crystals

Article
First-Principle Study on Correlate Structural, Electronic and
Optical Properties of Ce-Doped BaTiO3
Haojie Yue 1 , Kailing Fang 1 , Tiantian Chen 1 , Qinfang Jing 1 , Kun Guo 1, * , Zhiyong Liu 1 , Bing Xie 1 , Pu Mao 1 ,
Jinshan Lu 1 , Francis Eng Hock Tay 2 , Ivan Tan 3 and Kui Yao 3

1 School of Materials Science and Engineering, Nanchang Hangkong University, Nanchang 330063, China
2 Department of Mechanical Engineering, National University of Singapore, 9 Engineering Drive 1,
Singapore 117575, Singapore
3 Institute of Materials Research and Engineering, A*STAR (Agency for Science, Technology and Research),
2 Fusionopolis Way, Innovis, Singapore 138634, Singapore
* Correspondence: guokun@nchu.edu.cn

Abstract: The structural, electronic, and optical properties of pure and Ce-doped BaTiO3 were
investigated based on first-principle calculation. Here, we concentrate on understanding the effect
of the substitution of Ce for Ba and Ti sites in the equilibrium lattice parameters, DOS, electronic
band structure, and optical performance of the materials. The crystal structures with a 12.5% doping
ratio at different sites were constructed by superseding an atom of Ba (or Ti) site with a Ce atom and
investigating the optimized crystal structure parameters. The substitution of Ce leads to a reduction
in the band gap by inducing the movement of the conduction band minimum (CBM) and valence
band maximum (VBM). The reduction in the band gap has been shown to be beneficial in increasing
electrical conductivity. The density of states of the materials was calculated to gain insight into the
valence band, conduction band, and contribution of each orbital to the total density of states in the
electronic structure. The charge density, Mulliken charges, and bond overlap populations of pristine
and Ce-doped BaTiO3 were calculated to understand the nature of chemical bonds before and after
Citation: Yue, H.; Fang, K.; Chen, T.;
doping. In addition, the optical properties of the materials were calculated, and the substitution of
Jing, Q.; Guo, K.; Liu, Z.; Xie, B.; Mao, Ce for Ba site increased the static dielectric constant. In contrast, it decreased when Ce was doped
P.; Lu, J.; Tay, F.E.H.; et al. into the Ti site. The substitution of Ce for different sites reduced the reflectivity of the material, while
First-Principle Study on Correlate the transparency of the materials before and after doping was almost the same. The materials were
Structural, Electronic and Optical transparent to incident light when the photon energy was below 10 eV, whereas opacity was in the
Properties of Ce-Doped BaTiO3 . ultraviolet range of 10–13 eV and beyond 20 eV. The theoretical calculation of different properties
Crystals 2023, 13, 255. https:// provides a new idea for the theoretical study of the BaTiO3 -based system.
doi.org/10.3390/cryst13020255

Academic Editors: Luisa De Marco, Keywords: first-principle; BaTiO3 lead-free ceramic; perovskite structure; electronic property;
Jinyan Zhao, Zenghui Liu and Ting optical property
Zheng

Received: 14 December 2022

Revised: 28 January 2023
1. Introduction
Accepted: 30 January 2023
Published: 1 February 2023 With the advent of Industry 4.0, there will be a strong demand for numerous func-
tional devices, such as sensors, microactuators, and ultrasonic transducers, which utilize
piezoelectric ceramics with excellent and reliable properties [1–7]. Lead-based piezoelectric
materials, such as Pb(Zr, Ti)O3 , dominate the commercial market owing to their superior
Copyright: © 2023 by the authors. piezoelectric performance and temperature stability. However, lead-based piezoelectric
Licensee MDPI, Basel, Switzerland. materials bring severe environmental concerns because of the toxic lead components. Thus,
This article is an open access article developing lead-free piezoelectric materials with excellent performance has always been
distributed under the terms and an essential topic. The BaTiO3 -based system is one of the most extensively investigated
conditions of the Creative Commons lead-free piezoelectric material systems. The Curie temperature (TC ) of BaTiO3 is ~120 ◦ C,
Attribution (CC BY) license (https://
and some ion doping even lowers the TC of BaTiO3 -based ceramics to near ambient temper-
creativecommons.org/licenses/by/
ature [8–11]. In addition, due to the excellent dielectric and piezoelectric and ferroelectric
4.0/).

Crystals 2023, 13, 255. https://doi.org/10.3390/cryst13020255 https://www.mdpi.com/journal/crystals

Crystals 2023, 13, 255 2 of 13

performance at room temperature, BaTiO3 -based ceramics are widely applied for capacitors
and promising for electro-optical applications.
When the temperature is below 120 ◦ C, the Ti4+ ions located in the body center of the
crystal cell move close to a certain vertex of the surrounding oxygen octahedron, result-
ing in the entire crystal structure gradually changing from cubic to tetragonal. However,
BaTiO3 with the tetragonal structure is only stable when the temperature range is between
5 ◦ C and 120 ◦ C. As the temperature continues to decrease, a transition of crystal structure
from tetragonal to orthogonal will occur [12,13]. Due to the practical restrictions, various
chemical dopants have been applied to enhance the properties of BaTiO3 ceramics. On the
one hand, doping causes a change of TC in BaTiO3 , which can be explained straightfor-
wardly by ion-size effects and modifications to the tolerance factor [14–16]. On the other
hand, some doping can significantly increase the conductivity of BaTiO3 , which can be
attributed to the donor electron compensation effect [17]. In particular, rare-earth elements
have become effective dopants due to their strong electronic charges and large ionic ra-
dius BaTiO3 is often doped with rare-earth elements to improve mechanical and electrical
properties. Researchers have conducted numerous experimental studies on the mechanism
and physicochemical properties of BaTiO3 -based systems by various dopants. Some efforts
have been made to prepare Ce-doped BaTiO3 ceramic powders using the sol-gel method.
High dielectric constant and low dielectric loss were achieved at the Curie temperature
of 22 ◦ C [18]. (Ba1−x Cex )TiO3 and Ba(Ti1−y Cey )O3 ceramic powders, fabricated by the
liquid mix method, were investigated for their high-temperature equilibrium electrical
conductivity in terms of oxygen partial pressure, P(O2 ), and composition [19]. With the
increasing content of the Ce element, the Tc of BaCex Ti1−x O3 ceramics decreased and a
ferroelectric relaxation transition occurred [20]. However, the theoretical calculation studies
on the effects of rare earth doping into BaTiO3 are insufficient.
This paper demonstrated a systematic analysis of the structural, electronic, and optical
properties of Ce-doped BaTiO3 based on the first-principle method. In order to further
understand the mechanism of BaTiO3 and the effects of different sites doping on its perfor-
mance, theoretical calculations were performed for both Ba-site and Ti-site doping. The
effects of Ce doping on the crystal structures and electronic and optical properties of BaTiO3
are presented in detail.

