Journal of Crystal Growth 240 (2002) 613

Calculated strain energy of hexagonal epitaxial thin lms

Jianyun Shena,b,*, Steven Johnstona, Shunli Shangb, Timothy Andersona
a
University of Florida, Department of Chemical Engineering, Gainesville, FL 32611-6005, USA
b
Research Institute for Non-ferrous Metals of Beijing, 100088 Beijing, China

Received 21 June 2001; accepted 21 November 2001

Communicated by C.R. Abernathy

Abstract

Generalized formulae for the strain energy of hexagonal thin lms on both hexagonal and rhombohedral substrates
have been developed. These formulae require knowledge of the elastic stiffness coefcients and the lattice parameters of
the lm and only the lattice parameters of the substrate. Example calculations of the strain energy present in the
strained lm-substrate material combinations GaN/Al2O3 and GaN/LiGaO2 are presented for different lm
crystallographic directions and rotation with respect to the substrate. Finally, phase equilibrium calculations are
performed for the GaN binary system which show the substantial inuence of strain energy on equilibrium in the
system. r 2002 Elsevier Science B.V. All rights reserved.

PACS: 82.60.Hc; 82.60.
s; 64.; 82.20.Wt

Keywords: A1. Phase diagrams; B1. Gallium compounds; B1. Nitrides

1. Introduction cubic lm/cubic substrate combinations have been

The increased interest in heteroepitaxy of
semiconductor lms has motivated the develop-
ment of a reliable method to calculate the strain
energy produced by the mismatch between the
epitaxial growth layer and the underlying sub-
strate. Lattice mismatch as well as the subsequent
strain can have signicant inuence on the extent
of dislocation generation, the morphological,
electrical, and optical properties, and the phase
equilibrium behavior of the growth layer. While
*Corresponding author. Department of Chemical Engineer-
ing, University of Florida, Gainesville, FL 32611-6005, USA.
Tel.: +1-352-392-2420; fax: +1-352-392-9513.
E-mail address: jshen@che.u.edu (J. Shen).
analyzed previously [1], systems involving hexa-
gonally oriented material as either the lm or
substrate have not been thoroughly investigated to
date. Examples of important semiconductor ma-
terials that exist in the hexagonal crystal structure
include the wide band gap compound semicon-
ductors GaN, SiC, BN and many IIVI semi-
conductors such as CdS. These materials are
promising candidates for use in optoelectronic
applications including visible and ultraviolet emit-
ters, high powerhigh temperature electronics, and
in the case of cBN as an abrasive [2,3]. The lack of
large area bulk crystals for most of these
hexagonal compounds has necessitated the use of
alternative substrates with different lattice para-
meters and thermal expansion coefcients.

0022-0248/02/$ - see front matter r 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 0 2 4 8 ( 0 1 ) 0 2 2 0 9 - 6
 J. Shen et al. / Journal of Crystal Growth 240 (2002) 613 7

