, respectively. The plot of

ln(T1/2) versus 1/T is represented in Fig. 10. The slope of
this dependence is linear throughout the investigated
temperature range indicating the existence of grain boundary
scattering.17 It could be concluded from this fact that the
grain boundary scattering is characterized by an increasing of
Hall mobility with an increasing of carrier concentration, up
to approximately 1021 cm3 . 1

FIG. 6. Root mean square rms roughness of AZO films as a function of

substrate temperature.
JVST A - Vacuum, Surfaces, and Films

D. Optical property of AZO thin films

Figure 11 shows the transmittance of the AZO films deposited on glass substrates at different temperatures. In a
visible light region, the optical transmittance of AZO as
shown in Fig. 10, exhibit lower values compared to the transmittance 90% of pure ZnO.19 Such a transparency behavior
was attributed to light scattering that occurred due to Al2 O3
segregation into grain boundaries by doping Al2 O3 . 22 It is

FIG. 7. XPS data of typical O 1s according to substrate deposition temperature: a 20 C, b 70 C, c 95 C, and d 120 C.

1144

Seong et al.: Effect of low substrate deposition temperature

1144

FIG. 10. Plots of ln(T1/2) vs 103 /T of AZO films deposited at different

substrate temperatures.

also seen from this figure that the transmittance improves

from 70% to 80% with an increasing of the substrate temperature from RT to 120 C. This improvement of the transmittance is most likely related to the above-mentioned improvement of the crystallinity and surface roughness of the
films with an increasing of the deposition temperature.
IV. CONCLUSIONS

FIG. 8. Influence of substrate temperature on chemical composition of a

oxygen and zinc atomic percentage and b aluminum atomic percentage.

FIG. 9. Electrical properties of ZAO films deposited at various substrate

temperature --: Hall mobility, --: resistivity, --: carrier concentration.
J. Vac. Sci. Technol. A, Vol. 22, No. 4, JulAug 2004

We deposited AZO films on glass substrates under a range

of substrate deposition temperature by IBSD. We introduced
the ion beam sputtering deposition method and also changed
the substrate deposition temperature below 150 C. By the
adopting of ion beam sputtering deposition method and controlling of substrate deposition temperature as a processing
parameter, we can achieve high quality AZO films when
compared with other processing methods. We confirmed this

FIG. 11. Optical transmittance of AZO films prepared according to different

substrate temperature.

1145

Seong et al.: Effect of low substrate deposition temperature

fact by an analysis of the electrical and optical properties of

AZO films. As substrate deposition temperature increased,
the crystallinity and electrical properties of AZO films
showed improvement. The optical properties of AZO films
improved due to the introduction of a method of the ion
beam sputtering deposition.
T. Minami, MRS Bull. 25, 40 2000.
H. Kim and C. M. Gilmore, Appl. Phys. Lett. 76, 259 2000.
3
Landolt-Bornstein, Numerical Data and Functional Relationships in Science and Technology Springer, Berlin, 1984, Vol. 17b, p. 74.
4
V. Gupta and A. Mansingh, J. Appl. Phys. 80, 1063 1996.
5
K. Tominaga, H. Manabe, and N. Umez, J. Vac. Sci. Technol. A 15, 1074
1987.
6
M. Jin, J. Feng, Z. De-heng, M. Hong-lei, and L. Shu-ying, Thin Solid
Films 357, 98 1999.
7
B. D. Cullity, Elements of X-ray Diffraction Addison-Wesley, Reading,
MA, 1978, p. 102
8
C. H. Yi, I. Yasui, and Y. Shigesato, Jpn. J. Appl. Phys., Part 1 34, 1639
1995.
1
2

JVST A - Vacuum, Surfaces, and Films

1145

L. K. Rao and V. Vinni, Appl. Phys. Lett. 63, 608 1993.

S. Major, S. Kumar, M. Bhatnagar, and K. L. Chopra, Appl. Phys. Lett.
40, 60 1986.
11
M. Chen, Z. L. Pei, C. Sun, L. S. Wen, and X. Wang, J. Cryst. Growth
220, 254 2000.
12
K. H. Kim, K. C. Park, and D. Y. Ma, J. Appl. Phys. 81, 7764 1997.
13
T. Szoreny, L. D. Laude, I. Bertoti, and Z. Kantor, J. Appl. Phys. 78, 6211
1995.
14
J. C. C. Fan and J. B. Goodenough, J. Appl. Phys. 48, 3524 1977.
15
B. Szyszka, Thin Solid Films 351, 164 1999.
16
Y. Igasaki and H. Saito, J. Appl. Phys. 69, 2190 1991.
17
E. J. Tarsa, J. H. English, and J. S. Speck, Appl. Phys. Lett. 64, 2712
1994.
18
J. Y. Seto, J. Appl. Phys. 46, 5247 1975.
19
N. Taga, H. Odaka, Y. Shigesato, I. Yasui, M. Kamei, and T. E. Haynes, J.
Appl. Phys. 80, 978 1996.
20
F. Quaranta, A. Valentini, and F. R. Rizzi, J. Appl. Phys. 74, 244 1993.
21
A. Kuroyanagi, J. Appl. Phys. 66, 5492 1989.
22
O. Yamazaki, T. Mitsuyu, and K. Wasa, IEEE Trans. Sonics Ultrason.
SU-276 11, 369 1980.
23
R. Cebulla, R. Werndt, and K. Ellmer, J. Appl. Phys. 83, 1087 1998.
9

10