Optical materials

Synthesis, structure and spectral properties of transparent glass-ceramics based on nanocrystals of zinc aluminate spinel doped with Ti$^{3+}$ ions

K. N. Eremeev^a, O. S. Dymshits^bc, I. P. Alekseeva^c, A. A. Khubetsov^c, M. Ya. Tsenter^c, S. S. Zapalova^c, L. R. Basyrova^c, P. A. Loiko^a, A. A. Zhilin<sup>d

a</sup> Centre de Recherche sur les Ions, les Matériaux et la Photonique (CIMAP), UMR 6252 CEA-CNRS-ENSICAEN, Université de Caen Normandie, 14050 Caen Cedex 4, France
^b Ioffe Institute, 194021 St. Petersburg, Russia
^c All-Russian Research Center "S. I. Vavilov State Optical Institute", 192171 St. Petersburg, Russia
^d D. V. Efremov Scientific Research Institute of Electrophysical Apparatus, 196641 St. Petersburg, Russia

Abstract: The structure and spectral properties of transparent glass-ceramics of the zinc aluminosilicate system containing titanium dioxide as a nucleating agent have been studied. The glass-ceramics were obtained by secondary heat- treatments of glass melted under reducing conditions and studied by differential scanning calorimetry, X-ray diffraction analysis, Raman spectroscopy, absorption and luminescence. The heat-treatments were carried out in the temperature range from 720 to 1050$^\circ$C. According to the X-ray diffraction analysis, the main crystalline phase of glass-ceramics is zinc aluminate spinel (gahnite) with cubic structure and crystal size from 6 to 14 nm depending on the temperature of heat-treatment. At the temperature of 1000–1050$^\circ$ C crystals of TiO$_2$ (rutile) also appear in glass-ceramics. The volume fraction of gahnite and rutile crystals and their sizes increase with increasing temperature of heat-treatment. The lattice parameter of gahnite nanocrystals changes from 8.083 to 8.120 $\mathring{\mathrm{A}}$ and its change occurs due to the incorporation of titanium ions. In glass-ceramics, broadband absorption in the visible and near-infrared spectral regions is observed due to the incorporation of Ti$^{3+}$ ions into octahedral positions (positions of Al$^{3+}$ ions) in the gahnite structure. According to Raman spectroscopy data, phase transformations in glass melted under reducing conditions are similar to those in glasses melted under oxidizing conditions, which indicates a small influence of Ti$^{3+}$ ions on the processes of formation of glass-ceramics. Luminescence of the obtained materials is caused by superposition of luminescence of impurity Cr$^{3+}$ ions and Ti$^{3+}$ ions in octahedral positions in gahnite nanocrystals. The obtained regularities will be used in the development of glass-ceramics containing transition metal ions in lower oxidation states.

Keywords: transparent glass-ceramics, nanocrystals, zinc aluminate spinel, titanium ions, structure, optical spectroscopy, X-ray diffraction analysis, Raman spectroscopy.

Received: 01.12.2023
Revised: 01.12.2023
Accepted: 11.12.2023

DOI: 10.61011/OS.2024.02.57776.5815-23

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