2. Computational Details
The simulation calculations were based on density function theory (DFT) using
the Cambridge Serial Total Energy Package (CASTEP). The Ultrasoft pseudopotential
(UPP) [21] generalized gradient approximation (GGA) was adopted to deal with the inter-
action between ions and electrons, and Perdew–Burke–Ernzerhof (PBE) was to cope with
the exchange-correlation function [22–24]. The Hubbard energy U = 4 eV for Ti 3d orbitals
and U = 5 eV for Ce 4f orbitals were applied to deal with the on-site Coulomb interaction
and describe the exchange-correlation potential [25–28]. The cutoff energy was set to 580 eV
for BaTiO3 and Ce-doped BaTiO3 . The minimum energy tolerance was 10−6 eV per atom
and the force tolerance was 2 meV/Å. To investigate the irreducible Brillion zone (BZ),
Monkhorst-pack grids of 7 × 7 × 7 and 4 × 4 × 4 were implemented for pure BaTiO3 and
Ce-doped BaTiO3 , respectively [29,30].
The tetragonal unit cell of pure BaTiO3 belongs to the space group P4mm, containing
5 atoms. For Ce-doped BaTiO3 , Considering the practicability and cost of calculation,
a model with 40 atoms was constructed based on a 2 × 2 × 2 BaTiO3 supercell. The
crystal structures with a 12.5% doping ratio at different sites have been constructed by
superseding an atom of the Ba (or Ti) site with a Ce atom. Due to the symmetry of the
crystal structure and atomic equivalence, there is only one model for one-eighth of Ba or
Ti sites to be replaced by Ce atoms. Correspondingly, the concentrations are Ba0.875 Ce0.125
TiO3 for substituting the Ba site and BaTi0.875 Ce0.125 O3 for substituting the Ti site. As the
valence electrons play a decisive role in the physicochemical properties of materials, only
Crystals 2023, 13, 255 3 of 13

the valence electrons were considered in these calculations. The atomic valence electrons
involved in these materials are as follows
Ba: 6s2
Ti: 3d2 4s2
O: 2S2 2P4
Ce:4f1 5d1 6s2
The valency of cerium considered here was +3 and +4 when the cerium ion was
substituted for Ba2+ sites or Ti4+ sites, respectively. One measure of the stability of a
structure is the tolerance factor, which may be computed from

r0 + r A
t= √ (1)
2(r0 + r B )

where r A and r B are the ionic radius of A and B sites, respectively, whereas r0 is the ionic
radius of oxygen. For stable perovskite structure, the tolerance factor is considered in
the range of 0.85 < t < 1.10, and the high symmetry cubic structure value corresponds
to t = 1.00. The tetragonal symmetry of BaTiO3 has a tolerance factor of 1.06. When
the tolerance factor t deviates from this range, the perovskite crystal structure will be
distorted due to the tilt of the BO6 octahedron, inducing a crystal structure transition to a
non-perovskite structure [31].

3. Result and Discussion

3.1. Geometry Optimization
As presented in Table 1, the optimized lattice parameters and average bond length
of pure BaTiO3 and Ce-doped BaTiO3 were calculated. Meanwhile, the estimated values
and the experimental results were compared. The computed lattice parameter values for
pure BaTiO3 corresponded well with the previous theoretical results but were significantly
larger than the experimental result. Due to there being a wrong self-interaction in the GGA
method, the interaction between the electron and itself is improper, the delocalization of
the electron is enhanced, and the lattice parameters are larger than the real system. For
Ce-doped BaTiO3 , the lattice parameters were found to be slightly changed at both the A
and B sites, which were relatively compatible with the experimental results published in the
literature [19]. Figure 1 shows the crystal structures of pure BaTiO3 and Ce-doped BaTiO3
at different sites. For Ba0.875 Ce0.125 TiO3 , the lattice parameter a is somewhat larger than that
of pure BaTiO3 , while the lattice parameter c and cell volume (V) are marginally smaller.
In the case of BaTi0.875 Ce0.125 O3 , the parameters a, c, and volume (V) are all greater than
that of pristine perovskite. The Ti-O bond length was determined by the octahedral sites
occupied by Ti atoms, whereas the Ba-O bond length was associated with the dodecahedral
sites occupied by Ba atoms. The assessed Ba-O and Ti-O bond lengths of the optimized pure
BaTiO3 were 2.823 Å and 2.017 Å, respectively. The results were in good agreement with
previous theoretical findings and relatively consistent with the experimental results [32–34].
For the incorporation of the Ce element, both the Ti-O and Ba-O bond lengths significantly
increased due to the lattice distortion. It can be concluded that there is a long-range effect
of Ce doping on the perovskite, resulting in a modification of the interatomic bond lengths.

Table 1. Optimized lattice parameters, cell volume, and average bond length for pristine and Ce-
doped BaTiO3 .

