APPLIED PHYSICS LETTERS

VOLUME 84, NUMBER 7

16 FEBRUARY 2004

Radiative and nonradiative excitonic transitions in nonpolar 112 0

and polar 0001 and 0001 ZnO epilayers
T. Koida, S. F. Chichibu,a) and A. Uedono
Institute of Applied Physics and Graduate School of Pure and Applied Sciences, University of Tsukuba,
Tsukuba 305-8573, Japan; NICP, ERATO, Japan Science and Technology Agency (JST),
Kawaguchi 332-0012, Japan

T. Sota
Department of Electrical Engineering and Bioscience, Waseda University, Shinjuku 169-8555, Japan

A. Tsukazaki and M. Kawasakib)

Institute for Materials Research, Tohoku University, Sendai 980-8755, Japan

Received 25 August 2003; accepted 16 December 2003

0) ZnO
Polarized optical reflectance and photoreflectance spectra of an out-plane nonpolar (112
epilayer grown by laser molecular-beam epitaxy exhibited anisotropic exciton resonance structures
according to the polarization selection rules for anisotropically strained hexagonal material.
Consistently, the electric field component of its excitonic photoluminescence PL peak was
polarized perpendicular to the 0001 axis. Different from the case for GaN, nonradiative PL lifetime
at 293 K and the S parameter, which is a measure of Zn vacancy-related defect density obtained by
0) ZnO were comparable to those of state-of-the-art
positron annihilation spectroscopy, of the (112

polar (0001 ) and 0001 epilayers. Since the polar epilayers exhibited pronounced exciton
polariton emissions, the negligible impact of growth direction on the defect incorporation suggests
0) ZnO as polarization-sensitive optoelectronic devices operating in
a potential use of epitaxial (112
ultraviolet spectral regions. 2004 American Institute of Physics. DOI: 10.1063/1.1646749

Since ZnO has a bandgap of 3.37 eV and is an attractive

compound for the use of ultraviolet UV light emitting devices, much efforts in controling p-type conductivity as well
as reducing crystalline defects have been carried out exclu ) or 0001 orientation polar-face epilayers.
sively for (0001
ZnO is also known to show pronounced excitonic effects at
temperatures higher than 300 K due principally to the large
exciton binding energy 59 meV.1 Indeed, excitonic stimulated emission has been observed2,3 and low-temperature optical reflectance OR, photoreflectance PR, and photoluminescence PL spectra of ZnO epilayers have been
interpreted taking the contribution by exciton-polaritons into
account.4
Due to the C 6 v symmetry, ZnO exhibits an optical
anisotropy5 for transitions from three separate p-like valence
bands ( 9 v , u7 v , and l7 v in order of increasing transition
energy6,7 to the s-like 7c conduction band. Excitons related
to the respective valence bands are referred to as A, B, and C
excitons. The A and B transitions are allowed for light polarization E perpendicular to the c axis (Ec), where E is the
electric field component, and the C transition is allowed for
E parallel to the c axis (E c). This anisotropy may provide
various applications using polarized UV lights. Recently, the
00) and (112
0) faces of hexuse of out-plane nonpolar (11
agonal AlInGaN systems is attracting attention,8 since
strained quantum wells formed on those faces do not suffer
a

Author to whom correspondence should be addressed; also at: Photodynamics Research Center, RIKEN, Sendai 980-0868, Japan; electronic mail:
optoelec@bk.tsukuba.ac.jp
b
Also at: Combinatorial Materials Exploration and Technology COMET,
Tsukuba 305-0044, Japan.

from the quantum-confined Stark effect due to the polarization fields. However, little is known about the anisotropic
optical transitions and defect chemistry in nonpolar ZnO
epilayers.9
Positron annihilation is an established technique for detecting neutral or negatively charged defects in
semiconductors.1012 When a positron is implanted into a
condensed matter, it annihilates with an electron and emits
two 511 keV -rays. They are broadened due to the momentum component of the annihilating electronpositron pair.
Because the momentum distribution of electrons in such defects differs from that in defect-free regions, these defects
can be detected by measuring the Doppler broadening spectra of annihilation radiation. The resulting change in the
Doppler broadening spectra is characterized by the S parameter, which mainly reflects the change due to the annihilation
of positronelectron pairs with low-momentum distribution.
Since Zn vacancy (V Zn) is one of the most probable
candidates12 of positron trapping centers in ZnO, S parameter can be used as a measure of size / concentration of V Zn .
In this letter, polarized OR and PR spectra of a nonpolar

(112 0) ZnO epilayer are shown to identify the excitons in

anisotropically strained ZnO. Time-resolved PL TRPL and
positron annihilation measurements are carried out to compare the incorporation of nonradiative defects and
V Zn-related defects, respectively, during the nonpolar and polar orientation ZnO epitaxy.
Samples investigated were approximately 1 m-thick
undoped ZnO grown by laser molecular-beam epitaxy
L-MBE2,13 ablating a ZnO single crystal14 target using a

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1079
2004 American Institute of Physics
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1080

Koida et al.

