JOURNAL OF APPLIED PHYSICS

VOLUME 93, NUMBER 7

1 APRIL 2003

Epitaxial growth of high quality ZnO:Al film on silicon with a thin -Al2 O3
buffer layer
Manoj Kumar and R. M. Mehraa)
Department of Electronic Science, University of Delhi South Campus, New Delhi-110021, India

A. Wakahara, M. Ishida, and A. Yoshida

Toyohashi University of Technology, Tempaku-cho, Hibariga-oka-1-1, Toyohashi 441-8580, Japan

Received 12 August 2002; accepted 3 January 2003

ZnO:Al thin films were grown epitaxially on epi- -Al2 O3 /Si 111 substrates by rf sputtering and
pulsed laser deposition. The -Al2 O3 buffer layer was deposited on Si 111 at a low substrate
temperature of 500 C using the metalorganic chemical vapor deposition method. Reflection high
energy electron diffraction and x-ray diffraction measurements indicated a near alignment of the
ZnO:Al epilayer on -Al2 O3 /Si 111 as compared to those grown directly on Si 111. Atomic
force microscopy results of the films ZnO:Al/ -Al2 O3 /Si 111 deposited by pulsed laser
deposition revealed a smoother surface in comparison with the films deposited by rf sputtering. The
M band observed in the photoluminescence spectra of the films deposited by laser ablation suggests
that high quality epitaxial ZnO:Al/ -Al2 O3 /Si 111 films can be deposited by pulsed laser
deposition. 2003 American Institute of Physics. DOI: 10.1063/1.1556181

I. INTRODUCTION

species around the Si surface during the initial stage of ZnO

growth. Several efforts have been made to overcome the
problem of the oxidation of the Si surface by inserting an
MgO Ref. 4 or a GaN Ref. 5 buffer layer. It has been
reported earlier that growing GaN on Si using metalorganic
chemical vapor deposition MOCVD often results in
cracked films.6 This indicates that the films are under a significant amount of tensile stress during the postgrowth cooling. This stress is attributed to a relatively large difference in
their thermal expansion coefficients i.e., 3.6106 K1 of
Si vs 5.6106 K1 of GaN7 and also to a high growth
temperature over 1000 C. Recently, Nahhas et al.8 have
demonstrated that the use of a GaN buffer layer in conjunction with the rf sputtering technique is a viable way of growing a crack-free, epitaxial ZnO film on a Si substrate because
of the relatively low growth temperature, in the range of
650700 C.9 Also, the sputtered deposition process itself
usually induces a significant amount of compressive stress to
a film,10 thus compensating for the tensile stress.
In this article we report the epitaxial growth of ZnO:Al
films on Si substrate using a thin epitaxial -Al2 O3 buffer
layer. -Al2 O3 film was grown by means of MOCVD. The
use of a -Al2 O3 buffer layer is based on the following
reasons: i as it can be grown at a low substrate temperature
of 500 C, the thermal mismatch problem is expected to be
less serious; ii -Al2 O3 has the structure of hausmannite, a
tetragonal distortion of the spinal arrangement11 with a 0
7.95 and c 0 7.79 , and epitaxial -Al2 O3 111 films
on Si 111 have a lattice mismatch of 2.4%,12 which is
smaller than that of GaN on Si 4.2%; and iii -Al2 O3
films have a high electrical resistivity, and -Al2 O3 /Si structures have low interface states12 of 1.71011 cm1 eV1 .
The ZnO:Al films on -Al2 O3 /Si 111 were grown by
rf sputtering and pulsed laser deposition PLD. The films are
characterized by x-ray diffraction XRD, reflection high en-

Wide and direct band-gap semiconductors such as GaN

and ZnSe are of interest for blue and ultraviolet UV optical
devices.1 ZnO is another wide band-gap material which has
some advantages for short-wavelength applications compared with ZnSe- and GaN-based materials. The most unique
property of ZnO is its large exciton binding energy,2 60 meV,
which is about three times larger than that of ZnSe and GaN.
Because of this large binding energy excitonic recombination
is possible well above room temperature. The other physical
features that make ZnO attractive are i as a wide band-gap
semiconductor, ZnO is a relatively hard material. The
strength of the Zn-to-O bond is larger than that of the Gato-N bond. Their difference in bonding strength can lead to
significantly different results for p-type doping. ii ZnO has
a melting temperature of about 2000 C. Thus ZnO is sufficiently stable to withstand the high-temperature annealing
and treatment processes associated with doping and forming
of ohmic contacts. These features could conceivably expand
the lifetime of devices such as blue LEDs and blue LDs
fabricated with this material.
ZnO on Si will be useful for optoelectronic integration in
the future if the various functional properties of ZnO could
be combined with advanced Si electronics on the same substrate. The direct growth of epitaxial ZnO films on Si, however, is known to be an extremely difficult task. It usually
results in amorphous or polycrystalline films.3 The difficulty
basically stems from the fact that the Si surface gets easily
oxidized during the nucleation stage of a ZnO growth process, resulting in the formation of an amorphous silica layer.
This oxidation problem might be alleviated or avoided if
feasible ways are available to control the amount of oxygen
a

