Delicately Controlled Polymer Orientation for High-Performance Non-Fullerene Solar Cells with Halogen-Free Solvent Processing

Molecular orientation in polymer solar cells (PSCs) is a critical subject of investigation that promotes the quality of bulk heterojunction morphology and power conversion efficiency (PCE). Herein, the intrinsic polymer orientation transition can be found upon delicate control over the branching point position of the irregular alkoxy side chain in difluoroquinoxaline-thiophene-based conjugated polymers. Three polymers with branching points at the third, fourth, and fifth positions away from the backbone were synthesized and abbreviated as PHT3, PHT4, and PHT5, respectively. Temperature-dependent absorption behavior manifests the polymer aggregation ability in the order of PHT3 < PHT4 < PHT5. Surprisingly, the polymer orientation transition from typical face-on to edgeon emerged between PHT4 and PHTS, as evidenced by X-ray-scattering analysis. The enhanced face-on crystallinity of PHT4 endowed the o-xylene-processed PHT4:IT-4Cl-based devices with the highest PCE of 13.40%. For PHT5 with stronger aggregation, the related o-xylene-processed PSCs still showed a good PCE of 12.66%. Our results demonstrate that a delicate polymer orientation transition could be realized through a precisely controlled strategy of the side chain, yielding green-solvent-processed high-performance PSCs.