Polymer Donor with a Simple Skeleton and Minor Siloxane Decoration Enables 19% Efficiency of Organic Solar Cells

Abstract Development of polymer donors with simple chemical structure and low cost is of great importance for commercial application of organic solar cells (OSCs). Here, side‐chain random copolymer PMQ‐Si605 with a simply 6,7‐difluoro‐3‐methylquinoxaline‐thiophene backbone and 5% siloxane decoration of side chain is synthesized in comparison with its alternating copolymer PTQ11. Relative to molecular weight (M_n) of 28.3 kg mol⁻¹ for PTQ11, the random copolymer PMQ‐Si605 with minor siloxane decoration is beneficial for achieving higher M_n up to 51.1 kg mol⁻¹. In addition, PMQ‐Si605 can show stronger aggregation ability and faster charge mobility as well as more efficient exciton dissociation in active layer as revealed by femtosecond transient absorption spectroscopy. With L8‐BO‐F as acceptor, its PMQ‐Si605 based OSCs display power conversion efficiency (PCE) of 18.08%, much higher than 16.21% for PTQ11 based devices. With another acceptor BTP‐H2 to optimize the photovoltaic performance of PMQ‐Si605, further elevated PCEs of 18.50% and 19.15% can be achieved with the binary and ternary OSCs, respectively. Furthermore, PMQ‐Si605 based active layers are suitable for processing in high humidity air, an important factor for massive production of OSCs. Therefore, the siloxane decoration on polymer donors is promising, affording PMQ‐Si605 as a high‐performing and low cost candidate.