The development of polymerized small-molecule acceptors has boosted the power conversion efficiencies (PCEs) of all-polymer organic photovoltaic (OPV) cells to 17%. However, the polymer donors suitable for all-polymer OPV cells are still lacking, restricting the further improvement of their PCEs. Herein, a new polymer donor named PQM-Cl is designed and its photovoltaic performance is explored. The negative electrostatic potential and low average local ionization energy distribution of the PQM-Cl surface enable efficient charge generation and transfer process. When blending with a well-used polymer acceptor, PY-IT, the PQM-Cl-based devices deliver an impressive PCE of 18.0% with a superior fill factor of 80.7%, both of which are the highest values for all-polymer OPV cells. The relevant measurements demonstrate that PQM-Cl-based films possess excellent mechanical and flexible properties. As such, PQM-Cl-based flexible photovoltaic cells are fabricated and an excellent PCE of 16.5% with high mechanical stability is displayed. These results demonstrate that PQM-Cl is a potential candidate for all-polymer OPV cells and provide insights into the design of polymer donors for high-efficient all-polymer OPV cells.
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