Computational Condensed Matter 4 (2015) 13e22

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Computational Condensed Matter

journal homepage: http://ees.elsevier.com/cocom/default.asp

Regular article

Electronic structure, structural phase stability, optical and

thermoelectric properties of Sr2AlM'O6 (M' ¼ Nb and Ta) from first
principle calculations
Balasubramaniam Rameshe a, c, Mathrubutham Rajagopalan b, Balan Palanivel c, *
a
Department of Physics, Rajiv Gandhi College of Engineering and Technology, Puducherry 607 402, India
b
Department of Physics, Anna University, Chennai 600 025, India
c
Department of Physics, Pondicherry Engineering College, Puducherry 605 401, India

a r t i c l e i n f o a b s t r a c t

Article history: First principle calculations are performed to investigate the electronic structure, structural phase sta-
Received 4 December 2014 bility, optical properties and thermoelectric properties of double perovskite oxide semiconductors
Received in revised form namely Sr2AlM'O6 (M' ¼ Nb and Ta) in the cubic symmetry using WIEN2k. In order to study the ground
14 March 2015
state properties of these compounds, the total energies are calculated as a function of reduced volumes
Accepted 23 March 2015
Available online 24 March 2015
and fitted with Brich Murnaghan equation. The estimated ground state parameters are comparable with
the available experimental data. Calculations of electronic band structure on these compounds have been
carried out using generalized gradient approximations and modified Becke-Johanson potential (TB-mBJ).
Keywords:
Ab-Initio calculations
The calculated band gap for Sr2AlNbO6 and Sr2AlTaO6 with GGA and TB-mBJ reveal that these compounds
Double perovskites exhibit semiconducting behavior with a direct band gap. To explore the optical transitions in these
Electronic structure compounds, the real and imaginary parts of the dielectric function, refractive index, extinction coeffi-
Optical properties cient, reflectivity, optical absorption coefficient, real part of optical conductivity and the energy-loss
Thermoelectric properties function are calculated at ambient conditions and analyzed both with GGA and TB-mBJ potentials. In-
vestigations of the thermoelectric properties of these compounds have been carried out by the calcu-
lations of transport coefficients based on Boltzmann transport theory in order to analyze the variation of
Seebeck's coefficient at different temperatures for various carrier concentrations based on the electronic
structure near the valence band maxima.
© 2015 Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction
Double Perovskite structured oxides compounds with general
formula A2BB’O6 have been widely investigated in the past few
decades due to their diversity in their crystal structure and variety
of properties such as high temperature superconductivity and co-
lossal magneto-resistance [1,2] which are of great importance for
scientific and technological applications. These perovskite oxides
have become more and more important and are a key material in
developing oxide based electronic devices since they show some
important properties such as high dielectric constant, ferroelectric
polarization, catalysis and magnetic media [3,4]. Investigation of
double perovskite type compounds in the areas of fuel cells is very
* Corresponding author.
E-mail address: bpvel@pec.edu (B. Palanivel).
essential since these materials are a promising anode material for
the solid state fuel cells which are anticipated for operation at
moderate temperature [5,6]. Semiconducting oxide perovskites are
of technological importance since these oxides are used to develop
dielectric resonators and filters. These dielectric resonators and
filters are used in microwave signal devices like mobile phones and
other wireless devices [7]. Many microwave dielectric ceramics
adopts perovskite structure with low dielectric loss and high
dielectric constant, hence these materials are employed enor-
mously in microwave integrated circuits [8].
Enormous amount of work has been done experimentally on
these semiconducting oxides with perovskite structure in ideal,
double and complex structures. Mishra et al. [9] using angle
dispersive X-ray diffraction and Raman scattering, studied the
structure evolution of double perovskite Sr2MgWO6 under high
pressure. This compound is found to be structurally stable with
tetragonal structure (space group I4/m) up to the highest pressure

