A Maverick Asymmetrical Backbone with Distinct Flanked Twist Angles Modulating the Molecular Aggregation and Crystallinity for High Performance Nonfullerene Solar Cells

Abstract In this work, a new asymmetrical backbone thienobenzodithiophene (TBD) containing four aromatic rings is designed, and then four polymers PTBD‐BZ, PTBD‐BDD, PTBD‐FBT, and PTBD‐Tz are synthesized. The planar and high degree of π‐conjugation configuration can guarantee effective charge carrier transport and the distinct flanked dihedral angles between the TBD core and conjugated side chain can subtly regulate the molecular aggregation and crystallinity. The four polymer/3,9‐bis(2‐methylene‐(3‐(1,1‐dicyanomethylene)‐indanone)‐5,5,11,11‐tetrakis(4‐hexylphenyl)‐dithieno[2,3‐d:2′,3′‐d′]‐s‐indaceno[1,2‐b:5,6‐b′]‐dithiophene (ITIC) blending films exhibit predominantly face‐on orientation. The photovoltaic devices based on wide bandgap polymers PTBD‐BZ and PTBD‐BDD achieve power conversion efficiencies (PCEs) as high as 12.02% and 11.39% without any post‐treatment. For the medium bandgap polymers PTBD‐FBT and PTBD‐Tz, the devices also show good PCEs of 10.18% and 11.02% with high V_OC of 0.94 and 1.02 V, respectively, which indicates simultaneously achieving a V_OC > 1 V and a high J_SC is feasible to further improve the PSCs' performance by modifying this new backbone. This work reveals that the versatile asymmetric backbone is an excellent moiety to construct light‐harvesting copolymers and to modulate the microstructure for highly efficient PSCs.