ANNALS OF WEST UNIVERSITY

OF TIMISOARA PHYSICS
Vol. LXII, 2020
DOI: 10.2478/awutp-2020-0004

STRUCTURAL STABILITY AND MAGNETIC ORDERING IN BiFeO3

PEROVSKITE OXIDE: A COMPARATIVE STUDY GGA+U VS
L(S)DA+U

M. Derras and N. Hamdad*

Djillali Liabès University of Sidi Bel-Abbes, Faculty of Technology, Sidi Bel-Abbès 22000, Algeria
*Corresponding author: [email protected]

Article Info Abstract

Received: 03.06.2020 Ab initio calculations of BiFeO3 magnetic perovskite are carried. Accurate
Accepted: 30.06.2020 density functional theory calculations were performed considering a U-Hubbard
correction (DFT+U) to account for on-site Coulomb interactions of the 3d-Fe states.
We have applied the Full‐potential linearized augmented plane waves (FP‐LAPW)
Keywords: Perovskite
method. Exchange‐correlation effects are treated using the Local Spin Density
Oxide, GGA+U,
approximation (L(S)DA+U) vs generalized gradient approximations (GGA+U).
LSDA+U, Magnetic
Equilibrium lattices agree very well with other theoretical and experimental data.
moment, and Electronic
The magnetization energy differences between Spin Up and Spin Dn states are
structure
small. Spin effect and magnetic moment obtained from subsequent (L(S)DA+U)
and (GGA+U) calculations are also discussed in different magnetic configurations:
The Ferromagnetic cubic phase (Pm-3m), The A-type Antiferromagnetic (P4/mmc)
and The G-type Antiferromagnetic (Fm-3m). The nature of magnetism arises
mainly from the Fe-site exhibiting a G-type antiferromagnetic ordering. The
electronic structure shows that BiFeO3 has a metallic band gap. This multiferroic
exhibit strong hybridization of the 3d-Fe and 2p-O orbitals. Therefore, the
Multiferroic BiFeO3 perovskite has driven significant research interest due to their
promising technological potential. It’s a good candidate for potential applications in
spintronic, and to aid the development of the next generation of data storage and
multi-functional technological devices.

1. Introduction
Perovskite structure materials are of great interest in science researcher due to their
specific properties and simple structure ABX3 designated with (Pm-3m) space group where X
is a non-metal and A and B span a large portion of the periodic table [1–10]. They are
important in numerous high technology applications, they possess a large number of

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industrially important applications, including charge storage devices, Memories, Fuel Cells,
capacitors, actuators, chemical reactors, energy storage, non-volatile random access memory
devices, hydrogen sensors, microelectronics industry, optoelectronics sensors, piezoelectric
motors wave guides, laser frequency doubling, heterogeneous catalysts, catalytic activity,
atomic microscopes, ultrasound generators, , ink-jet printers and fuel injectors [11–20]. The
perovskite-type oxides ABO3 have also a multifunctional application in different area such as
Thermoelectricity, Ferroelectricity, Electricity, Superconductivity, Colossal magneto
resistance, (Anti)-Ferromagnetism, Multiferroism, Piezoelectricity, Semiconductivity,
Elasticity, Plasticity, Thermoelectricity, Mechanical-bending-induced, Thermodynamic
stability and compatibility in mechanical properties. [21-29]. Multiferroic materials oxides
have coupled electric, magnetic, or structural order parameters, as result ferroelectric,
ferromagnetic, or ferroelastic behavior. These type of oxide material have attracted scientific
researchers in different fields due to their specific and unique properties. These materials have
opportunities for potential applications in information [30] storage, spintronics, and sensors,
multiple state memory elements, in which data are stored both in the electric and the magnetic
polarizations, or novel memory media which might allow writing of a ferroelectric data bit.
Bismuth ferrite (Iron) oxide BiFeO3 is one of the very few multiferroic perovskite oxides, it
has particular interesting. Much researcher on the synthesis of BiFeO3 using different methods
have been done of these solid-state [14], [15], mechano-chemical [14], [15], [16], solution
chemistry method such as ions assisted controllable synthesis hydrothermal method [14], [18],
[20], sonochemical [14], [21], solution-combustion method [14], [22], and soft chemical
method [14], [23]. Most of mentioned procedures need high-temperature treatments (>800°C)
and the appearance of second phase still the major issue of them [14], [24]. he perovskite
Bismuth ferrite BiFeO3 (BFO) is considered to be a model multiferroic and offers a rare
multiferroelectric robustness since it presents a coexistence of ferroelectric and
antiferromagnetic order up to unusually high temperatures [31]. BiFeO3 is ferroelectric with
relatively high Curie temperature TC, approximately (1100 K) and exhibits antiferromagnetic
behavior with high Néel temperature TN, approximately (643 K) [30], [32-34]. In general,
BFO oxides [35-36] has a distorted perovskite ABO3 structure, with a room-temperature
ground state belonging to the rhombohedral space group R3c. In the hexagonal setting, the
unit-cell parameters are ahex=5.58 Å and chex=13.87 Å, corresponding to a rhombohedral angle
of 59.35°. Compared to an ideal cubic perovskite structure, oxygen octahedra are antiferro-
distortively rotated by 13.8° about the pseudocubic [111] axis, Fe and Bi atoms are both
shifted along the pseudocubic [111] direction by 0.13 Å and 0.54 Å, respectively, giving four

