Molecular beam epitaxy growth of ZnO using initial Zn layer and MgO

buffer layer on Si111 substrates

Miki Fujita,a) Noriaki Kawamoto, Masanori Sasajima, and Yoshiji Horikoshi
School of Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555, Japan
and Kagami Memorial Laboratory for Materials Science and Technology, Waseda University,
2-8-26 Nishiwaseda, Shinjuku-ku, Tokyo 169-0051, Japan

Received 5 November 2003; accepted 23 March 2004; published 8 June 2004

We have compared the quality of ZnO films grown on Si111 substrates by two different methods:
1 initial Zn layer deposition followed by its oxidation and 2 thin MgO buffer layer deposition
prior to the growth. All the layers are deposited by molecular beam epitaxy using a radio frequency
radical cell. X-ray diffraction measurements reveal that 0001-oriented ZnO films are grown on
Si111 substrates in both cases. However, the ZnO films grown by using initial Zn layer exhibit
straight lines along the principal axes of Si111 surface. In addition, their x-ray diffraction 2/
spectra often show double peaks. These results are probably caused by the cracks due to the
difference in thermal expansion coefficients between ZnO and Si. This phenomenon is alleviated
considerably by introducing a thin MgO buffer layer. The samples with thin MgO buffer layer show
no double peaks in their x-ray diffraction spectra, and the full width at half maximum value for both
2/, and scan are as narrow as 0.038 and 0.26, respectively. The photoluminescence emission
intensity is also improved by using thin MgO buffer layer. 2004 American Vacuum Society.
DOI: 10.1116/1.1740766
I. INTRODUCTION
Recently, wide-band-gap semiconductors have been paid
considerable attention for use in short-wavelength optical devices. Among these materials, ZnO is one of the most attractive materials due to its direct wide band gap 3.37 eV at
room temperature and its large exciton binding energy 60
meV.1,2 Therefore, various techniques for single-crystalline
ZnO film growth have been studied.3 6 In most studies, sapphire substrates are used. Since sapphire is an electrically
insulating material, it introduces complexity to device fabrication processes especially when grown crystals are applied
to injection-light-emitting devices. This problem can be
solved by using Si substrates. In addition, the crystal quality
of the Si substrate is expected to be markedly higher than
that of the sapphire substrate. On the other hand, ZnO substrates are now commercially available, and they are also
electrically conductive. Indeed, good quality ZnO films have
been grown on ZnO substrate.79 Nevertheless, we use Si
substrates instead of ZnO because we intend to develop
monolithic devices including ZnO and Si in the future.
Therefore, we have focused on the Si substrates for the
growth of ZnO films. The growth of epitaxial ZnO films on
Si is, however, known to be a difficult task because the Si
substrate surface is easily oxidized and covered with a resulting amorphous SiOx layer when it is exposed to reactive
oxygen sources.10,11 This amorphous SiOx layer degrades the
crystal quality of ZnO grown on the Si substrate. Therefore,
preventing the Si substrate surface from being oxidized in
the initial growth stage of ZnO is the most important issue
for the ZnO growth on Si.
To protect the Si surface from being oxidized and to improve the crystal quality of a ZnO layer grown on it, we have
a

Electronic mail: miki-f@ruri.waseda.jp

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J. Vac. Sci. Technol. B 223, MayJun 2004

previously attempted to grow ZnO films on Si substrates by

using an initial Zn layer deposition followed by its
oxidation.12,13 Although the grown ZnO films exhibit very
high photoluminescence PL efficiency, they suffer from
high density of microcracks along the principal axes on the
Si111 surface probably caused by the difference in thermal
expansion coefficients between ZnO and Si.
In this work, we investigate the effect of a thin MgO
buffer layer deposited prior to the growth to alleviate the
tensile strain imposed on the ZnO films. The results are compared with those observed in ZnO films grown using an initial Zn layer deposition. An excellent improvement is obtained with this method.
II. EXPERIMENTAL PROCEDURE
ZnO films are grown on Si111 substrates by molecular
beam epitaxy. Elemental Zn 6N and Mg 4N are evaporated using a conventional effusion cell. Pure oxygen 5N is
used for oxygen source and oxygen plasma is generated
through a radio frequency rf activated radical cell. The Si
substrates are chemically etched in 5% HF solution. Then the
Si substrates are inserted into an ultrahigh-vacuum chamber
and annealed at 750 C. After this surface cleaning process,
the reflection high energy electron diffraction RHEED pattern shows a well-defined 77 reconstruction. Then the
substrate temperature is lowered to an appropriate value for
growth. However, the growth process using an initial Zn
layer deposition is reported in detail previously.12 Therefore,
we describe here the growth procedure using a thin MgO
buffer layer.
After confirming the 77 pattern on the Si111 surface,
the substrate temperature is lowered to 350 C. Then the Si
substrate is exposed to a Mg flux with a beam equivalent
pressure BEP of 5107 Torr. After 2 min, oxygen gas