http://dx.doi.org/10.1016/j.cocom.2015.03.003
2352-2143/© 2015 Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
14 B. Rameshe et al. / Computational Condensed Matter 4 (2015) 13e22
of about 40 GPa. These experimental reports were also confirmed
with the use of first principles structural relaxation calculations.
Bouchaib Manoun et al. [10], reported the high temperature (up to
500 c) Raman spectroscopy phase transitions in Sr2MWO6 (M ¼ Zn,
Co) double perovskite oxides. It is observed that a first order phase
transition from monoclinic (P21/n) to tetragonal (I4/m) structure
occurs at a temperature of 80 c for Sr2ZnWO6, whereas Sr2CoWO6
undergoes phase transition from tetragonal (I4/m) to cubic (Fm-3m)
at a temperature of about 480 c. Yan Qian et al. [11] studied the
effect of high pressure on the electronic and magnetic properties of
Sr2FeMoO6 and reported a transition from a ferromagnetic half-
metallic state to nonmagnetic semiconductor state at a pressure
of about 33e36 GPa by replacing Ba with Sr using synchrotron X-
ray and neutron powder diffraction methods.
Alo Dutta et al. [12] synthesized Sr2AlNbO6 by a solid state re-
action and studied the dielectric property. The dielectric properties
of this compound show significant frequency dispersion. The
dielectric relaxation of Sr2AlNbO6 is studied by ColeeCole model.
Recently using first principles calculations Li et al. [13] reported
that Sr2AlTaO6 exhibit induced ferromagnetism due to vacancy in
Al and Ta. The induced magnetism is different for Al and Ta vacancy.
Their study reveals that Sr2AlTaO6 with O vacancy is nonmagnetic
but energetically more favorable than that of other vacancies.
It is well known that metals have very good electrical conduc-
tivity (~106 U1 cm1). However, their very low Seebeck coefficient
(~5 mVK1) and large thermal conductivity do not make them the
most desirable materials for thermoelectric applications. Semi-
conductors with large band gap are having large Seebeck coefficient
(~1000 mVK1) with very low electrical conductivity
(~1012 U1 cm1) results in a small value of S2s. In thermoelectric
materials research, favorable oxide thermoelectric materials have
been discovered, which include CaMnO3-based perovskites, Al-
doped ZnO, layered cobalt oxides represented by NaCo2O4 and
Ca3Co4O9, and SrTiO3-related phases. It is well known that TMF
(thermo electromotive force) generated by metals is generally less
than 50 mV/K, however semiconductors can generate the TMF of
several hundreds of mV/K.
From the above reports, it is interesting to note that several
experimental studies have been done on these Strontium based
double perovskites. However only few theoretical studies are re-
ported particularly on the optical and thermoelectric properties of
Strontium based compounds namely Sr2AlNbO6 and Sr2AlTaO6. It is
well known that Niobium and Tantalum based double perovskites
are of great importance since these materials are used extensively
in many technological applications such as interference filters,
optical fibers, solar energy conversion, reflecting coatings, pig-
ments and photo catalysts. Hence accurate knowledge of their
optical constants is essential. First principles calculations offer one
of the most powerful tools for carrying out theoretical studies of
these properties.
2. Method of calculations
In this work, the structural phase stability and electronic
structure calculation of Sr2AlM'O6 (M' ¼ Nb and Ta) compounds
were carried out using the full potential LAPW method imple-
mented in WIEN2K [14] within the generalized gradient approxi-
mation (GGA) to the exchange-correlation potential according to
the Perdew-Burke-Ernzerhof parameterization [15]. The muffin tin
radii for Sr, Al, Nb, Ta and O are 2.50, 1.80, 1.98, 1.97 and 1.75 a.u.
respectively. The Brillouin zone sampling was performed according
to the Monkhorst-Pack scheme [16]. For k-space integration 5000 k
points in the entire Brillouin zone were used. The number of plane
waves in a Fourier expansion of potential in the interstitial region
was restricted to RMT  kmax ¼ 7. For the total energy calculations
the energy convergence criterion was set to 106 Ry.
The transport calculations in the present study are carried out
using the code Boltztrap [17]. This calculation is based on the semi
classical treatment given by the solution of Boltzmann equation by
embedding certain approximations like relaxation time approxi-
mation and rigid body approximation. Considering these approxi-
mations, the Seebeck coefficient S (T,r) which depends on
temperature and doping is given by [18].
Z
dEsðEÞðE  mÞdf =dE
SðT; rÞ ¼ Z (1)
dEsðEÞdf =dE
where f is the Fermi function, m is the chemical potential and s (E) is
the transport function by
sðEÞ ¼ NðEÞn2 ðEÞtðEÞ (2)
where N(E) is the density of states (DOS), g(E) is the band velocity
and t (E) is the scattering time. Under the constant scattering time
approximation t (E) is independent of energy [17,18]. In order to
assess thermoelectric power factor S2s, the term s(T) is required
and is given by
Z
sðTÞ ¼ dEsðEÞdf =dE (3)
3. Crystal structure
An ideal single perovskites have the same crystal structure
similar to CaTiO3 a natural mineral with general formula AMX3,
where A is a cation normally with large radius and low charge, such
as an alkali or alkaline earth metal. The M cations are usually
transition metal ions having smaller radius with more electro
negativity. Generally the X anion is replaced by oxygen, fluorine or
nitrogen. In the ideal perovskite structure AMO3, if site of the M
cation is substituted partially in a 1:1 manner by M0 cation a crystal
structure of an ideal double perovskite is obtained with expanded
unit cell and the cell parameters of these double perovskite are
approximately twice those of an ideal pervoskite. Thus, the crystal
structure of an ideal double perovskite with general formula
A2MM'O6 can be described as a frame work of alternating MO6 and
M0 O6 octahedra in three dimension, with A-cations occupying the
interstitial spaces between the octahedra. At ambient conditions
Sr2AlM'O6 (M' ¼ Nb and Ta) crystallizes in a cubic structure (space
group Fm-3m). The atomic positions of Sr atom is at (8c) (0.25, 0.25,
0.25), Al atom is at (4a) (0,0,0), M0 atom is at (4b) (0.5, 0.0, 0.0) and
for O is at (24e) (u, 0, 0), where ‘u’ is the internal parameter of the
oxygen atom [23].
4. Structural phase stability
In the present calculation a complete structural optimization
was performed for both the compounds. The optimized lattice
parameter and the atomic positions show that these compounds
adopt the cubic symmetry with space group Fm-3m. To verify the
above result the tolerance factor (Tf) for these compounds is
calculated using the formula
R þ R0
Tf ¼ pffiffiffi A (4)
2ðRB þ R0 Þ
where RA denotes the ionic radius of Sr ion and Ro denotes the ionic
 B. Rameshe et al. / Computational Condensed Matter 4 (2015) 13e22 15