Compound Method a (Å) c (Å) V (Å3 ) Ba-O(Å) Ti-O (Å) Ce-O (Å)
4.023 4.161 67.344 2.823 2.017
GGA-PBE 4.007 [32] 4.186 [32] 67.211 [32]
BaTiO3
3.967 [33] 4.232 [33] 66.599 [33]
Experiment 4.000 [34] 4.024 [34] 64.384 [34]
Ba0.875 Ce0.125 TiO3 4.033 4.063 66.085 2.856 2.024 2.619
GGA-PBE
BaTi0.875 Ce0.125 O3 4.079 4.240 70.546 2.854 2.078 2.258
 4.023 4.161 67.344 2.823 2.017
GGA-PBE 4.007 [32] 4.186 [32] 67.211 [32]
BaTiO3
3.967 [33] 4.232 [33] 66.599 [33]
Experiment 4.000 [34] 4.024 [34] 64.384 [34]
Ba0.875Ce 0.125TiO
Crystals 2023,313, 255 4.033 4.063 66.085 2.856 2.0244 of 13 2.619
GGA-PBE
BaTi0.875Ce0.125O3 4.079 4.240 70.546 2.854 2.078 2.258
Figure 1. Crystal structures of (a) pure BaTiO3, (b) Ba site substitution, and (c) Ti site substituti
Ba is dark blue, Ti is purple, O is light green, and Ce is red.

3.2. Electronic Properties

The electronic band structure of pristine and Ce-doped BaTiO3 is presented in Figu
2. The energy band gap of pristine BaTiO3 reached 2.081 eV, which was in accordance w
the theoretical work [32]. Moreover, the band gap was indirect in nature as the CBM w
obtained at point Γ, and the VBM was obtained at point A. For Ce-doped BaTiO3, it w
evident that the substitution of Ce for the Ba site slightly decreased the band gap fro
Figure
2.081 eV 1. Crystal
Figure to1. 2.023
Crystalstructures
eV, whereas
structures of (a)pure
of (a) pure
the BaTiO
band
BaTiO (b)3,Ba
3 , gap (b)
was Basubstitution,
site site substitution,
significantly andsubstitution.
and (c)decreased
Ti site (c) Ti site Ba
from substituti
2.081 eV
Ba is dark
1.789 is dark
eV whenblue, TiCe
blue, Ti is purple,
is purple, O
replaced O is
is light
thelight
Ti green,
green, and
site. The Ce andreduction
is Ce is red. in band gap indicated easier int
red.

and intra-band
3.2. Electronicjumps Propertiesof electrons and increased electrical conductivity of the mater
3.2. Electronic
which was Properties
Theconsistent with the experimental work [19]. The
electronic band structure of pristine and Ce-doped BaTiO 3 isdecrease
presented in the band
in Figure 2. gap
The electronic
The
Ce-doped energy band
BaTiO3 was band
gap of structure
pristine
caused by theof pristine
BaTiO reached
increase
3 and
2.081 Ce-doped
in bondeV, which
lengths. BaTiO
was Due3 is
in to presented
accordance with
increases in inte Figu
2. The the theoretical
energy band workgap[32].
of Moreover,BaTiO
pristine the band gap was2.081
reached indirecteV,inwhich
nature as was thein CBM was
accordance w
tomic distances, it resulted in tight binding of electrons in valence shells, which requi
3
obtained at point Γ, and the VBM was obtained at point A. For Ce-doped BaTiO3 , it was
the theoretical
more energythat
evident forwork [32]. Moreover,
conversion
the substitutioninto of Cethe the band gap
forconduction
the Ba site slightly
wasdecreased
electrons indirect in nature
[35]. the as the CBM w
band gap from
obtained
The at
eVpoint
2.081substitution
to 2.023 Γ,eV,
and
of theCe
the
whereas VBM wasgap
element
the band obtained
for was the Baatsite
point
significantly alsoA.induces
For Ce-doped
decreased fromthe2.081
CBM BaTiO
eV and , it w
to 3VBM
evident
move to that
1.789 the the substitution
smaller
eV when energy states
Ce replaced ofTiCe
the andforThe
site. the
the Ba site inslightly
transition
reduction of the
band gapdecreased
band the band
gap easier
indicated from gap to
indirect
inter- fro
2.081as
rect, and
eVtheintra-band
to CBM
2.023 and jumps of
eV, whereas electrons
VBM arethe and increased
bandatgap
gained thewas electrical
same conductivity
significantly of
decreased
point Γ. Moreover, the material,
thefrom 2.081 eV
substitution
which was consistent with the experimental work [19]. The decrease in the band gap of Ce-
1.789
Ce for eVthewhenBa site Ce results
replaced in the
the Ti site. The reduction
conduction band overinthe bandFermigaplevel
indicated easier int
and produces
doped BaTiO3 was caused by the increase in bond lengths. Due to increases in interatomic
and intra-band
impurity band.
distances, jumps
For
it resulted oftight
Ce-doped
in electrons
at theand
binding Ti increased
site,
of electrons the in electrical
process
valence reduces
shells,conductivity
the CBM
which requires ofmore
the mater
compared to
which
pure energywas
perovskite, consistent with
while the
for conversion intobandthe experimental
gap is still
the conduction work
indirect.
electrons [19].
[35]. The decrease in the band gap
Ce-doped BaTiO3 was caused by the increase in bond lengths. Due to increases in inte
tomic distances, it resulted in tight binding of electrons in valence shells, which requi
more energy for conversion into the conduction electrons [35].
The substitution of the Ce element for the Ba site also induces the CBM and VBM
move to the smaller energy states and the transition of the band gap from indirect to
rect, as the CBM and VBM are gained at the same point Γ. Moreover, the substitution
Ce for the Ba site results in the conduction band over the Fermi level and produces
impurity band. For Ce-doped at the Ti site, the process reduces the CBM compared to
pure perovskite, while the band gap is still indirect.

Figure 2. Electronic
Figure band
2. Electronic bandstructures of(a)
structures of (a)pristine
pristine BaTiO
BaTiO , (b)
3 , (b)3Ba siteBa site doping,
doping, and (c) Tiand (c) Ti site dopi
site doping.

