Inflection of Resistive Switching Behavior in Atomically Precise Silver Cluster‐Assembled Materials

Abstract Bottom‐up design of electronic materials based on nanometer‐sized building blocks requires precise control over their self‐assembly process. Atomically precise metal nanoclusters (NCs) are the well‐characterized building blocks for crafting tunable nanomaterials. Here, a solution‐processed assembly of a newly synthesized molecular silver nanocluster (0 D Ag₁₂‐NC) into a 1D nanocluster chain (1 D Ag₁₂‐CAM) is mediated by 4,4′‐bipyridine linker Both 0 D Ag₁₂‐NC and 1 D Ag₁₂‐CAM consist of Ag₁₂ core that adopts the cuboctahedron geometry protected by organic ligands. The resistive switching devices are fabricated in a sandwich‐like structure of ITO (Indium tin oxide)/X/Ag (where X is either 0 D Ag₁₂‐NC or 1 D Ag₁₂‐CAM). The device based on 1 D Ag₁₂‐CAM exhibited excellent resistive switching behaviour, enduring up to 1000 cycles and boasting a fivefold higher I_on/I_off ratio compared to the device based on the molecular 0 D Ag₁₂‐NC nanocluster. Furthermore, the device based on 1 D Ag₁₂‐CAM demonstrated negative differential resistance (NDR) phenomena, achieving a peak‐to‐valley ratio of 2.34 with a switching efficiency of 23 Ns. This work highlights the importance of interconnecting molecular nanoclusters into 1D nanocluster chains for fine‐tuning resistive memory properties in futuristic electronic appliances.