Gap Size-Dependent Plasmonic Enhancement in Electroluminescent Tunnel Junctions

Nanoscale plasmonic structures have been primarily characterized through scattering studies, but electroluminescence offers an exciting alternative from a technological standpoint by removing the need for optical excitation. In sub-nanometer biased junctions, electronic tunneling can serve as the excitation source for plasmon-coupled electroluminescence, but the gap size dependence to this plasmonic enhancement has not been characterized. Here, we simultaneously probe the electroluminescence and conductance of Au tunnel junctions. We find that plasmonic enhancement increases as the gap size is reduced for junctions biased between 1.4 and 1.8 V, consistent with the behavior of charge transfer plasmons. At biases above 1.9 V, we see decreasing plasmonic enhancement with the decreasing gap, showing quenching due to tunneling in remarkable agreement with the trends observed for high energy plasmons in scattering experiments. Critically, we find that plasmonic enhancement of electroluminescence is gap size-dependent and, furthermore, is in agreement with the nature of modes excited by scattering

Too Hot for Photon-Assisted Transport: Hot-Electrons Dominate Conductance Enhancement in Illuminated Single-Molecule Junctions

We investigate light-induced conductance enhancement in single-molecule junctions via photon-assisted transport and hot-electron transport. Using 4,4′-bipyridine bound to Au electrodes as a prototypical single-molecule junction, we report a 20–40% enhancement in conductance under illumination with 980 nm wavelength radiation. We probe the effects of subtle changes in the transmission function on light-enhanced current and show that discrete variations in the binding geometry result in a 10% change in enhancement. Importantly, we prove theoretically that the steady-state behavior of photon-assisted transport and hot-electron transport is identical but that hot-electron transport is the dominant mechanism for optically induced conductance enhancement in single-molecule junctions when the wavelength used is absorbed by the electrodes and the hot-electron relaxation time is long. We confirm this experimentally by performing polarization-dependent conductance measurements of illuminated 4,4′-bipyridine junctions. Finally, we perform lock-in type measurements of optical current and conclude that currents due to laser-induced thermal expansion mask optical currents. This work provides a robust experimental framework for studying mechanisms of light-enhanced transport in single-molecule junctions and offers tools for tuning the performance of organic optoelectronic devices by analyzing detailed transport properties of the molecules involved

Probing the Conductance of the σ‑System of Bipyridine Using Destructive Interference

Guidelines to predict trends in the electrical conductance of molecules have been developed for the π-system of conjugated systems. Little is known, however, about the conductance of the underlying σ-systems because the π-system usually dominates the transport. Here we study a family of bipyridine-based molecules using STM-break junction experiments and density functional theory transport calculations. We use different lengths and substitution patterns to probe the role of both the σ-system and the π-system in controlling conductance. By exploiting the destructive interference feature found in the π-system of the meta-coupled six-membered aromatic rings, we show that the conductance of the σ-system of a meta-coupled molecule can be probed directly and can even exceed that of its para-coupled analog. These results add to the understanding of the conductance through the chemically hidden σ-electrons

Breaking Down Resonance: Nonlinear Transport and the Breakdown of Coherent Tunneling Models in Single Molecule Junctions

The promise of the field of single-molecule electronics is to reveal a new class of quantum devices that leverages the strong electronic interactions inherent to subnanometer scale systems. Here, we form Au–molecule–Au junctions using a custom scanning tunneling microscope and explore charge transport through current–voltage measurements. We focus on the resonant tunneling regime of two molecules, one that is primarily an electron conductor and one that conducts primarily holes. We find that in the high bias regime, junctions that do not rupture demonstrate reproducible and pronounced negative differential resistance (NDR)-like features followed by hysteresis with peak-to-valley ratios exceeding 100 in some cases. Furthermore, we show that both junction rupture and NDR are induced by charging of the molecular orbital dominating transport and find that the charging is reversible at lower bias and with time with kinetic time scales on the order of hundreds of milliseconds. We argue that these results cannot be explained by existing models of charge transport and likely require theoretical advances describing the transition from coherent to sequential tunneling. Our work also suggests new rules for operating single-molecule devices at high bias to obtain highly nonlinear behavior