Issue 46, 2020

First-principles exploration of oxygen vacancy impact on electronic and optical properties of ABO3−δ (A = La, Sr; B = Cr, Mn) perovskites

Abstract

ABO3−δ perovskites are utilized in many applications including optical gas sensing for energy systems. Understanding the opto-electronic properties allows rational selection of the perovskite-based sensors from a diverse family of ABO3−δ perovskites, associated with the choices of A and B cations and range of oxygen concentrations. Herein, we assess the impact of oxygen vacancies on the electronic structure and optical response of pristine and oxygen-vacant ABO3−δ (A = La, Sr; B = Cr, Mn) perovskites via first-principles calculations. The endothermic formation energy for oxygen vacancies shows that the generation of ABO3−δ defect structures is thermodynamically possible. LaCrO3 and LaMnO3 have direct and indirect ground-state band gaps, respectively, whereas SrCrO3 and SrMnO3 are metallic. In the presence of an oxygen mono-vacancy, however, the band gap decreases in LaCrO3−δ and vanishes in LaMnO3−δ. In contrast to the decrease in the band gaps, the oxygen vacancies in ABO3−δ are found to increase optical absorption in the visible to near-infrared wavelength regime, and thus lower the onset energy of absorption compared with the pristine materials. Our assessments emphasize the role of the oxygen vacancy, or other possible oxygen non-stoichiometry defects, in perovskite oxides with respect to the opto-electronic performance parameters that are of interest for optical gas sensors for energy generation process environments.

Graphical abstract: First-principles exploration of oxygen vacancy impact on electronic and optical properties of ABO3−δ (A = La, Sr; B = Cr, Mn) perovskites

Supplementary files

Article information

Article type
Paper
Submitted
16 Oct 2020
Accepted
11 Nov 2020
First published
12 Nov 2020

Phys. Chem. Chem. Phys., 2020,22, 27163-27172

First-principles exploration of oxygen vacancy impact on electronic and optical properties of ABO3−δ (A = La, Sr; B = Cr, Mn) perovskites

J. Park, Y. Wu, W. A. Saidi, B. Chorpening and Y. Duan, Phys. Chem. Chem. Phys., 2020, 22, 27163 DOI: 10.1039/D0CP05445C

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