Experimental and Theoretical Analysis of Nanotransport in Oligophenylene Dithiol Junctions as a Function of Molecular Length and Contact Work Function
- Publication date
- 2015
- Publisher
Abstract
We report the results of an extensive investigation of metal–molecule–metal tunnel junctions based on oligophenylene dithiols (OPDs) bound to several types of electrodes (M<sub>1</sub>–S–(C<sub>6</sub>H<sub>4</sub>)<i><sub>n</sub></i>–S–M<sub>2</sub>, with 1 ≤ <i>n</i> ≤ 4 and M<sub>1,2</sub> = Ag, Au, Pt) to examine the impact of molecular length (<i>n</i>) and metal work function (Φ) on junction properties. Our investigation includes (1) measurements by scanning Kelvin probe microscopy of electrode work function changes (ΔΦ = Φ<sub>SAM</sub> – Φ) caused by chemisorption of OPD self-assembled monolayers (SAMs), (2) measurements of junction current–voltage (<i>I</i>–<i>V</i>) characteristics by conducting probe atomic force microscopy in the linear and nonlinear bias ranges, and (3) direct quantitative analysis of the full <i>I</i>–<i>V</i> curves. Further, we employ transition voltage spectroscopy (TVS) to estimate the energetic alignment ε<sub>h</sub> = <i>E</i><sub>F</sub> – <i>E</i><sub>HOMO</sub> of the dominant molecular orbital (HOMO) relative to the Fermi energy <i>E</i><sub>F</sub> of the junction. Where photoelectron spectroscopy data are available, the ε<sub>h</sub> values agree very well with those determined by TVS. Using a single-level model, which we justify <i>via ab initio</i> quantum chemical calculations at post-density functional theory level and additional UV–visible absorption measurements, we are able to quantitatively reproduce the <i>I</i>–<i>V</i> measurements in the whole bias range investigated (∼1.0–1.5 V) and to understand the behavior of ε<sub>h</sub> and Γ (contact coupling strength) extracted from experiment. We find that Fermi level pinning induced by the strong dipole of the metal–S bond causes a significant shift of the HOMO energy of an adsorbed molecule, resulting in ε<sub>h</sub> exhibiting a weak dependence with the work function Φ. Both of these parameters play a key role in determining the tunneling attenuation factor (β) and junction resistance (<i>R</i>). Correlation among Φ, ΔΦ, <i>R</i>, transition voltage (<i>V</i><sub>t</sub>), and ε<sub>h</sub> and accurate simulation provide a remarkably complete picture of tunneling transport in these prototypical molecular junctions