APPLIED PHYSICS LETTERS

VOLUME 85, NUMBER 23

6 DECEMBER 2004

Reduced defect densities in the ZnO epilayer grown on Si substrates

by laser-assisted molecular-beam epitaxy using a ZnS
epitaxial buffer layer
T. Onuma, S. F. Chichibu,a) and A. Uedono
Institute of Applied Physics and Graduate School of Pure and Applied Sciences, University of Tsukuba,
1-1-1 Tennodai, Tsukuba 305-8573, Japan

Y.-Z. Yoo and T. Chikyow

COMET-NIMS, National Institute for Materials Science, 1-2-1 Sengen, Tsukuba 305-0047, Japan
and Materials and Structures Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta,
Midori-ku, Yokohama 226-8503, Japan

T. Sota
Department of Electrical Engineering and Bioscience, Waseda University, 3-4-1 Ohkubo,
Shinjuku 169-8555, Japan

M. Kawasaki
Institute for Materials Research, Tohoku University, Sendai 980-8755, Japan
and Combinatorial Materials Exploration and Technology (COMET), Tsukuba 305-0044, Japan

H. Koinuma
Materials and Structures Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta,
Midori-ku, Yokohama 226-8503, Japan and Combinatorial Materials Exploration and Technology
(COMET), Tsukuba 305-0044, Japan

(Received 6 July 2004; accepted 13 October 2004)

Nonradiative photoluminescence (PL) lifetime nr and point defect density in the 0001 ZnO
epilayer grown on 111 Si substrates by laser-assisted molecular-beam epitaxy (L-MBE) using a
0001 ZnS epitaxial buffer layer were compared with those in the ZnO films on 111 and 001 Si
substrates prepared by direct transformation of ZnS epilayers on Si by thermal oxidation [Yoo et al.,
Appl. Phys. Lett. 78, 616 (2001)]. Both the ZnO films exhibited excitonic reflectance anomalies and
corresponding PL peaks at low temperature, and the density or size of vacancy-type point defects
(Zn vacancies), which were measured by the monoenergetic positron annihilation measurement, in
the L-MBE epilayer was lower than that in the films prepared by the oxidation transformation. The
ZnO epilayer grown on a 0001 ZnS epitaxial buffer on 111 Si exhibited longer nr of 105 ps at
room temperature. 2004 American Institute of Physics. [DOI: 10.1063/1.1832734]
ZnO is an excellent candidate for use in visible and ultraviolet light emitters, due to its large band gap energy
3.37 eV, and large exciton binding energy 59 meV.1 The
use of Si substrate may enable one to integrate ZnO-based
optoelectronic devices with Si technologies. However, the
growth of ZnO on Si is difficult due to the formation of an
amorphous SiO2 at the ZnO/ Si interface. Therefore, there are
only a few reports on the growth of single crystalline ZnO
films on (111) Si using electron-beam (EB) evaporation,2,3
laser-assisted molecular beam epitaxy (L-MBE),4 metalorganic vapor phase epitaxy,5 and molecular beam epitaxy.6
Miyake et al.2 have grown ZnO films on Si substrates by EB
evaporation using ZnS buffer layers, and also prepared ZnO
films by direct transformation of epitaxial ZnS films on 111
Si by thermal oxidation.3 Yoo et al.4 expanded these techniques growing ZnS epilayers on 001 and 111 Si substrates by L-MBE followed by the oxidation transformation
into ZnO.
a)

Author to whom correspondence should be addressed; also at:

Photodynamics Research Center, Institute of Physical and Chemical
Research (RIKEN), Sendai, 980-0868, Japan; electronic mail:
optoelec@bk.tsukuba.ac.jp