radius of O ions. RB denotes the average ionic radius of the ions at -45361.45
M0 sites. The tolerance factor is an important parameter for a
Sr2AlTaO6
perovskite structure which provides direct information about the
-45361.50
structural stability. The perovskite structure is stable within the
tolerance range of 0.78 < Tf < 1.05. For calculation of tolerance

Total Energy (Ryd)

factor for Sr2AlNbO6 and Sr2AlTaO6 the ionic radius of Sr, Al, Nb, Ta -45361.55
and O ions are taken as 1.12, 0.535, 0.64, 0.64, and 1.4 Å, respec-
tively. The calculated tolerance factor is found to be 0.90 which -45361.60
supports that the cubic structure is stable.
Owing to the cubic symmetry, the equilibrium lattice constant of
these perovskite is determined by the minimization of the total -45361.65

energy of the system with respect to the volume of the unit cell as
similar to our earlier works [19e21]. The calculated total energies -45361.70
are fitted with BricheMurnaghan equation of state [22] to estimate
the equilibrium lattice constant. The double perovskite compounds 100 110 120 130 140
are characterized by the internal parameter ‘u’ which specify the
position of ‘O’ anion in the unit cell. In the present calculation, the
3
Volume (Å )
value of the internal parameters ‘u’ has been optimized at equi-
librium volume and the optimized parameters are also tabulated. Fig. 2. Total Energy versus volume Sr2AlTaO6.

The total energy as a function of the volume for these compounds is

shown in Figs. 1 and 2. The estimated lattice parameters are pre-
Table 1
sented in Table 1, together with the available experimental data Estimated equilibrium lattice constant (ao), internal atomic parameters u, bulk
[23]. modulus (B0) and pressure derivative of bulk modulus (B0 ) for Sr2AlM'O6 (M' ¼ Nb
and Ta) compounds.

5. Results and discussions Compound ao(Å) u B0(GPa) B0

Sr2AlNbO6 7.7832 0.2448 172.0 5.78

5.1. Electronic band structure 7.7858a 0.2450a
Sr2AlTaO6 7.7839 0.2460 170.4 5.80
7.7866a 0.2461a
The band structure of the double perovskite Sr2AlM'O6 (M' ¼ Nb
a
and Ta) at zero pressure along highly symmetrical points in the Expt [23].

Brillouin zone show that the bands just fall below the Fermi level
(EF) are derived from O-2p orbitals. The overall band profiles of two
band gap materials they are very useful in designing light emitting
compounds exhibit the same nature of band profiles. The calculated
diodes and laser diodes working in the visible and ultra-violet re-
band structures clearly show that valence band maximum and
gion. The calculated band gap of Sr2AlNbO6 and Sr2AlTaO6 is lower
conduction band minimum falls at G point. Therefore, the band gap
than that of experimental value [24]. It is well known that the band
of these materials is the G e G direct gap semiconductor with a
gap calculated using local density approximation (LDA) and GGA
band gap of 3.03 eV and 3.75 eV for Sr2AlNbO6 and Sr2AlTaO6
strongly underestimate experimental band gap [25]. In order to get
respectively. It is well known that in direct gap materials excess of
a good estimate of the energy band gap values, the modified Becke-
energy is released as photon when an electron in the conduction
Johanson potential (TB-mBJ) as proposed recently by Tran and
band annihilates a hole in the valence band. This emission of
Blaha [26] is also employed. This potential can be used to produce
photon energy is faster in direct band gap materials than in the
accurate gaps for a wide range of different materials [27e33]. The
indirect band gap materials. Because of this reason most of the wide
calculated band gap using TB-mBJ for Sr2AlNbO6 is exactly matches
band gap semiconductors are used in designing of optoelectronic
with experimental value of 3.8 eV. However, the calculated band
devices. Since the compounds Sr2AlNbO6 and Sr2AlTaO6 are wide
gap for Sr2AlTaO6 using TB-mBJ is 5.03 eV, which is slightly more
than the experimental energy gap. The calculated energy gaps for
these compounds with GGA and TB-mBJ are tabulated in Table 2,
-21750.20 along with the available experimental data.
Sr AlNbO The calculated band structure of Sr2AlNbO6 and Sr2AlTaO6 with
GGA and TB-mBJ are shown in Fig. 3(aed).
-21750.25 To further explain the nature of the electronic band structure
the total DOS of Sr2AlNbO6 and Sr2AlTaO6 are calculated and are
Total Energy (Ryd)

shown in Fig. 4(aed) with GGA and Tb-mBJ potentials. The GGA
-21750.30 density of states profile of these compounds clearly depicts that O-
p states electrons contribution is more in the valence band region
from 0 to 4.5 eV and hybridize with Al-p states. In the conduction
-21750.35

