Fig. 1. 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.

Fig. 2. (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.

Fig. 3. 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).

Fig. 4. 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.

Fig. 5. 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.

Fig. 6. 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.

Fig. 7. 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.