Furthermore, device applications often require fourth-rank transform of the sij values in the
alloying that introduces additional stress in the principle plane. The fourth-rank transform of the
lm. As an example, alloying GaN with InN to sij values in the principle plane is
lower the band gap energy increases the value of 3 X
X 3 X 3 X 3
the lattice parameter. s0ijkl aim ajn akp alq smnpq ; 4
The strain energy stored in a lm grown on a m1 n1 p1 q1
mismatched substrate increases the Gibbs energy where aim ; ajn ; akp ; and alq are the direction cosines
of the material. This strain energy contribution of the axes of the plane studied with respect to
modies such equilibrium quantities as melting those of the principle plane. It should be noted
temperature, vapor pressure, and miscibility limits. that sij is actually the reduced representation of the
While the growth of hexagonal materials has been fourth tensor sijkl according to Voigts notation [5].
extensively studied experimentally, quantitative In the case where the elastic compliances are
calculation of the inherent strain energy has not unknown but the elastic stiffness coefcients, cij ;
been fully performed [4]. Furthermore, the effect are available, the sij values can be calculated from
of the strain energy on the resulting equilibrium cij since the matrix of sij and that cij are mutually
has not been addressed. In this work elastic inverted.
compliance equations are developed and their The matrix of sij for the hexagonal crystal lattice
relationship to the overall strain energy of a is given by Lekhnitskii [5] as:
hexagonally oriented lm and substrate are pre- 2 3
sented. These general relations are then applied to s11 s12 s13 0 0 0
6 7
the growth of GaN on different substrates. 6 s12 s11 s13 0 0 0 7
6 7
6s 7
6 13 s13 s33 0 0 0 7
6 7
6 0 0 0 s 44 0 0 7
2. Analysis 6 7
6 0 0 0 0 s44 0 7
4 5
The development of the general equations 0 0 0 0 0 2s11
s12
necessary to calculate the strain energy of a
For the hexagonal lattice, the elastic compliances
hexagonal lm on either a hexagonal or rhombo-
in the plane of interest can be written as
hedral substrate is presented in this section.
The general form of strain energy for an elastic s011 1
l32 2 s11 l34 s33 l32 1
l32 2s13 s44 ;
body can be written as 5
1
U 2 sx ex sy ey sz ez txy gxy
s012 s11 l1 m1
l2 m2 2 s12 l1 m2
l2 m1 2
tyz gyz tzx gzx ; 1
s13 1
l32 m23 l32 1
m23  s33 l32 m23
where U is the strain energy per unit volume, sx ; s44 l3 m3 l2 m2
l1 m1 : 6
sy and sz are the normal stresses, txy tyz and tzx are
the shear stresses, ex ; ey and ez are the normal s022 1
m23 2 s11 m43 s33
strains, and gxy ; gyz and gzx are the shear strains.
m23 1
m23 2s13 s44 ; 7
Generally only the normal strain and stress in two
perpendicular axes are considered to be produced where l1 ; l2 and l3 are the direction cosines of the x0
as a result of lattice mismatch in epitaxial growth. axis of the plane studied with respect to the x; y;
Hooks law can be written as and z axes of the principle plane. Similarly m1 ; m2 ;
ex s011 sx s012 sy ; 2 and m3 are that of y0 axis. The relationship
between sij and cij in the principle plane can be
ey s022 sy s012 sx ; 3 written as
c11 c33
c213
s0ij
where are the elastic compliances of the plane of s11 ; 8
interest. These values can be obtained from the c11
c12 c11 c33 c12 c33
2c213
8 J. Shen et al. / Journal of Crystal Growth 240 (2002) 613

c213
c12 c33 When both the lm and substrate are hexagonal
s12 ; 9 and the basal plane of each is used in deposition,
c11
c12 c11 c33 c12 c33
2c213
the strain in the x and y directions are equal as

c13 required by symmetry and can be written as
s13 ; 10 a
a0
c11 c33 c12 c33
2c213 ex ey ; 15
a0
c11 c12
s33 ; 11 where a and a0 are the lattice parameters of the
c11 c33 c12 c33
2c213 growth layer and the substrate in the basal plane,
respectively. Using Eqs. (13) and (14), the normal
1
s44 : 12 stresses to the lm/substrate interface can then be
c44 written as
Once these relationships are known calculation 1 a
a0
of a meaningful elastic energy term can made. Two s x sy : 16
s11 s12 a0
different planes of lm growth were considered,
Thus from Eq. (1) the strain energy per unit
the (0 0 0 1) basal plane and the (1 0 1% 0) prism
volume is simply
plane (see Fig. 1). Since the (0 0 0 1) basal plane of