53
different O-O bond lengths. As in other perovskites, the bonding in BFO is mostly ionic with
Bi and Fe in a nominally 3+ state and O in 2−. These valences are altered by the introduction
of a covalent contribution to the bonding, and it is this covalency, however small, that is
responsible for the ferroic properties that make BFO interesting [30], [35]. The BiFeO3
studies have already given a lot of spectacular results, because of its possible novel
applications in the field of radio, television, microwave and satellite communications, audio-
video and digital recording and as permanent magnets [37- 38]. The unit cell of BiFeO3 can
be considered to be a deformed ideal cubic perovskite [39-40] By moving Bi and Fe atoms
along the pseudocubic [111] direction and O atoms along the pseudocubic [110] directions,
the unit cell is elongated with the neighboring octahedrons rotated in different directions
about the [111] axis. BiFeO3 is considered to be antiferromagnetic with a Néel temperature of
TN 640 K [39], [41-42]. The Fe spins form a G-type antiferromagnetic G-AFM structure, in
which the spins are coupled ferromagnetically in the pseudocubic [111] planes and
antiferromagnetically between neighboring [111] planes, so that each Fe atom couples
antiferromagnetically with its nearest Fe neighbors. [39], [43]. Besides BiFeO3, The G-type
antifferomagnetic character for Bismuth Ferrite oxide BiFeO3 is confirmed by many
researchers in different fileds [39], [43], [44-45]. In the present study we calculated lattice
constant, bulk modulus and total energy along with its components for Bismuth Ferrite (iron)
perovskite oxide BiFeO3. In order to characterize the electronic, magnetic properties as well
to understand the mechanical response of perovskite materials (ferroelectric or ferromagnetic
ie multifferoic), to rationalize the mechanical behavior, to external macroscopic stress by
using the lattice constants which are systematically related to interatomic bonding,
mechanical stability, thermal relaxation and internal strain., to analyses the spin-effect on the
electro-magnetic properties of the ABO3 perovskite oxide.

Figure 1. The different magnetic configurations ((FM), (A-AFM) and (G-AFM)) for Bismuth Ferrite (Iron)
BiFeO3 oxide with GGA+U in the present work.

54
 We give the Non-Ferromagnetic (NF) and Ferromagnetic (FM) configurations with
Cubic (Pm-3m) phase, A-type Antiferromagnetic (A-AFM) configuration is illustrated with
(P4/mmc) phase and G-type Antiferromagnetic configuration (G-AFM) with (Fm-3m) phase
respectively.

