Publication date: 11th March 2026
Intrinsic charge generation in pristione single-component organic semiconductors is commonly believed to result from an autoionization mechanism, and hence is not expected to occur upon excitation within the lowest excited singlet state due to the large exciton binding energy. Nevertheless, unexpectedly high charge generation ratios have been found in neat films when exciting at the absorption edge of some compounds, such as the non-fullerene-acceptor Y6.[1,2] In my presentation I shall discuss the role of exciton-exciton annihilation process in the photogeneration process for both singlet and triplet states, focussing on singlet-singlet annihilation processes in Y6 and triplet-triplet annihilation processes in the carbazole-based molecule mCBP-CN. We combine solar cell measurements, thermally stimulated luminescence measurements, fs-pump-probe measurements and kintetic Monte Carlo Studies to to illustrate how efficient delocalization and thermally activated diffusion of excitons can contribute to the overall carrier yield.[3,4,5] In this context, we discuss the relationship between the activation energy for photocurrent and the binding energy for photogenerated electron-hole pairs.
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