Dual-Additive-Driven Morphology Optimization for Solvent-Annealing-Free All-Small-Molecule Organic Solar Cells

All-small-molecule organic solar cells (ASM-OSCs), which consist of small-molecule donors and acceptors, have recently been studied extensively to eliminate the batch-to-batch variation from polymer-based donor or acceptor. On the other hand, the control of their active layer morphology is more challenging due to the similar chemical structure and miscibility of small-molecule donor and small-molecule accepter. Hence, this study develops a dual-additive-driven morphology optimization method for ASM-OSCs based on BTR-Cl:Y6. One solid additive - 1,4-diiodobenzene (DIB) and one liquid additive - diiodomethane (DIM) are selected, making use of their distinct interaction mechanisms with Y6 and BTR-Cl. It is found that DIB can form a eutectic phase with Y6, which can increase the intermolecular interactions and modulate the acceptor phase separation, while the simultaneous volatilization of DIM suppresses the over-aggregation of BTR-Cl during the film casting process. As a result of the synergistic morphology tuning, the optimized device delivers a power conversion efficiency (PCE) as high as 15.2%, among the highest PCE reported to date for binary ASM-OSCs without solvent annealing treatment. This work demonstrates the potential of morphology tuning via the incorporation of dual additives into ASM-OSCs, enabling them to achieve comparable efficiencies to those of conventional polymer/small-molecule based OSCs.