In Operando Modulation of Rectification in Molecular Tunneling Junctions Comprising Reconfigurable Molecular Self-Assemblies.

The reconfiguration of molecular tunneling junctions during operation via the self-assembly of bilayers of glycol ethers is described. Well-established functional groups are used to modulate the magnitude and direction of rectification in assembled tunneling junctions by exposing them to solutions containing different glycol ethers. Variable-temperature measurements confirm that rectification occurs by the expected bias-dependent tunneling-hopping mechanism for these functional groups and that glycol ethers, besides being an unusually efficient tunneling medium, behave similarly to alkanes. Memory bits are fabricated from crossbar junctions prepared by injecting eutectic Ga-In (EGaIn) into microfluidic channels. The states of two 8-bit registers were set by trains of droplets such that they are able to perform logical AND operations on bit strings encoded into chemical packets that alter the composition of the crossbar junctions through self-assembly to effect memristor-like properties. This proof-of-concept work demonstrates the potential for fieldable devices based on molecular tunneling junctions comprising self-assembled monolayers and bilayers.