APPLIED PHYSICS LETTERS 87, 141904 2005

Determination of crystallographic polarity of ZnO layers

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

H. Yoshikawa and H. Kanie

Tokyo University of Science, 2641 Yamazaki, Noda, Chiba 278-8510, Japan

Received 6 July 2005; accepted 22 August 2005; published online 26 September 2005
The crystallographic polarity of ZnO epilayers was determined by x-ray diffraction XRD using
anomalous dispersion near the Zn K edge. The method is not destructive and is straightforward to
carry out using a typical XRD measurement system. The polarity difference between the Zn 0001
surfaces could be easily determined using a 0002 diffraction peak and the
and O 0001
Bremstrahlung radiation from a Cu rotating anode source. By using the normalized pre- and post-Zn
K-edge diffraction intensity ratios of the 0002 diffraction peak, Zn polar and O polar ZnO layers
could always be distinguished but, the absolute value of the ratio was found to change with layer
thickness. The absolute value of the ratio with layer thickness was found to have a linear
dependence on layer thickness allowing determination of the polarity of 0001 ZnO epilayers with
a single x-ray measurement and the known layer thickness in conjunction with standard data. Acid
etching results confirmed the veracity of the polarity determination of the XRD measurement. To
test the technique, Zn and O polar ZnO layers were grown by radical source molecular beam epitaxy
RS MBE on MgO buffer layers on c-sapphire substrate and O polar ZnO layers were grown on
a-plane substrates and measured using the x-ray technique with excellent agreement. 2005
American Institute of Physics. DOI: 10.1063/1.2067689
To date, several groups have reported upon details of
ZnO-based LED structures as well as electroluminescence
EL properties;1,2 technology and knowledge related to
ZnO-based materials and devices are rapidly accruing.3
However, problems related to weak EL emission and a lack
of UV region emission due to defects remain to be solved,
leading to the need for further investigations into the quality
of ZnO layers, p-type doping, and device structures.
For wurtzite and zinc blende crystal structure materials,
the lack of a center of inversion symmetry leads to a define
polarity along the 0001 and 111 directions, respectively.
This is typified for the case of ZnO by the Zn polar 0001
. This property leads to various
and O polar faces 0001
differences in, for example, crystal growth modes, impurity
incorporation, piezoelectric and spontaneous polarization, as
well as surface stability. The control and confirmation of
ZnO polarity has become an important issue for ZnO-based
device fabrication. Recently, several groups have reported
upon methods to control the polarity of ZnO epilayers by
modification of the ZnO/ sapphire interface.48 The technique used for polarity determination in these studies have
been typically very complicated, for example, coaxial impact
collision ion scattering spectroscopy, convergent beam electron diffraction, scanning probe microscopy.49 These methods all exhibit underlying difficulties such as for the necessity for special equipment, low throughput, destructive
measurements, and only local area measurements.
In this study, the crystallographic polarity of ZnO layers
was determined by x-ray anomalous scattering at the Zn K
edge = 1.283 with a conventional rotating copper target. This method is not destructive, is simple to use, and
a

Author to whom correspondence should be addressed; electronic mail:

tampo-21@aist.go.jp

overcomes the problems mentioned earlier. Additionally wet

etching investigations were conducted to determine the polarity of ZnO layers. The determination of crystallographic
polarity by the use of x-ray anomalous dispersion of polar
materials dates back to the 1930s, where it was applied to
determine the polarity of the bulk cubic ZnS 111 face,10,11
and later to bulk ZnO 0001 faces.12,13 In this study, we
demonstrate that a similar technique can be used for the determination of the crystallographic polarity of ZnO epilayers.
ZnO films were grown by radical source molecular beam
epitaxy. Elemental Zn and rf radical oxygen were used as
groups II and VI sources, respectively. The substrates used
were a-plane and c-plane sapphire. Zinc and oxygen polar
ZnO layers on c-plane sapphire were grown by changing the
thickness of a MgO buffer, which was inserted between the
ZnO layer and the sapphire substrate. The precise growth

FIG. 1. The diffraction curves from the continuous spectrum produce by the
planes of ZnO epilayers on sapphire c-plane. These in0002 and 0002
tensities were normalized at 2 = 29.5. The normalized intensity ratio at
2 = 27.0 is 0.83, which is good agreement with the calculation value of
0.89.

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87, 141904-1
2005 American Institute of Physics
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141904-2

Appl. Phys. Lett. 87, 141904 2005

Tampo et al.

FIG. 3. The ZnO etched surfaces, Zn polar ZnO layer on c-sapphire a, O

polar ZnO layer on c-sapphire b, O polar ZnO layer on a-sapphire c.
0.012 M HCl was used.

