The use of two dimensional (2D) materials to improve the capabilities of electronic devices is a promising strategy that has recently gained much interest in both academy and industry. While the research on 2D metallic and semiconducting materials is well established, the knowledge and 2 applications of 2D insulators are still very scarce. In this report we study the presence of resistive switching (RS) in multilayer hexagonal boron nitride (h-BN) using different electrode materials, and we engineer a family of h-BN based resistive random access memories with tunable capabilities.The devices show the coexistence of forming-free bipolar and threshold type RS with low operation voltages down to 0.4 V, high current on/off ratios up to 10 6 , long retention times above 10 hours, as well as low variability. The RS is driven by the grain boundaries (GBs) in the polycrystalline h-BN stack, which allow the penetration of metallic ions from adjacent electrodes. This reaction can be boosted by the generation of B vacancies, which is more abundant at the GBs. To the best of our knowledge, h-BN is the first 2D material showing the coexistance of bipolar and threshold RS, which may open the door to additional functionalities and applications.Received: ((will be filled in by the editorial staff))Revised: ((will be filled in by the editorial staff))

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Boron Nitride (BN) is a two dimensional insulator with excellent chemical, thermal, mechanical, and optical properties, which make it especially attractive for logic device applications. Nevertheless, its insulating properties and reliability as a dielectric material have never been analyzed in-depth. Here, we present the first thorough characterization of BN as dielectric film using nanoscale and device level experiments complementing with theoretical study. Our results reveal that BN is extremely stable against voltage stress, and it does not show the reliability problems related to conventional dielectrics like HfO2, such as charge trapping and detrapping, stress induced leakage current, and untimely dielectric breakdown. Moreover, we observe a unique layer-by-layer dielectric breakdown, both at the nanoscale and device level. These findings may be of interest for many materials scientists and could open a new pathway towards two dimensional logic device applications

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