JOURNAL OF APPLIED PHYSICS

VOLUME 96, NUMBER 2

15 JULY 2004

Phonon scattering of excitons and biexcitons in ZnO

K. Hazua) and T. Sota
Department of Electrical, Electronics, and Computer Engineering, Waseda University, Shinjuku,
Tokyo 169-8555, Japan

S. Adachi
Department of Applied Physics, Hokkaido University, Kitaku, Sapporo 060-8628, Japan

Sf. Chichibu
Institute of Applied Physics, Graduate School of Pure and Applied Sciences, University of Tsukuba,
1-1-1 Tennodai, Tsukuba, Ibaraki 305-8573, Japan

G. Cantwell
Director of Research Zn-Technology, Inc. 910 Columbia St. Brea, California 92821

D. C. Reynolds and C. W. Litton

Materials and Manufacturing Directorate, Air Force Research Laboratory, Wright-Patterson Air Force
Base, Ohio 45433

Received 7 November 2003; accepted 21 April 2004

ex
The phase relaxation time of biexcitons T bi
2 and that of excitons T 2 in a bulk ZnO have been
measured by the use of femtosecond four-wave mixing as functions of excitation wavelength,
excitation power, and temperature. The biexciton-acoustic phonon interaction coefficient has been
bi
53 eV/K as an average value. For A excitons, the interaction coefficients
determined to be ac
ex
ex
8.4 eV/K and opt
with acoustic and optical phonons have been determined to be ac
14 meV, respectively. 2004 American Institute of Physics. DOI: 10.1063/1.1760831

Zinc oxide ZnO is a typical wide and direct gap II-VI

compound semiconductor. Its fundamental optical properties
near the band edge have been intensively studied for last four
decades. Recently progress in crystal growth technique has
been achieved to get its thin films and bulk of rather high
quality and, thus, there is a growing tendency for not only
the application study of the material to optical devices but
also the basic study to reconsider the fundamental optical
properties.
ZnO crystallizes in the wurtzite structure. The degeneracy of valence bands at point is lift up due to the crystal
field and spin-orbit splitting. The valence bands are usually
referred as A-, B-, and C-valence bands from the topmost
band.17 Therefore, excitons formed in the material are
called as A, B, and C excitons in the lowest order approximation. Their binding energies are known to be very large
because of both the small background dielectric constant and
the large effective masses. Excitons can couple and form
two-exciton bound states called biexcitons. Reflecting the
exciton structure, the structure of biexcitons is also complex.
Up to date, biexcitons consisting of two-A-hole excitons
(XX AA : AA biexciton, A-hole exciton and B-hole exciton
(XX AB : AB biexciton, and two-B-hole excitons (XX BB : BB
biexciton have been identified in the material by two-photon
reabsorption8,9 combined with two-photon Raman scattering
spectroscopy10 and by degenerate four-wave mixing
FWM.11
There are several reports on the dephasing property of
biexcitons in bulk and quantum structures1220 by means of

FWM, in addition to a number of reports on the exciton

dephasing. The dephasing rate or the homogeneous broadening is related to the corresponding dephasing time or coherent times T 2 via 2/T 2 for both excitons ( ex) and
biexcitons ( bi). FWM in a two-beam configuration can
determine directly the dephasing time of excitons biexcitons from the decay time d of the signal for positive negative delay times through the relation of T 2 2 d (T 2
4 d ) in the case of homogeneous inhomogeneous broadening limit and then the value of . 12 It is known for semiconductors that the temperature T dependence of has
the form

T 0 ac
T

where (0) is due to the radiative recombination rate, the

spin relaxation rate, and the elastic-scattering processes with

carriers and lattice imperfections, ac

is the acoustic phonon

interaction coefficient, and opt is the coupling coefficient

with optical phonon. E opt denotes the characteristic optical
phonon energy and k B is the Boltzmann constant. The excitation density also influences the homogeneous broadening.
In this paper, we have measured the excitation wavelength, excitation power, and temperature dependence of
FWM signals from a bulk ZnO. From them, the excitonphonon and the biexciton-phonon coupling coefficients have
been determined.
A sample studied herein was an insulating bulk ZnO
with c face, which was grown by the seeded vapor transport
method. The sample size was 2 mm3 mm500 m. The
sample was the same as that used in our previous papers.7,11

Electronic mail: kouji@moegi.waseda.jp

0021-8979/2004/96(2)/1270/3/$22.00

opt
,
exp E opt /k B T 1

1270

2004 American Institute of Physics

Downloaded 20 Feb 2006 to 130.158.130.96. Redistribution subject to AIP license or copyright, see http://jap.aip.org/jap/copyright.jsp

J. Appl. Phys., Vol. 96, No. 2, 15 July 2004

FIG. 1. a Temperature dependence of FWM signals in the time domain for

cross-linear polarization under the central photon energy of 3.362 eV. The
large signal intensity for 120 is attributed to biexcitonic contributions. b
bi(T) obtained from the data for 120 in the panel a shown by solid
circles. The solid line is a theoretically fitted line.