The substitution of the Ce element for the Ba site also induces the CBM and VBM
to move to the smaller energy states and the transition of the band gap from indirect to
direct, as the CBM and VBM are gained at the same point Γ. Moreover, the substitution
of Ce for the Ba site results in the conduction band over the Fermi level and produces an
impurity band. For Ce-doped at the Ti site, the process reduces the CBM compared to the
pure perovskite, while the band gap is still indirect.
In order to further understand the mechanism of electronic structure, the total density
of states (TDOS) and partial density of states (PDOS) of pristine and Ce-doped BaTiO3
were computed at the optimized crystal structure, as shown in Figure 3. For pristine
BaTiO
Figure 3 , it can beband
2. Electronic observed that Baofhas
structures (a)little contribution
pristine BaTiO3,to the
(b) BaCBM
site and VBM.and
doping, It just
(c) acts
Ti site dopi
as a charge balancer to balance the system charge [36]. All unoccupied Ti 3d states are
strongly hybridized with nearby O 2p states, and the CBM is mainly determined by the
 sity of states (TDOS) and partial density of states (PDOS) of pristine and Ce-doped BaT
were computed at the optimized crystal structure, as shown in Figure 3. For pristine
TiO3, it can be observed that Ba has little contribution to the CBM and VBM. It just acts
Crystals 2023, 13, 255 a charge balancer to balance the system charge [36]. All unoccupied Ti5 of 3d13 states
strongly hybridized with nearby O 2p states, and the CBM is mainly determined by
unoccupied Ti 3d transition metal states. As a result, the band gap is attributed to
energyunoccupied
magnitude Ti 3doftransition
Ti 3d and metal
O 2pstates. As For
states. a result, the band
Ce-doped BaTiOgap is3,attributed
as showntointhe Figure 3
energy magnitude of Ti 3d and O 2p states. For Ce-doped BaTiO
the main characteristics of CBM and VBM are consistent with pure BaTiO3. The VBM
3 , as shown in Figure 3b,c,
the main characteristics of CBM and VBM are consistent with pure BaTiO3 . The VBM is
still mainly hybridized by the Ti 3d and O 2p states, and the CBM is determined by the
still mainly hybridized by the Ti 3d and O 2p states, and the CBM is determined by the Ti
3d states andand
3d states thethe
presence
presence of theCe
of the Ce5d5d and
and 4f states.
4f states. The substitution
The substitution of Ba,
of Ba, which which resu
results
in the presence of impurity bands in the conduction band, is attributed to the metallizat
in the presence of impurity bands in the conduction band, is attributed to the metallization
of theofcrystal
the crystal structure.
structure.

Figure 3. The
Figure total
3. The density
total densityof
ofstates andpartial
states and partial density
density of states
of states of (a)3 ,BaTiO
of (a) BaTiO 3, (b)
(b) Ba site Ba site substitut
substitution,
and (c)
andTi(c)site substitution.
Ti site substitution.

For insight into the nature of chemical bonds before and after doping, the charge
For insight into the nature of chemical bonds before and after doping, the cha
density distribution maps of pure and Ce-doped BaTiO3 along the (0 0 1) plane have been
density distribution
calculated, mapsAs
respectively. ofshown
pure and Ce-doped
in Figure 4, in theBaTiO
presence3 along the
of O 2p and (0 Ti
0 1)
3d plane
hybrid have be
calculated,
states, Tirespectively.
and O atoms formAs weak
shown in Figure
covalent bonds,4,whereas
in the thepresence
Ba-O bondof O 2p and
shows Ti 3d hyb
an ionic
bond nature. When Ce was doped into the Ba and Ti sites, the nature
states, Ti and O atoms form weak covalent bonds, whereas the Ba-O bond shows an io of the ionic and weak
bondcovalent
nature.bonds
When between Ce and O was observed, respectively.
Ce was doped into the Ba and Ti sites, the nature of the ionic and we
In addition, as presented in Table S1, the Mulliken charges of pure and Ce-doped
covalent
BaTiObonds between Ce and O was observed, respectively.
3 were computed to quantify the number of charges transferred between atoms. It
Ina addition,
is as presented
necessary complement in electron
to the Table S1, thedensity
charge Mulliken mapscharges
of Figureof 4. pure and Ce-dop
The charge
BaTiO 3 were
spilling ofcomputed
the materialstowas
quantify the number
pretty low, of charges
which indicated transferred
that the basis set couldbetween
well atoms
is a necessary complement to the electron charge density maps of Figure 4. TiThe cha
represent the structural properties of electrons [37]. For pristine BaTiO 3 , both Ba and
atoms exhibit an electron loss, while the O atom is the opposite, indicating some electrons
spilling of the materials was pretty low, which indicated that the basis set could well r
have transferred to the O atom to form ionic bonding. The amount of charge transferred
resent thethe
from structural
O atom toproperties
the Ba atomof electrons
and Ti atom is [37].
1.44Forand pristine BaTiO3,which
0.74, respectively, both Ba and Ti ato
means
exhibit
thatan
theelectron
ionic bondloss, while
nature of thethe O bond
Ba-O atomis is the opposite,
greater than the Ti-O indicating
bond. As for some electrons ha
Ce-doped
BaTiO3 , the
transferred Mulliken
to the charge
O atom to of the Ce
form atom
ionic is 1.55 andThe
bonding. 0.92 amount
for Ba siteof
substitution and Ti
charge transferred fr
site substitution, respectively, while the charge transfer from Ba and Ti atoms to O atom
the O atom to the Ba atom and Ti atom is 1.44 and 0.74, respectively, which means t
change slightly compared to undoped. The overlap populations of pristine and Ce-doped
the ionic
BaTiObond nature of the Ba-O bond is greater than the Ti-O bond. As for Ce-dop
3 are listed in Table S2. The positive population number indicates that there is a
BaTiO3, the Mulliken charge of the Ce atom is 1.55 and 0.92 for Ba site substitution and
site substitution, respectively, while the charge transfer from Ba and Ti atoms to O at
change slightly compared to undoped. The overlap populations of pristine and Ce-dop
 BaTiO3 are listed in Table S2. The positive population number indicates that there i
covalent bonding between atoms, while the negative number shows that there is a mu
Crystals 2023, 13, 255 ally exclusive anti-bonding between atoms. In the case of the population equal 6 of 13 to zero

