Physica B 406 (2011) 363–367

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Physica B
journal homepage: www.elsevier.com/locate/physb

Electronic and thermodynamic properties of B2-FeSi from first principles

KaiMei Zhao a, Gang Jiang a,n, Lili Wang b
a
Institute of Atomic and Molecular Physics, Sichuan University, Chengdu 610065, China
b
Computer Application Institute of CAEP, Academy of Engineering Physics of China, Mianyang 621900, China

a r t i c l e in f o abstract

Article history: The electronic and thermodynamic properties of B2-FeSi have been investigated using the first-principles
Received 29 July 2010 method based on the plane-wave basis set. The calculated equilibrium lattice constant is in good
Received in revised form agreement with available experimental and theoretical data. Our results have shown that B2-FeSi was a
24 October 2010
narrow gap semiconductor of above 0.055 eV and exhibited metallic characteristics. The density of states
Accepted 27 October 2010
(DOS) can also describe orbital mixing. Using the quasi-harmonic Debye model, the thermodynamic
properties of B2-FeSi have been analyzed. Variations of the Debye temperature YD, thermal expansion a,
Keywords: heat capacity Cv, entropy S and the Grüneisen parameter g on temperature T and pressure P were obtained
First principles successfully in the ranges of 0–2400 K and 0–140 GPa.
Electronic properties
& 2010 Elsevier B.V. All rights reserved.
Thermodynamic properties
FeSi

1. Introduction It is confirmed that e-FeSi has been transformed to B2-FeSi at finite

Iron silicides have attracted a lot of attention in recent decades,
due to their unusual physical properties and functional applica-
tions. The semiconducting phase of b-FeSi2 has been studied as a
material for thermoelectric conversion, solar cells and optoelec-
tronic applications [1–4]. e-FeSi (B20 structure), being a semicon-
ductor with a small energy gap of about 0.05 eV, reveals metallic
properties above 100 K [5–9]. One of the interesting features of
e-FeSi is that its magnetic susceptibility increased with temperatures
above 100 K and reached a broad maximum at 500 K, which obeyed
the Curie Weiss behavior at high temperatures. For Earth scientists,
silicon has been proposed to be a potential light element in the Earth’s
core based on density, velocity, isotopic and geochemical data
[10–18]. To assess the possibility of Si as a constituent of the core,
physical properties of Si-bearing iron phase under extreme conditions
must be determined. At high pressure, the compressibility of the
silicides b-FeSi2 and e-FeSi has been reported [19–27]. More literature
[19,21,28–30] has described the pressure dependence of the struc-
tural, optical and elastic properties of b-FeSi2. Meanwhile, the
thermodynamic, elastic properties of e-FeSi on temperature and
pressure have also been investigated [23,31–35].
Dobson et al. [36] have reported a new high-pressure phase of
FeSi with the B2 structure, which has been synthesized by a high-
temperature reaction of Fe and Si mixtures at 24 GPa. The B2
structure has an eight-fold coordination for space group Pm3-m
(Z¼1) with a¼2.7917(1)Å, also frequently referred to as CsCl–FeSi.
n
Corresponding author.
E-mail address: gjiang@scu.edu.cn (G. Jiang).
temperatures and pressures [23,26,27,37]. Dobson et al. [38] and
Ono et al. [39] have measured the compressibility of B2-FeSi by
X-ray powder diffraction at pressures up to 40 or 67 GPa. The
compressibility of B2-FeSi has been calculated by ab initio methods
[23,26,27,38,39]. Caracas and Wentzcovitch [23] has reported
structural properties and elastic properties of B2-FeSi at different
pressures (0–140 GPa).
The thermodynamic properties of materials are the basis of
solid-state science and industrial applications. Furthermore, the
thermodynamic properties under high pressure and temperature
are of great interest to physicists and geophysicists. So, in this work,
our main purposes are to study thermodynamic properties at high
temperatures and pressures using the first-principles plane-wave
method combined with the quasi-harmonic Debye model. Electro-
nic properties were calculated as well.
2. Theoretical method
2.1. Electronic properties calculations
The calculations of FeSi are performed by the pseudopotential
plane-wave method based on the density function theory (DFT), as
implemented by the Cambridge Serial Total Energy Package (CASTEP)
[40–42]. The exchange-correlation energy adopts the generalized
gradient approximation (GGA) with norm-conserving pseudopoten-
tial using Perdew–Burke–Ernzerhof (PBE) [43,44]. Pseudo-atomic
calculations are performed for Fe (3d6 4s2) Si (3s2 3p2). Several sets
of convergence test are carried out in order to choose the grid of
special K points and the plane-wave kinetic energy cut-off properly.