A frequency-doubled, mode-locked Ti:sapphire laser was

used as an excitation source in FWM experiments. The fundamental laser produced pulses of 130 fs at repetition rate of
76 MHz. With respect to details of the other experimental
setup, see Ref. 11. The sample was held in a closed-cycle
helium cryostat and its temperature was varied from T
10 K to T70 K. All data presented herein were measured
from the c face of the sample.
Figure 1 shows the temperature dependence of FWM
signal in the time domain for cross-linear polarization. The
central photon energy of excitation laser L is 3.3662 eV,
which satisfies the relation of L E AA /2. Here E AA represents the eigenenergy of XX AA . As can be expected, the
signal intensity for 120 is larger than that for 120, to
indicate that transitions via biexcitons dominates the signal
generation process. The beating period has been found to be
about 0.79 ps, which is converted to the energy separation
of 5.2 meV. Thus, the beating structure for 120 is due to
the quantum interference between the XX AA X AT transition
with the XX AB X AT transition, where X AT denotes the transverse A exciton. For details, see Ref. 11. Therefore T bi
2 can be
for

directly estimated by the signal decay time bi

120. We
d

Hazu et al.

1271

FIG. 2. a Temperature dependence of FWM signals in the time domain for

colinear polarization under the central photon energy of 3.3725 eV. For
120(0), excitons biexcitons dominantly contribute to the signals. b
ex(T) obtained from the data for 120 in the panel a are shown by solid
circles. Solid diamonds denote ex(T) obtained from data which have been
measured for cross-linear polarization. The solid curve is the best-fit curve
of Eq. 1.

bi
have assumed the relation of bi
d T 2 /2 because biexciton
related FWM emission lines are narrow enough such that the
full width at half maximum is about 0.8 meV. Note that
increasing of the excitation power leads to decreasing of T bi
2 .
This is because scattering events occur more and more frequently. The same holds for the dephasing time of excitons
shown below.
Solid circles in the panel b show the temperature dependence of bi obtained from the data shown in the panel
a. bi(T) for XX AB alone could be obtained from FWM
traces for cocircular polarization according to the polarization selection rules,20 though they are not shown herein.
Those data imply that bi(T) are considered to be almost the
same for both XX AA and XX AB within experimental errors.
More accurate information will be obtained when picosecond
FWM experiments are carried out. bi(T) increases almost
linearly with T to indicates that biexcitons are scattered by
acoustic phonons. We have fitted the simple formula bi(T)
bi
T to the experimental data and, then, the solid
bi(0) ac
line shown in Fig. 2 is obtained as a best fit line with
bi
53 eV/K. In varying L in
bi(0)0.26 meV and ac

Downloaded 20 Feb 2006 to 130.158.130.96. Redistribution subject to AIP license or copyright, see http://jap.aip.org/jap/copyright.jsp

1272

Hazu et al.

J. Appl. Phys., Vol. 96, No. 2, 15 July 2004

the range of L E AB /2, where E AB is the eigenenergy of

bi
ranges from 49 eV/K to 61
XX AB , we have found that ac
eV/K. For T30 K, FWM signals almost coincided with
the laser profile for 120 and bi(T) could not be defined.
This is probably because a part of excitons bound to impurities is thermally released and acts as scatterers.
bi
2 eV/K for 12 nm well
It is known that ac
bi
In0.18Ga0.82As/GaAs single21 quantum well structures,18 ac
4.4 eV/K for a GaAs/Ga0.3Al0.7As single quantum well
bi
bi
4 eV/K in bulk CuCl,12,22 ac
of 25 nm thickness,14 ac
bi
19
11 eV/K in bulk Gal, ac19 eV/K a converted
bi
142 eV/K for threevalue in bulk CdS,23 and ac
dimensionally confined biexcitons in CdS/ZnS quantum
structure consisting of ultrathin layers with strongly fluctuatbi
is a very
ing thickness.24 Therefore the obtained value for ac
large value for bulk materials but appears not to be impossible value. Such strong biexciton-acoustic phonon interaction suggests that created biexcitons might be easily thermalized as dissipating excess energy.
Figure 2a shows the T dependence of FWM signal in
the time domain for colinear polarization. The central photon
energy of excitation laser L is 3.373 eV, which satisfies
the relation of L E AB /2. The corresponding FWM spectrum is dominated by X A , i.e., the contribution from X B
plays a minor role. This explains the smeared beats for 12
0. Note that for L E AB /2, the decay time of FWM
signal becomes drastically short. The reason will be published elsewhere.25 Assuming again the homogeneous broadening limit and analyzing the decay time ex
d for positive
delay times, ex(T) as shown in Fig. 2b by solid circles is
obtained. In Fig. 2b, ex(T) obtained from data for crosslinear polarization is also shown by solid diamonds. ex(T)
increases rapidly for T30 K. In such a case, we have to use
a general expression given by Eq. 1. Fitting Eq. 1 to both
data properly, we obtain the following values: ex(0)
ex
ex
8.4 eV/K, opt
14 meV, and E opt
0.25 meV, ac
ex
13 meV. The value of ac 8.4 eV/K is comparable to
911 eV/K for GaN.26,27 The optical phonon energy of 13
meV is converted to the wave number of 101 cm1, which
coincides with that of low frequency E 2 mode.28 30 Note that
E 2 mode phonons interact with excitons via the deformation
potential coupling.
In summary, we have experimentally studied phonon
scattering of excitons and biexcitons in a bulk ZnO by means
of femtosecond FWM. It has been found that the biexciton-

