Charge transport and contact effects in nanoscale electrical junctions formed via conducting probe atomic force microscopy

This thesis describes the fabrication and characterization of nanoscale molecular junctions using conducting probe atomic force microscopy (CP-AFM). This technique involves using a metal-coated AFM tip to contact a self-assembled monolayer (SAM) of an organic molecule tethered to a metal surface. This is one of several strategies for the formation of nanoscale electrical junctions designed to probe the current-voltage characteristics of very small numbers of organic molecules. The general goals of this research are to gain a better understanding of the nature of charge transport through molecules, and to begin to pave the way for their use in commercial electronic devices. Important concerns in molecular electronic research can be broken into two general categories, those being the metal contacts and the molecules themselves. In the contact subcategory, issues such as metal work function, electrode roughness, and electrode cleanliness are all important in determining the resistance of a given junction. The physical details of monolayer formation, such as surface coverage, tilt angle, and surface functionality combine with the electronic structure of the molecules to dictate how a given molecule performs in a junction.; Included in this thesis is the first direct evidence that resistance in molecular junctions comprised of alkyl repeat units depends on the work function of the metal electrodes. Because an increase in metal work function corresponds to a smaller offset between the molecular HOMO and the junction Fermi level, this dependence also suggests that transport in these aliphatic systems occurs chiefly via hole tunneling. Also included is an analysis of the contribution to junction resistance that arises from each metal-molecule contact, and across the molecule in alkanethiol and alkanedithiol junctions.; The aromatic phenylene and acene systems are examined briefly, and phenylenes are shown to be more efficient conduits for charge transport, contrary to expectation. We postulate that this may be caused by a difference in junction topology between the two systems. Finally, a system of norbornylog molecules is examined, in which a change in the monolayer structure causes difficulties in direct interpretation of the results.