44629

Abstract
ZnO buffer layers with different thicknesses were deposited on a-plane sapphire
substrates at 300 C. ZnO epilayers were grown on ZnO buffers at 600 C by
radio-frequency magnetron sputtering and vacuum annealed at 900 C for an
hour. Influence of nucleation layer thickness on the structural and quality of
ZnO thin films were investigated using X-ray diffraction (XRD), atomic force
microscopy (AFM), and Raman spectroscopy. The highest ZnO film quality was
obtained with a ZnO buffer layer of 45 nm thick which provided the smoothest
surface with RMS of 0.3 nm. In addition, the micro-Raman scattering
measurements at room temperature revealed the existence of Raman active
phonon modes of ZnO; A1(TO), A1(LO) and E2(high). The latter two were not
observed at thin buffer layer beside the disappearance of E 2(low) in all films
which confirms the quality of the prepared films ( E2(low) is related to
crystalline defects).

Introduction
ZnO has attracted attention as a wide band gap semiconductor (Eg= 3.37
at room temperature). Moreover, It is non-toxic, chemically stable, low cost in
production, commercially available with large area single crystal ZnO
substrates, piezoelectric, and bio-compatible [1, 2].It is widely used in the
development of thin film transistors, transparent conductors, gas sensors, photodetectors, window layer for solar cells, micro sensors, photo-catalysts, dilute
magnetic semiconductors (DMS), and ultra-violet/blue emission devices [3, 4].
ZnO is more efficient in optoelectronic applications than GaN [5], since, ZnO
has a larger exciton binding energy of 59 meV and the promising exciton
oscillating strength Of ZnO micro cavity structure [7]. However, the epitaxial
growth of ZnO films have been grown by a variety of methods, such as
chemical vapor deposition CVD [12], MOCVD [13], MBE [11], [17-21] pulsed
laser deposition PLD [8], and sputtering. Economically, sputtering method can
provide wide area films with well controlled composition. Despite these
advantages, there are still some problems associated with sputtering. The
properties of the sputtered films are not comparable to high vacuum techniques,
regarding to the film quality and roughness which do not match the
requirements of optoelectronic devices.
It is well known that different substrates can be used to grow high quality
ZnO films, like ZnO substrates [22], ScAlMgO4 [5], GaN [11], AlN [23]and

Al2O3 [24]. Due to the cost of ZnO substrates, high-quality ZnO buffer layers
on other substrates are of particular interest. Al2O3 is one of the most
extensively adopted substrates for the growth of ZnO epilayers because of its
hexagonal symmetry, commercial availability, low cost, and

the lattice

mismatch between -plane sapphire substrate and ZnO is small (0.08%). Some
of the recent reports were concerned about the growth of ZnO films on a buffer
layer using different substrates Si, GaN template,,,,,,,,,,,,, and c-plane sapphire.
In a previous study, we succeeded in the growth of high quality ZnO films
on -plane sapphire substrate [2], and found that the quality of the films were
improved on a particular growth conditions (deposition temperature of 600 C
and vacuum annealing at 900 C).Unfortunately, Due to the difference in
thermal expansion coefficients between ZnO and Sapphire substrate
(ZnO=6.51106K1 and Sapphire=8.00106K1), strain will be generated under the
high temperature growth conditions. Chen et al. demonstrated that introduction
of low temperature buffer layer followed by a growth step at high temperature
can relax the grown films. . Through this method a densely packed ZnO film
with larger grains and well-aligned crystallographic orientation can be obtained
[12]. Y. J. Chen, et.al Effect of temperature on lateral growth of ZnO grains
grown by MOCVD,

