Since 2001, 3D microfabrication based on two‐photon polymerization (TPP) has drawn extensive attention and interest in biology, optics, photonics, material science, and high‐energy physics. The in‐volume fabrication capability due to the threshold behavior of two‐photon absorption enables TPP higher flexibility compared with other nanofabrication techniques. However, as determined by the in‐volume fabrication feature as well as various reaction dynamics, the writing characteristics of TPP, such as throughput, accuracy, surface quality, and fabrication capability, are still limited. Herein, a comprehensive study is performed on the spatiotemporal behavior of reaction dynamics during TPP fabrication, mainly focusing on spatiotemporal characteristics of radical diffusion, photothermal effect, microscale mechanics, and voxel stacking process. Based on the study, a nonsequential fabrication method is established to simultaneously improve key writing characteristics of TPP and realize sharp features, high speeds, large overhang structure, and smooth surfaces. The method established in this work can be applied to improve the performance of functional devices for various fields.

中文翻译：

---

双光子聚合中的时空反应动力学控制以增强书写特性

自2001年以来，基于双光子聚合（TPP）的3D微加工引起了生物学、光学、光子学、材料科学和高能物理领域的广泛关注和兴趣。与其他纳米制造技术相比，由于双光子吸收的阈值行为而产生的批量制造能力使 TPP 具有更高的灵活性。然而，根据批量制造特征以及各种反应动力学，TPP 的写入特性（例如吞吐量、精度、表面质量和制造能力）仍然受到限制。本文对TPP制备过程中反应动力学的时空行为进行了全面的研究，主要集中在自由基扩散、光热效应、微尺度力学和体素堆积过程的时空特征。基于该研究，建立了一种非顺序制造方法，可以同时改善TPP的关键写入特性，并实现清晰的特征、高速、大悬垂结构和光滑的表面。这项工作中建立的方法可以应用于提高各个领域的功能器件的性能。