APPLIED PHYSICS LETTERS

VOLUME 83, NUMBER 14

6 OCTOBER 2003

In situ spectral control of Zn species during helicon-wave-excited-plasma

sputtering epitaxy of ZnO
T. Koyama, T. Onuma, and SF. Chichibua)
Institute of Applied Physics and Graduate School of Pure and Applied Sciences, University of Tsukuba,
1-1-1 Tennodai, Tsukuba 305-8573, Japan

Received 19 May 2003; accepted 11 August 2003

Atomic species in the sputtered plumes from undoped ZnO target were identified by means of
emission spectroscopy during helicon-wave-excited-plasma sputtering epitaxy. Luminescent Zn
species were found to be excited neutral zinc (Zn* ) and zinc cations (Zn * ), and Zn* density was
independently controlled by the target bias (V t ) that accelerates the velocity of Ar cations while
keeping the plasma density constant. The ZnO film formation seemed to have certain threshold V t
around 200 V at 600 C), and the growth rate increased with the magnitude of V t but decreased
with the substrate temperature, indicating that the growth rate is limited by the sticking coefficient
of Zn. As a result of the supply mode of Zn that is similar to the case for laser molecular-beam
0) sapphire substrate had ultra-smooth surfaces having
epitaxy, the epitaxial 0001 ZnO on (112
atomically flat terraces, and exhibited excitonic reflectance anomalies and luminescence peaks at
low temperature. 2003 American Institute of Physics. DOI: 10.1063/1.1616650

ZnO and related alloys are attracting attention due to

their potential use in ultraviolet light emitters, transparent
field-effect transistors, sensors, and piezoelectric devices. To
fabricate ultrathin quantum structures having abrupt interfaces, researches on the epitaxial formation of ZnO have
been accelerated by a variety of methods, such as laserassisted molecular-beam epitaxy L-MBE,1 4 MBE,5 8
chemical vapor deposition,9 and metalorganic vapor phase
epitaxy.10 Indeed, optically pumped lasing due to the excitonic gain has been reported,1 and clear excitonic polariton
structures have been observed in the ZnO epilayers grown by
L-MBE11 and MBE.12
On the other hand, sputtering methods can prepare largearea films of well-controlled compositions economically. In
order to make use of this advantage for thin-film epitaxy, the
authors have proposed13 the use of helicon-wave-excited
plasma HWP, of which physics and experiments have been
reported by several researchers,14 17 as a sort of remote
plasma source for the sputtering deposition of very smooth,
highly 0001-oriented, low-resistivity (5104 cm), and
transparent Al-doped ZnO conducting films as the first step.
These achievements are due to the properties of HWP, which
can be excited under relatively lower pressure
(104 Torr) producing a high density and lower ion energy plasma. Subsequently, completely a-axis-locked
0001-orientation ZnO epitaxial films have been successfully grown on 0001 sapphire substrates.18 According to the
achievement of near-band-edge emission from the epitaxial
films18 due to the surface-damage-free nature, the technique
was named helicon-wave-excited-plasma sputtering epitaxy HWPSE. However, the atomic species generated in
the sputtered plume, especially those responsible for the film
growth, is unidentified as yet.
In this letter, results of plume emission spectroscopy are
a

Author to whom correspondence should be addressed; electronic mail:

