| Summary: | Ultra-thin PTCDI-C8 films are vapor-deposited under ultra-high vacuum (UHV) conditions onto surfaces of p- or n-doped GaN(0001) samples. The X-ray photoelectron spectroscopy (XPS) results reveal a lack of strong chemical interaction between the PTCDI-C8 molecule and the substrate. Changes in the electronic structure of the substrate or the adsorbed molecules due to adsorption are not noticed at the XPS spectra. Work function changes have been measured as a function of the film thickness. The position of the HOMO level for films of thicknesses 3.2–5.5 nm has been determined. Energy diagrams of the interface between p- and n-type GaN(0001) substates and the PTCDI-C8 films are proposed. The fundamental molecular building blocks of the PTCDI-C8 films on GaN(0001), assembled by self-organization, have been identified. They are rows of PTCDI-C8 molecules stacked in “stand-up” positions in reference to the substrate, supported by the π–π bonds which are formed between the molecular cores of the molecules and monomolecular layers constituted by rows which are tilted in reference to the layer plane. The layers are epitaxially oriented. The epitaxial relation between the rows and the crystallographic directions of the substrate are determined. A model of the PTCDI-C8 film’s growth on GaN(0001) substrate is proposed. The 3D islands of PTCDI-C8 molecules formed on the substrate surface during film deposition are thermodynamically unstable. The Volmer–Weber type of growth observed here is a kinetic effect. Rewetting processes are noticeable after film aging at room temperature or annealing at up to 100 °C.
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