Table 2
-21750.40 The calculated and experimental band gaps for Sr2AlM'O6 (M' ¼ Nb and Ta)
compounds.
100 110 120 130 140 Compound GGA (eV) TB-mBJ (eV) Experiment (eV)
3
Volume (Å ) Sr2AlNbO6 3.03 3.80 3.80a
Sr2AlTaO6 3.75 5.03 4.60a
a
Fig. 1. Total Energy versus volume for Sr2AlNbO6. Expt [24].
16 B. Rameshe et al. / Computational Condensed Matter 4 (2015) 13e22
Fig. 3. (a). Band structure of Sr2AlNbO6 with GGA. (b). Band structure of Sr2AlNbO6 with TB-mBJ. (c). Band structure of Sr2AlTaO6 with GGA. (d). Band structure of Sr2AlTaO6 with TB-
mBJ.
band the transition metals Nb and Ta mainly contribute for the
bands in the energy range from 3 to 10 eV. The covalency nature
between Nb-4d to O-2p in Sr2AlNbO6 and Ta-5d to O-2p covalency
in Sr2AlTaO6 is because of the fact that at the valence band
maximum the Nb-4d contribution and Ta-5d contribution are zero
but it rises with increasing energy. On the other hand at the con-
duction band minimum the O-2p contribution rises from zero with
increase of energy. The density states profiles of these compounds
with TB-mBJ are similar with an energy shift of 0.77 eV for
Sr2AlNbO6 and 1.28 eV for Sr2AlTaO6 when compared with GGA.
5.2. Optical properties
The optical properties of matter can be described by the elec-
tronic dielectric function ε(u). Generally, there are two contribu-
tions for ε (u), namely intraband and interband transitions. The
latter contributions are crucial only for metals [34]. The interband
transitions can be further divided into direct and indirect transi-
tions. Here the indirect interband transitions are ignored since it
involves scattering of phonon and is expressed to give only a small
contribution to ε (u). The dielectric function of an anisotropic
material is a complex symmetric second-order tensor which de-
scribes the linear response of an electronic system to an applied
00
external electric field. It can be expressed as εðuÞ ¼ ε0 ðuÞ þ iε ðuÞ,
where ε (u) and ε (u) are the real and imaginary components of
0 00
the dielectric function, respectively. The imaginary part of the fre-
quency dependent dielectric function, is given by [35]:
 X Z
00 e2 Z
ε ðuÞ ¼ jMcv ðkÞj2 d½ucv ðkÞ  ud3 k (5)
pm2 u2 v;c
BZ
The integral is over the first Brillouin zone. The momentum
dipole elements: Mcv ðkÞ ¼ hucv jd$Vjuvk i, where d is the potential
vector defining the electric field, are matrix elements for direct
 B. Rameshe et al. / Computational Condensed Matter 4 (2015) 13e22 17

Fig. 4. (a). Density of states for Sr2AlNbO6 with GGA. (b). Density of states for Sr2AlNbO6 with TB-mBJ. (c). Density of states for Sr2AlTaO6 with GGA. (d). Density of states for
Sr2AlTaO6 with TB-mBJ.

transitions between valence- uvk ðrÞ and conduction-band uck ðrÞ

states, and the energy Zucv ðkÞ ¼ Eck  Evk is the corresponding pffiffiffi qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi 1=2
ε0 ðuÞ2 þ ε ðuÞ2  ε0 ðuÞ
00
IðuÞ ¼ 2 u (9)
transition energy. The real part of the dielectric function ε0 ðuÞ can
be derived from the imaginary part using the KramerseKronig
relations, 00
ε ðuÞ
Re½sðuÞ ¼ (10)
4p
Z∞ 00
2 u0 ε ðu0 Þ
ε0 ðuÞ ¼ 1 þ P du0 (6) .h i
p u02  u2 00
LðuÞ ¼ ε ðuÞ
00
ε0 ðuÞ2 þ ε ðuÞ2 (11)
0

