Microstructure and optical properties of epitaxial GaN on ZnO 0001 grown

by reactive molecular beam epitaxy

F. Hamdani
University of Illinois at Urbana-Champaign, Materials Research Laboratory and Coordinated Science
Laboratory, 104 S. Goodwin Ave., Urbana, Illinois 61801

M. Yeadon
University of Illinois at Urbana-Champaign, Materials Research Laboratory, 104 S. Goodwin Ave.,
Urbana, Illinois 61801

David J. Smith
Department of Physics and Astronomy and Center for Solid State Science, Arizona State University, Tempe,
Arizona 85287

H. Tang, W. Kim, A. Salvador, and A. E. Botchkarev

University of Illinois at Urbana-Champaign, Materials Research Laboratory and Coordinated Science
Laboratory, 104 S. Goodwin Ave., Urbana, Illinois 61801

J. M. Gibson
University of Illinois at Urbana-Champaign, Materials Research Laboratory, 104 S. Goodwin Ave.,
Urbana, Illinois 61801

A. Y. Polyakov and M. Skowronski

Department of Materials Science and Engineering, Carnegie Mellon University, Pittsburgh,
Pennsylvania 15213-3890

H. Morkoca)
University of Illinois at Urbana-Champaign, Materials Research Laboratory and Coordinated Science
Laboratory, 104 S. Goodwin Ave., Urbana, Illinois 61801

~Received 4 June 1997; accepted for publication 14 October 1997!

High quality GaN epilayers have been grown on oxygen and zinc surfaces of ZnO ~0001! substrates
by reactive molecular beam epitaxy and the effect of the intermediate buffer layer on the structural
and optical properties of the GaN films has been investigated. The optical and structural
characterization of the GaN epilayers and ZnO substrates were performed using photoluminescence,
reflectivity, x-ray double diffraction, atomic force microscopy, and transmission electron
microscopy. The optical results indicated that GaN was grown with compressive strain due to the
difference in thermal expansion coefficient between GaN and ZnO. The surface roughness has been
reduced by using an intermediate low temperature GaN buffer layer. The low temperature
photoluminescence spectra of GaN/ZnO epilayers did not reveal any sign of the well-known midgap
yellow signal. Linear polarized reflectivity and photoluminescence indicated that GaN epilayer
planes were not misoriented with respect to the ZnO substrate planes: this result was confirmed by
x-ray double diffraction measurements. 1998 American Institute of Physics.
@S0021-8979~98!05402-4#

I. INTRODUCTION

Gallium nitride ~GaN! has a direct energy gap of 3.42

eV at room temperature and high external photoluminescence quantum efficiency, as well as a high excitonic binding
energy of 20 meV. It is therefore a strong contender for
many optoelectronic devices such as light-emitting diodes
~LED!1 and lasers operating in the visible-to-ultraviolet region of the spectrum,2 as well as for high-temperature/highpower device applications.3 The challenge of growing high
quality and defect-free GaN and its alloys, In12x Gax N and
Al12x Gax N, remains unresolved due to the lack of a suitable
lattice-matched and isomorphic substrate. Most previous
work has been devoted to the growth of GaN on Al2O3 by
a!

On sabbatical leave at Wright Laboratories under a University Resident

Research Professor program funded by the Air Force of Scientific
Research.

J. Appl. Phys. 83 (2), 15 January 1998

metal-organic-vapor phase epitaxy ~MOVPE!1,2,4 or molecular beam epitaxy ~MBE!.3,5 Despite the demonstration of
LED1 and laser devices2 grown on Al2O3 ~sapphire!, the density of defects is still too high4,5 to achieve the highly sought
violet and/or blue lasers operating continuously at room temperature with the required longevity, and high power electronic devices.
Other groups have recently reported limited success for
homoepitaxial growth of GaN by MBE6 and MOVPE.7 The
GaN single-crystal substrates were grown by applying high
pressures and high temperatures to a dilute solution of nitrogen in liquid gallium. Due to the high dissociation pressure
of nitrogen at the growth temperature, the surface of the GaN
bulk platelets so far obtained using this method is less than a
few millimeter square which is not very convenient for device investigation. The crystal quality implied by the optical
and structural characteristics6,7 of the GaN substrates used in

