The current paper is focused on the rapidly developing field of nano-/micro three-dimensional production of inorganic materials. The fabrication method includes laserlithography of hybrid organic-inorganic materials with subsequent heat treatment lead-ing to a variety of crystalline phases in 3D structures. In this work, it was examineda series of organometallic polymer precursors with different silicon (Si) and zirconium (Zr) molar ratios, ranging from 9:1 to 5:5, prepared via sol-gel method. All mixtureswere examined for perspective used in 3D laser by manufacturing by fabricating nano-and micro-feature sized structures. Their deformation and surface morphology wereevaluated depending on chemical composition and crystallographic phase. The appear-ance of a crystalline phase was proven using single-crystal X-ray diffraction analysis,which revealed a lower crystallization temperature for microstructures compared tobulk materials. Fabricated 3D objects retain a complex geometry without any distortion after heat treatment up to 1400^oC. Under the proper conditions, a zircon phase (ZrSiO₄ - a highly stable material) can be observed. In addition, the highest newrecord of achieved resolution below 60 nm has been reached. The proposed prepara-tion protocol can be used to manufacture micro/nano-devices with high precision andresistance to high temperature and aggressive environment.

Fabrication of a true-3D inorganic ceramic with resolution down to nanoscale using sol-gel resist precursor is demonstrated. The method has an unrestricted free-form capability, control of the fill-factor, and high fabrication throughput. A systematic study of the proposed approach based on ultrafast laser 3D lithography of organic-inorganic hybrid sol-gel resin followed by a heat treatment enabled formation of inorganic amorphous and crystalline composites guided by the composition of the initial resin. The achieved resolution of 100 nm was obtained for 3D patterns of complex free-form architectures. Fabrication throughput of 50×10³ voxels/s is achieved; voxel - a single volume element was recorded by a single pulse exposure. After a subsequent thermal treatment, ceramic phase was formed depending on the temperature and duration of the heat treatment as validated by Raman micro-spectroscopy. The X-ray diffraction (XRD) revealed a gradual emergence of the crystalline phases at higher temperatures with a signature of cristobalite SiO₂, a high-temperature polymorph. Also, the tetragonal ZrO₂ phase known for its high fracture strength was observed. This 3D nano-sintering technique is scalable from nano- to millimeter dimensions and opens a conceptually novel route for optical 3D nano-printing of various crystalline inorganic materials defined by an initial composition for diverse applications for microdevices in harsh physical and chemical environments and high temperatures.