STRUCTURAL, ELASTIC AND MECHANICAL

PROPERTIES OF BiFeO3 AND BaTiO3

BY:

Kashif Jalal

Liaqat Ali

Naveed Anjum

DEPARTMENT OF PHYSICS
GOVERNMENT DEGREE COLLEGE WARI (DIR UPPER)
KHYBER PAKHTUNKHWA
PAKISTAN
2023
 STRUCTURAL, ELASTIC AND MECHANICAL

PROPERTIES OF BiFeO3 AND BaTiO3

Submitted by:

Kashif Jalal (12930)

Liaqat Ali (12955)

Naveed Anjum (12961)

Supervised by:

Mr.Bacha Muhammad
Lecturer in Physics
Govt Degree College Wari (Dir Upper)

Thesis submitted to the Department of Physics Govt Degree College Wari Dir
Upper as a partial fulfillment of the requirement of Shaheed Benazir Bhutto
University Sharingal Dir Upper for the award of Degree of BS (4-Year)2024.

DEPARTMENT OF PHYSICS
GOVERNMENT DEGREE COLLEGE WARI (DIR UPPER)
KHYBER PAKHTUNKHWA
PAKISTAN
Session (2019-23)

ii
 Certificate of Approval

This is to certify that the project presented in this thesis/report, entitled

“STRUCTURAL, ELASTIC AND MECHANICAL PROPERTIES OF BiFeO3 AND

BaTiO3” was conducted by Kashif Jalal, Liaqat Ali, and Naveed Anjum under the

supervision of Bacha Muhammad; no part of it has been submitted anywhere else for any

other degree. This work is submitted to the Government Degree College Wari (Dir Upper)

affiliated with Shaheed BB University Sheringal Dir Upper in partial fulfillment of the

requirements for the degree of BS (4-year) 2019-23.

Scholar’s Name: ____________________ Signature: ______________

(Roll No._______)

Scholar’s Name ____________________ Signature: ______________

(Roll No._______)

a) External Examiner 1:______________________ Signature: ______________

__________________________________________

__________________________________________

b) Internal Examiner:_________________________ Signature: ______________

___________________________________________

___________________________________________

QEC Focal Person Signature:_______________

Govt Degree College Wari (Dir Upper)
Khyber Pakhtunkhwa, Pakistan

iii
Dedication

iv
 Acknowledgments

First of all, thanks to Almighty Allah who gave us the strength to

complete our thesis.

This thesis is the result of great hard work where I have been supported

by many people. It is a pleasant aspect that I have now the opportunity to

express my gratitude to all of them. The first person I would like to thank is my

supervisor Mr Bacha Muhammad. During this one year, I have known him as

a sympathetic and principle-centered person. His guidance helped me in all the

time of research and writing of this thesis. Besides my supervisor, I am feeling

deep pleasure in expressing my cordial thanks to my parents and friends

v
 Table of Contents

Certificate of Approval ........................................................................................................................ iii

Dedication ............................................................................................................................................. iv
Acknowledgments ................................................................................................................................. v
Project in Brief ..................................................................................................................................... ix
ABSTRACT ........................................................................................................................................... x
1.1 Introduction ............................................................................................................................ 1
CHAPTER – 2 ....................................................................................................................................... 4
LITERATURE REVIEW .................................................................................................................... 4
2.1 Structural Properties................................................................................................................ 4
2.2 .1 Bismuth Ferrite BiFeO3 ...................................................................................................... 4
2.2.2 Barium Titanate BaTiO3 ........................................................................................................ 5
2.2 Elastic and Mechanical Properties .......................................................................................... 6
2.3 Electronic Properties ............................................................................................................... 8
2.4 Piezoelectric Properties ................................................................................................................ 9
CHAPTER – 3 ..................................................................................................................................... 11
Computational Detail.......................................................................................................................... 11
3.1 Density Functional Theory .......................................................................................................... 11
3.2 Hohnberg and Kohn Theorems ................................................................................................... 12
3.3 Kohn-Sham’s Equations. ............................................................................................................. 12
3.4 Local Density Approximation ...................................................................................................... 13
3.5 Generalized Gradient Approximation ......................................................................................... 14
3.6 Generalized Gradient Approximation with Hubble Potential (GGA+U)...................................... 14
3.7 Modified Becke Johnson Method ............................................................................................... 15
3.8 Tetra-Elastic Package .................................................................................................................. 16
3.9 WIEN2k Package ......................................................................................................................... 19
CHAPTER – 4 ..................................................................................................................................... 20
Results and Discussion........................................................................................................................ 20
4.1 Structural Properties ................................................................................................................... 20
4.2 Electronic Properties ................................................................................................................... 24
4.3 Elastic Properties......................................................................................................................... 27
4.4 Mechanical Properties ................................................................................................................ 29
CHAPTER – 5 ..................................................................................................................................... 36
CONCLUSION ................................................................................................................................... 36
Bibliography ........................................................................................................................................ 37

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 List of Tables

All the tables in the thesis will go here automatically

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vii
 List of Figures

4.1 The unit cell of BiFeO3 ...................................................................21

4.2 The unit cell of BaTiO3 ...................................................................21
4.3 Energy vs volume curve of BiFeO3 and BaTiO3 ..........................22
4.4 Spin-dependent total and partial density of state of BiFeO3
and BaTiO3 ............................................................................... 24
4.5 Spin-dependent electronic band structures of BiFeO3 and BaTiO3 25

viii
 Project in Brief

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ix
 ABSTRACT

In this thesis, the structural, elastic, and mechanical properties of perovskites BiFeO3 and

BaTiO3 in tetragonal crystal structure are investigated using generalized gradient

approximation (GGA) within DFT. The resultant structural parameters are found consistent

with experimental results. Band structures and the density of states of these compounds are

investigated for electronic properties, which reveals the metallic nature of BiFeO3 and the

semiconducting nature of BaTiO3 with a band gap of 2.7 eV. For describing the elastic

behavior, a tetra-elastic package in Win2k code is used to determine the six elastic constants

for the tetragonal phase. Mechanical properties of the compounds under study such as

Poisson's ratio (σ), Kleinman-parameter (ζ), anisotropy constant (A), and Lames coefficients