These compounds Sr2AlNbO6 and Sr2AlTaO6 have cubic sym-

where, P implies the principal value of the integral. The knowledge
metry. For cubic symmetry, the principal tensor component εxx, εyy
of both the real and imaginary parts of the dielectric function al-
and εzz will be equal. Hence only one component of the dielectric
lows the calculation of important optical functions such as,
function has to be calculated i,e, εxx ¼ εyy ¼ εzz. The variations in the
refractive index n(u), extinction coefficient k(u), reflectivity R(u),
real and imaginary (absorption) parts of the electronic dielectric
optical absorption coefficient I(u), real part of optical conductivity
function ðε0 Þ for Sr2AlNbO6 and Sr2AlTaO6 with GGA and TB-mBJ
Re[s(u)] and the energy-loss function L(u) using the following
are shown in Fig. 5a and b.
expression 00
The analysis of the ε ðuÞ curve with GGA shows that the first
optical critical point of the dielectric function occurs at 3.03 eV for
 .pffiffiffiqffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi 1=2
Sr2AlNbO6 and at 3.75 eV for Sr2AlTaO6, whereas with TB-mBJ po-
ε0 ðuÞ2 þ ε ðuÞ2 þ ε0 ðuÞ
00
nðuÞ ¼ 1 2 (7)
tential the first optical critical point of the dielectric function occurs
at 3.8 eV for Sr2AlNbO6 and at 5.03 eV for Sr2AlTaO6. This point is Gv
pffiffiffiffiffiffiffiffiffiffi e Gc splitting, which gives the threshold of direct optical transitions
εðuÞ  1 2 between the highest valence band maximum and the lowest con-

RðuÞ ¼ pffiffiffiffiffiffiffiffiffiffi (8)
εðuÞ þ 1 duction band minimum. This is known as the fundamental ab-
sorption edge. Beyond this point the curve increases rapidly. This is
00
due to the fact that the number of points contributing towards ε ðuÞ
18 B. Rameshe et al. / Computational Condensed Matter 4 (2015) 13e22

10 with GGA and TB-mBJ are given in Table 3. This important quantity
Sr2AlNbO6 Real (GGA) is related to the band gap and shows that a smaller energy gap
9
Imaginary (GGA) yields a larger value of the static dielectric constant ε΄ (0). This could
8 Real (TB-mBJ)
be explained on the basis of the Penn model [36]. The Penn model is
( )

7 Imaginary (TB-mBJ)
based on the expression ε0 ¼ 1 þ ðZup =Eg Þ2 . It is noted from the
6
expression that the static dielectric constant ε΄ (0) of a compound is
Dielectric Constant

5
inversely proportional to Eg. Hence, smaller Eg yields larger ðε0 Þ.
4 The refractive index n (o) of Sr2AlNbO6 and Sr2AlTaO6 calculated
3 with both potentials as obtained from expression (3) are shown in
2 Fig. 6. The maximum refractive index n (o) for Sr2AlNbO6 and
1 Sr2AlTaO6 is obtained at energy of 4.2 eV and 4.9 eV respectively for
0 GGA, whereas the maximum refractive index with TB-mBJ is ob-
-1 tained at 4.9 eV and 6.2 eV for Sr2AlNbO6 and Sr2AlTaO6 respec-
-2 tively indicating the shift towards the higher energies. The
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 maximum refractive index is established at the first transition of an
Energy (eV) electron from valence band to conduction band. This type of tran-
sition is called direct electron transition. At higher energies the
refractive index decreases for the reason that there is no possibility
10 for direct de-excitation of electron and consequently there is
9 Real (GGA)
Sr2AlTaO6 dissipation of energy. It is well known that semiconductors having
Imaginary (GGA)
8 lower refractive indices have wider band gap which dictate an in-
Real (TB-mBJ)
7
Dielectric Constant ( )

Imaginary (TB-mBJ) verse relation between the zero frequency limit of the refractive
6 index and band gap of semiconductor.
5 It is clear from Fig. 6 that the refractive index of both the com-
4 pounds and higher energies is lesser than unity which is a clear
3 indication that the two compounds are no longer active as a
2 transparent material. The refractive index is the complex variable
1 given as N(u) ¼ n(u) þ jk(u), where k(u) is called the extinction
0 coefficient.
-1 The variation of extinction coefficient with photon energy is
-2 shown in Fig. 7. The extinction coefficient of Sr2AlNbO6 increases
-3 with energy in the transparency region and reaches its maximum
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
value at about 4.6 eV whereas for Sr2AlTaO6 the maximum value is
Energy (eV) at energy of 5.4 eV. The larger values of extinction coefficient in
these compounds reveal that these compounds have the affinity to
Fig. 5. a. The optical spectrum of the dielectric constant as a function of the photon
absorb more light.
energy for cubic Sr2AlNbo6 with GGA and TB-mBJ. b. The optical spectrum of the
dielectric constant as a function of the photon energy for cubic Sr2AlTao6 with GGA and The important optical constants like reflectivity R(u), optical
TB-mBJ. absorption coefficient I(u), real part of optical conductivity Re
[s(u)] and the energy-loss function L(u) are calculated using ex-
00
pressions (7)e(11) and are shown in Fig. 8(aed) with GGA and TB-
increases abruptly. The main peak of ε ðuÞ spectrum for Sr2AlNbO6 mBJ. From Fig. 8(a) the reflectivity profile of Sr2AlNbO6 clearly
and Sr2AlTaO6 with GGA is situated at 4.4 eV and 5.3 eV respec- shows the location of four peaks at energy of 4.55, 8.28, 10.46, and
tively. For the real part (ε0 ðuÞ) spectrum, the main peak, with a 12.72 eV. However for Sr2AlTaO6 four peaks are observed at energy
magnitude of 8.5 for Sr2AlNbO6, is situated at 4.1 eV and for of 5.40, 9.37, 11.60, and 12.30 eV. The low value of reflectivity in
Sr2AlTaO6 the main peak with a magnitude of 8.2, is situated at these compounds makes sure its potential applications in the area
4.9 eV. The main peak of the real part and imaginary spectrum with
TB-mBJ occurs with a shift towards the higher energies as
compared to GGA.
The static dielectric constant ε΄ (0) is the most important
3.0
quantity which is obtained as the zero frequency limit of the real
part of the frequency-dependent dielectric function. The calculated
2.5
values of static dielectric function ε΄ (0) for both the compounds
Refractive Index n( )

