JOURNAL OF APPLIED PHYSICS

VOLUME 91, NUMBER 2

15 JANUARY 2002

Helicon-wave-excited-plasma sputtering epitaxy of ZnO

on sapphire 0001 substrates
S. F. Chichibu,a) T. Yoshida,b) and T. Onuma
Institute of Applied Physics, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8573, Japan

H. Nakanishi
Department of Electrical Engineering, Science University of Tokyo, 2641 Yamazaki, Noda,
Chiba 278-8510, Japan

Received 2 August 2001; accepted for publication 16 October 2001

A promising approach to obtain epitaxial films of oxide semiconductors was demonstrated, namely
helicon-wave-excited-plasma sputtering epitaxy. Due to the surface-damage-free nature, completely
a-axis-locked c(0001)-orientation ZnO epilayers were successfully grown on sapphire 0001
substrates having ultrasmooth surfaces with atomic steps. The ZnO epilayer exhibited a dominant
near-band-edge photoluminescence PL peak at 300 K. Since the PL was considered to be due to
the recombination of excitons bound to an impurity or a defect and certain tilting and twisting of the
films were observed when Ar/O2 were used as sputtering gases, purification and optimization of the
overall process are necessary to obtain improved epilayer qualities. 2002 American Institute of
Physics. DOI: 10.1063/1.1426238

I. INTRODUCTION

Recently, epitaxial growth of ZnO is attracting increased

attention since ZnO and related alloys are excellent materials
for use in visible to ultraviolet light emitters, transparent
field effect transistors, sensors, and piezoelectric devices due
to their crystal symmetry, large exciton binding energy 59
meV,6 and large band gap comparable7 to that of GaN. Epilayers of ZnO have been grown by a variety of methods,
such as excimer laser-assisted MBE L-MBE,8 11
MBE,1214 chamical vapor deposition,15 and MOVPE.16 Observation of excitonic stimulated emissions8,9,13 and attempts
to grow p-type ZnO11,15 have been reported to date.
In this paper, a promising epitaxial growth technique,
namely helicon-wave-excited-plasma sputtering epitaxy
HWPSE, is proposed for the growth of ZnO epilayers.
Completely a-axis-locked c(0001) orientation ZnO epilayers
were successfully grown on sapphire 0001 substrates,
which were preannealed in dry air ambient to prepare atomically ultrasmooth surfaces.

Among a variety of thin film fabrication methods, metalorganic vapor phase epitaxy MOVPE and molecularbeam epitaxy MBE are exclusively used for the epitaxial
growth of semiconductor ultrathin films and quantum hetero/
nanostructures due to their ability to fabricate well-defined
structures having atomically abrupt interfaces. On the other
hand, sputtering methods have several advantages since they
can prepare large-area films of well-controlled compositions
economically. The growth rate is high enough for thick films
and low enough for ultrathin films by changing the sputtering
rate of the target. However, the surface damage caused by
high energy sputtering particles, which are accelerated by a
field between the target and the substrate, is an essential
problem. Moreover, exposing the substrate in the plasma
sometimes causes contamination or resputtering.
To solve these problems, we have used a helicon-waveexcited plasma HWP, of which physics and experiments
have been reported by several researchers.1 4 Such a plasma
can be excited under relatively lower pressure
(104 Torr) and produces a higher density and lower ion
energy compared to those of the usual capacitively coupled
plasmas,4,5 and can be used as a sort of remote plasma source
for the sputtering deposition of Al-doped ZnO ZnO:Al
polycrystalline transparent thin films. As a result of the lower
gas pressure and reduced surface damage, very smooth,
highly 0001-oriented, low-resistivity (5104 cm),
transparent ZnO:Al films have been obtained without additional annealings using the HWP sputtering technique.5

II. EXPERIMENTAL EQUIPMENT

A schematic diagram of the HWPSE apparatus sc HW6P is shown in Fig. 1. It consisted of a vacuum deposition
chamber in which a 99.999% pure 2-in.-diam undoped ZnO
target and a 0001 sapphire substrate heated by a SiC heater
were placed; a 5-cm-diam 24-cm-long quartz tube inlet surrounded by a Nagoya type-III antenna17 through which a cw
rf field 13.56 MHz was supplied; two electromagnetic coils
to apply a weak field gradient; and a pumping system. The
HWP was introduced into the chamber, and the plasma beam
was directly irradiated on the tilted target. A permanent magnet was placed in back of a dc-biased target holder to focus
the HWP. Note here that discharging due to the dc bias was
not observed. Our configuration enables depositing thin films
softly due to the elimination of plasma-induced damage of
the substrate. The following major modifications were made

