Redox‐Active Polyaniline Covalently grafted Black Phosphorus Nanosheets for Integrated Digital‐Analogue Memristors

Abstract Surface covalent modification of black phosphorus (BP) with organic polymers represents a promising strategy to enhance its stability and tailor its electronic properties. Despite this potential, developing memristive materials through suitable polymer structures, grafting pathways, and polymerization techniques remains challenging. In this study, polyaniline (PANI)‐covalently grafted black phosphorus nanosheets (BPNS) are successfully prepared with redox functionalities via the in situ polymerization of aniline on the surface of 4‐aminobenzene‐modified BPNS. The PANI coating protects the BP from direct exposure to oxygen and water, and it endows the material with analog memristive properties, characterized by a continuously adjustable resistance within a limited voltage scan range. When subjected to a broader voltage scan, the Al/PANI‐g‐BPNS/ITO device demonstrates a typical bistable digital memristive behavior. The integration of both digital and analog memristive functionalities in a single device paves the way for the development of high‐density, multifunctional electronic components.