2.0

Table 3 1.5
The calculated static dielectric constant ε0 (0), refractive index n(0), extinction co-
efficient k (u), reflectivity R(u), optical absorption coefficient I(u), real part of optical 1.0 Sr2AlNbO6 (GGA)
conductivity Re[s(u)] and the energy-loss function L(u) for Sr2AlNbO6 and Sr2Al-
TaO6 with GGA and TB-mBJ exchange potentials (XC).
Sr2AlNbO6 (TB-mBJ)
0.5 Sr2AlTaO6 (GGA)
Compound XC 0
ε (o) n(o) k(u) R(u) I(u) s(u) L(u)
Sr2AlTaO6 (TB-mBJ)
(eV) (eV) (U cm)1 (eV)
0.0
Sr2AlNbO6 GGA 4.12 2.03 1.69 0.12 3.03 7214.70 5.84 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
TB-mBJ 3.17 1.78 1.55 0.08 3.80 7876.09 6.38
Energy (eV)
Sr2AlTaO6 GGA 3.72 1.90 1.60 0.10 3.75 6240.60 6.13
TB-mBJ 2.73 1.65 1.39 0.06 5.03 6604.45 7.38
Fig. 6. The Calculated refractive index for Sr2AlM'O6 (M' ¼ Nb and Ta).
 B. Rameshe et al. / Computational Condensed Matter 4 (2015) 13e22 19

1.8 9.37, 11.60, and 12.30 eV.

It is clear that for both the compounds the peaks obtained in the
1.6 absorption spectrum matches with the peaks of imaginary part of
Extinction Coefficient k( )

1.4 the dielectric function ε00 (u) which indicates that the origin of ab-
sorption is due to the imaginary part of the dielectric function. From
1.2
the absorption spectrum it is clear that at the lower energies the
1.0 absorption coefficient decreases rapidly which is a well known
0.8 behavior for semiconductors and insulators. The profile of real part
of optical conductivity shown in Fig. 8(c) shows similar peaks as
0.6
obtained in the absorption spectrum and the maximum optical
0.4 Sr AlNbO (GGA)
conductivity occurs at energy of 9.27 eV for Sr2AlNbO6 and 11.20 eV
Sr AlTaO (GGA)
0.2 Sr AlNbO (TB-mBJ)
for Sr2AlTaO6. The absorption spectral peaks in TB-mBJ are shifted
Sr AlTaO (TB-mBJ) about 0.77 eV for Sr2AlNbO6 and 1.28 eV for Sr2AlTaO6 towards the
0.0 higher energies.
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Fast moving electrons passing through a material can be
Energy (eV) described by an important optical parameter known as electron
loss function L (u). The energy at which this function becomes
Fig. 7. The Calculated extinction coefficient k (u) for Sr2AlM'O6 (M' ¼ Nb and Ta).
maximum is called Plasmon energy whose position corresponds to
the zero crossing point of the real part of the dielectric constant
of transparent coatings in the visible and deep UV region. The ε0 (u). The electron loss functions of Sr2AlNbO6 and Sr2AlTaO6 are
calculated linear absorption and the real part of optical conduc- calculated and are presented in Fig. 8(d). From the figure the
tivity from expressions (5) and (6) for Sr2AlM'O6 (M' ¼ Nb and Ta) highest energy loss function with GGA occurs at 5.84 eV and 6.13 eV
are shown in Fig. 8(b) and (c). For Sr2AlNbO6 the absorption spec- for Sr2AlNbO6 and Sr2AlTaO6 respectively. For TB-mBJ potential the
trum has four peaks located at energy of 4.63, 8.58, 9.26, and highest energy loss function occurs at 6.13 eV and 7.38 eV for
10.13 eV. For Sr2AlTaO6 four peaks are located at energy of 5.40, Sr2AlNbO6 and Sr2AlTaO6 respectively. The sharp peak obtained in

