Regulating the Sequence Structure of Conjugated Block Copolymers Enables Large‐Area Single‐Component Organic Solar Cells with High Efficiency and Stability

Abstract Single‐component organic solar cells (SCOSCs) based on conjugated block copolymers (CBCs) by covalently bonding a polymer donor and polymer acceptor become more and more appealing due to the formation of a favorable and stable morphology. Unfortunately, a deep understanding of the effect of the assembly behavior caused by the sequence structure of CBCs on the device performance is still missing. Herein, from the aspect of manipulating the sequence length and distribution regularity of CBCs, we synthesized a series of new CBCs, namely D18(20) ‐b‐ PYIT, D18(40) ‐b‐ PYIT and D18(60) ‐b‐ PYIT by two‐pot polymerization, and D18(40) ‐b‐ PYIT(r) by traditional one‐pot method. It is observed that precise manipulation of sequence length and distribution regularity of the polymer blocks fine‐tunes the self‐assembly of the CBCs, optimizes film morphology, improves optoelectronic properties, and reduces energy loss, leading to simultaneously improved efficiency and stability. Among these CBCs, the D18(40) ‐b‐ PYIT‐based device achieves a high efficiency of 13.4 % with enhanced stability, which is an outstanding performance among SCOSCs. Importantly, the regular sequence distribution and suitable sequence length of the CBCs enable a facile film‐forming process of the printed device. For the first time, the blade‐coated large‐area rigid/flexible SCOSCs are fabricated, delivering an impressive efficiency of 11.62 %/10.73 %, much higher than their corresponding binary devices.