High quality crystalline ZnO buffer layers on sapphire (001) by pulsed laser

deposition for IIIV nitrides

R. D. Vispute,a),b) V. Talyansky, Z. Trajanovic, S. Choopun, M. Downes, R. P. Sharma,
and T. Venkatesanc)
Center for Superconductivity Research, Department of Physics, University of Maryland, College Park,
Maryland 20742

M. C. Woods, R. T. Lareau, and K. A. Jones

Army Research Laboratory, AMSRL-PS-DS, Fort Monmouth, New Jersey 07703

A. A. Iliadis
Department of Electrical Engineering, University of Maryland, College Park, Maryland 20742

~Received 24 January 1997; accepted for publication 19 March 1997!

ZnO thin films with near perfect crystallinity have been grown epitaxially on sapphire ~001! by
pulsed laser deposition technique. The v-rocking curve full width at half-maximum of the ZnO~002!
peak for the films grown at 750 C, oxygen pressure 1025 Torr was 0.17. The high degree of
crystallinity was confirmed by ion channeling technique providing a minimum Rutherford
backscattering yield of 2%3% in the near-surface region (;2000 ). The atomic force
microscopy revealed smooth hexagonal faceting of the ZnO films. It has been possible to deposit
epitaxial AlN films of thickness 1000 on epi-ZnO/sapphire. Excellent crystalline properties of
these epi-ZnO/sapphire heterostructures are, thus, promising for lattice-matched substrates for IIIV
nitride heteroepitaxy and optoelectronics devices. 1997 American Institute of Physics.
@S0003-6951~97!02620-X#
Recent progress in IIIV nitride growth has enabled the
fabrication of high intensity blue light-emitting devices. Ga
AlIn nitrides are currently grown by heteroepitaxy on a
number of substrates16 including sapphire, SiC, MgAl2O4,
and MgO. Despite its poor structural and thermal match to
GaN, sapphire has been a substrate material of choice due to
its low cost, availability in large area wafer, and its wide
energy band gap. However, as-grown nitride films on sapphire are known to contain a high density of defects7 ~mainly
threading dislocations!, which affect both electrical and optical properties of the devices.8 In this context, ZnO is an
interesting buffer layer material for GaN,1,4,9,10 possessing
the following advantages: ~i! it is a wide band-gap ~3.3 eV!
semiconductor with crystalline properties ~wurtzite structure,
a53.25 , and c55.20 ! similar to those of GaN ~lattice
mismatch ;2%!, ~ii! it is highly transparent ~85%95%! in
the visible region, and ~iii! it can be grown epitaxially on c-,
a-, and r-plane sapphire, and hence, epi-ZnO/sapphire can be
useful as a lattice-matched semiconducting substrate for
GaN. For example, Akasaki et al.10 have employed sputter
ZnO buffer layers on sapphire for GaN. Hamdani et al.11
have reported high quality GaN films on bulk ZnO crystals
due to a near match of both lattice parameters and stacking
order between GaN and ZnO.
To date, ZnO thin films have been prepared by various
deposition techniques, such as chemical-vapor deposition
~CVD!,12 sputtering,13 and pulsed laser deposition
~PLD!.1417 Although growth of well-textured c-axis ~without in-plane alignment! and epitaxial films on various substrates have been well documented in the literature,4,9,10,1217
a much superior quality of the ZnO films is required for GaN
buffer layer application. Here, we report on the growth of
a!

Electronic mail: Vispute@squid.umd.edu

Also at Department of Materials and Nuclear Engineering.
c!
Also at Department of Electrical Engineering.
b!

