Energy-level alignments and photo-induced carrier processes at the heteromolecular interface of quaterrylene and N,N'-dioctyl-3,4,9,10-perylenedicarboximide.

Photo-induced carrier processes at the heteromolecular interface of N,N'-dioctyl-3,4,9,10-perylenedicarboximide (PTCDI-C(8)) and quaterrylene (QT) on a molecular scale were examined by optical and photoelectron spectroscopy. The energy level alignments of the molecules were determined by X-ray photoelectron spectroscopy and the optical absorption spectra for detailed investigation of the photo-induced carrier process were analysed. A reduction in photoluminescence from PTCDI-C(8) on QT was observed, clearly demonstrating that the excitons generated in the PTCDI-C(8) layer are effectively dissociated at the heteromolecular interface. One important factor inducing this effective charge dissociation is the highly ordered molecular packing, which acts to increase the exciton diffusion length. Moreover, a specific increase in the photoluminescence excitation spectrum was observed around 3 eV, indicating that simultaneous exciton generation in both the QT and PTCDI-C(8) layers effectively suppresses such charge dissociation of the excitons. In other words, the existence of excitons in each molecule at the heteromolecular interface and HOMO-LUMO level alignment at the interface play an essential role in charge dissociation. Our results provide a striking insight into intermolecular interactions in the carrier process at the heteromolecular interface such as exciton generation, the recombination and dissociation processes, and the photovoltaic effect in organic semiconductors.