Fast field-induced dissociation and recombination of optical excitations in a π-conjugated polymer

We present time resolved photoluminescence measurements on thin films of a phenyl-substituted poly(phenylene-vinylene) incorporated in a diode structure. Under reverse bias conditions rapid exciton dissociation is observed leading to luminescence quenching by up to 30%. In contrast, under forward bias conditions the initial quenching is substantially reduced due to shielding by space charges. At longer times thermally activated exciton quenching by injected polarons dominates the quenching process. At 3 ns after excitation, the external field is found to enhance the delayed luminescence. We attribute this to increased recombination of spatially correlated charge carrier pairs in the presence of the electric field, which are generated by exciton dissociation by bimolecular annihilation or on defect states.