Enhanced Switching Ratio and Long-Term Stability of Flexible RRAM by Anchoring Polyvinylammonium on Perovskite Grains

The ON/OFF ratio and long-term stability are two important issues for flexible organic-inorganic hybrid perovskite (OHP) resistive random access memory (RRAM) for practical applications. In this work, polyvinylammonium (PVAm) is applied to partially replace methylamine ions (MA⁺) to fabricate the stable and flexible polymeric OHP RRAM devices, wherein PVAm acts as nucleation sites and the template for crystalline growth of MAPbI₃ to tune the microscopic perovskite structure. Simultaneously, the multiple perovskite grain interfaces are strengthened through the long-carbochain polymeric backbone, hence producing a continuous and compact perovskite film. As a result, the PVAm-modified OHP RRAM device shows remarkable enhancement of the ON/OFF ratio, long-term stability, and flexibility compared with the unmodified OHP device. Specifically, the polymeric OHP device exhibits fast and stable nonvolatile resistive switching (RS) characteristics with an ON/OFF ratio of ∼10⁵ and a set voltage of -0.45 V under ambient conditions. Also, the distinct multilevel RS behavior can be realized in this device by controlling the compliance current in the SET process. Additionally, the unsealed polymeric OHP device manifests the striking long-term stability, which can still maintain the stable memory performance after 1 year exposure to the humid and thermal ambient environment. Furthermore, the flexible polymeric OHP device was also fabricated and affords the excellent bending endurance behavior by showing a reproducible RS property over 100-cycle bending experiments. This work provides a new perovskite-based material design strategy of polymeric OHP for stable and flexible RRAM devices with the high ON/OFF ratio.