Factors That Prevent Spin-Triplet Recombination in Non-fullerene Organic Photovoltaics

Managing the dynamics of spin-triplet electronic states is crucial for achieving high-performance organic photovoltaics. Here we show that the replacement of fullerene with non-fullerene acceptor (NFA) molecules leads to suppression of triplet recombination and thus more efficient charge generation. This indicates that the relaxation of charges to the local triplet exciton state, although energetically allowed, is outcompeted by the thermally activated separation of interfacial charge-transfer excitons (CTEs) in the NFA-based system. By rationalizing our results with Marcus theory, we propose that triplet recombination in the fullerene system is driven by the small energy difference and strong electronic couplings between the CTE state and the lowest-lying triplet exciton state (T₁) of fullerene acceptor molecules. In contrast, the large energy difference and small electronic couplings between these states in the NFA-based blends lead to sufficiently slow triplet relaxation rate compared to the charge separation rate (≪10¹⁰ s^-1), thus preventing triplet recombination.