A Mechanism for Conductance Switching in Carbon-Based Molecular Electronic Junctions

A molecular junction formed by a 10-15 Å organic monolayer between carbon and mercury contacts exhibited conductance switching for several monolayer structures. When the carbon potential was scanned to a sufficiently negative voltage relative to the mercury, the junction resistance suddenly decreased by at least an order of magnitude, and high resistance could be restored by a positive voltage scan. The high and low conductance states were persistent, and conductance switching was repeatable at least 100 cycles for the case of a terphenyl junction. The switching behavior is consistent with phenyl ring rotation and formation of a planar, quinoid structure as a consequence of electron injection into the monolayer. A unique feature of the junction structure is the strong electronic coupling between the monolayer p system and the graphitic carbon through a quinoid double bond. Not only does this interaction lead to high conductivity and possible practical applications as a molecular switch, it also combines the electronic properties of the conjugated monolayer with those of the graphitic substrate. The switching mechanism reported here is an example of ‘‘dry electrochemistry’’ in which a redox process appears to occur under the influence of a high electric field in the absence of solvent or electrolyte. © 2002 The Electrochemical Society. @DOI: 10.1149/1.1490716#