Unveiling Photovoltaic Performance Enhancement Mechanism of Polymer Solar Cells via Synergistic Effect of Binary Solvent Additives

Binary solvent additive engineering is an effective strategy to optimize photoactive films for high‐efficiency organic solar cells, however, the effect of single components on device performance and the combination principle of binary solvent additives remain unclear. Herein, synchrotron‐based grazing incident X‐ray diffraction, Derjaguin–Muller–Toporov modulus imaging, and plasmon energy shift imaging acquired by scanning transmission electron microscopy to investigate the effect of new binary solvent additive of 1,8‐diiodooctane (DIO) and less‐toxic and p‐anisaldehyde (AA) on device performance of solar cells based on poly[(5,6‐difluoro‐2,1,3‐benzothiadiazol‐4,7‐diyl)‐alt‐(3,3‴‐di(2‐octyldodecyl)2,2′;5′,2″;5″,2‴‐quaterthio‐phen‐5,5‴‐diyl)] (PffBT4T‐2OD) and [6,6]‐phenyl‐C61‐butyric acid methyl ester (PC61BM) are used. It is found that AA mainly favors polymer order and high crystallinity of PffBT4T‐2OD. Differently, DIO mainly enables PC61BM diffusing into PffBT4T‐2OD polymer matrix, leading to enlarged donor–acceptor (D–A) interface. As expected, by combining AA and DIO, the composite film provides large D–A interface and more balanced charge carrier transport. Consequently, their beneficial synergistic effect results in enhanced short circuit current and fill factor, and thereby increased power conversion efficiency of 10.64%, improved by 16% with respect to the control device. Herein, a general mechanism of enhancing device performance via the combination of solvent additives with different contributions to photoactive film is unveiled. The mechanism for binary solvent additives to enhance photovoltaic device performance via advanced technology characterizations is unveiled. The binary additives improve polymer order, maintain high crystallinity, and obtain the preferable morphology of photoactive films. As a result, new binary additives result in an enhanced short circuit current and fill factor, and the device performance is improved from 9.11% to 10.64%.