Superlattices and Microstructures 73 (2014) 268274

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Superlattices and Microstructures

journal homepage: www.elsevier.com/locate/superlattices

Ultra-smooth and lattice relaxed ZnO thin lms

A.N. Fouda a,, El Shazly M. Duraia a,b,, E.A. Eid c
a

Physics Department, Faculty of Science, Suez Canal University, 41522 Ismailia, Egypt
Texas State University-San Marcos, Department of Chemistry and Biochemistry, 601 University Dr., San Marcos, TX 78666, USA
c
Department of Basic Science, Higher Technological Institute, 44629 10th of Ramadan City, Egypt
b

a r t i c l e

i n f o

Article history:
Received 24 April 2014
Received in revised form 3 May 2014
Accepted 6 May 2014
Available online 5 June 2014
Keywords:
Zinc oxide thin lms
Vacuum annealing
Lattice relaxation
Raman spectroscopy

a b s t r a c t
The crystal structure and quality of ZnO thin lms were enhanced
by high temperature vacuum annealing. High quality ZnO thin
lms have been grown on a-plane sapphire substrate by radio
frequency (rf) magnetron sputtering method at a substrate
temperature of 600 C. A remarkable improvement in the epilayer
quality were established by in situ high temperature annealing.
The lm quality, smoothness, the in plane stress, and the degree
of epitaxy of the lms have been evaluated. The crystalline quality
was investigated by X-ray diffraction (XRD), scanning electron
microscopy (SEM), atomic force microscopy (AFM) and Raman
spectroscopy analyses. An extremely smooth ZnO lms were
achieved at higher annealing temperatures with root mean square
roughness of 0.3 nm. The transverse optical mode A1(TO) observed
in all the samples and the longitudinal optical mode A1(LO)
appeared only at higher annealing temperatures over 800 C in
the micro-Raman scattering measurements. The strain of c-axis
were relaxed and the lattice parameter was comparable to that
of bulk ZnO at high annealing temperature of 900 C.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
Zinc oxide has a wide band gap of 3.37 eV at room temperature. It has a potentially useful
properties including chemical stability, non-toxic (environmental friendly), catalytic activity,
Corresponding authors. Present address: Texas State University-San Marcos, Department of Chemistry and Biochemistry,
601 University Dr., San Marcos, TX 78666, USA. Tel.: +1 512 557 1495 (E.S.M. Duraia).
E-mail addresses: duraia_physics@yahoo.com, ed24@txstate.edu (E.S.M. Duraia).
http://dx.doi.org/10.1016/j.spmi.2014.05.022
0749-6036/ 2014 Elsevier Ltd. All rights reserved.

