Printed High‐Entropy Prussian Blue Analogs for Advanced Non‐Volatile Memristive Devices

Abstract Non‐volatile memristors dynamically switch between high (HRS) and low resistance states (LRS) in response to electrical stimuli, essential for electronic memories, neuromorphic computing, and artificial intelligence. High‐entropy Prussian blue analogs (HE‐PBAs) are promising insertion‐type battery materials due to their diverse composition, high structural integrity, and favorable ionic conductivity. This work proposes a non‐volatile, bipolar memristor based on HE‐PBA. The device, featuring an active layer of HE‐PBA sandwiched between Ag and ITO electrodes, is fabricated by inkjet printing and microplotting. The conduction mechanism of the Ag/HE‐PBA/ITO device is systematically investigated. The results indicate that the transition between HRS and LRS is driven by an insulating‐metallic transition, triggered by extraction/insertion of highly mobile Na + ions upon application of an electric field. The memristor operates through a low‐energy process akin to Na + shuttling in Na‐ion batteries rather than depending on formation/rupture of Ag filaments. Notably, it showcases promising characteristics, including non‐volatility, self‐compliance, and forming‐free behavior, and further exhibits low operation voltage ( V SET = −0.26 V, V RESET = 0.36 V), low power consumption ( P SET = 26 µW, P RESET = 8.0 µW), and a high R OFF / R ON ratio of 10 4 . This underscores the potential of high‐entropy insertion materials for developing printed memristors with distinct operation mechanisms.