0921-4526/$ - see front matter & 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.physb.2010.10.065
364 K. Zhao et al. / Physica B 406 (2011) 363–367

Plane-wave cut-off energy of 880 eV is employed in computation of 3. Results and discussions

both electronic properties and total energies. The self-consistent
convergence of total energies is 5.0  10  6 eV/atom. For the Brillouin 3.1. Electronic properties
zone sampling, in the calculation of total energies, we use an 8  8  8
Monkhorst–Pack mesh [45]; however, in the band structure calcula- By fitting the calculated energy and volume to Birch–Murnagham
tion we use a 10  10  10 Monkhorst–Pack mesh. These parameters (BM) [47], the lattice constant a is obtained. The calculated lattice
are sufficiently well-converged for both total energies and electric constant a, bulk modulus B0 and the pressure derivative of bulk
properties. modulus B00 for FeSi at zero pressure are listed in Table 1. Obviously,
our results are consistent with other theoretical results [23,26,27] and
experimental values [26,38]. In Fig. 1, we illustrate V/V0 as a function
2.2. Thermodynamic properties
of pressure P. It is not difficult to find that the calculated equation of
state (EOS) agrees very well with the experimental result [38].
In order to investigate thermodynamic properties of FeSi, we
The dependence of bulk modulus B on temperature reflects
adopt the quasi-harmonic Debye model. Our calculations are
anharmonic interactions due to the fact that harmonic crystal bulk
implemented through the Gibbs code by Francisco et al. [46].
modulus is independent of temperature. Meanwhile, because the
The non-equilibrium Gibbs function G*(V;P,T)of FeSi can be written
bulk modulus is obtained through second derivatives of internal
in the form of
energy with respect to strains, it is related to interatomic poten-
G ðV; P,TÞ ¼ EðVÞ þ PV þ Avib ðYðVÞ; TÞ ð1Þ tials. The dependence of bulk modulus B on temperature is plotted
ranging from 0 to 2400 K in Fig. 2.
where E(V) is the total energy per unit cell for FeSi, PV corresponds
In Fig. 2, it is noted that the bulk modulus B is nearly constant
to the constant hydrostatic pressure condition and Avib (Y(V);T) is
when To50 K corresponding to a constant lattice parameter.
the vibrational term, which can be written as
When T450 K, however, B rapidly declines as T increases
   
9Y Y
Avib ðYðVÞ; TÞ ¼ nKT þ 3 lnð1eY=T Þ D ð2Þ
8T T

n is the number of atoms in the molecule and D(Y/T) is the Debye Table 1
integral. For an isotropic solid, Y is expressed by Lattice constant a (Å), volume V (Å3), bulk modulus B0 (GPa) and pressure derivative
rffiffiffiffiffi 0
of bulk modulus B0 for B2-FeSi at zero pressure.
_ BS
Y¼ ð6p2 V 1=2 nÞ1=3 f ðsÞ ð3Þ 0
kB M a (Å) V (Å3) B0 (GPa) B0

f(s) is given in Ref. [46] and the Poisson s is taken as 0.25. M is the Theoretical
molecular mass per unit cell and BS the adiabatic bulk modulus. Present work 2.785 21.60 199 4.78
Vocadlo et al. [27] 2.768a 226a 5.4a
Since BS may measure the compressibility of the crystal, it can be
Caracas and Wentzcovitch [23] 2.7721b
approximated by the static compressibility, as follows [26]: 2.7076c
 2  Moroni et al. [26] 2.72d 2.77e 263d 221e
d EðVÞ
BS C BðVÞ ¼ V 2
ð4Þ
dV Experimental
Dobson et al. [38] 2.791 21.747 0.02 1847 5 4.2 7 0.3
Therefore, the non-equilibrium Gibbs function G*(V;P,T) can be Ono et al. [39] 2.773 21.32 225 4 (fix)
obtained by minimizing with respect to V:
a
   DFT with ultrasoft non-norm-conserving Vanderbilt pseudopotentials in
@G ðV; P,TÞ GGA.
¼0 ð5Þ b
@V DFT with Hartwigsen–Goedecker–Hutter pseudopotentials in generalized
P,T
gradient approximation GGA.
c
According to Eq. (5), the isothermal bulk modulus is defined by the The same as above, but in local density approximation (LDA).
d
DFT with ultrasoft pseudopotentials in local-spin-density (LSD).
equilibrium thermodynamic relation e
DFT with ultrasoft pseudopotentials in GGA.
" ! #
@2 G ðV; P,TÞ
BT ðP,TÞ ¼ V ð6Þ
@V 2
P,T VðP,TÞ

in which V is the equilibrium volume.

