Optik - International Journal for Light and Electron Optics 211 (2020) 164611

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Original research article

Electronic, structural and optical properties of BaTiO3 doped with

T
lanthanum (La): Insight from DFT calculation
Muhammad Rizwana, Hajraa, I. Zebab, Muhammad Shakila, S.S.A. Gillanic,*,
Zahid Usmand
a
Department of Physics, University of Gujrat, HH-Campus, Gujrat 50700, Pakistan
b
Department of Physics, Lahore College for Woman University, Lahore 54000, Pakistan
c
Department of Physics, GC University Lahore, Lahore 54000, Pakistan
d
Department of Physics, University of Education Lahore, DG Khan Campus 32200, Pakistan

A R T IC LE I N F O ABS TRA CT

Keywords: We have studied the barium titanate (BaTiO3) by using the CASTEP which based on density
Doping functional theory (DFT) under the correlation function of GGA and PBE. Material under study has
Density of states been doped by Lanthanum (La) at the sites of Barium (Ba). Before and after doping we have
Band gap calculated the different optical, structural and electronic properties and have been discussed in
Dielectric function
detail. After doping, reduction of band gap is noticed and as well as nature of band gap is also
Refractive index
changed from indirect band gap (IBG) to direct band gap (DBG). This variation in band gap has
Absorption
been explained clearly on the behalf of partially and total density of states. Refractive index (n ) is
2.598 for pure and 2.482 for doped system. Absorption peak also effected by inclusion of La.

1. Introduction

A compound having the structure like calcium titanate known as perovskites. It’s general formula which used is ABX3 [1]. In this
formula A and B are positive ions and X is negative charged atom which makes bond with cations. It also can be any halogen atom.
Perovskite is first discovered by Russian mineralogist Gustave Rose from Ural mountain in Russia. It was named after Russian
mineralogist Lev Perovski. SrTiO3 is considered as an ideal perovskite and its structure is cubic [2]. In this cubic isometric structure,
Ti ions are located at corners and Sr ion is body centered (BC). The oxygen is face centered (FC) at twelve edges of cube which give us
corner shared strings of TiO6 octahedra and it extends in three dimensions.
Perovskite family has many oxides like BaTiO3, CaTiO3 exhibit as an insulator, some behaves as metals and some shows magnetic
behavior and these are all transition metal oxide [3]. Perovskite of the form ABO3 are considered as the most interesting materials for
investing and exploring the properties due to number of application in electronics and optoelectronic devices [4–6].
BaTiO3 is a synthetic perovskite that crystalizes itself in ideal perovskite structure or in hexagonal modification [7]. Goldschmidt
firstly studied and prepared synthetic perovskites on varying composition together with Barium titanate. However, the past of Barium
Titanate is meticulously related with mica which was only insulator material (with dielectric constant of 10) used in capacitors.
Scientists were finding material with high dielectric constant (starting from 80). In 1940−41 Germany reported different alkaline
earth titanate in production. Wainer and Solomon identified BaTiO3 has possibly high dielectric constant [8]. After this many sci-
entists in different labs declared it as a most suitable insulator for dielectric with high dielectric constant. It is a perovskite which exist

⁎
Corresponding author.
E-mail address: [Link]@[Link] (S.S.A. Gillani).

[Link]
Received 4 February 2020; Accepted 20 March 2020
0030-4026/ © 2020 Elsevier GmbH. All rights reserved.
M. Rizwan, et al. Optik - International Journal for Light and Electron Optics 211 (2020) 164611

Fig. 1. Structure of cubic BaTiO3 [9].

