Morphological Stabilization by Supramolecular Perfluorophenyl‐C₆₀ Interactions Leading to Efficient and Thermally Stable Organic Photovoltaics

A new PC₆₁BM‐based fullerene, [6,6]‐phenyl‐C₆₁ butyric acid pentafluorophenyl ester (PC₆₁BP^F) is designed and synthesized. This new n‐type material can replace PC₆₁BM to form a P3HT:PC₆₁BP^F binary blend or serve as an additive to form a P3HT:PC₆₁BM:PC₆₁BP^F ternary blend. Supramolecular attraction between the pentafluorophenyl group of PC₆₁BP^F and the C₆₀ cores of PC₆₁BP^F/PC₆₁BM can effectively suppress the PC₆₁BP^F/PC₆₁BM materials from severe aggregation. By doping only 8.3 wt% PC₆₁BP^F, device PC₆₁BP^F651 exhibits a PCE of 3.88% and decreases slightly to 3.68% after heating for 25 h, preserving 95% of its original value. When PC₆₁BP with non‐fluorinated phenyl group is used to substitute PC₆₁BP^F, the stabilizing ability disappears completely. The efficiencies of PC₆₁BP651 and PC₆₁BP321 devices significantly decay to 0.44% and 0.11%, respectively, after 25 h isothermal heating. Most significantly, this strategy is demonstrated to be effective for a blend system incorporating a low band‐gap polymer. By adding only 10 wt% PC₆₁BP^F, the PDTBCDTB:PC₇₁BM‐based device exhibits thermally stable morphology and device characteristics. These findings demonstrate that smart utilization of supramolecular interactions is an effective and practical strategy to control morphological evolution.