Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 149 (2015) 127–131

Contents lists available at ScienceDirect

Spectrochimica Acta Part A: Molecular and

Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa

Influence of homo buffer layer thickness on the quality of ZnO epilayers

E.A. Eid a, A.N. Fouda b,⇑
a
Department of Basic Science, Higher Technological Institute, 44629 10th of Ramadan City, Egypt
b
Physics Department, Faculty of Science, Suez Canal University, 41522 Ismailia, Egypt

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Low temperature ZnO buffer layer Raman spectra of ZnO films on homo buffer layer with different buffer thickness.
with different thickness.
 High temperature vacuum annealed
A1(LO)
A1(TO)

E2H
A1g

tb= 60nm
Eg
A1g
INTENSITY (arb. units)

ZnO epilayers.
 c-Axis oriented and single phase ZnO
tb= 45nm
films.
 Smooth surface, little tilt and active
phonon modes confirm the epilayers tb= 30nm
quality.
tb= 15nm

400 600 800 1000 1200

-1
WAVE NUMBER(cm )

a r t i c l e i n f o a b s t r a c t

Article history: ZnO buffer layers with different thicknesses were deposited on a-plane sapphire substrates at 300 °C. ZnO
Received 11 December 2014 epilayers were grown on ZnO buffers at 600 °C by radio-frequency magnetron sputtering and vacuum
Received in revised form 10 March 2015 annealed at 900 °C for an hour. Influence of nucleation layer thickness on the structural and quality of
Accepted 27 March 2015
ZnO thin films was investigated using X-ray diffraction (XRD), atomic force microscopy (AFM), and
Available online 21 April 2015
Raman spectroscopy. The best ZnO film quality was obtained with the ZnO buffer layer of 45 nm thick
which provided the smoothest surface with RMS value of 0.3 nm. X-ray diffraction measurements reveal
Keywords:
that the films have a single phase wurtzite structure with (0 0 0 1) preferred crystal orientation. As evident
ZnO films
Buffer layer
from narrow FWHM of ZnO (0 0 0 2) rocking curve, ZnO buffer can serve as a good template for the growth
Raman spectroscopy of high-quality ZnO films with little tilt. In addition, the micro-Raman scattering measurements at room
AFM temperature revealed the existence of Raman active phonon modes of ZnO; A1(TO), A1(LO) and E2(high).
Threading dislocation The latter two modes were not observed in thin buffer layer beside the dis-appearance of E2(low) mode
in all films.
Ó 2015 Elsevier B.V. All rights reserved.

Introduction available with large area single crystal substrates and possess
piezoelectric and bio-compatible properties [1,2]. It is widely used
ZnO has attracted attention as a wide band gap semiconductor in the development of thin film transistors, transparent conduc-
(Eg = 3.37 at room temperature). Moreover, this material is non- tors, gas sensors, photo-detectors, window layer for solar cells,
toxic, chemically stable, low cost in production, commercially micro sensors, photo-catalysts, dilute magnetic semiconductors
(DMS), and ultra-violet/blue emission devices [3,4]. ZnO is more
⇑ Corresponding author. efficient in optoelectronic applications than GaN [5], since, ZnO
E-mail addresses: dr_eid_hti@yahoo.com (E.A. Eid), alynabieh@yahoo.com has larger exciton binding energy of 59 meV and the promising
(A.N. Fouda). exciton oscillating strength of ZnO micro cavity structure [6].