in different phases at different temperatures e. g cubic structure exist at 120 °C, and it is most stable state and as temperature is
decreased it undergoes three ferroelectric phases e. g below 120 °C it shifts into tetragonal structure which exist down to 5 °C [2].
Barium titanate exists in five different polymorphic crystalline forms; there are three (tetragonal, orthorhombic, and rhombo-
hedral) which are ferroelectric, and two paraelectric (cubic as well as hexagonal). The paraelectric cubic form of BaTiO3 belongs to
pm3m space group. BaTiO3 cubic unit cell consists of five atoms. In its structure Ba is placed at origin (0.0,0.0,0.0) a, Ti sitting at body
center and oxygen is face centered [8] (Fig. 1).
It is utilized in several application like capacitors, piezoelectric sensors, transducer, thermistors, mover of energy etc. [10–13]. In
multilayer capacitor, the BaTiO3 is used as dielectric material because of high capacitance [14]. BaTiO3 also offers better electrical
property and mechanical properties at room temperature [15].
Pure BaTiO3 shows a great variation in dielectric constant. For the modification of the properties and for broaden the number of
applications the BaTiO3 is doped with impurities. Adding of PbTiO3 rises the transformation (Curie) temperature [16–19]. The Excess
of TiO2 enhances the solubility of CeO2 in BaTiO3 [20,21]. The niobium shows a notable influence on the dielectric properties of
BaTiO3 [22]. Benlahrache et al. [22–24] found that by adding NaNbO3 exhibits a significant variation of the microstructure and also
increases dielectric constant. We have noticed that lanthanum with symbol La with atomic number 57 and most abundant rare earth
elements [25]. Its physical appearance is white silvery metallic. Lanthanum has 57 electrons revolving around the nucleus and its
configuration is 1s22s22p2 3s23p63d104s24p64d10 5s25p65d16 s2 and its more compact form as [Xe] 5d16 s2. Three electrons in valence
shell. One electron in 5d and two electrons in 6 s subshell are responsible for chemical properties and form +3 oxidation state. As we
want to dope lanthanum in the place of barium, and it has radius close to the Ba. It may result in significance change in structure and
microstructure. This will change the band structure and ultimately change in dielectric constant [26,27].

2. Computational details

CASTEP program was used in material studio package to study the structural, electronic and optical properties of BaTiO3, which
follows quantum mechanical codes and specially developed for band gap and bond lengths investigation. This programme was first
developed by Payne and his companions in the beginning of 1990’s [28]. With the help of DFT, this Programme is used for designing
different materials and for doping. These materials can be crystalline solids, amorphous solids, molecules etc. The whole work
occupies DFT plane-wave pseudo/full potential method, which permits to perform first principles calculations that discover the
crystals properties and measures the dielectric constant which describes the optical properties of material.
BaTiO3 exist in cubic structure at 120 °C with space group pm3m. In this structure Ba locates at corners, Ti is BC and oxygen are
FC. The lattice constant, we have calculated is 4.034 Å. Before understanding the doping of La at Ba sites, we formed the supercell
study method to evade the boundary effects. The host compound was doped with La at Ba positions and k-mesh 2×2×1 of supercell
was utilized for calculation as illustrated in Fig. 2.
We have completed the calculations by using CASTEP which follows DFT including plane-wave-pseudopotential approach. Plane-
wave-pseudopotential approach guarantees rapid calculations with better efficiency. It has considered that a core of ion is made by
interactions of valance electron and nuclei. The ultrasoft pseudopotential (USP) put forward by Perdew-Burke-Ernzerhof (GGA-PBE)
has been utilized to confrontation of electron-ion interaction and generalized gradient approximation(GGA) and also electron ex-
change interaction. Cut-off energy for this calculation was set to 340 eV. Electronic configuration of Ba is 1s22s22p63s23p6
3d104s24p64d105s25p66 s2 and compact form is [Xe] 6 s2 where configuration of lanthanum is 1s22s22p2
3s23p63d104s24p64d105s25p65d16 s2. The single point energy calculation has been done after accomplishing the geometry optimi-
zation. In this calculation self-consistent energy convergence accuracy was set as 5 × 10−5eVatom-1 and the remaining forces on the
atoms have been considered below than 2 meV/Å while studying the geometry optimization for the structure of pure and doped
system.

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M. Rizwan, et al. Optik - International Journal for Light and Electron Optics 211 (2020) 164611

Fig. 2. Supercell of BaTiO3 (a) and La-doped supercell of BaTiO3 (b).

