Chemical Conformation Induced Transport Carrier Switching in Molecular Junction based on Carboxylic-Terminated Thiol...

The paper demonstrates the effect of the chemical conformation of the -COOH group on the transport characteristic including conductance, rectification, and length effect in molecular junctions (MJs) formed by self-assembled monolayers of carboxylic-terminated thiol molecules. For an alkyl chain shorter than C₁₁, the transport mechanism was attributed to a direct off-resonant tunneling of a hole carrier, located at the Au-S interface, whereas a hopping mechanism was assigned to the alkyl chain longer than the C₁₁ chain located at the -COOH group. The hopping mechanism may be operated by electron transport associated with the breaking of the -OH bonding likely driven by a voltage. Importantly, at the C₁₁ alkyl chain, we observed that the transport carrier operating in MJs could change from a hole carrier into an electron carrier. The result strongly proves that the chemical conformation should be considered in analyzing molecular electronics and provides a basis for the rational design of molecular electronic devices.