http://dx.doi.org/10.1016/j.saa.2015.03.125
1386-1425/Ó 2015 Elsevier B.V. All rights reserved.
128 E.A. Eid, A.N. Fouda / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 149 (2015) 127–131
However, the epitaxial growth of ZnO films have been conducted
by a variety of methods, such as chemical vapor deposition CVD
[7], MOCVD [8], MBE [9], pulsed laser deposition PLD [10], low
thermal gradient Czochralski technique [11], and sputtering
[12–16]. Economically, sputtering method can provide wide area
films with well controlled composition. Despite these advantages,
there are still some problems associated with sputtering. The prop-
erties 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 [17], ScAlMgO4 [5],
GaN [9], AlN [18] and Al2O3 [19]. Due to high cost of ZnO sub-
strates, high-quality ZnO buffer layers on other substrates are of
particular interest. Al2O3 is one of the most widely adopted sub-
strates for the ZnO epilayer growth because of its hexagonal sym-
metry, commercial availability, low cost, and as low lattice
mismatch as 0.08% between a-plane sapphire substrate and ZnO
[20]. Several recent reports were concerned about the ZnO films
growth on a buffer layer (ZnO and MgO) using Si, GaN, and sap-
phire substrates [21–25]. Unfortunately, strains are generated after
the high temperature growth conditions due to difference in ther-
mal expansion coefficients between ZnO and sapphire substrate
(asapphire = 8.00  106 K1, and aZnO = 6.51  106 K1). Chen
et al. reported that introduction of low temperature buffer layer
RMS= 3.3nm
RMS= 2.2nm
Fig. 1. AFM images (2  2 lm) of atomically smooth ZnO films grown on ZnO buffer layer with different thickness (a) a-plane sapphire substrate, (b) tb = 15 m, (c) tb = 30 nm
(d) tb = 45 m. (e) tb = 60 m and (f) graphical representation of thickness dependence of RMS values for ZnO epilayers.
followed by high temperature growth step can relax the strains.
Through this method a densely packed ZnO film with larger grains
and well-aligned crystallographic orientation can be obtained [26].
Previously, the growth of high quality ZnO films on a-plane sap-
phire substrate was succeeded [27], and it was found that the film
quality can be improved at particular growth conditions (deposi-
tion temperature of 600 °C and vacuum annealing at 900 °C). In
the present work, the buffer layer thickness influence on the struc-
tural and top surface characteristics has been investigated to find
out the optimal growth conditions.
Experimental
The sapphire substrates (Epistone Company-Semi Materials
Inc.) were cleaned using organic solvents and rinsed in DI water.
ZnO buffer layers with different thicknesses of 15, 30, 45, and
60 nm were directly deposited at temperature of 300 °C on a-plane
sapphire substrates. After vacuum annealing of buffer layer at
600 °C for 10 min, 150 nm thick ZnO thin films were grown by
RF magnetron sputtering, using radio frequency source (RF
frequency = 13.56 MHz, RF power = 700 W). Growth temperature
of 600 °C were obtained by SiC heater. The films were deposited
at working pressure of 5  104 Torr, background pressure of
2  106 Torr, and a bias voltage of 360 V. The ZnO target
(99.999) with diameter of 5.1 cm was used. High purity Ar
RMS= 2.4 nm 18.7nm
0nm
20.2nm RMS= 0.3 nm 3nm
0nm 0nm
15.2nm 4
3
RMS VALUE (nm)
0
20 30 40 50 60
0nm BUFFER LAYER THICKNESS (nm)
 E.A. Eid, A.N. Fouda / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 149 (2015) 127–131 129

(99.999), O2 (99.999) with Ar to O2 ratio of (Ar/O2 = 4/1) were used Raman spectra
and the flow rate was controlled by mass flow controller. The
growth chamber was backed at 800 °C, and the target pre-sputter- The crystalline quality of ZnO epilayers was identified by
ing was performed to remove contaminations. In situ high temper- Raman spectroscopy measurements. Wurtzite ZnO belongs to the
ature vacuum annealing of ZnO films was conducted for an hour at
900 °C.
The XRD measurements were performed by a Burker-D8

(11-20)Al2O3
(0002) ZnO
diffractometer using Cuka radiation. The surface morphology of

INTENSITY (arb. units)

the deposited films was evaluated by AFM in non-contact mode.
To control the local vibration modes, Raman spectra measurements
were carried out at room temperature using Micro-Raman spec-
troscopy system (Model Renishaw system 2000) equipped by Ar+ Buffer=60nm
laser working at wavelength of 488 nm and power of 100 mW.
Buffer=45nm