a hexagonal crystal is isotropic, the x and y axes 1 a
a0 2
can be chosen coincident with those of the U : 17
s11 s12 a0
principle plane. Therefore,
In the second case, when either the growth layer
ex s11 sx s12 sy ; 13 or substrate is not hexagonal, the strain in the x
and y directions will not be equal (ex aey ) as a
ey s22 sy s12 sx : 14 result of the departure from symmetry. From
Eq. (13) and (14), the following relations are
For a growth on the (0 0 0 1) basal plane there
evident:
are two possible lm/substrate crystallographic
s11 ex
s12 ey
relationships. The rst one occurs when the planes rx 2 ; 18
of lm growth and the underlying substrate are s11
s212
both hexagonal. The second one is when either the s11 ey
s12 ex
lm growth plane or the substrate is not hexagonal ry 19
s211
s212
(e.g., zincblende, rhombohedral). Each case was
analyzed. with a resulting strain energy expression of
s11 e2x e2y
2ex ey s12
3.189 U : 20
(0001) 2s211
s212
[0001] (1010)
Deposition on the [1 0 1% 0] prism plane in the
[1% 2 1% 0] and [0 0 0 1] directions (dened as x0 and y0
5.185

direction of the plane studied as shown in Fig. 1)

was also considered. On this plane the direction
[1010]
a3 -a1 cosines of the x0 and y0 axes are l1 0; l2 1; l3
0; m1 0; m2 0; and m3 1: Therefore the
-a2 a2 elastic compliances can be transformed from the
[1210] [1210] plane of interest to the principle plane using
s011 s11 ; 21
a1 -a3
s012 s13 ; 22
Fig. 1. Basal plane (0 0 0 1) and prism plane (1 0 1% 0) of a
hexagonal crystal. The [1% 0 1 0] direction is parallel to the lower
basal plane. s022 s33 ; 23
 J. Shen et al. / Journal of Crystal Growth 240 (2002) 613 9

The strains in the [1% 2 1% 0] and [0 0 0 1] directions Table 1

( of GaN, Al2O3, and LiGaO2
Lattice constant (A)
are thus
ex0 sx0 s011 sy0 s012 sx0 s11 sy0 s13 ; 24 Material a b c

GaN (wurtzite) 3.189 F 5.185

ey0 sy0 s022 sx0 s012 sy0 s33 sx0 s13
and the normal stresses are
ex0 s33
ey0 s13
rx 0 ; 26
s11 s33
s213
ey0 s11
ex0 s13
ry 0 : 27
s11 s33
s213
It directly follows as before that the strain
energy per unit volume is:
e2x0 s33 e2y0 s11
2ex0 ey0 s13
U :
2s11 s33
s213
If a hexagonal lattice structured lm with lattice
parameters a and c is grown with its prism plane
on a rectangular face of a substrate with lattice
parameters a0 and c0 ; then the systems strain is
ex0 a
a0 =a0 ; ey0 c
c0 =c0 ; and its resulting
strain energy is
a
a0 =a0 2 s33 c
c0 =c0 2 s11
U
2s11 s33
s213
2a
a0 =a0 c
c0 =c0 s13

