Time resolved photoluminescence studies of long lived emissive specie in F8BT:PFB blends

Type-II heterojunctions play a crucial role in organic optoelectronic devices. We use donor-acceptor polyfluorene blends as a model system to understand excited-state dynamics at heterojunctions. These interfacial excitations are intrachain singlet and triplet excitons, geminate polaron pairs, and exciplexes (interfacial charge-transfer excitons). Time-resolved photoluminescence (PL) spectra were taken at 10\,K and room temperature to investigate the interconversion dynamics of these species. We observe delayed PL with sub-linear excitation fluence dependence. This implies that delayed singlet exciton generation involves a bimolecular annihilation mechanism. By means of kinetic modeling, we propose triplet-triplet exciton annihilation as a regeneration route to singlet excitons, and subsequently to exciplexes. This points to a significant ($<15$\,\%) yield of triplet excitons after interfacial charge separation, and to the central role of these species on the interfacial dynamics.