APPLIED PHYSICS LETTERS

VOLUME 84, NUMBER 4

26 JANUARY 2004

V defects of ZnO thin films grown on Si as an ultraviolet optical path

Y.-Z. Yoo,a) T. Sekiguchi, and T. Chikyow
National Institute for Materials Science, 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, Japan

M. Kawasaki
Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan

T. Onuma and S. F. Chichibub)

Institute of Applied Physics and Graduate School of Pure and Applied Sciences, University of Tsukuba,
Tsukuba, 305-8573, Japan

J. H. Song and H. Koinuma

Materials and Structures laboratory, Tokyo Institute of Technology, 4259, Yokohama 226-8503, Japan

Received 8 September 2003; accepted 24 November 2003

V defects were observed in the ZnO films epitaxially grown on the ZnS-buffered Si. Although the
1 facets of
defects were located on the surface, strong near-bandedge emission confined to the 101
V defects was observed at room temperature. The near-bandedge emission spreads out over the
whole film centering at V defects at 30 K. The detailed optical characterization shows that activation
of excitonic absorption is responsible for this unique optical behavior. 2004 American Institute
of Physics. DOI: 10.1063/1.1643535

With the increasing demand for high-brightness light

emitters operating in the ultraviolet UV region, substantial
effort is concentrated on optimizing emission properties of
wide-band-gap materials. One of the surface defects that are
most directly associated with the light emission is a V-shaped
one. Investigating the impact of the V defects on the optical
properties is crucial not only for the improvement of the
device performance but also for understanding of the nature
of the light emission phenomenon. The V defects were observed in typical IIIV semiconductor thin films, such as
GaN, InGaN, and their quantum well structures, and their
properties were studied in detail.1,2
Among IIVI semiconductors, ZnO is one of the most
promising candidates for the UV emitter applications due to
its wide band gap 3.3 eV and high exciton binding energy
60 meV.3 Extensive research including growth, band-gap
engineering, and doping of ZnO has recently been
performed.4,5 ZnO and GaN have similar structural properties and thin-film growth mechanisms. However, no reports
on the formation and properties of the V defects in ZnO have
been published yet. The study of the formation and optical
properties of V defects in ZnO is a pressing issue and essential for the optimization of ZnO emission.
There is growing interest in the growth of ZnO on Si
because of large scale integration using matured Si technology. However, deposition of ZnO onto Si causes the formation of an amorphous interface (SiO2 ) between the film and
the substrate, which leads to the poor quality of the ZnO
films. It is reasonable to use a buffer layer to prevent SiO2
formation. For the growth of ZnO on Si, a buffer with the
same hexagonal symmetry as ZnO is desirable to minimize
the structural mismatch. In this respect, wurtzite ZnS Wz
Zns can be a suitable buffer.
a

Electronic mail: yoo.youngzo@nims.go.jp

Also at: Photodynamic Research Center, RIKEN, Sendai, 980-0868, Japan.

In this letter, we report on the epitaxial growth of ZnO

films on Wz ZnS-buffered Si, and describe optical properties
of the V-defects in the ZnO films. Both ZnO and Wz ZnS
buffer were grown by the pulsed laser deposition using a KrF
excimer laser (248 nm, 10 Hz. The base pressure was
7107 Torr. A single-crystal ZnS target was ablated for 5
min onto a Si111 substrate and then a ZnO target was ablated for 60 min under a typical laser fluence of 5 J/cm2 in
the same chamber without breaking the vacuum. The Wz
ZnS buffer was grown at 750 C under the base pressure.
ZnO films were grown at 700 C in O2 of 5105 Torr. The
structural and optical properties of the films were determined
by the four-circle x-ray diffraction XRD, atomic force microscopy AFM, scanning electron microscopy SEM,
cathodoluminescence CL, and optical reflectance OR.
The accelerating voltage of the incident electron beam was
fixed at 5 kV in CL measurement.
Figure 1a shows 2 XRD pattern of a ZnO thin film
on Wz ZnS-buffered Si 111 deposited at 750 C. The microstructure of Wz ZnS thin films on Si 111 has been described elsewhere.6,7 ZnO films show only two reflections:
0002 and 0004 at the 2 angle of 34.4 and 72.4, respectively, indicating c-axis-oriented growth. The full width at
half maximum value of the -rocking curve of 0002 peak
was only 0.25 indicating excellent film crystallinity.
5) peak for ZnO
Figure 1b shows phi scan of each (101
5) peaks were
on Wz ZnS-buffered Si. The Wz ZnS (101
5) peaks appeared at the
separated by 60 and the ZnO (101
same angles as those of ZnS. This suggests that ZnO was
epitaxially grown on a Wz ZnS buffer and had the same
stacking orientation as the Wz ZnS. Epitaxial growth takes
place regardless of the large lattice mismatch between the
two crystal lattices ( f m (a ZnOa ZnS)/a ZnS100
14.8%). The epitaxial relationship of the ZnO 0001 film
on ZnS 0001 buffered Si 111 is 220
5 ZnS// 101
5 ZnO which makes five Wz ZnS fit
Si// 101
six ZnO lattices and in turn yields a domain mismatch of

