Connection between Bandgap Evolution and Strains of Octahedron in non-Perovskite \b{eta}-MnO2 under pressure: A First Principle Study

TL;DR

This study uses first-principles calculations to explore how pressure-induced lattice distortions in ta-MnO2 affect its bandgap, revealing mechanisms for tuning electronic properties in non-Perovskite materials.

Contribution

It provides a detailed analysis of pressure effects on bandgap evolution in ta-MnO2 and related oxides, introducing new insights into pressure-induced electronic property tuning.

Findings

Bandgap enlarges or shrinks with pressure due to bondlength and angle competition.

Pressure can tune the bandgap of ta-MnO2 to 1.34 eV, suitable for photovoltaic applications.

High-pressure phases can be quenched to ambient conditions.

Abstract

Lattice distortion due to octahedral rotation and distortion are high focussed, and it produces profound effect on a material's properties, such as its bandgap, magnetism and optical properties etc. Rutile-type \b{eta}-MnO2 is a wide used non-Perovskite magnetic material with octahedrons. We systematically studied its stability, electronic structures, magnetic structures, and optical properties within 0-100 GPa with density-functional theory (DFT). We find that the competition between bondlength and bonding angle leads its bandgap enlarging or shrinking within in the Pnnm phase with increasing pressure, because of the interaction of Mn-d and O-p states. We also find same pressure indused bandgap evolutions in the Pnnm phases of SiO2, GeO2, SnO2 and PbO2. The different ways of octahedral connection in Pnnm phase and Pa-3 phase leads to an interesting pressure-induced bandgap enlarging. And in the Pa-3 phase, the band gap can be tuned to 1.34 eV by pressure to meet the Shockley-Queisser limit. Moreover the two high pressure phases can be quenched to ambient pressure. Together with its mechanical, optical and antiferromagnetic properties, it ensures MnO2's application as a photovoltaic material for all working condition with multi-purpose. This study extends MnO2's application and give some new mechanism of pressure induced bandgap enlargement.