Regulation of Molecular Packing and Blend Morphology by Finely Tuning Molecular Conformation for High-Performance Nonfullerene Polymer Solar Cells

The asymmetric thienobenzodithiophene (TBD) structure is first systematically compared with the benzo­[1,2-b:4,5-b′]­dithiophene (BDT) and dithieno­[2,3-d:2′,3′-d′]­benzo­[1,2-b:4,5-b′]­dithiophene (DTBDT) units in donor–acceptor (D–A) copolymers and applied as the central core in small molecule acceptors (SMAs). Specific polymers including PBDT-BZ, PTBD-BZ, and PDTBDT-BZ with different macromolecular conformations are synthesized and then matched with four elaborately designed acceptor–donor–acceptor (A–D–A) SMAs with structures comparable to their donor counterparts. The resulting polymer solar cell performance trends are dramatically different from each other and highly material-dependent, and the active layer morphology is largely governed by polymer conformation. Because of its more linear backbone, the PTBD-BZ film has higher crystallinity and more ordered and denser π–π stacking than those of the PBDT-BZ and PDTBDT-BZ films. Thus, PTBD-BZ shows excellent compatibility with and strong independence on the SMAs with varied structures, and PTBD-BZ-based cells deliver high power conversion efficiency (PCE) of 10–12.5%, whereas low PCE is obtained by cells based on PDTBDT-BZ because of its zigzag conformation. Overall, this study reveals control of molecular conformation as a useful approach to modulate the photovoltaic properties of conjugated polymers.