Harnessing Molecular Photon Upconversion in a Solar Cell at Sub‑solar Irradiance: Role of the Redox Mediator

Self-assembled bilayers offer a promising strategy to directly harness photon upconversion via triplet–triplet annihilation (TTA-UC) and increase maximum theoretical solar cell efficiencies from 33% to >43%. Here we demonstrate that the choice of redox mediator in these solar cells has a profound influence on both the light harvesting and TTA-UC efficiency. Devices with CoII/III(phen)3 as the redox mediator produced the highest photocurrent yet generated from TTA-UC (0.158 mA cm–2) under 1 sun. Despite generating less photocurrent, CoII/III(pz-py-pz)2 devices achieved maximum TTA-UC efficiency at excitation intensities well below solar irradiance (0.8 mW cm–2), which is on par with the lowest value yet reported for any TTA-UC system. The large variation in performance with respect to mediator is attributed to triplet excited-state quenching via (1) energy transfer or paramagnetic quenching by the CoII species and (2) excited-state electron transfer to CoIII species.