An ordered Ga2Te3 phase in the ZnTe/GaSb interface

C. T. Chou, J. L. Hutchison, D. Cherns, M.J. Casanove, J. W. Steeds, R. Vincent, B. Lunn, and D. A.

Ashenford
Citation: Journal of Applied Physics 74, 6566 (1993); doi: 10.1063/1.355118
View online: http://dx.doi.org/10.1063/1.355118
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An ordered GasTea hase in the ZnTe/GaSb

interface

C. T. Chou
H. H. Wills Physics Laboratory,

University of Bristol, Tyndall Avenue, Bristol BS8 1 TL, United Kingdom

J. L. Hutchison
Department of Materials, University of Oxford, Parks Road, Oxford OX1 3PH, United Kingdom
D. Cherns
H. H. Wills Physics Laboratory,

University of Bristol, Tyndall Avenue, Bristol BS8 I TL, United Kingdom

M. J. Casanove
Department of Materials,

University of Oxford, Parks Road, Oxford OXI 3PH. United Kingdom

J. W. Steeds and R. Vincent

H. H. Wills Physics Laboratory,

University of Bristol, Tyndall Avenue, Bristol BS8 I TL, United Kingdom

B. Lunn and D. A. Ashenford

Department of Engineering Design and Manufacture,
United Kingdom

University of Hull, Hull HU6 7Rx,

(Received 18 May 1993; accepted for publication

12 August 1993)

A Ga2Te3 interfacial phase has been observed in a ZnTe/( OO1)GaSb heterostructure by high
resolution electron microscopy under special imaging conditions. This phase exists in domains
5-10 nm in size on the ZnTe side of, and usually 24 nm away from, the interface. A structural
model has been proposed for this phase that is derived from the sphalerite cell with cation sites
occupied either fully (occupancy 1) or partially (occupancy J/9) by Ga atoms. The fully
occupied Ga sites form a regular array of uninterrupted chains along the [ 1 lo] direction of the
sphalerite unit cell. The partially occupied Ga sites can also be considered as forming chains
containing both Ga atoms and vacancies along the [ 1 lo] direction. Within these chains vacancies
are highly mobile, resulting in an average Ga occupancy of 5/9. The unit cell of Ga,Te, is
orthorhombic with the space group Amm2. The lattice parameters of the unit cell have been
derived from electron diffraction data.

INTRODUCTION
Many wide band-gap II-VI semiconductor thin layers
are now epitaxially grown on lattice matching III-V
substrates. In the interfaces of the II-VI/III-V
heterostructures, formation of thin interfacial layers, consisting
mainly of III-VI
compounds, has been reported in
CdTe/InSb,2 ZnSe/GaAs,3 and ZnTe/GaSb.45 It has also
been reported that an interfacial GazSe3 layer can improve
the crystallinity of an epitaxially grown ZnSe layer on the
GaAs substrate.6 In addition, III-VI compounds are themselves wide band-gap semiconductors and have the potential to become materials for blue-emitting devices.7 Efforts have been made to deliberately grow these III-VI
epitaxial layers onto suitable III-V substrates.7 Interest in
these III-VI phases is increasing both for control of the
interface quality of the II-VI/III-V
heterostructures and
for exploring the properties of new semiconductor materials.

The properties of bulk GalSej, In2Te3, Ga,S3, and

GazTe3 have been reported in several recent papers.289
The authors of these works all suggest that III-VI compounds have structures based on the sphalerite unit cell
(for Ga2S3 it is a structure based on the wurzite unit cell)
with 2/3 of cation sites occupied and l/3 of sites vacant,
whereas the anion sites are fully occupied. Evidence has
been presented that, under a slow cooling condition, vacancy ordering develops in these compounds. The com6566

