APPLIED PHYSICS LETTERS 86, 011921 (2005)

Polarity control of ZnO films grown on nitrided c-sapphire

by molecular-beam epitaxy
Xinqiang Wang, Yosuke Tomita, Ok-Hwan Roh, Masayuki Ohsugi, Song-Bek Che,
Yoshihiro Ishitani, and Akihiko Yoshikawaa)
Center for Frontier Electronics and Photonics, Department of Electronics and Mechanical Engineering,
Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan

(Received 28 June 2004; accepted 8 November 2004; published online 27 December 2004)
The polarity of molecular-beam epitaxy grown ZnO films was controlled on nitrided c-sapphire
substrate by modifying the interface between the ZnO buffer layer and the nitrided sapphire. The
ZnO film grown on nitrided sapphire was proven to be Zn-polar while the O-polar one was obtained
by using gallium predeposition on nitrided sapphire, which was confirmed by coaxial impact
collision ion scattering spectroscopy and chemical etching effect. The Zn-polar ZnO film showed
higher growth rate, slightly better quality, and different surface morphology in comparison to the
O-polar one. 2005 American Institute of Physics. [DOI: 10.1063/1.1846951]
ZnO is now receiving much attention due to its potential
use in short wavelength optoelectronic devices.13 Like GaN,
ZnO has wurtzite crystal structure, which has different polar
surfaces along the c axis, i.e., Zn-polarity and O-polarity.
These two faces have different surface configuration, composition, and chemical structure.4,5 In addition, the different
polar films also differ in their electronic properties.6 As frequently demonstrated in the research of nitrides, the polarity
has large effect on the growth process, material property, and
even in devices fabrication.710 Furthermore, the polarity influences the impurity doping efficiency, for example, Mg
doping has been reported to be much easier on Ga-polar GaN
than on N-polar one.11 Although there is still controversy as
to which polarity is better for p-type doping of ZnO, there is
no question that the polarity influences the doping efficiency
because the number of dangling bonds of each Zn or O atom
on growth surface is different for different polarities. This is
important in the research of ZnO because reproducible
p-type doping is the key point and has not been solved successfully. Therefore, it is very helpful to control the polarity
before we do p-type doping of ZnO.
Sapphire nitridation is a very effective method to improve crystalline quality in the epitaxy of nitrides. We reported previously that it was also very effective in the elimination of the rotation domains and the improvement of the
quality of ZnO epitaxial film.12 Since the AlN thin layer
formed by deep nitridation is N-polar, it provides the unipolar surface for the subsequent epitaxy of ZnO. Hence, it becomes easier to control the polarity of ZnO on this unipolar
surface in comparison to the nonpolar sapphire surface. The
polarity control of ZnO has been studied and realized on
Ga-polar GaN template.13 However, there is scarce report
about the polarity control of ZnO on N-polar nitrides.
In this letter, we will report the polarity control of the
ZnO film grown on nitrided sapphire. Since the formed AlN
layer by nitridation is N-polar, it is thought that the O-polar
ZnO should be grown because they are both anion-polar,
which is similar to that the N-polar GaN is usually obtained
on nitrided sapphire by molecular-beam epitaxy (MBE).
However, Zn-polar ZnO film was obtained in our case. We
a)

Electronic mail: yoshi@faculty.chiba-u.jp

found that single monolayer (ML) deposition of Ga on the

nitrided sapphire was effective to get the O-polar ZnO film.
The ZnO film was grown by rf-plasma-assisted MBE.
Both the nitrogen and oxygen plasma cells are present in the
same chamber. The as-polished c-sapphire substrate was nitrided for 2 h with a rf power of 520 W and a nitrogen flow
rate of 1.6 sccm at 400 C after being thermally cleaned at
880 C for 30 min. Then, two kinds of samples were grown,
which would be called ZnO / N* and ZnO / Ga/ N*. In the
case of ZnO / N*, a ZnO buffer layer was grown directly after
nitridation at 400 C with a thickness of 15 nm, where the
Zn beam flux was 2.4 107 Torr while the oxygen flow rate
was 0.5 sccm with a chamber pressure of about 1.2
105 Torr and the rf power was 200 W. Then, the temperature was raised to 680 C to grow a ZnO epilayer under
stoichiometric condition. The Zn beam flux was 5.0
107 Torr. The oxygen flow rate was 1.2 sccm with the
chamber pressure of about 2.8 105 Torr and the rf power
was 300 W. For the ZnO / Ga/ N*, the Ga layer deposition
was performed at 400 C just before the growth of the ZnO
buffer layer. Other growth conditions were the same as those
of ZnO / N*.
The polarity of ZnO films was determined by the coaxial
impact collision ion scattering spectroscopy (CAICISS)14,15
and confirmed by chemical etching in 0.05% HCl solution
for 1 min. In brief, in CAICISS measurement, a low energy
(about 2 keV) pulsed He+ ion beam stroke onto ZnO film
surface and the scattered He+ ions from the surface were
detected at a backscattering angle of 180 by a time-of-flight
(TOF) energy analyzer. Since the TOF of He+ ions scattered
from Zn atoms was different from that from O atoms, we
could easily get the intensity of signals from Zn or O.
CAICISS spectrum in this letter is the dependence of Zn
0
signal intensities on the incident polar angles along 112
azimuth of the ZnO. The polarities of ZnO films were determined by the comparison of the experimental CAICISS
spectra and the simulated ones. Surface morphologies were
characterized by atomic force microscope (AFM) while high
resolution x-ray diffraction (Philips Xpert-MRD) measurements were performed to investigate the crystal quality.
Figure 1 shows the experimental CAICISS results of the
ZnO / N* and the ZnO / Ga/ N*, together with the simulated

