JOURNAL OF APPLIED PHYSICS

VOLUME 84, NUMBER 5

1 SEPTEMBER 1998

Defects and interfaces in epitaxial ZnO/ a -Al2 O3 and AlN/ZnO/ a -Al2 O3

heterostructures
J. Narayan, K. Dovidenko, A. K. Sharma, and S. Oktyabrsky
Department of Materials Science and Engineering, North Carolina State University, Raleigh, North
Carolina, 27695-7916

~Received 23 February 1998; accepted for publication 1 June 1998!

We have investigated the nature of epitaxy, defects ~dislocations, stacking faults, and inversion
domains!, and heterointerfaces in zinc oxide films grown on ~0001! sapphire and explored the
possibility of using it as a buffer layer for growing group III nitrides. High quality epitaxial ZnO
films were grown on sapphire using pulsed laser deposition in the temperature range 750800 C.
The epitaxial relationship of the film with respect to ~0001! sapphire was found to be
0 # i@1
21
0# . This in-plane
(0001) ZnOi~0001!sap , with in-plane orientation relationship of @ 011
ZnO
sap
orientation relationship corresponds to a 30 rotation of ZnO basal planes with respect to the
sapphire substrate, which is similar to the epitaxial growth characteristics of AlN and GaN on
0 & Burgers vectors.
sapphire. The threading dislocations in ZnO were found to have mostly 1/3^ 112
The planar defects ~mostly I 1 stacking faults! were found to lie in the basal plane with density of
about 105 cm21 . We have grown epitaxial AlN films at temperatures around 770 C using ZnO/
sapphire heterostructure as a substrate and observed the formation of a thin reacted layer at the
AlN/ZnO interface. The implications of low defect content in ZnO films compared to IIIV nitrides
and the role of ZnO films as a buffer layer for IIIV nitrides are discussed. 1998 American
Institute of Physics. @S0021-8979~98!05917-9#

I. INTRODUCTION

an energy density in the range of 3 to 4 J/cm2 . The oxygen

partial pressure and the substrate temperatures for the growth
of these films were in the range 1024 1025 Torr and 750
800 C, respectively. The base vacuum prior to deposition
was in the range of 131027 to 531028 Torr. The AlN
films were deposited on ZnO films at the substrate temperatures between 700800 C without nitrogen partial pressure
using a bulk AlN target. The base vacuum during the deposition of the AlN films was ;1 331026 Torr. The slow
cooling of the ZnO and AlN films were done sequentially in
1023 Torr of oxygen and nitrogen, respectively. The characterization of the films was carried out using TEM ~Topcon
002 B electron microscope operating at 200 kV! and XRD
techniques. The electrical resistivity measurements were performed at room temperature using the four-point probe
method. The samples for TEM were prepared using conventional sample preparation techniques including mechanical
polishing and dimpling, Ar1 ion milling at 6.5 and 2 kV at
the final stage.

The majority of the applications based on zinc oxide,

such as varistors, transparent conducting electrodes, and
surface-acoustic-wave devices, use polycrystalline material.
However, there is a considerable interest in growing high
quality crystalline ZnO ~bandgap53.3 eV! films on practical
substrates such as sapphire ( a -Al2O3 ) for UV light emitting
diodes ~LEDs!, emitter and laser applications.1 These
ZnO/a-Al2O3 heterostructures can also be used to grow III
nitrides where the band gap can be tailored between 3.39 eV
~GaN! and 6.2 eV ~AlN!, which exhibit a complete solid
solubility. The ZnO films have been grown using a variety of
thin film growth techniques such as chemical vapor deposition ~CVD!,2 sputtering,3 and pulsed laser deposition.48
More recently, high-quality ZnO films were grown by pulsed
laser deposition by Vispute et al.9 with Rutherford channeling yield, x min;2%3%, on sapphire and AlN films on
ZnO/a-Al2O3 with considerably higher x min ~60%70%!. A
much higher minimum channeling yield clearly indicates the
film to be highly defective and textured only in @0001# orientation. The objective of this work is to optimize pulsed
laser deposition conditions to produce epitaxial layers with a
low defect content, and investigate in detail the nature of
epitaxial growth, and characteristics of defects and interfaces
using transmission electron microscopy ~TEM! and x-ray
diffraction ~XRD! techniques.

