No abstract

The promise of transition voltage spectroscopy (TVS) is that molecular level positions can be determined in molecular devices without applying extreme voltages. Here, we consider the physics behind TVS in more detail. Remarkably, we find that the Simmons model employed thus far is inconsistent with experimental data. However, a coherent molecular transport model does justify TVS as a spectroscopic tool. Moreover, TVS may become a critical test to distinguish molecular junctions from vacuum tunnel junctions.

Transition voltage spectroscopy (TVS) has been proposed as a tool to analyze charge transport through molecular junctions. We extend TVS to Au-vacuum-Au junctions and study the distance dependence of the transition voltage V(t)(d) for clean electrodes in cryogenic vacuum. On the one hand, this allows us to provide an important reference for V(t)(d) measurements on molecular junctions. On the other hand, we show that TVS forms a simple and powerful test for vacuum tunneling models.

We discuss the relationship between the π-conjugation pattern, molecular length, and charge transport properties of molecular wires, both from an experimental and a theoretical viewpoint. Specifically, we focus on the role of quantum interference in the conductance properties of cross-conjugated molecules. For this, we compare experiments on two series of dithiolated wires. The first set we synthesized consists of three dithiolated oligo(phenylene ethynylene) (OPE) benchmark compounds with increasing length. The second series synthesized comprises three molecules with different π-conjugation patterns, but identical lengths, i.e. an anthracene (linear conjugation), an anthraquinone (cross-conjugation), and a dihydroanthracene (broken conjugation) derivative. To benchmark reliable trends, conductance experiments on these series have been performed by various techniques. Here, we compare data obtained by conductive-probe atomic force microscopy (CP-AFM) for self-assembled monolayers (SAMs) with single-molecule break junction and multi-molecule EGaIn data from other groups. For the benchmark OPE-series, we consistently find an exponential decay of the conductance with molecular length characterized by β = 0.37 ± 0.03 Å(-1) (CP-AFM). Remarkably, for the second series, we do not only find that the linearly conjugated anthracene-containing wire is the most conductive, but also that the cross-conjugated anthraquinone-containing wire is less conductive than the broken-conjugated derivative. We attribute the low conductance values for the cross-conjugated species to quantum interference effects. Moreover, by theoretical modeling, we show that destructive quantum interference is a robust feature for cross-conjugated structures and that the energy at which complete destructive interference occurs can be tuned by the choice of side group. The latter provides an outlook for future devices in this fascinating field connecting chemistry and physics.

Charge transport in networks of nanoparticles linked by molecular spacers is investigated. Remarkably, in the regime where cotunneling dominates, the molecular signature of a device is strongly enhanced. We demonstrate that the resistance ratio of identical networks with different molecular spacers increases dramatically, from an initial value of 50 up to 10(5) , upon entering the cotunneling regime. Our work shows that intrinsic molecular properties can be amplified through nanoscale engineering.

Mechanically controllable break junctions allow for an impressive level of control over the distance between two electrodes, but lack stability at room temperature. On the other hand, two-dimensional (2D) networks of nanoparticles bridged by molecules form a stable device structure for investigating molecular conductance properties. Here, we combine both techniques to create a robust platform for molecular charge transport with control over the inter-electrode distance on the picometer scale. The resistance change due to bending of our structures is dependent on the molecular species present between the nanoparticles.