J. Appl. Phys. 74 (1 I), 1 December 1993

pound GazTeJ has been reported to have an ordered vacancy structure based on the sphalerite unit cell.
However, the exact ordering pattern is unknown. When
the cooling rate is high, then the vacancies are likely to be
disordered. There are structural models for vacancy ordering in GazSe3 (Refs. 7, 11, and 12) suggesting that
cation sites are either fully occupied or completely vacant,
resulting in supercells of three times the size of the sphalerite unit cell along certain directions. As a consequence, the
symmetry of the cubic sphalerite is lost, and a monoclinic
or orthorhombic structure is formed.
Raman scattering experiments5 have shown the existence of GazTes layers in ZnTe/GaSb heterostructures
grown by molecular-beam epitaxy (MBE). In photoluminescence (PL) studies of similar specimens, Duddles
et al. I3 reported a blue shift of the heavy-hole exciton
(X&I emission of 7 meV that could not be explained by
the mismatch of 0.1% between ZnTe and GaSb and corresponding to a shift of 2 meV in the heavy-hole band edge
of the PL spectrum when the growth was pseudomorphic.
They suggested that formation of an interface layer involving GazTe, may contribute to this additional strain.
A direct imaging method would clearly be of great
advantage for revealing the structure, the distribution of
Ga,Te3, and the strain situation in the interfacial area of
ZnTe/GaSb. In this article we show the images of this
phase obtained by a new technique of high resolution electron microscopy (HREM), discuss the strain condition in

0021-8979/93/74(11)/6566/5/$6.00

0 1993 American Institute of Physics

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the interfacial area caused by the distribution of this phase,

and derive a structure model based on the domain structure of the HREM images.
EXPERIMENT
A 2.2~pm-thick ZnTe layer was grown on a [OOl]
GaSb substrate in a VG V80H MBE system. l3 The growth
rate was 0.5 ,um/h at 300 C with the ratio of the Zn/Te jet
flow rates J&J,
= 1.2.
Cross-section samples of [llO] orientation were prepared by preliminary mechanical grinding and then iodine
ion-beam (I) milling at 6 kV and at liquid nitrogen temperature, until perforation. In the final stage of the ionbeam milling, 4-5 kV was used in order to further decrease
the surface damage of the thin foil samples. Samples were
then examined at 400 kV in a high resolution JEOL
4000EX II electron microscope with an objective lens
spherical aberration coefficient C,=O.9 mm.
RESULTS
It was found that at certain unusual defocus conditions, a superlattice structure could be seen in the ZnTe
side of the interface. In Fig. 1, micrographs of the same
inter-facial area are shown. Fig. 1 (a) was taken at defocus
Af =-47
nm (Scherzer defocus condition); ordinary
[llO] sphalerite lattices were observed with no sign of any
GazTe3 superlattice. Figures 1 (b) and 1 (c) were taken at
defocus A f = 60 and 130 nm, respectively, demonstrating a
superlattice of double periodicity in the ZnTe side of the
interface. It should be emphasized that these high overfoGUSsettings are not normally used for HREM imaging, in
view of the very rapid oscillations of the contrast transfer
function (CTF) and the strong attenuation in the chromatic damping envelope. However, a careful analysis of the
CTFs indicates that it is possible to image the superlattice
by tuning a crossover of the CTF to the position of dominant {l 113, reflections (s indicates sphalerite reflections)
while simultaneously enhancing the superlattice reflections
(l/2 l/2 l/2),. A detailed discussion of this novel HREM
technique is presented elsewhere. l4
Selected area electron diffraction patterns also reveal
the existence of a superlattice with about twice the periodicity (see Fig. 2) of the sphalerite structure. The superlattice reflections overlap with the fundamental reflections
along directions within the growth plane, showing that this
interface phase lattice-matches with ZnTe in the growth
plane. On the other hand, the superlattice reflections deviate significantly from the fundamental ones aZong the
growth direction, as shown by the arrows in Fig. 2. This
leads to different lengths for the axes of the sphalerite unit
cell of the superlattice in the interface. If the sphalerite
lattice parameter parallel to the growth plane is written as
all and that along the growth direction a, , we find
all =0.6089 nm, and al =0.5580 nm.
This results in a unit cell volume of 0.2065 nm3. Previous x-ray diffraction measurement for bulk GazTe3 gave
a sphalerite lattice parameter of 0.5896-0.5898 nm.9v5
Thus the unit cell volume is 0.2050 nm3, in reasonable

