Journal of the Korean Physical Society, Vol. 56, No. 6, June 2010, pp.

1833∼1837

Effects of Growth Interruption of ZnO Buffer Layers on the Structural and

the Optical Properties of ZnO Thin Films Grown by Using PA-MBE

Min Young Cho, Min Su Kim, Hyun Young Choi, Su Min Jeon,
Ghun Sik Kim, Do Yeob Kim, Kwang Gug Yim and Jae-Young Leem∗
Department of Nano Systems Engineering, Center for Nano Manufacturing, Inje University, Gimhae 621-749

Dong-Yul Lee
Epi-manufacturing Technology, Samsung LED Co., Ltd., Suwon 443-373

Jin Soo Kim

Division of Advanced Materials Engineering, Chonbuk National University, Jeonju 561-756

Jong Su Kim
Department of Physics, Yeungnam University, Gyeongsan 712-749

Joo In Lee
Advanced Instrument Technology Center, Korea Research Institute of Standards and Science, Daejeon 305-340

(Received 31 March 2010, in final form 27 April 2010)

ZnO thin films with ZnO buffer layers were grown on Si substrates by using plasma-assisted
molecular beam epitaxy (PA-MBE). The ZnO buffer layers were grown with the growth interrup-
tion technique. The structural and the optical properties of the ZnO thin films were investigated by
using X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), and photo-
luminescence (PL). The surface morphology of the ZnO thin films was changed from an island to a
net-like shape. An evident net-like shape was observed, and the optical properties were enhanced
with increasing number of growth interruptions.

PACS numbers: 73.61.Ga, 81.15.Hi, 68.55.Jk

Keywords: Zinc oxide, Molecular beam epitaxy, Interruption, X-ray diffraction, Field-emission scanning
electron microscopy, Photoluminescence
DOI: 10.3938/jkps.56.1833