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86, 011921-1
2005 American Institute of Physics
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011921-2

Wang et al.

FIG. 1. Incident angular dependencies of the Zn signal intensity along

0 azimuth for the ZnO / N* and ZnO / Ga/ N*. The simulated results are
112
also shown inset.

results of ZnO bulk in different polarities. The simulated

CAICISS spectrum of Zn-polar ZnO is quite different from
that of O-polar one. The former is characterized by three
dominant peaks at = 22, 48, and 72 while six peaks can
be found in the latter at = 16, 22, 32, 52, 68, and 74.
These simulated results agree well with experimental ones
and have been used by many researchers to determine the
polarity.16 As shown in Fig. 1, the CAICISS spectrum of the
ZnO / N* is dominant by three peaks at = 22, 48, and 72,
which coincides with that of simulated Zn-polar one well,
indicating that the ZnO / N* is Zn-polar. The CAICISS spectrum of the ZnO / Ga/ N* is characterized by six peaks at
= 16, 22, 32, 50, 64, and 74, which agrees with that of
the simulated O-polar one, indicating the O-polar film.
Hence, we can know that the ZnO / N* is Zn-polar while the
ZnO / Ga/ N* is O-polar.
In our study, we found that the polarity of ZnO film was
determined by the interface between the nitrided sapphire
and the ZnO buffer layer while the epilayer growth condition
had no influence. Figure 2(a) shows the schematics of atomic
arrangement of the ZnO / N*. The thin AlN layer formed by
deep sapphire nitridation has been proven to be N-polar and
is terminated by the N atom plane. The ZnO layer should be
O-polar if it also follows the polarity of the AlN layer because they are both anion-polar. However, the ZnO was
proven to be Zn-polar. This indicates that the polarity is inverted at the interface between the nitrided sapphire and the
ZnO buffer layer as shown in Fig. 2(a). So how does this
interface serve as the inversion center? At the initial growth
of the ZnO buffer layer, it seems that the Zn atom should
bond with N atom first because the cationanion bond would
be easily formed. In this case, if the ZnN bond belongs to

Appl. Phys. Lett. 86, 011921 (2005)

hexagonal structure, the polarity should not be inverted.

