Interplay between polarization, strain and defect-pairs in Fe-doped SrMnO$_{3-\delta}$

TL;DR

This study demonstrates how defect pairs involving Fe substitution and oxygen vacancies can induce and enhance ferroelectric polarization in SrMnO₃ through strain engineering, revealing new pathways for functional property design in transition metal oxides.

Contribution

It introduces a self-consistent DFT+$U$ approach to predict defect-induced polarity in non-polar perovskites, showing how defect chemistry and strain can be used to engineer ferroelectricity.

Findings

Defect pairs induce net electric dipoles in SrMnO₃.

Epitaxial strain enhances defect-induced polarization.

High defect concentrations lead to coupled defect dipoles and ferroelectricity.

Abstract

Defect chemistry, strain, and structural, magnetic and electronic degrees of freedom constitute a rich space for the design of functional properties in transition metal oxides. Here, we show that it is possible to engineer polarity and ferroelectricity in non-polar perovskite oxides via polar defect pairs formed by anion vacancies coupled to substitutional cations. We use a self-consistent site-dependent DFT+$U$ approach that accounts for local structural and chemical changes upon defect creation and which is crucial to reconcile predictions with the available experimental data. Our results for Fe-doped oxygen-deficient SrMnO$_3$ show that substitutional Fe and oxygen vacancies can promote polarity due to an off-center displacement of the defect charge resulting in a net electric dipole moment, which polarizes the lattice in the defect neighborhood. The formation of these defects and the resulting polarization can be tuned by epitaxial strain, resulting in enhanced polarization also for strain values lower than the ones necessary to induce a polar phase transition in undoped SrMnO$_3$. For high enough defect concentrations, these defect dipoles couple in a parallel fashion, thus enabling defect- and strain-based engineering of ferroelectricity in SrMnO$_3$.