Improving Miscibility of Polymer Donor and Polymer Acceptor by Reducing Chain Entanglement for Realizing 18.64 %...

All-polymer solar cells have experienced rapid development in recent years by the emergence of polymerized small molecular acceptors (PSMAs). However, the strong chain entanglements of polymer donors (P_Ds) and polymer acceptors (P_As) decrease the miscibility of the resulting polymer mixtures, making it challenging to optimize the blend morphology. Herein, we designed three P_As, namely PBTPICm-BDD, PBTPICγ-BDD and PBTPICF-BDD, by smartly using a BDD unit as the polymerized unit to copolymerize with different Y-typed non-fullerene small molecular acceptors (NF-SMAs), thus achieving a certain degree of distortion and giving the polymer system enough internal space to reduce the entanglements of the polymer chains. Such effects increase the chances of the P_D being interspersed into the acceptor material, which improve the solubility between the P_D and P_A. The PBTPICγ-BDD and PBTPICF-BDD displayed better miscibility with PBQx-TCl, leading to a well optimized morphology. As a result, high power conversion efficiencies (PCEs) of 17.50 % and 17.17 % were achieved for PBQx-TCl : PBTPICγ-BDD and PBQx-TCl : PBTPICF-BDD devices, respectively. With the addition of PYFT-o as the third component into PBQx-TCl : PBTPICγ-BDD blend to further extend the absorption spectral coverage and finely tune microstructures of the blend morphology, a remarkable PCE of 18.64 % was realized finally.