Author to whom correspondence should be addressed; electronic mail:

chichibu@bk.tsukuba.ac.jp
b
On leave from Dept. of Electrical Engineering, Science University of
Tokyo, 2641 Yamazaki, Noda, Chiba 278-8510, Japan; present address:
Research and Development Center, Hitachi Cable Ltd., 5-1-1 Hitaka,
Ibaraki 319-1414, Japan.
0021-8979/2002/91(2)/874/4/$19.00

874

2002 American Institute of Physics

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Chichibu et al.

J. Appl. Phys., Vol. 91, No. 2, 15 January 2002

FIG. 1. Schematic diagram of the HWPSE apparatus sc HW-6P. The

helicon-wave plasma was excited in a 5-cm-diam quartz tube. The
continuous-wave rf 13.56 MHz power was supplied from a Nagoya typeIII antenna, and the magnetic field 100 G was supplied from the two coils
to adjust the field gradient.

on the equipment reported previously;5 i an O2 gas line was

added to the Ar gas line and each flow rate was controlled by
a mass-flow controller independently, which enabled precise
control of the mixed gas composition; ii another O2 gas line
was added to enable sending the O2 beam directly onto the
substrate; iii the substrate heater was replaced by SiC
which enabled high temperature growth; and iv the rf
source and matching box were replaced to increase the
power up to 1 kW.
III. MAGNETIC FLUX DENSITY

The magnetic field flux density B and normalized ion

drift velocity along the z axis of the quartz tube (Vd z ) cal-

875

FIG. 3. XRD patterns of ZnO films on wet-etched and thermally annealed

sapphire 0001 substrates. The inset shows the -rocking curve for the ZnO
0002 diffraction of the film on the annealed sapphire.

culated below are shown in Fig. 2, where the z axis is along

the center of the tube cross section and is normal to the
chamber inlet. The x y plane is parallel to the tube cross
section. The value of Vd was calculated using the relation
Vd(mV r2 /2qB 2 )grad B, where m is the mass, q is the
charge, and V r is the cyclotron velocity. Other parameters
were set for our experimental conditions. As can be seen, the
field strength exhibits a maximum of 29 mT at the upper part
of the tube and a saddle point at the lower part of the tube
above the chamber. Note that the field is nearly uniform from
the lower half of the source of the throat. According to the
gradient, the plasma ion has a maximum velocity toward the
chamber at the bottom of the tube. The plasma can thus be
smoothly extracted from the tube to the target, which is located 6 cm apart from the tube exit. These estimations are
similar to previous reports.3
IV. EPILAYER PROPERTIES

FIG. 2. Profiles of a magnetic field flux density B and b normalized ion

drift velocity, Vd z on z axis (xy0) of our appatarus. The z axis is at the
center of the quartz tube cross section and is normal to the vacuum chamber
inlet.

By using the HWP, approximately 0.20.5-m-thick

ZnO epilayers were grown on sapphire 0001 substrates.
The substrate was either wet etched by a H2SO4:H3PO4
3:1 solution at 160 C or annealed at 1000 C for 1 h in a
pure dry air ambient.18 The surfaces were observed using an
atomic-force microscope. The annealed sapphire exhibited
an ultrasmooth surface with well-defined atomic steps whose
height was 0.22 nm. The growth temperature was varied
from 430 to 700 C typically 600 C. Typical rf power, dc
bias of the target, chamber pressure, and the background
pressure were 750 W, 300 to 400 V, 5104 Torr, and
2107 Torr, respectively. The epitaxial growth was carried
out for 1 h in 99.9995% pure Ar/99.99% pure O2 mixture
ambient typically 9:1.
The epilayers were characterized using x-ray diffraction
XRD 2 and scans for (000n) diffraction, and a
scan was used to determine the in-plane orientations. Photoluminescence PL was excited by the 325.0 nm line of a cw

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876

Chichibu et al.

