Epitaxial Strain-Dependence of Band Gaps in Oxynitrides compared to Oxides

TL;DR

This study uses density functional theory to explore how epitaxial strain affects the band gaps of oxynitrides, revealing unique strain-dependent behaviors and the impact of ferroelectric distortions on light absorption.

Contribution

It provides the first detailed analysis of band-gap evolution in epitaxially strained oxynitrides, highlighting the role of anion order and ferroelectric distortions, and comparing these effects to oxides.

Findings

Anion order causes non-degenerate N 2p bands at zero strain.

Polar distortions can increase the band gap by up to 1 eV at 4% strain.

Ferroelectric distortions significantly affect light absorption in oxynitrides.

Abstract

Perovskite oxynitrides are a promising class of material for photocatalytic water-splitting due to their small band gaps and suitably aligned band edges. Recently, epitaxially strained oxynitrides started to attract interest due to the possibility to engineer the anion order and ferroelectric distortions. However, contrary to oxides there have been no studies on the band-gap evolution in oxynitrides with epitaxial strain. Here, we investigate, using density functional theory calculations, the influence of epitaxial strain on the band gap of two different oxynitrides and compare our results with oxides. As opposed to cubic oxides, where both compressive and tensile strain narrow the band-gap, we find that the anion order leads to non-degenerate N \textit{2p} bands already at zero strain, which leads to opposite and anion order-dependent evolutions of the band gap under compressive and tensile strain. Further, we find that in oxynitrides polar distortions increase the band gap by up to 1 eV for 4% strain whereas for oxides the increase is only about 0.1 eV for the same amount of strain. The reason for this difference is the larger ionic radius of nitrogen leading to larger ferroelectric distortions and a stronger dependence of the band gap on the distortions amplitude. These results imply that ferroelectric distortions are strongly detrimental to light absorption and that their suppression, for example above a critical temperature, should result in a marked decrease in band gap and enhanced absorption of visible light.