Supramolecular Order of Solution‐Processed Perylenediimide Thin Films: High‐Performance Small‐Channel n‐Type Organic Transistors

N,N ′‐1 H ,1 H ‐perfluorobutyl dicyanoperylenecarboxydiimide (PDIF‐CN 2 ), a soluble and air stable n‐type molecule, undergoes significant reorganization upon thermal annealing after solution deposition on several substrates with different surface energies. Interestingly, this system exhibits an exceptional edge‐on orientation regardless of the substrate chemistry. This preferential orientation is rationalized in terms of strong intermolecular interactions between the PDIF‐CN 2 molecules. The presence of a pronounced π–π stacking is confirmed by combining near‐edge X‐ray absorption fine structure spectroscopy (NEXAFS), dynamic scanning force microscopy (SFM) and surface energy measurements. The remarkable charge carrier mobility measured in field‐effect transistors, using both bottom‐ and top‐contact (bottom‐gate) configurations, underlines the importance of strong intermolecular interactions for the realization of high performing devices.