0021-8979/98/83(2)/983/8/$15.00

1998 American Institute of Physics

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the homoepitaxy of GaN, while improving, is low in comparison with the thick GaN single crystals grown by hydride
vapor-phase epitaxy ~HVPE!8 where sapphire has still been
used as a substrate. Transmission electron microscopy
~TEM! results7 obtained for the homoepitaxial growth of
GaN show a high density of defects occurring close to the
substrate surface. These defects are related to surface contamination and point to the challenge of developing good
substrate surface preparation methods before initiating the
growth.
GaN semiconductor crystals have two stable phases: 3Ccubic zincblende and 2H-hexagonal ~wurtzite!. Theoretical
calculations performed using first-principles local-density
formalism9 show that the hexagonal phase is the most stable
for the nitride semiconductor compounds, i.e., GaN, InN,
and AlN. Wurtzitic-GaN has been grown by MBE and
MOVPE on various substrates such as 6H-SiC,1012
MgAl2O4, 13 Si~111!,14 GaAs,15 and ZnO ~0001!.1618 TEM
images10,11 have revealed the presence of planar defects in
GaN epitaxial layers grown on Al2O3 and SiC. Sverdlov
et al.10 discussed the possible causes of the dense network of
threading defects in epitaxial hexagonal GaN films grown on
nonisomorphic substrates and suggested that stacking mismatch between the substrate material and epitaxial layer was
responsible for many of these defects. Two types of defects
have been considered: double positioning boundaries, also
called stacking mismatch boundaries ~SMB!, and inversion
domain boundaries ~IDB!.
ZnO is being considered as a suitable substrate for GaN
growth because of its stacking order match and close lattice
match. The lattice mismatch between GaN and ZnO is e
50.017, which leads to a range of critical thickness between
80 and 120 , estimated using different elastic models.19
This implies that coherently strained layers of GaN could be
pseudomorphically grown with thickness up to 100 on
ZnO substrates. On the other hand, in the case of SMB
there is an equal probability of nucleating two different
fcc stacking sequences ~ABC and ACB!. Since the steps on
~0001! 2H-ZnO would be bilayer ones, SMB type defects are
less likely to occur. It is worth noting that the design of
lattice matched heterostructures such as Inx Ga(12x) N/
Inx Ga(12x2y) Aly N for both lasers and electronic devices is
possible with ZnO substrates. Owing to the absence of stress
relief and stacking mismatch boundaries, it is expected that
such heterostructures would contain several orders of magnitude less dislocations compared to those grown on sapphire
and SiC substrates.
An early investigation of the most suitable substrate for
GaN growth was conducted by Sitar et al.18 Their TEM
cross-sectional images of different heteroepitaxial systems
such as GaN/SiC, GaN/Al2O3, GaN/Si, GaN/TiO2, and GaN/
ZnO grown under similar conditions by MBE, revealed that
GaN had highest quality when ZnO was used as the substrate. Matsuoka et al.16 used zinc-face ZnO substrates to
grow lattice-matched alloy In0.22Ga0.78N by MOVPE. Sputtered layers of ZnO have been used by Detchprohm et al.8 to
grow reproducible single crystalline films of GaN by HVPE.
Using the sputtered ZnO layer as the buffer layer, the electrical, crystalline, and optical properties of the GaN film was
984

J. Appl. Phys., Vol. 83, No. 2, 15 January 1998

found to be superior to those grown directly on sapphire.

More recently, ZnO has been proposed as a compliant buffer
layer20 for the growth of GaN. Nevertheless, ZnO buffer layers grown on substrates with which it does not share a common stacking sequence, suffer from stacking faults which
would cause the GaN films to have a high density of SMBs.
It is therefore not surprising that the quality of GaN epilayers
grown on compliant buffer layers is still inferior to the quality of the buffer layer used.20
In this article, we present structural and optical characteristics of epitaxial GaN grown by reactive-ammonia MBE
~RMBE! on ZnO ~0001! substrates. The experimental details
are given in Sec. II and the structural and optical characterizations obtained for GaN grown using different buffer layers
on both oxygen and zinc-surface of ZnO ~0001! substrates
are presented in Sec. III. The calculation of thermal strain in
different heterostructures, such as GaN/ZnO, GaN/SiC, and
AlN/ZnO, occurring during cool down from the growth temperature is also discussed.
II. EXPERIMENTAL DETAILS

