APPLIED PHYSICS LETTERS

VOLUME 80, NUMBER 16

22 APRIL 2002

Photoreflectance spectra of a ZnO heteroepitaxial film on the nearly

lattice-matched ScAlMgO4 0001 substrate grown by laser
molecular-beam epitaxy
S. F. Chichibua)
Institute of Applied Physics, University of Tsukuba, Tsukuba 305-8573, Japan;
Photodynamics Research Center, RIKEN (Institute of Physical and Chemical Research),
Sendai 980-0845, Japan

A. Tsukazakib) and M. Kawasakic)

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

K. Tamurab) and Y. Segawa

Photodynamics Research Center, RIKEN (Institute of Physical and Chemical Research),
Aoba, Sendai 980-0845, Japan

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

H. Koinumac)
Frontier Collaborate Research Center and Materials and Structure Laboratory,
Tokyo Institute of Technology, Yokohama 227-8503, Japan

Received 10 January 2002; accepted for publication 19 February 2002

Photoreflectance spectra of a high-quality ZnO epilayer on the ScAlMgO4 0001 substrate grown
by laser molecular-beam epitaxy exhibited clear excitonic resonances due to three excitons
associated with uppermost valence bands A, B, and C excitons. The oscillator strengths of the B
and C excitons are larger than that of the A exciton. Their broadening was interpreted to be due to
the contribution by excitonpolaritons in terms of large longitudinaltransverse splitting of
respective excitons. Dependence of the exciton energy on temperature was well fitted assuming the
BoseEinstein statistics giving the Einstein characteristic temperature E of 380 K 33 meV.
2002 American Institute of Physics. DOI: 10.1063/1.1471374

Epitaxial growth of ZnO is attracting attention, since

ZnO and related alloys are excellent materials for use in
visible to ultraviolet light emitters, transparent field effect
transistors, sensors, and piezoelectric devices due to the large
exciton binding energy 59 meV,1 large band gap and the
crystal symmetry. Epilayers of ZnO have been grown by
excimer laser-assisted molecular-beam epitaxy L-MBE,25
MBE,6 8 chemical vapor deposition,9 metalorganic vapor
phase epitaxy,10 and helicon-wave excited plasma sputtering
epitaxy.11 Observation of excitonic stimulated emissions2,3,7
and attempts to grow p-type ZnO5,9 have been reported.
Since the excitonic effect is obvious even at temperatures higher than 300 K,2,3,7 studies of the band structure and
excitons in ZnO are necessary to obtain precise knowledge
of the material. In 1960 Thomas1 and Hopfield12 assigned the
sequence of p-like valence bands in the order, 7u , 9 , and
7l in order of increasing transition energy to the s-like 7c
conduction band. Excitons related to the respective valence
bands are referred to as A, B, and C excitons. On the contrary, Reynolds et al.13 have assigned the ordering as A- 9 ,
B- u7 , and C- 7l by means of polarized magnetoluminesa

Electronic mail: chichibu@bk.tsukuba.ac.jp

On leave from Department of Innovative and Engineered Materials, Tokyo
Institute of Technology, Yokohama 226-8502, Japan.
c
Also at Combinatorial Materials Exploration and Technology COMET,
Tsukuba 305-0044, Japan.
b

cence measurements. Gil14 has supported the latter by calculating the oscillator strengths of respective excitons. The
band assignment is thus still in debate. Nevertheless, either
model predicts that A and B transitions are allowed for the
light polarization E perpendicular to the optic (c-) axis
(Ec), where E is the electric field component, and C transition is essentially allowed for the light polarization E parallel to the c-axis (E c). The resonance energies of the A, B,
and C excitons in bulk ZnO crystals have been determined
by means of optical reflectance OR measurements1,13 to be
E A 3.3770.0003 eV, E B 3.3860.003 eV, and E C
3.4215 eV, respectively, at 4.2 K. The exciton spectra of
ZnO epitaxial films have recently been investigated15,16 by
means of optical absorption measurements showing that the
A- and B-exciton resonances dominate the spectra of
c(0001) orientation epilayers grown on 0001 sapphire15
and ScAlMgO4 SCAM substrates.16
Electroreflectance ER yields a sharp transition structure related to the third derivative of dielectric functions,17
and is a useful technique to obtain the band gap. ER can be
also used to investigate exciton transitions involving
excitonpolaritons18 in wide band gap materials in the limit
of low electric field.
In this letter, spectra of the photo-modulated ER, which
is referred to as photoreflectance PR, in a ZnO epilayer
grown on the nearly lattice-matched 0.09% in-plane SCAM

0003-6951/2002/80(16)/2860/3/$19.00
2860
2002 American Institute of Physics
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Chichibu et al.