(λ and µ) are calculated using first principle calculations. The calculated Pugh ratio (B/G)

shows the brittle and ductile nature of BiFeO3 and BaTiO3 respectively. The resultant values

of σ clear that these compounds have less tendency to compressibility and are stable against

the deforming force. The results of A show that these compounds are anisotropic. The

thermo-physical properties like transverse sound- velocity (νs), longitudinal sound velocity

(νl) average sound velocity (νm), and Debye temperature θ(D) are also explored based on

mechanical properties which confirm that these materials are stiffer, which satisfied the

results obtained from Poisson ratio σ.

x
CHAPTER –1 1INTRODUCTION

CHAPTER – 1
INTRODUCTION

1.1Introduction

Structural, elastic, and mechanical properties give important information about the

materials which are associated with many physical properties such as sound velocities,

phonon spectra, and inter-atomic potentials and also related thermodynamically to Debye

temperature, specific heat, melting point, thermal expansion, etc. These properties are

pressure-dependent; the effect of pressure on materials is more complex because the behavior

of different materials is not the same. Perovskite oxides show greater stability against

hydrostatic pressure. Some perovskites such as GdFeO3, CaTiO3, and LaAlO3 [1, 2, 3]

decrease their tilt angle due to pressure and undergo phase transitions, structural changes, loss

of magnetic orders and metallization has also been observed [4]. The effect of pressure on

perovskite oxides is important for various technological applications like laser frequency

doubling, waveguides, high-capacity computers, nano and thin film electronic devices,

piezoelectric sensors, actuators, etc. [5, 6]. Perovskites have general formula ABO3 where

"A" and "B" are two different cations like lead zirconate titanate (PZT), calcium titanate

(CaTiO3), lead-titanate (PbTiO3), lead-lanthanum zirconate titanate (PLZT), Bismuth ferrite

(BiFeO3) and Barium titanate (BaTiO3 ) are most popular [7, 8]. 1 Bismuth ferrite BiFeO3

(BFO) is multiferroic material. In multiferroics, there are a couple of ferroelectric and

ferromagnetic properties, the ferroelectric property can be controlled by the magnetic field,

whereas its magnetism can be manipulated by the electric field [9, 10, 11]. BFO is the only

multifferroic material that shows ferroelectric behavior below Curie temperature Tc of about

1103 K, and anti-ferromagnetic properties below Neel temperature TN of 643 K [12]. Barium

titanate BaTiO3 (BTO) is a well-known piezoelectric, ferroelectric, and optical material [13].

1
CHAPTER –1 1INTRODUCTION

Under different conditions of temperature and pressure, there are many possible crystal

structures of BFO and BTO such as cubic phase [14], triclinic phase [15], rhombohedral [16],

monoclinic phase [17], tetragonal phase and orthorhombic phase [18]. The physical

properties depend upon the crystal structure of BFO and BTO. At room temperature, BFO is

crystalized in a rhombohedral phase with space group P3c and BTO is crystalized in the

tetragonal phase with space group P4mm [13]. The interesting physical properties of BFO

and BTO attract much attention from scientists and industrialists. Extensively experimental

and theoretical research recently has been performed on the characterization of the other

properties of BFO and BTO [9, 13, 19, 20]. The study of structural properties is important

because all the physical properties are related to domain structures and phase states, which

help us to understand how the phase and their corresponding physical properties vary with

temperature and pressure [21]. Electronic properties give information about the nature of the

material such as whether it is an insulator, conductor, or semiconductor. These properties are

directly or indirectly related to the band gap of the material. The band gap of any crystal

structure of a compound varies with pressure and temperature. Such a change in band gap

occurs in BFO and BTO due to which the electronic nature of these compounds is 2 varied

with increase and decrease of pressure and temperature [13, 19]. The knowledge of elastic

properties such as shear modulus (S), Young's modulus (Y), bulk modulus (B), elastic

anisotropy (A), and Poisson's ratio (σ), etc. is very important. These properties give

information about the behavior of materials under external pressure. Elastic properties are

determined with the help of elastic constants. Elastic constants are parameters that describe

the elasticity of a material and provide significant information about the forces operating in

solids, as well as for understanding the bonding nature, structural stability, and crystal

structure. Mechanical properties such as ductility brittleness, hardness, and toughness are

studied based on the elasticity of a material. Elasticity is the property of a material to regain

2
CHAPTER –1 1INTRODUCTION

its original shape after the removal of the deforming force. With the help of these elastic

constants, the mechanical properties can also be determined. Mechanical properties explain

various physical properties of a material. Which helps in a good understanding of material

nature. Various properties of BFO and BTO are studied but several aspects of these

compounds at different crystal structures such as in the tetragonal phase need to be

determined. In the present work, theoretical studies have been performed on the structure,

elastic and mechanical properties of BFO and BTO

3
CHAPTER – 2 LITERATURE REVIEW

CHAPTER – 2

LITERATURE REVIEW
Bismuth ferrite (BFO) and Barium titanate (BTO) are well-known materials in the field

of microelectronics and electro-ceramics due to their multiple characteristics. The high

dielectric constants of these materials make them an excellent choice for many applications,

such as energy storage devices, capacitors, and many other electrical devices. Doped BFO

and BTO have also found wide applications in positive temperature coefficient resistors,

semiconductors, piezoelectric devices, and ultrasonic transducers. Some of the features of

BFO and BTO are explained in the following sections.