A.N. Fouda et al. / Superlattices and Microstructures 73 (2014) 268274

269

piezoelectricity, low cost in production, commercial availability of large area single crystal ZnO substrates, and bio-compatibility [1,2]. ZnO has a wide range of applications like gas sensors, photo-catalysts, transparent electrodes, dilute magnetic semiconductors (DMS), photo-detectors, microsensors,
window layer for solar cells, and active channel layer of transparent thin lm transistor (TTFT) waveguides, surface acoustic wave devices, and ultra-violet/blue emission devices [3,4].
Light emitting diodes and lasing development have been focused on GaN with exciton binding
energy of 24 meV. However, ZnO is more efcient emitter and promising in optoelectronic applications than GaN [5]. ZnO has a large exciton binding energy of 59 meV and the major challenge for
ZnO in optoelectronic device applications is the production of good quality and wide area ZnO lms
by low cost method [6]. Based on BoseEinstein condensation, Zamrescu et al. proposed a model
for ZnO microcavity structure with a promising exciton oscillating strength toward the fabrication
of excitonpolariton laser in ZnO [7].
The epitaxial growth of ZnO have been conducted by a variety of methods, such as pulsed laser
deposition PLD [8], laser assisted molecular beam epitaxy L-MBE [9], plasma assisted MBE [10],
MBE [11], chemical vapor deposition CVD [12], MOCVD [13] chemical spraying [14], sol gel [15],
ion beam deposition [16] and sputtering [1721]. Among these, sputtering method can produce wide
area lms with controlled composition economically. However, the lm quality and roughness do not
match the requirements of optoelectronic devices. Epitaxial growth of ZnO lms can be established on
different kind of substrates like ZnO [22], GaN [11], AlN [23], ScAlMgO4 [5] and Al2O3 [24]. Al2O3 is one
of the most extensively adopted substrates for the growth of ZnO epilayers because of its hexagonal
symmetry, low cost and commercial availability. Many researchers try to grow high quality ZnO lms
on sapphire substrate. Lin et al. [25] succeeded in the growth of high quality ZnO lms on c-plane sapphire substrate without a buffer layer. However, for epitaxially grown (0 0 0 1) ZnO on (0 0 0 1) Al2O3
defects are easily generated, because of the large lattice mismatch 18.4% which decreases to 0.08%
for (0 0 0 1) ZnO grown on (1120) Al2O3 [26].
In the present paper, high quality ZnO lms were grown by rf magnetron sputtering on a-plane
sapphire substrate. The inuence of high temperature vacuum annealing on the epilayer quality,
microstructure and crystalline perfection has been investigated. We try to nd out the optimum
growth and heat treatment conditions.
2. Experimental
150 nm thick ZnO thin lms were deposited by rf magnetron sputtering, using radio frequency
source (RF, 13.56 MHz). High purity ZnO target (99.999) with 5.1 diameter has been used. Growth
temperature of 600 C were established by SiC heater. The lms deposited at a bias voltage of
350 V, working pressure of 5  104 Torr, background pressure of 2  106 Torr and radio frequency
power of 700 W. High purity Ar (99.999), O2 (99.9999) with Ar to O2 ratio of (Ar/O2 = 4/1) were used.
Ar and O2 ow were controlled by mass ow controller. Pre-sputtering was performed to remove contaminations on the target. Smooth a-plane sapphire substrate were cleaned using organic solvents,
rinsed in DI-water and baking in high vacuum at 750 C before deposition. The smoothness of the substrate is shown in Fig. 2e. In situ high temperature vacuum annealing of (0 0 0 1) ZnO lms was carried
out for an hour at 700 C, 800 C, 850 C and 900 C respectively.
The lm thickness were measured using the cross-section prole of scanning electron microscopy
(Model JEOL JSM-840). XRD measurements were performed by using Burker-D8 diffractometer with
Cu Ka radiation. In non-contact mode, AFM was used to study the roughness and surface morphology
of the deposited lms. The characterizations were extended by 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 to investigate the local vibration
modes from ZnO epilayers grown on a-plane sapphire substrates.
3. Results and discussion
SEM has been used to investigate the lm thickness. Fig. 1 depicts the side view of the lm at different locations. The growth rate was 73 nm/h and it can be seen that, the thickness of the grown lms

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A.N. Fouda et al. / Superlattices and Microstructures 73 (2014) 268274

Fig. 1. Side view of SEM image for c-plane ZnO on a-plane sapphire substrate.