FIG. 2. The intensity ratio between 2 = 27.0 and 29.5 for each one polar
ZnO layer. The intensity ratio was dependent on the layer thickness independent of sapphire orientation.

procedures are reported in Refs. 5, 14, and 15.

The structure factor for a general hkl x-ray reflection in
Cartesian coordinates is given by
Fhkl = f 0 + f + if jexp2ihx j + ky j + lz j,

where f 0 is the atomic scattering factor, f and f are

anomalous dispersion corrections, and x j y jz j are the spatial
coordinates of each of the j atoms in the unit cell. The wurtzite structure contains four atoms per unit cell, two of the A
species i.e., Zn at positions 0,0,0 and 1 / 3 , 2 / 3 , 1 / 2 and
the B species i.e., O at 0 , 0 , u and the 1 / 3 , 2 / 3 , 1 / 2
+ u. For noncentrosymmetric materials, the structure factor
of hkl and hkl planes are different when the effects of
anomalous dispersion are significant and Friedels law is broken. The x-ray diffraction XRD intensity Ihkl is proportional to the product Fhkl F*hkl, leading to a value for
Ihkl different from Ihkl for noncentrosymmetric materials
with anomalous dispersion present. As ZnO forms in the
wurtzite structure, for a ZnO crystal with 0001 faces, it is
possible to use this phenomena to determine which one of
two opposite faces is terminated by the Zn 0001 face and
face. As the structure of ZnO is
which one by the O 0001
not centrosymmetric, Friedels law does not hold, and there
will be a difference between the intensities I000l and
. For the determination of absolute configuration, or
I0001
polarity, in noncentrosymmetric crystals in the wurtzite family, the 000l amily of reflections must be considered, as
they are normal to the polar axis. Referring to Eq. 1, if l is
odd, I000l is equal to zero like other hcp crystals; if l
= 4n, where n is zero or an integer and u = 3 / 8 , I000l is
equal to I000l, and for l = 4n 2 , I000l I000l as is apparent from Eq. 2. For the ideal close pack tetrahedral arrangement, u is exactly equal to 3 / 8. For ZnO the value u
differs slightly from 3 / 8, and I000l is not equal to I000l
for l = 4n. However, as u is close to 3 / 8, and the difference
D000l for l = 4n 2 is much larger than for when l = 4n.
Here, the 0002 case is chosen for the value of l to be
measured, where f = f 0 + f :
D000l = FF*000l FF*000l

f o f of Zn
.
= 16 sin2luf Zn

Since the dispersion corrections, in effect, are related to

the differential absorption of incident radiation by the scattering atoms, the maximum effect will occur on the shorter
wavelength side of the absorption edge of one of the elements. The anomalous dispersion effect becomes quite small
immediately adjacent to the long wavelength side of the
edge. A comparison of experimental and calculated
I000l / I000l values near both sides of the absorption edge
provides a highly sensitive and convenient method for the
unambiguous determination of crystallographic polarity. All
other variables cancel in the calculated intensity ratios except
I000l / I000l. For 0002 the intensity ratio is given by
I002 FF*002

FF*002

I002
=

+ bf o2 + bf o + f Zn
+ af 2
af o + f Zn
bf o2 + bf o + f Zn
+ af 2
af o + f Zn

where a = cos4u and b = sin4u.

reflections from
The intensity of the 0002 and 0002
ZnO are obtained as a function of from the continuous
spectrum of a rotating copper x-ray anode. The samples were
placed in a symmetric scattering geometry with 0002
planes satisfying the Bragg relation, and scans were taken
along the -2 axis. As 2 was scanned continuously, varied as well.
For the calculation reported below, the following ZnO
lattice constants were adapted a = 3.2501 , c = 5.2071 ,
and u = 0.3817.16 Henke atomic scattering factors were used
for the values of the anomalous dispersion corrections.17
Figure 1 shows diffraction curves from the continuous
planes of ZnO
spectrum produced by the 0002 and 0002
epilayers grown on c-plane sapphire. A clear differential absorption edge effect due to anomalous dispersion was ob at
served. Since the calculated intensity ratio 0002 / 0002
2 = 29.5 = 1.326 of 0.97 is very close to unity, and
different ZnO epilayers were used as Zn polar and O polar
planes are
ZnO, the XRD intensity of the 0002 and 0002
normalized below the Zn edge at 2 = 29.5. In order to make
the effect of the anomalous dispersion near the edge apparent, the normalized intensity ratios NR are also plotted in
Fig. 1. The effects of anomalous dispersion can be clearly
seen in the figure: the NR remained almost constant at unity
below the edge higher 2 and rapidly decreased just above
the edge. The NR become approximately 0.83 at 2
= 27.0 = 1.216 . The measured value was close to the
calculated value of 0.89; the agreement between calculated
and experimental values was good. The peak-like shape of
the diffraction curve in Fig. 1 is concluded to be due to Zn
K-edge absorption fine structure, not due to additional diffraction peaks or other fluorescence peaks, because the shape

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141904-3

Appl. Phys. Lett. 87, 141904 2005

Tampo et al.
TABLE I. Crystal quality and electrical properties for etched ZnO epilayers.