2.1 Structural Properties

2.2 .1 Bismuth Ferrite BiFeO3

Bismuth ferrite BFO belongs to a class of ferromagnetoelectric materials

(multiferroics) [9], which exist in different crystal structures [22, 23, 24]. However, because

of a very narrow range of synthesis temperature for phase stability the synthesizing of single-

phase BFO is very difficult. Hence, for preparing single-phase BFO powder different

synthesis techniques have been used such as 4 solid state reaction routes, wet chemical

methods like high energy ball milling [25], hydrothermal [26] sol-gel [27, 28], co-

precipitation [29], sonochemical [30] microwave-hydrothermal and auto combustion methods

[31, 32]. BFO was synthesis by Achenbach et al. [33], using a solid-state synthesizing

method, and showed that the structure of BFO is rhombohedral (space group R3c) with lattice

parameters (a= 3.958 ˚A) and atomic parameters are Bi (0, 0, 0.9491), Fe (0.5, 0.5, 0.51804)

and O (0.5, 0.5, 0.1428) (0, 0.5, 0.1673). Wang et al. [24] synthesize the tetragonal phase of

4
CHAPTER – 2 LITERATURE REVIEW

BFO. Among all the stable phases of the tetragonal (space group P4mm) of BFO is of

particular interest because of the large polarization value per unit cell [34]. Tetragonal BFO

was investigated by Ricinschi et al. [35] (a = 3.67 ˚A and c = 4.64 ˚A, c/a = 1. 26), Ederer et

al. [37] with (a = 3.665 ˚Aand c = 4. 655 ˚A, c/a = 1.27), and Ravindran et al. [34](a = 3.7859

˚Aand c = 4.8525 ˚A, c/a = 1.28) using first principle calculations having polarization up to

150 C/ cm2 [35, 36]. Spontaneous polarization in the bulk is very interesting for potential

applications in modern ferroelectric devices. Several experiments were conducted for

exploring of super tetragonal phase with giant c/a ratio and polarization [23, 37]. From the

initial report, the c/a ratio of BFO is 1.04 and the polarization value is 63.2 C/cm2 [19]. Yun

et al. [38] 2004 reported that a tetragonal BFO has a c/a ratio of 1.264 and polarization of 158

C/cm2. Recently, Liu et al. [39] have grown tetragonal BFO with a large c/a ratio of 1.23.

The knowledge of the structural, elastic, and mechanical properties of BFO is desired for the

integration of BFO in nano- and thin-film electronic devices [40]. However, the elastic and

mechanical properties are unknown for tetragonal BFO from either experimental

measurements or theoretical calculations. The lack of this information has hindered the

fundamental understanding of tetragonal BFO and its applications. The present attempt is 5 to

cover the knowledge gap.

2.2.2 Barium Titanate BaTiO3

Barium titanate (BTO) is the most studied perovskite of the type ABO3. After the

discovery of piezoelectricity and ferroelectricity in BTO it became one of the most studied

materials. BTO was synthesized by Megaw [41] in 1945 by sol-gel method and shows that at

room temperature the structure of this compound is tetragonal with space group P4mm and

lattice parameter a = 3.9860 ˚A, c = 4.0263 ˚Aand c/a = 1.0101 and the atomic parameters are

Ba (0, 0, 0), Ti (0.5, 0.5, 0.4820) and O (0.5, 0.5, 0.0160) (0.5, 0, 0.5150). Each Ti atom lies

at the center of the unit cell and is surrounded by six oxygen ions, hence each Ti ion has a +4

5
CHAPTER – 2 LITERATURE REVIEW

charge, and the degree of polarization is very high when it is displaced by external voltage or

pressure which results in a high dielectric constant of BTO [42]. Wul and Goldman [43]

discovered the ferroelectricity in BTO. At temperature above 398K the symmetry of BTO is

cubic with Ba2+ on A site at the corner Ti4+ as is on B at the center and O at the face center

of the unit cell. When the temperature of the sample decreases the phase of the BTO is

changed from cubic to different ferroelectric crystal structures. When the temperature of BTO

is further decreased from 393K then the phase of BTO is changed to tetragonal phase. The

two crystallographic axes are decreased in length from 4.010 to 4.004 and the other one

increases in length unit cell going from 4.010 to 4.022 ˚A. The spontaneous increase in

positive charge is an increase in the direction where the Ti4+ ion moves off-center toward

one of the two oxygen ions of the long axis which results in a ferroelectricity and reversal

polarization [42]. In the temperature range from 278 to 183 K the phase of BTO changes

from tetragonal to orthorhombic and finally, the phase of BTO is transferred from

orthorhombic to 6 rhombohedral below 183K. Each of these transitions can be assumed as

elongations of the unit cell along an [001] edge for change in phase from cubic to tetragonal,

along a face-diagonal [011] edge from tetragonal to orthorhombic and along a body-diagonal

[111] edge from orthorhombic to rhombohedral [44]. Li et al. [45] and Richerson et al. [42]

found that the phase transition and dielectric properties of BTO are dependent on temperature

and grain size. The tetragonal BTO is the most widely used because of its excellent

ferroelectric, piezoelectric, and thermoelectric properties [46].

2.2 Elastic and Mechanical Properties

When materials are used for practical application, they are subjected to forces. These

forces are studied by mechanical engineers and how the materials deform (compress,

elongate, twist) or break due to these forces, temperature, pressure, and other conditions are

calculated by material scientists. This response of a material is known as elasticity. Elastic

6
CHAPTER – 2 LITERATURE REVIEW

properties such as Young's modulus (Y), shear modulus (S), bulk modulus (B), elastic

anisotropy (A), and Poisson's ratio (σ), and mechanical properties like brittleness, ductility,

toughness, and hardness are determined from elasticity. Elastic properties are obtained from

the results of single-crystal elastic constants. Elastic constants are parameters that describe

the elasticity of a material and give us significant information about the nature of the forces

operating in solids, understanding the bonding nature, structural stability, crystal structure,

and many other properties of materials are determined with the help of elastic constants.

Dong et al. [19] calculated the elastic constant of BFO. Meng et al. [13], and Berlincourt and

Jaffe [47] worked on the elastic and piezoelectric properties of tetragonal BTO. Schaefer et

al. [48] and Li et al. [49] clearly that the elastic and mechanical properties of BTO are

dependent 7 upon the resonance frequency of the sample. Using Brillouin scattering the

elastic constants of BTO are also determined by Ishidate and Sasaki [50]. Turik et al. [51]

have studied the dielectric spectrum and found that the dielectric relaxation may also affect

the mechanical, and elastic properties of tetragonal BTO. When materials are used for

electronic components not only the dielectric properties but the mechanical properties are

also taken into account. For example, during the end terminating and soldering of a capacitor

a stress of 3 to 50 MPa is generated [52]. For the calculation of elastic constants. The stress

tensor (external force) is applied to the material. which produced strain tensor (deformation).

