Electronic structure of epitaxial thin films of bay-substituted perylene bisimide dyes

We have investigated epitaxial thin films of three air-stable organic n-type semiconducting perylene tetracarboxylic acid bisimides (PBIs) with fluoroalkyl groups in the imide position with a combination of X-ray, UV, and inverse photoelectron spectroscopy. We explore the applicability of film preparation by organic molecular beam deposition (OMBD) under ultra-high vacuum conditions to these compounds. By means of fluorine and chlorine substituents in the bay area a systematic torsion of the pi-conjugated core of these three PBIs is achieved. Accordingly, these molecules offer a model system to analyze the interplay between the molecular conformation, the film structure, and the electronic structure. Our results show that the PBIs can be deposited intact and contamination free by OMBD and relatively smooth films with layer-to-layer growth can be established. Moreover, the valence spectra reveal the effect of the electro-negative bay substituents as well as of the twisting of the perylene core, which leads to energy shifts of the occupied and unoccupied frontier orbitals.