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Isovalent and aliovalent cation substitutions in the anion sublattice of whitlockite-type ferroelectrics Ca9RE(VO4)7 with RE =Y and Yb
- Source :
- Journal of Solid State Chemistry. 279:120966
- Publication Year :
- 2019
- Publisher :
- Elsevier BV, 2019.
-
Abstract
- A solid state route was used for the preparation of whitlockite-type solid solutions Ca9Y(NbO4)x(VO4)7–x and Ca9+0.5xYb (GeO4)x(VO4)7–х in both powder and ceramic forms. The complex of methods, including synchrotron powder diffraction were applied for the characterization of the first-time obtained compounds. The limits of the anionic substitution were found up to х = 0.28 (Nb) and 0.35 (Ge). The synthesized solid solutions show ferroelectric properties. The Curie temperatures Tc were determined and gradually rise with x. The increase of Tc correlates with the enlargement of tetrahedral units upon Nb5+ or Ge4+ substitutions for V5+ cations. The intensity of optical second harmonic generation (SHG) induced by a Nd:YAG laser depends non-monotonically on the grain size in powder Ca9Y(NbO4)x(VO4)7–x samples, marking the length of the phase matching lc = 15 μm for x = 0.28 in comparison with lc = 9.14 μm in Ca9Y(VO4)7. Manifold increase in the SHG intensity in both solid solutions is partly related to the appearance of more polarizable Nb5+ and Ge4+ cations in the E1O4 tetrahedra on the 3-fold axis, resulting in an enlarged birefringence of the materials. The photoluminescence study of the Ca9+0.5xYb(GeO4)x(VO4)7–х reveals the same environment of the Yb3+ ions all alone the solid solution. The intensity of the luminescence rises with germanium substitution for vanadium about 2 times.
- Subjects :
- Materials science
Photoluminescence
chemistry.chemical_element
Vanadium
Germanium
02 engineering and technology
Crystal structure
010402 general chemistry
01 natural sciences
Inorganic Chemistry
Materials Chemistry
Ceramic
Physical and Theoretical Chemistry
021001 nanoscience & nanotechnology
Condensed Matter Physics
Ferroelectricity
0104 chemical sciences
Electronic, Optical and Magnetic Materials
Crystallography
chemistry
visual_art
Ceramics and Composites
visual_art.visual_art_medium
0210 nano-technology
Luminescence
Solid solution
Subjects
Details
- ISSN :
- 00224596
- Volume :
- 279
- Database :
- OpenAIRE
- Journal :
- Journal of Solid State Chemistry
- Accession number :
- edsair.doi...........d0c9145ad7e3d47250fdf810b5d0dec3