I. INTRODUCTION It is also well-known that an interruption in the MBE

ZnO is an n-type semiconductor with a hexagonal
wurtzite structure and a large exciton binding energy
of 60 meV, which is 2.4 times that of GaN [1]. ZnO has
been studied extensively for its potential use in various
applications, such as gas sensors [2], solar cells [3], pho-
todetectors [4], and light emitting diodes [5]. ZnO lay-
ers can be prepared by using various techniques such as
sputtering [6], pulsed laser deposition (PLD) [7], metal-
organic chemical vapor deposition (MOCVD) [8], the sol-
gel method [9], and molecular beam epitaxy (MBE) [10].
Among the above-mentioned methods, MBE has the ad-
vantage of being able to facilitate atomic layer control
during film growth under ultra-high vacuum (UHV) [11].
∗ E-mail: jyleem@inje.ac.kr; Fax: +82-55-320-3631
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growth can significantly modify the surface or interface
of the heterostructure [12]. Further, in quantum dots
(QDs), the size and optical properties of the QDs are af-
fected by growth interruption [13]. The ability to control
the surface morphology of nanocrystals is an important
objective in their growth as size and shape can influence
various properties [14].
Nanometer-scale semiconductors have attracted atten-
tion because they exhibit curious structures and vari-
ous remarkable physical, chemical, and electrical prop-
erties distinctive from those of conventional bulk mate-
rials [15,16]. ZnO can be formed into specific nanostruc-
tures such as nanowires [17], nanorods [18], nanoparti-
cles [19], nanobelts [20], and nanotetrapods [21]. There
have been reports of ZnO morphology control of hun-
dreds of nanometer to micron-sized particles [22], and
researchers have reported the elongation of particles into
-1834-
Fig. 1. Zn cell shutter ON/OFF interruption cycle for all
the samples.
rods at high precursor concentrations [23]. However, a
simple, generic, synthetic method that is morphologically
tunable at the tens of nanometer scale has not been de-
veloped yet [24-26].
In this study, the ZnO thin films were grown on ZnO
buffer layers by using plasma-assisted molecular beam
epitaxy (PA-MBE). The buffer layers were grown on Si
substrates using a two-step process with growth inter-
ruption technique in an oxygen plasma. The effects of
growth interruption on the surface morphology and the
optical properties of the ZnO thin films were investigated
by using X-ray diffraction (XRD), field-emission scan-
ning electron microscopy (FE-SEM), and photolumines-
cence (PL) measurements.
II. EXPERIMENTAL PROCEDURE
ZnO thin films with ZnO buffer layers were grown on
p-type Si (100) substrates by using a growth interrup-
tion technique with a PA-MBE system equipped with
a Zn effusion cell and an O2 plasma cell. Elemental
zinc with 99.9999% purity was used as the precursor.
Oxygen radicals were produced from ultra-high-purity
O2 gas by using a radio frequency (RF). The Si sub-
strates were cleaned in a piranha solution (H2 SO4 :H2 O2
= 8:1) at 110 ◦ C for 15 min and then hydrofluoric acid
(HF 50%:H2 O = 1:9) for 5 min. The Si substrates were
thermally cleaned at a substrate temperature of 300 ◦ C
for 10 min in a load-lock chamber. Then, the substrates
were inserted into an UHV working chamber and an-
nealed at 850 ◦ C for 60 min. The initial Zn layers with
a thickness of 120 Å were grown at a temperature of 350
◦
C to prevent the oxidation of the Si substrates by the
O2 plasma source. The ZnO buffer layers were grown us-
ing a two-step process. In the first step, the ZnO buffer
Journal of the Korean Physical Society, Vol. 56, No. 6, June 2010
Fig. 2. X-ray diffraction patterns of the ZnO films as a
function of the number of growth interruptions.
layers were grown with a conventional growth technique,
which resulted in an uninterrupted growth for 14 min
(sample A). In the second step, a growth interruption
technique was used. The growth interruption technique
was a combination of conventional MBE and migration
enhanced epitaxy. It consists of a sequence of ON/OFF
cycles of the Zn beams while the O2 plasma is kept con-
stant during the buffer layer growth. The Zn cell shutter
ON/OFF interruption cycle is shown in Fig. 1. The Zn
beam ON time of 18 s (sample B), 12 s (sample C), or
9 s (sample D) was followed by a Zn beam OFF time of
10 s. The cycle was repeated 20 (sample B), 30 (sample
C), or 40 times (sample D), respectively. The ZnO thin
films were grown at a substrate temperature of 600 ◦ C.
III. RESULTS AND DISCUSSION
Figure 2 shows the θ - 2θ XRD spectra of samples A, B,
C, and D. The diffraction peaks of ZnO (002) and ZnO
(004) are seen in all the samples. This indicates that
all the ZnO thin films were crystallized with a wurtzite
structure; the preferred orientation axis was the c-axis.
The c-axis orientation is common in ZnO thin films be-
cause the (001) basal plane of ZnO has the lowest surface
energy [27,28]. Consistent with this theory, all samples
in our experiments exhibited the preferred orientation of
(001), inferred from the observed (002) reflections in the
XRD spectra. The full width at half maximum (FWHM)
of ZnO (002) decreased from 0.24◦ to 0.21◦ , indicating
enhancement in the crystal quality of the ZnO thin films
with increasing number of growth interruptions .
Figure 3(a) shows the (002) peak positions of samples
A, B, C, and D as a function of the number of growth
interruptions. Since the peak position of the ZnO pow-
der with a (002) orientation was at 2θ = 34.43◦ [29], the
shifts of the (002) peaks of the samples indicate the exis-
tence of residual stress [30]. The c-axis strain (εzz ) values
were calculated using the following equation:
Effects of Growth Interruption of ZnO Buffer Layers on the Structural and the Optical · · · – Min Young Cho et al.
Fig. 3. (a) Peak position and (b) stress of the ZnO thin
films as functions of the number of growth interruptions.
c − c0
εzz (%) = × 100. (1)
c0
The lattice constant c was calculated using Bragg’s
law on the basis of the XRD results: 2dsinθ = λ; co
(5.2066 Å) was the unstrained lattice parameter of ZnO
[31]. The strain of samples A, B, C, and D were 0.206,
-0.319, -0.318, and -0.279, respectively. The biaxial films
stress σ is related to the measured c-axis strain as follows
