Fabrication of 3D glass-ceramic micro- /nano-structures by direct laser writing lithography and pyrolysis

Glass-ceramics play an important role in todays science and industry as it can withstand immense heat, mechanical and other hazards. Consequently, there is a need to find ever-new ways to acquire more sophisticated free-form 3D ceramic and glass structures. Recently, stereo-lithographic 3D printing of hybrid organic-inorganic photopolymer and subsequent pyrolysis was demonstrated to be capable of providing true 3D ceramic and glass structures. However, such approach was limited to (sub-)millimeter scale, while one of the aims in the field is to acquire functional 3D glass-like structures in micro- or even nano-dimensions. In this paper, we explore a possibility to apply ultrafast 3D laser nanolithography in conjunction with pyrolysis to acquire glass-ceramic 3D structures in micro- and nano-scale. Laser fabrication allows production of initial 3D structures with relatively small (hundreds of nm) feature sizes out of hybrid organic-inorganic material SZ2080. Then, a post-fabrication heating at different temperatures up to 1000°C in Ar , air or O2 atmospheres decomposes organic part of the material leaving only the glass-ceramic component of the hybrid. As we show, this can be done to 3D woodpiles and bulk objects. We uncover that the shrinkage during sintering can reach up to 40%, while the aspect ratio of single features as well as filling ratio of the whole object remains the same. This hints at homogeneous reduction in size that can be easily accounted for and pre-compensated before manufacturing. Additionally, the structures prove to be relatively resilient to focused ion beam (FIB) milling, hinting at increased rigidity. Finally, thermal gravimetric analysis (TGA) and Fourier transform infrared micro-spectroscopy measurements are performed in order to uncover undergoing chemical and physical phenomena during pyrolysis and composition of the remnant material. The proposed post-processing approach offers a straightforward way to downscale true 3D micro-/nanostructures for applications in nanophotonics, microoptics and mechanic devices with improved performance while being highly resilient to harsh surrounding conditions.