JOURNAL OF APPLIED PHYSICS

VOLUME 94, NUMBER 2

15 JULY 2003

Brillouin scattering study of ZnO

T. Azuhataa)
Department of Materials Science and Technology, Hirosaki University, Hirosaki, Aomori 036-8561, Japan

M. Takesada and T. Yagi

Research Institute for Electronic Science, Hokkaido University, Sapporo 060-0812, Japan

A. Shikanai
Venture Business Laboratory, Kyoto University, Sakyo, Kyoto 606-8501, Japan

SF. Chichibub)
Institute of Applied Physics and Graduate School of Pure and Applied Sciences, University of Tsukuba,
Tsukuba, Ibaraki 305-8573, Japan, NICP, ERATO, Japan Science and Technology Corporation (JST),
Chiyoda, Tokyo 102-0071, Japan, and Photodynamics Research Center, RIKEN (Institute of Physical
and Chemical Research), Aoba, Sendai, Miyagi 980-0845, Japan

K. Torii,c) A. Nakamura, and T. Sota

Department of Electrical, Electronics, and Computer Engineering, Waseda University, Shinjuku,
Tokyo 169-8555, Japan

G. Cantwell and D. B. Eason

Eagle-Picher Technologies, LLC, 200 B.J. Tunnell Boulevard, Miami, Oklahoma 74354

C. W. Litton
Air Force Research Laboratory (AFRL/MLPS), WrightPatterson Air Force Base, Ohio 45433

Received 7 March 2003; accepted 29 April 2003

Polarized Brillouin scattering measurements were carried out for a bulk ZnO single crystal. The
whole set of elastic stiffness constants was determined to be c 1119.0, c 1211.0, c 139.0, c 33
19.6, c 443.9, and c 664.0 in units of 1011 dyn/cm2 . The relationships between photoelastic
constants at wavelength of 514.5 nm were also obtained: p 11 , p 13 , p 44 , and p 661.8, 2.3, 0.50, and
0.38, respectively, relative to p 12 . 2003 American Institute of Physics.
DOI: 10.1063/1.1586466

I. INTRODUCTION

powerful tool with which to investigate elastic properties of

materials. Sound velocities and thus elastic stiffness constants can be determined with high precision.
Photoelastic constants can be also determined from Brillouin scattering intensity. ZnO has six independent photoelastic constants p i j (i j12, 13, 31, 33, 44, and 66, and
p 11 p 122 p 66 . There are three reports on photoelastic constants of ZnO: Tell et al.6 reported relative values of p 11 ,
p 12 , and p 31 between 415 and 630 nm; Berkowicz and
Skettrup7 measured Brillouin scattering and piezobirefringence to evaluate p 44 and p 66 from 400 to 560 nm; Sasaki
et al.8 and Kushibiki et al.9 reported photoelastic constants at
632.8 nm. However, the whole set of photoelastic constants
at 514.5 nm is still not known.
In this article, polarized Brillouin scattering measurements are carried out for a bulk ZnO single crystal to determine the whole set of the elastic stiffness constants and also
to get information on the photoelastic constants. The results
are compared with those reported previously.

ZnO is one of the key materials in surface acoustic wave

devices, piezoelectric and pyroelectric devices, and gas sensors. It is also a promising material for visible to ultraviolet
light emitters and transparent field effect transistors. For efficient design of these devices, it is important to determine
the fundamental material parameters.
ZnO crystallizes in a wurtzite structure and its space
group is C 46 v . There are five independent elastic stiffness
constants, c i j (i j11, 13, 33, 44, and 66, and c 12c 11
2c 66 . The whole set of elastic stiffness constants of ZnO
was reported by Bateman1 and by Kobiakov2 for single crystals and by Carlotti et al.3 for 0001-oriented polycrystalline
films on sapphire using ultrasonic techniques. Carlotti et al.4
also measured Brillouin scattering spectra of 0001-oriented
polycrystalline films on Si and estimated their elastic stiffness constants. Solbrig5 reported elastic stiffness constants
except for c 44 using single crystals by means of an ultrasonic
resonance method. There is, however, no report on elastic
stiffness constants of single crystal ZnO by Brillouin scattering. Brillouin scattering spectroscopy is contactless and is a

II. EXPERIMENT

The sample used herein was a colorless bulk ZnO single

crystal. It was a 0001 substrate with both sides polished
and it was 1060.5 mm3 . Brillouin scattering measurements were performed at room temperature using a
Sandercock-type six-pass tandem Fabry-Perot as a spectrom-

Electronic mail: azuhata@cc.hirosaki-u.ac.jp

Electronic mail: chichibu@bk.tsukuba.ac.jp
c
Present address: Institute of Industrial Science, University of Tokyo,
Meguro, Tokyo 153-8505, Japan.
b

0021-8979/2003/94(2)/968/5/$20.00

968

2003 American Institute of Physics

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Azuhata et al.