[32]:
2c213 − c33 (c11 + c12 ) c − c0
σ= × , (2)
2c13 c0
where cij are the elastic stiffness constants for single-
crystal ZnO (C11 = 208.8 GPa, C33 = 213.8 GPa, C12
= 119.7 GPa, and C13 = 104.2 GPa) [33]. The stresses
of samples A, B, C, and D were -0.479, 0.743, 0.740, and
0.649 GPa, respectively. The stress in the ZnO films con-
tains a thermal component and an intrinsic component.
If the stress is positive, the biaxial stress is tensile; if
the stress is negative, the biaxial stress is compressive
[34]. The thermal stresses are a result of the differences
in the thermal expansion coefficients between the ZnO
films and the Si substrates. The thermal expansion co-
efficient of ZnO (4.75 × 10−6 K−1 ) [35] is larger than
that of silicon (2.6 × 10−6 K−1 ) [35], resulting in a ten-
sile lateral stress in the ZnO film due to the cooling af-
ter the growth. On the other hand, the intrinsic stress
has its origin in the imperfections of the crystallites dur-
ing the growth. Several growth parameters, such as the
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Fig. 4. FE-SEM images of samples A, B, C, and D.
growth temperature, the gas pressure, the RF power, and
the gas mixtures, can contribute to the intrinsic stress.
In the normal growth of ZnO film, the intrinsic stress
of the as-grown ZnO films has been shown to be com-
pressive [36–38]. During the growth process, the magni-
tude of the compressive stress component is larger than
that of the thermal (tensile) stress component; there-
fore, the as-grown ZnO films exhibits an overall com-
pressive residual stress. In the case of ZnO films grown
on interrupted buffer layers, the stress of the ZnO thin
films changed from compressive to tensile as shown in
Fig. 3(b) because the lattice constant of the samples de-
creased. Compared to the unstrained lattice parameter
of ZnO (5.2066 Å), the larger value of the lattice con-
stant in sample A (5.2173 Å) indicated that the unit cell
was elongated along the c-axis and that the compressive
forces were acting in the plane of the films [39,40]. How-
ever, in samples B to D, the lattice constant decreased
to around 5.19 Å.
Figure 4 shows FE-SEM images of the ZnO thin films.
The surface morphology of sample A was island shaped,
and samples B, C, and D had a net-like shape. In par-
ticular, an evident net-like shape was observed at the
surfaces of samples C and D, which indicates that the
net-like shape becomes clearer with increasing number
of growth interruptions. The net-like shape was first
observed by Wei et al. under nanorods grown on AlN
buffer layers by using MOCVD [41]. They reported that
the ZnO net-like films under the nanorods had tensile
in-plane strains because the AlN film were oxidated by
the O2 at the interface due to the bond of Al-O being
stronger than that of Al-N [42]. The buffer layers grown
with the interruption had abundant oxygen on the sur-
face because the growth interruption was performed in
the oxygen plasma. The ZnO net-like films were grown
on abundant oxygen surfaces because ZnO could eas-
ily grow on an O surface, but not on a N surface [42].
Although the formation mechanism of the ZnO net-like
-1836-
Fig. 5. PL spectra of the ZnO thin films as a function of
the number of growth interruptions.
films is still not known, it is obvious that ZnO net-like
films are related to the oxidation or oxygen states of the
buffer layers. A net-like shape could be useful for ZnO
applications such as gas sensors because the increase in
the effective surface area could be attributed to an in-
crease in gas-adsorption quantities [43].
In order to investigate the optical properties of the
ZnO thin films, we carried out PL measurement at room
temperature by using a He-Cd laser with an excitation
power of 30 mW and a 1-m single-grating monochroma-
tor with a photomultiplier tube. The PL spectra of the
ZnO thin films are shown in Fig. 5. The PL spectra
showed sharp near band edge (NBE) emissions, which
were generated by the free-exciton recombination at 380
nm, and the intensity of NBE emissions increased with
increasing number of growth interruptions. The broad
deep level emission (DLE), which was caused by impu-
rities and structural defects, was blue-shifted from 646
(orange emission) to 568 nm (green emission) with in-
creasing number of growth interruptions. In general, the
origin of the DLE is considered to be caused by an oxygen
vacancy (VO ), a zinc vacancy (VZn ), an oxygen atom at
the zinc position in the crystal lattice (OZn ), a zinc atom
at the oxygen position in the crystal lattice (ZnO ), an in-
terstitial oxygen (Oi ), and an interstitial zinc (Zni ). The
orange emission is due to Zni , and the green emission is
associated with OZn [44]. Zni is easily formed in ZnO
grown by using conventional growth techniques because
the radius of the zinc atom is much smaller than that
of oxygen [45]. An increased number of oxygen atoms
were absorbed into the ZnO buffer layers because of the
growth interruption in the oxygen plasma. This suggests
that the green emission is closely related to the abundant
oxygen in the buffer layer. The details of the mechanism
for green emission are still a subject of controversy.
Journal of the Korean Physical Society, Vol. 56, No. 6, June 2010
IV. CONCLUSIONS
ZnO thin films were prepared with ZnO buffer layers
on Si substrates by using PA-MBE. The ZnO buffer lay-
ers were grown by using a two-step growth process with
a variation of 20 - 40 times in the number of growth in-
terruptions. A change in the surface morphology of the
ZnO thin films from an island shape to a net-like shape
was observed with increasing number of growth inter-
ruptions. The FWHM of the ZnO (002) diffraction peak
decreased and the intensity of the NBE emission of the
PL spectra increased with increasing number of growth
interruptions. Control of the surface morphology, as well
as an enhancement of the luminescence properties, was
achieved using the growth interruption technique in PA-
MBE.
ACKNOWLEDGMENTS
This research was supported by Basic Science Research
Program Through the National Research Foundation of
Korea (NRF) funded by the Ministry of Education, Sci-
ence and Technology (No. 2010-0016147)
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