is considered to be an ideal ionic bonding, and the larger the population value,
stronger the effect of the bonds [38]. For pure BaTiO3, there is no covalent bond betw
covalent bonding between atoms, while the negative number shows that there is a mutually
Ba and O atoms but only an ionic bond, and there is a weak covalent bond between Ti a
exclusive anti-bonding between atoms. In the case of the population equal to zero, it is
O atoms. For Ba
considered 0.875
to be anCeideal
0.125TiO
ionic3,bonding,
except anti-bond,
and the largerthethepopulation of Ba-O
population value, and Ti-O bon
the stronger
rangethefrom
effect0.06 tobonds
of the 0.07 and[38]. 0For
to pure
0.64,BaTiO
respectively. The
3 , there is no resultsbond
covalent show that the
between Ba anddoping of
at the Ba site has exerted weak covalent bond characteristics between Ba and OOatoms a
O atoms but only an ionic bond, and there is a weak covalent bond between Ti and
atoms. For Ba0.875 Ce0.125 TiO3 , except anti-bond, the population of Ba-O and Ti-O bonds
reduced the covalent bond strength between Ti and O atoms. Moreover, the populat
range from 0.06 to 0.07 and 0 to 0.64, respectively. The results show that the doping of Ce at
of the
theCe-O
Ba sitebond almost
has exerted all approximates
weak zero, which
covalent bond characteristics indicates
between that
Ba and the Ce-O
O atoms and bond
mainly an ionic band and weak covalent bond nature. In terms
reduced the covalent bond strength between Ti and O atoms. Moreover, the population of BaTi 0.875 Ce 0.125O3, it

be concluded
of the Ce-Ofrom the results
bond almost that the doping
all approximates zero, whichof Ce at Ti that
indicates sitethealso
Ce-Oexerted
bond has a weak T
mainly an ionic band and weak covalent bond
covalent bond and reduced the covalent bond strength of the Ti-O nature. In terms of BaTi Ce
bond.
0.875 O
0.125The3 , it
populat
can be concluded from the results that the doping of Ce at Ti site also exerted a weak Ti-O
of the Ce-O bond is significantly greater than Ce doping at the Ba site, which indica
covalent bond and reduced the covalent bond strength of the Ti-O bond. The population of
that the Ce-Obond
the Ce-O bond exhibits a strong
is significantly covalent
greater than bond
Ce doping at and
the Baweak ionic indicates
site, which bond nature. that The c
culated results
the Ce-O ofexhibits
bond Mulliken charges
a strong and
covalent overlap
bond populations
and weak accordThe
ionic bond nature. with the charge d
calculated
results
sity map. of Mulliken charges and overlap populations accord with the charge density map.

Figure 4. Charge
Figure 4. Chargedensity mapsinin
density maps thethe
(0 0(0
1) 0 1) plane
plane for (a) BaTiO
for (a) pristine pristine
3 , (b)BaTiO , (b) Ba site
Ba site 3substitution, substitut
and
and (c)
(c) Ti sitesubstitution.
Ti site substitution.
3.3. Optical Properties
3.3. Optical properties
In order to investigate the optical properties of the materials, the dielectric function,
In order toabsorption,
reflectivity, investigate the optical
refractive index, properties of thewere
and loss function materials, theThe
calculated. dielectric
optical functi
properties are all functions of frequency or photon energy, and all
reflectivity, absorption, refractive index, and loss function were calculated.the properties of the
The opt
medium were computed from the complex dielectric function given as:
properties are all functions of frequency or photon energy, and all the properties of
medium were computed from the ε(ωcomplex
) = ε R (ω )dielectric
+ iε I (ω ) function given as: (2)

where ε R (ω ) and ε I (ω ) represent thereal ( )

 and ( )
=  Rimaginary
 + i I  ( )
parts of the complex dielectric
function, respectively. The imaginary part is related to momentum matrix elements. If
where 𝜀𝑅 (𝜔) and
the imaginary part𝜀ε𝐼 (I (𝜔
ω)) ofrepresent thefunction
the dielectric real and imaginary
is known, parts
the real partofε Rthe
(ω ) complex
can be die
tric function,
obtained viarespectively. The imaginary
the Krammers–Kroning relationspart is related toother
[39]. Furthermore, momentum matrix elemen
optical parameters
If thecan also be calculated
imaginary part 𝜀by the concerned formulas. The relations of all optical parameters
𝐼 (𝜔) of the dielectric function is known, the real part 𝜀𝑅 (𝜔)
such as refractive index n(ω ), extinction coefficient k(ω ), absorption coefficient α(ω ),
be obtained via the Krammers–Kroning relations [39]. Furthermore, other optical para
reflectivity R(ω ) and energy loss function L(ω ) are shown as follows [40,41]:
eters can also be calculated by the concerned formulas. The relations of all optical para
Z ∞ 0
ε 1 (ω 𝑛(𝜔), 𝑘(𝜔), absorption
eters such as refractive index 2 (ω )
) = 1 + extinction
ω ε 2coefficient
ρ0 0 2 2
dω (3)coeffici
0 ω −
𝛼(𝜔), reflectivity 𝑅(𝜔) and energy loss function 𝐿(𝜔) are shown as follows [40,41]:
π ω
C 2
( )
Z
| Mc,v2(k)|2 •δ 
Eck' 
−2E
 
∑ ( )
k 3


ε 2 (ω ) = v − }ω d k (4)
ω c,v  (
2
2π =
3 1 +  d
BZ 1 ) 
0
0  ' −
2 2

 2 ( ) =
C
2
  (2 )
2
3
2
(
M c,v (k ) •  Eck − Evk −  d 3k )
c,v BZ
Crystals 2023, 13, 255 7 of 13

 q 1/2
ε 1 (ω ) + (ε 1 (ω ))2 + (ε 2 (ω ))2
n(ω ) = √ (5)
2
v 
u q
2 2
(ε 1 (ω )) + (ε 2 (ω )) − ε 1 (ω )
u
u
t
K (ω ) = (6)
2
√ q 1/2
2
α(ω ) = 2ω ε 1 (ω ) + (ε 2 (ω )) − ε 1 (ω ) (7)