J. Appl. Phys., Vol. 94, No. 2, 15 July 2003

FIG. 1. Scattering geometries used in the present study. koi and kso are wave
vectors of incident and scattered light outside the sample, respectively.

eter and a 514.5 nm line of an Ar-ion laser as a light source.

When necessary, a mechanical shutter was set in front of the
photodetector to avoid damage from Rayleigh scattering.
Further details of the system are described elsewhere.10
III. RESULTS AND DISCUSSION
A. Elastic stiffness constants

obtained B and Q obtained from Eq. 1a. Note that all

wave vectors in Eqs. 1a are those inside the sample and that
ki and ks depend on the refractive indices of the material.
Strictly speaking, ZnO has optical anisotropy, and refractive indices for ordinary and extraordinary rays are different
even at the same wavelength. However, the results of spectroscopic ellipsometry11 show the difference is very small at
the wavelength used in our measurements. Thus, we considered the refractive index n as isotropic and used n2.04 for
both ordinary and extraordinary polarization. The value was
interpolated from the data in Ref. 11. Under these conditions,
the relation ki ks holds.
The scattering geometries used in this study are illustrated in Fig. 1. koi and kso are wave vectors of incident and
scattered light outside the sample, respectively. In the A
and B geometries, Q is perpendicular and parallel to the c
axis, respectively. In the C geometry, the angle between Q
and the c axis, , is about 20, which is evaluated by Snells
law. Expressions for Q are

In Brillouin scattering spectroscopy, sound velocity V

can be determined by Debye approximation from the following expressions:
ki ks Q,

1a

h i h s h B ,

1b

969

Q & koi ,

2a

Q 2 n 2 1/2 koi ,

2b

Q 2n koi

2c

and

and
Q
B V
,
2

1c

where ki ( i ) and ks ( s ) are wave vectors frequencies of

incident and scattered light, respectively. Q is the wave vector of phonons observed. B is the Brillouin shift and is small
enough to be negligible compared with i and s . The value
of V can be calculated through Eq. 1c using experimentally

in the A, B, and C geometries, respectively. Note that

Q in the A geometry is independent of n. In this article the
polarization perpendicular parallel to the scattering plane is
defined as V H polarization. For example, VH polarization
denotes that incident light is V polarized and scattered light
is H polarized.

TABLE I. Acoustic phonon modes, sound velocities, and polarization selection rules for ZnO. is the crystal
density.
Selection rule
Geometry

Propagation direction

Mode

Q 100

Longitudinal

Sound velocity

Transverse

Q 001

Q sin , 0, cos

Quasilongitudinal
Quasitransverse
Transverse

c 11

Allowed

Forbidden

c 44

Forbidden

Forbidden

c 66

Forbidden

Allowed

c 33

Allowed

Forbidden

c 44

Forbidden

Allowed

V QL a
V QT b

Allowed
Allowed
Forbidden

Forbidden
Forbidden
Allowed

Longitudinal
Transverse

VH

Transverse

VV

c 66 sin2 c44 cos2

2
V QL
(c 11 sin2 c33 cos2 c44)/2 (c 11c 44)sin2 (c33c 44)cos2 2 /4(c 13c 44) 2 sin2 cos2 .
2
V QT
(c 11 sin2 c33 cos2 c44)/2 (c 11c 44)sin2 (c33c 44)cos2 2 /4(c 13c 44) 2 sin2 cos2 .

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970

J. Appl. Phys., Vol. 94, No. 2, 15 July 2003

Azuhata et al.

FIG. 2. Brillouin scattering spectra in A geometry for a VH and b VV

polarization. The peaks at 7.3 and 15.9 GHz are, respectively, due to transverse and longitudinal mode phonons that propagate perpendicular to the c
axis. The free spectral range FSR is 30.0 GHz.

FIG. 3. Brillouin scattering spectra in B geometry for a VH and b VV

polarization. The peaks at 19.5 and 43.7 GHz are, respectively, due to transverse and longitudinal mode phonons that propagate parallel to the c axis.
The FSR is 54.5 GHz.

