Formation of Solid-State Excitons in Ultrathin Crystalline Films of PTCDA: From Single Molecules to Molecular Stacks

We directly follow the evolution of the absorption spectrum from a single molecule to a dimer and further to a one-dimensional molecular stack: We determine the optical absorption properties of ordered monolayer to multilayer films of PTCDA (3,4,9,10-perylenetetracarboxylic dianhydride) on muscovite mica(0001) surfaces by in situ differential reflectance spectroscopy. The data clearly show the transition from the single molecule to a dimer spectrum, followed by the exciton delocalization to a molecular crystal exciton. The accompanying spectral shifts compare favorably with recent model concepts.