Characterization of Tungstates of the Type Hf(1-x)Ln(x)W(2)O(8-x/2) (Ln = Eu, Tm, Lu) Synthesized Using the Hydrothermal Method

Pure HfW2O8- and Ln(3+)-containing solid solutions, Hf(1-x)Ln(x)W(2)O(8-x/2) (Ln = Eu, Tm, Lu), were synthesized using the hydrothermal method. The lanthanide ions were selected based on the differences between their ionic radii. A content of the Ln(3+) ions in the range of 0.01-0.15 mol with a step of 0.02 was used for Hf(1-x)Ln(x)W(2)O(8-x/2) preparation, although the main research was performed on x = 0.01 and 0.05 samples because of an inhomogeneity detected by powder X-ray diffraction (XRD) when the content of Ln(3+) was above 0.07-0.09 mol. X-ray diffraction measurements were supported by Raman and infrared spectroscopy. A new band in the Raman spectra of the samples with 0.05 mol Ln(3+), as well as a red shift of the most intensive band (assigned to valence stretching of W-O-W bonds) as a result of the Ln(3+) presence, was detected. The Scanning Electron Microscopy and Transmission Electron Microscopy micrographs revealed well-crystalized microcrystals with lengths in the range of 2-5 mu m, with larger interplanar distances, measured in the solid solutions of the same crystal plain. The alpha-HfW2O8 -> beta-HfW2O8 order-to-disorder phase transition was followed by high temperature XRD, and its reversibility was evident. The influence of the Ln(3+) both on the unit cell parameters of the solid solutions and on the temperature of phase transition and on the coefficient of thermal expansion, CTE, was observed. A band gap energy in the range of 2.8-3.1 eV for pure HfW2O8 and for the solid solutions Hf(1-x)LnxW(2)O(8-x/2) (x = 0.01 and 0.05) was determined.