Asymmetric Bipolar Resistive Switching of Halide Perovskite Film in Contact with TiO₂ Layer

Halide perovskite materials such as methylammonium lead iodide (CH₃NH₃PbI₃) have attracted considerable interest for the resistive random-access memory applications, which exploit a dramatic change in the resistance by an external electric bias. In many semiconductor films, the drift, accumulation, and chain formation of defects explain the change in the resistance by an external bias. This study demonstrates that the interface of CH₃NH₃PbI₃ with TiO₂ has a significant impact on the formation and rupture of defect chains and causes the asymmetric bipolar resistive switching in the Au/CH₃NH₃PbI₃/TiO₂/FTO device (FTO = fluorine-doped tin oxide). When a negative bias is applied to the Au electrode, iodine interstitials with the lowest migration activation energy move toward TiO₂ in the CH₃NH₃PbI₃ layer and pile up at the CH₃NH₃PbI₃-TiO₂ interface. Under the same condition, oxygen vacancies in the TiO₂ layer also travel to the CH₃NH₃PbI₃-TiO₂ interface and strongly attract iodine interstitials. As a result, a Schottky barrier appears at the CH₃NH₃PbI₃-TiO₂ interface, and the resistance of Au/CH₃NH₃PbI₃/TiO₂/FTO becomes much larger than that of Au/CH₃NH₃PbI₃/FTO in the high resistance state. The frequency dependence of the capacitance confirms the asymmetric appearance of a large space charge polarization at the CH₃NH₃PbI₃-TiO₂ interface, which causes the unique bipolar resistive switching behavior with the on/off ratio (10³) and retention time (>10⁴ seconds) at -0.85 V in Au/CH₃NH₃PbI₃/TiO₂/FTO film.