ALGERIAN JOURNAL OF ADVANCED MATERIALS 4, 403(2008)

Lattice-dynamical and thermodynamic properties of SiSn and GeSn compounds.

M. Souadkia*, B. Bennecer, Y. Chaouche, A. Mellouki, F. kalaresse.

Physics labortory at Guelma, faculty of sciences and Engineering, University of Guelma,

P. O. Box 401 Guelma 2400, Algeria.
*
Corresponding author: somourad@gmail.com
Abstract

We report on first principles calculations of the vibrational and thermodynamic properties of zinc blende SiSn
and GeSn compounds. All the calculations are carried out using the plane wave pseudopotential method within the
density functional theory (DFT) in the local-density approximation. The equilibrium lattice parameters are obtained
by minimizing the energy with respect to volume. The phonon spectra and the corresponding density of states for
the studied compounds are obtained by using the density functional perturbation (DFPT). The Born effective
charges are also calculated and satisfy the acoustic sum rule. The obtained LO-TO splitting decreases in this order
SiSn-GeSn, which is similar to the one encountered for the Born effective charges. By using the calculated phonon
frequencies and the density of states the constant volume specific heat and the entropy are evaluated in function of
temperature.

Key words: pseudopotential, DFT, phonon, semiconductor.

1. Introduction
The IV-IV alloy systems are attractive for band
gap and strain engineering of heterostructures [1].
The lattice mismatch between C, Si, Ge and α-Sn is
very high, the difference of electro negativity is
important, and the solubility between them is very
low [2]. The IV-IV semiconductor alloys have
recently emerged as a possible candidate for the
creation of non polar semiconductor, with carrier
mobilities higher than those of III-V and II-VI
compounds [3]. In recent years, first principles
investigations of the structural, electronic properties
and band structure of SiGe, SiSn and GeSn have been
performed by many groups [4-9]. The effect of strain
on the thermodynamic properties of Ge-Si, Ge-Sn,
Si-Sn, SiC thin solid films have been studied by
Deibuk et al. [4] using molecular dynamics
simulation.
The dispersion relations for phonon in strained Si
and Ge have been calculated by several groups. For
example Gianozzi et al. [10] and Qteish and Molinari
[11], who recently used an ab –initio approach based
on density-functional theory in the local-density
approximation to investigate lattice dynamics in
isotropically and biaxially strained structures. By
using the interatomic force constants approach
(IFC’s) Stefano de Gironcoli [12] studied the phonon
in Si-Ge systems. Using a much simpler, but less
fundamental approach, Zi, Zhang and Xie [13]
examined phonon dispersion in biaxially strained Si
and Ge (001) layers and in Si/Ge SLS’s by using a
keating model with strain-modified force constants.
ISSN 1111-625X/06/$18
In this study, we present first-principles
calculations of the structure, lattice dynamics and
some thermodynamics properties of SiSn and GeSn
compounds. The remainder of this paper is organised
as follows: in section 2 the calculation details are
described. In section 3 we present the obtained results
and discuss them. Finally, a conclusion is given in
section 4.
2. Details of the calculations:
The ab initio calculations of zinc-blende SiSn and
GeSn were carried out using the density functional
theory, thanks to the ABINIT code [14]. The
exchange-correlation energy functional was
evaluated within the local density approximation
[15]. The electronic wave functions were expanded in
plane waves up to a kinetic energy cutoff of 32 Ha
for SiSn, and 36 Ha for GeSn. Integrations over the
Brillouin zone were approximated by sums on 4x4x4
mesh of special k points. We used norm- conserving
Troullier-Martins pseudo-potentials [16].
3. Results
All the studied systems crystallise in the zinc-
blende structure, which have two atoms per unit cell.
The two atoms have coordinates τ1= (0,0,0) and τ2 =
a(1/4,1/4,1/4). In order to calculate the ground state
properties of SiSn and GeSn, the total energies are
calculated for different volumes around the
equilibrium cell volume v0. The calculated total
energies are fitted to the Murnaghan’s equation of
state [17] to determine the equilibrium lattice
constant a0, the bulk modulus B0 and its pressure
403 @2008 Algerian Materials Research Society
M. Souadkia et al. ALGERIAN JOURNAL OF ADVANCED MATERIALS 4, 403(2008)

derivative B’. The calculated equilibrium parameters 300

(a0, B0, B’) are given in table 1. To our best
knowledge, there is not experimental data for the 250