III. RESULTS AND DISCUSSION

Figures 1~a! and 1~b! show typical XRD scans from an

optimized ZnO film deposited at the substrate temperature of
790 C and of the AlN films deposited on the ZnO film at a
temperature of ;770 C, respectively. The rocking curve
width of the ~0002! reflection of ZnO in as-deposited films
was measured to be 0.16 whereas the rocking curve width
of the ~0006! peak of sapphire was 0.09. The ZnO film
deposited at the substrate temperature of 750 C showed the
rocking curve width of 0.17. These are some of the best
results in the literature, as shown by XRD. The consistent

II. EXPERIMENT

The ZnO films with the thickness of ;250 nm were

synthesized by ablating a sintered zinc oxide target with a
pulsed excimer laser ~l5248 nm, pulse width525 ns! with
0021-8979/98/84(5)/2597/5/$15.00

2597

1998 American Institute of Physics

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2598

J. Appl. Phys., Vol. 84, No. 5, 1 September 1998

Narayan et al.

FIG. 1. ~a! X-ray diffractogram from ZnO film deposited at the substrate
temperature of ;790 C; ~b! XRD scan of the AlN/ZnO/a-Al2O3 heterostructure with the AlN film deposited at the optimized temperature
;770 C.

results were obtained from several optimized films. The AlN

film @Fig. 1~b!# was found to be epitaxial c-axis oriented. As
can be seen in the diffractogram, there are no other orientations except the (000l) reflections of ZnO and AlN films.
However, the AlN films deposited on ZnO/a-Al2O3 heterostructures at the substrate temperatures of 700, 740, and
800 C were found to be highly textured polycrystalline.
The ZnO/a-Al2O3 and AlN/ZnO/a-Al2O3 thin film heterostructures were investigated to determine the nature of
defects and interfaces and assess their potential for device
applications. Figure 2~a! shows a plan-view TEM micrograph of a ZnO/a-Al2O3 film under two-beam diffraction
21
0). The selected area diffracconditions with vector g5(1
tion ~SAD! pattern from an area about 0.5 mm in diameter
containing both the film and the substrate is shown in Fig.
2~b!. The SAD pattern was taken along the film and substrate
0 #
normal @0001# where the arrows indicate @ 011
ZnO and

@ 1210 # sap reflections. Additional weaker spots visible in the

SAD pattern arise from the double diffraction of the substrate and the film. From diffraction patterns, we determined
the following epitaxial relationship between the film and the
0 # i@1
21
0# , and
substrate: (0001) ZnOi~0001!sap , @ 011
ZnO
sap

FIG. 2. ~a! Plan-view ~0001! TEM image of ZnO film taken under g
21
0) two-beam conditions. ~b! Selected area diffraction pattern of ZnO
5(1
epilayer and sapphire substrate taken in the @0001# direction of both the film
0)

and the substrate, (011
ZnO and (1210) sap reflections are indicated by arrows.

0 # i@011
0# . This relationship corresponds to a 30
@ 121
ZnO
sap
in-plane rotation of the film with respect to the substrate.
This 30 rotation strongly suggests that the epitaxial relationship is dictated by AlO bonding at the interface. The epitaxial relationship is the same as that for group III-nitrides
grown on ~0001! sapphire substrate.10 This rotation leads to
0) ~spacing 2.814 ! planes of ZnO
an alignment of (011

with (1210) planes ~spacing 2.379 ! of sapphire. Under

these conditions seven planes of sapphire match with six
planes of ZnO. Thus, the epitaxial growth of ZnO on
a -Al2O3 is controlled by domain matching epitaxy11,12
~similar to the growth of group III nitrides on sapphire10!
where integral multiples of planes or lattice constants match
across the interface.
Figures 3~a! and 3~b! show cross-section TEM images
0)
using diffraction vectors g5(011
ZnO and g5(0002) ZnO

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J. Appl. Phys., Vol. 84, No. 5, 1 September 1998

FIG. 3. Cross-section TEM images of AlN/ZnO/a-Al2O3 heterostructure

10 #

near the @ 21
ZnO zone. ~a! Image was taken under g5(0110) ZnO twobeam conditions. Arrows indicate stacking faults. ~b! Image was taken under
g5(0002) ZnO . Arrows point the inversion domains in ZnO.