During the course of this investigation epitaxial AlN and

GaN films were grown by RMBE using a Riber 1000 MBE
system. The growth chamber was equipped with a turbomolecular pump. Ga and Al fluxes were supplied by Knudsen
cells. Ammonia (NH3) was provided through an injector fabricated by SVT, Inc. of Eden Prairie, MN and maintained at
300 C. The purity of NH3 gas was 99.9995% which was
filtered and purified before being fed into the growth chamber. In order to ensure a controlled change of the ratio of
group V to group III atomic species, the flow rate of NH3
was regulated by a MKS flow controller having a range of
0100 sccm. The chamber pressure was kept at 2 5
31025 Torr during film growth. The substrate temperature
was monitored by a pyrometer focused on the surface of the
growing film. The ZnO substrate were rinsed with methanol
and deionized water and dried by blowing filtered nitrogen
prior to introduction into the growth chamber. Due to its
reactivity with ZnO, indium was not used to mount ZnO
substrates on Si templates. Instead, the ZnO substrates were
mounted by using carbon screws at the substrate corners. In
order to reach higher temperature, ceramic paste was used to
mount ZnO on Si templates which were mounted on molybdenum ~Mo! blocks. Since the ZnO substrate are conductive
~n type!, the electrical characterization such as Hall measurement do not provide valuable information about the residual
carrier concentration of GaN.
X-ray diffraction ~XRD! u 2u scans and double-crystal
v scans were carried out subsequently by an x-ray diffractometer using Cu K a and Mo K a lines, respectively. The optical properties of the films were characterized by photoluminescence and reflectivity spectroscopy using, respectively,
325 nm excitation produced by a HeCd laser and a polychromatic xenon lamp. Polarization of the reflected light was
obtained using an ultraviolet linear polarizer. Hamamatsu
GaAs photomultiplier with flat spectral response in the energy range between 1.73.6 eV and a grating blazed at 250
nm with 1200 gm/mm were employed to record the optical
data. The surface morphology of the samples was characterHamdani et al.

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TABLE I. Atomic force microscopy data obtained for 232 m m scans, on

different samples grown by reactive ammonia MBE. Ra is the average
roughness, rms is the root mean square roughness, Av.ht is the average
height and Max range is the maximum range.

Sample/polarity

Buffer

ZnO substrate
O face
Zn face

FIG. 1. AFM images obtained for ~a! Zn surface and ~b! O surface of ZnO
~0001! substrates.

ized using a TopoMetrix Explorer atomic force microscope

~AFM! with oxide-sharpened silicon nitride probes. Samples
were prepared for transmission electron microscopy ~TEM!
using the rod-and-tube method, by first mechanically thinning to a thickness of about 20 mm, and then ion-milling to
electron transparency with 4.5 keV argon ions at liquid nitrogen temperature. Micrographs and selected-area electron
diffraction patterns were recorded with a JEM-4000EX highresolution electron microscope operated at 400 kV.

III. RESULTS AND DISCUSSION

A. Atomic force microscopy

ZnO substrates used in this investigation were grown by

the hydrothermal method. The ZnO substrates were cut into
wafers of size 1031031 mm with the ~0001! surface orientation. These surfaces are polar since one surface is formed
only by the group-VI atoms, labeled as O face while the
opposite surface is formed by only the group-II atoms, labeled as Zn-face. The crystallographic polarity of the noncentrosymmetric material has been determined using a variety of methods including x-ray absorption, electrical
conductivity, piezoelectric, and etching experiments.21 We
used etching and electrical conductivity in order to identify
the surface polarity of the ZnO employed for the growth of
GaN. Owing to the absence of dangling bonds, the Zn face is
less affected by the etchant, and the surface electrical conductivity is three orders of magnitude lower compared to the
O face. Figure 1 shows the surface morphology of oxygen
and zinc faces of ZnO substrate obtained after etching in
20% nitric acid solution for 2 min followed by rinsing in
acetone and methanol. The Zn face presents a smoother surface compared to the O face. The rms roughness of the O
J. Appl. Phys., Vol. 83, No. 2, 15 January 1998

Ra
~nm!

rms
~nm!

Av.ht
~nm!

Max
range ~nm!

