Abstract3D printing offers enormous flexibility in fabrication of polymer objects with complex geometries. However, it is not suitable for fabricating large polymer structures with geometrical features at the sub-micrometer scale. Porous structure at the sub-micrometer scale can render macroscopic objects with unique properties, including similarities with biological interfaces, permeability and extremely large surface area, imperative inter alia for adsorption, separation, sensing or biomedical applications. Here, we introduce a method combining advantages of 3D printing via digital light processing and polymerization-induced phase separation, which enables formation of 3D polymer structures of digitally defined macroscopic geometry with controllable inherent porosity at the sub-micrometer scale. We demonstrate the possibility to create 3D polymer structures of highly complex geometries and spatially controlled pore sizes from 10 nm to 1000 µm. Produced hierarchical polymers combining nanoporosity with micrometer-sized pores demonstrate improved adsorption performance due to better pore accessibility and favored cell adhesion and growth for 3D cell culture due to surface porosity. This method extends the scope of applications of 3D printing to hierarchical inherently porous 3D objects combining structural features ranging from 10 nm up to cm, making them available for a wide variety of applications.

By in-situ measuring the scattered light during microstructure formation, the polymerization kinetics of three-dimensional direct laser writing are investigated in detail. Oxygen quenching, oxygen diffusion, and inhibitor depletion are shown to have substantial impact on the kinetic behavior. For typical photoresists based on multifunctional acrylates, the polymerization occurs in less than a millisecond.

An instrument brings 3D laser printing to a new level, exemplified by 3D fluorescent microstructures composed of five materials.