Xolography for rapid volumetric production of objects from the nanoscopic to macroscopic length scales

Light-mediated 3D printing has revolutionized additive manufacturing, progressing from pointwise stereolithography, to layer-by-layer digital light processing, and most recently to volumetric 3D printing. Xolography, a novel light-sheet-based volumetric 3D printing approach, offers high-speed and high-precision fabrication of complex geometries unattainable with traditional methods. However, achieving nanoscale control (<100 nm) within these 3D printing systems remains unexplored. This work leverages polymerization-induced microphase separation (PIMS) within the xolography process to prepare network polymer materials with simultaneous control over feature sizes at the nano-, micro-, and macro-scale. By controlling the chain length and mass fraction of macromolecular chain transfer agents used in the PIMS process, precise manipulation of nanodomain size within 3D printed materials is demonstrated, while optimization of the other resin components enables the fabrication of rigid materials with feature sizes of 80 µm. Critically, the rapid one-step fabrication of complex and multi-component structures such as a functional waterwheel with interlocking parts, at high volume-building rates is showcased. This combined approach expands the design space for functional nanomaterials, opening new avenues for applications in diverse fields such as polymer electrolyte membranes, biomedical delivery systems, and semi-permeable microcapsules.