Electronic mail: rammehra@netscape.net

0021-8979/2003/93(7)/3837/7/$20.00

3837

2003 American Institute of Physics

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3838

Kumar et al.

J. Appl. Phys., Vol. 93, No. 7, 1 April 2003

FIG. 1. RHEED pattern of the -Al2 O3 buffer layer deposited on Si 111

substrate.

ergy electron diffraction RHEED, atomic force microscopy

AFM, and photoluminescence PL spectra.

II. EXPERIMENT
A. Substrate preparation

Considering the manufacture of emitting devices and

optical-electric integration in the future, p-type Si 111 was
chosen as the deposition substrate. The substrate was cleaned
in a boiling mixture of NH4 OH:H2 O2 :H2 O at the ratio of
1:1:6 for approximately 10 min. After boiling, the substrate
was rinsed in overflowing deionized water for 10 min. Before it was inserted into the MOCVD chamber, the substrate
was treated with a 2% HF solution to remove the native
oxide, then washed with deionized water and blown off by
dry nitrogen gas. The -Al2 O3 buffer layer was deposited on
Si 111 at a low substrate temperature of 500 C using the
MOCVD method. The thickness of the -Al2 O3 buffer layer
was kept around 3 nm. Figure 1 shows the RHEED pattern
of the -Al2 O3 bu`ffer layer on Si 111. The observed sharp
streaky pattern indicates a clean and flat surface of the
-Al2 O3 buffer layer on the Si 111 substrate.

B. rf sputtered films

Epitaxial ZnO:Al films on bare Si 111 and on

-Al2 O3 /Si 111 substrates were deposited using a conventional radio frequency 13.56 MHz diode sputtering system
as shown in Fig. 2a. ZnO purity 99.99% doped with 2.5
wt % Al2 O3 purity 99.99% was used as a target. The deposition was carried out in a vacuum chamber evacuated to a
base pressure of 3.0106 Torr. High purity Ar 99.99%
was used as a sputtering gas. The Ar gas pressure was maintained at 40 mTorr during deposition. During the film deposition the substrate temperature of 300 C, rf power of 250
W, and deposition time of 30 min. were kept constant. The
thickness of the ZnO:Al film was around 560 nm. The deposition of the ZnO:Al film was done at a slant axis configu-

FIG. 2. a Schematic diagram of the rf sputtering system. b Slant axis

configuration of the substrate.

ration of the substrate with respect to the target as shown in

Fig. 2b. This configuration was used to reduce the sputtering damage.

C. Pulsed laser deposited films

Epitaxial ZnO:Al films on -Al2 O3 buffer layer were

also grown by PLD using the same target by focusing a XeCl
(308 nm) laser onto a target rotating at 15 rpm. The
schematic diagram of the PLD system is shown in Fig. 3.
The laser pulse duration was kept at 20 ns. The distance
between target and substrate was 30 mm. The deposition
chamber was initially evacuated to a pressure of 6.0
106 Torr and the deposition was done at 1.0 mTorr of
oxygen pressure at a pulse repetition rate of 5 Hz for 60 min.
The substrate temperature was kept at 400 C. The thickness
of the ZnO:Al film was around 500 nm.
The film thickness was measured with a DEKTAK3 ST
profilometer. The crystal orientation of the film was evaluated by XRD using Cu K radiation XRD Riggaku and
RHEED using a HITACHI-H 300 electron microscope. The
surface morphology of the film was observed by AFM using

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Kumar et al.