In the present study, the influence of buffer layer thickness on the structural,
crystalline perfection and surface characteristics has been investigated to find
out the optimum growth conditions.
2. Experimental
The substrates were cleaned using organic solvents and rinsed in DIwater.
ZnO buffer with different thicknesses of 15, 25, 30, and 40nm were directly
deposited at temperature of 300C on a plane sapphire substrate. After thermal
annealing of buffer layer at 0000Cfor 0000min, 150nm thick ZnO thin films
were grown by rf magnetron sputtering, using radio frequency source (RF,
13.56MHz). Growth temperature of 600 C were obtained by SiC heater. The
films deposited at working pressure of 510 -4Torr, background pressure of
210-6Torr, radio frequency power of 700W and a bias voltage of -360V. ZnO
target (99.999) with 5.1 diameter has been used. High purity Ar (99.999),
O2(99.9999) with Ar to O2 ratio of (Ar/O2=4/1) were selected and the flow rate
was controlled by mass flow controller. The growth chamber was backed at 800
C and pre-sputtering of the target was performed to remove contaminations. In
situ high temperature vacuum annealing of ZnO films was conducted for an
hour at 900 C .
XRD measurements were performed using Burker-D8 diffractometer with
Cuk radiation. The characterizations were extended to study the roughness and
surface morphology of the deposited films using AFM in non-contact mode. To

find out the local vibration modes, Raman spectroscopy measurements at room
temperature, Micro-Raman spectroscopy system (Model Renishaw system
2000) with Ar+ laser at wavelength of 488 nm with power of 100 mW has been
used.

3. Result and discussion

ZnO thin films were grown on a-plane sapphire substrate at growth
temperature of 600 C by RF magnetron sputtering. Different thickness of
buffer layers (tb= 15, 30, 45 and 60 nm) were pre-deposited at relatively low
temperature of (300 C). The crystalline quality of ZnO epilayers was identified
by Raman spectroscopy measurements. Wurtzite ZnO belongs to the C6v
symmetry group and According to the selection rules, the Raman active phonon
modes E2(low), E2(high), A1(TO) , A1(low) , E1(TO) and E1(low) are expected to be observed in
un-polarized Raman spectra [29]. The room temperature Raman spectra of the
grown ZnO films on different thicknesses of buffer layers is shown in Fig. 1.
ZnO phonon peaks at 380.5, 577 and 441 is assigned to A1(TO) ,A1(LOW) , and E2H
respectively. E2H phonon mode is the characteristic mode for hexagonal ZnO
and the low intensity of E2H at 441 cm-1 indicates the small stress after inserting
low temperature ZnO buffer layer. It relaxes the grown ZnO epilayers, in spite
of the difference in the thermal coefficients between sapphire and zinc oxide
[35]. However, the longitudinal optical mode A1(LO) at 577 cm-1 and E2H at
441cannot be observed at thin buffer layers(tb=15 nm).Therefore, the distinct
ZnO Raman active phonon modes were observed only after introducing an
appropriate thick buffer layer. The other peaks at 418, 647 cm-1 were attributed
to the A1g of Al2O3 substrate beside Eg phonon modes of sapphire at 430 and 750
cm-1 [32, 33]. On the other hand, The disappearance of E 1(LO) at 590cm-1 in all

samples indicates that the commonly detected defects in ZnO films like zinc
interstitials, oxygen vacancies, are so little in our samples have [30, 31,34,35].
3. 2. Atomic Force Microscope (AFM) Measurements.
AFM measurements were used to identify the roughness and surface
morphology of the grown films. AFM images over the scanned size of
2m2m are shown in Fig. 3. Clearly, from the AFM images of Fig.3(a), Assupplied sapphire substrates has a smooth surface. Fig. 3(b,c) shows that, the
grains assemble close to each other and its size increase from

to

nm with

increasing the thickness of the buffer layer from 15 to 30 nm, but pits can be
observed. The coalescence among adjacent grains, facilitates the formation of a
flat and dense surface. The AFM pattern exhibits a smoother surface after
introducing 45nm buffer layer and a detectable reduction in z height to 3nm,
with respect to the ZnO thin films on other different thicknesses of buffer
layers.As can be seen in Fig. 1e, as the thickness of buffer layer increases, small
grains can be observedand the disappearance of the above mentioned pits.
Unexpected feature was detected in Fig 1e, as the thickness of buffer layer
increases to 60nm,small grains can be observed and the disappearance of the
above mentioned pits. However, the influence of pre-deposition of homo-buffer
layers on root mean square (rms) surface roughness is shown in fig.1f.
Thedependence of surface morphology on buffer layer thickness indicates that,
the buffer layer facilitates the ZnO film nucleationand growth. Therefore, during