2. Theory and Computational Methods

In this section, the calculations were done by using the projector Full Augmented Plane
wave method (FP-LAPW) [46-53] as implemented in Vienna ab initio Simulation Package
(Wien2K) [54]. The current studies were performed within the framework of Density
Functional Theory (DFT+U) [55, 56]. (DFT+U) are good to predict the correlation in the
centered metal in organometallics, it’s accurate as description for d and f orbitals in the
transition metal elements with localized orbitals existing in extended states, as in the case of
many strongly correlated materials and perovskites, where localized 3d or 4f orbitals are
embedded in elongated s-p states.
In general, the U value is not known and practically is often tuned semi empirically to
make a good agreement with experimental or higher level computational results. The value of
U implemented by Cococcioni et al. [57] is Ueff = U−J, where J is indirectly assumed to be
zero in order to obtain a simplified expression. In our work, the on-site effective U parameter
(Ueff U-J= 0.47 eV). We have chosen as atomic sphere radii (RMT) 2.5, 1.7, and 1.5 a.u
respectively for Bi, Fe and O atoms. The exchange-correlation potential is examined using the
generalized gradient approximation with additional U- Hubbard term for indulging on-site
Coulomb interaction. The spin effect between (FM) and (AFM) states can be described
accurately by the Hubbard correction, while the pure (DFT) fails, because it doesn’t give
more description in the strong states due to the correlation in the d or f orbitals of the centered
metal. Different approaches are employed in the present work to describe the exchange and
correlation potential interaction, such as (Perdew-Wang) local spin density approximation
(LSDA) [58] and corrected (LSDA+U) [59], the generalized gradient approximation (GGA)
[60-61] and corrected (GGA+U) [62-64] in the structural properties calculation. The
(GGA+U) as (LSDA+U) method are introduced to capture the strong correlation in d
localized orbitals. Crystal sis divided up into two main regions, inside muffin-tin spheres, and
an interstitial region.

55
 Figure 2. The total energy (eV) as a function of volume (Â3) for the (FM), (A-AFM) and (G-AFM)
configurations considered for BiFeO3 oxide with GGA+U.

The basis set inside each MT sphere is split into core and valence subsets. The core
states are treated within the spherical part of the potential only and are assumed to have a
spherically symmetric charge density totally confined inside the MT spheres. The Brillouin
zone integrations is carried out with a modified tetrahedron method [65], The cut-off energy
to separate the core states from valence states is set to be −9 Ryd. Inside the sphere, Fourier
expanded up to Gmax = 14 with a cut-off. In order to describe correctly the wave functions in
the interstitial region like spherical harmonics have been expanded up to the value of lmax =
10. The semi core d states were treated as core states. The irreducible Brillion zone were
performed by using 10 × 10 × 10 Monkhorst-Pack meshes [66] centered k-point grid.

56
3. Results and Discussions
3.1. Structural properties
Many oxides crystallize in the ABO3 cubic perovskite structure with the space group
Pm-3m (221). The perovskite crystal structure can be considered as a three-dimensional
network of BO3 octahedral units and this network constitutes a cubic array in which B-O-B
angle is 180°. The X-site anions are coordinated by two B-site cations and four A-site cations.
This cubic structure is regarded as an ideal perovskite structure. We note that ABO3
perovskite materials contain a large family of crystal structures (cubic (Pm-3m) [67-68],
Hexagonal (2H, 4H, 6H) [69-71], orthorhombic (Pnma, Pbnm, Amm2, CmCm) [72-74],
tetragonal (P4/mmc) [75], rhombohedral [76] etc, because their properties are sensitive to
temperature, pressure and phase changes. In the ideal cubic structure, the majority of
perovskites are distorted due to rotation or tilting of regular, rigid BX6 octahedra or due to a
distortion of the BX6 octahedra themselves. Tilting of the octahedra occurs when the size of
the A cation is too small for the 12-fold site within a BX6 polyhedral framework. This tilting
of the BX6 polyhedral necessarily induces a distortion of the AX12 polyhedral which
eventually results in a decrease in the A-cation coordination number [77]. In this section, we
analyses the overall performance of the (LSDA+U) vs the (GGA+U) approaches in describing
the structural properties of BiFeO3 perovskite. We have optimized the lattice parameters (a)
and (c) in order to estimate the ground-state properties of this oxide the bulk modulus (B) and
the pressure derivatives of the bulk modulus (B’) of this oxide by minimizing the total energy
for different magnetic configurations. (Figure.1) show (a) the Ferromagnetic (FM)
configuration, (b) A-type Antiferromagnetic (A-AFM) configuration, and (c) G-type
Antiferromagnetic (G-AFM) configuration.

Table 1: The calculated lattices parameters for the Non-Ferromagnetic (NF) configuration
considered for the cubic BiFeO3 oxide calculated with the L(S)DA and (GGA) approaches.

Lattice parameters Approaches

LSDA GGA
a(Å) 3.4925 3.8083
B(GPa) 179 198
B’ 4.4 4.7

The total energy at different unit cell volumes for multifferoic BiFeO3 oxide is shown
in (Figure 2). We fit the volume of (FM, A-AFM, and G-AFM) respectively versus energy by
the Murnaghan equation of state [78]. We listed in (Table.1), and (Table.2) respectively

57
together with the available experimental and theoretical data for comparison the equilibrium
lattices for Non-Ferromagnetic configuration using both (LSDA) and (GGA) approach, the A-
type Antiferromagnetic (A-AFM) and G-type Antiferromagnetic (G-AFM) using (LSDA+U),
(GGA) and (GGA+U) approaches.