Heat capacity Cv, entropy S and thermal expansion a in the
quasi-harmonic Debye model are defined as

S ¼ nk½4DðY=TÞ3 lnð1eY=T Þ ð7Þ

 
3Y=T
Cv ¼ 3nk 4DðY=TÞ Y=T ð8Þ
e 1

gCn
a¼ ð9Þ
BT V
where the Grüneisen parameter g is defined as
d ln YðVÞ
g¼ ð10Þ
d ln V
According to the above relation, Cp is given as follows:
Fig. 1. Relative volume V/V0 versus pressure at 300 K, where the dark squares
Cp ¼ Cn ð1 þ agTÞ ð11Þ represent our obtained results and the blank circles are results from Ref. [24].
 K. Zhao et al. / Physica B 406 (2011) 363–367
Fig. 2. Relationships between bulk modulus and temperature at different pressures
for B2-FeSi.
Fig. 3. Calculated band structure at zero pressure for B2-FeSi.
corresponding to an increase in primitive cell volume. That is, it is
the variation in lattice constants that makes the bulk modulus B
change. It is found that the dependence of bulk modulus B on
pressure is more significant than that of temperature.
The energy band structure of B2-FeSi at the equilibrium volume
is plotted in Fig. 3 along the high-symmetry direction of the first
Brillouin zone. The Fermi level EF is chosen to be located at 0 eV,
i.e. the top of the valence band. As shown in Fig. 3, the energy band
gap is 0.055 eV, indicating that B2-FeSi has narrow band gap
semiconduction. It is noted that some bands cross the Fermi energy
level EF, which describes the metallic behavior for B2-FeSi. The
nearest-neighbor bond lengths affect overlaps and bandwidths,
which lead to these changes of band structure. Fig. 4 shows the total
and partial density of state (DOS) of different atoms at zero
pressure. The energy band part of DOS can be decomposed into
four regions. The low valence band region between 13 and –
2.7 eV is dominated mainly by the contribution of Si 3p, showing
hybridization with Si 3p and Si 3s. The structure situated in the
range of  2.7 to 0 eV originates mainly from Fe 3d and shows
hybridization with Si 3p. In the region from 0 to 1.5 eV, some bands
originated predominantly from Fe 3d and show hybridization with
Si 3s as well as Si 3p. The upper conduction bands from 1.5 to 20 eV
are dominated by Si 3p, which hybridizes with Si 3s. Therefore, the
valence electrons are mainly around Fe atoms though there is a
weak covalence between Fe and Si.
365
Fig. 4. Calculated total and partial density of state at zero pressure for B2-FeSi.
3.2. Thermodynamic properties
The Debye temperature (YD) is a fundamental physical property
and used to distinguish between high- and low- temperature
regions for a solid. If To YD, we expect all modes to have energy
kBT, and if To YD, one expects the high-frequency modes to be
frozen [48]. We apply the Gibbs code to obtain the thermodynamic
properties of B2-FeSi.
In Table 2, the heat capacity Cn, the Grüneisen parameter g and
entropy S at different pressures (0, 20, 40, 60, 80, 100, 120 and
140 GPa) and at different temperatures (0, 300, 600, 1200, 1800 and
2400 K) are described. As can be seen clearly from Table 2, Cn is
proportional to T3 when temperature is below 600 K, which is due
to the anharmonic approximation. At higher temperatures, how-
ever, the anharmonic effect on Cn is suppressed, and Cn is very close
to the Dulong–Pettit limit [Cn(T)-3R], which is common to all
solids at high temperatures. For a given temperature (300, 600,
1200, 1800 and 2400 K), entropy S reduces by 61%, 44%, 33%, 31%
and 29% when pressure P changes from 0 to 140 GPa, respectively.
However, S increases dramatically with temperatures.
The Grüneisen parameter g, which illustrates the anharmonic
effects in the vibrating lattice and gives the volume dependence of
the Debye temperature YD, can correctly predict the anharmonic
properties of a material, such as the thermal expansion coefficient,
the temperature dependence of phonon frequencies and line-
widths [48]. In Table 2, we list a series of g at different temperatures
and pressures. From Table 1, one can find the following: when the
applied pressure is from 0 to 140 GPa, the Grüneisen parameter g
decreases by 29%, 30%, 33.5%, 38% and 45.7% at temperatures of
300, 600, 1200, 1800 and 2400 K, respectively; correspondingly,
when the pressure is kept constant, g increases with increase in
temperatures.
The heat capacity Cn and the Debye temperature YD as functions
of pressure P are shown in Fig. 5. The heat capacity Cv drops quickly
at low temperatures as pressure enhances. With increase in
temperature, the effect of pressure on Cv decreases gradually,
but the Debye temperature YD increases almost linearly with
applied pressures. The temperature dependence of YD is plotted in
Fig. 6. It is noted that YD decreases significantly with temperature
(0 2400 K), and decreases by 46%, 13%, 7.8%, 5.2% and 3.7%,
respectively at pressures of 0, 30, 60, 100 and 140 GPa when
temperature changes from 0 to 2400 K. It is obvious that the higher
the pressure, the smaller the effect of pressure on YD.
366 K. Zhao et al. / Physica B 406 (2011) 363–367