Result and discussion

Buffer=30nm
Surface morphology

Buffer=15nm
AFM measurements were used to identify the roughness and
surface morphology of the grown films. The AFM images scanned
over the field of 2  2 lm are shown in Fig. 1. Evidently, the as-
33 34 35 36 37 38 39
supplied sapphire substrates have a smooth surface. Fig. 1(b and
c) shows that the grain size increases with increasing the thickness 2θ (deg.)
of the buffer layer from 15 to 30 nm. The pits can be observed. The
coalescence between adjacent grains facilitates the formation of a Fig. 3. h–2h scan of (0 0 0 1) ZnO on with different thickness of ZnO buffer layer.
flat and dense surface. The AFM pattern exhibits a smoother sur-
face for 45 nm buffer layer, and the detectable reduction in z height
to 3 nm, with respect to other films. The unexpected feature was 0.11
detected in Fig. 1e. When the buffer layer thickness increased to 0.44
60 nm, small grains and the disappearance of the above mentioned
0.10

(0002) Δω (deg.)
pits were observed. The dependence of RMS parameter on the buf-
(0002)Δ2θ (deg.)

fer layer thickness is shown in Fig. 1f. The dependence of surface 0.40
morphology on buffer layer thickness indicates that, the buffer 0.09
layer facilitates the ZnO film nucleation and growth. Therefore,
during the consequent film deposition, the lateral growth of ZnO
0.08 0.36
is promoted, which leads to the improvement of surface morphol-
ogy. Surface migration of ad-atoms at distinct thickness of buffer
layer (an extremely flat surface) resulted in high quality ZnO crys- 0.07
tals on sapphire. Fisher et al. reported that from a thermodynamic 0.32
viewpoint, grain boundaries are not stable, the coalescence of 0.06
grains is driven by a reduction in surface energy which force them 20 30 40 50 60
to stretch and unite together when sufficient energy is supplied Buffer layer(ZnO) THICKNESS (nm)
[28].
Fig. 4. The dependence of FWHM D(2h) and D(x) on buffer layer thickness.
A1(LO)
A1(TO)

E2H
A1g

tb= 60nm
Eg
A1g
INTENSITY (arb. units)

