Revealing Suppressed Intermolecular Coupling Effects in Aggregated Organic Semiconductors by Diluting the Crystal: Model System Perfluoropentacene:Picene.

In order to investigate the effects of intermolecular interactions on the optical properties of organic semiconductors, we employ mixing of the organic semiconductor perfluoropentacene (PFP; C22F14) with the wide band-gap organic semiconductor picene (PIC; C22H14). The binary mixed thin films are prepared by simultaneous coevaporation of PIC and PFP in vacuum. We determine the optical properties of the blends by differential reflectance spectroscopy (absorption) and photoluminescence (emission). PFP:PIC thin films are a rare case of mixed thin films with a known molecular packing. The formation of equimolar mixed domains with a crystal structure clearly different from that of the pure compounds is, in the case of nonequimolar blends, accompanied by pure domains of the excess compound. Due to the wide band gap of PIC, the effect of reduced intermolecular interactions between PFP molecules can be studied in detail without any direct contributions of PIC to the spectra. We find a strongly enhanced emission from PFP in the mixed thin films, which can be explained by decoupling. Real-time investigations of the absorption spectra during growth provide further insight into intermolecular coupling effects on optical properties.

Epitaxial Growth of an Organic p-n Heterojunction: C60 on Single-Crystal Pentacene.

Designing molecular p-n heterojunction structures, i.e., electron donor-acceptor contacts, is one of the central challenges for further development of organic electronic devices. In the present study, a well-defined p-n heterojunction of two representative molecular semiconductors, pentacene and C60, formed on the single-crystal surface of pentacene is precisely investigated in terms of its growth behavior and crystallographic structure. C60 assembles into a (111)-oriented face-centered-cubic crystal structure with a specific epitaxial orientation on the (001) surface of the pentacene single crystal. The present experimental findings provide molecular scale insights into the formation mechanisms of the organic p-n heterojunction through an accurate structural analysis of the single-crystalline molecular contact.