Room‐Temperature AFM Electric‐Field‐Induced Topotactic Transformation between Perovskite and Brownmillerite SrFeOx with Sub‐Micrometer Spatial Resolution

Abstract Reversible structural transformations between perovskite (PV) ABO 3− δ and brownmillerite (BM) ABO 2.5 (A = Ca 2+ , Sr 2+ ; B = Fe 4+/3 , Co 4+/3+ ) oxides can be induced by topotactic oxygen exchange at moderate temperatures under reducing/oxidizing conditions. The combination of a large oxide‐ion conductivity and a small free energy difference between the 4+/3+ oxidation states of many 3d transition metal ions enables these topotactic transformations. Herein, it is demonstrated that the electric field produced by a voltage‐biased atomic force microscopy tip can induce such transformation between PV SrFeO 3− δ and BM SrFeO 2.5 at room temperature and with sub‐micrometer spatial resolution. Interestingly, the structural transformation is kept after the electric field is removed, allowing a nonvolatile control of the local chemical, electrical, optical, and magnetic properties. Thus, the results presented in this paper open the door for the fabrication of stable ionic‐based devices through the electric field patterning of different crystallographic phases.