Effect of oxygen vacancies on electrical conductivity of LaSrFeO from first-principles calculations

We use first-principles density functional theory calculations to understand how oxygen vacancies degrade the electrical conductivity of mixed ionic-electronic conductor (MIEC) at low oxygen partial pressure ( P O 2 ). Analysis focused on La 0.5 Sr 0.5 FeO 3− δ , which shows the highest mixed conductivity among cobalt-free iron-based perovskite oxides. Calculation results show that hole compensation by electrons released from oxygen vacancies lowers the electrical conductivity and eventually leads to metal-to-semiconductor transition at low P O 2 . Analyses of effective mass change and charge-density show that holes are the major charge carrier of electrical conductivity, but the contribution of electrons to conductivity increases as temperature increases. We suggest several possible ways to reduce the degradation of electrical conductivity at low P O 2 . Our results provide guidelines to design highly effective oxygen-selective membranes. Metal to semiconductor transition by hole compensation of excess electrons from V O and localized V O state in La 0.5 Sr 0.5 FeO 3− δ under low P O 2 .