J. Appl. Phys., Vol. 91, No. 2, 15 January 2002

FIG. 5. PL spectra of ZnO 0001 on sapphire 0001 measured at 77 and

300 K. The PL peak is assigned to a neutral donor bound exciton emission.
3) diffraction of
FIG. 4. In-plane XRD scan patterns for a sapphire (112
3) diffraction of the 0001 orientation
the 0001 substrate, b ZnO (101
3) diffraction of the
epilayer on annealed sapphire 0001, and c ZnO (101
film grown on wet-etched sapphire 0001. The patterns b and c show
that the a axis of the ZnO film on the annealed sapphire is rotated by 30
from the a axis of the sapphire substrate and perfectly locked, but the a axes
of the film on the wet-etched substrate are not aligned.

HeCd laser, and was dispersed by a grating monochromator

and detected phase sensitively by a GaAs:Cs photomultiplier.
The ZnO film grown at 600 C showed the c(0001) orientation growth on the annealed sapphire, as shown in Fig. 3.
The value of full width at half maximum FWHM of the
scan for the 0002 diffraction peak was 0.13, which is
comparable to those of other sputtering methods19 or that of
the L-MBE method on 0001 sapphire.9 However, an increase of the temperature to higher than 620 C or an introduction of excess O2 caused a degradation of the epilayer
quality. Conversely, the film on the wet-etched sapphire
0) and (101
1)
sometimes showed XRD peaks due to (101
diffractions in addition to (000n) diffractions, as shown in
Fig. 3.
3)
The in-plane XRD -scan patterns for the ZnO (101
peak are shown in Figs. 4b and 4c together with that of
3) in Fig. 4a. The ZnO films on
the substrate sapphire (112
the annealed sapphire exhibit an a-axis locked growth, as
0)
shown in Fig. 4b. The epitaxial relation is thus ZnO (101

sapphire (112 0) and ZnO 0001 sapphire 0001. In this

case the lattice mismatch is 18.3%. The value of the FWHM
of the scan is nearly 1.5, showing that the twisting of the
epitaxial grains is still larger than that found in L-MBE or
MBE layers.8 14 Conversely, the film on the wet-wetched
sapphire showed a multidomain growth whose a axes are
0 or 101
0 . These results
parallel to either sapphire 112
prove the importance of preparing an atomically flat substrate surface for the highly lattice-mismatched epitaxy.
Representative PL spectra of the ZnO epilayers on the
annealed sapphire measured at 77 and 300 K are shown in
Fig. 5. The spectra exhibit a predominant near-band-edge
peak at 3.36 eV at 77 K and 3.21 eV at 300 K. The 7
7 free exciton energy of the strain-free ZnO is 3.3768 eV
at 4.2 K.20 The epilayer is considered to have a small compressive strain due to the thermal mismatch, which might
cause a slight blueshift of the exciton energies. Therefore the

PL is assigned to the emission of an exciton bound to an

impurity or a defect. Note that the exciton energy shows very
weak dependence on strain in the epilayer.21 The value of the
FWHM of the PL peak of this particular sample is 56 meV at
77 K. The smallest value was 36 meV, but the epilayers
sometimes exhibited a broad emission band around 2.4 eV,
which might be due to defects. Free exciton emission was
hardly observed at 77 K. The PL results imply that the epilayer still contains a number of impurities/defects. Therefore
the overall growth process must be optimized to obtain
higher quality epilayers.
V. CONCLUSIONS

The HWPSE method was shown to have a potential for

the epitaxial growth of oxide semiconductors. The ZnO epilayers were successfully grown on air-annealed sapphire
0001 substrates. The epitaxial relation of the films was ZnO
0) sapphire (112
0) and ZnO 0001 sapphire 0001.
(101
The PL spectra exhibited predominant bound excitonic peaks
at 77 and 300 K. Futher purification of the overall process
will enable better quality materials.
ACKNOWLEDGMENTS

The authors are grateful to Dr. H. Okumura of AIST and

Dr. M. Tanaka and Dr. T. Shibata of NGK Insulators Inc. for
supplying sapphire substrates. They wish to thank Professor
M. Kawabe and Professor F. Hasegawa for providing analytical equipment. They are grateful to M. Sugiyama and T.
Hotate for help with the experiments. This work was supported in part by the Ministry of Education, Culture, Sports,
Science and Technology of Japan Grant-in-Aid for Encouragement of Young Scientists No. 13750264 and The Futaba
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