3. Result and discussion

3.1. Geometry optimization

From Birch-Murnaghan equation of state [29] the lattice parameters of BaTiO3 have been optimized i.e a = b = c =4.034 Å. this
calculated value of lattice constant in our work is approximately same as experimentally reported 4.00 Å [30]. The difference
between experimental and our calculated value is just 0.034 Å (less than 1%). This shows the cogency of this work. Earlier theo-
retically conveyed lattice constants are a = b = c = 4.03 Å [31,32] which are in best agreement with our calculated value and the
difference is only 0.004 Å. Lattice constants (a = b = c = 3.971 Å) of La doped BaTiO3 shows the reduction in lattice parameters as
compare to pure BaTiO3. Table 1 contains the lattice parameters as well as volume of reported theoretically and experimentally
values and current values of pure and doped systems. The volume for unit cell of pure material is 65.6459 Å3 and for La doped BaTiO3
material is 62.6180 Å3.

3.2. Band structure

Band structure of materials is studied since it reveals a useful information to understand the nature of paraelectricity and fer-
roelectricity. Band structure of pure BaTiO3 and doped BaTiO3 are shown in Fig. 3(a–b). Calculations for electronic band gap diagram
of cubic BaTiO3 in direction of Brillouin zone with high symmetry is illustrated in Fig. 3(a–b). Maxima of VB which has been occurred
at fermi level at 0 eV is directed by the Oxygen O-2p states. whereas the minima of CB lie at G point and dominated by Titanium (Ti)
3d-states. Fig. 3(a) shows that electronic band for pure BaTiO3 in this study is indirect with the value 1.723 eV at R-G points which is
very close to reported value 1.778 eV [9]. The experimental band gap of BaTiO3 ∼3.2 eV [34,35] and it is smaller than calculated
value in this study which is due to pd repulsion of anion and cation of Generalized Gradient Approximation implementation.
In Fig. 3(b) after doping BaTiO3 with Lanthanum (La) at Barium sites, calculations show that electronic band structure has shifted
towards conduction band and its value at G is 1.569 eV. calculation shows that the nature of band structure has been changed from
indirect (pure) to direct in doped material. Minimum energy required for excitation of electron is determined by band gap in
insulators and semiconductors, but it cannot completely describe that phonon will be absorbed by material or not. It is noticed that
indirect band gap shows the weak optical transition due to finite momentum. The shifting of band gap in BaTiO3 after doping La
indicates the enhancement of conductivity of material due to readily of hole electron recombination in direct band gap.

Table 1
Volume of unit cell and optimized parameters of pure and La-doped BaTiO3.
Lattice Parameters (Å) Volume (Å3)

a b c

Earlier Reported (Pure) [31,32,33] 4.03 4.03 4.03 65.4508

Experimental Value [30] 4.00 4.00 4.00 64.00
Current Study (Pure) 4.034 4.034 4.034 65.6459
Current Study 3.971 3.971 3.971 62.6180
(Doped)

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M. Rizwan, et al. Optik - International Journal for Light and Electron Optics 211 (2020) 164611

Fig. 3. (a) Band Structure of pure BaTiO3 and (b) La-doped BaTiO3.

Fig. 4(a–f) demonstrate the partial and total density of states for pure and La-doped BaTiO3 systems. Under the study pure BaTiO3
has the main contribution of 6p states in the valance band (VB), and it has changed after La-doping. We have noticed that the top of
VB demonstrates main contribution by p-density of states and d-density of [Link] Fig. 4-b the density of states has been increased
after doping. It has been noticed that p-DOS and d-DOS have dominant contribution in Fig. 4a. In Fig. 4d La has sharp peak of d-DOS.
Fig. 4c illustrates that peak of d-DOS become sharper by doping than pure material. Therefore, the main contribution of d-DOS from 0
to 10 eV may be the reason of reduction of band gap. Hence, we have concluded the two results of La doped BaTiO3. First is that the
band gap reduction after doping La at Ba sites. Secondly, band gap also transformed into direct band gap. Therefore, La doped BaTiO3
will be more suitable for optoelectronic devices.