Acoustic phonon modes, their sound velocities, and polarization selection rules are tabulated in Table I for the three
scattering geometries. Here, is the crystal density and we
used 5.677 g/cm3 calculated from the lattice constants
(a3.2497 and c5.2065 ) and atomic masses of Zn
and O. The lattice constants were determined from 0006
5) diffraction peaks by the Bond method12 using a
and (202
high resolution x-ray diffractometer, the Rigaku ATX-E. The
transverse mode in the B geometry is doubly degenerate.
With the polarization selection rules, c 11 , c 33 , c 44 , and c 66
can be directly determined from corresponding sound velocities, and c 12 is calculated from the relation c 12c 112c 66 .
To determine c 13 , quasilongitudinal and quasitransverse
modes in the C geometry can be utilized.
Figure 2 shows Brillouin scattering spectra in the A
geometry with Fig. 2a for VH polarization and Fig. 2b for
VV polarization. According to polarization selection rules,
the peaks at 7.3 and 15.9 GHz are assigned to modes corresponding to c 66 and c 11 , respectively. In Fig. 3, Brillouin
scattering spectra in the B geometry are presented. The
peaks at 19.5 and 43.7 GHz are attributed to transverse and
longitudinal acoustic phonons propagating along the c axis,
respectively. Figure 4 shows Brillouin scattering spectra in
the C geometry. The peaks at 22.0 and 45.9 GHz in Fig.
4b are, respectively, due to quasitransverse and quasilongitudinal modes. Additional peaks are also found at 7.3 GHz in
Fig. 4a and 16.0 GHz in Fig. 4b. These two peaks are
assigned to phonons excited by the incident light reflected
from the backside of the sample, because the peaks satisfy
the polarization selection rules for A geometry and their
Brillouin shifts are almost the same as those in Fig. 2. Signals due to transverse acoustic phonons in the C geometry,
which are expected to appear at 20.8 GHz in VH polarization, are not observed although the phonon is allowed. The
reason for this will be discussed in Sec. III B.

The elastic stiffness constants of ZnO obtained from the

Brillouin shifts are tabulated in Table II together with previous results. Yamaguchi et al.13 reported that there is some
discrepancy between the elastic stiffness constants of epitaxial GaN on sapphire and those of free-standing GaN, which
is considered to be caused by residual strain. Thus, we compare our results with those for single crystals. As seen from
Table II, most c i j in Refs. 1, 2, and 5 are larger than ours by
2%18%. Only c 12 in Ref. 5 is 7% smaller than the value in

FIG. 4. Brillouin scattering spectra in C geometry for a VH and b VV

polarization. The FSR is 54.5 GHz. The peaks at 22.0 and 45.9 GHz are,
respectively, due to quasitransverse and quasilongitudinal mode phonons.
The peaks at 7.3 and 16.0 GHz are attributed to phonons excited by the
incident light reflected from the backside of the sample. Transverse mode
phonons expected to appear at 20.8 GHz in VH polarization are not observed.

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Azuhata et al.

J. Appl. Phys., Vol. 94, No. 2, 15 July 2003

971

TABLE II. Elastic stiffness constants of ZnO in units of 1011 dyn/cm2 .

Sample
a

Single crystal
Single crystalb
0001-oriented polycrystal on sapphirec
0001-oriented polycrystal on Sid
Single crystale
Present result

c 11

c 12

c 13

c 33

c 44

c 66

20.97
20.7
15.7
20.6
19.4
19.0

12.11
11.77
8.9
11.7
10.2
11.0

10.51
10.61
8.3
11.8
9.4
9.0

21.09
20.95
20.8
21.1
21.7
19.6

4.247
4.48
3.8
4.43

3.9

4.429
4.46
3.4
4.46
4.6
4.0

Ultrasonic pulse technique Ref. 1.

Ultrasonic resonance method Ref. 2.
c
Acoustic investigation technique Ref. 3.
d
Brillouin scattering spectroscopy Ref. 4.
e
Ultrasonic resonance method Ref. 5.
a

this study. As mentioned before, crystal density and refractive indices are used to calculate elastic stiffness constants
from Brillouin shifts. To investigate the influence of those
material parameters on the values of c i j , a comparison was
made Table III in terms of sound velocities in the A geometry where Q is independent of n. Since a clear discrepancy is also found in sound velocities, the material parameters are not responsible for the difference in c i j . The cause
of the difference might be the sample quality, the accuracy of
each experimental method, and phonon dispersion.

T H 1

L
I B,VV

T
I B,VH

T
I A,VH

2
p 12
2
p 66

QT
I C,VV

c 66
TV
.
2
c 11 cos T H

Here, is the angle between ki and the c axis. T V (T H ) is

transmittance for V(H)-polarized light on the surface of the
sample and is calculated to be 78.8% 95.5% by using
T V 1

sin2 /4
sin2 /4

4a

and

TABLE III. Sound velocities of ZnO for the modes observable in the A
geometry in units of 105 cm/s. Corresponding c i j are shown in parentheses.
Values of used in each calculation are also listed in units of g/cm3.
Mode
Reference

Longitudinal (c 11)

Transverse (c 66)