optoelec@bk.tsukuba.ac.jp

shown to identify the atomic species responsible for the ZnO

epitaxial formation. The dominant precursor for Zn is assigned to the excited neutral Zn (Zn* ), as well as nonradiative species such as ZnO, and the density is found to be
controlled by the target bias V t that accelerates the Ar cation
velocity while keeping the plasma density constant.
A schematic representation of the HWPSE system sc
HW-6P will be found elsewhere.18 It consisted of 1 a
vacuum deposition chamber in which a 99.999% pure 2 in.
0) sapphire substrate
diam. undoped ZnO target and a (112
heated by a SiC heater were placed; 2 a 5 cm diam., 24 cm
long quartz tube inlet surrounded by a Nagoya type-III
antenna19 through which a cw rf field 13.56 MHz was supplied; 3 the electromagnetic coils to apply a weak field
gradient, and 4 a pumping system. The HWP excited from
99.9995% pure Ar/99.99995%-pure O2 mixture was introduced into the chamber by the field gradient. Accordingly,
the plasma beam was even softly irradiated on the tilted target, under which a permanent magnet was placed to focus
the HWP. The velocity of Ar cations onto the target was
accelerated by the negative dc-bias V t applied on back of the
target holder. Our configuration enables depositing thin films
softly due to the elimination of plasma bombardment of the
substrate. The background and growth pressure were 4
106 and 5104 Torr, respectively. The epitaxial
growth was carried out between 600 and 750 C applying V t
0) of sapphire
between 0 and 400 V on the a-face (112
7
substrates to ensure better lattice-matching than that on the
c-face.18
The emission of sputtered plumes was introduced to a
monochromator through a pure quartz viewport located between the target and the substrate. The emission was dispersed by a grating and detected using a charge-coupleddevice array. The plume emission spectra of the ZnO target
sputtered under V t 0 and 360 V with the rf power ( P rf)
of 700 W are shown in Figs. 1a and 1b, respectively. The
sputtering HWP consists of20 excited oxygen atom (O* ), Ar

0003-6951/2003/83(14)/2973/3/$20.00
2973
2003 American Institute of Physics
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2974

Appl. Phys. Lett., Vol. 83, No. 14, 6 October 2003

Koyama, Onuma, and Chichibu

FIG. 3. AFM image and cross-sectional height profile of the ZnO film
0) sapphire substrate. The step height of 0.26 nm
grown at 700 C on a (112
corresponds to a half of the c-lattice parameter.

FIG. 1. Plume emission spectra of undoped ZnO target sputtered under a

V t 0 V and b V t 360 V with rf power of 700 W. Emission lines at

tributable to Zn* , Zn * , O* , O
2 * , O * , Ar* , and Ar * are indicated by
respective superimposed combs after Ref. 20. The line at 307 nm is due to
Zn* .

atom (Ar* ), oxygen cation (O * ), and oxygen molecule

(O
2 * ), as shown in Fig. 1a. As the magnitude of V t increases, the emission line due to excited zinc atom (Zn* )
appears at 307 nm,21 while the intensities of O* , Ar* , O * ,
and O
2 * are nearly unchanged, as shown in Fig. 1b. Note
that very weak Zn* and zinc cation (Zn * ) signals are observed even for V t 0 V, which is due to the weak but finite
plasma velocity onto the target accelerated by the field gradient and by the magnet on back of the target holder. The
intensity of Zn* increases with the increase in V t . The results indicate that Zn* is the dominant Zn source for the film
growth in our HWPSE system, and its density can be controlled by V t that changes the velocity of Ar cations keeping
the plasma density unchanged, as shown by closed circles in
Fig. 2. Note that nonradiative species such as ZnO also con-

tribute to the growth. Although the HWP density gradually

increases with P rf even after the mode hopping,14 17 this
result is different from that for the conventional sputtering
methods such as dc and rf magnetron sputtering, in which the
plume density is proportional to the plasma density. Since the
atomic Zn species are involved for the growth, oxygen is
considered to be supplied from the gas phase; the growth
mechanisms of HWPSE are similar to those for L-MBE. The
growth rate increases with the increase in V t , as shown in
Fig. 2. On the other hand, the growth rate decreases with the
increase in deposition temperature (T g ) and the film growth
seems to have a threshold V t around 150 V at 600 C).
These results indicate that the film growth rate is limited by
the Zn* flux from the target and re-evaporation of the film
itself sticking coefficient of Zn.
ZnO films prepared in this way exhibit completely
0001-oriented, a-axis-locked, sixfold symmetry epitaxial
0) sapphire substrates, as is the case with
growth on (112
MBE.7 Value of the full width at half-maximum FWHM of
the ZnO 0002 diffraction peak for the film grown at 700 C
(V t 360 V and P rf700 W) is 0.13, and that of the
-scan is 0.48. In addition, the film grown at 700 C shows
very smooth surface having atomically flat two-dimensional
2D terraces, as shown in the atomic force microscope
AFM image in Fig. 3. Each 2D island has the terrace width
of approximately 50100 nm and the step height of 0.26 nm,
which corresponds to a half of the c-lattice parameter. These
structural and surface features resemble those typically obtained for the films grown by conventional 2D epitaxial
growth methods such as L-MBE and MBE.
Photoluminescence PL and optical reflectance OR
spectra of the ZnO epilayer measured at 8 K are shown in
Figs. 4a and 4b, respectively. For comparison, the OR
spectrum of the bulk ZnO single crystal measured under the
light polarization E perpendicular to the optic (c-)axis
(Ec) is also shown in Fig. 4c, where E is the electric
field after Ref. 22. The OR spectrum of the ZnO epilayer
exhibits noticeable excitonic reflectance anomalies at 3.377
and 3.386 eV in addition to the internal multiple reflection
fringes, as shown in Fig. 4b. The energies agree with those
of free A and B excitonic resonances, as indicated by dotted
lines labeled A and B on the trace c. The PL spectrum