J?IG. 1. [110] orientation HREM micrographs of the interface area of

ZnTe/GaSb. (a) Af=-47
nm, (b) Af=60 nm, and (c) Af=130 MI.
Insets show image simulations based on our structure model.

agreement with that of the interface phase (error of less

than 0.8%). In comparison, the unit cell volume of ZnTe
(0.2256 nm3) is about 9% greater than that of the interface phase. The interfacial phase can thus be considered as
having a tetragonally distorted sphalerite cell of bulk
Ga2Te3, compressed along the growth direction and expanded in the growth plane with a tetragonal distortion of
8%. The strain caused by the coherent existence of GazTe3

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Chou et al.
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RIG. 4. [l lo] HREM micrograph taken at Af = - 10 nm showing domain structure of the interfacial phase. Insets demonstrate image simulations for two different variants.
FIG. 2 A selected area [IlO], diffraction pattern. Double periodicity
superlattice is clearly demonstrated. Arrows show that superlattice reflex
tions along the growth direction deviate from the corresponding fundamental reflections.

in ZnTe is sufficient for the 7 meV blue shift of the X,

emission in ZnTe, which can be ascribed to a biaxial compressive strain of the ZnTe of the order of 0.3%.13 We note
from Fig. 3 that the distribution of GazTe3 in the interfacial area is nonuniform; the strain distribution in ZnTe is
therefore complicated and further study is required to
quantify the effects.
X-ray energy dispersive spectra from small areas have
been acquired on a Hitachi HF2000 transmission electron
microscope fitted with a field emission gun. These gave Ga,

Te and Zn signals from the region of the superlattice, but

no quantitative analysis of the composition has yet been
carried out.
The superlattice areas appear to be in domains along
the interface on the ZnTe side, frequently several nanometers away from the interface, although sometimes they can
be in direct contact with the GaSb substrate as seen in Fig.
3. It is not clear at this stage why this phase can be some
distance away from the interface between ZnTe and GaSb.
A structural model of the inter-facial phase has been derived from the HREM observations. In Fig. 4 a micrograph taken at Af = - 10 nm is shown. Domains of different variants (indicated by A, B, and C) separated by a
variant boundary (indicated by VB in Fig. 4) and antiphase domains of the same variant (B) separated by an
antiphase boundary (APB) can be found in this figure.
STRUCTURE DETERMlNATlON

FIG. 3. Low magnitlcation [l lo] orientation HREM micrograph showing

the distribution of the ordered interfacial phase in ZnTe/GaSb.

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J. Appl. Phys., Vol. 74, No. 11, 1 December

1993

A distribution of strong and weak spots on a [llO],

projection image in domain A is also clearly seen in Fig. 4.
It is not unreasonable to assume that this distribution originates from the different occupancies of Ga atoms in the
cation sublattice. From this assumption, we conclude that
the strong spots correspond to the cation sublattice sites
with a high occupancy of Ga atoms, whereas the weak
spots are related to the sites of low Ga occupancy. Assuming the high occupancy sites to be fully occupied by Ga
atoms (occupancy 1 ), then the stoichiometry requires the
low occupancy sites of a Ga occupancy of S/9. A great
difference between the two occupancies is required by the
strong contrast demonstrated in Fig. 4, and other possible
combinations of two occupancies will inevitably result in
smaller contrast. We would like to point out that certain
cation sites in this compound may be occupied by Zn atChou

et al.