3.3. Optical properties

Optical properties of BaTiO3 can be calculated from real and imaginary parts of dielectric functions (DF) i.e. loss function,
reflectivity R(ω), refractive index n(ω) and extinction coefficient k(ω) and are related with following relations [36,37].
2
⎡ ε (ω) − 1 ⎤
R (ω) = ⎢ ⎥
⎣ ε (ω) + 1 ⎦ (1)

ε2 (ω)
L (ω) =
ε1 (ω)2 + ε2 (ω)2 (2)

1 1
k (ω) = [ ε1 (ω)2 + ε2 (ω)2 − ε1 (ω)] 2
2 (3)

Fig. 4. (a-f) Partial density of states for BaTiO3, for Ba, for Ti, for O, for La respectively and total density of states for BaTiO3 (f). (pure in black and
doped in red). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

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M. Rizwan, et al. Optik - International Journal for Light and Electron Optics 211 (2020) 164611

Fig. 5. (a-f) Optical properties of BaTiO3 for pure (black) and doped (red) with lanthanum (La). (For interpretation of the references to colour in this
figure legend, the reader is referred to the web version of this article.)

1 1
n (ω) = [ ε1 (ω)2 + ε2 (ω)2 − ε1 (ω)] 2
2 (4)

n + iK − 1
r (ω) =
n + iK + 1 (5)

ε (ω) = n (ω) + iK (ω) = N (ω) (6)

ε1 (ω) = n2 − K 2 (7)

ε2 (ω) = 2nK (8)

ε (ω) = ε1 (ω) + iε2 (ω) is equation of dielectric function, where ε1 (ω) represents real part of equation and ε2 (ω) represents imaginary
part and it is principally related to the electronic response. The ε2 (ω) can be found by the momentum matrix elements between the
occupied and unoccupied wave functions and given as [38].
ve 2
ε (ω) =
2πħm2ω2
∫ d3k∑ Bm,n |<kn| p|kn" > | × f (kn)(1 − f (kn′)) δ (Ekn − Ekn − ħω) ′
m, n

In Eq. (8), ħ ω is the incident phonon energy, momentum operator is represented by

∂
p = ( ħ i ) ( ∂x ) , wave function of crystal and fermi function is represented by | kn > and f (kn ) respectively. From ε1 (ω) , we can
calculate the ε2 (ω) using Kramer-Kronig relations. Other optical constants are calculated from ε1 (ω) and ε2 (ω) are listed above. The
ε1 (ω) and ε2 (ω) are shown in Fig. 5(a–b). ε1 (ω) tells us about the polarization and ε2 (ω) corresponds to loss of energy in medium and
always positive. The ε2 (ω) is zero at 0 eV in case of doped where loss of energy is occurring at 0 eV. In Fig. 5b ε2 (ω) shows three
prominent peaks at 3.8 eV, 7.5 eV and 18.6 eV after doping and are relating with three absorption peaks. La doped BaTiO3 has a fine
edge around the 4.3 eV corresponding to pure system, whereas in doped system it has been reduced. For pure case the absorption
peak lies at 19.1 eV and has also been reduced for doped system which might be by reason of reduction of BG and transferring of IBG
to DBG. This optical absorption involves highest VB O-2p to CB Ti-3d states [39].
Loss function of energy are those energy areas in atom, where electrons are not characteristically bound in their lattice sites and
shows plasma frequency when exposed to light [40]. In Fig. 5d we observe that peak of loss function is sharper than pure system and
it has been shifted towards higher energy relating with major peak of ε2 (ω) . In Fig. 5e one can also observe that reflection peaks are
maximum where absorption is minimum.
Complex refractive index N = n + ik consist of refractive index (n ) and its imaginary part is extinction coefficient k which is
frequency (energy) dependent. In Fig. 5f the refractive index for pure is 2.598 and for doped system is 2.482 which is slightly less
than pure system.

4. Conclusion

Structural electronic and optical properties of pure BaTiO3 and doped with La have been investigated by first principles calcu-
lations. The properties studied with regarding of La doped system shows good agreement with earlier reported results. The BG of pure
and doped BaTiO3 have been calculated. The band structure has been elaborated in regarding with TDOS and PDOS. Band gap has

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M. Rizwan, et al. Optik - International Journal for Light and Electron Optics 211 (2020) 164611

been decreased with La-doping and conduction band has been partially shifted towards valance band with appearance of new gamma
points. The band gap reduction is due to La-5d states which have more contribution in conduction band. All the optical properties
including DF, absorption, refractive index etc. are also changed as well and well corelated with the electronic and structural de-
terminations.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to
influence the work reported in this paper.

Acknowledgement

The corresponding author would like to thank Higher Education Commission (HEC) of Pakistan for financial support under the
grant number 6934/NRPU/HEC.

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