Appl. Phys. Lett., Vol. 84, No. 7, 16 February 2004

0) ZnO and
TABLE I. Exciton parameters in anisotropically strained (112
) and 0001 ZnO epilayers at 8 K.
nearly strain-free (0001
)
Nearly strain-free (0001
and 0001ZnO

0)ZnO
Strained (112
Excitona Polarizationb
E1
E2
E3

00
E 11
E 0001
0
E 112

Energy
eVc Exciton Polarization
3.402
3.439
Not
allowed

A
B
C

E 0001
E 0001
E 0001

Energy
eVd
3.377
3.383T, 3.393L

Notation according to Ref. 15.

Calculation according to Ref. 15.
c
Resolution is approximately 100 eV.
d
Resolution is 56 eV.
b

0) ZnO epilayer
FIG. 1. a Polarized PR, OR, and PL spectra of the (112
) and 0001 ZnO epilayers measured at 8 K.
and b PL spectra of the (0001
For comparison, PL spectrum of the bulk ZnO single crystal is also shown
after Ref. 7.

0) ZnO film grown on

KrF excimer laser. They were a (112

)
a (101 2) Al2 O3 at 650 C, (0001 ) films grown on a (0001
14

ZnO single crystal at 670 C and on the (0001 ) ZnO

self-buffer13 prepared on a 0001 ScAlMgO4 SCAM at
680 C, and a 0001 film grown on a 0001 ZnO single
0)
crystal at 550 C. The in-plane orientation for the (112

ZnO/(101 2) Al2 O3 was 0001 ZnO 01 11 Al2 O3 , and

the value of full-width at half-maximum FWHM of the
0) x-ray rocking curve XRC was as large as 1100
ZnO (112
arcsec, while those of ZnO 0002 XRC of polar films were
comparable to those of the substrates.13
0) ZnO
Polarized PR, OR, and PL spectra of the (112
measured at 8 K are shown in Fig. 1a. The resolutions for
the particular spectra are approximately 560, 110, and 340
eV, respectively, at the wavelength of 370 nm. The PR and
OR spectra exhibit excitonic resonance structures at 3.402
and 3.439 eV for Ec and E c, respectively. These energies
are larger than those of AB and C excitons in strain-free
ZnO,4,6,7 as listed in Table I. The energy shift is due to anisotropic strains15 caused by the lattice and thermal expansion mismatches. The strains are quantified by x-ray diffraction XRD measurements to be 0.41%, 0.49%, and
0 , and 0001 directions, re 00 , 112
0.19% along 11
spectively, where minus and plus signs represent compressive and tensile, respectively. Since these anisotropic strains
change the crystal symmmetry from C 6 v to C 2 v , the labels5,6
A, B, and C can no longer be used. Therefore, nomenclature
E 1 , E 2 , and E 3 for the ground state of the three excitons are
used, as Ghosh et al.15 have used to describe exciton struc 00) GaN. They have calculated the ostures in nonpolar (11
cillator strengths and transition energies of excitons in

anisotropically-strained GaN,15 which also has C 6 v symmetry and valence band ordering of A- 9 , B- 7 , and C- 7 .
According to their calculation,15 E 1 , E 2 , and E 3 excitons in
0) ZnO are predominantly polarized to
our strained (112

0 , respectively. Therefore, transi 11 00 , 0001, and 112

tion structures observed under Ec 3.402 eV and E c
3.439 eV are assigned to E 1 and E 2 transitions, respectively, as shown in Table I. The E 3 transition is not observed,
0 direction is normal to the surface.
since the 112
Consistent with the polarization selection rules for the
E 1 transition, a near-band-edge PL peak at 3.384 eV in the
0) ZnO film is polarized to Ec parallel to 11
00 ),
(112
as shown in Fig. 1a. Because the peak energy is smaller by
18 meV than the E 1 transition energy, the peak is tentatively
assigned to I6 16 bound exciton emission 3.36 eV in strainfree ZnO. On the other hand, PL spectra at 8 K of the
) and 0001 ZnO epilayers exhibit pronounced peaks
(0001
and shoulders due to the emission of A and B
exciton-polaritons7,17 at the higher energy side of a bound
excitonic emission at 3.366 eV, as shown by the arrows and
broken lines in Fig. 1b. For comparison, the PL spectrum of
bulk ZnO single crystal7 is shown, in which well-resolved PL
lines due to bound excitonexciton complexes 3.3553.372
eV, transverse lower and longitudinal upper A-exciton
and
A L
polariton
branches
(A T 3.3765 eV
3.3783 eV, respectively, and those of B-exciton polaritons (B T 3.3830 eV and B L 3.3941 eV) were observed. As listed in Table I, energies of A-exciton, B T , and
) and 0001 epilayers agree with those of
B L of the (0001
7
the bulk ZnO, indicating that the films are of high-quality
and nealy strain-free.
To compare the nonradiative defect density, TRPL signals of free excitonic emission peaks in the ZnO epilayers
0) film and 3.30 eV for the (0001
) and
3.32 eV for the (112
0001 films, which were excited by a frequency-tripled
mode-locked Ti:sapphire laser, were collected using a standard streak-camera acquisition technique at 293 K, since the
PL lifetime PL at room temperature is in general dominated
) and
by the nonradiative lifetime. The signals of (0001
0001 epilayers exhibit a single exponential decay giving
) homoepitaxial film,
PL of 33, 22, and 12 ps for the (0001