:
2s11 s33
s213
Eq. (29) is general and can thus be used for all the
other prism planes as well as internal planes
such as (1 2% 1 0) because of the isotropic nature of
the basal plane.
3. Lattice mismatch and strain energy calculation
Three independent sets of calculations were
performed to demonstrate the strain energy
calculation of a GaN lm grown on Al2O3 and
LiGaO2 substrates, using the fundamental data
provided in Tables 1 and 2 [6]. Table 3 summarizes
the strain energy calculated for three different lm/
substrate orientations and their corresponding
lattice mismatches. From both Eqs. (17), (20) and
(29) and the data in Table 3, it is clear that an
increase in the lattice mismatch increases the
systems strain energy.
25 Al2O3 (wurtzite) 4.758 F 12.991
LiGaO2 (orthorhombic) 5.402 6.372 5.007
Table 2
Elastic stiffness coefcients cij and compliances sij of GaN
cij (Gpa) c11 c12 c13 c33 c44
374 106 70 379 101
sij (1/GPa) s11 s12 s13 s33 s44
0.00297
0.00077
0.00041 0.00279 0.00990
28
The minimum lattice mismatch in the GaN/
Al2O3 system occurs when the GaN lm is rotated
301 with respect to the sapphire substrate so that
the (0 0 0 1)8(0 0 0 1), [1% 0 1 0]8[1 2% 1 0] GaN/Al2O3
interface is formed and a 3:1 lm/substrate unit
cell ratio is used. For instance, the lattice mismatch
for no rotation and 301 rotation with a 3:1 GaN/
Al2O3 unit cell ratio are 33% and 16.1%,
respectively. Rotation of GaN lms on Al2O3
29 has been observed experimentally [7] and is
illustrated in Fig. 2. The strain energy of the
16.1% mismatched system is 11.755 GPa or
161.49 kJ/mol. Of course these values of lattice
mismatch exceeds the limits to maintain elastic
deformation in the growth layer. Therefore,
experimentally, a relaxation of the strain energy
by large-scale dislocation formation would be
inevitable without the use of a buffer layer
(typically GaN or AlN). Consistent with experi-
mental results and a recent set of calculations we
have performed it is energetically favorable for the
majority of the stress in the GaN/Al2O3 system to
be compensated by dislocation formation with
approximately a 2% residual strain remaining at
the interface [8].
Deposition of the (0 0 0 1)8(0 0 1), [1% 2 1% 0]8[0 1 0]
GaN/LiGaO2 system (Fig. 3) is an attractive
alternative due to its lower mismatch [9]. LiGaO2
has an orthorhombic structure consisting of an
alternate stacking of a two-dimensional array
10 J. Shen et al. / Journal of Crystal Growth 240 (2002) 613

Table 3
Strain energy produced by lattice mismatch

Growth layer/substrate Growth orientation Lattice mismatch (%) Strain energy

ex ey GPa kJ/mol

w-GaN / w-Al2O3 (0 0 0 1)8(0 0 0 1) [1% 0 1 0]8[1 2% 1 0] 16.1 F 11.76 161.5

w-GaN /o-LiGaO2 (0 0 0 1)8(0 0 1), [1% 2 1% 0]8[0 1 0] 2.25 0.09 0.094 1.3
w-GaN /o-LiGaO2 (1 2% 1 0)8(0 1 0) [1 0 1% 0]8[1 0 0] 2.25 3.56 0.36 4.9

p
tion, the normal strains are ex 3 3:189

5:402=5:402 2:25% and ey 2 3:189

6:372=6:372 0:09%: Thus the strain energy is
reduced by Eq. (20) to 0.094 GPa or 1.29 kJ/mol.
Another possible lm/substrate orientation
for prism plane growth is the (1 2% 1 0)8(0 1 0),
GaN [1 0 1% 0]8[1 0 0] GaN/LiGaO2 system (Fig. 4). The
normal strains
p for this material combination are
then ex 3 3:189
5:402=5:402 2:25% and
ey 5:185
5:007=5:007 3:56%: The strain
Al2O3 energy for this orientation is then calculated using
[1010] of GaN
Eq. (29) to be 0.359 GPa or 4.94 kJ/mol.
[1210] of Al2O3

