High‐Efficiency Polymer Solar Cells Over 13.9% With a High VOC Beyond 1.0 V by Synergistic Effect of Fluorine and Sulfur

A novel phenyl substituted benzo(1,2‐b:4,5‐b’)dithiophene (BDT) derivative containing both fluorine and sulfur atoms is designed and synthesized. Furthermore, a wide bandgap polymer PBTA‐PSF based on the derivative shows a low highest occupied molecular orbital energy level and slightly reduces the donor materials’ optical bandgap, which has a complementary absorption with a narrow‐bandgap n‐type small molecule ITIC. As a result, a power conversion efficiency of 13.91% is achieved with a high open‐circuit voltage of 1.01 V, and a large short‐circuit current density of 18.51 mA cm −2 . The result demonstrates that PBTA‐PSF is a promising candidate for high‐performance donor and phenyl‐containing BDT derivatives and has potential in the design of high‐performance polymers for organic photovoltaics.