1.7
0.24

2.2
0.3

11.3
1.2

20.7
2.3

0.08

0.11

0.5

0.8

Sapphire substrate
GaN/ZnO
Sample 1/O face
Sample 2/Zn face
Sample 3/O face
Sample 4/O face

without buffer
without buffer
AlN buffer
GaN buffer

18
23
24
9

23
29
29
11

GaN/sapphire

AlN buffer

11

13.6

66
105
78
33

124
178
157
71

70

140

surface is an order of magnitude larger compared to the Zn

surface, which has a surface roughness comparable to that of
sapphire substrates, as indicated in Table I.
The growth of GaN on polar substrates is strongly dependent on the polarity of the surface used which determines
the interface polarity between the GaN epilayer and the substrate. We used the same growth conditions, i.e., the same
III/V flux ratio, sample thickness, and growth temperature
(T g ), in order to study the effect of the surface polarity on
the GaN quality. Table I shows AFM data obtained from
GaN, samples 1 and 2, which are grown at T g 5760 C, with
different surface polarities and without any buffer layer. Despite the fact that the Zn faces present smoother substrate
surfaces, samples grown on Zn-terminated surfaces have increased surface roughness compared to the those grown on
O-terminated surfaces. For substrate temperatures above
760 C, GaN layers grown on ZnO without any buffer peeled
off. This effect is due to the reactivity of NH3 with the ZnO
surface during the early stages of growth. In order to minimize this interaction and to avoid any layer peeling, a lowtemperature buffer layer was incorporated as an intermediate
step in the growth process. AFM images obtained for
samples grown with two different buffer layers are presented
in Fig. 2. Figure 2~a! shows that the surface roughness is
increased due to the AlN buffer on the ZnO surface. This is
expected since the lattice mismatch between these two materials is higher than that between GaN and ZnO. Figure
2~b!, obtained for the sample grown with GaN buffer layer at
T g 5700 C, shows a very smooth surface morphology, the
smoothest obtained in our laboratory for ZnO or sapphire
substrates ~see Table I!.
B. Transmission electron microscopy

Figure 3 shows an electron micrograph obtained from a

1 mm-thick GaN film grown on the O face ZnO substrate
without any buffer. Most of the dislocations that are visible
do not originate from the substrate and many of them start
and terminate within the field of view, indicating a short
propagation length. We note the presence of some isolated
stacking defects parallel to the substrate surface, and the forHamdani et al.

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FIG. 2. AFM images obtained for ~a! GaN grown on O-face ZnO, with low
temperature AlN buffer, and ~b! GaN grown on O-face ZnO, with GaN low
temperature buffer.

mation of facets on the upper surface which may indicate

that the surface is nitrogen-terminated and that the interface
is thus formed by the OGa bonding.
As indicated above, in order to avoid any peeling off of
the GaN from the substrate, we used a low temperature
buffer layer to minimize the reactivity of NH3 with the ZnO
surface. An improvement of crystal quality between the
buffer layer region and the thick GaN film has been observed
by TEM on GaN/ZnO samples grown on a series of low
temperature buffer layers. Figures 4~a! and 4~b! show TEM
images obtained from 1.5 mm-thick GaN grown at 720 C on
O face ZnO substrate, with an AlN/GaN superlattice buffer
layer grown at 650 C. Figure 4~a! is from a region including
the buffer layer and the ZnO substrate, and it shows that the
buffer layer and the initial GaN epilayer are heavily disordered. Similar disorder is indicated by the appearance of the
electron diffraction pattern from a low temperature-GaN
buffer layer region of another GaN/ZnO sample, shown in
Fig. 5~a!. Conversely, as shown in Fig. 4~b! the crystal struc-

FIG. 3. Cross-sectional transmission electron micrograph of GaN grown on

O-face ZnO substrate, without buffer layer.
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J. Appl. Phys., Vol. 83, No. 2, 15 January 1998

FIG. 4. Cross-sectional transmission electron micrographs of 1.5 mm-thick

GaN grown with AlN/GaN superlattice low temperature buffer layer on
O-face ZnO substrate: ~a! interfacial region; and ~b! upper GaN surface.

ture becomes well ordered close to the top GaN surface, and
the defect density of about 108 cm22 is at least three orders
of magnitude lower compared to the buffer layer region and
comparable to that observed previously with sapphire
substrates.11 This considerable improvement in crystal quality away from the substrate is also apparent from comparing
the corresponding electron diffraction pattern in Fig. 5~a!
with that shown in Fig. 5~b! which is from the upper GaN
surface.
C. Reflectivity and photoluminescence

In a previous article,17 we have reported the optical characterization of GaN grown on ZnO indicating that ZnO is a
promising substrate for the growth of GaN. Since both semiconductors share the same crystal symmetry ~wurtzite! as

FIG. 5. Electron diffraction patterns from 4 mm-thick GaN grown with low
temperature GaN buffer layer on O-face ZnO substrate: ~a! interfacial region; and ~b! upper GaN surface.
Hamdani et al.