existence of the zinc-blende SiSn and GeSn. We

Frequency (cm )
-1
200

notice that our predicted structural parameters such as

lattice constants, bulk modulus and its pressure 150

derivative are compared with the available theoretical 100

values.
50

Table 1 0
Γ K X Γ L X W L DOS

Structural parameters of SiSn and GeSn 400

éclatement LO-TO

compounds.
300

Frequency(cm )
-1
Parameter Present Others 200
work calculations Expt

SiSn 100

a0 (Å) 5.79 5.9a, 5.86b 0

Γ K X Γ L X W L DOS
a
B (GPa) 72.01 63

B’ 4.35

GeSn Fig. 1. Calculated phonon dispersion and density of

states (DOS) for zinc-blende GeSn and SiSn,
a0 (Å) 5.83 6.06a, respectively.
6.09b,
6.09c, 6.20d The calculated Born effective charge is 1.42 for SiSn
while the other theoretical studies is 1.98 [5],on the
B (GPa) 65.90 56a, 54c, other hand, the calculated Born effective charge for
53d GeSn is 1.34 while the other theoretical studies is
1.58 [5]. The LO-TO decreases in this order SiSn
B’ 4.64 5.03c, 6.9d (6.82cm-1), GeSn (2.95cm-1) whish is similar to the
one encountered for the Born effective charges SiSn
a
Ref. [18], bRef. [6], cRef. [7], dRef. [8]. (1.42), GeSn (1.34).The reported values of the
effective charges satisfy the Acoustic Sum Rule
(ASR).
Our calculated for the bulk phonon dispersion along The calculated total phonon DOS was used to
several symmetry lines together with the evaluate the temperature dependent of
corresponding densities of states , are displayed in thermodynamic properties of SiSn and GeSn in a
figure 1, for SiSn and GeSn compounds qauasi-harmoniquc approximation.
The calculated frequencies at the Γ point in SiSn are Figure 1 and 2 shows the calculated entropy S and
365.38 cm-1 and 372.20 cm-1 for the transverse and specific heat Cv of SiSn and GeSn, respectively, in
longitudinal modes respectively, the former compares the temperature range of 0 and 600 K. At high
well with the theoretical of 363.33 cm-1 obtained by temperature, the calculated Cv approaches the
Rùcker et al. [18]. The calculated LO-TO splitting is limiting Dulong-Petit value of 6R ( 49.86 J/mol),
6.82 cm-1. On the other hand, The calculated where R is the perfect gas constant ( R= 8.31451
frequencies at the Γ point in GeSn are 253.24 cm-1 J/mol).
and 256.16 cm-1 while the others theoretical is 250
cm-1 for the transverse mode [18]. The calculated
LO-TO splitting is 2.95 cm-1.

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M. Souadkia et al. ALGERIAN JOURNAL OF ADVANCED MATERIALS 4, 403(2008)
50 100

80
40

Specific heat ( J/mol. k)

Entropy ( J/mol. k)
60
30

40
20

20
10

0
0 0 100 200 300 400 500 600
0 100 200 300 400 500 600 Température (K)
Température (K)

Fig. 1. Calculated the constant-volume specific heat Cv, the entropy S of SiSn.

50

40 100
Specific heat (J/mol. k)

Entropy (J/mol. k)
30

20 50

10

0 0
0 100 200 300 400 500 600 0 100 200 300 400 500 600
Température (K) Température (k)

Fig. 2. Calculated the constant-volume specific heat Cv, the entropy S of GeSn.

In the comparison between SiSn and GeSn, the such as the constant-volume specific heat Cv and the
thermodynamic properties such as Cv are quite similar entropy S are also evaluated in function of the
at high temperature. For example, the calculated temperature. The calculated Cv at high temperature
values Cv at 500k for SiSn is 47.7 J/mol.K, and for approaches the limiting Dulong-Petit value.
GeSn is 48.8 J/mol.K, the difference is 2.25%.
However, the thermodynamic properties at low
temperature are quite different between SiSn and References
GeSn, for example, the calculated value for Cv at 100
K for SiSn is 14.4 J/mol.k, and for GeSn is 32.5 J/mol. [1] K. Brunner, K. Ebert, W. Winter, E.
K, and the difference is 55.56%. Bulgiel, Appl. Surf. Sci. 102 (1996)17.
[2] R. I. Scase, G. A. Slack, J. Chem. Phys. 30
4. Conclusion
(1959) 1551.
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structural and lattice dynamics, and some [3] V. G. Deibuk, Yu. G. Korlyuk.
thermodynamic properties of SiSn and GeSn within Semiconductor Physics. Quantum
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theory in the local-density approximation. The N 3. P. 247-253.
equilibrium lattice parameters are obtained by [4] R. Khenata, H. Baltache, M. Sahnoun, M.
minimizing the energy with respect to volume. The Driz, M. Rérat and B. Abbar, Physica B
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Born effective charge decreases with decreasing LO- 843- 848.
TO splitting. The computed thermodynamic properties [6] A. Zaoui, M. Ferhat, M. Certier, B. Khelifa,

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[13] J. Zi, K. Zhang, and X. Xie, Phys. Rev B
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[14] the ABINIT code is common project of université
catholique de Louvin, coming incorporated, and
other contributors, URL: www.abinit.org.
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