A Novel Wide‐Bandgap Polymer with Deep Ionization Potential Enables Exceeding 16% Efficiency in Ternary Nonfullerene Polymer Solar Cells

Ternary strategies have attracted extensive attention due to their potential in improving power conversion efficiencies (PCEs) of single‐junction polymer solar cells (PSCs). In this work, a novel wide bandgap polymer donor ( E g opt ≈ 2.0 eV) named PBT(E)BTz with a deep highest occupied molecular orbital (HOMO) level (≈−5.73 eV) is designed and synthesized. PBT(E)BTz is first incorporated as the third component into the classic PBDB‐T‐SF:IT‐4F binary PSC system to fabricate efficient ternary PSCs. A higher PCE of 13.19% is achieved in the ternary PSCs with a 5% addition of PBT(E)BTz over binary PSCs (12.14%). Similarly, addition of PBT(E)BTz improves the PCE for PBDB‐T:IT‐M binary PSCs from 10.50% to 11.06%. The study shows that the improved PCE in ternary PSCs is mainly attributed to the suppressed charge carrier recombination and more balanced charge transport. The generality of PBT(E)BTz as a third component is further evidenced in another efficient binary PSC system—PBDB‐TF:BTP‐4Cl: an optimized PCE of 16.26% is realized in the ternary devices. This work shows that PBT(E)BTz possessing a deep HOMO level as an additional component is an effective ternary PSC construction strategy toward enhancing device performance. Furthermore, the ternary device with 5% PBT(E)BTz displays better thermal and light stability over binary devices.