• • FSVA-treated PF8:L8BO devices achieve 18.89% PCE at 110 nm, 17.54% at 300 nm, and 15.59% at 500 nm, demonstrating a thickness tolerance that reduces material waste and enables high-throughput roll-to-roll coating with fewer defects.
• • The 300-nm FSVA-treated blend films exhibit enhanced packing order and well-defined fibrillar morphology, which suppresses non-radiative recombination and facilitates charge transport along the fiber network, directly addressing the trade-off between thickness and fill factor in industrial-scale production.
• • Fluorination of the polymer backbone and fluorous solvent vapor annealing synergistically increase crystallinity, mitigating energy disorder and tail state density; this dual approach offers a transferable materials engineering strategy for other optoelectronic systems requiring thick active layers.
• • The retention of 15.59% PCE at 500 nm thickness surpasses many reported thick-film OSCs, indicating that the PF8:FSVA system can tolerate the thicker films necessary for large-area modules without catastrophic loss in open-circuit voltage or short-circuit current.