8000
Sr AlNbO (GGA)
0.7 Sr2AlNbO6 (GGA)
7000 Sr AlNbO (TB-mBJ)
-1

Sr2AlNbO6 (TB-mBJ) Sr AlTaO (GGA)

0.6
Optical Conductivity ( cm)

Sr2AlTaO6 (GGA) 6000 Sr AlTaO (TB-mBJ)

0.5 Sr2AlTaO6 (TB-mBJ)

Reflectivity R( )

5000
0.4 4000

0.3 3000

0.2 2000

1000
0.1
0
0.0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Energy (eV)
Energy (eV)

220 0.55
Sr AlNbO (GGA)
200 Sr2AlNbO6 (GGA) 0.50 Sr AlNbO (TB-mBJ)
Electron Loss Function L( )

Sr2AlNbO6 (TB-mBJ) 0.45

Absorption Coefficient I( )

180 Sr AlTaO (GGA)

Sr2AlTaO6 (GGA) 0.40 Sr AlTaO (TB-mBJ)
160
140 Sr2AlTaO6 (TB-mBJ) 0.35
120 0.30
100 0.25
80 0.20
60 0.15
40 0.10
20 0.05
0 0.00
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Energy (eV) Energy (eV)

Fig. 8. Calculated optical spectra for Sr2AlM'O6 (M' ¼ Nb and Ta), (a) the reflectivity R(u), (b) absorption coefficient L (u), (c) optical conductivity (in (U cm)1) (d) electron loss
function I(u) with GGA and TB-mBJ.
20 B. Rameshe et al. / Computational Condensed Matter 4 (2015) 13e22

the electron loss spectrum corresponds to the abrupt reduction of
reflectivity spectrum of these compounds. The calculated value of
refractive n(0), extinction coefficient k(u), reflectivity R(u), optical
absorption coefficient I(u), real part of optical conductivity Re
[s(u)] and the energy-loss function L(u) for both the compounds
with GGA and TB-mBJ potentials are tabulated in Table 3.
5.3. Thermoelectric properties of Sr2AlM'O6 (M' ¼ Nb and Ta)
In the present scenario it is very clear that conventional energy
resource is fast degrading. An investigation for alternative energy
resources coupled with the anxiety to reduce the environmental
impact is essential, since the demand of energy is fast increasing.
The new alternative way of generation of electricity is the Seebeck
effect because this effect is one of the most environmental friendly
methods of generating electricity. The materials which generate
this nature of electricity are called as thermoelectric materials.
The major challenge of this effect is the generation of very low
efficiency thermoelectricity when compared with the conventional
ways of producing electricity. The efficiency of thermoelectricity
generated by this method is specified by a dimensionless quantity
called the figure of merit (ZT). Generally the ZT is given by
ZT ¼ S2sT/k, where S is the Seebeck coefficient, also known as
thermo power, s is the electrical conductivity, T is the absolute
temperature and k is the total thermal conductivity of the material.
It is well known that the thermal conductivity of a material is the
sum of lattice thermal conductivity kl and electronic thermal con-
ductivity ke.
From the expression of figure of merit it is very clear that
increasing the efficiency of thermoelectricity can be achieved by
two possible routes. (i) To attain larger values of S and s and smaller
value of ke of thermoelectric materials. This might be possible by
tuning the electronic structure of these materials thereby
increasing the thermoelectric performance. (ii) Reducing the ther-
transport theory, based on the electronic structure. To obtain reli-
able transport properties, a dense k point mesh comprising about
5000 k points in the entire Brillouin zone was used. Calculations
based on BoltzTraP code with actual band structures have proven
useful in rationalizing and predicting transport properties of
known compounds [17,41,42]. The variation of Seebeck coefficients
at different temperatures versus the varying hole concentrations
for both the compounds are given in Fig. 9(a) and (b).
It is clear from the figure that for low carrier concentrations and
with the increase in temperature the Seebeck coefficient increases
monotonously. This behavior of increase in Seebeck coefficients
with temperature is expected for large band gap materials since in
these materials there is an absence of compensation between holes
and electrons [43]. The Seebeck coefficients for both the com-
pounds at different temperatures for hole concentration of
1019 cm3 are tabulated in Table 4.
Fig. 10(a) and (b) show the calculated power factors with respect
to the relaxation time S2s/t of Sr2AlM'O6 compounds as a function
of hole concentration. The peak obtained in the figure give the
direct information about the doping range, suggesting that the
thermoelectric performance can be enhanced by adopting appro-
priate doping concentrations. The maximum value of doping con-
centration for Sr2AlNbO6 is 1.0051  1021 cm3 and for Sr2AlTaO6 is
1.3153  1021 cm3. Calculated Seebeck coeffieients and þdS/dT of
Sr2AlMO6 are comparable with large band gap materials. Power
factor in the usual units of W/mK2 can be calculated by substituting
the relaxation time in units of 1014 s. The estimated power factor
230
Sr2AlNbO6 300K
220
400K
210 500K
600K
200
800K
S (10 V/K)