high quality single-crystal ZnO films on sapphire ~001! by

PLD.
Details of our PLD system can be obtained elsewhere.18
In brief, a KrF excimer laser ~l5248 nm, t 525 ns! was
used for ablation of a commercially available, hot pressed,
stoichiometric ZnO ~99.99 purity! target. The beam was focused to produce an energy density of ;2 3 J/cm2. The
films were deposited on sapphire ~001! at a repetition rate
ranging from 10 to 15 Hz, for 10 to 15 min. In this study,
5005500 thick ZnO films were deposited at the substrate
temperature (T s ) range of 300800 C, under an oxygen
(O2) pressure of 1025 1022 Torr. The average growth rate
was found to be ;0.9 /pulse. The crystalline quality of
ZnO layers was evaluated using four-circle x-ray diffraction
~XRD!, and Rutherford backscattering spectroscopy ~RBS!/
ion channeling using well-collimated 1.5 MeV He1 ions.
The surface morphology and optical properties were studied
by atomic force microscopy ~AFM! and UV-visible spectroscopy, respectively.
The critical parameters for the fabrication of highly crystalline ZnO films are found to be the deposition temperature,
pulse repetition rate, and O2 pressure. The ZnO grows epitaxially at T s as low as 300 C, however, the crystalline quality of the films improves with increasing T s , up to 800 C.
The XRD Q2Q angular scans of the films deposited in
the range of processing parameters @see Fig. 1~a!# show only
the $ 00l % family of planes of ZnO and sapphire, indicating
that the films are highly c-axis oriented. The rocking curves
for the ;600 and 5500 thick films grown at 750 C are
shown in Fig. 1~b! and the FWHM are given in Table I. The
narrowest rocking curve FWHM was 0.17 for the films
grown at 750 C, and in the O2 pressure of
1025 1024 Torr, indicating an excellent alignment of
(00l) lattice planes with that of sapphire ~001!.
The in-plane alignment of the films for various T s , O2
pressures, and deposition rates were obtained using F scans,

Appl. Phys. Lett. 70 (20), 19 May 1997

0003-6951/97/70(20)/2735/3/$10.00
1997 American Institute of Physics
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FIG. 2. Random and aligned Rutherford backscattering spectra of an epitaxial ZnO film on sapphire.

FIG. 1. XRD results of the PLD ZnO films grown at various conditions: ~a!
and ~b! are the Q2Q scan and rocking curves for the films grown at
750 C, and in the O2 pressure of 1025 Torr, and ~c! and ~d! are the F scans
of the ZnO ~101! family reflections of the films grown at T s 5500 C with a
pulse repetition rate of 15 Hz, and T s 5750 C, with a pulse repetition rate
of 10 Hz, respectively.

and the results are shown in Figs. 1~c! and 1~d!. The film
prepared at 500 C with the pulse repetition rate of 15 Hz
showed 12 broadened peaks @Fig. 1~c!#, indicating two inplane orientations with a 30 rotation of the unit cells with
respect to each other. A perfect alignment with a single inplane orientation is achieved for the films grown at T s of
750 C and a pulse rate of 10 Hz @Fig. 1~d!#. The increase of
surface mobility of the adatoms at the high growth temperature is responsible for improvement of the film alignment.
The in-plane epitaxial relationship was found to be
0#iAl O @112
0#, indicating a 30 rotation of the
ZnO@101
2 3
ZnO unit cell with respect to the sapphire, which is similar to
that of AlN and GaN on sapphire.1,5,6 The optimum O2 pressure regime was found to be ranging from
1025 1024 Torr.
The epitaxial quality of the PLD ZnO films were investigated by the ion channeling technique. The ratio of the
backscattered yield with the 1.5 MeV He1 beam incident
along @001# ~channeled! and random directions, respectively,
reflects the epitaxial quality of the film, and was found to be
strongly dependent on growth temperature. This ratio

@x min# decreases with an increase of T s above 600 C. It is

interesting to note that the XRD-v and F scans for the films
grown at 600 C show epitaxial nature with good crystalline
properties ~Table I!. However, the RBS channeling was poor,
indicating that the films had low-angle grain boundaries. Figure 2 shows the aligned and random backscattering spectra
for a 5500 epitaxial ZnO film deposited at 750 C. The
aligned spectra show a large reduction of the backscattered
yield in the film. The minimum yield near the surface region
is ;2%, indicating high quality epitaxy of the ZnO film on
sapphire ~001!. Due to a large lattice mismatch between the
film and the substrate ~16.7%!, one would expect a large
density of misfit dislocations to be observed within the first
few hundred angstroms from the interface. Our channeling
results, as shown in Fig. 2 ~aligned spectra!, clearly indicate
an increase of minimum yield up to ;10% near the interface
region, suggesting the presence of displaced Zn atoms close
to the interface. The XRD-rocking curve for the ;600
thick film also supports these findings. The increase of
FWHM for the thinner film is in accordance with the increase of disorder near the interface.
Figure 3 shows an AFM image of the epitaxial ZnO film
grown at T s of 750 C and O2 pressure of 131025 Torr.
The hexagonal terraces with a high density of atomic steps
observed on the surface of the film may be useful for a subsequent epitaxial growth of GaN. The surface features can be
controlled as a function of T s and O2 pressure. The optical
properties of these films were studied by UV-visible spectroscopy and the results are shown in Fig. 4. An average
transmission of 90% in the visible region with a sharp ab-

