Abstract
A molecule-scale diode is an essential component for the concept of molecular electronics. Here we report on heterogeneous contact-mediated rectifying behavior in single-molecule junctions. We performed massive current versus voltage characteristics measurements of metal-molecule-metal structures under stretching by a mechanical break junction method. In-situ deformations of the molecular bridges were revealed to induce stochastic switching of the rectifying direction to varying rectification ratio derived from the induced asymmetry in the contact motifs at the molecule termini. Aromatic molecules were found to enable stronger rectifications via the more pronounced Fermi pinning effect to shift the molecular orbital levels by the applied voltage. Dissimilar anchoring groups also served to stabilize the single-molecule diode properties by bestowing a chemically defined difference in the electronic coupling strengths at the electrode-molecule links. The present findings provide a guide to design diodes with the smallest and simplest structures.
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