Redox‐based memristive devices are one of the most attractive candidates for future nonvolatile memory applications and neuromorphic circuits, and their performance is determined by redox processes and the corresponding oxygen‐ion dynamics. In this regard, brownmillerite SrFeO2.5 has been recently introduced as a novel material platform due to its exceptional oxygen‐ion transport properties for resistive‐switching memory devices. However, the underlying redox processes that give rise to resistive switching remain poorly understood. By using X‐ray absorption spectromicroscopy, it is demonstrated that the reversible redox‐based topotactic phase transition between the insulating brownmillerite phase, SrFeO2.5, and the conductive perovskite phase, SrFeO3, gives rise to the resistive‐switching properties of SrFeOx memristive devices. Furthermore, it is found that the electric‐field‐induced phase transition spreads over a large area in (001) oriented SrFeO2.5 devices, where oxygen vacancy channels are ordered along the in‐plane direction of the device. In contrast, (111)‐grown SrFeO2.5 devices with out‐of‐plane oriented oxygen vacancy channels, reaching from the bottom to the top electrode, show a localized phase transition. These findings provide detailed insight into the resistive‐switching mechanism in SrFeOx‐based memristive devices within the framework of metal–insulator topotactic phase transitions.

We had discovered novel resistance switching phenomena in SrCoOx epitaxial thin films. We have interpreted the results in terms of the topotactic phase transformation between their insulating brownmillerite phase and the conducting perovskite phase and the existence of a rather vertical conducting filament due to its inherent layered structure. However, the rough interface observed between the SrCoOx and the Au top electrode (area ~10000 μm2) was assumed to result in the observed fluctuation in key switching parameters. In order to verify the effect of rough interface on the switching performance in the SrCoOx device, in this work, we studied the resistive switching properties of a SrCoOx device by placing a Au-coated tip (end area ~0.5 μm2) directly on the film surface as the top electrode. The resulting device displayed much improved endurance and showed high uniformity in key switching parameters as compared to the device having a large top electrode area. A simulation result confirmed that the Au-coated tip provides a local confinement of the electrical field, resulting in confinement of oxygen ion distribution and therefore localization of the conducting filament. By minimizing other free and uncontrollable parameters, the designed experiment here provides the most direct and isolated evidence that the rough interface between electrode and ReRAM matrix is detrimental for the reproducibility of resistivity switching phenomena.

Oxygen-vacancy-ordered brownmillerite oxides offer a reversible topotactic phase transition by significantly varying the oxygen stoichiometry of the material without losing its lattice framework. This phase transition leads to substantial changes in the physical and chemical properties of brownmillerite oxides, including electrical and ion conductivity, magnetic state, and oxygen diffusivity. In this study, the variations in the resistive switching mode of the epitaxial brownmillerite SrFeO 2.5 thin film in the device were studied by systematically controlling the oxygen concentration, which could be varied by changing the compliance current during the first electroforming step. Depending on the compliance current, the SrFeO 2.5 devices exhibited either low-power bipolar resistive switching or complementary resistive switching behaviors. A physical model based on the internal redistribution of oxygen ions between the interfaces with the top and the bottom electrodes was developed to explain the complementary resistive switching behavior. This model was experimentally validated using impedance spectroscopy. Finally, the gradual conductance variation in the brownmillerite SrFeO 2.5 thin films was exploited to realize synaptic learning.

Epitaxial brownmillerite SrFeO2.5 thin films were deposited on conductive Nb-doped SrTiO3 single crystal (001) and (111)-oriented substrates using pulsed laser deposition, and their resistive switching behavior was investigated. In both the (001) and (111) device configuration, the bottom SrFeO2.5/Nb:SrTiO3 interface exhibited Ohmic behavior, while the top Au/BM-SrFeO2.5 interface displayed Schottky-like contact. Unfortunately, no resistive switching behavior was observed in the (001) devices, where the oxygen vacancy channels of SrFeO2.5 are ordered along the in-plane direction of the device. Conversely, the (111)-grown SrFeO2.5 thin films with out-of-plane oriented ordered oxygen vacancy channels displayed excellent resistive switching behavior with a high on/off ratio (∼104). The discrepancies between the (001) and (111) devices were explained in terms of their oxygen dynamics and corresponding topotactic phase transition in the SrFeO2.5 switching layer.

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