In this work, we bridge the gap between short-range tunneling in molecular junctions and activated hopping in bulk organic films, and greatly extend the distance range of charge transport in molecular electronic devices. Three distinct transport mechanisms were observed for 4.5–22-nm-thick oligo(thiophene) layers between carbon contacts, with tunneling operative when d < 8 nm, activated hopping when d > 16 nm for high temperatures and low bias, and a third mechanism consistent with field-induced ionization of highest occupied molecular orbitals or interface states to generate charge carriers when d = 8–22 nm. Transport in the 8–22-nm range is weakly temperature dependent, with a field-dependent activation barrier that becomes negligible at moderate bias. We thus report here a unique, activationless transport mechanism, operative over 8–22-nm distances without involving hopping, which severely limits carrier mobility and device lifetime in organic semiconductors. Charge transport in molecular electronic junctions can thus be effective for transport distances significantly greater than the 1–5 nm associated with quantum-mechanical tunneling.

Surface grafting from diazonium solutions triggered by localized surface plasmon has been investigated. An organic layer that is 20–30 nm thick is easily grafted onto gold nanoparticles (AuNPs) by visible-light illumination in a few minutes without any reducing agent or molecular photocatalyst. Grafting depends on the wavelength and polarization of the incident light. As a consequence, the orientation of the growth of the layer deposited on the AuNPs can be controlled by polarized light. Grafting is also highly enhanced between adjacent AuNPs or at the corners of triangular AuNPs, that is, in plasmonic hot spots. These results clearly demonstrate plasmon enhancement and strongly suggest that the transfer of hot electrons from the excited plasmonic NPs to the diazonium is the main mechanism. They also confirm that localized surface plasmon resonance can induce nanolocalized electrochemical reactions, thus contributing to the field of “plasmonic electrochemistry”.