Structural and optical studies of annealed zirconia nanocrystals: Phase transformations, defect dynamics, and magnetic behaviour

The present study is a continuation of our previous work, where we synthesized and characterized t-ZrO₂ nanocrystals through the combustion method. Further, t-ZrO₂ nanocrystals are annealed at 600, 900, 1200, and 1400°C and characterized through XRD, Raman, FESEM, XPS, photoluminescence (PL), and thermoluminescence (TL) techniques. XRD and Raman patterns reveal that the as-synthesized ZrO₂ nanocrystals exhibit a tetragonal phase, and annealing at different temperatures induces phase transformations. Annealing at 600 °C restores the metastable nature of the tetragonal phase, although monoclinic nucleation is visualized through Raman spectroscopy. Annealing at higher temperatures leads to a complete transformation into the monoclinic phase. FESEM micrographs reveal extensive crystal growth and consolidation upon annealing. XPS analysis shows a reduction in the binding energies of the Zr 3d doublet due to the removal of lattice oxygen and the formation of oxygen vacancies upon annealing. The annealing of the synthesized material at 1400 °C induced a transformation to ferromagnetic behaviour at 300 K, with increased saturation magnetization (Ms) and coercivity (Hc), reflecting the stabilization of magnetic ordering and residual defects in the grain boundary. PL responses confirm the formation of luminescent defects in the crystal lattice. The TL response varies with the crystalline phase, annealing temperature, and radiation dose, suggesting defect creation, migration, and localization in the lattice. Overall, the study provides valuable insights into the structural and optical properties of ZrO₂ nanoparticles annealed at different temperatures.