mal conductivity due to lattice contributions kl which in turn re-

190 1000K
duces the total conductivity k of the material. The above discussion
clearly indicates that the thermoelectric behavior of a material is 180
based on the electronic structure, hence in the present work it is 170
mainly focused on the thermoelectric behavior of Sr2AlM'O6 com-
160
pounds by looking into its electronic structure from the first prin-
ciples calculations. 150
A material being thermoelectric is mainly based on the elec- 140
tronic structure particularly near the valence band maximum 1E19 1E20 1E21 1E22
(VBM). The thermoelectric performance of a material is based on Hole Concentration (cm )
-3

figure of merit and it is directly proportional to Seebeck coefficient

and electrical conductivity s. For improving the Seebeck coefficient
the key factor is the presence of flat bands at the valence band 240
Sr2AlTaO6 300K
maximum which corresponds to a large effective mass. On the 230 400K
other hand the electrical conductivity s is increased by the pres- 220 500K
ence of more dispersive band at the valence band maximum which 600K
210
corresponds to lighter effective mass implying higher mobility [37]. 800K
200
S (10 V/K)

The band structure of Sr2AlM’O6 compounds depicted in Fig. 1000K

3(aed), show similar nature of flat and more dispersive bands at 190
the valence band maximum which dictates that these compounds 180
may be a promising material for generating thermoelectricity, 170
which could be an alternate source of energy to the conventional 160
ways of producing electricity. Single perovskite SrTiO3 is essentially 150
a band insulator with an empty conduction band. Intensive electron 140
doping under the reducing conditions, SrTiO3 has power factor 1E19 1E20 1E21 1E22
values of ~10  104 W/mK2 for polycrystalline samples [38], and Hole concentration (cm )
-3

20e30  104 W/mK2 for single crystal [39]. Heavily doping by Nb

or La turns SrTiO3 into an n-type degenerate semiconductor with
large thermoelectric figure of merit of 0.34 at 1000 K [40]. In order Fig. 9. (a) Variation of Seebeck coefficient with doping concentration at different
to study the thermoelectric properties of double perovskite temperatures of Sr2AlNbO6. (b).Variation of Seebeck coefficient with doping concen-
Sr2AlMO6, transport properties are calculated within Boltzmann tration at different temperatures of Sr2AlTaO6.
 B. Rameshe et al. / Computational Condensed Matter 4 (2015) 13e22 21

Table 4 estimate the band gap accurately, the modified Becke-Johanson

The Seebeck coefficients for Sr2AlM'O6 (M' ¼ Nb and Ta) compounds at different potential is also used which gives a better description of the band
temperatures for hole concentration of 1019 cm3.
structures and yields a significant improvement to the value of the
Temperature(K) Seebeck coefficient (10m VK1) energy gap with GGA. The calculated band gap with TB-mBJ for
Sr2AlNbO6 Sr2AlTaO6 Sr2AlNbO6 is 3.8 eV which matches well with the experimental
value, whereas the band gap of 5.03 eV for Sr2AlTaO6 is slightly
300 208.95 209.66
400 213.18 213.73 more than the experimental value. The electronic structure calcu-
500 215.48 215.90 lation reveals that the interaction between the d states of transition
600 217.98 218.32 metals and 2p states of oxygen mainly contribute for the electrical
800 220.75 221.53
properties in these materials. The real and imaginary parts of the
1000 222.08 223.01
dielectric function at ambient conditions were investigated and
analyzed to identify the optical transitions. The static dielectric
constants, refractive, extinction coefficient, reflectivity, optical ab-
sorption coefficient, real part of optical conductivity and the
energy-loss function have also been calculated with GGA and TB-
mBJ potentials. Thermoelectric properties of Sr2AlM'O6 (M' ¼ Nb
and Ta) in the Fm-3m cubic configuration have been studied based
on the electronic structure of these compounds. The mixture of
heavy and light bands near the valence band enhances the Seebeck
coefficient which increases the thermoelectric performance in
these compounds. Calculated Seebeck coeffieients and þdS/dT of
Sr2AlMO6 are comparable with large band gap materials. The esti-
mated power factor values of Sr2AlMO6 are about ~3  102 mW/
mK2 which are lesser than that of polycrystalline samples of SrTiO3
(~10  104 W/mK2). Based on the calculated power factor of these
compounds the optimal doping concentrations were also
estimated.

Acknowledgments

The authors are thankful to Professors Peter Blaha, Karlheinz

Schwarz, Georg Madsen, Dieter Kvasnicka and Joachim Luitz,
Vienna University of Technology, Institute of Physical and Theo-
retical Chemistry, Getreidemarkt 9/156, A-1060, Vienna, Austria for
providing the WIEN2K code.

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