Additive-Manufacturing of 3D Glass-Ceramics down to Nanoscale Resolution

Abstract

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.

Fabrication of Glass‐Ceramic 3D Micro‐Optics by Combining Laser Lithography and Calcination

“…To this date (end of 2022) direct comparison of laser-induced damage threshold (LIDT) value change for HTA ceramic micro-optics has not been performed, however, increase in materials irradiation resiliency, compared to their polymer counterparts, [67,131] has been proposed [132] and experimentally validated. [133] Furthermore, LIDT of polymeric structures research results published so far, low material irreversible damage threshold is commonly attributed to organic compounds within the polymeric structures, with most significant being the use photo-initiator range. [134] Organic compounds are associated with increased absorption in shorter UV-vis spectral regions.…”

Processes of Direct Laser Writing 3D Nano-Lithography

“…No less important is that the process is highly repeatable and compatible with harsh industrial conditions. Further adjustment of chemical composition of hybrid photo-curable resins is possible and could be considered as a proper direction towards nano-printing of unique glassceramic or even crystalline materials (Gailevičius et al, 2018). Currently, the state-of-the-art technique is right in between scientific research and industrial applications, the next generation burst mode lasers and dynamic tuning of polarization together with parallelization of the process will make it cost-efficient true 3D micro-/nano-fabrication tool.…”

Comparative Analysis of Wollastonite‐Diopside Glass‐Ceramic Structures Fabricated via Stereo‐Lithography

“…Future investigations will be conducted on both heating conditions and formulations. More precisely, we could think at localized heating (e.g., by means of lasers) or hybrid binding materials, that could bind with glass powders in a nearly molecular way (on one hand, ORMOSIL class materials have been already used in ceramic additive manufacturing; on the other one, silicones may be considered as novel silica‐yielding binders …”