Interface enhancement of ferroelectricity in CaTiO$_3$/BaTiO$_3$ superlattices

TL;DR

This study uses first-principles calculations to show that interfaces in CaTiO$_3$/BaTiO$_3$ superlattices can enhance ferroelectricity, especially in short-period structures, due to suppressed octahedral rotations and increased ferroelectric instability.

Contribution

It reveals how interface effects and octahedral rotations influence ferroelectricity in CaTiO$_3$/BaTiO$_3$ superlattices, highlighting enhanced polarization in short-period superlattices.

Findings

Strong octahedral rotations occur between CaO layers.

Suppression of rotations near BaO layers enhances ferroelectricity.

Short-period superlattices exhibit larger polarization than longer ones.

Abstract

We carry out first-principles calculations for CaTiO$_3$/BaTiO$_3$ superlattices with epitaxial strain corresponding to growth on a SrTiO$_3$ substrate, and consider octahedral rotations as well as ferroelectric distortions. The calculations are done as a function of electric displacement field, and both a macroscopic and a local electrostatic analysis are carried out. We find that strong octahedral rotations occur for TiO$_6$ octahedra sandwiched between CaO layers on both sides, but are strongly suppressed if either neighboring layer is a BaO layer. Due to the resulting enhancement of the ferroelectric instability in the BaO-neighboring octahedra, we find that overall the ferroelectric instability of the superlattice is enhanced by the interface. Thus, short-period superlattices in this system have a larger ferroelectric polarization than longer-period ones of the same average composition, contrary to the expected trend.