A new polymer donor (PBDB-T-SF) and a new small molecule acceptor (IT-4F) for fullerene-free organic solar cells (OSCs) were designed and synthesized. The influences of fluorination on the absorption spectra, molecular energy levels, and charge mobilities of the donor and acceptor were systematically studied. The PBDB-T-SF:IT-4F-based OSC device showed a record high efficiency of 13.1%, and an efficiency of over 12% can be obtained with a thickness of 100-200 nm, suggesting the promise of fullerene-free OSCs in practical applications.

Optimizing the molecular structures of organic photovoltaic (OPV) materials is one of the most effective methods to boost power conversion efficiencies (PCEs). For an excellent molecular system with a certain conjugated skeleton, fine tuning the alky chains is of considerable significance to fully explore its photovoltaic potential. In this work, the optimization of alkyl chains is performed on a chlorinated nonfullerene acceptor (NFA) named BTP‐4Cl‐BO (a Y6 derivative) and very impressive photovoltaic parameters in OPV cells are obtained. To get more ordered intermolecular packing, the n‐undecyl is shortened at the edge of BTP‐eC11 to n‐nonyl and n‐heptyl. As a result, the NFAs of BTP‐eC9 and BTP‐eC7 are synthesized. The BTP‐eC7 shows relatively poor solubility and thus limits its application in device fabrication. Fortunately, the BTP‐eC9 possesses good solubility and, at the same time, enhanced electron transport property than BTP‐eC11. Significantly, due to the simultaneously enhanced short‐circuit current density and fill factor, the BTP‐eC9‐based single‐junction OPV cells record a maximum PCE of 17.8% and get a certified value of 17.3%. These results demonstrate that minimizing the alkyl chains to get suitable solubility and enhanced intermolecular packing has a great potential in further improving its photovoltaic performance.