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c1101s

~oilisI

riolis

o0

0
.ft
c

--*-.
11Olls,

IOTlls

FIG. 5. Cation sublattice projections along different ( 1 lo), . Closed circles represent Ga positions of occupancy 1, open circles represent Ga
positions of occupancy 5/9, and hatched circles represent the alternate
arrangement of the above two positions.

oms, forming an alloy of Ga,Te3 and ZnTe. When this

situation arises, the occupancies of the cation sites would
vary accordingly, however, in any,case the assumption that
an ordered distribution of fully and partially occupied cation sites exists is still required. Based on this ordered distribution of Ga on the cation sublattice sites of the crystal
in the [l lo] projection [shown in Fig. 5(a)], a threedimensional distribution of the Ga atoms in the cation
sublattice can be constructed and is shown in Fig. 6. From
the three-dimensional distribution, we can then derive all
of the different ( 1 lo), projections illustrated in Figs. 5 (b),
5(c), and 5(d).
The relationship between the unit cell for the ordered
structure and that of the sphalerite is as follows (the lattice
parameter of which is ao, ignoring the difference between
alI anda,):

IrIG. 7. Unit cell of the GarTes ordered interfacial phase projected along
the c axis. Atom types, z coordinates, and occupancies of different sites
are given in the attached table.

all[ W ,,bll[iloi,,cllwi,,
[al =(42/2)ao,

lb1 =J2ao,

14 =2ao.

The projection of this new unit cell along its c axis,

including both cation and anion sites, is shown in Fig. 7. In
the attached table the Z coordinates of atoms, atom species, and the occupancies are given. Related symmetrical
elements can be derived from this unit cell. It can be concluded that this structure belongs to the space group
Amm2. The unit cell volume would be 2ai. There are 8 Te
atoms and an average of 5f Ga atoms in the unit cell, giving
the average composition 2Ga: 3Te as required. Multislice
image simulations based on this structure model have been
performed, and the results confirm this model (see insets in
Figs. 1 and 4).
DISCUSSION

FIG. 6. Threedimensional view of the cation sites. Atomic positions fully

occupied by Ga atoms are represented by large spheres and those with 5/9
Ga occupancy are shown by smaller spheres.

A new phase, likely to be GazTe3, has been imaged in

MBE grown ZnTe/GaSb by HREM under special imaging
conditions. This phase is distributed nonuniformly in the
ZnTe side of, and frequently 2-4 nm away from, the interface. It has a domain structure with a domain size of 5-10
nm. The thickness of this interface phase varies from 5 to
45 mn. Antiphase domain boundaries and variant domain
boundaries have been observed. We recognize, of course,
that the ordering may be influenced to some extent by
factors such as growth conditions, cooling rate after
growth, and residual strain.
The phase exists coherently in the ZnTe layer, with a
significantly shortened lattice parameter along the growth
direction (a1 =0.5580 run). This provides an additional
source of strain in the ZnTe/GaSb heterostructure and
may be responsible for a blue shift of X,
emission of 7
meV in the PL spectra.

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J. Appl. Phys., Vol. 74, No. 11, 1 December 1993
Chou et al.
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This analysis is based on two samples grown under

rather similar conditions and Zn rich in order to suppress
the formation of Ga2Te3 at the interface. Raman signals
from these specimens indicated thin layers of Ga2Te3, but
no Te compared to the earlier data.5 Furthermore, an apparent discrepancy with Raman data from eadier samples,
in which the presence of unstrained Ga2Te3 and Te at the
interface was inferred, could be due to local area variations or the strain in the thin layers, described in the
present work, being sufficiently large to severely broaden
the Raman lines.
CONCLUSIONS
A structure model has been proposed for Ga2Te3 based
on the contrast distribution and the domain structure that
matches image simulations well. This model suggests that
vacancies in this structure are highly mobile in the cation
lattice, resulting in lattice sites with an average 5/9 Ga
occupancy, whereas the fully occupied Ga sites form continuous and regularly arranged chains along the [l lo], direction. Our model disagrees with previous x-ray and eleo
tron diffraction studies of bulk III-VI
compounds that
suggest superlattice structures based on either fully occupied or completely vacant cation sites in the sphalerite cell.
ACKNOWLEDGMENTS
We are grateful to the Science and Engineering Research Council for its support of this work, and to the

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J. Appl. Phys., Vol. 74, No. 11, 1 December 1993

Materials Modelling Laboratory

provision of computing facilities.
Society and the Centre National
fique for a visiting fellowship for

at Oxford University for

We also thank the Royal
de la Recherche Scientione of us (M.J.C.).

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