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 (PC61BPF) is designed and synthesized. This new n‐type material can replace PC61BM to form a P3HT:PC61BPF binary blend or serve as an additive to form a P3HT:PC61BM:PC61BPF ternary blend. Supramolecular attraction between the pentafluorophenyl group of PC61BPF and the C60 cores of PC61BPF/PC61BM can effectively suppress the PC61BPF/PC61BM materials from severe aggregation. By doping only 8.3 wt% PC61BPF, device PC61BPF651 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 PC61BPF, 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% PC61BPF, 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. A new PC61BM‐based fullerene, [6,6]‐phenyl‐C61 butyric acid pentafluorophenyl ester (PC61BPF) is presented. Supramolecular attraction between the pentafluorophenyl group of PC61BPF and the C60 cores of PC61BPF/PC61BM can effectively suppress the n‐type PC61BPF/PC61BM materials from severe aggregation to mitigate the morphological evolution and preserve the device performance.