TABLE I. The characteristics of the epitaxial ZnO films grown by PLD on sapphire at various T s , O2 pressure
of 1025 Torr, and a pulse repetition rate of 10 Hz. For comparative studies, the crystalline properties of
commercially available MOCVD GaN on sapphire ~001! are also presented.

Heterostructure
ZnO/sapphire
ZnO/sapphire
ZnO/sapphire
ZnO/sapphire
GaN/sapphire
Al2O3 ~001!

Lattice mismatch
16.74%
16.74%
16.74%
16.74%
14.79%

Film
thickness

Growth
temperature

v-curve
FWHM

DF
FWHM

x min

5000
5500
5500
600
15 000

400 C
600 C
750 C
750 C
.1000 C

0.85
0.48
0.17
0.25
0.16
0.12

3.1
1.1
0.41
0.86
0.43
0.34

Not channeled
60%70%
2%3%
10%12%
2%3%
;2%

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Appl. Phys. Lett., Vol. 70, No. 20, 19 May 1997
Vispute et al.
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FIG. 5. XRD Q2Q and F ~inset! scans of the PLD AlN on epi-ZnO/
Sapphire ~001! grown at T s 5750 C, indicating epitaxial growth of AlN.

FIG. 3. Phase mode AFM image of epitaxial ZnO film grown at 750 C,
O2 pressure of 1025 Torr, and a pulse repetition rate of 10 Hz. With its
infinite depth of focus, the phase mode allows one to see very fine surface
features irrespective of their topological height.

sorption edge at 383 nm was achieved in the epitaxial ZnO

films. We could also observe the peak in the absorption spectrum due to the existence of a possible excitonic state.19 The
plot of the absorption coefficient versus photon energy in the
region of high optical absorption showed an optical band gap
of 3.3 eV, which is the same as that of a single-crystal ZnO.
We have explored the epi-ZnO/sapphire substrate for
growth of AlN. The AlN films (;1000 ) were also deposited by PLD. Figure 5 shows XRD patterns of AlN film on
ZnO grown at T s 5750 C. The films were found to be epitaxial with the v-rocking curve FWHM of 0.23, which is
lower by 40%50% than that of AlN film grown on sapphire
under identical conditions.6 The RBS studies showed that
there is no severe reaction between AlN and ZnO at the
interface. The minimum yield for AlN film was
;60% 70% and could improve upon optimization of nitrides. It should be noted that the growth of nitrides by PLD
is relatively new and may, in time, yield more superior materials. The metalorganic chemical-vapor deposition
~MOCVD! and molecular beam epitaxy are matured tech-

FIG. 4. Optical transmission and absorption spectra of an epitaxial ZnO film

grown on sapphire at 750 C, O2 pressure of 1025 Torr, and a pulse repetition rate of 10 Hz.

niques and may benefit from utilizing epi-ZnO/sapphire for

growing GaN.
In conclusion, ZnO films with high crystalline and optical quality have been grown on sapphire by PLD. The films
deposited under the optimized growth conditions exhibited
FWHM, DF, and x min of 0.17, 0.41, and 2%, respectively.
The optical transparency in the visible region and the energy
gap were 90% and 3.3 eV, respectively. Our results clearly
indicate that these films provide a suitable host lattice for
epitaxial growth of AlN and could be useful for heteroepitaxy of GaN and future optoelectronics devices on sapphire.
The authors thank Dr. J. T. Cheung of the Rockwell
International Science Center for useful discussions and
Mathew Stanton and R. Shreekala for technical assistance.
This work was supported with a MRCP Army Grant, No.
DAAL 019523530.
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Vispute et al.
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