(0001 ) film on the ZnO/SCAM buffered substrate, and

0001 homoepitaxial film, respectively. On the other hand,
0) ZnO epilayer exhibits a biexpothe decay curve of (112
nential behavior. The fast decay component 18 ps probably

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Koida et al.

Appl. Phys. Lett., Vol. 84, No. 7, 16 February 2004

1081

TABLE II. Growth temperatures T g , PL lifeteimes PL at 293 K, and S parameters of ZnO epilayers.
0) ZnO
(112

0001 ZnO

) ZnO
(0001

T g (C)
650
550
670
PL ps
18
12
33
S parameter 0.42860.0006 0.42820.0010 0.42880.0009

) ZnOZnO buffer
(0001

Bulk ZnOa

680
22
0.43000.0008

970
0.41960.0002

Reference 12.

represents the lifetime of free excitons, and the slow one

(200 ps) might represent carrier lifetime including capturing and escaping processes involving certain trapping centers. As summarized in Table II, PL values of the present
ZnO epilayers 1233 ps are much shorter than that of the
bulk ZnO single crystal 970 ps,12 suggesting the presence
of higher density nonradiative defects.
The monoenergetic positron beam line11,12 was used to
determine the S parameters11 in the ZnO epilayers. The S
parameters of all the films are nearly the same being 0.43,
which is larger than that in the bulk ZnO single crystal
0.4196.12 The result suggests that the epilayers contain
higher density or larger size negatively charged vacancytype defects such as V Zn or V Zn-impurity complexes. How ) and 0001 epilayers
ever, it should be noted that the (0001
exhibit well-resolved excitonpolariton emissions at 8 K. In
addition, since the values of PL for the fast decay compo 0)
nent 18 ps and the S parameter 0.4286 of the (112
) and 0001 ZnO
epilayer are comparable to those of (0001
0) epilayer are
epilayers, overall defect density in the (112
considered to be comparable to that in the polar ones; i.e.,
either the nonradiative defect density or V Zn density are not
directly limited by the growth polarity or the growth direction. This result is different from the case for GaN that incorporation of O, C, and Al impurities18 as well as V Ga and
V Ga O defect complexes11 is enormously enhanced for the
polar growth during the metalorganic vapor phase
0001
epitaxy. For L-MBE of ZnO on SCAM substrates, nonradiative defect density and V Zn-related defect density have been
reported12 to depend mainly on the growth temperature. As a
matter of fact, longitudinal-transverse splitting of the
B-excitonic polariton emissions is remarkable only in the
) ZnO epilayers grown at 670 680 C, although the
(0001
emission of B T is found in the 0001 film grown at
550 C, as shown in Fig. 1b. From the fact that all the
) and 0001 films are nearly strain-free, residual an(0001
0) ZnO film
isotropic and inhomogeneous strains in the (112
are considered to degrade the electronic quality to observe
free excitons and simultaneously cause the broadening of
FWHM values of XRD and PL peaks. Therefore, a lattice
and thermally matched substrate is necessary to further im 0) ZnO epilayers.
prove the exciton spectra of the (112
In summary, polarized OR, PR, and PL spectra of non 0) ZnO epilayer grown by L-MBE exhibited
polar (112
polarization-dependent excitonic resonance structures according to the polarization selection rules for anisotropically
strained ZnO. Different from the results for GaN epilayers
grown toward different polar directions, both the nonradiative defect density and V Zn-related defect density in the
0) ZnO film were comparable to those in polar 0001
(112
) ZnO epilayers. Since the polar epilayers exhiband (0001

ited well-resolved excitonpolariton emissions, the negligible impact of growth direction on the defect incorporation
0) ZnO-based optoelecis encouraging in designing (112
tronic devices.
The authors would like to thank T. Onuma for help in the
experiment and Professor S. Nakamura of UCSB for continuous supports. This work was supported in part by the
inter university cooperative program of the Institute for Materials Research, Tohoku University, the Inamori foundation,
and MEXT, Japan 21st Century COE program Promotion
of Creative Interdisciplinary Materials Science for Novel
Functions, Grant-in-Aid for Exploratory Research
#15656080, and one for Creative Scientific Research
#14GS0204.
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