ε 2 (ω )
L(ω ) = (8)
(ε 1 (ω ))2 + (ε 2 (ω ))2
[n(ω ) − 1]2 + [k(ω )]2
R(ω ) = (9)
[n(ω ) + 1]2 + [k(ω )]2
where subscripts c, v, and BZ represent the conduction band, valence band, and first
Brillouin zone, respectively. | Mc,v (k)|2 is the momentum matrix element, k is the reciprocal
lattice vector, C is constant, ω is the angular frequency, Evk and Eck are intrinsic energy levels.
The generation of the spectrum is related to the electron transition between energy levels,
and the above formula lays a theoretical foundation for the calculation of band structure
and optical properties.
The tetragonal structure has different lattice parameters along two directions, inducing
different optical properties. For the comparison of the optical spectra changes in different
lattice parameter directions, the optical parameters of all the materials along the x- and
z-axis were calculated in this work. The values of the real and imaginary parts of the
dielectric function along the x- and z-directions are shown in Figure 5. The static dielectric
constants (ε 0 ) can be gained when the photon energies of the real part are equal to zero. As
presented in Figure 5a, the static dielectric constant (ε 0 ) of pristine BaTiO3 is recorded as
6.09 and 5.83 along the x- and z-axis, respectively, which was consistent with the previous
theoretical works [42]. In addition, for Ba0.875 TiCe0.125 O3 , the value of ε 0 are recorded as
8.38 along the x-direction and 7.00 along the z-direction. In terms of BaTi0.875 Ce0.125 O3 , the
static dielectric constants along the x-axis and z-axis are 5.911 and 5.709, respectively. As
a result, it can be concluded that the substitution of Ce for the Ba site increased the static
dielectric constant. In contrast, the static dielectric constant decreased at both the x-axis
and z-axis when Ce was doped into the Ti site. The value of ε 0 represents the magnitude
of the electronic polarization features of optical materials. The electron polarizability was
improved significantly in terms of Ce doping at Ba sites, whereas the Ti site doping was the
opposite. Moreover, ε R achieved the maximum in the lower part of the photon energies
at approximately 3.11, 3.32, and 3.15 eV for pristine BaTiO3 , Ba site substitution, and Ti
site substitution, respectively, whereas the dispersion of ε R decreased abruptly with the
photon energies continuously increasing and obtained negative values. The positive and
negative values of ε R depicted the dielectric and metallic behaviors of the materials [43].
The peaks of the imaginary part ε I (ω ) are related to the band structure, representing
the electron transition between the occupied states in the valence band and the unoccupied
states in the conduction band [44]. According to Figure 5b, the peaks that simultaneously
emerge in the x- and z-axis for pure BaTiO3 towards the lower photon energies are believed
to be originated from the electron transitions across forbidden bands. It can be inferred from
the band structure that the sharp peaks are contributed by the electron transition from VBM
located at point A in the BZ to the CBM located at point Γ. In terms of the incorporation
of the Ce element, as shown in Figure 5d,f, several peaks have also been observed in the
dispersion at a lower photon energy range, which is mainly due to the optical transition
between the occupied states in the VBM at the point Γ, R and the unoccupied states in the
CBM at the point Γ, Z. In addition, as shown in Figure 5d, for the substitution of Ce for the
Ba site, a slight peak can be seen along the x- and z-axis at a lower photon energy of 0.13 and
 the optical transition between the occupied states in the VBM at the point Γ, R and th
unoccupied states in the CBM at the point Γ, Z. In addition, as shown in Figure 5d, for th
Crystals 2023, 13, 255 8 of 13
substitution of Ce for the Ba site, a slight peak can be seen along the x- and z-axis at
lower photon energy of 0.13 and 0.09, respectively. The peaks at the lower photon energy
range are mainly due to the effect of the impurity band in the band structure. Several low
0.09, respectively. The peaks at the lower photon energy range are mainly due to the effect
intensity peaks can
of the impurity be in
band easily observed
the band in the
structure. higher
Several photon energy
low-intensity range.
peaks can They are at
be easily
tributed to the
observed electron
in the transition
higher photon energyfrom theThey
range. low-energy valence
are attributed to the band totransition
electron the unoccupied
states
frominthe
thelow-energy
conduction band.
valence band to the unoccupied states in the conduction band.

Figure
Figure The The
5. 5. realrealandand imaginaryparts
imaginary parts ofof the
the dielectric
dielectric function:
function: (a,b)
(a,b)pure
pureBaTiO3 , 3, (c,d
BaTiO
(c,d) Ba
Ba0.875TiCe0.875 TiCe O ,
0.125 (e,f)
0.125O3, and 3 and (e,f) BaTi
BaTi0.875Ce0.875 Ce O
0.125O3.0.125 3
.