Under the homogenous condition crystalline material elastic constants described by fourth

rank tensor are denoted in terms of generalized Hook's law as

Where σij term is for stress tensor, Cijkl is the fourth rank tensor for elastic stiffness

which consists of 81 elastic constants and δij is the strain tensor. The number of elastic

constants can depend on the symmetry of the crystal structure. In Voigt’s notation we replace

7
CHAPTER – 2 LITERATURE REVIEW

xx = 1, yy = 2, zz = 3, yz = 4, xz = 5, and xy = 6. The elastic tensors Cijkl are reduced to 6

cross 6 matrix. Elastic constants for single crystal in matrix notation can be written as [53]:

The number of elastic constants is further reduced with the material sym8 metrics. The

highest number of elastic constants is for the triclinic structure, while the cubic structure has

the minimum number of elastic constants. For tetragonal symmetry X and Y axes are

identical then the above matrix is reduced to the form

Hence for the tetragonal system, we have to find six elastic constants which are C11, C12, C13,

C33, C44, and C66. For tetragonal phase six elastic constants are satisfying the following condition

they are [54] (C11 − C12) > 0,

(C11 + C33 − 2C13) > 0, C11 > 0,

C33 > 0, C44 > 0, C66 > 0

2.3 Electronic Properties

Electronic properties are important to visualize the nature of materials. Many physical

properties are related to the band structure of the materials. Electronic properties change

8
CHAPTER – 2 LITERATURE REVIEW

with the phase transition. These properties of BTO are studied by Piskunov et al. [55]

who calculate the band gap of BTO as 2.87 eV, which is an underestimate of the

experimental band gap of 3.2 eV [56]. By electronic structure calculations, the band gap

of BFO in the rhombohedral phase was found to be 2.5 eV and from the density of states

analysis, the conduction band was composed of Bi-p and Fe-d states and the valence band

consisted of O-p and Fe-d states [57]. Arora et al. [58] from absorption coefficient spectra

investigated the electronic properties of BFO and calculated 9 that the band gap of BFO

is 2.17 eV. Du et al. [59] found that doping La on the Bi site in BFO changes its dielectric

properties. Simes et al. [60] investigated those electrical properties of BFO increased by

depositing the Nb on the Bi site in BFO films. The band gap of Ni-doped BFO is 2.75 eV

measured by Mishra and Qi [61] which is synthesized by the sol-gel method.

Kazhugasalamoorthy et al. [62] found the properties of pure and rare earth-doped BFO

ceramics. Many other research groups calculated the band gap, optical properties, and

stress constants [63, 64, 65, 66].

2.4 Piezoelectric Properties

French scientists Jacques and Pierre Curie [67] discovered Piezoelectricity in 1880.

When a stress is applied on a single crystal of some material then polarization occurs at

one side of the crystal, derives a net negative charge and the other side derives a net

positive charge. There are 32 crystal classes of materials, 20 of them are piezoelectric

only those materials that have no center of symmetry are piezoelectric. Even not in all

directions, in specific directions, it shows a piezoelectric nature [68]. Piezoelectric

materials generate quantifiable piezoelectricity when their stable structure is distorted by

0.1 %, conversely, the same crystals are deformed by 0.1 % from their static dimensions

by applying the external field to that material [69]. The electro-mechanical property is

produced from the coupling of spontaneous polarization with lattice strain. Many devices

9
CHAPTER – 2 LITERATURE REVIEW

such as piezoelectric actuators and ultrasonic transducers have been developed which are

based on various transducing principles such as piezo-resistance [70], piezo-capacitance

[71], piezo-optics [72], piezoelectricity [73] and form billions of dollars market

worldwide [74, 75]. Various piezoelectric materials such as lead-titanate (PbTiO3),

calcium titanate (CaTiO3) lead lanthanum zirconate titanate (PLZT), lead magnesium

niobate (PMN) and 10 lead zirconate-titanate (PZT) are identified. piezoelectric lead

ceramics are widely used in modern technologies such as ultrasonic generators, sensors,

resonators, and actuators for various purposes. But these materials contain 60 - 70 % of

PbO which can cause environmental pollution [76] Therefore, lead-free piezoelectric

materials with excellent piezoelectric responses are desirable due to recent environmental

legislation. BTO and Bi contained perovskites such as BiScO3 [77], BiFeO3 (BFO) [78],

Bi (Mg0.5Ti0.5O3 and Bi (Zn0.5 Ti0.5)O3 [79] are the alternative discovered lead-free

piezoelectric materials with superior properties [80]. BFO and BTO are the most

multifunctional and interesting lead-free materials that have been extensively studied in

recent years [81]. They show excellent piezoelectric, multiferroic, and optical properties

[82]. They belong to the perovskite family and are crystalized in a tetragonal lattice with

space group P4mm (No99) [68, 83]. In BFO, the Bi3+ ion positioned on A site, and its

6s2 active lone pair are responsible for dislocations of the Bi atoms from the

centrosymmetric to the non-centrosymmetric structure which induces a symmetry-

lowering structural change led to piezoelectricity [84]. In BTO the average relative

displacement along the c axis of the Ti atom from its symmetric position in the unit cell

and subsequently permanent electric dipoles are formed. Which indicates the presence of

the ferroelectric phase and leads to piezoelectricity [85].

10
CHAPTER – 3 Computational Detail

CHAPTER – 3

Computational Detail
In the present chapter, the theory and method of calculations performed in this work are

discussed. Different computational methods and different approximations are used for

calculating better results which describe the structural, mechanical, and elastic properties of

BFO and BTO. The methods of calculating elastic constants are also discussed in this section.

