Above 100% Efficiency Photocharge Generation in Monolayer Semiconductors by Singlet Fission Sensitization.

Sensitizing inorganic semiconductors using singlet fission (SF) materials, which produce two excitons from one absorbed photon, can potentially boost their light-to-electricity conversion efficiency. The SF sensitization is particularly exciting for two-dimensional (2D) layered semiconductors with atomically flat surface and high carrier mobility but limited light absorption. However, efficiently harnessing triplet excitons from SF by charge transfer at organic/inorganic interface has been challenging, and the intricate interplay among competing processes remains unresolved. Here, we investigate SF sensitization in high-quality organic/2D bilayer heterostructures featuring TIPS-Pc single crystals. Through transient magneto-optical spectroscopy, we demonstrate that despite an ultrafast SF process in sub-100 fs, a significant fraction of singlet excitons in TIPS-Pc dissociate at the interface before fission, while triplet excitons from SF undergo diffusion-limited charge transfer at the interface in ∼10 ps to ns. Remarkably, the photocharge generation efficiency reaches 126% in heterostructures with optimal thickness, resulting from the competitive interplay between singlet exciton fission, dissociation, and triplet exciton transport. This presents a promising strategy for advancing SF-enhanced 2D optoelectronics beyond the conventional limits.