Achieving 19.4% Efficiency Polymer Solar Cells by Reducing Backbone Disorder in Donor Terpolymers

Abstract The ternary copolymerization strategy has emerged as a promising strategy for developing high‐efficiency donor polymers in polymer solar cells (PSCs). Terpolymers based on the star polymer PM6 have already realized good photovoltaic performance. However, challenges such as the intricate synthesis of fluorine‐substituted benzodithiophene (F‐BDT) unit of PM6 and entropy increase induced by backbone disorder have hindered the construction of high‐performance donor terpolymers. In this work, these challenges are addressed by opting for the cost‐effective chlorinated‐substituted benzodithiophene unit (Cl‐BDT) as an alternative to F‐BDT and incorporating the large dipole moment and electron‐deficient TPD group as the third component into the high‐performance donor polymer of PM7. As expected, this approach effectively suppresses terpolymer backbone disorder while enhancing crystallinity, thereby optimizing morphology and improving charge generation and transport. Remarkably, the PM7‐TPD‐10‐based device with 10% TPD replacement achieves a champion power conversion efficiency (PCE) of 18.26%. After introducing PM7‐TPD‐10 as the third component into D18:L8‐BO blend, a dual mechanism for improving the efficiency to 19.40% is realized. This work demonstrates that the high dipole moiety as the third component to construct terpolymers is an important strategy to suppress the backbone disorder and increase the crystallinity, facilitating the optimization of morphology and device performance.