bi
acoustic phonon interaction coefficient is as large as ac
53 eV/K. For A excitons, the interaction coefficient with
ex
8.4 eV/K and the
the acoustic phonon scattering is ac
coupling constant with the low frequency E 2 mode phonon is
ex
opt
14 meV.

D. G. Thomas, J. Phys. Chem. Solids 15, 86 1960.

J. J. Hopfield, J. Phys. Chem. Solids 15, 97 1960.
3
B. Honerlage, R. Levy, J. B. Grun, C. Klingshirn, and K. Bohnert, Phys.
Rep. 124, 161 1985, and references cited therein.
4
Y. S. Park, C. W. Litton, T. C. Collins, and D. C. Reynolds, Phys. Rev.
143, 512 1966.
5
D. C. Reynolds, D. C. Look, B. Jogai, C. W. Litton, G. Cantwell, and W.
C. Harsch, Phys. Rev. B 60, 2340 1999.
6
B. Gil, Phys. Rev. B 64, R201310 2001.
7
Sf. Chichibu, T. Sota, G. Cantwell, D. B. Eason, and C. W. Litton, J. Appl.
Phys. 93, 756 2003.
8
H. Schrey and C. Klingshirn, Phys. Status Solidi B 93, 679 1979.
9
J. M. Hvam, G. Glattner, M. Reuscher, and C. Klingshrin, Phys. Status
Solidi B 118, 179 1983.
10
H. Schrey and C. Klingshrin, Solid State Commun. 28, 9 1979.
11
K. Hazu et al., Phys. Rev. B 68, 033205 2003.
12
E. Vanagas, J. Kudrna, D. Brinkmann, P. Gilloit, and B. Honerlage, Phys.
Rev. B 63, 153201 2001.
13
T. F. Albrecht et al., Phys. Rev. B 54, 4436 1996.
14
W. Langbein and J. M. Hvam, Phys. Rev. B 61, 1692 2000.
15
W. Langbein, T. Meier, S. W. Koch, and J. M. Hvam, J. Opt. Soc. Am. B
18, 1318 2001.
16
H. P. Wagner, A. Schatz, W. Langbein, J. M. Hvam, and A. L. Smirl, Phys.
Rev. B 60, 4454 1999.
17
H. P. Wagner, W. Langbein, and J. M. Hvam, Phys. Rev. B 59, 4584
1999.
18
P. Borri, W. Langbein, J. M. Hvam, and F. Martelli, Phys. Rev. B 60, 4505
1999.
19
K. Kyhm, R. A. Taylor, J. F. Ryan, T. Aoki, M. Kuwata-Gonokami, B.
Beaumont, and P. Gibart, Phys. Rev. B 65, 193102 2001.
20
S. Adachi, S. Muto, K. Hazu, T. Sota, K. Suzuki, Sf. Chichibu, and T.
Mukai, Phys. Rev. B 67, 205212 2003.
21
W. Langbein, J. M. Hvam, M. Umlauff, H. Kalt, B. Jobst, and D. Hommel,
Phys. Rev. B 55, R7383 2000.
22
H. Akiyama, T. Kuga, M. Matsuoka, and M. Kuwata-Gonokami, Phys.
Rev. B 42, 5621 1990.
23
Ch. Mann, W. Langbein, U. Waggon, and A. L. Ivanov, Phys. Rev. B 64,
235206 2001.
24
K. Hild, D. Miller, W. Langbein, U. Woggon, H. Hetterich, and C. Klingshirn, Phys. Status Solidi B 224, 379 2001.
25
K. Hazu et al. unpublished.
26
K. Hazu, A. Shikanai, T. Sota, K. Suzuki, S. Adachi, S. F. Chichibu, and T.
Mukai, Phys. Rev. B 65, 195202 2002.
27
S. Pau, J. Kuhl, F. Scjolz, V. Haerle, M. A. Khan, and C. J. Sun, Appl.
Phys. Lett. 72, 557 1998.
28
T. C. Damen, S. P. S. Porto, and B. Tell, Phys. Rev. 142, 570 1966.
29
S. S. Mitra and J. J. Bryant, Bull. Am. Phys. Soc. 10, 333 1965.
30
J. M. Calleja and M. Cardona, Phys. Rev. B 16, 3753 1977.
1
2

Downloaded 20 Feb 2006 to 130.158.130.96. Redistribution subject to AIP license or copyright, see http://jap.aip.org/jap/copyright.jsp