Mechanical Deformation Distinguishes Tunneling Pathways in Molecular Junctions.

Developing a clearer understanding of electron tunneling through molecules is a central challenge in molecular electronics. Here we demonstrate the use of mechanical stretching to distinguish orbital pathways that facilitate tunneling in molecular junctions. Our experiments employ junctions based on self-assembled monolayers (SAMs) of homologous alkanethiols (C nT) and oligophenylene thiols (OPT n), which serve as prototypical examples of σ-bonded and π-bonded backbones, respectively. Surprisingly, molecular conductances ( Gmolecule) for stretched C nT SAMs have exactly the same length dependence as unstretched C nT SAMs in which molecular length is tuned by the number of CH2 repeat units, n. In contrast, OPT n SAMs exhibit a 10-fold-greater decrease in Gmolecule with molecular length for stretched versus unstretched cases. Experiment and theory show that these divergent results are explained by the dependence of the molecule-electrode electronic coupling Γ on strain and the spatial extent of the principal orbital facilitating tunneling. In particular, differences in the strain sensitivity of Γ versus the repeat-length ( n) sensitivity can be used to distinguish tunneling via delocalized orbitals versus localized orbitals. Angstrom-level tuning of interelectrode separation thus provides a strategy for examining the relationship between orbital localization or delocalization and electronic coupling in molecular junctions and therefore for distinguishing tunneling pathways.

Hopping transport and the Hall effect near the insulator-metal transition in electrochemically gated poly(3-hexylthiophene) transistors.

Despite 35 years of investigation, much remains to be understood regarding charge transport in semiconducting polymers, including the ultimate limits on their conductivity. Recently developed ion gel gating techniques provide a unique opportunity to study such issues at very high charge carrier density. Here we have probed the benchmark polymer semiconductor poly(3-hexylthiophene) at electrochemically induced three-dimensional hole densities approaching 10(21) cm(-3) (up to 0.2 holes per monomer). Analysis of the hopping conduction reveals a remarkable phenomenon where wavefunction delocalization and Coulomb gap collapse are disrupted by doping-induced disorder, suppressing the insulator-metal transition, even at these extreme charge densities. Nevertheless, at the highest dopings, we observe, for the first time in a polymer transistor, a clear Hall effect with the expected field, temperature and gate voltage dependencies. The data indicate that at such mobilities (~0.8 cm(2)V(-1) s(-1)), despite the extensive disorder, these polymers lie close to a regime of truly diffusive band-like transport.