Table 2: The calculated lattices parameters for different magnetic configuration considered
for the cubic BiFeO3 oxide using (GGA), (L(S)DA+U) and (GGA+U).

Lattice parameters Approaches Theoretical Experimental

FM GGA L(S)DA+U GGA+U

a(Å) 3.8621 3.8649 3.8728 3.89 a, 3.96b 3.93 d
3.835c
B(GPa) 156 193 185 238 c
B’ 4.9 4.2 3.6 2.2 c

A-AFM
a(Å) 3.9027 3.9101 3.9154
c(Å) 3.6184 3.6598 3.6647
B(GPa) 182 178 158
B’ 4.5 4.1 3.9

G-AFM
a(Å) 3.8095 3.7972 3.7940
B(GPa) 172 233 180
[79]: Ref a, [80]: Ref b, [81]: Ref c, [82]: Ref d.

In general, the computed structural parameters are in good agreement with experimental
and theoretical study. From these results given by (Table.2) for (FM, A-AFM, and G-AFM),
we remark that (GGA+U) overestimated the lattice parameters in comparison with
(LSDA+U) approach, as well (GGA) in comparison with (LSDA) for (NF) configurations
illustrated by (Table.1). The bulk moduli is also taken in consideration; it has been obtained
using the equation of state fit for the total energy as a function of volume. Experimental bulk
modulus values are not available for the BiFeO3 perovskite oxide. We remark, that (GGA+U)
underestimated the bulk modulus B (GPa) and it’s pressure derivative B’ vs (LSDA+U). We
remark also that pressure derivative of Bulk modulus increase using (GGA+U) approach as
following 3.6 (FM) < 3.9(A-AFM) < 4.7(G-AFM), it’s very clear that BiFeO3 exhibit the
G-AFM behavior, and it will be more stable in this magnetic configuration, and more
hardness.

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3.2. Magnetic properties
To investigate the Electro-magnetic properties, we compute the magnetic moment for
the Bismuth Iron Oxide BiFeO3 in all the magnetic configurations (FM, A-AFM, and G-
AFM) considered in our work. The total magnetic moment on the cell is increased by
(GGA+U) approach in all the magnetic configurations considered (FM, A-AFM, and G-
AFM) in our work. From (Table.3), (Table.4) and (Table.5) given for the (FM, A-AFM, and
G-AFM) magnetic configurations respectively, we see clearly that magnetic moment values
on Fe site is bigger than the others elements on BiFeO3 oxide. By applying U-Hubbard
correction on 3d –Fe states, the exchange split of d-Fe band continues to increase as µFe
(GGA), µFe (L(S)DA+U), and µFe (GGA+U). We concluded that the origin of the local
magnetic moment is due essentially to the Ferrite element (Fe).

Table 3. Calculated magnetic moment µ (Bohr Magneton) for the ferromagnetic (FM)
configuration calculated for BiFeO3 oxide using different approaches.

Materials Approaches µInterstitiel µTotal/cell (µB) µBi µFe µO

BiFeO3 GGA 0.2 4.3 0 3.9 0.1
L(S)DA+U 0.2 4.9 0 4.1 0.1
GGA+U 0.2 5.1 0 4.3 0.1

Table 4. Calculated magnetic moment µ (Bohr Magneton) the A-type anti-ferromagnetic (A-
AFM) configuration calculated for BiFeO3 oxides using both different approaches.

Materials Approaches µInterstitiel µTotal/cell (µB) µBi µFe1 µFe2 µO1 µO2 µO3
GGA 0 0 0 3.7 -3.7 0 0.1 -0.1
BiFeO3 L(S)DA+U 0 0 0 4.1 -4.1 0 0.1 -0.1
GGA+U 0 0 0 4.4 -4.4 0 0.1 -0.1

Table 5. Calculated magnetic moment µ (Bohr Magneton) for the G-type anti-ferromagnetic
(G-AFM) configuration calculated for BiFeO3 oxide using different approaches.