the consequent film deposition, the lateral growth of ZnO is promoted, which
leads to the improvement of surface morphology. Surface migration of adatoms
at distinct thickness of buffer layer (an extremely flat surface) resulted in high
quality ZnO crystals on sapphire.
Fisher et al. reported that From a thermodynamic viewpoint, grain boundaries
are not stable, the coalescence of grains is driven by a reduction in surface
energy which force them to stretch and unite together when sufficient energy is
supplied[28].
28] I.M. Fisher, D.A. Smith, Textures Microstruct. 13 (1991) 91

For further insight into the quality of ZnO epilayers, XRD measurements
were investigated. XRD patterns of ZnO films grown on different thicknesses of
ZnO buffer layers are shown in Fig. They are similar with only sharp and high
intensity ZnO 0002 peak in addition to the substrate peak,no extra
diffractionpeaks wereobserved. This indicates that ZnO films are single
phasewurtzite structure andthe preferred crystal orientation was along the caxis. However, there were no detectable changes in peak positions, but a change
in FWHM can be observed. Fig shows that there is a remarkable change in
FWHM of q-2q scan with increasing the buffer layer thickness The full-width at
half-maximum (FWHM) of the (00 0 2) ZnO peakis less than ,,,for all the films.
The ZnO buffer layer with thickness of 30 nm shows the smallest FWHM.

The full-width at half-maximum of XRC for thesymmetric (0 0 0 2) diffraction

is related to the density of screw type threadingsdislocations which implies the
in-plane mosaic misorientation (tilt) for the ZnO films.After introducing the
buffer layers, the Crystalline quality was evaluated from the (0 0 0 2) ZnOyrocking curve as shown in Fig. .The extremely narrow width ( ) of thefull width
at half maximumof the (0002) rocking curve implying little tilt in the c planes
which confirm the perfect ordering along c-axis of ZnO.

Conclusion
In this paper, we made a systematic study of the
influence of the buffer layer thickness on the crystal structure and quality of
ZnO films. In order to improve the film quality, a low temperature buffer layers
with different film thickness were deposited before the growth of ZnO films.All
the films were smooth and rms values extended from to,,,.The highest ZnO film
quality was obtained with a 30 nm thick ZnO buffer layer and the
surfaceroughnesswas 5.47 nm
X-ray diffraction measurements reveal that the films have a single-phase
wurtzite structure with 0001 preferred crystal orientation. As evident from
narrow FWHM of ZnO(0 0 0 2)o-rocking curve, ZnOlayer can serve as a good
template for the growth of high-quality ZnO films with little tilt. Introducing a

thin ZnO buffer layer plays an important role in preventing screw dislocations
and very effectiveon the improvement of surface morphology during the initial
growth stage, which eventually leadsto an atomically flat surface

Figure caption
Fig. 1. XRD patterns of ZnO films with different buffer layer
thicknesses: (a) no buffer layer; (b) 5 nm; (c) 15 nm; (d) 25 nm;
(e) 40 nm; and (f) 55 nm.

RAMAN SCL [24] J.D. Ye, S. Tripathy, F.F. Ren, X.W. Sun, G.Q. Lo, K.L. Teo,
Appl. Phys. Lett. 94
(2009) 011913.
[25] H.F. Liu, N. Xiang, S. Tripathy, S.J. Chua, J. Appl. Phys. 99 (2006) 103503

Ref
[2] I. Vallsa, M. Cantu, ENERGY & ENVIRONMENTAL SCIENCE 2
(2009) 19-34.

[1] D. C. Look, J. W. Hemsky, and J.R. Sizelove, Phys. Rev. Lett. 82

(1999) 2552.