FIG. 2. Emission intensity of Zn* at 307 nm closed circles and the ZnO
growth rate as a function of the magnitude of target bias V t . The growth
temperature was varied between 600 and 750 C.
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Appl. Phys. Lett., Vol. 83, No. 14, 6 October 2003

Koyama, Onuma, and Chichibu

2975

AIST for supplying sapphire substrates. They are grateful to

Dr. T. Koida for fruitful discussions and M. Sugiyama for
help with the experiments. This work was supported in part
by the 21st Century COE Center of Excellence program
Promotion of Creative Interdisciplinary Materials Science
for Novel Functions and Exploratory Research No.
15656080 under MEXT and The Inamori Foundation.

0)
FIG. 4. Low-temperature a PL and b OR spectra of 0001 ZnO/(112
sapphire grown at 700 C, V t 360 V, and P rf700 W. For comparison,
c OR spectrum at 8 K of the bulk ZnO crystal measured under the light
polarization E perpendicular to the c-axis (Ec) after Ref. 22 is also
shown. Dotted lines labeled A and B show the energy positions of free A and
B excitons. Peaks marked by crosses on the a PL spectrum are scattered
laser plasma lines.

exhibits a peak at 3.356 eV and noticeable higher energy

shoulders between 3.37 and 3.39 eV. They are assigned as
being due to the convolution of radiative recombination of
excitons bound to a neutral donor and free A and B excitons,
respectively. Note that the peaks higher than 3.4 eV are due
to scattered plasma lines of a cw He-Cd laser 325 nm.
Observation of these excitonic features in the OR and PL
spectra and predominant near-band-edge emission peak at
3.28 eV at 300 K exhibiting the FWHM of 107 meV data
not shown indicates that the epilayer is of good optical quality material. Indeed, the FWHM value of 107 meV is comparable to that of the films grown by L-MBE11 or MBE.12,23
In summary, atomic species responsible for ZnO formation in HWPSE were identified to be neutral Zn as well as
nonradiative species such as ZnO by means of plume emission spectroscopy on the sputtered ZnO target. The Zn* density was found to be controlled by the target bias, which
accelerates the velocity of Ar cations onto the target, independently to the excited plasma density. According to the
supply mode of Zn elements similar to the case for L-MBE
the growth rate was found to be determined by the sticking
coefficient of Zn. Achievement of very smooth surface having atomically flat terraces and excitonic features in the optical spectra indicates that HWPSE is one of the promising
epitaxial growth methods to fabricate ultrathin quantum heterostructures having atomically abrupt interfaces for future
device applications.
The authors are grateful to Dr. M. Tanaka and Dr. T.
Shibata of NGK Insulators Inc. and to Dr. H. Okumura of