Materials Approaches µInterstitiel µTotal/cell (µB) µBi µFe1 µFe2 µO1

GGA 0 0 0 3.95 -3.95 0
BiFeO3 L(S)DA+U 0 0 0 4.11 -4.11 0
GGA+U 0 0 0 4.50 -4.50 0

The contribution of the oxygen element is very small and negligible in comparison with
the (Fe) contribution. The Bismuth (Bi) element did not contribute to this effect. We reveal
zero value in all the magnetic configurations (FM, A-AFM, and G-AFM) given here. We

59
remark also that the two elements of the Ferrite (Fe1) and (Fe2) in both Antiferromagnetic
configurations (A-AFM, and G-AFM) contribute similarly, we note the same value but with
sign opposite. Although the correction of U-Hubbard is given by the two approximations
(L(S)DA+U), and (GGA+U), but the (GGA+U) gives the best results and show clearly the
spin effect and the magnetic behavior in all configurations. The (GGA+U) is more accurate.
From the three tables, we remark also that G-type Antiferromagnetic (G-AFM) configurations
gives the higher value with all approaches used here (GGA, L(S)DA+U, and GGA+U)
respectively. They can be classified as follows using (GGA+U) approach: µFe = 4.3 (FM) <
µFe = 4.4 (A-AFM) < µFe = 4.5 (G-AFM). We concluded that our Bismuth Ferrite oxide
exhibit the (G-AFM) character which agree very well with different scientific researchers
which confirmed that BiFe03 is (G-AFM) [39], [43], [44-45].

4. Electronic Properties
4.1. Band structure and Densities of states
In order to give a detailed analysis on the spin effect on the electronic structure and
magnetic properties of Bismuth Ferrite oxide BiFeO3, we plot the band structures, the total
and partial densities of states for all magnetic configurations studied (FM, A-AFM, and G-
AFM) given in the present work. Calculation of Band structure, total and partial densities of
states Non-Ferromagnetic (NF) configuration are presented in (FiG. 3) and (FiG. 4)
respectively. From these figure computed using (GGA) approach, we reveal the metallic
character who tends to be insulating except that the expanding states are above the Fermi level
(EF). We remark that the (Fe) contribution is important while the oxygen (O) is negligible and
the Bismuth (Bi) contribution is very small. Figures 5, 6, 7 and 8, respectively, show the
total (TDOS) and partial densities (PDOS) of states (FM, A-AFM, and G-AFM) and band
structure for (FM, and G-AFM) configurations using (GGA+U) approach. The spin up and
spin down resolved Dos are mutual mirror reflections, with some differences will be
negligible. The (FM) plot reveal that the BiFeO3 oxide exhibit the metallic character.
A higher contribution is evaluated by the (Fe) element in comparison with the oxygen
and Bismuth elements which is small. We remark also that the f-Bi states contribute more
than d-Bi states. d-Fe Up-states is more dominant than the d-Fe Dn-states, which made a
small difference between the Up and Dn states. The same remark is revealed also in the (A-
AFM) and (G-AFM) configurations.

60
Figure 3. The calculated band structures and total density of states for the cubic BiFeO3 oxide using (GGA) in the
NF configuration.

The metallic character is a common factor between all the magnetic configurations
studied in the present work. A small difference is given between Up and Dn states more
remarkable in d-Fe states which explain clearly that the magnetic behavior of the Bismuth
Ferrite oxide is caused by the d-Fe states, this agree very well with the magnetic moment
values given in the last section of our work. Here also, we can confirm that the Bismuth
Ferrite oxide BiFeO3 exhibit the G-AFM character, because d-Fe states exceeds (7.5 eV) in
(G-AFM) configuration, it near (4eV) in (A-AFM), and (5.4eV) in (FM) configurations
respectively. We concluded that BiFeO3 exhibit the (G-AFM) character with metallic
behavior due essentially to the higher d-Fe contribution which explain the spin effect given
the U-Hubbard correct which treat with efficiency the d-states. We note that Fe-site ions
having partially filled 3d orbitals are considered to contribute to its antiferromagnetic
properties.

61
Figure 4. The calculated partial densities of states for the cubic BiFeO3 oxide using GGA in the (NF)
configuration.

62
Figure 5. The total and partial densities of states for the cubic BiFeO3 oxide using (GGA+U) in the (FM)
configuration.

63
Figure 6. The total and partial densities of states for the cubic BiFeO3 oxide using (GGA+U) in the (A-AFM)
configuration.

64
Figure 7. The total and partial densities of states for the cubic BiFeO3 oxide using (GGA+U) in the (G-AFM)
configuration.

