Interface dipole formation of different ZnPcCl8 phases on Ag(111) observed by Kelvin probe force microscopy

Recently, we investigated the adsorption of octachloro zinc phthalocyanine (ZnPcCl8) on Ag(111) by scanning tunneling microscopy. Compared to the standard phthalocyanine, halogenated phthalocyanine molecules show a much more complex binding behavior, which results in the formation of three different structural phases. These phases follow from the ordering process with the formation of 8, 4 and 0 intermolecular hydrogen-halogen bonds (Abel et al 2006 ChemPhysChem 7 82). In the present work we investigate these phases by Kelvin probe force microscopy in order to quantitatively deduce the electric interface barrier of the first monolayer. Our measurements reveal that the binding behavior does not only affect the structural ordering but also the interface dipole formation, which leads to different work functions. The fact that we observe interface barriers of opposite signs between ordered and disordered molecular layers underlines the importance of exactly knowing the molecular arrangement at the interface when assembling organic molecule devices.