The hierarchical assembly of conjugated polymers has gained much attention due to its critical role in determining optical/electrical/mechanical properties. The hierarchical morphology encompasses molecular-scale intramolecular conformation (torsion angle, chain folds) and intermolecular ordering (π–π stacking), mesoscale domain size, orientation and connectivity, and macroscale alignment and (para)crystallinity. Such complex morphology in the solid state is fully determined by the polymer assembly pathway in the solution state, which, in turn, is sensitively modulated by molecular structure and processing conditions. However, molecular pictures of polymer assembly pathways remain elusive due to the lack of detailed structural characterizations in the solution state and the lack of understanding on how various factors impact the assembly pathways. In this mini-review, we present possible assembly pathways of conjugated polymers and their characteristics across length scales. Recent advances in understanding and controlling of assembly pathways are highlighted. We also discuss the current gap in our knowledge of assembly pathways, with future perspectives on research needed on this topic.

共轭聚合物的分级组装因其在决定光学/电学/机械性能方面的关键作用而受到广泛关注。层次形态包括分子尺度的分子内构象（扭转角、链折叠）和分子间排序（π-π堆积）、介观尺度域的大小、方向和连接性，以及宏观尺度的排列和（副）结晶度。这种固态的复杂形态完全由溶液态的聚合物组装途径决定，而溶液态的组装途径又受到分子结构和加工条件的敏感调节。然而，由于缺乏溶液状态下的详细结构表征以及对各种因素如何影响组装途径的了解，聚合物组装途径的分子图片仍然难以捉摸。在这篇小综述中，我们提出了共轭聚合物的可能组装途径及其跨长度尺度的特征。重点介绍了在理解和控制组装途径方面的最新进展。我们还讨论了目前我们在组装途径知识方面的差距，以及对该主题所需研究的未来展望。