Impact of the Siloxane-Terminated Side Chain on Photovoltaic Performances of the Dithienylbenzodithiophene–Difluorobenzotriazole-Based Wide Band Gap Polymer Donor in Non-Fullerene Polymer Solar Cells

To thoroughly disclose the role of the siloxane-terminated side chain with different substituent positions, three difluorobenzotriazole–dithienylbenzodithiophene (FTAZ–BDTT)-based polymers PBZ-1Si, PBZ-2Si, and PBZ-3Si with the siloxane-terminated side chain on the FTAZ unit (PBZ-1Si), on the BDTT unit (PBZ-2Si), and both on BDTT and FTAZ units (PBZ-3Si), respectively, were synthesized. The different side chain substitutions have slight influences on absorption behavior, thermal stability, and frontier molecular orbitals but have shown a great effect on the aggregation of the polymers. Grazing-incidence wide-angle X-ray scattering measurements reveal that, relative to PBZ-1Si with branched alkyl on the BDTT unit, polymers PBZ-2Si and PBZ-3Si, bearing the siloxane-terminated side chains on the BDTT unit, exhibit smaller π–π stacking distances and larger crystal coherence lengths, suggesting that adopting the siloxane-terminated side chain on the BDTT unit can promote the interchain π–π interaction and the ordering of molecular packing. With IT-M as the non-fullerene acceptor, among the three polymers, the PBZ-2Si-based active layer possesses the highest ordered crystals for both polymers and IT-M as well as the purest domain, which affords efficient exciton dissociation, the most balanced hole–electron transport, and reduced recombination, leading to the highest short-circuit current density (Jsc) and fill factor (FF) and then the highest power conversion efficiency (PCE) of 11.14%. In contrast, PBZ-1Si- and PBZ-3Si-based devices show lower PCEs of 8.98 and 9.92%, respectively. Moreover, PBZ-2Si:IT-M also exhibits good thickness tolerance, and its thick active layer of 240 nm shows the most limited decrease of efficiency after 77 days of storage, supplying good potential for mass fabrication. Our work suggests that the fine pairing of a siloxane-terminated side chain and an alkyl side chain is beneficial for the optimizing of a conjugated polymer donor toward high-performance non-fullerene polymer solar cells.