3.1 Density Functional Theory

The Schrodinger wave equation applies to a simpler system and a numerical solution

can be found for a very few number of molecules and atoms. However, most cases, such as

electron-electron interaction in solids and reaction surfaces in chemistry require the use of a

model Hamiltonian or simple computational scheme. Density functional theory (DFT) [86] is

one of the methods used to calculate the ground state properties of electronic systems, which

is widely used in chemistry and computational physics to investigate the electronic,

thermoelectric, magnetic, and optical properties of solids. Using DFT we can calculate

different properties of complex as well as simpler compound systems and also to different

layers and interfaces of 12 solid materials. The relativistic effect of heavy nuclei can also

investigated by this method. The results obtained by DFT are generally agreeable with the

experimental available literature. DFT was formulated by Hohenberg, Kohn, and Sham [87]

for the theoretical investigation of the electronic structure of many-particle systems like

atoms, molecules, and solids. Due to the formulation of DFT, W. Kohn and A. Pole were

awarded by Nobel Prize in chemistry in 1998. The designing of a multi-scale model for the

complex system was the main achievement of these materials scientists. They explain that in

the cloud of a fully interacting electronic system the electron density, in a rigorous way, be

11
CHAPTER – 3 Computational Detail

obtained from simple one-electron theory. DFT is different from the wave function-based

methods because in this approach the electron density ρ(r) is used as the core quantity.

Therefore, dimensionality is much reduced by using the idea of electronic density over the

wave function, which is an important advantage of DFT. If there is any number of electrons

present in a system, the density at all times is 3 dimensional. Due to this reason, DFT is

readily applied to many complex systems. Nowadays, DFT is widely used for electronic

structure approaches, mostly in the condensed matter physics community [88].

3.2 Hohnberg and Kohn Theorems

Two theorems were formulated by Hohenberg and Kohn [87]. In these theorems, the

electronic density is the basic component. The following are the statements of these theorems

for non-degenerate ground electronic states.

Theorem (i):

This theorem states that "In the absence of an electromagnetic field there is a one-to-

one correspondence between external potential and ground state density.

Theorem (ii):

According to this theorem, "The density which minimizes the complete energy will be

exactly the ground state density".

In the first theorem, using the concept of electronic density we can determine the ground

state properties of many electronic systems. According to the second theorem using the

concept of density, we can bring a system with N electrons to 3 coordinates.

3.3 Kohn-Sham’s Equations.

Kohn-Sham's equations help solve many body problems [89]. Utilizing the Kohn-Sham

method we can obtain an accurate approximation [90]. The main advantage of this scheme is

the determination of a large part of the kinetic energy in a simple way and used to solve

complex systems in the solid state which is

12
CHAPTER – 3 Computational Detail

In this equation, Ei shows the energy of the K-S one-electron orbital, and ϕi is the state

function. The first term shows kinetic energy and the second term shows the effective

potential, where the effective potential Veff can be expressed as

Where

The ρ(r) shows the exact ground state density of the N electron system can be calculated by

using the equation given as

3.4 Local Density Approximation

Local density approximation (LDA) is the most common and simplest used DFT exchange-

correlation energy functional. Kohn and Sham originally introduced this approximation [90].

In this approximation, the exchange-correlation in terms of the electronic density ρ(r) is

written as

Here Exc is the exchange energy per particle of a uniform electron gas of density (ρ). This

function Exc is not measured exactly but approximated values can be found. Thus, the X-C

energy function is the sum of exchange and correlation energy functional.

13
CHAPTER – 3 Computational Detail

The LDA results are valid only for constant densities but for variable densities, their results

are not agreed with the experimental results [91].

3.5 Generalized Gradient Approximation

the LDA results are in good agreement with the experimental for uniform densities. However,

for non-uniform densities, its results are not comparable to experimental. Due to this reason,

the next step of gradient correction of the electron gas is to be taken such that exchange-

correlation energy Exc is given as

Here ρ(r) is electron densities ∇ρ(r) is its gradient. There are so many flavors of GGA but

among them, the most common type is GGA(PBE), formulated by Perdew and Wang Burke

[92], and Perdew and Ernzerhof [93]. GGA is used in the case of slowly varying charge

densities. GGA used a gradient of charge density which helps in removing the deficiencies of

LDA. In more cases, the results obtained by GGA are most near to experimental values as

compared to LDA. In our calculation we have used GGA (PBEsol), to study the structural,

electronic properties, elastic and mechanical properties of BTO and BFO.

3.6 Generalized Gradient Approximation with Hubble Potential (GGA+U)

Standard DFT (LDA, GGA) methods often fail in describing the electronic and magnetic

properties of highly correlated electronic systems i.e. the 3d and 4f orbitals of transition

metals and lanthanides. The 3d and 4f orbital do not form high overlaps with the ligand

(group of ions or molecules) orbital. Thus, the 3d or 4f orbital energy of the systems

produced a self-interaction error in LDA and GGA calculations. The GGA+U approach,

corrects the strong correlated system or material, by adding an on-site coulomb repulsion

(consite Hubbard parameter U) to the GGA. Anisimov et al. [94] Ebert et al. [95] and

14
CHAPTER – 3 Computational Detail

Dudarev et al [96] are different formulations used for GGA+U approximation. In GGA+U

the total exchange correlation of 16 energy is

EGGA+U = EGGA + EU 3.8

Where

Here J is the exchange parameters, U electron-electron Coulomb interaction respectively and

n is the occupation number of a d-orbital of number m with spin σ.

3.7 Modified Becke Johnson Method

Usually, we use LDA to follow GGA based on DFT to study the ground state properties such

as lattice constant, electronic charge density, ground state energy, and band structure. These

two approximations are good for estimating the band gap of complex metallic material

exactly, but underestimate the band gap of semiconductors and insulators. To solve this

problem Becke and Johnson developed a new exchange-correlation potential method based

on the optimized potential method (OPE) [97]. Tran and Blaha [98] further modified the BJ

function (mBj) which improved the band structure. It is also possible to add an onsite-

Hubbard parameter U term to the d and f electron form mBJ+U functional, which is used in

this work. Tran and Blaha [98] modified Becke Johnson's potential (mBJ) to be written as

Where tσ(r) is the kinetic-energy density, ρσ(r) is the electronic density, and UBR x,σ(r)represent

the Becke and Roussel potential [97]. In Eq 3.10, the ’c’ parameter value is calculated with

15
CHAPTER – 3 Computational Detail

Where α = -0.012 and β = 1.023 are two free parameters and Vcell means the united cell

volume.

