Nanoscale Work Function Contrast Induced by Decanethiol Self-Assembled Monolayers on Au(111).

In this paper, we obtain maps of the spatial tunnel barrier variations in self-assembled monolayers of organosulfurs on Au(111). Maps down to the sub-nanometer scale are obtained by combining topographic scanning tunneling microscopy images with d/d spectroscopy. The square root of the tunnel barrier height is directly proportional to the local work function and the d/d signal. We use ratios of the tunnel barriers to study the work function contrast in various decanethiol phases: the lying-down striped β phase, the dense standing-up φ phase, and the oxidized decanesulfonate λ phase. We compare the induced work function variations too: the work function contrast induced by a lying-down striped phase in comparison to the modulation induced by the standing-up φ phase, as well as the oxidized λ phase. By performing these comparisons, we can account for the similarities and differences in the effects of the mechanisms acting on the surface and extract valuable insights into molecular binding to the substrate. The pillow effect, governing the lowering of the work function due to lying-down molecular tails in the striped low density phases, seems to have quite a similar contribution as the surface dipole effect emerging in the dense standing-up decanethiol phases. The d/d spectroscopy map of the nonoxidized β phase compared to the map of the oxidized λ phase indicates that the strong binding of molecules to the substrate is no longer present in the latter.