Refined structural studies on the fluorite-related polymorphs of sol–gel undoped and Eu3+-doped yttrium tantalates†
Abstract
Compounds with the general formula RE3MO7 (RE = rare earth ions; M = Ta, Nb, Sb, Ru, Ir, Os, Re, etc.), crystallize as a fluorite-related structure, forming polymorphs with different space groups. The space group strongly depends on the RE3+ and M5+ ionic radii and processing conditions. Structural characterization is well-established for the lanthanide series, but literature studies have divergent views about how to attribute yttrium tantalate (Y3TaO7) space groups—some authors have described the Y3TaO7 structure as orthorhombic and belonging to space group C2221 or Ccmm, whereas others have assigned a cubic Fmm structure to it. Here, we have characterized the structure of undoped and Eu3+-doped Y3TaO7 (0.1 to 50 mol% of Eu3+) samples synthesized by the sol–gel method that crystallized as a cubic disordered fluorite-type structure, space group Fm
m. Their powder X-ray diffraction measurements, Rietveld analyzes and Raman spectra were used as a conclusive technique of the structural properties. We have also investigated whether a secondary phase (M′-YTaO4) emerged in the samples and compared the phase composition of each sample to their Raman spectra. Low-temperature photoluminescence measurements (∼15 K) using Eu3+ as a structural probe helped us analyze the inhomogeneous broadening observed in the emission spectra. These measurements can be used as an important tool to attribute the crystalline phases of rare earth tantalates and niobates.