65
 Figure 8. The calculated band structure for the cubic BiFeO3 oxide using (GGA+U). Top: Spin majorities (Up)
and Spin minorities (Dn) for FM configuration. Bottom: Spin majorities (Up) and Spin minorities (Dn) for G-
AFM configuration.

5. Conclusion
We have perceived structural, electronic and magnetic properties of (FM) and two
Antiferromagnetic A-type (A-AFM) and G-type (G-AFM) for Bismuth Ferrite oxide BiFeO3
by means of ab-initio calculations using (DFT+U) method employing (LSDA+U) vs

66
(GGA+U) functional. The equilibrium lattices constants for multiferroic BiFeO3 were
calculated and different modulus such as bulk were determined for the Non –Ferromagnetic
(NF), Ferromagnetic (FM), A-type Antiferromagnetic (A-AFM), and G-type
Antiferromagnetic (G-AFM). The minimization of energy as a function of volume using the
Murnaghan’s state equation the equilibrium lattice parameter and cohesive properties of this
compound were obtained. From structural optimization, the BiFeO3 is observed to be (G-
AFM). Calculated band structures and density of states plots with an integer magnetic
moment reveal metallic character. Fe-site ions having partially filled 3d orbitals are
considered to contribute to its antiferromagnetic properties. Our calculations suggested that
GGA+U functional gives satisfactory results for the band gaps, densities of states and the
magnetic moments on (Fe) in BiFeO3.

References
[1] Noura Hamdad, Superlattices and Microstructures 76, 425 (2014).
[2] M. Derras and N. Hamdad, Results in Physics 3, 61 (2013).
[3] M. Derras, N. Hamdad, M. Derras, A. Gessoum, Results in Physics 3, 219 (2013).
[4] Noura, Hamdad, Physica B 406, 1194 (2011).
[5] Abbes Labdelli, Noura Hamdad, Results in Physics, 5, 38 (2015).
[6] L. Yang, X. Kong, F. Li, H. Hao, Z. Cheng, H. Liu, J. F. Li and S. Zhang, Prog. Mater Sci.
102, 72 (2019).
[7] L. Pálová, P. Chandra and K. M. Rabe, Phys. Rev. Lett. 104, 037202 (2010).
[8] Erik Ekström, Arnaud le Febvrier, Daniele Fournier, Jun Lu, Vladimir-Lucian Ene, Ngo
Van Nong, Fredrik Eriksson, Per Eklund and Biplab Paul, Journal of Materials Science
54, 8482 (2019).
[9] YangLiu, Vladimir Motalov, Stefan Baumann, Dmitry Sergeev, Michael Müller, Yoo
Jung Sohn, Olivier Guillon, Journal of the European Ceramic Society, 39, 4874, (2019).
[10] T. Ishihara, Springer Handbook of Electronic and Photonic Materials, 1, 405 (2017).
[11] R.I. Eglitis, D. Vanderbilt, Phys. Rev. B 78, 155420 (2008).
[12] H.Y. Hwang, Y. Iwasa, M. Kawasaki, B. Keimer, N. Nagaosa, Y. Tokura, Nat. Mater.
11, 103 (2012).
[13] C. E. Deluque-Toro, D. A. Landínez-Téllez and J. Roa-Rojas, Revista, DYNA, 85, 27
(2018).
[14] G. M. Taha , M. N. Rashed , M. S. El-Sadek and M. A. Moghazy, Nanopages 1, 11
(2019).