However, if the ZnN bond has the same structure as that of
Zn3N2, it is possible to invert the polarity because the Zn3N2
may play the same role as the Mg3N2, which has been found
to invert the polarity during the GaN epitaxy.17 If the Zn3N2
could serve as the inversion center, it should also invert the
O-polar ZnO film to the Zn-polar one. However, we could
not find this phenomenon in our experiment. Furthermore,
the formation of the Zn3N2 would be difficult from the viewpoint of the bonding configuration. Each N atom on the AlN
surface has only one dangling bond but the formation of the
Zn3N2 requires more. Therefore, the Zn3N2 cannot be
formed.
In our in situ RHEED monitoring of the ZnO buffer
layer growth, a halo pattern was observed shortly before the
appearance of a ZnO RHEED pattern. This indicated that an
amorphous layer was formed. This is reasonable because O
atom may replace the N atom partly at the interface due to
the stronger bond of AlO in comparison to that of AlN.
Hence, a very thin amorphous layer including Al, N, O, and
Zn is probably formed at the interface. This amorphous layer
is so thin that it does not change the growth epitaxial relationship between the ZnO and the nitrided sapphire, i.e.,
0ZnO 101
0AlN 112
0Al O . On this amorphous
101
2 3
layer, the Zn-polar ZnO is more thermodynamically stable
due to the low growth temperature, resulting in Zn-polar
film. This coincides with previous report about the temperature dependence of the polarity of ZnO on sapphire.18 According to their results, although the misfit between ZnO and
Al2O3 was as large as 31.8%, the Zn-polar ZnO was obtained
at 450 C. This indicates that the Zn-polar ZnO is more thermodynamically stable at low temperature. The growth temperature of 400 C in our case is lower than 450 C, which
leads to the growth of Zn-polar ZnO. Here, we notice that the
formation of the amorphous layer was due to the fact that the
AlN layer under it was terminated by the N atom plane.
Therefore, if we deposit only 1 ML Ga, the top layer is not N
but Ga. In this case, the amorphous layer should not be
formed because the GaO bond will form at the interface as
shown in Fig. 2(b). Actually, we did not find the halo pattern
from the RHEED in situ investigation during the ZnO buffer
layer growth. Hence, the polarity should not be inverted, i.e.,
O-polar ZnO should be obtained. In fact, our CAICISS result
confirmed that the ZnO / Ga/ N* was O-polar as shown in
Fig. 1.
The thickness of both samples grown in 3 h was 700 nm
for the ZnO / N* and 500 nm for the ZnO / Ga/ N*, corresponding to the growth rate of 0.65 and 0.46 / s, respectively. This indicates that the growth rate of Zn-polar ZnO is
about 1.4 times that of the O-polar one. The reason for the
different growth rates is the different dangling bond configuration of the growing surfaces. Since each O atom on an
O-polar ZnO surface has only one dangling bond along c
axis while each O atom has three dangling bonds on the
Zn-polar one, the Zn sticking coefficient on the O atom plane
of the Zn-polar ZnO is higher than that of the O-polar one.19
Therefore, the growth rate of the Zn-polar ZnO is higher than
that of the O-polar one. Both samples show high crystalline
quality as shown in Fig. 3. The full width at half maximum
(FWHM) values of (002) and (102) scans for Zn-polar
ZnO were 119 and 486 arcsec while those for O-polar one
were 73 and 673 arcsec, respectively. The Zn-polar sample
shows better (102) value and worse (002) one in comparison

FIG. 2. Schematic of atomic arrangement of the ZnO / N* (left) and the

ZnO / Ga/ N* (right). The ZnO / N* shows Zn-polar while the ZnO / Ga/ N* is
O-polar.
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011921-3

Appl. Phys. Lett. 86, 011921 (2005)

Wang et al.

FIG. 3. The comparison of the high

resolution XRD symmetric and asymmetric scans of the ZnO / N* and the
ZnO / Ga/ N*.

to the O-polar one. In general, the FWHM value of (002)

scan is related to screw-type threading dislocations (TDs)
while that of (102) scan is responsible for the edge-type
TDs, which is usually dominant in the epitaxial growth such
as GaN and ZnO.20 Therefore, the Zn-polar film generally
shows better crystalline quality than the O-polar one.
The surface morphology can be a possible way to check
the polarity because ZnO films in opposite polarities show
quite different surface morphologies under the same growth
condition as shown in Figs. 4(a) and 4(c). The surface contains hexagonal pits in the Zn-polar ZnO while the hexagonal
hillock can be observed in the O-polar one. The smooth surface of Zn-polar ZnO can be obtained under O-rich condition
while hexagonal pits are usually observed under stoichiometric and Zn-rich condition. On the other hand, the hexagonal hillock is usually found in the O-polar ZnO, even under
Zn-rich condition. Both samples were chemically etched to
confirm the polarity. The surface morphologies after being
etched are shown in Figs. 4(b) and 4(d) because they have
seldom been reported by AFM. Large hexagonal pits can be
observed from the Zn-polar surface while hexagonal islands
are clearly found from the O-polar one. The Zn-polar ZnO
kept mirror-like while the O-polar one changed drastically
during the etching. The etching rate of O-polar sample is
much higher than that of the Zn-polar one. This coincides

with previous reports21 and confirms our CAICISS results.

In summary, we controlled the polarity of the ZnO films
on nitrided sapphire substrate. The ZnO / N* was Zn-polar
due to the low growth temperature and the formation of thin
amorphous layer at the interface. One ML Ga is effective to
prevent the formation of this amorphous layer, resulting in
O-polar ZnO film. The Zn-polar ZnO shows better crystalline quality and higher growth rate than the O-polar one. The
ZnO in opposite polarities show quite different morphologies, which could be a possible way to check the polarity.
This work was partly supported by the grant-in-aid for
Scientific Research (B) #13450121, Japan Society for the
Promotion of Science, and the CREST, Japan Science and
Technology Agency.
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