According to the advantages of using a combination of

time-resolved photoluminescence (TRPL) and positronannihilation7 measurements, one can discuss the correlation
between the photoluminescence (PL) lifetime PL, which is
dominated by the nonradiative lifetime nr at elevated temperatures, and density or size of vacancy-type defects in
semiconductors. The authors have investigated bulk and epitaxial ZnO using this complementary method8 and concluded that nonradiative recombination processes are not
solely governed by single point defects, but by certain defect
species introduced by the presence of Zn vacancies VZn
such as vacancy complexes.
In this letter, results of optical reflectance (OR), PL,
TRPL, and monoenergetic positron annihilation measurements on the ZnO films on Si substrates are shown to visualize the reduction of nonradiative defect and point defect
densities in the L-MBE films using a ZnS epitaxial buffer
layer. The results are compared with those obtained for the
ZnO films transformed from ZnS by thermal oxidation, bulk
ZnO single crystal,9 and ZnO epilayers grown by L-MBE on
the nearly lattice matched ScAlMgO4 (SCAM) substrates.8
The ZnO films investigated were (i) a 300-nm-thick
0001 ZnO epilayer grown on a 50-nm-thick 0001 ZnS
epitaxial buffer layer prepared on a 111 Si substrate, (ii) a

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2004 American Institute of Physics
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Appl. Phys. Lett., Vol. 85, No. 23, 6 December 2004

Onuma et al.

5587

FIG. 2. TRPL signals measured at 293 K of the near-band-edge emission at

3.28 eV for the 0001 ZnO/ 0001ZnS/ 111 Si epilayer and that at
1 ZnO/ 001 Si films pre3.25 eV for the 0001 ZnO/ 111 Si and 101
pared by the oxidation transformation. The curve denoted by system represents the gross system response.

FIG. 1. PL and OR spectra measured at 8 K of (a)

0001 ZnO/ 0001ZnS/ 111 Si
grown
by
L-MBE,
and
(b)
1 ZnO/ 001 Si films prepared by trans0001 ZnO/ 111 Si and (c) 101
formation of ZnS by the thermal oxidation. For comparison, polarized OR
spectra of the bulk ZnO single crystal are also shown in the insets (i) and (ii)
(after Ref. 9).

100-nm-thick 0001 ZnO film on a 111 Si substrate prepared by the transformation of a 350-nm-thick ZnS epilayer
1 ZnO
by thermal oxidation, and (iii) a 90-nm-thick 101
film on a 001 Si substrate prepared by the transformation of
a 300-nm-thick 001 ZnS epilayer by thermal oxidation.
The ZnO and ZnS epilayers were grown by L-MBE using a
KrF excimer laser,4 and the thermal oxidation for the latter
two samples was carried out in an O2 ambient at 900 C for
1 h. It should be noted that the thickness of the two transformed ZnO films 90 100 nm was decreased from the initial ZnS film thickness 300 350 nm; this sublimation
problem is one of the characteristics of this method. The
former two 0001 ZnO films on 111 Si exhibited the
wurtzite structure with sixfold symmetry having in-plane ep 00 Si 110. The 001 ZnS epilitaxial relation ZnO 11
1-oriented wurtzite
ayer on 001 Si was transformed to 101
ZnO film, in which the c axis is 56 tilted from the substrate
normal. The growth details will be found elsewhere.4
PL and OR spectra of the ZnO/ Si films at 8 K are shown
in Fig. 1. The PL was excited using the 325.0 nm line of a
cw He Cd laser 2 mW. Considering the large absorption
coefficient of ZnO (5 105 cm1 at 325 nm), the penetration depth of the laser is estimated to be 20 nm. For comparison, polarized OR spectra of the bulk ZnO single crystal9
are also shown [upper two traces (i) and (ii)]. Due to the C6v
symmetry, ZnO exhibits an optical anisotropy911 for transitions from three separate valence bands to the conduction
band. Three excitons are referred to as A, B, and C excitons
in order of increasing the transition energy.10 The A and B
exciton transitions are allowed for light polarization E perpendicular to the c axis E c, where E is the electric field
component, and the C transition is allowed for E parallel to
the c axis E c. All ZnO/ Si films exhibited excitonic
anomalies in their OR spectra at around 3.37 3.39 eV in
addition to the internal multiple reflection fringes. Although
the 0001 ZnO epilayers suffer from certain biaxial tensile

