APPLIED PHYSICS LETTERS

VOLUME 84, NUMBER 22

31 MAY 2004

Degenerate layers in epitaxial ZnO films grown on sapphire substrates

H. Tampo,a) A. Yamada, P. Fons, H. Shibata, K. Matsubara, K. Iwata, and S. Niki
National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Umezono, Tsukuba,
Ibaraki 305-8568, Japan

K. Nakahara and H. Takasu

Optical Device R&D Division, ROHM Corp., Ltd., 21 Mizosaki-cho, Saiin, Ukyo-ku, Kyoto 615-8585, Japan

Received 1 December 2003; accepted 14 April 2004; published online 12 May 2004
ZnO films were grown on low-temperature LT buffer layers on sapphire a-plane 1120
substrates by radical source molecular-beam epitaxy. The LT buffer layers were found to effect the
electrical properties of subsequently grown undoped ZnO films, and their presence was found to be
indispensable for the growth of films with low carrier concentrations and high mobilities.
Temperature-dependent Hall measurements showed the existence of a degenerate region related to
the LT buffer layers. It was found that the effects of degenerate layers could be reduced by using
annealing treatments and nitrogen doping of the LT buffer layers. The dominant residual donor
energy of 110 meV was found to be different than previously reported. The carrier concentration of
a ZnO film fabricated using a nitrogen-doped buffer layer was 7.51016 cm3 with a mobility of
132 cm2 /V s at room temperature. 2004 American Institute of Physics.
DOI: 10.1063/1.1758295

ZnO-based material is a good candidate for optoelectronic devices due to the large 59 meV excitonic binding
energy of ZnO.1 GaN-based alloys have been applied to
light-emitting diodes LEDs and laser diodes LDs in the
visible wavelength region, however, high In concentration
InGaN is needed for efficient emission,2 4 making it difficult
to use GaN-based alloys for ultraviolet UV LDs and LEDs.
On the contrary, ZnO systems have a strong possibility for
UV LD and LED applications by the utilization of the large
exciton binding energy and use ZnOMgO alloys.5,6 UV
light sources are needed for numerous applications, such as
light sources for phosphors excitation, high density optical
recording, medical equipment, and treatment of environmental pollution materials.7,8
ZnO-based optoelectronic devices need to be based upon
single-crystal films with p type as well as n-type conductivities. Unfortunately, as-grown ZnO epitaxial films are naturally only n type, and therefore the reproducible fabrication
of p-type ZnO is one of the key issues remaining. To make
extrinsic p-type doping of ZnO films possible, one of the
most important prerequisites is that undoped ZnO films with
high carrier mobility and low residual carrier concentration
can be reproducibly grown. To date, we have grown undoped
ZnO by using a-plane sapphire substrates, a high-purity
plasma tube low aluminum impurity levels, and use of lowtemperature LT buffer layers.9,10
A LT buffer layer is necessary for the fabrication of
high-quality ZnO films, however, it is unknown how LT
buffer layers effect undoped ZnO film properties, in particular electrical properties. In this letter, we use temperaturedependent Hall-effect measurements to investigate changes
in the electrical properties of undoped ZnO films due to the

presence of LT buffer layers for a variety of growth conditions.

ZnO films were grown by radical source molecular-beam
epitaxy MBE. Elemental Zn and rf radical oxygen were
used as group-II and group-VI sources, respectively. rf radical nitrogen was used for doping the LT buffer layers. In this
study, the oxygen and nitrogen flow rates were fixed at 0.5
sccm and 0.7 sccm, respectively. The substrates used were
a-plane sapphire. After thermal cleaning in situ at 700 C for
10 min, LT buffer layers were grown at 350 C. As an additional treatment, as-grown buffer layers were postannealed in
situ at 600 C for 20 min in a vacuum. Following the annealing step, undoped ZnO films were grown on top of the LT
buffer layers at 600 C. The undoped ZnO films grown at
high temperature were about 0.5 m in thickness.
The electrical properties of ZnO films were studied by
Hall effect measurements using the van der Pauw geometry
with a magnetic field of 0.77 T. Hall measurements were
conducted over the temperature range 5 to 300 K using a
continuous flow helium cooling system.
For growth of high-quality ZnO films, a relatively high

FIG. 1. Electrical properties of ZnO films as a function of LT buffer layer

thickness.