67
[15] V. Singh, S. Sharma, M. M. Kumar, R. K. Kotnala, R. K. Dwivedi, Journal of
Magnetism and Magnetic Materials 349, 264 (2014).
[16] P. Fischer, M. Polomska, I. Sosnowska, M. Szymanski, Journal of Physics C: Solid State
Physics 13, 1931 (1980).
[17] I. Szafraniak, M. Potomska, B. Hilczer, Journal of the European Ceramic Society 27,
4399 (2007).
[18] C. Tabares-Munoz, J. Rivera, A. Bezinges, A. Monnier, H. Schmid. Japanese Journal of
Applied Physics 24, 105 (1985).
[19] C. Chen, J. Cheng, S. Yu, L. Che, Z. Meng, Journal of Crystal Growth 291, 135 (2006).
[20] K. Suzuki, Y.Tokudome, H.Tsudad, T. Masahide, Applied Crystallography 49, 168
(2016).
[21] S. Das, S. Rana, S. Mursalin, P. Rana, A. Sen, Sensors and Actuators B: Chemical 218,
122 (2015).
[22] V. Fruth, L. Mitoseriu, D. Berger, A. Lanculescu, C.Matei, S. Preda, , M. Zaharescu
Progress in Solid State Chemistry 35, 193 (2007).
[23] S. Ghosh, S. Dasgupta, A. Sen, H. S. Maiti. J. Am. Ceram. Soc. 88, 1349 (2005).
[24] J. Silva, A. Reyes, H. Esparza, H. Camacho, L. Fuentes, Integrated Ferroelectrics 126, 47
(2011).
[25] Anoop Singh Yadav, Sammat Singh, Sunil Kumar Pandey, Rakesh Kumar, Anoop Singh
Yadav et al., East African Scholars J Eng Comput Sci 1, 13 (2018).
[26] E A Kotomin et al, J. Phys.: Conf. Ser. 117, 012019 (2008).
[27] S. Piskunov, E . A . K o t o m i n , E. Heifets, Ab initio calculations of the atomic and
electronic structures for ABO3 perovskite (001) surfaces (2004).
[28] B. Akgenc, A. Kinaci, C. Tasseven, T. Cagin, Materials Chemistry and Physics 205, 315
(2018).
[29] Shiferaw Kuma and Menberu Mengesha Woldemariam, Advances in Condensed Matter
Physics 12, 3176148 (2019).
[30] P. Ravindran, R. Vidya, A. Kjekshus, H. Fjellvåg and O. Eriksson, Phys. Rev. B 74,
224412 (2006).
[31] R. Haumont, J. Kreisel and P. Bouvier, A Multinational Journal 79, 1043 (2006).
[32] V. G. Bhide and M. S. Multani, Solid State Commun. 3, 271 (1965).
[33] J. M. Moreau, C. Michel, R. Gerson and W. J. James, J. Phys. Chem. Solids 32, 1315
(1971).
[34] Y. N. Venevtsev and V. V. Gagulin, Inorg. Mater. 31, 797 (1995).

68
[35] Ragnhild Sæterli, Sverre Magnus Selbach, Ponniah Ravindran, Tor Grande and Randi
Holmestad, Phys.Rev. B 82, 064102 (2010).
[36] F. Kubel and H. Schmid, Acta Crystallogr., Sect. B: Struct. Sci. 46, 698 (1990).
[37] J. Dzik, A. Lisinska -Czekaj, A. Zarycka, D. Czekaj, A rchives of Metallurgy and
Materials, 58, 4 (2013).
[38] A. Johari, Synthesis and characterization of bismuth ferrite Nanoparticles, AKGEC
Journal of Technology 2, 0975 (2011).
[39] Lei Bi, Alexander R. Taussig, Hyun-Suk Kim, Lei Wang, Gerald F. Dionne, D. Bono, K.
Persson, Gerbrand Ceder and C. A. Ross, Phys. Rev. B 78, 104106 (2008).
[40] J. Wang, Ph.D. thesis, University of Maryland (2005).
[41] S. V. Kiselev, R. P. Ozerov and G. S. Zhdanov, Sov. Phys. Dokl. 7, 742 (1963).
[42] J. R. Teague, R. Gerson and W. J. James, Solid State Commun. 8, 1073 (1970).
[43] B. Ruette, S. Zvyagin, A. P. Pyatakov, A. Bush, J. F. Li, V. I. Belotelov, A. K. Zvezdin
and D. Viehland, Phys. Rev. B 69, 064114 (2004).
[44] J. T. Heron, D. G. Schlom and R. Ramesh, App. Phys. Rev. 1, 021303 (2014).
[45] C. Ederer and N. A. Spaldin, Phys. Rev. B 71, 060401(R) (2005).
[46] J. P. Perdew and A. Zunger, Phys. Rev. B 23, 5048 (1981).
[47] J. P. Perdew , J. A. Chevary, S. H. Vosko, K. A. Jackson, M. R. Pedreson, D. J. Singh
and C. Fiolhais, Phys. Rev. B 43, 6671 (1992).
[48] J. P. Perdew, S. Burke and M. Ernzerhof, Phys. Rev. Lett. 77, 3865 (1996).
[49] J. P. Perdew and Y. Wang, Phys. Rev. B 33, 8800 (1986).
[50] J. P. Perdew in ‘Electronic Structure of Solids’, Academie Verlag, Berlin, 11 (1991).
[51] J. P. Perdew and K. Burke, Int. J. Quantum Chem. 57, 309 (1996).
[52] F.Tran and P.Blaha, Phys Rev. Lett. 102, 226401 (2009)
[53] A. D. Becke and E. R. Johnson, J. Chem. Phys. 124, 221101 (2006).
[54] P. Blaha, K. Schwarz, G. K. H. Madsen, D. Kvasnicka and J. Luitz, WIEN2k, K.
Schwarz, Techn.University at Wien, Austria, 3, 9501031 (2001).
[55] P. Hohenberg and W. Kohn, Phys. Rev. B 136, 864 (1964).
[56] W. Kohn and L. J. Sham, Phys. Rev. 140, A1133 (1965).
[57] M. Cococcioni and S. de Gironcoli, PRB 71, 035105 (2005).
[58] Peter Blaha, Karlheinz Schwarz, Georg K. H. Madsen, Dieter Kvasnicka, Joachim Luitz,
Robert Laskowski, Fabien Tran and Laurence D. Marks, User’s Guide, WIEN2k (2019).
[59] Burak Himmetoglu, Andrea Floris, Stefano de Gironcoli and Matteo Cococcioni,
Quantum Chemistry 114, 14 (2014).

