All-polymer solar cells (all-PSCs) have seen rapid progress enabled by the development of high-performance polymer acceptors. Most polymer acceptors are based on the monomers of a classic small molecular acceptor (SMA) named Y6 by polymerizing at the position of the end groups, forming an “end-to-end” linkage. In this work, we report a completely different “core-to-core” linking mode by polymerizing the Y-series monomers at the central core position instead. This innovative strategy results in a drastically altered molecular configuration that resembles a “double decker,” with intramolecular packing between different monomer units in the same polymer. The overall molecular packing is improved, benefiting charge delocalization and charge transport. As a result, the PffBQx-T-based ternary blend achieved an outstanding efficiency of 18.7%, attributed to the enhanced absorption response, improved packing, and efficient charge dynamics. Our work demonstrates a novel polymer design rationale that serves as a promising avenue toward highly efficient and stable all-PSCs.

由于高性能聚合物受体的开发，全聚合物太阳能电池（全PSC）取得了快速进展。大多数聚合物受体基于名为 Y6 的经典小分子受体 (SMA) 的单体，通过在端基位置聚合，形成“端到端”连接。在这项工作中，我们通过在中心位置聚合Y系列单体，报告了一种完全不同的“核对核”连接模式。这种创新策略导致分子构型发生了巨大变化，类似于“双层”，同一聚合物中不同单体单元之间存在分子内堆积。整体分子堆积得到改善，有利于电荷离域和电荷传输。结果，基于 PffBQx-T 的三元混合物实现了 18.7% 的出色效率，这归因于增强的吸收响应、改进的填充和高效的电荷动力学。我们的工作展示了一种新颖的聚合物设计原理，它是实现高效、稳定的全 PSC 的一条有前途的途径。