Table 2
Heat capacity Cn (J mol  1 K  1), Entropy S (J/mol K) and Grüneisen constant g of B2-FeSi at temperatures T (K) and pressures P (GPa).

T (K) P 0 20 40 60 80 100 120 140

0 Cv 0 0 0 0 0 0 0 0
c 2.244 2.012 1.883 1.797 1.732 1.681 1.637 1.602
S 0 0 0 0 0 0 0 0

300 Cv 40.39 37.03 34.37 32.15 30.24 28.55 27.02 25.70

c 2.262 2.019 1.887 1.80 1.734 1.68 1.638 1.6
S 34.56 27.52 23.23 20.23 17.98 16.20 14.71 13.53

600 Cv 47.37 46.25 45.28 44.42 43.63 42.89 42.19 41.54

c 2.304 2.038 1.898 1.807 1.739 1.686 1.642 1.606
S 66.67 57.63 51.89 47.74 44.48 41.82 39.52 37.60

1200 Cv 49.33 49.00 48.73 48.48 48.26 48.04 47.83 47.63

c 2.428 2.086 1.924 1.825 1.753 1.697 1.697 1.614
S 103.97 92.69 85.89 81.16 77.36 74.27 71.67 69.39

1800 Cv 49.68 49.52 49.40 49.28 49.18 49.08 48.98 48.89

c 2.618 2.145 1.957 1.846 1.769 1.710 1.663 1.623
S 129.00 114.92 107.30 102.04 98.02 94.73 91.96 89.54

2400 Cv 49.8 49.71 49.63 49.56 49.50 49.44 49.39 49.33

c 3.006 2.220 1.994 1.870 1.786 1.723 1.674 1.631
S 151.0 131.85 123.16 117.44 113.14 109.68 106.77 107.2

Fig. 6. Relationship between the Debye temperature and temperature at different

Fig. 5. Variation of thermodynamic parameters with pressures P. They are normal- pressures for B2-FeSi.
ized by (X  X0)/X0, where X and X0 are the Debye temperature or heat capacity under
any pressure P and zero pressure P0 at the temperatures of 300, 1200 and 2400 K.

In Fig. 7, pressure and temperature dependences of thermal

expansion a are shown. The thermal expansion a increases as T3 at
low temperatures and gradually approaches a linear increase at
high temperatures. The thermal expansion a, however, decreases
dramatically with pressure. It is found that at zero pressure the
change of a with temperatures is abnormal, which is due to the
anharmonic effect.

4. Conclusions

In summary, we have investigated the electronic properties for

B2-FeSi as well as the thermodynamic properties under high
temperatures and pressures using plane-wave pseudopotential
density functional theory within the generalized gradient approx-
imation (GGA). The obtained lattice constant a and the equation of
state (EOS) are in good agreement with experimental results. We
have analyzed the bulk modulus B, which decreased with Fig. 7. Thermal expansion of temperature T and pressure P for B2-FeSi.
 K. Zhao et al. / Physica B 406 (2011) 363–367
increasing temperatures, especially at high temperatures. The
energy band structure has shown that B2-FeSi was a narrow gap
semiconductor above 0.055 eV. The density of state (DOS) has
revealed that the valence electrons are mainly around Fe atoms.
The thermodynamic properties of B2-FeSi were predicted success-
fully using the quasi-harmonic Debye model. The variations of
thermal expansion a, heat capacity Cv entropy S and the Grüneisen
parameter g with temperature T and pressure P were analyzed
systematically in the ranges of 0–2400 K and 0–140 GPa.
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