Atomic-scale observation of strain-dependent reversible topotactic transition in La_0.7Sr_0.3MnO_x films under an ultra-high vacuum environment

Reversible topotactic phase transition between perovskite (PV) and oxygen-vacancy-ordered brownmillerite (BM) structures provides an effective platform for realizing the control of physical properties in complex tran-sition metal oxides. However, such reversibility always requires extreme external conditions, that is, a high temperature and vacuum environment during the PV-BM transition, while an oxidizing atmosphere and rela-tively low temperature vice versa. Here, we experimentally observe the reversible process in strained La0.7Sr0.3MnOx films at atomic scale by using in-situ heating aberration-corrected scanning transmission electron microscopy (STEM). Apart from the conventional reduction reaction of creating oxygen-vacancy-ordered frameworks after heating in the TEM, the inverse process of BM-to-PV transition is unexpectedly discovered under such an ultra-high vacuum atmosphere (similar to 10(-9) Torr) at room temperature. Moreover, this abnormal behavior is strain-dependent. The large compressive strain is found to be detrimental to the inverse phase transition. The density functional theory (DFT) calculations show that the high oxygen affinity of La0.7Sr0.3MnO2.5 is responsible for the reversible transitions. Our findings provide a new insight into the redox reactions of manganite and might be further utilized for potential applications in solid fuel cells, oxygen sensors or resistive switching memories.