Dual Polymerized Y-Acceptors of Distinct-Dimensionality Create Neuron-Like Interpenetrating Hierarchical Network towards Efficient and Stable All-Polymer Solar Cells.

All-polymer solar cells have garnered particular attention thanks to their superior thermal, photo, and mechanical stabilities for large-scale manufacturing, yet the performance enhancement remains largely restrained by inherent morphological challenges of the bulk-heterojunction active layer. Herein, a 3D Y-branched polymerized small-molecule acceptor named PYBF, characteristic of high molecular weight and glass transition temperature, is designed and synthesized by precisely linking C-symmetric benzotrifuran with Y6 acceptors. In comparison to the benchmark thiophene-bridged linear PYIT acceptor, an optical blue-shift absorption is observed for PYBF yet a slightly higher power conversion efficiency (PCE) of 15.7% (vs 15.14%) is obtained when paired with polymer donor PM6, which benefit from the more crystalline and face-on-oriented PYBF domains. However, the star-like bulky structure of PYBF results in the nucleation-growth dominant phase-separation in polymeric blends, which generates stumpy droplet-like acceptor fibrils and impairs the continuity of acceptor phases. This issue is however surprisingly resolved by incorporating a small amount of PYIT, which leads to the formation of the more interconnective neuron-like dual-acceptor domains by long-chain entanglements of linear acceptors and alleviates bimolecular recombination. Thus, the champion device realizes a respectable PCE of up to ≈17% and importantly exhibits thermal and storage stabilities superior to the linear counterpart.