Oxygen-related Bandgap State in Single Crystal Rubrene

A molecular exciton signature is established and investigated under different ambient conditions in rubrene single crystals. An oxygen-related bandgap state is found to form in the ambient atmosphere. This state acts as an acceptor center and assists in the fast dissociation of excitons, resulting in a higher dark- and photoconductivity of oxidized rubrene. The bandgap state produces a well-defined photoluminescence band at an energy 0.25 eV below the energy of 0-0 molecular exciton transition. Two-photon excitation spectroscopy shows that the states are concentrated near the surface of naturally oxidized rubrene.