LAUSR

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.