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Fujita et al.: Molecular beam epitaxy growth of ZnO

and Si 11
0 direction in different
FIG. 1. RHEED patterns along Si 112
stages of ZnO growth by using a MgO buffer layer: a before growth; b a
Mg evaporated surface; c a MgO buffer layer; and d a ZnO layer.

supply is started at a flow rate of 0.9 sccm. This growth is

continued until the grown MgO buffer layer thickness
reaches approximately 20 nm. Then 1-m-thick ZnO layer is
grown at 575 C using a Zn BEP of 2106 Torr and an
oxygen flow rate of 0.9 sccm. The resulting growth rate of
ZnO is approximately 1.5 /s. The substrate temperature is
reduced to RT at the rate of 6 C/min after growth as with the
growth using the initial Zn layer. The crystalline quality of
ZnO films is investigated by RHEED observation during
growth, and by x-ray diffraction XRD, photoluminescence
PL, atomic force microscopy AFM, and optical microscopy after growth.
III. RESULTS AND DISCUSSION
The RHEED patterns in the different stages of ZnO
growth by using a thin MgO buffer layer are shown in Fig. 1.
After the surface cleaning process described above, a clear
77 pattern is confirmed at 750 C as shown in Fig. 1a.
When Mg deposition is performed on the Si111 substrate at
350 C, the RHEED pattern changes to a Si16 pattern as
shown in Fig. 1b. Although this surface reconstruction has
never been reported in the Mg/Si system,14,15 this pattern
appears quite reproducibly in the above growth process.
When MgO growth is started, i.e., the oxygen gas supply is
started, a spotty RHEED pattern corresponding to MgO
11 with sixfold symmetry appears as shown in Fig. 1c.
This result indicates that the grown MgO is 111-oriented.
Although not shown here, the XRD measurement also indicates that the grown MgO layer is 111-oriented and no
rotational domain exists. This RHEED pattern is unchanged
even when the substrate temperature is increased to 575 C
for ZnO growth. When ZnO growth is started, a ZnO 11
spotty pattern with sixfold symmetry appears as shown Fig.
1d. This pattern is unchanged during the whole ZnO
growth.
The observed RHEED patterns show that both MgO and
ZnO lattices are not rotated by 30 with respect to the Si
0 direction of ZnO and the
surface. In other words, the 112

direction of
112 direction of MgO are parallel to the 112
0
the Si surface, and the 1000 direction of ZnO and 11

direction of MgO is parallel to the 110 direction of the Si

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FIG. 2. Microscopic images of the ZnO films grown by using a initial a Zn

layer and b a MgO buffer layer.