P. Yu, Z. Tang, G. Wong, M. Kawasaki, A. Ohtomo, H. Koinuma, and Y.

Segawa, Proceedings of the 23rd International Conference on Physics of
Semiconductors, Berlin, 1996, edited by M. Scheffler and R. Zimmermann
World Scientific, Singapore, 1996, Vol. 2, p. 1453; Solid State Commun.
103, 459 1997.
2
A. Ohtomo, M. Kawasaki, Y. Sakurai, Y. Yoshida, H. Koinuma, P. Yu, Z.
Tang, G. Wong, and Y. Segawa, Mater. Sci. Eng. 54, 24 1998.
3
S. Choopun, R. Vispute, W. Noch, A. Balsamo, R. Sharma, T. Venkatesan,
A. Iiadis, and D. Look, Appl. Phys. Lett. 75, 3947 1999.
4
M. Joseph, H. Tabata, and T. Kawai, Jpn. J. Appl. Phys., Part 2 38, L2505
1999; M. Joseph, H. Tabata, H. Saeki, K. Ueda, and T. Kawai, Physica B
302303, 140 2001.
5
J. Cook and F. Schetzina, J. Electron. Mater. 25, 855 1996.
6
D. Bagnall, Y. Chen, Z. Zhu, T. Yao, S. Koyama, M. Shen, and T. Goto,
Appl. Phys. Lett. 70, 2230 1997; ibid. 73, 1038 1998.
7
K. Iwata, P. Fons, A. Yamada, K. Matsubara, and S. Niki, J. Cryst. Growth
209, 526 2000.
8
D. C. Look, D. C. Reynolds, C. W. Litton, R. L. Jones, D. B. Eason, and
G. Cantwell, Appl. Phys. Lett. 81, 1830 2002.
9
K. Minegishi, Y. Koiwai, Y. Kikuchi, K. Yano, M. Kasuga, and A.
Shimizu, Jpn. J. Appl. Phys., Part 2 36, L1453 1997.
10
K. Ogata, T. Kawanishi, K. Maejima, K. Sakurai, Sz. Fujita, and Sg.
Fujita, Jpn. J. Appl. Phys., Part 2 40, L657 2001.
11
SF. Chichibu, A. Tsukazaki, M. Kawasaki, K. Tamura, Y. Segawa, T. Sota,
and H. Koinuma, Appl. Phys. Lett. 80, 2860 2002.
12
SF. Chichibu, T. Sota, P. J. Fons, K. Iwata, A. Yamada, K. Matsubara, and
S. Niki, Jpn. J. Appl. Phys. 41, L935 2002.
13
K. Yamaya, Y. Yamaki, H. Nakanishi, and S. Chichibu, Appl. Phys. Lett.
72, 235 1998.
14
F. Chen, Plasma Phys. Controlled Fusion 33, 339 1991; J. Vac. Sci.
Technol. A 10, 1389 1992.
15
R. Boswell, Proceedings of 21st International Conference on Phenomena
in Ionised Gases, edited by G. Ecker, U. Arendt, J. Boseler, and A. Brunn
Arbeitsgemeinschaft Plasma Physik, Bochum, 1993, pp. 18.
16
T. Nakano, K. Giapis, R. Gottscho, T. Lee, and N. Sadeghi, J. Vac. Sci.
Technol. B 11, 2046 1993.
17
H. Sugai, Oyo Butsuri 63, 559 1994 in Japanese.
18
S. F. Chichibu, T. Yoshida, T. Onuma, and H. Nakanishi, J. Appl. Phys. 91,
874 2002.
19
T. Watari, Phys. Fluids 21, 2076 1978.
20
C. E. Moore, Atomic Energy Levels Government Printing Office Washington, D. C., 1949; G. Herzberg, Molecular Spectra and Molecular
Structure Van Nostrand, New York, 1967.
21
F. Claeyssens, A. Cheesman, S. J. Henley, and M. N. R. Ashfold, J. Appl.
Phys. 92, 6886 2002; Y. Chen, D. M. Bagnall, H. Koh, K. Park, K.
Hiraga, Z. Zhu, and T. Yao, ibid. 84, 3912 1998.
22
SF. Chichibu, T. Sota, G. Cantwell, D. B. Eason, and C. W. Litton, J. Appl.
Phys. 93, 756 2002.
23
Y. Chen, D. M. Bagnall, H. Koh, K. Park, K. Hiraga, Z. Zhu, and T. Yao,
J. Appl. Phys. 84, 3912 1998.

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