4. Results and discussion

Fig. 2. Scheme for the deposition of the (0 0 0 1)8(0 0 0 1),
[1% 0 1 0]8[1 2% 1 0] GaN/Al2O3 system. Thermodynamic equilibrium calculations were
carried out on the strained GaN system to
demonstrate the importance of strain energy on a
[1210] of GaN Interfacial bond of Ga (or Li)-N; systems nal equilibrium state. Thermochemical
Ga and Li from LiGaO 2,
[010] of LiGaO2
N from GaN
data for all species except for GaN(s) were taken
from the ThermoCalc version K sub94 database
3.136 [10]. The data for GaN(s) were reassessed by
6.372 3.189
GaN Davydov and Anderson [11]. Their results were
3.186 incorporated. A strain energy term calculated from
Eqs. (16), (21) or (29) was added to the value of
5.402 after deformation GHser for GaN(s).
before deformation The effect of strain energy on the strained GaN
LiGaO2
equilibrium binary system is shown in Figs. 5 and
Fig. 3. Scheme for the deposition of the (0 0 0 1)8(0 0 1), 6. Fig. 5 depicts equilibrium in the unstrained Ga
[1% 2 1% 0]8[0 1 0] GaN/LiGaO2 system. N heterogeneous system at 0.1 MPa and will be
used as a reference for the strained GaN/LiGaO2
consisting of oxygen tetrahedra centered Ga and and GaN/Al2O3 equilibrium systems. Fig. 6 illus-
Li ions. Therefore the material has a wurtzitic trates the effect of strain energy on the resulting
superstructure with a small departure from hex- GaN equilibrium. A decrease in the GaN
agonal symmetry as a result of the need to thermodynamic stability (i.e., its melting point
accommodate metallic atoms of different size. temperature) results from the addition of a
When GaN is grown on LiGaO2 in this orienta- positive term to the Gibbs energy expression of
 J. Shen et al. / Journal of Crystal Growth 240 (2002) 613 11

GaN (1210) 3.189

(1210) GaN / (010)
LiGaO2 interface

5.185
a3 -a1

-a2 a2

LiGaO2
a1
[1010] -a3

Fig. 4. Scheme for the deposition of the (1 2% 1 0)8(0 1 0), [1 0 1% 0]8[1 0 0] GaN/LiGaO2 system.

3000
3000
Gas Gas
2500 2500
Temperature (K)

Temperature (K)

2000 2000
Liquid + Gas Liquid + Gas
1500 1500

1055K
1055 K 1000
1000
GaN + Liquid GaN + Gas
GaN + Liquid GaN + Gas 500
500 303K
303K Ga + GaN
Ga + GaN 0
0 0.0 0.2 0.4 0.6 0.8 1.0
0.0 0.2 0.4 0.6 0.8 1.0 (a) N Mole Fraction
N Mole Fraction 1100
No Strain
Fig. 5. T
x diagram of the unstrained heterogeneous system U = 1.29 kJ/mol
GaN as a function of temperature and N mole fraction at 1080 U = 4.94 kJ/mol
0.1 MPa.
Liquid + Gas
Temperature (K)

