Frenkel and Charge-Transfer Excitonic Couplings Strengthened by Thiophene-Type Solvent Enables Binary Organic Solar Cells with 19.8 % Efficiency

Overcoming the trade-off between short-circuited current (Jsc) and open-circuited voltage (Voc) is important to achieving high-efficiency organic solar cells (OSCs). Previous works modulated the energy gap between Frenkel local exciton (LE) and charge-transfer (CT) exciton, which served as the driving force of exciton splitting. Differently, our current work focuses on the modulation of LE-CT excitonic coupling (tLE-CT) via a simple but effective strategy that the 2-chlorothiophene (2Cl-Th) solvent utilizes in the treatment of OSC active-layer films. The results of our experimental measurements and theoretical simulations demonstrated that 2Cl-Th solvent initiates tighter intermolecular interactions with non-fullerene acceptor in comparison with that of traditional chlorobenzene solvent, thus suppressing the acceptor's over-aggregation and retarding the acceptor crystallization with reduced trap. Critically, the resulting shorter distances between donor and acceptor molecules in the 2Cl-Th treated blend efficiently strengthen tLE-CT, which not only promotes exciton splitting but also reduces non-radiative recombination. The champion efficiencies of 19.8 % (small-area) with superior operational reliability (T80: 586 hours) and 17.0 % (large-area) were yielded in 2Cl-Th treated cells. This work provided a new insight into modulating the exciton dynamics to overcome the trade-off between Jsc and Voc, which can productively promote the development of the OSC field. Frenkel and charge-transfer excitonic couplings at donor:acceptor interfaces strengthened by 2-chlorothiophene (2Cl-Th) solvent promote exciton splitting and reduce non-radiative voltage loss in organic solar cells. Finally, in 2Cl-Th treated cells, the champion efficiencies of 19.8 % (small-area) with superior operational reliability (T80: 586 hours) and 17.0 % (large-area) were yielded. image