Electronic structures and lattice dynamics of BaTiO3 and BiFeO3 : a comparative first-principles study

TL;DR

This study uses first-principles calculations to compare the electronic structures and lattice dynamics of BaTiO3 and BiFeO3, revealing mechanisms behind their ferroelectric properties and predicting improved multiferroic materials.

Contribution

It provides a detailed first-principles comparison of BaTiO3 and BiFeO3, highlighting the role of hybridization and stereochemical activity in ferroelectricity, and predicts new multiferroic materials.

Findings

BiFeO3 has higher spontaneous polarization than BaTiO3.

Bi-6s lone pair activity drives ferroelectricity in BiFeO3.

Predicted new multiferroic materials with better magnetic ordering.

Abstract

First-principles calculations were performed to investigate the ferroelectric properties of barium titanate and bismuth ferrite, as well as phonon dispersion of BaTiO3, using density functional theory and density functional perturbation theory. Results show that the strong hybridization of Ti-O and Bi-O lead to the corresponding mechanisms for stabilizing the distorted structure. The spontaneous polarization of 59.4 \mu C/cm2 and 27.6 \mu C/cm2 were calculated for BiFeO3 and BaTiO3 respectively, using berry phase method within the modern theory of polarization. The stereochemical activity of Bi-6s long-pair, which was the driven mechanism for ferroelectricity in BiFeO3, was able to produce greater polarization than the Ti off-centring displacement in BaTiO3. New multiferroic perovskite type materials combined with these two ferroelectric instabilities were predicted to have a better ferromagnetic ordering in comparison with BiFeO3.