Development of Highly Crystalline Donor–Acceptor-Type Random Polymers for High Performance Large-Area Organic Solar Cells

We developed donor–acceptor (D–A)-type random polymers based on 3,3′-difluoro-2,2′-bithiophene with various relative amounts of 5,6-difluoro-4,7-bis­(5-bromo-(2-decyl­tetradecyl)­thiophen-2-yl)-2,1,3-benzothiadiazole (2FBT) and 5,6-difluoro-4,7-bis­(5-bromo-(2-octyldodecyl)­thiophen-2-yl)-2-(3,4-dichloro­benzyloxybutyl)-2<i>H</i>-benzo­[<i>d</i>]­[1,2,3]­triazole (DCB-2FBTZ). Introducing small relative amounts of DCB-2FBTZ into the polymer was found to effectively enhance its solar cell performance, resulting in a power conversion efficiency of 9.02%, greater than the 7.29% that resulted from the PFBT-FTh copolymer. Moreover, when the active area of the BHJ film was increased to 1 cm<sup>2</sup>, the solar cell reproducibly showed a high performance, here with an efficiency of 8.01% even when the thickness of the active layer was 313 nm. Our studies revealed that including the DCB-2FBTZ group in the polymer simultaneously improved the solution processability and crystallinity of the polymer. These improvements resulted in the formation of highly homogeneous BHJ films throughout large areas with only minor amounts of defects resulting from overaggregation and hence with appropriate morphologies for effective charge generation and transport.