The emerging field of lead halide perovskite-sensitized triplet-triplet annihilation (TTA) in rubrene shows great promise in upconversion applications. By rapidly transferring single charge carriers instead of bound triplet states, perovskites enable a high triplet population in rubrene, yielding low I values. In this contribution, we investigate the role of the triplet population on the upconverted emission. Interestingly, two independent rates of TTA can be observed, as well as a sharp drop in the visible emission intensity over several seconds. This effect can be attributed to the triplet-density-based diffusion length: (i) at low triplet populations slow diffusion-mediated TTA yields singlets far from the interface and (ii) higher triplet populations lead to rapid TTA close to the perovskite/rubrene interface. Because of the proximity of the strongly absorbing perovskite, the singlet states created closer to the interface undergo stronger back-transfer to the perovskite film and therefore appear to exhibit a lower photoluminescence quantum yield.
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