where defects and the interface between the ZnO film and the
substrate are clearly delineated. Most of the defects in the
film are dislocations and planar defects ~stacking faults indicated by white arrows! which align along the basal ~0001!
planes. The threading dislocation density decreases rapidly
with the distance from the interface. Their density near the
interface ~first 100 nm! can be estimated as 2.0
31010 cm22 whereas at the top of the ZnO film the density
drops to about 107 cm22 . This value is several orders of
magnitude lower than the typical values (109 1010 cm22 ) in
group III-nitride films.13,14
The density of planar defects (;105 cm21 ) is quite high
in the ZnO film and decreases only by a factor of 3 in the top
region of the film. The origin of these defects is likely due to
some nonstoichiometry of the film, which results in the fault
nucleation at the ~0001! terraces. These defects were found
to be mostly low-energy I 1 stacking faults having a single
stack of fcc sequence. The average width of the stacking
faults is 100 nm giving rise to a partial dislocation density of
approximately 1010 cm22 . The value of 1010 cm22 can be
obtained using a plan-view micrograph, Fig. 2~a!, which
shows the projection of the entire ZnO film.
A remarkable feature of the observed dislocation configuration is that most of the dislocations lie in the basal
plane. This is opposite to the case of group III-nitride films
where the majority of the dislocation lines are normal to the
~0001! plane and constitute low-angle sub-boundaries and
columnar film morphology.14 However, as in the nitride
films, the contrast from most of the dislocations in ZnO
cross-sectional specimens disappear when the scattering vector is g5(0002) @Fig. 3~b!#, indicating that the Burgers vectors are parallel to the basal plane. Therefore, perfect dislo 0 # Burgers vector, as the majority of
cations have a 1/3@ 112

Narayan et al.

2599

dislocations in the group III-nitride films. The micrographs

in Figs. 2 and 3 reveal numerous dislocation reactions in the
dislocation network. The main result of these reactions is the
decrease of the threading dislocation density with the film
thickness.
We have also observed the formation of small inversion
domains at the ZnO/sapphire interface. These domains are
indicated by arrows in the micrograph taken with g
5(0002) ZnO @Fig. 3~b!#. The inversion domains are domains
having the crystal polarity opposite to that of the matrix
material.15 ZnO is a polar crystal and, therefore, the direc are not equivalent ~the direction of the
tions 0001 and 0001
atomic bond is from Zn to O or from O to Zn, respectively!.
To prove the inversion nature of these domains we used a
0 # zone
multiple beam dark-field technique16 in the @ 112
axis. The contrast from the domains was inverted in the im in this
ages taken using opposite reflections ~0002 and 0002
case!, which is a characteristic feature of the inversion domains. The domains nucleated at the interface and had the
thickness of about 15 nm and the lateral dimensions of ;30
nm. The polarity of the growing film is an important issue
since, for example, in group III nitrides the characteristic
features are columnar-looking inversion domains sometimes
going through the entire film thickness.14,17 Also, the surface
roughness seems to be dependent on the crystal polarity in
the case of GaN crystals18 and thin films.19 If the ZnO films
are to be used for the subsequent IIIV nitride growth, the
polarity of the ZnO can influence significantly the polarity
and final quality of the growing nitride layer. Using convergent beam electron diffraction, we determined the polarity of
our ZnO films to be Zn terminated ~the direction of the bond
along c axis is from Zn to O!. Further implications of these
on defect characteristics are being studied.
High-resolution TEM studies were carried out to investigate the nature of the interfaces between ZnO/a-Al2O3 .
10 # i@101
0#
The micrograph taken in @ 21
ZnO
sap zone axes
@Fig. 4~a!# clearly shows that the ZnO/a-Al2O3 interface is
atomically sharp with no mixed layer near the interface. The
misfit dislocations are also visible at the interface and con10) plane of sapphire ~on
stitute the array when every 7th (21
average! terminates at the interface. The nature of domain
epitaxy is clearly illuminated in Fig. 4~b!, where there is a
missing plane in the film after every six to seven planes. This
Fourier-filtered image also shows that most of the dislocations during domain epitaxy are formed during the initial
stages of film growth and are confined to the interface region.
In the second part of this study, we investigated the
growth characteristics of IIIV nitrides on ZnO/a-Al2O3
substrates. Since AlN and ZnO lattice constants are closely
matched within 4.0% ~as shown in the Table I!, we expect a
lattice matching epitaxy between the AlN film and ZnO substrate as opposed to a domain matching epitaxy between the
ZnO film and a -Al2O3 substrate. Figure 5~a! shows a crosssection TEM micrograph of the AlN/ZnO/a-Al2O3 heterostructure. From the diffraction pattern containing AlN/ZnO
interface @Fig. 5~b!#, we determined that AlN grows on ZnO
without any rotation. We also observed a 3060--wide

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J. Appl. Phys., Vol. 84, No. 5, 1 September 1998

