Realizing Metastable Cobaltite Perovskite via Proton-Induced Filling of Oxygen Vacancy Channels

The interaction between transition-metal oxides (TMOs) and protons has become a key issue in magneto-ionics and proton-conducting fuel cells. Until now, most investigations on oxide-proton reactions rely on electrochemical tools, while the direct interplay between protons and oxides remains basically at simple dissolution of metal oxides by an acidic solution. In this work, we find classical TMO brownmillerite SrCoO2.5 (B-SCO) films with ordered oxygen vacancy channels experiencing an interesting transition to a metastable perovskite phase (M-SCO) in a weak acidic solution. M-SCO exhibits a strong ferromagnetism (1.01 mu B/Co, Tc > 200 K) and a greatly elevated electrical conductivity (similar to 104 of pristine SrCoO2.5), which is similar to the prototypical perovskite SrCoO3. Besides, such M-SCO tends to transform back to B-SCO in a vacuum environment or heating at a relatively low temperature. Two possible mechanisms (H2O addition/active oxygen filling) have been proposed to explain the phenomenon, and the control experiments demonstrate that the latter mechanism is the dominant process. Our work finds a new way to realize cobaltite perovskite with enhanced magnetoelectric properties and may deepen the understanding of oxide-proton interaction in an aqueous solution.

Automated summary

In this study, researchers discovered that classical transition-metal oxide (TMO) brownmillerite SrCoO2.5 films can transition to a metastable perovskite phase in a weak acidic solution. This metastable perovskite exhibits strong ferromagnetism and greatly elevated electrical conductivity, similar to prototypical perovskite SrCoO3. Two possible mechanisms were proposed to explain this phenomenon, with the control experiments indicating that the dominant process is active oxygen filling.