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502
2004 American Institute of Physics
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Appl. Phys. Lett., Vol. 84, No. 4, 26 January 2004

FIG. 1. a 2 XRD patterns along the surface normal direction for the
ZnO film grown on Wz ZnS-buffered Si. Owing to the very close lattice
constants of ZnS and Si, ZnS reflections overlap with strong Si reflections,
so they are not seen in Fig. 1a. b Diffraction profile along the azimuthal
5 peaks of the ZnO 350 nm film on Wz ZnS 50 nm
circle at W 101
buffered Si111.

only 2.1%. Both ZnS and ZnO are highly ionic with an
ionicity above 0.6. Thus, interfacial bonds between the two
phases would acquire a high ionic nature as well. This highly
ionic interface is believed to help domain matching at highgrowth temperatures instead of energetically unfavorable lattice matching.8
Figure 2a shows AFM image of the ZnO deposited
onto Wz ZnS-buffered Si. It has been reported that surface of
ZnO film typically exhibits large hexagonal islands grown at
the expense of small grains with higher surface energy.9 In
contrast, ZnO on Wz ZnS-buffered Si showed unique surface
morphology of hexahedron cones that were aligned along the
same orientation. The inset in Fig. 2a shows an AFM line
profile along the path indicated by a dotted line in Fig. 2a.
Depths of the hexahedron cones are approximately 30 nm,
shown in Fig. 2a. In terms of facet angles, it is found that
the hexahedron cones are composed of two polar planes of
1) and partially 0002. We tentatively conclude
mainly (101
that the hexahedron cones are a kind of V defect that is
closely associated with a growth mode originated from ZnO/
ZnS interface polarity and columnar growth, because the
1 facets are propahexahedron cone with symmetry 101
gated by the insertion and growth of the 0002 planes.
Figure 2b is an SEM image of the ZnO on Wz ZnSbuffered Si. The V-defect regions were shown as dark areas
in Fig. 2b. Figure 2c shows a CL microscopy image in the
same area as Fig. 2b at room temperature RT. The CL
was measured at the photon energy with the highest intensity
3.26 eV. It is interesting that the V-defect regions show a
brighter near-bandedge emission than pure c-plane regions in
Fig. 2c, regardless of its defect nature. Figure 2d shows a
CL microscopy image of the area which is shown in Fig.
2b, taken at 30 K. While the most near-bandedge emission

Yoo et al.

503

FIG. 2. a AFM image of the ZnO film on Wz ZnS-buffered Si (1000 nm

1000 nm). Inset shows an AFM line profile along the path indicated by
the dotted line in a. b SEM image of the ZnO on Wz ZnS-buffered Si. c
CL microscopy image in the same area as b at RT. V-defect regions, dark
areas in b, show a brighter near-bandedge emission than c-plane regions.
d CL microscopy image in the same area as b at 30 K. The nearbandedge emission diffused over the whole surface regions centering at the
V-defect regions.

was apparently confined to the V-defect region at RT, it

spread in laterally random orientations at 30 K.
Figure 3a shows a RT CL profile along the path indicated by the dotted line in the inset. The intensity of nearbandedge emission was larger by approximately 20% at the
V-defect region compared with that of the c-plane region.
This reflects the results illustrated in Fig. 2c.
Figure 3b shows a CL profile at 30 K along the path
indicated by the dotted line in the inset. The intensity of the
near-bandedge emission at 30 K quadrupled compared with
that at RT. In contrast with the result presented in Fig. 3a,
near-bandedge emission at 30 K did not show a significant
intensity fluctuation throughout the whole scan range, compared to that at RT. It was reported that V-defect regions on
InGaNGaN multilayers also showed bright emission.2 This
phenomenon was explained by exciton localization caused
1 facets and
by compositional unbalance between the 101
the c-plane regions. In general, deep level emission is very
sensitive to defects and impurities associated with irregularities of the film stoichiometry.10 However, the intensity of the
deep level emission from the ZnO on Wz ZnS-buffered Si
was almost constant throughout the whole scan range, irrespective of the V-defect regions, as shown in Figs. 3a and
3b. This suggests that there were no stoichiometric differences between the V-defect areas and other regions. Also, the
center of the near-bandedge emission remains unchanged
throughout the whole surface region. Therefore, the exciton
localization could be excluded in this case. In order to explain the unique optical behavior presented in Figs. 2 and 3,
another mechanism is needed. It was suggested that the bulk
ZnO has an exciton-free surface region, called an exciton
dead layer, located around 50 in the body of oxide, owing
to a strong repulsive potential for exciton states near the
surface.11 Thus, this layer does not emit but absorbs photons

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504

Yoo et al.

Appl. Phys. Lett., Vol. 84, No. 4, 26 January 2004

FIG. 4. a and b OR and CL from the ZnO film on Wz ZnS-buffered Si at

RT and 30 K, respectively. The regions that had higher energy than the
optical gap are shaded in the CL spectra. Emission within the shaded region
will be absorbed significantly in the exciton dead layer. Inset represents
exciton dead layer dark shaded, bulk region light shaded, and V-defect
V grooved region, respectively. Arrows represent each emission that has
photon energy according to x axis.