surface. This is one of the most important effects of a MgO

buffer layer on ZnO growth, because the ZnO lattices grown
using the initial Zn layer are always rotated by 30.
Figure 2 compares the microscopic images of the ZnO
films grown by using the initial Zn layer and MgO buffer
layer. The surface of ZnO layers grown with the initial Zn
layer shows straight crack lines along the principal axes of
0 directions as shown in Fig.
the Si111 surface, i.e., 11
2a. In contrast, almost no cracks are observed on the layers
with a MgO buffer layer Fig. 2b. These straight cracks
probably stem from the difference in the thermal expansion
coefficient between ZnO (475108 K1 ) 16 and Si (256
108 K1 ). 16 While the substrate is cooled down to room
temperature RT after growth, tensile strain will be imposed
to ZnO layer by Si substrate, resulting in the formation of
cracks. As shown in Fig. 2, the effect of the MgO thin buffer
layer is very clear. As described later, the XRD and PL characteristics are also improved considerably by introducing
the thin MgO layer. The thermal expansion coefficient of
MgO is 1040108 K1 at RT16 and it is larger than those
of Si and ZnO. Therefore, introducing a thin MgO buffer
layer between a Si substrate and a ZnO epitaxial layer may
produce a compressive stress component to the ZnO layer,
thus alleviating the tensile strain from Si substrate. Therefore, the density of cracks on the ZnO surface is decreased
considerably.
To investigate the structural quality of ZnO films grown
by using a MgO buffer layer, XRD measurements are carried
out and compared with those obtained in the samples grown
with an initial Zn layer. Although not shown here, the result
of the XRD 2/ scan measurement shows that both ZnO
films with an initial Zn layer and with a MgO buffer layer are
c-oriented. Besides, the XRD result of a scan for the
1) planes for these two samples are sixfold symmetry
(101
above surface normal, indicating that no rotational domain of
c-oriented ZnO exists.
The XRD 2/ scan spectra of the ZnO 0002 peak in
the ZnO films with the initial Zn layer and with the MgO
buffer layer are shown in Fig. 3. As shown in Fig. 3a, a
clear doublet appears in the ZnO films grown with initial Zn
layer. This is probably caused by the cracks in ZnO films
grown with a Zn layer. However, no such doublet is observed
in the films grown with MgO buffer layer. Figure 3b shows
the rocking curves of these two samples. The full width at

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Fujita et al.: Molecular beam epitaxy growth of ZnO

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useful to reduce the density of cracks on the ZnO films

grown on Si substrate. The x-ray diffraction measurements
reveal that 0001-oriented ZnO films are grown on Si111
substrates regardless of the introduction of the MgO buffer
layer. However, the samples with a thin MgO buffer layer
show very sharp XRD spectra. The FWHM values for 2/
and scan are as small as 0.038 and 0.26, respectively.
The PL intensity is also improved by using a thin MgO
buffer layer.
FIG. 3. Comparison of ZnO 0002 XRD spectra for the samples grown by
using initial a Zn layer and a MgO buffer layer a 2/ scan spectra and b
scan spectra.

half maximum FWHM of the diffraction peak of ZnO

0002 is improved by applying a MgO buffer layer. The
FWHM values for 2/ and scan are as small as 0.038
and 0.26, respectively. This means that the MgO buffer
layer reduces the mosaic structure of the epitaxial layers.
These FWHM values are better than those reported for ZnO
films grown on Si substrates,10,17,18 and almost equal to the
films grown on sapphire substrates.7,18 20
Figure 4 shows the PL spectra of the ZnO films grown
with an initial Zn layer and with a MgO buffer layer. The
measurement is carried out at 10 K using a HeCd laser for
excitation. Both samples show PL spectra due to bound excitons in the range of 3.353.37 eV16 23 and also near 3.31
eV. However, as shown in the figure, the PL intensity is
improved considerably by using MgO buffer layer. This result indicates that the PL characteristic is also improved by
introducing the MgO buffer layer.
IV. SUMMARY
When high crystal quality ZnO films are grown on
Si111, a high density of cracks inevitably appears along the
principal axes of the Si111 surface. This is caused by the
large difference of thermal expansion coefficients between Si
and ZnO. Although very high quality ZnO films have been
grown by using an initial Zn layer, the grown surface is
covered with a high density of cracks. We have attempted to
introduce a thin MgO buffer layer between ZnO and Si to
alleviate this problem. The thin MgO buffer layer has proved

FIG. 4. PL spectra of ZnO films grown by using initial a Zn layer and a MgO
buffer layer.

J. Vac. Sci. Technol. B, Vol. 22, No. 3, MayJun 2004

ACKNOWLEDGMENTS
This work is partly supported by the Grant-in-Aid for Scientific Research on Priority Areas program Photonics
Based on Wavelength Integration and Manipulation, the
Grant-in-Aid for Scientific Research B from Japan Society
for the Promotion of Science JSPS, and the COE Program
Molecular Nano-Engineering, and 21 COE Practical
Nano-Chemistry from the Ministry of Education, Science,
Sports and Culture, Japan.
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