Development and character of gap states on alkali doping of molecular films

Here we study the alkali metal induced effects on an ordered and aligned sexiphenyl monolayer on Cu(110) with angle-resolved UV spectroscopy (ARUPS). The caesium (Cs) induced gap states could clearly be identified by orbital tomography, a method based on ARUPS, which allows both the orbital character of these states and the molecular orientation to be determined. We show that with increasing alkali metal dose, doping proceeds in three distinct steps. Initially, Cs decouples the molecular monolayer from the substrate, with emptying of the lowest unoccupied molecular orbital (LUMO) that had been filled on hybridization with the substrate. Further Cs exposure refills the LUMO. Finally a filling of the LUMO + 1 by charge transfer from the alkali metal occurs. Remarkably, although long range order is not preserved and the molecular planes tilt away from the surface, the molecules remain aligned parallel to the [1¯10] azimuth during the whole doping process