Optical Absorption Induced by Small Polaron Formation in Transition Metal Oxides -- The Case of Co$_3$O$_4$

TL;DR

This study uses first-principles calculations to clarify how small polarons form and affect optical properties in Co$_3$O$_4$, resolving previous conflicting reports and providing insights for energy applications.

Contribution

It provides a detailed first-principles analysis of small polaron formation in Co$_3$O$_4$, clarifying its impact on electronic structure and optical absorption, and proposes a general computational approach for similar materials.

Findings

Intrinsic band gap of Co$_3$O$_4$ is 1.6 eV.

Hole small polarons cause a 0.8 eV optical transition.

Uniaxial strain can probe Jahn-Teller distortions of SP states.

Abstract

Small polarons (SPs) are known to exist in most important transition metal oxides (TMOs); however, the nature of small polaron formation remains enigmatic, and a fundamental understanding of how SPs impact the intrinsic electronic structure and optical properties of these materials is largely lacking. In this work, we employ first-principles calculations to investigate SP formation in Co$_{3}$O$_{4}$, a highly promising material for a wide range of emerging energy applications, and we resolve the conflicting findings that have been reported on the electronic structure of the system. We confirm that the intrinsic band gap of Co$_{3}$O$_{4}$ is 1.6 eV, and we show that the formation of hole small polarons significantly influences the optical absorption spectra, leading to a 0.8 eV transition that is often misinterpreted as the band edge that defines the fundamental gap. In addition, we discuss how uniaxial strain can be utilized to probe the Jahn-Teller distortion of SP states and in turn, effect their optical transitions. Beyond Co$_{3}$O$_{4}$, our study suggests a general roadmap for establishing a first-principles computational approach that can simultaneously achieve an accurate description of SP states, electronic band structure and optical transitions of polaronic magnetic oxides.