1060 1055K
GaN. As Fig. 6 shows, at a system pressure of
1044K
0.1 MPa the melting temperature of GaN de-
1040
creases by 11 and 43 K with the addition of the
strain energies associated with the (0 0 0 1)8(0 0 1), GaN + Liquid GaN + Gas
[1% 2 1% 0]8[0 1 0] GaN/LiGaO2 and (1 2% 1 0)8(0 1 0), 1020
1012K
[1 0 1% 0]8[1 0 0] GaN/LiGaO2 growth systems, re-
spectively. The smaller change in the melting 1000
temperature corresponds to less strained GaN 0.0 0.2 0.4 0.6 0.8 1.0
basal plane deposition (Fig. 3) while the larger (b) N Mole Fraction
melting temperature is represents GaN prism Fig. 6. T
x diagram of the strained heterogeneous system
plane growth (Fig. 4). Due to the decrease in the GaN on LiGaO2 at 0.1 MPa system pressure. (a) Overall
GaN melting point temperature the liquid+gas diagram; (b) Zoomed view of change of melting point.
12 J. Shen et al. / Journal of Crystal Growth 240 (2002) 613
stability domain will increase as the lm/substrate
strain energy is increased. However, since the
strain energy only affects solid GaN there is no
change in the dew point line. Furthermore, the
GaN+liquid/GaN+gas as well as the GaN+
liquid/Ga+GaN equilibrium lines remain un-
changed because the strain energy affects the
GaN in both phases equally. Thus its impact on
each phase cancels.
It is desirable in most semiconductor deposition
techniques including CVD, MOCVD, and MBE to
have only solid and gas phases present. Thus, from
a thermodynamic viewpoint, deposition of GaN
on LiGaO2 at near atmospheric conditions must
occur below 1012 or 1044 K (1055 K in the unstrained
case) and Ga:N molar ratios less than unity.
Fig. 7 shows the thermodynamic equilibrium
deposition of GaN on Al2O3. A striking difference
between Figs. 5 and 7 can be seen immediately.
The strain energy of the GaN lm deposited on
Al2O3, 161.5 kJ/mol, is so large that it prevents
GaN from being a stable solid equilibrium phase
at any temperature or mole fraction. Other
calculations revealed that the maximum allowable
strain energy that would still result in a region of
GaN stability is E89 kJ/mol. Hence the strain
3000
Gas
2500
Temperature (K)
2000
Liquid + Gas
1500
1000
500 303K
Ga + Gas
0
0.0 0.2 0.4 0.6 0.8
N Mole Fraction
Fig. 7. T
x diagram of the strained heterogeneous system
GaN on Al2O3 at 0.1 MPa system pressure.
energy present when GaN is deposited on sapphire
is over 80% too large for solid GaN stability. The
phase diagrams shown in Fig. 7 are experimentally
inaccurate because a high dislocation density
would occur at this large of a lattice mist which
would signicantly relax the strained growth layer.
Therefore the phase diagram should be calculated
by combining the strain and the dislocation
energies with the Gibbs energy of GaN. This
calculation will be published in our next paper.
A general relationship between the decrease of
the GaN melting point temperature and the lattice
mismatch at 0.1 MPa system pressure is presented
in Fig. 8. As shown in Fig. 5, the maximum
possible change in the melting temperature, and
thus the limit of GaN stability, is 752 K (1055
303 K). Therefore, the maximum symmetric strain
the GaN system can possess and still have solid
GaN stability is when ex and ey equal 0.12. Elastic
incorporation of this much lattice mismatch
induced strain energy to enable epitaxial growth
is unreasonable and would experimentally result in
dislocation formation and strain relief. Changes in
the GaN melting point temperature are evident
even at lower lm strain energy values character-
istic of high quality lms.
1.0
Fig. 8. Generalized T
x diagram of the strained heteroge-
neous system GaN at 0.1 MPa system pressure.
 J. Shen et al. / Journal of Crystal Growth 240 (2002) 613
5. Conclusions
A series of generalized equations have been
developed from fundamental stress/strain princi-
ples to calculate the lattice mismatch induced
strain energy of a hexagonal lm on hexagonal
and rhombohedral substrates. Addition of strain
energies to the thermodynamic equilibrium calcu-
lations of the GaN phase diagram shows
dramatic differences between the strained and
unstrained cases. At 0.1 MPa system pressure the
GaN melting point decreased 11 and 43 K
depending on the lm/substrate orientation when
GaN was deposited on LiGaO2. Even more
interesting was the disappearance of a thermo-
dynamically stable GaN region when the strain
energy arising from its deposition on Al2O3 was
included. This contradicts what is observed
experimentally. The dew point line and Ga melting
point temperature lines were unchanged due to the
canceling effect of the GaN in each adjacent
deposition region. At equilibrium N2 partial
pressures, deposition on LiGaO2 again decreased
the GaN melting point temperature though a large
GaN+liquid phase remained. The profound effect
of strain energy in a lattice mismatched system
indicates that the predicted equilibrium behavior
of epitaxial thin lms may differ greatly from that
13
of unstrained thermodynamic systems. These
calculations suggest that strain energy has sig-
nicant inuence on both the experimental and
equilibrium deposition processes of semiconductor
materials. Further renement of this model by the
inclusion of dislocation and surface energy effects
will be presented in a future paper.
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