was around 150 nm. The sharpness of the interface between lm and substrate indicate the uniformity, smoothness and homogeneity of the grown lms.
Fig. 2 shows AFM images for the lms annealed at 700 C (Fig. 2a), 800 C (Fig. 2b), 850 C (Fig. 2c),
and 900 C (Fig. 2d), respectively. Small grains can be observed in little rough surface in Fig. 2a and b
for the vacuum annealed lms at 700 C and 800 C. In addition, with increasing the annealing temperature, coalescence process of grains is extended. Atomically clearly at ZnO epilayers exhibiting
z-axis height less than 3 nm were conducted and RMS value decreases to 0.3 nm. The variation of
RMS values with annealing temperature is shown in Fig. 2f. RMS values regularly decrease with
increasing the annealing temperature up to 850 C and the increment at 900 C is related to the formation of intermediate hexagonal pits. Small typically hexagonal pits were observed for the lms
annealed at 900 C, which illustrate the backing of ZnO on a nearly lattice matched substrate [26].
The formation of similar hexagonal pits was also reported by Wang et al. for ZnO lms grown by
MBE [27]. The obtained small roughness is so much smaller than the values reported for sputtered
ZnO lms [1821] and even comparable to high quality lms grown by MBE [11] and PLD [8]. To
our knowledge, this is one from the best result reported for sputtered ZnO lms on sapphire
substrates. Such enhancement was attributed to the fact that thermal annealing enhances the mass
transport and coalescence of adjacent grains [28] besides selecting the optimum preparation
conditions on a smooth a-plane sapphire substrate as shown in Fig. 2e.
Micro-Raman measurements have been carried out to investigate the nature of crystalline quality.
Wurtzite ZnO belongs to the C6v symmetry group. According to the well-known selection rules, there
are the Raman active phonon modes E2(low), E2(high), A1(TO), A1(LO), E1(TO), and E1(LO). The E2
modes and the A1(LO) mode are expected to be observed in un polarized Raman spectra [29]. Fig. 3
represents the room temperature Raman spectrum of ZnO lms at different annealing temperatures
and Optical surface images for the spots of incidence. From the gure, one can see that; The transverse
optical mode A1(TO) appears at 380 cm1 for all the samples. While the longitudinal optical mode
A1(LO) at 576 cm1 appears only at higher annealing temperatures over 800 C. The disappearance
of E1(LO) in all samples indicates that our samples have little defects such as Zn interstitials, oxygen
vacancies, and the free carrier lack [30,31]. The other peaks at 417, 650 and 750 cm1 are attributed to
the Al2O3 substrate [32,33]. The peaks are slightly asymmetric and broadening, this is due to the quantum connement of the phonons. Therefore, the contribution to the Raman spectrum will not only
from the phonons of Brillouin zone center but also from the other phonons that is conned due to
the nanoscale effect [34]. The low intensity E2 at 430 cm1 indicates the small stress due to the
difference in the thermal coefcients between sapphire and zinc oxide [35].
h2h scan for ZnO thin lms annealed at 700 C, 800 C, 850 C and 900 C are shown in Fig. 4a. The
dominant diffraction peak in all scans is the (0 0 0 2) peak beside the substrate (1120) Al2O3 peak.
(0 0 0 2) ZnO peak arises from diffraction from basal ZnO planes with c-axis perpendicular to the substrate. The sharpness and symmetric nature of the peak conrm the quality of the epilayers. FWHM

A.N. Fouda et al. / Superlattices and Microstructures 73 (2014) 268274

271

e
0nm

RMS VALUE (nm)

1nm
2.5
2.0
1.5
1.0
0.5
0.0

f
700

750

800

850

900

ANNEALING
TEMPERATURE (C)
Fig. 2. AFM images (2 lm  2 lm) and cross-sectional height proles of atomically smooth ZnO lms grown on a-plane
sapphire substrates which annealed at (a) 700 C, (b) 800 C, (c) 850 C and (d) 900 C. (e) AFM for the used smooth a-plane
sapphire substrate. (f) Graphical representation of annealing temperature dependence of RMS values for ZnO epilayers.

decreases with increasing the annealing temperature and for the lms annealed at 900 C, (0 0 0 2) ZnO
peak with FWHM of 0.0672 was observed in Fig. 4a. No reections corresponding to other planes
were observed except (0 0 0 2) ZnO which is very symmetric. This indicates the absence of any other
phases. The sharpness of ZnO (0 0 0 2) reection shows a good c-axis orientation perpendicular to
a-plane sapphire substrate without the well-known rotation by 30 which ZnO lms exhibited on
c-plane sapphire substrate [25,26]. x scan for the lms annealed at 900 C is shown in Fig. 4b. The
value of FWHM for rocking curve scan has a very small value of 0.0026, implying the ordering and
little tilt in c-plane.
Fig. 5 shows the lattice constant obtained from ZnO (0 0 0 2) reection in comparison with bulk ZnO
lattice constant. A well identied lattice relaxation by high temperature annealing were conrmed.
This implies that the lm was relaxed by increasing the annealing temperature and the lattice constant is comparable to bulk ZnO [4]. High temperature annealing enhances the quality and orientation
of the grown ZnO epilayers.