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FIG. 6. Photoluminescence spectra at 300 and 4.2 K of ZnO ~0001! substrate and 2 mm-thick GaN/ZnO grown at T g 5760 C with low temperature
GaN buffer layer. Labels A1 and DX identify free and bound excitons.

well as close lattice parameter and energy gap, we compare,

in Figs. 6 and 7, the photoluminescence and reflectivity spectra from a ZnO substrate and GaN epilayers grown on ZnO
by reactive MBE. The full width at half maximum ~FWHM!
of room temperature photoluminescence ~PL! falls from 80
to 36 meV, on going from ZnO to GaN grown on ZnO,
indicating the higher quality of the epitaxial GaN. The appearance of free excitons in low temperature PL spectra of
both ZnO and GaN/ZnO is another indication of the high
quality of both materials. The identification of the free exciton in PL spectra is from its energy position compared to the
reflectivity spectra which give the positions of the intrinsic
free excitons, as shown in Fig. 7. The intensity ratio between
the free and bound excitons indicates that GaN/ZnO epilayers have higher quality compared to the ZnO substrates. The
A and B ground state excitons of ZnO are observed at A

FIG. 7. Reflectivity derivative spectra at 4.2 K of ZnO ~0001! substrate and

2 mm-thick GaN/ZnO grown at T g 5760 C, with InGaN buffer layer. Labels Ai , Bi , and Ci with i51,2,3 identify ground and excited levels of free
excitons.
J. Appl. Phys., Vol. 83, No. 2, 15 January 1998

FIG. 8. Photoluminescence spectra at 4.2 K of GaN/ZnO samples grown on

O- and Zn-faces of ZnO ~0001! substrates, and with different low temperature buffer layers: ~a! without buffer on O-face; ~b! without buffer on Znface; ~c! with AlN buffer on O-face; and ~d! with GaN buffer on O-face.
Labels A1, DX, and AX identify, in order, free exciton, donor-bound exciton, and acceptor-bound exciton. The inset displays the logarithmic scale of
photoluminescence spectra of Fig. 8~a!.

~3375 meV! and B ~3386 meV!. The positions of the ground

state of A, B, and C excitons of GaN grown on ZnO are
dependent on the buffer layer used as well as on the growth
temperature. The scattering range of the energy positions of
these excitons is much smaller than the scattering range observed for samples grown on sapphire substrates. These excitonic energy positions are slightly shifted to higher energy
(1 5 meV) compared with the positions given for bulk
GaN.68 This positive energy shift is indicative of the small
compressive strain present in the GaN layers on ZnO. The
origin of this strain effect is discussed later.
The PL spectra for GaN grown on ZnO ~0001! of different surface polarities and with different buffer layers are
shown in Fig. 8. The growth mechanisms involved in the
deposition of a polar semiconductor on the top of a polar
substrate, as is the case for GaN on ZnO ~0001!, is not only
dependent on the lattice mismatch between the two materials
but also on the surface polarity of the substrate, since this
determines the polarity of the epilayer. The identification of
free excitons is given in comparison to that obtained by reflectivity at the same temperature and with normal incidence
of light with respect to the sample. We used the same growth
conditions, in order to study only the effect of surface polarity on the quality of GaN. It was a general trend that, although the Zn-terminated surfaces could be prepared with
Hamdani et al.

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very smooth surfaces, as indicated in Fig. 1, they did not lead

