Exciton–dopant and exciton–charge interactions in electronically doped OLEDs

The electronic dopants, like tetrafluorocyanoquinodimethane (F₄–TCNQ) molecules, used for p-doping of hole transport layers in organic light-emitting diodes (OLEDs) are found to quench the electroluminescence (EL) if they diffuse into the emissive layer. We observed EL quenching in OLED with F₄-TCNQ doped N,N′-diphenyl-N′N′-bis(1-naphthyl)-1,1′-biphenyl-4,4′-diamine hole transport layer at large dopant concentrations, >5%. To separate the effects of exciton–dopant quenching, from exciton–polaron quenching we have intentionally doped the emissive layer of (8-tris-hydroxyquinoline) with three acceptors (A) of different electron affinities: F₄-TCNQ, TCNQ, and C₆₀, and found that C₆₀ is the strongest EL-quencher, while F₄-TCNQ is the weakest, contrary to intuitive expectations. The new effects of charge transfer and usually considered energy transfer from exciton to neutral (A) and charged acceptors (A⁻) are compared as channels for non-radiative Ex–A decay. At high current loads the EL quenching is observed, which is due to decay of Ex on free charge carriers, hole polarons P⁺. We consider contributions to Ex–P⁺ interaction by short-range charge transfer and describe the structure of microscopic charge transfer (CT)-processes responsible for it. The formation of metastable states of ‘charged excitons’ (predicted and studied by Agranovich et al. Chem. Phys. 272 (2001) 159) by electron transfer from a P to an Ex is pointed out, and ways to suppress non-radiative Ex–P decay are suggested.