Redox-active oxygen in oxides: emergent applications, including field-induced resistive switching, flash luminescence, p–n junctions and high capacity battery cathodes

Abstract

Oxide ions are traditionally regarded as forming the inert anion sub-lattice of oxide structures whose properties are largely dominated by the cations present. This viewpoint is being increasingly challenged by examples of a diverse range of phenomena in which some of the oxide ions present are redox-active. The source of this activity in ionic structures is the inherent instability of O²⁻ ions in the gas phase which are stabilised in crystal lattices by the additional lattice energy associated with doubly-charged anions. Oxide ions located either at sample surfaces or adjacent to lower valence (acceptor) substitutional cations, may not be fully stabilised, as they are surrounded by an effective positive charge of less than 2+. They are under-bonded and may ionise, either spontaneously or with reduced ionisation potential. Examples of oxygen redox include: high capacity Li and Na battery cathodes in which there is insufficient redox-active transition metal component present to account for the observed charge/discharge capacities; electroceramic materials such as some doped titanate perovskites which exhibit hopping p-type conductivity and in which the only realistic location of the electron holes is on lattice oxide ions; novel resistive switching phenomena and insulator-metal transitions in oxide ceramics; resistance degradation of insulating ceramics prior to dielectric breakdown; flash luminescence by creation of p–n junctions in oxide ceramics; possible origin of 2-dimensional electron gases in layered superlattices formed from oxide insulators. The underlying principles of oxygen redox activity are set out and its possible contribution to emergent phenomena are discussed.