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900

INTENSITY (arb. units)

TA= 900C

10 m

TA= 850C

850

TA= 800C
800

T = 700 C
A
700

400

600

800

1000

1200

WAVE NUMBER (cm-1)

INTENSITY (arb.units)

(a)

(11-20) Al2O3)

(0002) ZnO

Fig. 3. Raman spectra of ZnO lms on a-plane sapphire substrates measured at room temperature under various annealing
conditions and optical images for the measuring spot.

T = 900C
T =850C
T = 800C

T = 700C

33

34

35

36

37

38

39

2 (deg.)

INTENSITY (arb.units)

(0002) ZnO
FWHM=0.0026

-1.0

(b)

-0.5

0.0

0.5

1.0

(deg.)
Fig. 4. (a) Shows h2h scan of (0 0 0 1) ZnO on (1120) Al2O3 substrate, ZnO (0 0 0 2) reection is observed. (b) Shows x-scan
rocking curve recorded for the (0 0 0 2) line with a width of only 0.0026.

273

5.217

0.18

5.214
0.12
5.211
0.06
5.208
c - BULK (ZnO)
5.205

c - AXSIS STRAIN (%)

c - LATTICE CONSTANT ()

A.N. Fouda et al. / Superlattices and Microstructures 73 (2014) 268274

0.00

700

800

900

ANNEALING TEMPERATURE (C)

IN PLANE STRESS (dyn/cm2)

Fig. 5. Relation between c-lattice parameter and strain for ZnO thin lms under various annealing conditions.

5x109
4x109
3x109
2x109
1x109
0
700

750

800

850

900

ANNEALING TEMPERATURE (C)

Fig. 6. The in plane stress of ZnO epilayers on a-plane sapphire substrates under different annealing temperatures.

The residual stress in the c-plane of annealed ZnO lms can be calculated based on biaxial strain
model for hexagonal lattice [36]

r 233  1010



cfilm  cbulk
dyne=cm2
cbulk

Here r is the in plane stress, clm is the lattice constant obtained from the (0 0 0 2) reection in the XRD
prole, cbulk is the corresponding bulk value [37,38]. The calculated in-plane stress values for thermally
annealed ZnO lms are shown in Fig. 6. The value of stress in our samples is two order of magnitude
lower than the values reported by some other groups [36]. Generally, intrinsic stress and thermal
stress can be found in ZnO lms. Due to the small lattice mismatch in our lms, the intrinsic stress
induced by lattice mismatch is small. We believe that the resultant stress is mainly due to thermal
stress which is attributed to the difference in the thermal expansion coefcients of the substrate
and lm [35]. High temperature annealing reduce the in plane stress in ZnO lms and promote grain
growth.

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A.N. Fouda et al. / Superlattices and Microstructures 73 (2014) 268274

4. Conclusions
The effect of vacuum annealing on the relaxation of ZnO lms was illustrated. ZnO epilayer had a
smooth surface comparable to layer by layer lms grown by MBE and PLD. As determined by XRD
measurements, the sharpness of ZnO (0 0 0 2) reection shows a good c-axis orientation perpendicular
to a-plane sapphire with a small FWHM. Our result suggests few threading dislocations which is
related to x-rocking curve of ZnO (0 0 0 2) reection and high temperature annealing improves the
ordering of the lms. A well identied lattice relaxation by high temperature annealing were conrmed. This implies that the lm was relaxed by increasing the annealing temperature and the lattice
constant is comparable to bulk ZnO. Micro-Raman analysis conrm the small stress in the lms.
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