FIG. 4. ~a! High resolution TEM cross-sectional image of the ZnO film near
the film/substrate interface ~shown by black arrows!. The terminating planes
corresponding to the misfit dislocations are indicated by white arrows. ~b!
0 % i$112
0% reflexes showing
Fourier-filtered image using opposite $ 101
ZnO
sap
the match of the corresponding planes. Misfit dislocations at the interface
are indicated. Numbers in the bottom of the picture correspond to the number of planes between the misfit dislocations. Note that every 7th or 6th
10) plane of sapphire terminates at the interface.
(21

mixed layer at AlN/ZnO interface. This reacted layer is polycrystalline. From the diffraction pattern analysis and the calculation of power spectra of high-resolution images, we determined the structure of the layer to be spinel ZnAl2O4 (a
58.0848 ). The polycrystallinity of the layer and the fact
that AlN maintains expected epitaxial relationships with the
ZnO substrate indicate that the spinel layer was most probably formed as a result of a reaction after AlN has already
grown to a certain thickness. Therefore, initial epitaxial
growth of AlN is not affected by this reaction. The surface of
the ZnO layer is rough which can be seen in Fig. 5~b!. Despite that, the AlN film showed good crystallinity and epitaxial growth near 770 C. However, the films grown at
700740 C and at 800 C were polycrystalline. We envisage that below this temperature the crystallinity of the film

TABLE I. Lattice constants and thermal expansion coefficients of sapphire,

ZnO, and AlN.

Material

a -Al2O3
~R-3c, hexagonal!
ZnO
~P6 3 mc, hexagonal!
AlN
~P6 3 mc, hexagonal!

Lattice
constant,
a54.758
c512.991
a53.249
c55.206
a53.111
c54.979

Thermal expansion
coefficient, 1026 /K
7.5
8.5
2.9
4.75
4.2
5.3

Narayan et al.

FIG. 5. ~a! Cross-sectional TEM micrograph of the AlN/ZnO/a-Al2O3 heterostructure taken under g50002 two-beam conditions. Columnar morphology of the AlN layer is clearly visible. ~b! SAD patterns of
10 #
AlN/ZnO/a-Al2O3 heterostructure taken in the @ 21
ZnO zone.

becomes poor due to insufficient adatom mobility causing

the random nucleation whereas at higher temperatures interfacial reaction between AlN and ZnO creates a polycrystalline mixed layer which leads to formation of polycrystalline
AlN films. The predominant defects in the AlN films are
0 # Burgers vector
threading dislocations with the 1/3@ 112
aligned normal to the basal plane with a density of
;1010 cm22 . These dislocations result from the columnar
morphology of the film. Further studies are needed to completely understand the role of the interfacial reaction and to
optimize the growth conditions ~including the elimination of
ZnO surface roughness! to obtain higher quality AlN films.
The electrical resistivity measured at room temperature
for the ZnO films is in the range of 58 V cm for as-grown
films which is two orders of magnitude higher than that obtained by other researchers9 for their high quality films. This
points towards better stoichiometry of the films grown in our
work. Zinc oxide is known20 to grow with nonstoichiometry
having oxygen vacancies. However, it may be possible to
improve stoichiometry and also reduce defect density by
postannealing the films in O2 . Our recent experiments before
and after annealing show a substantial improvement in the
optical properties of ZnO films21 as well as an increase of
resistivityup to 53102 V cm. We were able to resolve
three exciton resonances in the optical transmission spectra

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Narayan et al.

J. Appl. Phys., Vol. 84, No. 5, 1 September 1998

of the annealed films. The determination of valence band

splitting, exciton binding energies, and band gaps at 77 and
300 K clearly show these films to be comparable to highquality bulk single crystals.
IV. SUMMARY

We have grown high-quality epitaxial ZnO films on

~0001! sapphire. A 30 rotation of the ZnO film with respect
to the a -Al2O3 substrate is similar to the growth of group III
nitrides on a a -Al2O3 substrate. This rotation is dictated by
the oxygen sublattice in sapphire which matches with the Zn
sublattice in the ZnO film. The predominant defects in the
ZnO film were found to be dislocations, planar defects
~stacking faults!, and inversion domains. Most of the dislocations lie in the basal plane giving a layered growth morphology contrary to the group III-nitride films having columnar morphology. The density of threading dislocations in
0 # ! decreases with the film
ZnO ~Burgers vector 1/3@ 112
thickness giving a value of about 107 cm2 for the 250 nm
thickness. This is considerably lower than encountered in
thin films of group III nitrides which are around
109 1010 cm22 . Epitaxial AlN films were grown around
770 C on a ZnO/a-Al2O3 substrate showing no rotation of
the crystal lattice of AlN with respect to ZnO. At these
growth temperatures, an interfacial reaction creates a polycrystalline layer whose effect has to be minimized to obtain
high-quality epitaxial AlN films.
ACKNOWLEDGMENTS

This research was supported by the National Science

Foundation under the Center for Advanced Materials and

2601

Smart Structures. We acknowledge useful discussions with

Dr. R. D. Vispute.
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