Oxide enthalpy of formation and band gap energy as accurate descriptors of oxygen vacancy formation energetics

Ann M. Deml, Vladan Stevanović, Christopher Muhich, Charles B. Musgrave, Ryan O'Hayre

Research output: Contribution to journalArticle

48 Citations (Scopus)

Abstract

Despite the fundamental role oxygen vacancy formation energies play in a broad range of important energy applications, their relationships with the intrinsic bulk properties of solid oxides remain elusive. Our study of oxygen vacancy formation in La1-xSrxBO3 perovskites (BCr, Mn, Fe, Co, and Ni) conducted using modern, electronic structure theory and solid-state defect models demonstrates that a combination of two fundamental and intrinsic materials properties, the oxide enthalpy of formation and the minimum band gap energy, accurately correlate with oxygen vacancy formation energies. The energy to form a single, neutral oxygen vacancy decreases with both the oxide enthalpy of formation and the band gap energy in agreement with the relation of the former to metal-oxygen bond strengths and of the latter to the energy of the oxygen vacancy electron density redistribution. These findings extend our understanding of the nature of oxygen vacancy formation in complex oxides and provide a fundamental method for predicting oxygen vacancy formation energies using purely intrinsic bulk properties. This journal is

Original languageEnglish (US)
Pages (from-to)1996-2004
Number of pages9
JournalEnergy and Environmental Science
Volume7
Issue number6
DOIs
StatePublished - Jan 1 2014
Externally publishedYes

Fingerprint

Oxygen vacancies
enthalpy
Oxides
Enthalpy
Energy gap
energetics
oxide
oxygen
energy
Electronic structure
Carrier concentration
Materials properties
electron density
defect
Metals
Oxygen
Defects
metal

ASJC Scopus subject areas

  • Renewable Energy, Sustainability and the Environment
  • Environmental Chemistry
  • Pollution
  • Nuclear Energy and Engineering

Cite this

Oxide enthalpy of formation and band gap energy as accurate descriptors of oxygen vacancy formation energetics. / Deml, Ann M.; Stevanović, Vladan; Muhich, Christopher; Musgrave, Charles B.; O'Hayre, Ryan.

In: Energy and Environmental Science, Vol. 7, No. 6, 01.01.2014, p. 1996-2004.

Research output: Contribution to journalArticle

Deml, Ann M. ; Stevanović, Vladan ; Muhich, Christopher ; Musgrave, Charles B. ; O'Hayre, Ryan. / Oxide enthalpy of formation and band gap energy as accurate descriptors of oxygen vacancy formation energetics. In: Energy and Environmental Science. 2014 ; Vol. 7, No. 6. pp. 1996-2004.
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