Synchrotron X-ray diffraction and Raman spectroscopy of Ln3NbO7 (Ln=La, Pr, Nd, Sm-Lu) ceramics obtained by molten-salt synthesis.

Abstract

Ln3NbO7 (Ln=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) ceramics were obtained by molten- salt synthesis and their structures were systematically investigated by synchrotron X-ray diffraction (SXRD), second harmonic generation (SHG) and Raman spectroscopy. It was observed that ceramics with the largest ionic radii (La, Pr, Nd) crystallized in to the Pmcn space group, while the ceramics with intermediate ionic radii (Sm-Gd) exhibited different crystal structure belonging to the Ccmm space group. For this last group of ceramics, this result was corroborated by SHG and Raman scattering and ruled out any possibility for the non-centrosymmetric C 2221 space group, solving a recent controversy in the literature. Finally, according to SXRD, Tb-Lu containing samples exhibited an average defect fluorite structure (Fm3m space group). Nonetheless, broad scatter in gat forbidden Bragg reflections indicates the presence of short-range domains with lower symmetry. Vibrational spectroscopy showed the presence of six Raman-active modes, inconsistent with the average cubic fluorite structure, and in line with the existence of lower-symmetry nano-domains immersed in the average fluorite structure of these ceramics.