A Benzo[1,2‐ b :4,5‐ c ′]Dithiophene‐4,8‐Dione‐Based Polymer Donor Achieving an Efficiency Over 16%

It is of great significance to develop efficient donor polymers during the rapid development of acceptor materials for nonfullerene bulk‐heterojunction (BHJ) polymer solar cells. Herein, a new donor polymer, named PBTT‐F, based on a strongly electron‐deficient core (5,7‐dibromo‐2,3‐bis(2‐ethylhexyl)benzo[1,2‐ b :4,5‐ c ′]dithiophene‐4,8‐dione, TTDO), is developed through the design of cyclohexane‐1,4‐dione embedded into a thieno[3,4‐ b ]thiophene (TT) unit. When blended with the acceptor Y6, the PBTT‐F‐based photovoltaic device exhibits an outstanding power conversion efficiency (PCE) of 16.1% with a very high fill factor (FF) of 77.1%. This polymer also shows high efficiency for a thick‐film device, with a PCE of ≈14.2% being realized for an active layer thickness of 190 nm. In addition, the PBTT‐F‐based polymer solar cells also show good stability after storage for ≈700 h in a glove box, with a high PCE of ≈14.8%, which obviously shows that this kind of polymer is very promising for future commercial applications. This work provides a unique strategy for the molecular synthesis of donor polymers, and these results demonstrate that PBTT‐F is a very promising donor polymer for use in polymer solar cells, providing an alternative choice for a variety of fullerene‐free acceptor materials for the research community.