Exciton Regeneration at Polymeric Semiconductor Heterojunctions

Control of the band-edge offsets at heterojunctions between organic semiconductors allows efficient operation of either photovoltaic or light-emitting diodes. We investigate systems where the exciton is marginally stable against charge separation and show via E-field-dependent time-resolved photoluminescence spectroscopy that excitons that have undergone charge separation at a heterojunction can be efficiently regenerated. This is because the charge transfer produces a geminate electron-hole pair (separation 2.2–3.1 nm) which may collapse into an exciplex and then endothermically (E_A=100–200  meV) back transfer towards the exciton.