Appl. Phys. Lett., Vol. 80, No. 16, 22 April 2002

FIG. 1. OR, PR, and PL spectra of a ZnO epilayer on the ScAlMgO4 0001
substrate at 8 K. EXA, EXB, and EXC represent the excitonic resonances and FEA represents a free A-exciton emission.

substrate19 are compared with the OR and photoluminescence PL spectra as a function of temperature to show the
contribution by excitonpolaritons.
The sample investigated was an 1-m-thick c(0001) oriented undoped ZnO epitaxial film grown by L-MBE on the
SCAM 0001 substrate.19 The epilayer had a small in-plane
compressive strain presumably due to the thermal mismatch;
the strain along the c-axis, zz , was estimated by x-ray diffraction measurement to be smaller than 5104 . PR and
PL spectra were modulated using the 325.0 nm line of a cw
HeCd laser. The PR measurement system was the same as
that used previously.18 The incidence angle for both OR and
PR measurements was smaller than 15. The spectral resolution was 0.09 nm nearly 0.8 meV at the wavelength of 370
nm.
OR, PR, and PL spectra at 8 K are summarized in Fig. 1.
The OR spectrum exhibits two strong reflection anomalies
between 3.37 and 3.40 eV, and a weak saddle around 3.44
eV. The PR spectrum exhibits clear resonance structures labeled EXA, EXB, and EXC. They are principally due to
the ground state A, B, and C exciton transitions,1,1214 since
the signal intensities are strong enough to be accounted for
direct transitions without phonon assistance.
To obtain the resonance energies, the PR spectrum was
analyzed by the low-field ER line shape function17
R
Re
R

j1

C j e i j E j i j m j ,

where p3 is the number of the spectral function to be

fitted, C j , j , E( j), and j are the amplitude, phase, resonance energy, and broadening parameter of the jth feature,
respectively. m j is a parameter that depends on the critical
point type. In this study, the value m j 2 exciton transition
gave the best fit to experimental data. The fitting result is
shown in Fig. 2 the second trace. The first trace shows the
experimental data, and the bottom three traces represent A-,
B-, and C-exciton components. The fitting curve agrees well
with the experimental one except for a dip around 3.44 eV,
which is considered to come from the excited states of the B
exciton, since the energy difference between the dips at

2861

FIG. 2. PR spectrum at 8 K of the ZnO 0001 epilayer on the SCAM

substrate upper trace. The second trace shows the fitting result using Eq.
1. Bottom three traces represent the A-, B-, and C-exciton components, in
which the resonance energies E A, B, and C are shown by the arrows. Vertical lines labeled L and T show the energies of longitudinal
and transverse exciton in the strain-free ZnO, respectively, which are
taken from Ref. 20.