to higher quality of GaN layers as shown by the absence of
any free exciton in the low temperature PL spectra. A comparison of the PL and reflection data obtained from GaN
layers grown on ZnO surfaces of both polarities indicates
that the O surface appears more suitable for the growth of
GaN, since it provides more dangling bonds compared to the
Zn-terminated surface. We note that Zn atoms located at Gasites and O atoms located at N sites act as acceptors and
donors in GaN,8,22 respectively. As shown in Figs. 8~a! and
8~b!, and PL peaks related to the impurities ~donor and acceptor! bound exciton have higher intensities on samples
grown on Zn-terminated surfaces compared to those grown
on O-terminated surfaces. This may be induced by the variation with the surface polarity of the diffusion rates of both O
and Zn atoms from the substrate to the GaN layers.
In order to optimize the quality of GaN, the effect of
various buffer layers was investigated by paying attention to
the reactivity of NH3 with ZnO. Low temperature (T g
;650 C) buffer layers such as AlN, GaN, and In0.20Ga0.80N
were used to initiate the growth process. The PL and reflectivity data clearly indicate that low temperature buffers
grown with radio frequency MBE lead to improved optical
quality compared to the same buffer layers grown using
RMBE. Figure 7 shows the derivative of the reflectivity
spectra for a GaN layer grown on an InGaN buffer layer on
O face of ZnO substrates. The smallest FWHM of the three
free excitons ~A, B, and C! of GaN epilayer was obtained
through the use of a nearly lattice matched In0.20Ga0.80N
buffer layer grown by RMBE. The positions of these three
excitons are shifted to lower energies as compared to the
results obtained so far. The observation of excited states of
free excitons ~A2, B2, C2, and C3! is an indication of the
high quality of the GaN epilayers. Conversely, PL and reflectivity spectra for GaN grown on AlN buffer layers do not
show any free exciton indicative of the fact that AlN buffer
layers grown on ZnO are at present detrimental for GaN
crystal quality.
Within the detection limit of the measurement setup, no
yellow signal was observed in the low temperature PL spectra in any of the samples grown on ZnO ~0001! substrates.
As shown in the inset of Fig. 8, the near-band-edge transitions, i.e., the free and shallow bound excitons and their
phonon replicas, are the only transitions observed in these
samples. Even with the monochromator slit wide open to 600
mm, the yellow band was completely absent. The room temperature PL spectrum of GaN/ZnO shows a very small yellow signal with an intensity level three to four orders of
magnitude lower compared to the band edge PL peak. Recently, Northrup et al.23 performed first-principles calculations of domain wall energies for both IDB and SMB in
GaN. Their calculations indicate that IDB do not induce
electronic states in the band gap and would therefore not
adversely impact photoluminescence efficiency, although
SMB gave rise to occupied N-derived interface states in the
band gap. Therefore, SMB are expected to give rise to a
photoluminescence peak around 2.3 eV which could be the
origin of the yellow luminescence commonly observed in
GaN grown on Al2O3. 24 We point out that the yellow lumi988

J. Appl. Phys., Vol. 83, No. 2, 15 January 1998

FIG. 9. ~a! Linear polarized photoluminescence spectra of GaN/ZnO. ~b!

Linear polarized reflectivity spectra of GaN/ZnO. Light propagation is parallel to the @0001# direction and E is the electric field direction.

nescence usually observed in GaN grown on Al2O3 has a

FWHM of 500 meV, which can involve electronhole recombination processes from different types of impurities or
native point defects such as deep acceptor levels,24 Ga
vacancies,25 and SMB.23 If so, the absence of yellow photoluminescence in our GaN samples grown on ZnO17 is an
indication of reduced defect density.
The intensities of PL and reflectance peaks corresponding to the free exciton transitions reflect their oscillator
strengths,26,27 which are dependent on crystallographic directions due to the anisotropy of the wurtzite structure. Therefore, using linearly polarized PL and reflectivity measurements we are able to detect the misorientation of the epilayer
planes with respect to the substrates. The misorientation of
strained epitaxial layers has been previously studied in several III-V and II-VI heterostructures, and it was shown to be
dependent on the amount of lattice mismatch and the substrate miscut.26,28 Our results for GaN grown on ~0001!
Al2O3 show a variation of the exciton oscillator strength with
the direction of polarization, indicating that the GaN layers
are tilted with respect to the substrate axis. As shown in Fig.
9, the free exciton intensities observed in both PL and reflectivity of GaN grown on ~0001! ZnO are independent from
the polarization direction, indicating the absence of any tilting effect detectable by this method. Double-crystal x-ray
diffraction measurements performed in two different configurations by interchanging the incident and the reflection
Hamdani et al.