FIG. 3. a CL profile at RT along the path indicated by dotted line in the

inset. b CL profile at 30 K along the same path as in the inset.

internally, resulting from the absence of excitons. This absorption is maximized when an incident photon energy coincides with the exciton transition energy. The absorption begins from a slightly lower energy than the optical gap at
higher temperature if band tailing is considered. Figures 4a
and 4b show OR and CL from the ZnO film on Wz ZnSbuffered Si taken at RT and 30 K, respectively. The OR
spectra reveal that excitonic absorption processes at RT and
30 K occur at 3.29 eV and 3.38 eV, respectively.12 As shown
in Fig. 4a, the main emission originated from impuritybound exciton takes place in the bulk region, but the emitted
photons could be absorbed at the exciton-free surface region
owing to the coincidence of the emission energy and the
optical gap at RT. However, the V-shaped defects with approximately 30 nm depth can act as the optical paths and,
consequently, the near-bandedge emission can be transmitted
through a ZnO layer without the internal absorption in the
exciton-dead layer. The amount of the intensity drop, I, for
the near-bandedge emission transmitted through the ZnO
film is roughly estimated to be 10% using II 0 e x formula, assuming the presence of the 50 exciton-free surface
region and the ideal transmittance 100% of the bulk region.
Parameters and x are the absorption coefficient of ZnO
(1.8105 cm1 ) and the depth of exciton-free surface region, respectively.13 The estimated value 10% is less than
the actual intensity drop 20% of CL in Fig. 4a. This dif-

ference also suggests that the a-plane regions in V defects

have optically high transparency.14 At 30 K, most of the
near-bandedge emission at 3.22 and 3.32 eV can be transmitted throughout exciton dead layer without significant absorption because excitonic absorption activates only at higher
than 3.38 eV. This can explain the spreadout nature of the
near-bandedge emission from the V-defect region in Fig.
2d.
In summary, high-quality ZnO films were grown on Si
using hexagonal ZnS buffer. V defects were observed in the
ZnO films. They acted as ultraviolet optical paths by penetrating the exciton dead layer at RT, resulting in the local
increase of UV emission.
1

Z. Liliental-Weber, Y. Chen, S. Ruvimov, and J. Washburn, Phys. Rev.

Lett. 79, 2835 1997.
2
X. H. Wu, C. R. Elsass, A. Abare, M. Mack, S. Keller, P. M. Petroff, S. P.
DenBaars, J. S. Speck, and S. J. Rosner, Appl. Phys. Lett. 72, 692 1998.
3
Z. K. Tang, G. K. L. Wong, P. Yu, M. Kawasaki, A. Ohtomo, H. Koinuma,
and Y. Segawa, Appl. Phys. Lett. 72, 3270 1998.
4
R. D. Vispute, V. Talyansky, S. Choopun, R. P. Sharma, T. Venkatesan, M.
He, X. Tang, J. B. Halpern, M. G. Spencer, Y. X. Li, L. G. SalamancaRiba, A. A. Iliadis, and K. A. Jones, Appl. Phys. Lett. 73, 348 1998.
5
D. C. Look, Mater. Sci. Eng., B 80, 383 2001.
6
Y.-Z. Yoo, T. Chikyow, M. Kawasaki, S. F. Chichibu, and H. Koinuma,
Jpn. J. Appl. Phys., Part 1 42, 7029 2003.
7
Y.-Z. Yoo, T. Chikyow, P. Ahmet, M. Kawasaki, T. Makino, Y. Segawa,
and H. Koinuma, Adv. Mater. Weinheim, Ger. 23, 1624 2001.
8
T. Kato, H. Ohsato, T. Okuda, P. Kung, A. Saxler, C.-J. Sun, and M.
Razeghi, J. Cryst. Growth 183, 131 1998.
9
I. Ohkubo, Y. Matsumoto, A. Ohtomo, T. Ohnishi, A. Tsukazaki, M. Lippmaa, H. Koinuma, and M. Kawasaki, Appl. Surf. Sci. 159, 514 2000.
10
D. C. Reynolds, D. C. Look, B. Jogai, and H. Morkoc, Solid State Commun. 101, 643 1997.
11
J. J. Hopfield and D. G. Thomas, Phys. Rev. 132, 563 1963.
12
Two excitonic transitions at 3.377 eV A exciton and 3.385 eV B exciton were observed at 30 K. 3.38 eV, in this letter, was the averaged value
of the two. About OR measurement for ZnO, see S. F. Chichibu, T. Sota,
P. Fons, K. Iwata, A. Yamada, K. Matsubara, and S. Niki, Jpn. J. Appl.
Phys., Part 2 41, L935 2002.
13
Y.-Z. Yoo, Zhengwu Jin, T. Chikyow, T. Fukumura, M. Kawasaki, and H.
Koinuma, Appl. Phys. Lett. 81, 3798 2002.
14
T. Sekiguchi, S. Miyashita, K. Obara, T. Shishido, and N. Sakagami, J.
Cryst. Growth 214, 272 2000.

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