Figure 6 shows the absorption coefficient and reflectivity of these materials in different
Figure 6As
directions. shows
shownthe absorption
in Figure 6a,c,e, coefficient and reflectivity
the incorporation of Ce slightly of these
affects thematerials
absorptionin differ
ent of
directions.
incident light.As shown in Figureabsorption
Several moderate 6a,c,e, the incorporation
peaks can be observedof Ce slightly
within affects the ab
the photon
energy range of 0–15 eV. The absorption peaks of all the
sorption of incident light. Several moderate absorption peaks can be observedinvestigated materials are signifi-
within th
photon energy range of 0–15 eV. The absorption peaks of all the investigatedrange.
cantly enhanced with the photon energy increased continuously in the ultraviolet materials ar
Although the lattice parameters show anisotropy in the x- and z-axis, all perovskites obtain
significantly enhanced with the photon energy increased continuously in the ultraviole
almost identical absorption spectra along different directions. For pure BaTiO3 , the maxi-
range.
mumAlthough
absorptionthe lattice approaches
coefficient parameters show
5.10 × 105anisotropy
cm−1 at 19.26 ineVtheandx-5.20
and×z-axis,
105 cm−all
1 perov
skites
at 19.20 eV in the x- and z-axis, respectively. The maximum absorption coefficient ofpure Ba
obtain almost identical absorption spectra along different directions. For
TiOBa3, 0.875
the Cemaximum absorption
0.125 TiO3 reaches 105 cm−1 at approaches
4.80 × coefficient 19.23 eV in the5.10 × 10
x-axis and5 cm 5 cm−1 at
4.82−1×at1019.26 eV and 5.2
19.23 eV along the z-directions, respectively. In addition, there
× 10 cm at 19.20 eV in the x- and z-axis, respectively. The maximum absorption coeffi
5 −1 is a small absorption peak
within the range of 3–6 eV, which is consistent
cient of Ba0.875Ce0.125TiO3 reaches 4.80 × 105 cm−1with the experimental results [45,46]. In 5
at 19.23 eV in the x-axis and 4.82 × 10 cm−
terms of BaTi0.875 Ce0.125 O3 , the maximum absorption coefficient closes to 4.78 × 105 cm−1
at 19.23 eV along the z-directions, respectively. In addition, there is a small absorption
at 19.29 eV. Figure 6b,d,f illustrate the reflectivity of the materials. For the pristine and
peakthewithin the range
substitution of Ce offor3–6
the eV, which
Ti site, is consistent
the materials exhibitwith the difference
a slight experimental in theresults
x- and [45,46]
In terms
z-axis, of BaTi0.875
whereas theCe 0.125O3, the
reflectivity maximum
is almost absorption
identical coefficient
in both directions closes
for the to 4.78 of
substitution × 105 cm−
at 19.29 eV. Figure 6b,d,f illustrate the reflectivity of the materials. For the pristine and th
substitution of Ce for the Ti site, the materials exhibit a slight difference in the x- and z
axis, whereas the reflectivity is almost identical in both directions for the substitution o
Crystals 2023, 13, x FOR PEER REVIEW 9 of 12

Crystals 2023, 13, 255 9 of 13

Ce for the Ba site. The intensity of reflection along the z-axis is stronger than that in the x-
axis for all materials in the ultraviolet range of 5–10 eV. Several moderate reflection peaks
Ce for the Ba site. The intensity of reflection along the z-axis is stronger than that in the
can be observed
x-axis in the in
for all materials lowtheultraviolet range
ultraviolet range (below
of 5–10 15 eV),moderate
eV. Several whereas all materials
reflection peaks show
the strongest reflection peaks within the photon energy range of 15–20 eV.
can be observed in the low ultraviolet range (below 15 eV), whereas all materials show In addition, the
maximum reflection
the strongest of BaTiO
reflection reaches
peaks 3within 0.58 at energy
the photon 25.10 eV onofthe
range x-axis
15–20 and
eV. In 0.59 atthe
addition, 24.69 eV
maximum reflection of BaTiO reaches 0.58 at 25.10 eV on the x-axis and 0.59
on the z-axis, respectively. For3 the Ba site substitution, the maximum reflection in the x- at 24.69 eV
on the
and the z-axis,
z-axis respectively.
is 0.55 at 24.78 For
eV the
andBa siteat
0.56 substitution, the maximumIn
24.78 eV, respectively. reflection
the caseinofthe
Cex-doping
and the z-axis is 0.55 at 24.78 eV and 0.56 at 24.78 eV, respectively. In the case of Ce doping
at the Ti site, the maximum reflection approaches 0.46 at 20.84 eV and 0.48 at 20.47 eV,
at the Ti site, the maximum reflection approaches 0.46 at 20.84 eV and 0.48 at 20.47 eV,
respectively. It can
respectively. bebeconcluded
It can concluded that boththe
that both theBaBa and
and Ti sites
Ti sites of Ce-doped
of Ce-doped BaTiO3BaTiO
can 3 can
reduce the the
reduce reflectivity
reflectivityofofthe
thematerial.
material.

Figure 6. The
Figure absorption
6. The absorption spectra
spectra(a,c,e) andreflectivity
(a,c,e) and reflectivity spectra
spectra (b,d,f)
(b,d,f) of theofmaterials.
the materials.
The (top) The (top)
represents pure
represents BaTiO
pure 3, 3the
BaTiO , the(middle) is Ba
(middle) is Ba0.875 TiCe0.125
0.875TiCe O3 3, ,and
0.125O andthe
the (bottom)
(bottom) is BaTi
is BaTi0.875 Ce
0.875 CeO0.125
0.125 3 . O3.

In addition, the refractive index and energy loss function (ELF) of the materials
In addition, the refractive index and energy loss function (ELF) of the materials have
have been calculated to study the optical transparency and energy state of the electrons,
beenrespectively.
calculated As to study
seen inthe optical
Figure 7a,c,e,transparency and energy
the refractive index of these state of the
materials electrons,
in visible light respec-
tively.
andAs seenpart
a large in Figure 7a,c,e,
of the low the refractive
ultraviolet index
range are larger of one
than these materials
unity. in visible
The refractive index light
of and
a large
the part of the low
investigated ultraviolet
materials decreases range
to lessare
thanlarger thanwith
one unity onetheunity.
photonThe refractive
energy increaseindex of
to the range ofmaterials
the investigated 10–13 eV as well as beyond
decreases to less20 eV. Studies
than one unityhave shown
with thethat materials
photon withincrease
energy
a refractive
to the range of index
10–13greater
eV as than
wellorasequal
beyond to one
20unity are transparent
eV. Studies to incident
have shown thatlight [47]. with
materials
Therefore, it can be concluded that the materials are transparent to incident light when the
a refractive index greater than or equal to one unity are transparent to incident light [47].
photon energy is below 10 eV, and non-transparent in the ultraviolet range of 10–13 eV
Therefore, it can
and beyond 20beeV.concluded
For pure BaTiOthat3 , the materialsrefractive
the maximum are transparent to incident
index is recorded light
as 3.11 at when
the photon
3.27 eV atenergy is below
the x-axis 10 at
and 3.14 eV, and
3.64 eVnon-transparent
at the z-axis. For Ce in doping
the ultraviolet
at the Ba range of 10–13
site, the
eV and beyond
maximum 20 eV. For
refractive indexpure BaTiO3,3.09
approaches theatmaximum refractive
3.44 eV at the x-axis andindex
3.14 is
at recorded
3.53 eV at as 3.11
theeV
at 3.27 z-axis. In the
at the caseand
x-axis of Ti3.14
site doping,
at 3.64 eV the at
calculated maximum
the z-axis. For Cerefractive
doping index
at thealong
Ba site, the
maximum refractive index approaches 3.09 at 3.44 eV at the x-axis and 3.14 at 3.53 eV at
the z-axis. In the case of Ti site doping, the calculated maximum refractive index along the
x- and z-directions is the same, which is recorded as 2.99 at 3.27 eV. The energy loss func-
 Crystals 2023, 13, 255 10 of 13

