New class of planar ferroelectric Mott insulators via first principles design

TL;DR

This paper uses first-principles calculations to design a new class of inorganic layered double perovskite ferroelectrics with low band gaps and high polarization, suitable for photovoltaic applications.

Contribution

It introduces a novel design strategy for inorganic ferroelectric Mott insulators using layered double perovskite oxides, combining size mismatch, charge transfer, and lone-pair effects.

Findings

Designed materials like BaBiCuVO$_6$ with low band gaps.

Achieved high ferroelectric polarization in proposed structures.

Potential for stable, high-efficiency photovoltaic devices.

Abstract

Inorganic perovskite oxide ferroelectrics have recently generated substantial interest for photovoltaic applications; however, existing materials suffer from excessive electronic band gaps and insufficient electric polarization. The recent resurgence of hybrid perovskite ferroelectrics addresses the aforementioned deficiencies, but they are highly unstable against environmental effects and an inorganic resolution may still be optimal. Here we use first-principles calculations to design a low band gap, planar ferroelectric by leveraging the complexity of layered double perovskite oxides AA$^\prime $BB$^\prime$O$_6$. We exploit A$\ne$A$^\prime$ size mismatch, a nominally empty $d$-shell on the B-site, and A cations bearing lone-pair electrons to achieve a large ferroelectric polarization. Additionally, B$^\prime\ne$B is chosen to achieve full charge transfer and a Mott susceptible filling on the B$^\prime$-site, yielding a low band gap. These principles are illustrated in BaBiCuVO$_6$, BaBiNiVO$_6$, BaLaCuVO$_6$, and PbLaCuVO$_6$, which could be realized in layer-by-layer growth. This new class of materials could lead to stable, high-efficiency photovoltaic.