Additive Manufacturing of SiOC, SiC, and Si₃N₄ Ceramic 3D Microstructures

Herein, the fabrication of hard ceramic SiOC 3D microstructures by precursor synthesis, laser lithography, and pyrolysis combination is proposed. Precursors are hybrid organosilicon materials prepared via sol–gel method using trimethoxymethylsilane and 3‐(trimethoxysilyl)propyl methacrylate, which has an acrylate functional group enabling laser photopolymerization process. Hard 3D ceramic structures (hardness up to ≈15 GPa, reduced elastic modulus ≈105 GPa) from soft organometallic derivatives are obtained after high‐temperature pyrolysis under nitrogen atmosphere. The advantage of the proposed method is the absence of shrinkage defects leading to a uniform repetitive decrease in the volume of printed microstructures. In contrast to slurry‐based printing technology, the proposed method is focused on homogeneous monolithic molecular resins resulting in visual smooth surfaces of prepared microstructures. Moreover, the printing resolution of the proposed method is substantially improved through the absence of predispersed ceramic microparticles in mixtures, which is a necessary element in a slurry‐based technology.