|Citation:||Merkininkaitė G, Aleksandravičius E, Malinauskas M, Gailevičius D, Šakirzanovas S. Laser additive manufacturing of Si/ZrO2 tunable crystalline phase 3D nanostructures. Opto-Electron Adv 5, 210077 (2022). doi: 10.29026/oea.2022.210077|
The current study is directed to the rapidly developing field of inorganic material 3D object production at nano-/micro scale. The fabrication method includes laser lithography of hybrid organic-inorganic materials with subsequent heat treatment leading to a variety of crystalline phases in 3D structures. In this work, it was examined a 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 mixtures were examined for perspective to be used in 3D laser manufacturing by fabricating nano- and micro-feature sized structures. Their spatial downscaling and surface morphology were evaluated depending on chemical composition and crystallographic phase. The appearance of a crystalline phase was proven using single-crystal X-ray diffraction analysis, which revealed a lower crystallization temperature for microstructures compared to bulk materials. Fabricated 3D objects retained a complex geometry without any distortion after heat treatment up to 1400 °C. Under the proper conditions, a wide variety of crystalline phases as well as zircon (ZrSiO4 - a highly stable material) can be observed. In addition, the highest new record of achieved resolution below 60 nm has been reached. The proposed preparation protocol can be used to manufacture micro/nano-devices with high precision and resistance to high temperature and aggressive environment.
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|Supplementary information for Laser additive manufacturing of Si/ZrO2 tunable crystalline phase 3D nanostructures|
Graphical abstract showing precursors, their molar ratios in (a) syntheses, (b) photopolymerization and calcination technology and (c) formed crystalline phase lattices after calcination (Cristobalite, SiO2, ZrSiO4, monoclinic ZrO2 and tetragonal ZrO2). These phases can be observed depending on the treatment temperature and initial hybrid materials compositions.
(a) TGA data of SiX:ZrY showing weight loss vs. temperature (red line). (b) Theoretical (square symbols) and practical (circle symbols) weight loss for the phase transition from the polymeric to the glass/ceramic phase (black) and volumetric shrinkage (red) (theoretical- square symbols, practical- circle symbols) of cubes at the same phase transition (error bars of volumetric shrinkage represent Std. dev., n = 3, TGA measurements were performed once for each material, so it is not possible to include error bars for the weight loss). SEM images of the Si7:Zr3 cube before (c) and after (d) heat treatment at 1000 °C.
Si9:Zr1 woodpiles (a–c) before heat treatment and (d–f) after heating at 1000 °C under air atmosphere. (a, d) Woodpiles fabricated at 200 μm/s speed (on the top line) and at 500 μm/s speed (on the bottom line) with 48, 56, 64 μW incident irradiation power. (b, c, e, and f) The highest resolution of woodpiles was obtained by applying 200 μm/s and 64 μW parameters. (g) The dependence of Si9:Zr1, Si7:Zr3, Si5:Zr5 woodpiles lines width on the laser irradiance at 200 μm/s speed. Before heat treatment- solid lines, after- dashed lines. (h) The dependence of Si9:Zr1, Si7:Zr3, Si5:Zr5 woodpiles lines width on the laser irradiance at 500 μm/s speed (error bars represent Std. dev., n = 3).
X-ray diffractograms of structures (SEM images) annealed at 1000 °C (a-Si5:Zr5, b-Si6:Zr4, c-Si7:Zr3, d-Si8:Zr2, e-Si9:Zr1, f-reference data) and X-ray diffractograms of powders annealed at 1000 °C (g-Si5:Zr5, h-Si6:Zr4, i-Si7:Zr3, j-Si8:Zr2, k-Si9:Zr1, l-reference data). SEM images show corresponding 3D scaffolds treated at 1000 °C. SEM images correspond to the same scale bar.
X-ray diffractograms of structures (SEM images) annealed at 1200 °C (a-Si5:Zr5, b-Si6:Zr4, c-Si7:Zr3, d-Si8:Zr2, e-Si9:Zr1, f-reference data) and X-ray diffractograms of powders annealed at 1200 °C (g-Si5:Zr5, h-Si6:Zr4, i-Si7:Zr3, j-Si8:Zr2, k-Si9:Zr1, l-reference data). SEM images show corresponding 3D scaffolds treated at 1200 °C temperature. SEM images correspond to the same scale bar.
X-ray diffractograms of structures (SEM images) annealed at 1400 °C (a-Si5:Zr5, b-Si6:Zr4, c-Si7:Zr3, d-Si8:Zr2, e-Si9:Zr1, f-reference data) and X-ray diffractograms of powders annealed at 1400 °C (g-Si5:Zr5, h-Si6:Zr4, i-Si7:Zr3, j-Si8:Zr2, k-Si9:Zr2, l-reference data). SEM images show corresponding 3D scaffolds treated at 1400 °C temperature. SEM images correspond to the same scale bar.
X-ray diffraction measurements. (a) X-Ray diffraction pattern of Si6:Zr4 structure annealed at 1200 °C temperature. (b) Reference patterns. (c) Debye-Scherrer rings obtained after X-ray diffraction measurement. (d) Photograph of Si6:Zr4 structure annealed at 1200 °C temperature before measurement.