Molecular Design and Organic Photovoltaic Applications of Carboxylate‐Functionalized P‐type Polymers

Abstract The significant progress of p‐type and n‐type active layer materials in the past several years has pushed the power conversion efficiency (PCE) of organic solar cells (OSCs) toward 19%. Due to the relatively low synthesis cost and simple synthesis method of carboxylate‐containing building blocks, including thiophene, thieno[3,2‐b]thiophene, thieno[3,4‐b]thiophene, furan, pyrazine, benzodithiophene, benzothiazole, quinoxaline, etc., are widely used to construct p‐type photovoltaic polymers. These resulting carboxylate‐bearing polymers present downward energy levels, high absorption coefficient, narrow bandgap, high hole mobility, and strong aggregation behavior, which have dabbled in the fabrication of mechanically stretchable, semitransparent, indoor, and tandem OSCs, etc., and produce excellent photovoltaic performance. The low‐cost carboxylate‐containing copolymers exhibit a satisfying PCE approaching 17%, and the random terpolymer systems achieve a high PCE over 19%. This review focuses on the progress of carboxylate‐containing photovoltaic polymers, summarizes the molecular characteristics, discusses their structure‐performance relationship, and offers a summary and outlook on the challenges for future molecular development.