A single atom change turns insulating saturated wires into molecular conductors

Abstract

We present an efficient strategy to modulate tunnelling in molecular junctions by changing the tunnelling decay coefficient, β, by terminal-atom substitution which avoids altering the molecular backbone. By varying X = H, F, Cl, Br, I in junctions with S(CH₂)_(10-18)X, current densities (J) increase >4 orders of magnitude, creating molecular conductors via reduction of β from 0.75 to 0.25 Å⁻¹. Impedance measurements show tripled dielectric constants (ε_r) with X = I, reduced HOMO-LUMO gaps and tunnelling-barrier heights, and 5-times reduced contact resistance. These effects alone cannot explain the large change in β. Density-functional theory shows highly localized, X-dependent potential drops at the S(CH₂)_nX//electrode interface that modifies the tunnelling barrier shape. Commonly-used tunnelling models neglect localized potential drops and changes in ε_r. Here, we demonstrate experimentally that $\beta \propto 1/\sqrt{{\epsilon }_r}$, suggesting highly-polarizable terminal-atoms act as charge traps and highlighting the need for new charge transport models that account for dielectric effects in molecular tunnelling junctions.

In molecular junctions, where a molecule is placed between two electrodes, the current passed decays exponentially as a function of length. Here, Chen et al. show that this exponentially attenuation can be controlled by changing a single atom at the end of the molecular wire.