All‐Polymer Solar Cells with 17% Efficiency Enabled by the “End‐Capped” Ternary Strategy

Abstract Recently, all‐polymer solar cells (all‐PSCs) have received increasing attention and made tremendous progress. However, the power conversion efficiency (PCE) of all‐PSCs still lags behind the polymer‐donor‐small‐molecule‐acceptor based organic solar cells, owing to the excessive phase separation with poor miscibility between polymer donor and acceptor. In this research, an “end‐capped” ternary strategy is proposed by introducing PM6TPO as a third component to fabricate highly efficient all‐PSCs. The PM6:PM6TPO:PY‐IT based ternary devices exhibit impressive PCE of 17.0% with enhanced light absorption and optimal morphology, and the introduction of PM6TPO significantly reduces the phase separation. The ternary devices also exhibit improved stability, outstanding tolerance of active layer thickness, and high performance of 1 cm2 unit cells. More importantly, the “end‐capped” ternary strategy enables efficient and facile improvement of all‐PSCs performance without additional selection and complicated synthesis for the third component.