Photopolymerization is a key enabling technology offering spatial and temporal control to allow for future functional materials to be made to meet societal needs. However, gaining access to robust experimental techniques to describe the evolution of nanoscale morphology in photo-initiated polymeric systems has proven so far to be a challenging task. Here, we show that these physical transformations can be monitored and quantified at the nanoscale in situ and in real-time. It is demonstrated that the initial structural features of the liquid precursors significantly affect the final morphology and the physical properties of the resulting solid via the occurrence of local heterogeneities in the molecular mobility during the curing transformation. We have made visible how local physical arrestings in the liquid, associated with both cross-linking and vitrification, determine the length scale of the local heterogeneities forming upon curing, found to be in the 10–200 nm range.

光聚合是一项关键的使能技术，可提供空间和时间控制，使未来的功能材料能够满足社会需求。然而，迄今为止，获得可靠的实验技术来描述光引发聚合物系统中纳米级形态的演变已被证明是一项具有挑战性的任务。在这里，我们展示了这些物理转变可以在纳米级原位实时监测和量化。结果表明，液体前体的初始结构特征通过固化转化过程中分子流动性的局部异质性显着影响最终形态和所得固体的物理性质。我们已经让液体中的局部物理逮捕变得可见，