Molecular Rectifying Diodes Based on an Aluminum/4′-Hydroxy-4-biphenyl Carboxylic Acid/p+-Silicon Junction†

The charge transport mechanism of a wire can be revealed by how its electrical resistance varies with length. We have measured the resistance and current-voltage characteristics of conjugated molecular wires ranging in length from 1 to 7 nanometers, connected between metal electrodes. We observe the theoretically predicted change in direct-current transport from tunneling to hopping as a function of systematically controlled wire length. We also demonstrate that site-specific disruption of conjugation in the wires greatly increases resistance in the hopping regime but has only a small effect in the tunneling regime. These nanoscale transport measurements elucidate the role of molecular length and bond architecture on molecular conductivity and open opportunities for greater understanding of electrical transport in conjugated polymer films.