Heads and tails: simultaneous exposed and buried interface imaging of monolayers.

We have simultaneously imaged the chemically bound head groups and exposed tail groups in bicomponent alkanethiolate self-assembled monolayers on Au{111} with molecular resolution. This has enabled us to resolve the controversy of scanning tunneling microscopy image interpretation and to measure the molecular polar tilt and azimuthal angles. Our local measurements demonstrate that ordered domains with different superstructures also have varied buried sulfur head group structures.

Self-assembly of carboranethiol isomers on Au111: intermolecular interactions determined by molecular dipole orientations.

Self-assembled monolayer (SAM) structures and properties are dominated by two interactions: those between the substrate and adsorbate and those between the adsorbates themselves. We have fabricated self-assembled monolayers of m-1-carboranethiol (M1) and m-9-carboranethiol (M9) on Au[111]. The two isomers are nearly identical geometrically, but calculated molecular dipole moments show a sizable difference at 1.