Probing Site Symmetry Around Eu3+ in Nanocrystalline ThO2 Using Time Resolved Emission Spectroscopy

ThO₂:Eu³⁺ nanoparticles were synthesized at 300°C by combustion route using urea as a fuel and characterized by thermogravimetric/differential thermal analysis, X‐ray diffraction, transmission electron microscopy, and photoluminescence techniques. To investigate the effect of annealing temperature, as synthesized powder were heated further at 500°C, 700°C, and 900°C. It was observed that extent of asymmetry around Eu³⁺ at 700°C/900°C is very high as compared to as‐prepared or 500°C annealed sample. Based on the time resolved emission spectroscopic investigations, it was inferred that two different types of Eu³⁺ ions were present in the ThO₂ nanoparticles. In ThO₂ structure, Eu³⁺ ions occupy two sites; cubic (O_h) and noncubic (2v) as can be confirmed from our emission studies. Short‐lived species T₁ (~1.3–3.4 ms) predominates at higher annealing temperature arises because of Eu³⁺ ions occupying noncubic (2v) sites without inversion symmetry, whereas long‐lived species T₂ (~4.6–6.6 ms) can be ascribed to Eu³⁺ ions occupying cubic sites (O_h) with inversion symmetry.