Molecular photon upconversion via triplet-triplet annihilation (TTA-UC), combining two or more low energy photons to generate a higher energy excited state, is an intriguing strategy to surpass the maximum efficiency for a single junction solar cell (<34%). Here, we introduce self-assembled bilayers on metal oxide surfaces as a strategy to facilitate TTA-UC emission and demonstrate direct charge separation of the upconverted state. A 3-fold enhancement in transient photocurrent is achieved at light intensities as low as two equivalent suns. This strategy is simple, modular and offers unprecedented geometric and spatial control of the donor-acceptor interactions at an interface. These results are a key stepping stone toward the realization of an efficient TTA-UC solar cell that can circumvent the Shockley-Queisser limit.