3.8 Tetra-Elastic Package

There are different methods of calculation of elastic constants in the tetragonal phase. the

present calculations we used a tetra-elastic package [99, 100] for the investigation of the

elastic properties of BFO and BTO. For the calculation of total energy under Eulerian strain,

we use Taylor expansion in the following way [101].

Where V0 in this equation represents the initial volume, δi shows the element of stress tensor

and ξ factor is for the symmetry of deformation, which takes value 1 in Voigt index are 1,2,3

and got value 2 if Voigt index are 4,5,6. Also using Voigt notations to substitute xx=1, yy=2,

zz=3, yz=4, zx=5, xy=6 and using the tetragonal symmetries i.e. x=y the elastic-tensor Cijkl

for tetragonal symmetry can be written as

Only six elastic constants C11, C12, C13, C33, C44, and C66 can be calculated for tetragonal

symmetry. For the measurement of the total energy of stress applied crystal and for obtaining

the strain unit cell the distortion matrix D is applied to the lattice vector L according to the

rule Lo=LD. Where L0 gives us the components of strained lattice vectors. The distortion

matrix D with a symmetry δxy =δyx is given as.

16
CHAPTER – 3 Computational Detail

the distortion matrix D11 and D33

are first applied to a crystal, as assume that the distortion in the lattice along the z, and x-axis

respectively, keeping the symmetry of the lattice still tetragonal. However, a small change is

produced in volume. The corresponding energy of these distortions can be obtained by

putting the values of the matrices D11 and D33 in Eq 3.16 as

And

respectively. From these equations, we can calculate the elastic constants C11 and C33.

Similarly, using the following volumetric monoclinic shear distortions,

And

17
CHAPTER – 3 Computational Detail

for obtaining C44 and C66 from the energy equations such as

And

respectively. Also, applying the volumetric orthorhombic distortions

And

To the lattice, C12 and C13 can be calculated from

And

respectively. The already calculated elastic constant C11, which is equal to C22, and C33 are

used in the calculations of C12 and C13. Therefore, all six independent elastic constants of

tetragonal BTO and BFO are determined.

18
CHAPTER – 3 Computational Detail

3.9 WIEN2k Package

Win2k software helps us in the calculation of different properties with the help of DFT.

Peter-Blaha and Karlheinz Schwarz [100] first introduced this code in 1990, For various

purposes and developments several changes have been made. Nowadays it is widely used for

determining the ground state properties of solids. Present calculations are performed using

the WIEN2k package.

19
CHAPTER – 4 Results and Discussion

CHAPTER – 4

Results and Discussion

Band theory provides significant information about various physical properties of solid

materials. In this work, structural parameters like lattice constants, tetragonal distortion (η),

and internal-parameter (µ) are calculated. Band structural (Eg) and density of state (DOS)

calculations are performed to study the electronic properties. Elastic properties such as young

modulus (Y), bulk modulus (B), shear modulus (G), and mechanical properties like ductility,

brittleness, Poisson's ratio (υ), anisotropy constant (A), Kleinman parameter (ζ) and Lame's

coefficient (λ and µ) are investigated by first principle calculations. The thermo-physical

properties like transverse sound velocity (υs), longitudinal sound velocity (υ1) average sound

velocity (υm), and Debye temperature θ(D) are also determined.

4.1 Structural Properties

Structural properties of a compound are very important for the better understanding of other

physical and chemical properties. The structural parameters are responsible for the elastic and

mechanical behavior of a material. BFO and BTO both exist in the tetragonal crystal structure

of space group P4mm. 22 In the unit cell of BFO and BTO, the Bi and Ba atoms lie at corners

Fe and Ti in the body center and oxygen O lies at the faces of the unit cell. The unit cells of

BFO and BTO are shown in Fig 4.1 and 4.2. In the first step optimization is performed to get

the ground state structural properties, we minimize the total energy of the unit cell concerning

volume for both BFO and BTO by using the Birch Muranghan equation of states [101] which

is given as

20
CHAPTER – 4 Results and Discussion

In the optimization, we relax the lattice structure by removing the external stresses, due to

which the volume of the lattice expands. The energy versus volume optimization curves for

the compounds under study are shown in Fig 4.3. From these plots, we calculate lattice

constants and lattice energy, and from these ground state constants, we can find η and µ.

Which gives us information about the geometrical distortion of ions and molecules that are

connected with the electronic configuration of materials. µ and η can be obtained by using the

formula

And

The calculated and experimental values of BFO and BTO are listed in Table 4.1. From the

table, it is clear that our measured values are in good agreement with the experimental results.

Table 4.1 Calculated and experimental values of lattice constants in a,c in( Ao ),c/a, internal

parameter (u), tetragonal distortion (ᶯ), and Bulk modulus (Bo) GPa.

21
CHAPTER – 4 Results and Discussion

22
CHAPTER – 4 Results and Discussion

23
CHAPTER – 4 Results and Discussion

Figure 4.3: Energy vs volume curve of BiFeO3 and BaTiO3

4.2 Electronic Properties

The electronic properties of a material are related directly or indirectly to many physical

properties of a solid. That's why the knowledge of band structure is so important for their

practical applications. The unique electronic properties of each compound depend upon its

band structure. Fig 4.4 (a) and 4.4 (b) show the band structures of BFO and BTO in both

spin-up and spin-down states. The Fermi level is set on a reference point of 0 eV. From Fig

4.4 (a) the conduction band minima crosses the valance band as well as cross the fermi level,

hence there is no bang gap across the fermi level which shows the metallic nature of

tetragonal BFO. Fig 4.4 (b) clearly shows an indirect band gap of 2.7 eV of BTO because the

minima of the conduction band and maxima of the valence band lie at different symmetries of

the Brillouin zone. The maxima of the valence band lie at M point and the minima of the

conduction band lie at Γ point which is in complete agreement with the experimental result

[56]. As the band gap of BTO is 2.7 eV, in optoelectronic devices operating in the visible

region of the electromagnetic spectrum. Density of state (DOS) illuminates the nature of

different orbital in conduction and valence bands. The total and partial densities of states of

BFO and BTO are plotted in Fig 4.4. The obtained DOSs energies are distributed concerning