69
[60] Fabien Tran and Peter Blaha, Phys. Rev. Materials 2, 120801 (2018).
[61] Philipp Haas, Fabien Tran, Peter Blaha and Karlheinz Schwarz, Phys. Rev. B 83, 205117
(2011).
[62] E.Sjöstedt, L.Nordström, D.J.Singh, Solid State Commun. 114, 15 (2000).
[63] Karlheinz.Schwarz, InTech, Chapter 10, 275 (2015).
[64] C. Loschen, J. Carrasco, K.M. Neyman and F. Illas, Phys. Rev. B 75, 035115 (2007).
[65] P. E. Blochl, O. Jepsen and O. K. Anderson, Phys. Rev. B 49, 16223 (1994).
[66] H. J. Monkhorst, J. D. Pack, Phys. Rev. B 13, 5192 (1976).
[67] R. S. Roth, Journal of Research of the National Bureau of Standards 58, 2736 (1957).
[68] Safari Amisi, Computational Condensed Matter, 20, e00383 (2019).
[69] Hans-Conrad zur Loye, Qingbiao Zhao, Daniel E. Bugaris and W. Michael Chance,
Cryst. Eng. Comm, 14, 23 (2012).
[70] M.K. Lee, C.B. Eom, J. Lettieri, I. W. Scrymgeour, D.G. Schlom, W. Tian, X. Q. Pan, P.
A. Ryan, F. Tsui, Appl. Phys. Lett. 78, 329 (2000).
[71] Hitoshi Yusa, Nagayoshi Sata and Yasuo Ohishi, American Mineralogist, 92, 648 (2007).
[72] Roger H. Mitchell, Mark D. Welch, Anton R. Chakhmouradian, Supplementary materials
81, 411 (2017).
[73] R Ubic, Subodh Ganesanpotti, Journal of Alloys and Compounds, 488, 374 (2009).
[74] J. M. Longo, P. M. Raccah, J. B. Goodenough, J. Appl. Phys. 39, 1327 (1968).
[75] W. Zhang, N. Kumada, Y. Yonesaki, T. Takei, N. Kinomura, T. Hayashi, M. Azuma M.
Takano, Journal of Solid State Chemistry 179, 4052 (2006).
[76] Markus Kubicek, Alexander H. Borkac and Jennifer L. M. Rupp, Mater. Chem. A 5,
11983 (2017).
[77] Sodena, S. Stolen, P. Ravindran, T. Grande, Phys. Rev. B 75, 214307 (2007).
[78] F.D. Murnaghan, Proc. Natl. Acad. Sci. USA 30, 5390 (1944).
[79] Alison J. Hatt and Nicola A. Spaldin, Phys. Rev. B 81, 054109 (2010).
[80] Florian Johann, Alessio Morelli, Daniel Biggemann, Miryam Arredondo and Ionela
Vrejoiu, Phys. Rev. B 84, 094105 (2011).
[81] P. Ravindran, R. Vidya, A. Kjekshus, H. Fjellvåg and O. Eriksson, Phys. Rev. B 74,
224412 (2006).
[82] F. Sugawara, S. Ihda, Y. Syono and S. Akimoto, Journal Physical Society 25, 1553
(1968).

70