Author to whom correspondence should be addressed; electronic mail:

tampo-21@aist.go.jp

0003-6951/2004/84(22)/4412/3/$22.00
4412
2004 American Institute of Physics
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Tampo et al.

Appl. Phys. Lett., Vol. 84, No. 22, 31 May 2004

4413

TABLE I. Electrical properties of ZnO films with different LT buffer treatments and LT buffer layers alone
at RT.
Buffer treatment
Dopant

Annealing

n (cm3 )

(cm2 /V s)

s /

ZnO films
with buffer layers

Nitrogen

Vacuum
Vacuum

17

1.04 10
7.71 1016
7.45 1016

95
125
132

1.14 104
1.17 104
1.30 104

ZnO buffer layers

alone

Nitrogen

Vacuum
Vacuum

1.50 1019
1.42 1019
3.36 1018

26
31
3

5.28 103
4.75 103
2.05 105

growth temperature is needed. However, unless LT buffer

layers are introduced, ZnO films that exhibit twodimensional growth are not obtained. The use of a growth
temperature 600 C for which re-evaporation of Zn atoms
is large Zn cell temperature 260 C leads to a very short
lifetime for physisorped Zn and inhibits surface migration.
This phenomenon is similar to the case of GaN growth on
sapphire substrates for which it is indispensable to grow LT
buffer layers to obtain high-quality films.1113
To investigate the influence of LT buffer layers, a series
of ZnO films were grown with varying thickness LT buffer
layers and the electrical properties were measured. The LT
buffer layers were confirmed to be c-oriented epitaxial
growth by in situ reflection high-energy electron diffraction,
which was the same growth orientation as the hightemperature-grown layers.9,14 Figure 1 shows the carrier concentrations and mobilities of undoped ZnO films at room
temperature RT as a function of LT buffer layer thickness.
The LT buffer layers were grown at 350 C, so ZnO growth
occurred without inhibited adatoms migration; the surfaces
of the LT buffer layers were atomically flat.14 As a result, the
thickness of the LT buffer layers was found to linearly increase by 8 nm/min. On the contrary, without the use of LT
buffer layers, films grown at 600 C were found to have
rough surfaces and poor electrical properties due to the
dominance of the nucleation step. For increasing film thickness, the carrier concentration mobility was found to decrease increase as the crystallinity of the ZnO layers recovered with increasing thickness.14 Above a given thickness,
however, the carrier concentrations were found to increase
and the mobilities decrease. This is felt to be due to a
tradeoff between the influence of the buffer layer and the
high-temperature epilayer on film properties parallel conduction Table I. A detailed discussion follows.
In order to reduce the effects from the LT buffers and

obtain higher-quality ZnO films, we have grown ZnO films

on various postgrowth processed LT buffers keeping the LT
buffer thickness constant at 40 nm. Table I shows the electrical properties at RT of undoped ZnO films grown on LT
buffers with/without nitrogen doping and in situ vacuum annealing. Using both nitrogen-doped and vacuum-annealed LT
buffers, a ZnO film with a carrier concentration of 7.5
1016 cm3 and a mobility of 132 cm2 /V s at RT was obtained.
The variation in the electrical properties of ZnO films
with buffer layer treatment was examined. In order to clarify
the relationship between the undoped film and the buffer
layer, temperature-dependent Hall measurements were conducted. Figure 3 shows the results of Hall measurements for
the three samples shown in Table I with various LT buffer
treatments. For samples prepared with untreated and
vacuum-annealed buffer layers, in Hall measurements beginning at high T and proceeding toward low T, classical donor
freeze out can be observed as can be seen in Fig. 2a. However, both samples exhibit increasing carrier concentration
with decreasing temperature between 50 K and 100 K. This
behavior is indicative of parallel conduction between the LT
buffer and high-temperature films. GaN films on sapphire
substrates are usually grown by two-stage growth, and the
presence of a degenerate layer near the GaN/sapphire interface has been reported.15 Due to the presence of this degenerate layer, the carrier concentration in the untreated sample
is independent of T for low T. The vacuum annealing of the
buffer can be considered to reduce the influence of the degenerate layer, and may reduce the dislocations as reported
in a ZnO/LT MgO system,16 and hence lead to the enhancement of electrical properties. To further reduce the influence
of the buffer layer, a nitrogen-doped buffer layer was used to
reduce the electron carrier concentration. Secondary ion
mass spectrometry profile analysis showed that the nitrogen

