Rapid development of non-fullerene polymer solar cells (NF–PSCs) with high efficiency have gained wide research attention recently, however, high-performance large-area NF–PSCs are still lacking since most developed NF–PSCs use a thin active layer around 100 nm, which is not compatible with the fabrication of large-area devices. Herein, we fabricate high-performance and green-solvent processed NF–PSCs with thick active layer using a random copolymer (2TRA) and non-fullerene acceptors. Compared to its highly-crystallized analogue (2TRR), 2TRA with rearranged backbone enables better blend morphology, higher exciton generation rate, more efficient excitons dissociation, and less recombination in NF–PSCs. With O-IDTBR and IEICO-4F as non-fullerene electron acceptors, highly-efficient photovoltaic devices with PCE of 10.08% and 12.06% are achieved. Moreover, 2TRA-based NF–PSCs show good compatibility with multiple processing solvents, low sensitivity to the active layer thickness (up to 300 nm), and excellent photostability. The combined advantages of 2TRA-based solar cell devices indicate that 2TRA is a promising polymer donor for the application in large-area PSC modules through roll-to-roll technology, and the rearrangement design on polymer donors could be useful to design high-performance polymers for practical application.

近年来，非富勒烯聚合物太阳能电池（NF-PSC）的快速发展得到了广泛的研究关注，但是，由于大多数已开发的NF-PSC在其周围使用了薄的活性层，因此仍缺乏高性能的大面积NF-PSC。 100 nm，与大面积器件的制造不兼容。本文中，我们使用无规共聚物（2TRA）和非富勒烯受体制造了具有厚活性层的高性能，绿色溶剂处理的NF-PSC。与其高度结晶的类似物（2TRR）相比，具有骨架重排的2TRA具有更好的共混物形态，更高的激子生成速率，更有效的激子解离和更少的NF-PSCs重组。使用O-IDTBR和IEICO-4F作为非富勒烯电子受体，可实现PCE分别为10.08％和12.06％的高效光伏器件。此外，基于2TRA的NF-PSC与多种处理溶剂具有良好的相容性，对活性层厚度（最高300 nm）的敏感性较低，并且具有出色的光稳定性。基于2TRA的太阳能电池设备的综合优势表明，2TRA是通过卷对卷技术应用于大面积PSC模块的有前途的聚合物供体，并且聚合物供体上的重排设计可用于设计高性能实际应用中的聚合物。