J. Appl. Phys., Vol. 93, No. 7, 1 April 2003

3839

FIG. 3. Schematic diagram of the pulse laser deposition system.

an SPI-3700 and the optical properties were investigated by

measuring PL spectra using a 325 nm beam of a HeCd laser
at 13 K.
III. RESULTS AND DISCUSSION
A. Structural properties

1. rf sputtered films

Figures 4a and 4b show the x-ray diffraction spectrum of the ZnO:Al films grown on bare Si 111 deposited at
300 C and ZnO:Al films deposited on -Al2 O3 /Si 111 at
300 C, respectively. ZnO:Al films grown on the bare Si
0), and 0004 x-ray
111 substrate showed 0002, (112
diffraction peaks, whereas ZnO:Al films grown on
-Al2 O3 /Si 111 showed only 0002 and 0004 peaks.
Multiphase was observed for the ZnO:Al film deposited on
the bare Si 111 substrate, whereas the ZnO:Al films on
-Al2 O3 /Si 111 showed a highly c-axis orientation. The
full widths at half maximum FWHM of the 0002 peak of
the ZnO:Al film deposited on the bare Si 111 substrate and
on -Al2 O3 /Si 111 were found to be 0.42 and 0.2, respectively.
The crystallite size t of the films was determined by
using the Scherrer formula13
t

0.9
,
B cos B

where is the x-ray wavelength 1.54 060 , B is the Brag

diffraction angle, and B is the FWHM of the 0002 peak,
respectively. The crystallite sizes of the ZnO:Al films grown
on the bare Si 111 substrate and on -Al2 O3 /Si 111 were
found to be 4.83 and 7.26 nm, respectively.
Figure 5a shows the RHEED pattern of the ZnO:Al
films deposited at 300 C on the bare Si 111 substrate. The
pattern consists of two sets of spots with darker and lighter
contrast, indicating more than one phase in the ZnO:Al layer.
This may be due to the oxidation of the Si surface during
film deposition or the large lattice mismatch with ZnO:Al.
The multiphase nature of the film is also supported by our
x-ray diffraction measurements Fig. 4a. Figure 5b
shows the RHEED pattern of the film annealed at 850 C for
1 h in air. This pattern is similar to the pattern for as-grown
film, indicating no improvement in the quality of the film.

FIG. 4. X-ray diffraction pattern of rf sputtered ZnO:Al film grown a on

bare Si 111 substrate at 300 C and b on -Al2 O3 /Si 111 substrate at
300 C.

Figures 6a and 6b show two kinds of RHEED patterns of the ZnO:Al films grown on -Al2 O3 /Si 111 corresponding to the diffraction patterns of the two major zones,
which are perpendicular to the basal plane. Each zone was
found to be repeated after rotation of the films every 60, and
the patterns also alternated after every 30 rotation of the
films with respect to the direction of the incident electron
beam. This behavior is expected from a crystal with a sixfold
symmetry. This indicates that our ZnO:Al film grew epitaxially on the -Al2 O3 buffer layer. The in-plane epitaxial relationship was found to be (111) ZnO (111) -Al2 O3 (111) Si
0 ZnO 1 12 -Al O 11
0 Si and (111) ZnO
and 112
2 3

0 ZnO 11
0 -Al O 1 12 Si
(111) -Al2 O3 (111) Si and 101
2 3
0 and 112
0 , respectively, indicatfor electron beam 101
ing a 30 rotation of ZnO:Al film with respect to the substrate.
Figures 7a and 7b show atomic force microscopy images of the ZnO:Al film on the bare Si 111 substrate and on
-Al2 O3 /Si 111. The ZnO:Al film deposited on the bare Si
111 substrate showed a rough surface in comparison with
the ZnO:Al film deposited on -Al2 O3 /Si 111. The root

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3840

Kumar et al.

J. Appl. Phys., Vol. 93, No. 7, 1 April 2003

FIG. 5. RHEED pattern of rf sputtered ZnO:Al film deposited on bare Si

111 substrate a as-grown and b annealed at 850 C.

mean square rms values of the ZnO:Al films grown on the

bare Si 111 substrate and on -Al2 O3 /Si 111 were found
to be 60 and 4.2 nm, respectively. Since the quality of the rf
sputtered ZnO:Al films grown on -Al2 O3 /Si 111 were
found to be much superior to the films grown on the bare Si
111 substrate, the growth of the ZnO:Al films by the PLD
technique was investigated only on the -Al2 O3 buffer layer.
2. Pulsed laser deposited films

Figure 8 shows the x-ray diffraction pattern of the

ZnO:Al film on -Al2 O3 /Si 111 deposited by PLD. The
x-ray diffraction pattern shows 0002 and 0004 peaks
only, indicating highly c-axis oriented films. The full width
at half maximum of the ZnO:Al film was found to be 0.2
which is equal to that of the ZnO:Al film deposited by rf
sputtering.
Figures 9a and 9b show the RHEED patterns of the
ZnO:Al film deposited on -Al2 O3 /Si 111. The patterns
change with a change of the direction of the incident electron
beam with respect to the film in the same manner as observed in the case of the rf sputtered films. This indicates that