Crystals 2023, 13, x FOR PEER REVIEW 10 of 12

the x- and z-directions is the same, which is recorded as 2.99 at 3.27 eV. The energy loss
function (ELF) represents the energy loss process of rapidly moving electrons passing
throughby
As shown thepeaks
materials, attributed
in Figure to the
7b,d,f. Theplasmon
energyresonance due to oscillations
of the maximum at 𝜀I (𝜔) <
of valence
peaks occurs
1 and 𝜀R (𝜔) is zero, which is generally recorded as the volume plasma frequencyat 𝜔𝑝 . For
electrons. As shown by peaks in Figure 7b,d,f. The energy of the maximum peaks occurs
ε (ω ) < 1 and ε R (ω ) is zero, which is generally recorded as the volume plasma frequency
pure IBaTiO3, the plasma frequency values (𝜔𝑝 ) along the x- and z-axes is estimated to be
ω p . For pure BaTiO3 , the plasma frequency values (ω p ) along the x- and z-axes is estimated
25.79to be 25.79 eV and 25.67 eV, respectively. In termsthe
eV and 25.67 eV, respectively. In terms of doping
of the dopingofofCeCeatatthe
theBa
Ba site, the 𝜔𝑝 is
site, the
almost the same along different directions, which is recorded as 26.71 eV.
ω p is almost the same along different directions, which is recorded as 26.71 eV. For Ti siteFor Ti site dop-
the 𝜔𝑝theisωrecorded
ing, doping, as as
p is recorded 26.50
26.50eV
eVand
and 26.3 eVininthe
26.3 eV thex-x- and
and z-directions,
z-directions, respectively.
respectively.

Figure 7. The refraction spectra (a,c,e) and energy loss function (ELF) (b,d,f) of BaTiO3 (top),
Figure 7. The refraction spectra (a,c,e) and energy loss function (ELF) (b,d,f) of BaTiO3 (top)
Ba0.875 Ce0.125 TiO3 (middle), and BaTi0.875 Ce0.125 O3 (bottom).
Ba0.875Ce 0.125 TiO3 (middle), and BaTi0.875Ce0.125O3 (bottom).

4. Conclusions
4. Conclusions
The structural, electronic, and optical performance of pure BaTiO3 and Ce substitution
for
Thedifferent lattice electronic,
structural, sites were investigated
and optical based on first-principle
performance calculation.
of pure BaTiO3 It andis found
Ce substitu-
that the substitution of Ce for different sites leads to significant lattice distortion and a
tion for different lattice sites were investigated based on first-principle calculation. It is
significant increase in the bond lengths of Ti-O and Ba-O. The substitution of Ce for the Ba
found
sitethat theCBM
causes substitution
and VBM to ofmove
Ce for
to adifferent sites state,
smaller energy leadsreducing
to significant
the band lattice
gap anddistortion
and inducing
a significant increase
the band in the
gap shift frombond lengths
an indirect to of Ti-O band
a direct and Ba-O. The
gap. For substitution
Ti site doping, theof Ce for
the process
Ba site lowers
causesCBMCBM and
and VBMthe
reduces to band
movegap,to whereas
a smaller theenergy
band gapstate, reducing
remains the band
indirect.
gap For
andpristine BaTiOthe
inducing 3 , there
bandis no
gapcovalent bond between
shift from Ba and
an indirect toOaatoms
directbut an ionic
band gap.bond,
For Ti site
while there is a weak covalent bond between Ti and O atoms. The
doping, the process lowers CBM and reduces the band gap, whereas the band gap doping of Ce at the Baremains
site exerts mainly an ionic band and weak covalent bond nature between Ce and O atoms.
indirect. For pristine BaTiO3, there is no covalent bond between Ba and O atoms but an
ionic bond, while there is a weak covalent bond between Ti and O atoms. The doping of
Ce at the Ba site exerts mainly an ionic band and weak covalent bond nature between Ce
and O atoms. In the case of Ti site doping, the Ce-O bond exhibits a strong covalent bond
Crystals 2023, 13, 255 11 of 13

In the case of Ti site doping, the Ce-O bond exhibits a strong covalent bond and weak ionic
bond nature. The substitution of Ce for the Ba site increases the static dielectric constant,
whereas it decreases when Ce is doped into the Ti site. In addition, the substitution of Ce for
different sites reduces the reflectivity of the material, while the transparency of the materials
before and after doping is almost the same. The materials are transparent to incident light
when the photon energy is below 10 eV, whereas opacity is in the ultraviolet range of
10–13 eV and beyond 20 eV. This study provides a new theoretical basis for exploring the
different properties of the BaTiO3 -based system.

Supplementary Materials: The following supporting information can be downloaded at:

https://www.mdpi.com/article/10.3390/cryst13020255/s1, Table S1: Atomic Mulliken charges
populations of pure and Ce-doped BaTiO3 . Table S2: Bond overlap populations of pure and Ce-
doped BaTiO3 .
Author Contributions: Conceptualization, H.Y. and K.G.; Data curation, I.T.; Formal analysis, Z.L.,
B.X., and P.M.; Investigation, J.L.; Methodology, H.Y.; Resources, F.E.H.T. and K.Y.; Software, K.F.;
Supervision, K.G.; Validation, T.C. and Q.J.; Writing—original draft, H.Y.; Writing—review and
editing, K.G., K.Y. All authors have read and agreed to the published version of the manuscript.
Funding: This research was funded by the National Natural Science Foundation of China (Grant No.
52002164), and the Natural Science Foundation of Jiangxi Province of China (Grant No. 20202BABL204013).
Data Availability Statement: The data presented in this study are available on request.
Conflicts of Interest: The authors declare no conflict of interest.

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