Novel High-Efficiency Polymer Acceptors via Random Ternary Copolymerization Engineering Enables All-Polymer Solar Cells with Excellent Performance and Stability.

Continuous breakthroughs have been achieved in improving the efficiency of all-polymer solar cells (all-PSCs) using diimide-based polymer acceptors, and their easy-to-synthesize, low-cost, and high stability attributes make them potential candidates for use in commercial all-PSCs. However, their low light absorption coefficient, strong aggregation, and poor adaptability with high-efficient polymer donors still limit further improvements in the device performance. Here, we combine the advantages of fluorinated bithiophene and rhodanine dye molecules to create low-cost diimide-based polymer acceptors, PNDI-2FT-TR10 and PNDI-2FT-TR20, by random copolymerization for achieving highly efficient and stable all-PSCs. The synergistic effects of fluorine atoms and rhodanine dye molecules not only significantly improve the absorption coefficient but also enable enhanced miscibility and stability of the blend film. When blended with a PM6 donor, the PNDI-2FT-TR10-based device exhibits a notable power conversion efficiency (PCE) of 10.71% with a short-circuit current () of 17.32 mA cm. Note that both the PCE and show outstanding values for diimide-based all-PSCs, and this is the first report on blending diimide-based polymer acceptors with the PM6 donor to achieve high-performance all-PSCs. Moreover, the favorable morphology of the active layer enables the device to have good thickness tolerance and thermal stability. The results demonstrate that the absorption coefficients, blend morphology, and photovoltaic properties of all-PSCs could be rationally optimized by a random copolymer.