FIG. 6. RHEED pattern of rf sputtered ZnO:Al film deposited on

0 and b electron
-Al2 O3 /Si 111 substrate a electron beam 101
0.
beam 112

the ZnO:Al film grown on -Al2 O3 /Si 111 by PLD is also

epitaxial in nature. The in-plane epitaxial relationship was
0 ZnO
found to (111) ZnO (111) -Al2 O3 (111) Si and 101

1 12 -Al O 11 0 Si and (111) ZnO (111) -Al O (111) Si and

2 3

2 3

0 ZnO 1 12 -Al O 11
0 Si for electron beam 101
0
112
2 3
0 , respectively, indicating no in-plane rotation beand 112
tween the ZnO:Al film and the substrate.
Figure 10 shows an atomic force microscopy image of
the ZnO:Al film deposited on -Al2 O3 /Si 111 by PLD.
The rms value of the ZnO:Al films grown on -Al2 O3 /Si
111 was found to be 1.94 nm, which is nearly half of the
value observed for the rf sputtered ZnO:Al film on
-Al2 O3 /Si 111.
B. Optical properties

1. rf sputtered films

Figure 11 shows the photoluminescence spectra of the

ZnO:Al film deposited on the bare Si 111 substrate at 13 K.

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J. Appl. Phys., Vol. 93, No. 7, 1 April 2003

FIG. 7. AFM image of rf sputtered ZnO:Al film deposited a on bare Si

111 substrate and b on -Al2 O3 /Si 111 substrate.

Kumar et al.

3841

FIG. 9. RHEED patterns of pulsed laser deposited ZnO:Al films on

0 and b electron
-Al2 O3 /Si 111 substrate a electron beam 101
0.
beam 112

A single peak is observed at 3.23 eV having a linewidth of

120 meV. Figure 12 shows the PL spectrum of the epitaxially
grown ZnO:Al film on -Al2 O3 /Si 111 at 13 K. The dominant peak was observed at 3.34 eV, having a linewidth of 20

FIG. 8. X-ray diffraction pattern of pulsed laser deposited ZnO:Al films on

-Al2 O3 /Si 111 substrate at 400 C.

FIG. 10. AFM image of pulsed laser deposited ZnO:Al films on

-Al2 O3 /Si 111 substrate.

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3842

Kumar et al.

J. Appl. Phys., Vol. 93, No. 7, 1 April 2003

FIG. 11. PL spectrum of rf sputtered ZnO:Al film deposited on bare Si111

at 13 K.

meV with a broad emission tail extending to the deep level

emission. This broad emission tail may be due to oxygen
deficiency, excess zinc, or point defects in the film. Since the
x-ray diffraction spectrum does not show any peak corresponding to excess Zn, this broad emission may be due to
oxygen deficiency or point defect. A small hump is observed
at 3.41 eV, which is due to the recombination of excitons
bound to neutral donors or acceptors.
2. Pulsed laser deposited films

Figure 13 shows PL spectrum of the ZnO:Al film on

-Al2 O3 /Si 111 deposited by PLD. This spectrum shows a
sharp dominant emission at 3.35 eV. The peaks at 3.29 and
3.22 eV result from the radiative recombination of free excitons associated with 1-LO and 2-LO phonons, respectively.
The linewidth of the emission at 3.35 and 3.29 eV was found
to be 20 and 22 meV, respectively. The dominant emission
observed at 3.35 eV corresponds to biexciton emission,
which is known as M band.14 The PL spectrum does not
show any broad emission tail corresponding to the deep level
emission as observed in the rf sputtered films. The presence

FIG. 13. PL spectrum of pulsed laser deposited ZnO:Al film on -Al2 O3 /Si
111 at 13 K.

of the M band and the absence of a broad emission tail in the

PL spectrum is a consequence of the high quality of the
ZnO:Al epilayer.

IV. CONCLUSIONS

Results from this work demonstrate that a -Al2 O3

buffer layer is suitable to grow high quality epitaxial ZnO:Al
film on Si 111 substrate using both rf sputtering and PLD.
The ZnO:Al film deposited by PLD was found to possess a
smoother surface than rf sputtered film. The observation of
the M band without a broad emission tail in the PL spectrum
for the film deposited on -Al2 O3 /Si by PLD also confirms
that the quality of the film is superior to the film grown by rf
sputtering.

ACKNOWLEDGMENTS

Manoj Kumar gratefully acknowledges the financial support of AIEJ, Japan and R. M. Mehra wishes to acknowledge
the partial financial support of DRDO, Government of India,
India.

FIG. 12. PL spectrum of rf sputtered ZnO:Al film on -Al2 O3 /Si 111 at

13 K.

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