Confinement of electron holes via the peroxo group formation in the negative charge-transfer materials on the example of SrFeO3: plane-wave density functional theory predictions

Abstract

The present work puts forward a concept that the thermostable O1s XPS peaks with energy of about 531 eV in negative charge-transfer SrFeO_{3-\delta} perovskite are determined by the peroxo-like oxygen species. The peroxo group forms via coupling two oxygen anions coordinated to iron cations with d^5\bar-under{L} (\bar-under{L}-oxygen electron hole) configuration. By means of plane-wave DFT+U approach there have been shown that the peroxo group represents a metastable state in the absence of oxygen vacancies nearby. The O-O bonding confines two electron holes freezing the 3+ oxidation state for two iron cations bridged by peroxide. Increasing the peroxo group numbers makes the ferrite a semiconductor with charge-transfer gap of about 0.6 eV.