1
2
5
Present result

6.078
6.02
5.85
5.79

2.793
2.80
2.9
2.7

5.676
5.704
5.66
5.677

2
p 13
2
p 44

c 44
TV
.
c 33 sin2 T H

Although p 44 includes the rotational effect,14 the effect can

be neglected in this case because of the small optical
anisotropy.11 For the C geometry,

B. Photoelastic constants

L
I A,VV

4b

Similarly,

QL
I C,VV

Since Brillouin scattering efficiency is a function of photoelastic constants,14 information on photoelastic constants
can be obtained by analyzing the intensity of scattered light.
Here, we define the scattering intensity of mode M for VH
M
, for example. M is
polarization in the A geometry as I A,VH
L, T, QL, and QT for longitudinal, transverse, quasilongitudinal, and quasitransverse modes, respectively. The ratio of
L
T
and I A,VH
is given by
I A,VV

tan2 /4
.
tan2 /4

2
V QT
p 12 sin QL sin p 13 cos QL cos 2
2
p 12 sin QT sin p 13 cos QT cos 2
V QL

and
T
I C,VH
QT
I C,VV

2
V QT
c 66 sin2 c 44 cos2

TH
sin2 cos2 p 66 p 44 2
,
p 12 sin QT sin p 13 cos QT cos 2 T V

where QL ( QT ) is the angle between the displacement for

a quasilongitudinal quasitransverse mode and the c axis.
The value of ( QL or QT ) is calculated using
tan

V Q2 c 44 sin2 c 33 cos2 c 13c 44 sin cos

V Q2 c 11 sin2 c 44 cos2 c 13c 44 sin cos

8
Here, V Q V QL for QL and V QT for QT . By substituting
experimental Brillouin scattering intensity ratios into Eqs.
3, 5, and 6, the relationship of p 12 , p 13 , p 44 , and p 66
can be obtained. The ratios of integrated Brillouin scattering
L
T
L
T
/I A,VH
1.4, I B,VV
/I B,VH
27, and
intensity were I A,VV
QL
QT
I C,VV /I C,VV 11. Because all the phonon modes observed in
A, B, and C geometries were confirmed to appear in VV
or VH polarization exclusively, the ratios were obtained
from the spectra measured with V-polarized incident light
and unpolarized scattered light to avoid any experimental
error in intensity caused by rotation of the polarizer. It is
reasonable to regard all values of p i j at 514.5 nm as negative, because those at 632.8 nm were reported to be negative9

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972

Azuhata et al.

J. Appl. Phys., Vol. 94, No. 2, 15 July 2003

and also the resonant cancellation point of p 44 and p 66 was

observed at 432.8 nm.7 Thus, we obtained two sets of solutions: (p 13 ,p 44 ,p 66)(2.3,0.50,0.38) and 0.77, 0.17, 0.38
T
QT
/I C,VV
0.02 is prerelative to p 12 . For the former set, I C,VH
dicted and for the latter, 0.48. As is mentioned in Sec. III A,
transverse mode phonons were not observed in Fig. 4. Therefore, the former set is adopted. The missing transverse mode
is explained by its very low scattering efficiency. The mode
is found to be accidentally forbidden at 514.5 nm. As for
p 11 , p 111.8p 12 is obtained from p 11p 122 p 66 .
With our Brillouin scattering intensity, previously reported photoelastic constants at 514.5 nm can be checked.
Tell et al.6 obtained p 660.09p 12 . Since the relation yields
L
T
/I A,VH
27, it is inconsistent with our Brillouin scatterI A,VV
ing data. Similarly, it is difficult to reproduce the missing
transverse mode in the C geometry using p 66 0.3 p 44 reported by Berkowicz and Skettrup.7 The results in this study
are the most plausible at present.
IV. CONCLUSIONS

Polarized Brillouin scattering measurements were performed for a bulk ZnO single crystal. From the Brillouin
shifts observed, the whole set of elastic stiffness constants
was determined: c 1119.0, c 1211.0, c 139.0, c 3319.6,
c 443.9, and c 664.0 in units of 1011 dyn/cm2 . The relationships between the photoelastic constants at 514.5 nm
were also obtained from the Brillouin scattering intensity:
p 11 , p 13 , p 44 , and p 661.8, 2.3, 0.50, and 0.38, respectively, relative to p 12 .

ACKNOWLEDGMENTS

The authors are grateful to Dr. R. Matsuo, Rigaku Corporation, for his help in x-ray diffraction measurements. One
of the authors M.T. would like to express his thanks for a
Grant-in-Aid for Young Scientists A from Ministry of Education, Culture, Sports, Science and Technology of Japan
MEXT No. 14702006. This work was supported in part by
the 21st Century COE program Promotion of Creative Interdisciplinary Materials Science for Novel Functions under
MEXT.

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