24
CHAPTER – 4 Results and Discussion

Fermi energy, ranging from -15 eV to 15 eV. In Fig 4.4 (a) total and partial spin up and spin

down DOS for BFO are plotted, the total density of the state plot shows that the fermi level is

covered by electron densities and lengthens to conduction band which gives evidence about

the metallic nature of tetragonal BFO and satisfy our calculated band structure results. While

partial DOS of the spin-up state of BFO conforms that the Fe-s state lies at its maximum peak

located at -4 eV near the fermi level in the valence band and the O-p state crosses the fermi

level, whose peak lies at 1 eV in the conduction band which makes the compound metallic. In

The spin-down DOS of BFO the maximum contribution is of the Fe-s state which crosses the

fermi level and its peak lies at 2 eV in the conduction band. The minimum contribution on

both sides of the fermi level is of the O-p state whose peak lies at -2 eV in the valence band

and 2 eV in the conduction band. The total and partial DOS for BTO are plotted in the range

of -15 eV to 15 eV in Fig 4.4 (b). These DOS's plots conform to the calculated band gap of

BTO. The band distribution between -15 eV and 0 eV is called valence state. In this region,

the main contribution is of the O-p state and the minimum contribution is of the Ba-s state.

Above 0 eV the conduction region starts and the main contribution in this region comes from

Ti-d state and the minimum contribution O-p state. Also, The calculated partial and total

DOSs confirm the band gap between the valence and conduction band of BTO.

25
CHAPTER – 4 Results and Discussion

Figure 4.4: Spin-dependent total and partial density of state of BiFeO3 and BaTiO3

26
CHAPTER – 4 Results and Discussion

Figure 4.5: Spin-dependent electronic band structures of BiFeO3 and BaTiO3

4.3 Elastic Properties

Elastic behavior of a material is that behavior when it undergoes stress, distorts, and then

recovers or regains its original dimension after removal of stress. The response of a material

to applied stress is described by elastic constants. From these elastic constants, various

physical properties of solids such as characteristics between adjusting atomic plane, thermal

expansion, specific heat, structure stability, stiffness, and many other properties are

described. We optimized the structural parameters of BFO and BTO in the tetragonal phase

and then calculated the six independent elastic constants C11, C12, C13, C33, C44, and C66 with

the help of tetra-elastic package embedded in Win2k code. The calculated elastic constants

27
CHAPTER – 4 Results and Discussion

are listed in Table 4.2. The obtained results of BFO compared with the results of Dong et al.

[19]. There is little disagreement because the calculations performed by Dong et al. [19] are

in C C-type and G-type antiferromagnetic phase and our results are obtained for the

ferromagnetic phase. The calculated results of BTO are compared in Table 4.2 with

experimental values [13]. The disagreement is due to temperature differences, the

experimental values are obtained at room temperature (296 K) and our calculations for BTO

are obtained at O K temperature. However there is a stability criterion for each symmetry of

the materials, furthermore, our calculated elastic constants satisfied the required stability

criteria. The stability criteria for the tetragonal phase of both compounds are given as

(C11 − C12) > 0, (C11 + C33 − 2C13) > 0,

C11 > 0, C33 > 0, C44 > 0, C66 > 0

The fulfillment of these criteria justifies that these compounds are elastically stable.

Table 4.2 calculated and Experimental values of elastic constants C11, C12, C13, C33, C44, and

C66 in (GPa) using GGA for tetragonal BTO and BFO.

28
CHAPTER – 4 Results and Discussion

4.4 Mechanical Properties

The knowledge of the mechanical properties of a material is important for its practical

application. The mechanical behavior of a material is determined by its mechanical

parameters. In the present work, we calculated mechanical parameters such as young

modulus (Y), bulk modulus (Bo), shear modulus (G) paugh (B/G) ratio, Poisson's ratio (υ),

Shear constant (C/) anisotropy constant (A), Lames Coefficient (λ and µ) and Kleinman

parameter (ζ). All these parameters are obtained from the independent elastic constants of the

materials under study. Our calculated results are listed in Table 4.3. we calculate their

mechanical parameters for the first time as there is no experimental or any other calculated

data available on this parameter for the tetragonal phase of BFO and BTO in the literature.

The resistance to plastic deformation upon stress is explained by the average shear modulus

GH=G [102]. According to Hill [103] the average shear modulus is determined from the

average of Reuss shear modulus GR and Voigt shear modulus Gu;

Where the value of GR and GV are calculated from elastic constants by using equations

And

Our calculated values of GH for BFO and BTO are given in Table 4.3. The calculated values

of GH for BFO and BTO are 139.33 and 77.55 respectively. The obtained values of the shear

moduli of both compounds show that these materials have high resistance to plastic

deformation. Similarly, the resistance of solid material to the linear strain along the edge is

determined by the young modulus (Y). This means that the stiffness of materials is

29
CHAPTER – 4 Results and Discussion

determined with the help of Y. It can be obtained using Reuss shear modulus GV and bulk

modulus BR.

The results of Y are presented in Table 4.3. The stiffness of compounds can be revealed from

the comparison of the bulk modulus (B) to the higher values of Y. From the present

calculations we conclude that BTO is stiffer than BFO. The brittle or ductile behavior of a

material can be calculated from the Pugh ratio [104]. This is the ratio between the bulk

modulus and shear modulus B/G. The critical value for which the ductile material is

distinguished from the brittle one is found to be 1.75. The high value of B/G corresponds to a

ductile nature, whereas the lower values of a material correspond to a brittle nature. The

calculated value of B/G for BTO is 1.07 and for BFO is 0.291, which is given in Table 4.3.

These values show that BTO has nearly ductile behavior due to which this material can be

used for making sheet and piezoelectric plates but the due to brittle nature of BTO fractures

occur in it when external stress is applied to it. That's why we cannot use pure BTO for the

production of piezoelectricity. While the BFO is completely brittle. The compressibility of a

material is explained with the help of Poisson's ratio (υ). The relation used for the calculation

of υ from bulk modulus (B) and young modulus (Y) is given as

The material tends to become incompressible when the (υ) value reaches 0.5. Below this

value, the materials show incompressibility, and above this value, materials show a tendency

to compressibility. Our calculated values for BTO and BFO are 0.144 and 0.089 which

indicate that these materials are stable against elastic deformation and incompressible.

