Revealing the effect of substitutional cation doping in the A-site of nanoscale APbI₃ perovskite layers for enhanced retention and endurance in optoelectronic resistive switching for non-volatile bipolar memory devices

The effect of substitutional cation doping in the A-site of the nanoscale APbI₃ perovskite layer has been systematically investigated to achieve improvements in the charge-carrier dynamics and endurance of non-volatile bipolar (NVB) memory devices. We successfully adopted an energy-efficient, ultra-fast microwave-assisted solvothermal (MW-ST) synthesis route to prepare a sequence of APbI₃ (A = MA⁺, FA⁺, MAFA⁺, CsMA⁺ and CsMAFA⁺) perovskite powders with morphological transitions from cube-like polyhedrons to mixed polyhedrons and rods within 10 minutes at 120 °C without requiring any inert-gas atmosphere under high-humid ambient conditions. As-prepared APbI₃ powders were dissolved in DMSO:DMF, followed by the fabrication of a thin film via spin-coating. Upon annealing at 120 °C, the nanoscale self-assembled thin-film layer was formed. We observed that devices with the inorganic Cs⁺ cation with organic cations, (CsMAPI and CsMAFAPI) device showed improved endurance (3500 and 5000 cycles, respectively) and outstanding retention (60 000 s) owing to effective charge-carrier dynamics, compared to organic cation-based MAPI, FAPI and MAFAPI (1800, 1200 and 1300 cycles, respectively). Significantly, various cation-doped APbI₃-powders obtained via the MW-ST method remained to be stable for up to 5-months under high-humid conditions. Thus, enhanced optoelectronic-memory performance studies could provide an opportunity for next-generation nanoscale ORSNVB-memory devices for artificial intelligence (AI) and Internet of Things (IoT) applications.