Realizing 19.05% Efficiency Polymer Solar Cells by Progressively Improving Charge Extraction and Suppressing Charge Recombination

Improving charge extraction and suppressing charge recombination are critically important to minimize the loss of absorbed photons and improve the device performance of polymer solar cells (PSCs). In this work, highly efficient PSCs are demonstrated by progressively improving the charge extraction and suppressing the charge recombination through the combination of side‐chain engineering of new nonfullerene acceptors (NFAs), adopting ternary blends, and introducing volatilizable solid additives. The 2D side chains on BTP‐Th induce a certain steric hindrance for molecular packing and phase separation, which is mitigated by fluorination of side chains on BTP‐FTh. Moreover, by introducing two highly crystalline molecules as the second acceptor and volatilizable solid additive, respectively, into the BTP‐FTh‐based host blend, the molecular crystallinity is significantly improved and the blend morphology is finely optimized. As expected, enhanced charge extraction and suppressed charge recombination are progressively realized, contributing to the largely improved fill factor (FF) of the resultant devices. Accompanied by the enhanced open‐circuit voltage (Voc) and short‐circuit current density (Jsc), a record high power conversion efficiency (PCE) of 19.05% is realized finally. The progressive improvement of charge extraction and suppression of charge recombination by side‐chain engineering of Y‐series nonfullerene acceptors (NFAs), employing a ternary blend and introducing a volatilizable solid additive, fine‐tunes the electronic properties of the NFAs and optimizes the morphology of the active layer and contributes to a record power conversion efficiency of 19.05% for single‐junction polymer solar cells.