Electronic structure of PbTiO3 perovskite based on density functional calculation

Vivek Kumar Shukla

Citation: AIP Conference Proceedings 1953, 110035 (2018); doi: 10.1063/1.5033060

View online: https://doi.org/10.1063/1.5033060
View Table of Contents: http://aip.scitation.org/toc/apc/1953/1
Published by the American Institute of Physics
 Electronic structure of PbTiO3 perovskite based on density
functional calculation
Vivek Kumar Shukla

Department of Applied Physics, Gautam Buddha University, Greater Noida, Gautam Budh Nagar (U.P.) India,
201312

Corresponding author: vkshuk@gmail.com

Abstract. The electronic structures of tetragonal structure of PbTiO3 are analyzed by density functional theory using the
PBE exchange–correlation functional and the local density approximation (LDA) in Quantum Espresso simulation
package. The calculated relaxed lattice parameters are a = 3.79 Å and c = 3.85 Å, yielding a c/a ratio of 1.015 and indirect
band gap of 1.63 eV. We find that PbTiO3 preserves the tetragonal P4mm structure. Our results show that it is effective
technique to find lattice parameters and tune the band gap.

INTRODUCTION
Local-Density Approximation (LDA) was considered by transforming the problem into the non-interacting
system in an effective potential. Wavefunction can be easily represented by a Slater determinant of orbitals, the
kinetic energy functional of this system is exactly known but the exchange-correlation part of the total energy
functional remains unknown [1]. Various terms of the total energy are defined as functionals of the electron density,
and some formal properties of these functionals are discussed. The most widely used density functionals are the
local spin density and generalized gradient approximations [2].
It will be interesting to focus on small total-energy changes associated with re-arrangements of the outer or
valence electrons, to which the inner or core electrons of the atoms do not contribute. There, we can replace each
core by the pseudopotential; it presents to the valence electrons, and then expands the valence-electron orbitals in an
economical and convenient basis of plane waves. Pseudopotentials are routinely combined with density functionals.
Although the most realistic pseudopotentials are nonlocal operators and not simply local or multiplication operators,
and although density functional theory in principle requires a local external potential, this inconsistency does not
seem to cause any practical difficulties [3].
Hellmann-Feynman results may be used to find the equilibrium geometries of a molecule or solid by varying all
the nuclear position until the energy is a minimum. It also forms the basis for a possible density functional molecular
dynamics, in which the nuclei move under these forces by Newton’s second law. In principle, all we need for either
application is an accurate electron density for each set of nuclear positions [4, 5].
Generalized gradient approximation (GGA) and hybrid approximations have reduced the LDA errors of
atomization energies of standard set of small molecules by a factor 3-5. This improved accuracy. All the present
functionals are inadequate for situations where the density is not a slowly varying function. Examples are (a) Wigner
crystals; (b) Vander Waals energies between non overlapping subsystems; (c) electronic tails evanescing into the
vacuum near the surfaces of bounded electronic systems. However, this does not preclude that DFT with appropriate
approximations can successfully deal with such problems [6].
Here, we use density functional theory (DFT) to study the structural and electronic properties of hypothetical
perovskite of the chemical formula PbTiO3. We desire to identify new photovoltaic materials for efficient solar
energy conversion, which may be organic-inorganic combination. Photovoltaic materials must have band gap in the
range 1.1-2 eV to provide strong light absorption and energy conversion.

2nd International Conference on Condensed Matter and Applied Physics (ICC 2017)
AIP Conf. Proc. 1953, 110035-1–110035-4; https://doi.org/10.1063/1.5033060
Published by AIP Publishing. 978-0-7354-1648-2/$30.00

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 The classic PbTiO3 (PTO) is a ferroelectric perovskite oxide as a basis for alloying with sulfur on the oxygen
sites. PTO is highly polar and has an indirect band gap of around 3.45–3.60 eV. Excitation across the gap is
essentially a charge transfer from the O2(p) orbitals to the Ti 3(d) orbitals. Therefore substitution of the more
electronegative oxygen by the less electronegative sulfur should lead to a lower band gap, while possibly preserving
the ferroelectricity.