Sample

ncm3

cm2 / V s

Full width
at half maximum
002 arc sec

A
B
C

2.5 1016
9.4 1015
4.6 1015

125
83
144

756
42
316

of peaks is similar to those from the 0004 diffraction

curve. In other words, the shape of the fine structure is similar to a x-ray absorption fine structure spectrum. In these
XRD measurements, the acceleration voltage use for the copper target was fixed, and the background air scattering
noise was negligible.
To investigate the deviation between the measured and
calculated intensity ratios, similar XRD measurements were
conducted for many samples with both O polar and Zn polar
ZnO epilayers. For a ZnO bulk sample, the measured value
of the NR was 0.89, in excellent agreement with the calculated value. Figure 2 shows the XRD intensity ratio R of
2 = 27.0 and 29.5 for the same 0002 diffraction curve as
a function of ZnO epilayer thickness. Here, R is equal to the
diffraction intensity ratio of I2 = 27.0 / I2 = 29.5 for
the same sample. As can be seen in the figure, the value of R
decreased linearly with thickness increasing both for Zn polar and O polar ZnO as well as for ZnO epilayers on a-plane
sapphire substrates. Since the growth conditions of them
were systematically changed, for example, the VI/II ratio or
the growth temperature, many variation in ZnO epilayers
qualities and electrical properties exists,18 however, the trend
in R with thickness was found to be the same regardless of
polarity. Furthermore, the ratio of R between the Zn polarity
and O polarity ZnO with the same thickness, which is same
as the normalized intensity NR, was nearly equal to 0.89. A
least-squares best fit line through the data yield a value of
0.86 for a 1-m-thick layer. This implies that one can determine the polarity by knowing the layer thickness and measuring only one face of a ZnO layer by use of the standard
curve shown in Fig. 2. The origin of the monotonic decrease
in R is unclear at this time and is a subject of ongoing investigation. Nevertheless the agreement between calculated and
experimental value is very good and the polarity determination was unambiguously determined for the ZnO epilayers.
The relationship of these x-ray results was confirmed via
etching as is explained later.
There have been several reports on the differences in the
etching behavior as a function of crystallographic polarity
for wurtzite bulk crystals including ZnO.12,19,20 In order to
confirm layer polarity, etching studies were carried on ZnO
epilayers using a 0.012 M hydrochloric acid solution for 2
min. Table I shows the crystalline qualities and electrical
properties of the ZnO layers used in this work. Remarkable
differences have been observed as a function of polarity in
etching experiments. Remarkable differences with polarity
for ZnO bulk crystal have been reported, for example, the
etched surface shape, the roughness of the etched surface,
and the etching rate. For example, for etching of Zn surfaces
hexagonal pits was reported, while for O surfaces the formation of rough hillocks was noted. For bulk crystals, the etching rate was found to be slower for the Zn polarity, and a
much faster rate for O polarity. Similar etching behavior
was found for ZnO epilayers and a clear morphological

Full width
at half maximum
101 arc sec

Substrate

Polarity

1190
1140
529

Sapphire c-plane
Sapphire c-plane
Sapphire a-plane

Zn
O
O

difference between the two faces was noted as can be seen in

Fig. 3. The etching rate for a Zn polar ZnO layer, however,
was not much different from that of O polar ZnO, due to the
larger dislocation density of ZnO epilayers compared to ZnO
bulk. The dislocation density for Zn polar ZnO was estimated using the etch pit density, and a density of 2
109 cm2 was determined for ZnO layer, respectively, as
can be seen in Fig. 3a.
In summary, we have demonstrated a simple and nondestructive method for the determination of the crystallographic polarity of ZnO epilayers using x-ray diffraction
with anomalous dispersion near the Zn K edge. Although, the
jump of the diffraction curve near the Zn K edge was affected by the thickness of the ZnO layer, the polarity could
be unambiguously determined using the standard curve
shown in Fig. 2 independent of layer quality and the substrate orientation. The surface morphology of ZnO layers
after etching by diluted hydrochloric acid showed hexagonal
pits and rough hillocks for Zn polar and O polar surfaces,
respectively, the etching results confirmed the veracity of
x-ray diffraction analysis for the polarity determination in
ZnO layers.
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