strain due to the in-plane lattice-mismatch 0.15%, the energies of the anomalies nearly agreed with those of free A
and B excitons at 3.377 and 3.386 eV,911 reflecting a weak
strain dependency of A and B exciton energies in ZnO.12 The
spectral broadening in the excitonic resonances is due to the
partial relaxation of the residual lattice strain and crystal imperfections. Indeed, the full width at half maximum
(FWHM) value of the x-ray 0002 ZnO diffraction peak,
which reflect the distribution of out-plane lattice constant,
were as large as 0.16 for ZnO/ ZnS/ 111 Si and 0.19 for
1-oriented
ZnO/ 111 Si. The OR spectrum of the 101
ZnO/ 001 Si film exhibited an additional reflectance
anomaly due to C-exciton resonance at 3.42 eV,911 as
shown in Fig. 1(c). It should be noted that the sample suffers
from triaxial anisotropic strains, and the crystal symmetry is
no longer C6v.
PL spectra of the samples exhibited a peak at 3.356 eV
and noticeable higher energy shoulders at around 3.37 and
3.39 eV. They are assigned as being due to the radiative
recombination of excitons bound to neutral In donor13 and a
convolution of free A and B exciton emissions, respectively.
The results indicate that the qualities of present ZnO films
are high enough to observe excitons. However, a dominant
deep emission band at 2.4 eV (green luminescence: GL) was
observed, and the FWHM values of the near-band-edge
(NBE) emission peak were as large as 130 150 meV at
293 K (data not shown). The NBE emission peak energies at
293 K were 3.28 eV for ZnO/ ZnS/ 111 Si and 3.25 eV for
ZnO/ 111 Si and ZnO/ 001 Si. They were 20 50 meV
lower than the free A and B exciton emission energy
3.3 eV at 300 K,8 implying the presence of certain bound
states originating from impurities or defects.
To compare the nonradiative defect density in the films,
TRPL signals of the NBE peak were measured at 293 K,
since PL at room temperature is in general governed by nr.
The PL was excited by a frequency-tripled mode-locked
Ti:sapphire laser (276 nm, 100 fs), and the signal was collected using a standard streak-camera acquisition system.
The TRPL signals exhibited a biexponential behavior, as
shown in Fig. 2. Both the fast and slow decay components (
1 and 2, respectively) may represent the nonradiative free
carrier lifetimes in ZnO. As summarized in Table I, 1 and 2
values of the ZnO/ Si films 23 105 ps were much shorter
than those of the bulk ZnO single crystal (1 = 970 ps and
2 = 14 ns).8 The results indicate the presence of high density

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5588

Onuma et al.

Appl. Phys. Lett., Vol. 85, No. 23, 6 December 2004

TABLE I. Free exciton emission lifetimes (1 and 2), S parameters for the
annihilation ray, and diffusion lengths of positrons Ld at 293 K in ZnO
films on Si substrates.
Sample
0001 ZnO/ ZnS/ 111 Si
0001 ZnO/ 111 Sia
1 ZnO/ 001 Sia
101
ZnO single crystalb
ZnO/ SCAM 800 Cb
a

1 ps

2 ps

Ld nm

40
23

105
40

0.43
0.46

5.9
3.8

35
970
110

80
14 000

0.45
0.4196
0.4259

3.6
52
21

Transformed from ZnS epilayers by the direct thermal oxidation.