FIG. 2. Temperature-dependent electron concentrations of ZnO films with untreated and vacuum-annealed LT buffer layers a and with nitrogen-doped and
vacuum-annealed LT buffer layers b, and mobilities of these three samples c. The solid line in b is a single-level donor model fit.
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4414

Tampo et al.

Appl. Phys. Lett., Vol. 84, No. 22, 31 May 2004

FIG. 3. Temperature-dependent electron concentrations of LT buffer layers

alone with different treatments.

concentration was 1019 cm3 in the nitrogen-doped LT

buffer layer, and there was no significant diffusion of nitrogen from the nitrogen doped buffer layer. As shown in Fig.
2b, using a nitrogen-doped buffer layer, the influence of the
degenerate layer can be seen to have become negligible resulting in enhanced measured mobilities Fig. 2c. The
temperature-dependent Hall data was well fitted by a single
donor level model as can be seen in Fig. 2b. From charge

p, the donor concentration N D and the

neutrality nN D
donor energy E D were estimated to be 3.21017 cm3 and
110 meV, respectively. The value of the donor energy in this
work 110 meV is larger than the previously reported values
of 30 meV and 60 meV.17 As the former was obtained
from epitaxial films, and the latter from bulk ZnO, the
mechanism for the formation of the donor levels may be
different.
As shown in Table I, ZnO LT buffers alone show lower
sheet resistivity than ZnO films with buffer layers except for
the simultaneously nitrogen-doped and vacuum-annealed
samples, strongly suggesting the existence of parallel conduction due to LT buffers. In order to investigate the electrical characteristics of the LT buffers independently, we have
conducted temperature-dependent Hall measurement of LT
buffers alone Fig. 3. For the untreated buffer layer and the
vacuum-annealed sample, the electron concentration was
found to be independent of temperature with n1.5
1019 cm3 Fig. 3a which is characteristic of degenerate semiconductors, since the Mott transition concentration
in ZnO is estimated to be 61018 cm3 , 18 and the
conduction-band
effective
density
of
states
4
1018 cm3 (m * 0.3m 0 ). On the contrary, the nitrogendoped buffer layer did not exhibit degenerate electrical be-

havior with an electron concentration of 3.51018 cm3 in

the saturation range Fig. 3b. However, as the decrease in
carrier concentration was not monotonic and a small peak
was observed near 70 K, a small degenerate layer at the
ZnO/sapphire interface may still be present.
From these results, an optimum thickness of the LT
buffer layer was found to be 20 40 nm. Moreover it was
found that by changing the treatment of the LT buffer layers,
ZnO films with lower carrier concentrations and higher mobility than untreated samples could be grown.
We have grown high-quality ZnO films with a carrier
concentration of 7.51016 cm3 and a mobility of 132
cm2 /V s at RT by using a nitrogen-doped and vacuumannealed buffer layer. We confirmed that untreated and
vacuum-annealed LT buffer layers exhibit degenerate behavior which in turn effects the electrical properties of undoped
ZnO films. Nitrogen-doped and vacuum-annealed buffer layers displayed little degenerate behavior and were found to
enhance the electrical properties of undoped ZnO films
grown on them. The presence of a previously unreported
donor level of 110 meV was also found in MBE-grown epitaxial ZnO.
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