Average Structure, Local Structure, Photoluminescence, and NLO Properties of Scheelite Type NaCe(WO4)2

Abstract

Phase pure nanoparticles of NaCe(WO4)2 green phosphor were synthesized via a template-free solvothermal method using water (NaCeW-a) and ethylene glycol (NaCeW-b) as reaction solvents. Rietveld refinements using powder neutron diffraction (NPD) data confirms that both NaCeW-a and NaCeW-b crystallize in the Scheelite-like tetragonal I41/a space group. However, local structure analysis using total scattering atomic pair distribution function (PDF) refinements in a shorter ‘r’ range (1.5 to 10 Å) established the noncentrosymmetric I4̅ space group where Na/CeO8 polyhedra are slightly distorted, distributed in 2b and 2d sites. The interesting observation of noncentrosymmetry locally in both NaCeW-a and NaCeW-b is supported by optical nonlinear second harmonic generation (SHG) measurements. Closer inspection of the scanning electron micrograms showed a distinct difference in the particle morphology as a function of reaction solvent. Observation of the +3 valence state of the cerium ion in NaCe(WO4)2 via X-ray photoelectron spectroscopy measurements was further corroborated by magnetic (VSM) measurements. In addition, both the samples emitted bright narrow green emission upon UV excitation with no considerable change in emission intensity with respect to solvent. Hence, the sharp green light emission and SHG properties make the NaCe(WO4)2 a potential candidate for solid state display and nonlinear optical applications.