tb= 45nm

tb= 30nm

tb= 15nm

400 600 800

1000 1200
-1
WAVE NUMBER(cm )
Fig. 2. Raman spectra of ZnO films on different thicknesses of ZnO buffer layer
measured at room temperature. Fig. 5. x-Scan rocking curve recorded for the (0 0 0 2) ZnO line.
130 E.A. Eid, A.N. Fouda / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 149 (2015) 127–131
Table 1
The variation of FWHM D(2h), FWHM D(x), c-lattice parameter, strain, stress and density of screw dislocation with buffer layer thickness.
Sample and thickness FWHM D(2h)° FWHM D(x)° Lattice parameter c-nm
a (15 nm) 0.102 0.396 0.5223
b (30 nm) 0.088 0.398 0.5220
c (45 nm) 0.086 0.384 0.5224
d (60 nm) 0.085 0.385 0.5075
C6v symmetry group and according to the selection rules, the
Raman active phonon modes E2(low), E2(high), A1(TO), A1(LO),
E1(TO), and E1(LO) are expected to be observed in un-polarized
Raman spectra [29]. The room temperature Raman spectra of the
ZnO films grown on buffer layers with different thicknesses are
shown in Fig. 2. ZnO phonon peaks at 380.5, 577, and 441 are
assigned to A1(TO), A1(LO), and E2H respectively. E2H phonon mode
is the characteristic mode for hexagonal ZnO and the low intensity
of E2H at 441 cm1 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 sap-
phire and zinc oxide [30]. However, the longitudinal optical mode
A1(LO) at 577 cm1 and E2H at 441 cannot be observed in thin buf-
fer layers (tb = 15 nm). Therefore, the distinct Raman active ZnO
phonon modes were observed only after introduction of the buffer
layer with appropriate thickness. The other peaks at 418, 647 cm1
and 430, 750 cm1 were attributed to the A1g and Eg phonon modes
of sapphire, respectively [31–34]. On the other hand, The disap-
pearance of E1(LO) at 590 cm1 in all samples indicates that such
commonly detected defects in ZnO films as zinc interstitials and
oxygen vacancies are at low level in our samples [35–37].
XRD measurements
For further insight into the quality of ZnO epilayers, XRD mea-
surements were implemented. The XRD patterns of ZnO films
grown on the ZnO buffer layers with different thicknesses are
shown in Fig. 3. The Patterns are similar with only sharp and high
intensity ZnO (0 0 0 2) peak in addition to the substrate peak, no
extra diffraction peaks were observed. This indicates that ZnO films
possess single phase wurtzite structure and preferred crystal ori-
entation along the c-axis. However, there were no detectable
changes in peak positions, but a change in FWHM can be observed.
Fig. 4 shows that there is a remarkable change in FWHM with
increasing the buffer layer thickness. The full-width at half-maxi-
mum-FWHM D(2h) of the (0 0 0 2) ZnO peak is less than 0.102 for
all the films. The results imply the high crystallinity of the pre-
pared films. The full-width at half-maximum of X-ray rocking
curves (XRC) for the symmetric (0 0 0 2) diffraction is related to
the density of screw type threading dislocations which implies
the in-plane mosaic mis-orientation (tilt) for the ZnO films. The
crystalline quality of ZnO films grown on the buffer layers was
evaluated from the (0 0 0 2) rocking curve, as shown in Fig. 5. The
extremely low FWHM value (<0.4 deg) of the peak confirms the
perfect ordering along c-axis of ZnO (0 0 0 2). The ZnO buffer layer
with thickness of 45 nm shows the smallest FWHM D(x), as tabu-
lated in Table 1. Moreover, the density of screw type threading
dislocations was estimated using the equation.
! [4] Irene Gonzalez Vallsa, Monica Lira Cantu, Energy Environ. Sci. 2 (2009) 19.
b2s
Ns ¼ ;
4:36  jbs j2
where bS is the lengths of the Burger vector of the screw component
(bS = h0 0 0 1i) and bs is Dx (0 0 0 2) [38]. According to Van der Drift
model, nucleation with various orientations can be established at
the initial growth stage, and only nuclei having the fastest growth
Strain e Stress r-GPa Ns density of screw dislocation (cm2)
3.254  10 3
0.7577 3.94  109
2.688  103 0.6257 4.09  109
3.538  103 0.8237 3.81  109
2.508  103 +5.8382 3.83  109
rate can survive, i.e. highly oriented growth along c-axis is achieved
[39].
Considering the inter-planar space for the hexagonal system
[40]:
!1=2
2 2 2
1 4 h þ hk þ k l
¼ þ 2
d 3 a2 c
We calculated the unit cell parameters of the ZnO films, as
shown in Table 1. To obtain the film stress with a hexagonal crystal
structure, the following formula is used [41]:
2c213  c33 ðc11  c12 Þ c  c0
r¼ 
2c13 c0
The elastic constant values of ZnO crystal are employed, c11 =
208.8 GPa, c33 = 213.8 GPa, c12 = 119.7 GPa and c13 = 104.2 GPa. c–
is the lattice constant of ZnO film, and c0 is the lattice constant
of bulk ZnO. The calculated results are tabulated in Table 1. The
samples a, b and c are subjected to compressive stresses. But in
sample d, a positive stress is found which indicates that the film
is stretched. Basically the stress in film includes a thermal stress
originating from thermal mismatch between film and substrate
and another intrinsic stress originating from the crystal defects
of thin film [42]. Since all ZnO epilayers were prepared at the same
conditions, intrinsic stress originating from the crystal defects of
thin film must be similar for all ZnO thin films. Thus, these stresses
are mainly caused by the thermal stress originated from the differ-
ence of buffer layer thickness.
Conclusion
In this study, we perform a systematic observation of the buffer
layer thickness influence on the structure and quality of ZnO films.
In order to improve the film quality, a low temperature buffer lay-
ers with different film thickness were deposited before the growth
of ZnO films. All the films were smooth and RMS values extended
from 0.3 to 3.3 nm. The highest ZnO film quality was obtained with
a 45 nm thick ZnO buffer layer and z height was 3 nm. Introduction
of a thin ZnO buffer layer plays an important role in preventing
screw dislocations development and is very efficient for the surface
morphology improvement at the initial growth stage, which
eventually leads to an atomically flat surface.
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