Highly Efficient Ternary All‐Polymer Solar Cells with Enhanced Stability

Abstract Developing organic solar cells (OSCs) based on a ternary active layer is one of the most effective approaches to maximize light harvesting and improve their photovoltaic performance. However, this strategy meets very limited success in all‐polymer solar cells (all‐PSCs) due to the scarcity of narrow bandgap polymer acceptors and the challenge of morphology optimization. In fact, the power conversion efficiencies (PCEs) of ternary all‐PSCs even lag behind binary all‐PSCs. Herein, highly efficient ternary all‐PSCs are realized based on an ultranarrow bandgap (ultra‐NBG) polymer acceptor DCNBT‐TPC, a medium bandgap polymer donor PTB7‐Th, and a wide bandgap polymer donor PBDB‐T. The optimized ternary all‐PSCs yield an excellent PCE of 12.1% with a remarkable short‐circuit current density of 21.9 mA cm⁻². In fact, this PCE is the highest value reported for ternary all‐PSCs and is much higher than those of the corresponding binary all‐PSCs. Moreover, the optimized ternary all‐PSCs show a photostability with ≈68% of the initial PCE retained after 400 h illumination, which is more stable than the binary all‐PSCs. This work demonstrates that the utilization of a ternary all‐polymer system based on ultra‐NBG polymer acceptor blended with compatible polymer donors is an effective strategy to advance the field of all‐PSCs.