<title>Design of domain size and molecular interactions in organic semiconductors to control the emission yield of thin films</title>

Perylene- and phthalocyanine- pigment molecules were systematically modified and consequences were studied for their solid state properties. Thin films (1 - 150 nm) were prepared by physical vapor deposition. Intermolecular interactions were probed by optical measurements in absorption and emission. Atomic force microscopy served to analyze the morphology of films. Different interactions among the molecules and with the substrate surfaces allowed to prepare either crystalline or amorphous films. Crystalline films of perylene pigments were typically characterized by strong chromophore coupling leading to a characteristic splitting, well- defined shifts of the optical absorption bands and emission mainly from excimer species whereas the chromophore coupling in amorphous films was suppressed sufficiently to provide a significantly increased optical emission yield from uncoupled monomer states. Temperature-dependent optical emission experiments are presented which allow a detailed discussion of monomer vs. excimer emission. Decoupling of the chromophores could be obtained by appropriate chemical substitutions at the aromatic core system of phthalocyanines and perylene pigments that led to strong deviations from planarity. This was achieved by the introduction of bulky substituents in the bay position of the aromatic perylene core and by changes in the coordination number of the central group in phthalocyanines. The strategy led to a strongly enhanced optical emission for both classes of materials. This could be obtained, however, either in an amorphous arrangement of the molecules or under conservation of crystallinity, both offering alternative advantages.