Further the difference in the value of (υ) for BTO and BFO shows that the tendency to

compressibility for BFO is less than BTO. Poisson's ratio (υ) also explains the characteristic

30
CHAPTER – 4 Results and Discussion

of bonding force. For central forces in material the upper and lower value of (υ) is 0.25 and

0.5 respectively [106]. The calculated (υ) values, are 0.144 and 0.089 for BTO and BFO

showing that the interatomic forces are not central. The idea of the relative tendency of bond

stretching versus bond bending can be explained by a parameter known as the Kleinman

Parameter (ζ) which is introduced by Kleinman and known as the internal strain parameter

[107]. The upper limit of ζ explains the bond stretching and the lower limits lead to

minimizing bond bending. Kleinman Parameter (ζ) is calculated in an approximated way

using elastic constants using an equation explained by Harrison [108] which is given as.

Our obtained value of ζ for BFO and BTO 0.646 to 0.654 explains that the bond bending is

high in our material. The larger value of ζ indicates that the role of bond stretching is also

involved in BTO and BFO. The equality of various physical properties in different directions

is very important in the mechanical response of a material. This property is explained by

another parameter known as anisotropic ratio (A). In this study, we determine whether the

elastic properties remain constant in different directions or not. The possibility of inducing

micro-cracks in the material is closely related to A which is calculated from the given

equation [103].

For isotropic material, the value of A is one, A= 1. The elastic anisotropic behavior of a

material is explained based on the deviation of its value from unity. The calculated value of A

given in the table clearly shows that BTO and BFO are anisotropic. Another important

parameter that describes the stability of the material is the shear constant (C/) which is

calculated using the relation given as

31
CHAPTER – 4 Results and Discussion

This constant is also called tetragonal shear modulus. The stability condition for the given

phase of the compounds is C / > 0. The values of our calculated C / are given in the Table 4.3.

Our calculated positive values of C / for BFO and BTO clearly show that these compounds

are stable in the tetragonal phase. Moreover, a higher value corresponds to a high stability of

the tetragonal symmetry. The calculated values are 51.77 and 177.374 of C / for BTO and

BFO which show that BFO is more stable than BFO in tetragonal symmetry. Lame's

constants (λ, µ) are other important parameters. In which λ is called Lame's first parameter

and µ is called Lame's second parameter and are obtained from poison's ratio and young

modulus using the equations.

And

The above equations clear that the values of these coefficients are dependent upon Young

modulus, the greater the value of Young modulus (Y) greater Lam's constant. Lame's

constants (λ, µ) together constitute a parametrization of elastic moduli for isotropic

homogenous media. For isotropic compounds, the value of λ = C12 and µ= C / our calculated

values of Lame's constants λ, µ are given in the table (4.3). This clearly shows that BTO and

BFO is anisotropic material because they cannot fulfill the condition for isotropic material of

λ = C12 and µ= C / Transverse sound velocity (υs), longitudinal sound velocity (υl) average

sound velocity (υs) and Debye temperature θ(D) like thermo-physical properties of BFO and

BTO are also investigated. Transverse and longitudinal sound velocities are obtained from

32
CHAPTER – 4 Results and Discussion

the bulk modulus (B) and shear modulus (G) using the equations known as Navier’s

equations [109] which are given as

And

Where ρ is the density of the material. The average sound velocity υm and Debye

temperature θ(D) are calculated using classical relation given as [110]

And

Where NA is Avogadro number, h is the plank's constant, M is the molecular weight, υm is

the average sound velocity, kB is Boltzmann's constant, and n is the number of atoms per

formula unit. The calculated results of (υs), (υl), (υm), and θ(D) for BFO and BTO are

presented in Table 4.3. There is no experimental data available on the studied parameters for

the compounds under study. As the material with a high value of θ(D) shows greater thermal

conductivity we'll be stiffer. 0ur obtained results of θ(D) show that both.

Table 4.3 Calculated and experimental values of Voigt’s bulk modulus (BV), Reussís bulk

modulus (BR), Hillís bulk modulus (BH), Voigtís shear modulus (GV ), Reussís shear modulus

(GR), Hillís shear modulus (GH), B/G ratio, Poissonís ratio (υ) Kleinman Parameter (υ),

Anisotropy constant (A) Lames Coefficient (υ and µ), and Shear Constant (C/ ) in (GPa)

33
CHAPTER – 4 Results and Discussion

Table 4.4 The obtained values of Transverse sound velocity (υ s), longitudinal sound velocity

(υ l), average sound velocity (m) in m/s, and Debye temperature (D) in K of BiFeO3 and

BaTiO3

34
CHAPTER – 4 Results and Discussion

35
CHAPTER – 5 CONCLUSION

CHAPTER – 5

CONCLUSION
The structural, elastic, and mechanical calculations are performed using GGA. Structural

parameters such as lattice constants, internal parameter (µ), and tetragonal distortion (η) of

BFO and BTO are investigated. Our obtained results for this parameter are in good agreement

with the experimental results. Using GGA and mBJ potential electronic properties of these

compounds are determined. The calculated band structure of BFO shows that this compound

is metallic. While BTO gives an indirect band gap of 2.7 eV which is underestimated from

experimental results of 3.2eV but agrees with other calculated results. The results of band

structure calculations are also satisfied by the density of state calculations. Elastic and

mechanical calculations show that tetragonal BFO and BTO are elastically stable. The

smaller values of shear modulus and bulk modulus than Young's modulus indicate that these

compounds are stiffer. B/G value showed the brittle and ductile behavior of BFO and BTO

respectively. Resultanted Poisson's ratio confirms that these compounds are unstable against

external force and tendency to compressibility. It also indicates in these materials that the

inter-atomic forces are central. Lame's constants clear the anisotropic nature of these

compounds. Thermo-physical properties like transverse sound velocity (υs), longitudinal

sound velocity (υl ), average sound velocity (υm ), and Debye temperature θ(D) of the BTO

and BFO show that these materials are stiffer which satisfied the results obtained from

Poisson ratio. The high value of θ(D) indicates that these compounds exhibit high thermal

conductivity.

36
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