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FIG. 10. Double XRD measurement investigating tilting effect on GaN/

ZnO. Dashed lines represent diffraction spectrum obtained by rotating the
sample by 180, as described in inset. Da is the tilting angle.

directions of the x-rays, as shown in Fig. 10, lead to diffraction peaks appearing at the same positions, confirming the
conclusions drawn from the polarized optical data. The x-ray
measurements for GaN grown on Al2O3 point to the presence
of a tilting effect due to the lack of coherence in the atomic
stacking between the sapphire and GaN and the high lattice
mismatch.
D. Thermal-induced strain calculations

Strain due to lattice mismatch and the difference between the thermal expansion coefficients of the layers and
the substrate induce a shift and an alteration of the free and
bound exciton energies as well as the Raman frequency of
the optical phonons of GaN. It has been pointed out that the
strain state of GaN depends on the growth conditions, the
substrate, and the buffer layer used. Gil et al.29 presented a
theoretical model using the Pikus and Bir Hamiltonian, taking into account the relaxation of thermal and lattice mismatch between GaN and the substrate in order to fit the energy shift of the conduction and valence bands. X-ray and
optical measurements indicate that GaN layers grown on
sapphire substrate undergo compressive strain and GaN layers grown on SiC substrate are under tensile strain. An accurate calculation of the temperature variation of the thermal
strain ( e th) due to the difference of the thermal expansion
coefficients between GaN and the substrate used is given by
Eq. ~1!:

e th~ T ! 5 @ Da 1 ~ T ! 2Da s ~ T !# /a s ,

~1!

where Da 1 (T) and Da s (T) are integrals representing the

variation of the lattice parameter in the temperature range
between the growth temperature and room temperature for
the GaN layers and the substrate, respectively. Figure 11
shows the variation of the calculated thermal strain e th with
growth temperature for different heterostructures, using the
temperature dependence of the thermal expansion coefficient
given in the literature.30 It is important to note from Fig. 11
that the thermal strain increases linearly with growth temJ. Appl. Phys., Vol. 83, No. 2, 15 January 1998

FIG. 11. Variation of thermal strain with growth temperature calculated for
GaN/ZnO, AlN/ZnO, and GaN/SiC heterostructures.

perature, meaning that MBE grown samples should undergo

less thermal strain compared to MOVPE-grown samples that
are grown at higher temperature. Owing to the close thermal
expansion coefficients between GaN and ZnO, it is important
to note that the thermal strain in GaN/ZnO is about half that
of GaN/SiC and AlN/ZnO heterostructures, as well established from Fig. 11. This implies that the cracking of GaN
layers observed on SiC substrates could be avoided in cases
where ZnO is used as a substrate. The high thermal strain
occurring in AlN/ZnO heterostructures provide an explanation for the fact that AlN is not a suitable buffer layer for
growth on ZnO substrates. We mention that the thermal
strain e th has negative values for GaN/ZnO and AlN/ZnO
indicating compressive strain and positive values for GaN/
SiC and AlN/SiC heterostructures, indicating tensile strain.
This is congruent with the shift of the energy position of free
excitons observed in both reflectivity and photoluminescence
spectra obtained in some of these heterostructures.29

IV. CONCLUSIONS

Photoluminescence and reflectivity data show that high

quality GaN epilayers can be grown on ZnO ~0001! substrates using reactive ammonia MBE. X-ray measurements
as well as polarized optical data confirm that the GaN ~0001!
planes are parallel to the ZnO ~0001! planes. Our calculations of thermal strain indicate that the cracks observed in
GaN/SiC and GaN/sapphire are not likely to occur in the
case of ZnO substrates. The deterioration of the quality of
GaN epilayers grown with AlN buffer layers is explained by
the presence of high thermal strain occurring for AlN/ZnO
heterostructures. Investigation of the effect of the surface
polarity indicate that the best quality GaN epilayers can be
obtained using the oxygen face of ZnO as the growth surface. A low temperature thin buffer layer of GaN or InGaN
leads to better optical quality and smoother surface of GaN
layers grown on ZnO.
Hamdani et al.

989

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ACKNOWLEDGMENTS

The research at the University of Illinois was funded by

grants from the Office of Naval Research, with Dr. C. E.
Wood, Dr. Y. S. Park, Dr. R. G. Brandt, and M. Yoder monitoring, and Air Force Office of Scientific Research with Dr.
G. L. Witt monitoring. We thank Dr. S.-C. Y. Tsen for assistance with TEM sample preparation. H.M. would like to
thank C. W. Litton, D. C. Reynolds, D. C. Look, P. Hemenger, W. Harsch, and G. Cantwell for many useful discussions and encouragement.
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