METHODOLOGY
Here, calculations are performed using the local density approximation (LDA) with a plan wave cutoff of 408 eV
in the framework of density functional theory (DFT). The density functional theory (DFT) we use in QUANTUM
ESPRESSO simulation package. The atoms are represented by ultra soft pseudopotentials which generated with
scalar-relativistic calculation. Relaxation calculations are done in order to determine unit cell parameters and atomic
positions. For band gap calculation, we do self consistent calculation and for projected density of states calculations,
we do non-self consistent calculation. For the standard perovskite unit cell of five atoms, a Monkhorst-Pack (MP) k-
point grid of 8×8×8 is used with a cutoff energy of 408 eV. In order to find the unit cell parameter, atomic positions
of different atoms in unit cell, band gap and projected density of states we used a five-atom unit cell.

RESULTS AND DISCUSSION

Structural and Electronic Results for PbTiO3

Our calculated results for PbTiO3 are in agreement with earlier published theoretical work [18]. The calculated
relaxed lattice parameters are a = 3.79 Å and c = 3.85 Å, yielding a c/a ratio of 1.015. We find an indirect band gap
of 1.632 eV. We find that PbTiO3 preserves the tetragonal P4mm structure.
The optimized lattice parameters and band gap are shown and compared (Table 4.1) with earlier published
theoretical work [7]. It has a highly strained lattice due to strong orbital hybridization and subsequent non-
centrosymmetric lattice distortion. PbTiO3 has the highest tetragonal distortion (c/a∼1.015) which makes it
significantly more ferroelectric with highest spontaneous polarization. At 766 K PbTiO3 switches to tetragonal phase
and becomes ferroelectric.
TABLE 1: Calculated structural properties and local density approximation (LDA) band gap of PbTiO 3 for five-
atom tetragonal structure unit cell. In comparison, the structural properties and band gap has been calculated
(Ref.7).
PbTiO3 (Tetragonal, P4mm) (Ref.7 results) (LDA) Calculated Result (LDA)
a 3.87 3.79
b 3.87 3.79
c 4.07 3.85
Eg 1.47 1.632

Calculated lattice parameter underestimates and band gap and overestimates the earlier published data. The
Local density approximation (LDA) functional confirms the capability of PbTiO 3 for the solid-state applications.
As shown in Table 1, the local density approximation (LDA) band gap result is in the visible range for PbTiO3.
Band structure diagram for PbTiO3 are shown in figure 1. The conduction bands are moved up and the valence band
moved down due to the well-known local density approximation (LDA) underestimation of E g.

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FIGURE 1: Calculated local density approximation (LDA) band structure with the conduction bands moved up and the valence
bands moved down of PbTiO3.
The calculated projected density of states for PbTiO3, Pb, Ti and O atoms are shown in Fig. 2. As we can see, the
valence band is mainly the anti-bonding component of the hybridization between Pb 3(d), Ti 2(p), O 2(p) and O 1(s)
states, while the conduction band is almost a nonbonding state dominated by the Pb 1(s), Pb 2(p), Ti 4(d) and O 2(p)
states. The electronic levels from rest atoms states are located deep within the valence band and the conduction
band, without contribution to the states near the Fermi level. The maximum value of calculated projected density of
states for PbTiO3 and Pb 3(d) is 14 electron/eV at -5 eV.

(a) (b)

(c) (d)

FIGURE.2: Calculated projected density of states plots for PbTiO3: (a). Projected density of states for Pb atom, (b). Projected
density of states for Ti atom, (c). Projected density of states for O atom, (d). Total projected density of states for PbTiO3.

CONCLUSIONS

The lattice parameters a = 3.79 Å , c = 3.85 Å, and indirect band gap of 1.63 eV is calculated using Quantum
Espresso. We find that PbTiO3 preserves the tetragonal P4mm structure. Our results show that Quantum Espresso
has effective capabilities to find lattice parameters and tune the band gap in perovskite structures.

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 ACKNOWLEDGEMENTS
Quantum ESPRESSO Foundation is gratefully acknowledged for offering QE-FORGE, a free service for
simulation and modeling. Technical support from Saurabh Kumar, Master’s student at Gautam Buddha University,
Greater Noida, UP, India is also acknowledged.

REFERENCES
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