Reference 8.

nonradiative defects. However, as shown in Fig. 2 and Table

I, 1 and 2 values for the 0001 ZnO/ ZnS/ 111 Si epilayer were increased by a factor of approximately 2, indicating the reduced nonradiative defect density. Note that 2 of
ZnO/ ZnS/ 111 Si 105 ps was comparable to PL of the
high-quality ZnO epilayer grown by L-MBE on the SCAM
substrate 110 ps.8
The monoenergetic positron beam line8 was used to detect point defects in the ZnO films as a function of depth. A
positron implanted into a condensed matter annihilates with
an electron and emits two 511 keV rays, which are broadened due to the momentum component of the annihilating
electronpositron pair. Because the momentum distribution
of electrons in neutral or negatively charged vacancy-type
defects (positron trapping centers) differs from that in defectfree regions, these defects can be detected by measuring the
Doppler broadening spectra of annihilation radiation. The resulting change in the spectra is characterized by the S
parameter,7,8 which reflects the change due to the annihilation of electronpositron pairs with low momentum distribution. Since VZn is one of the most probable positron trapping
centers in ZnO,8 S parameter can be used as a measure of
size/concentration of VZn. On the other hand, the positron
diffusion length Ld decreases with increasing the gross density of positron trapping and scattering centers such as interstitials and neutral or positively charged defects [Zn interstitials Zni, oxygen interstitials Oi, and oxygen vacancies
VO]. The physical backgrounds and experimental conditions have been given in Refs. 7 and 8. The S parameters
were measured as a function of incident positron energy E,
which define the mean positron implantation depth. The S
value of a particular film and Ld were determined from the
S E curve (the data are not shown, but are similar to those in
Ref. 8), and are summarized in Table I. The S parameters of
the films prepared by the oxidation transformation (0.45 and
0.46) were larger than those of the bulk ZnO 0.41968 and
the ZnO epilayer grown on SCAM (0.4259).8 Moreover, the
Ld values (3.6 and 3.8 nm) were an order of magnitude
shorter than those in the bulk ZnO 52 nm8 and
ZnO/ SCAM 21 nm.8 The results indicate that oxidized
films contain high density (large size) VZn and positively
charged point defects, respectively. Conversely, S
of the 0001 ZnO epilayer grown on ZnS/ 111 Si was
0.43,
which
was
comparable
to
that
of
ZnO/ SCAM 0.4259.8 The decrease in S indicates the decrease in size/density of VZn-related defects, and the result
was consistent with the TRPL results that the nonradiative
defect density in ZnO/ ZnS/ 111 Si was the lowest among

the present ZnO/ Si films. Note that Ld in ZnO/ ZnS/ 111 Si

5.9 nm was also improved by a factor of 1.6. However, it
was still far shorter than those in the bulk ZnO 52 nm8 or
ZnO/ SCAM 21 nm,8 implying the presence of extensive
neutral and positively charged defects (Zni, Oi, and VO) and
defect complexes. As a matter of fact, PL spectra at 293 K of
the ZnO/ Si films were dominated by the deep GL band (data
not shown), of which origin has been proposed to be VO or
Zni-related donor-type defect complexes.14 Further purification processes to reduce In donors and optimization processes to reduce the positron scattering centers are required
to obtain improved qualities of ZnO films on Si substrates.
In summary, reductions in the nonradiative defect density and point defect density in the ZnO epilayer grown on
111 Si by L-MBE using the ZnS epitaxial buffer layer were
shown. Both the ZnO/ ZnS/ 111 Si epilayer and the
ZnO/ Si films prepared by the oxidation transformation of
ZnS/ Si exhibited excitonic features in their low-temperature
OR and PL spectra. The ZnO/ ZnS/ 111 Si exhibited the
longest nonradiative PL lifetime 105 ps and the smallest S
parameter (0.43) at 293 K.
This work was supported in part by the inter-university
cooperative program of the Institute for Materials Research,
Tohoku University and MEXT, Japan (21st Century COE
program Promotion of Creative Interdisciplinary Materials
Science for Novel Functions and Grant-in-Aid for Scientific
Research Nos. 15656080, 16360146, and 14GS0204).
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