3.395 and 3.445 eV nearly agrees with that between the

ground and the first excited state of B exciton.1 Transition
energies are thus obtained to be E A 3.378 eV, E B
3.386 eV, and E C 3.425 eV, which are indicated by arrows in Fig. 2.
The value E A agrees with that of the shoulder labeled
FEA in the PL spectrum at 8 K, as shown in Fig. 1. Therefore FEA is assigned as being due to the free A-exciton
recombination. The value of E A is approximately 1 meV
larger than that in strain-free bulk ZnO crystals.1,13,21 This
blue shift is due to the residual biaxial compressive stress in
our epilayer; according to Makino et al.,22 the strain zz 5
104 causes a blueshift of E A by 1 meV. Also, E A , E B ,
and E C in our sample fit to the relation of those energies as a
function of stress arranged by Gil et al.23
Values of B and C are 9.3 and 21 meV, respectively,
which are more than three times larger than A 2.7 meV.
One of the plausible explanations of this is an inhomogeneous distribution of the strain, since E C shifts more rapidly
than E B that itself shifts more rapidly than E A under strain.23
If whole B 9.3 meV is attributed to the strain distribution,
A and C are expected to be 2 and 12 meV, respectively.23
Although this effect should not be disregarded, the C value
is too large to be accounted only by the strain inhomogeneity. The broadness of the B- and C-exciton resonances
is explained considering the contribution by exciton
polaritons,20,21 as follows. Hummer and Gebhardt20 and
Lagois21 have investigated the bulk and surface exciton
polaritons in the OR spectra of ZnO single crystals taking the
exciton dead layer into account, where A, B, and C free
excitons couple simultaneously to an electromagnetic wave.
According to Ref. 20, differences in energies of longitudinal
and transverse excitons L and T , respectively, LT , for
the A, B, and C excitons are 2, 11, and 16 meV, respectively.
The values of L and T for the respective excitonic polaritons in the strain-free ZnO are shown by vertical lines in Fig.
2. Note that the large LT for the B and C excitons is indicative of large oscillator strength, since LT f 0 / 0 ,
where f and 0 are the oscillator strength and dielectric
constant normal to the optic axis, respectively, and 0 is the

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2862

Chichibu et al.

Appl. Phys. Lett., Vol. 80, No. 16, 22 April 2002

SCAM substrate by L-MBE. The spectral line shape was

well fitted considering A-, B-, and C-exciton transitions, taking the contribution by excitonic polaritons into account. As
is the case with GaN, PR method was shown to be sensitive
to excitonpolaritons.
The authors would like to thank Dr. D. Look, Dr. C.
Litton, Professor B. Gil, and Dr. T. Makino for fruitful discussions. This work was supported in part by the Ministry of
Education, Culture, Sports, Science and Technology of Japan
Grant-in-Aid for Encouragement of Young Scientists No.
13750264 and Proposed Based Program of NEDO Grant
No. 99S12010.

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D. Reynolds, D. Look, B. Jogai, C. Litton, G. Cantwell, and W. Harsch,
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M. Cardona, Modulation Spectroscopy, in Solid State Phys. Suppl. 11,
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S. F. Chichibu, K. Torii, T. Deguchi, T. Sota, A. Setoguchi, H. Nakanishi,
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1
2

FIG. 3. a PR and b PL spectra and c excitonic transition energies of the

ZnO 0001 epilayer on SCAM as a function of temperature.

exciton resonance energy. Indeed, f of the B and C excitons

have been reported to be more than four times that of the A
exciton.1 The values of LT for the A and B excitons nearly
agree with A and B , respectively. The slight increase in
C 21 meV compared to LT for the C exciton 16 meV
can be interpreted to be due to omitting of the excited state A
and B excitons and independent broadenings of C L and
C T by the strain inhomogeneity mentioned above.
PR and PL spectra are shown as a function of temperature in Figs. 3a and 3b, respectively. The PR signal intensity due to the A transition decreases rapidly with the increase in temperature, and the spectra are dominated by B
and C transitions at higher temperatures. The result is consistent with larger f of B and C excitons. Since the PR signal
was too weak at 300 K, ER spectrum was measured using
MgZnO:Al/SiO2 /ZnO/SCAM metaloxidesemiconductor
structure to determine the transition energy. PL spectra at low
temperatures are characterized by a series of bound exciton
emissions between 3.373 and 3.358 eV, and the spectra
above 100 K are dominated by FEA and FEB, which are
A and B free exciton emissions, respectively. The dependence of E A and FEA, which is marked by vertical lines in
Fig. 3b, on temperature can be fitted by the BoseEinstein
relation, as shown by the solid curve in Fig. 3c giving an
Einstein characteristic temperature E of 380 K 33 meV or
268 cm1. This value is in good agreement with the energy
maximum of the low-energy group of bulk phonon density of
states 8 THz33 meV or 380 K.24
In summary, exciton structures were identified by means
of PR measurements on a ZnO epitaxial film grown on the

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