Issue 79, 2016

Low variability of single-molecule conductance assisted by bulky metal–molecule contacts

Abstract

A detailed study of the trimethylsilylethynyl moiety, –C[triple bond, length as m-dash]CSiMe3 (TMSE), as an anchoring group in metal|molecule|metal junctions, using a combination of experiment and density functional theory is presented. It is shown that the TMSE anchoring group provides improved control over the molecule–substrate arrangement within metal|molecule|metal junctions, with the steric bulk of the methyl groups limiting the number of highly transmissive binding sites at the electrode surface, resulting in a single sharp peak in the conductance histograms recorded by both the in situ break junction and I(s) STM techniques. As a consequence of the low accessibility of the TMSE group to surface binding configurations of measurable conductance, only about 10% of gold break junction formation cycles result in the clear formation of molecular junctions in the experimental histograms. The DFT-computed transmission characteristics of junctions formed from the TMSE-contacted oligo(phenylene)ethynylene (OPE)-based molecules described here are dominated by tunneling effects through the highest-occupied molecular orbitals (HOMOs). This gives rise to similar conductance characteristics in these TMSE-contacted systems as found in low conductance-type junctions based on comparably structured OPE-derivatives with amine-contacts that also conduct through HOMO-based channels.

Graphical abstract: Low variability of single-molecule conductance assisted by bulky metal–molecule contacts

Supplementary files

Article information

Article type
Paper
Submitted
14 Jun 2016
Accepted
04 Aug 2016
First published
04 Aug 2016
This article is Open Access
Creative Commons BY license

RSC Adv., 2016,6, 75111-75121

Author version available

Low variability of single-molecule conductance assisted by bulky metal–molecule contacts

R. R. Ferradás, S. Marqués-González, H. M. Osorio, J. Ferrer, P. Cea, D. C. Milan, A. Vezzoli, S. J. Higgins, R. J. Nichols, P. J. Low, V. M. García-Suárez and S. Martín, RSC Adv., 2016, 6, 75111 DOI: 10.1039/C6RA15477H

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