Three‐Dimensional SiCN Ceramic Microstructures via Nano‐Stereolithography of Inorganic Polymer Photoresists

We report a newly synthesized inorganic polymer photoresist with a high ceramic yield by the functionalization of polyvinylsilazane (KiON VL20) with 2‐isocyanatoethyl methacrylate via linkage or insertion reaction routes. The chemistry of the synthesis and the pyrolytic conversion as well as the mechanical evaluation were investigated by using various analytical instruments. We show for the first time that this photosensitive resin is a novel precursor for the fabrication of complex 3D SiCN ceramic microstructures with a 210 nm resolution via a two‐photon absorbed crosslinking process and subsequent pyrolysis at 600 °C under a nitrogen atmosphere. Moreover, the dimensional deformation during pyrolysis was significantly reduced by adding silica nanoparticles as a filler. In particular, the ceramic microstructures containing 40 wt % silica nanoparticles exhibited a relatively isotropic shrinkage owing to its sliding free from the substrate during pyrolysis.