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Pure, lithium- or magnesium-doped ferroelectric single crystals of Ca9Y(VO4)7: cation arrangements and phase transitions

  • Bogdan I. Lazoryak , Dina V. Deyneko EMAIL logo , Sergey M. Aksenov , Sergey Yu. Stefanovich , Elena A. Fortalnova , Darya A. Petrova , Oksana V. Baryshnikova , Miron B. Kosmyna and Aleksey N. Shekhovtsov
Published/Copyright: March 16, 2018
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Zeitschrift für Kristallographie - Crystalline Materials
From the journal Zeitschrift für Kristallographie - Crystalline Materials Volume 233 Issue 7

Abstract

Single crystals of Ca9Y(VO4)7 (1), Ca9Y(VO4)7:Li+ (2) and Ca9Y(VO4)7:Mg2+ (3) were grown by the Czochralski method. Their chemical composition was analyzed by ICP spectroscopy and their crystal structure was examined by single crystal X-ray analysis. The crystals are characterized by trigonal symmetry, space group R3c. Hexagonal unit-cell parameters are as follows: a=10.8552(1) Å, c=38.0373(2) Å, V=3881.65(1) Å3 for 1; a=10.8570(1) Å, c=38.0161(3) Å, V=3880.77(4) Å3 for 2; a=10.8465(1) Å, c=38.0366(2) Å, V=3875.36(3) Å3 for 3. All crystals are characterized by β-Ca3(PO4)2-type structure with statistical distribution of Ca2+ and Y3+ over M1, M2 and M5 sites in different ratios and with completely empty M4-cationsite. The impurity of Mg2+cations in structure 2 has been detected in octahedral M5 site. Ferroelectric phase transitions are evidenced by DSC and SHG. At about 1220 and 1300 K, they demonstrate phase transitions. Upon heating the symmetry of the crystal structure changes according to the scheme R3c→R3̅c→R3̅m and is restored during consequent cooling. The first of them is of ferroelectric and the second of non-ferroelectric nature. Even a small amount of impurities in Ca9Y(VO4)7 structure is accompanied by a noticeable decrease in the temperature of the ferroelectric-paraelectric phase transition.

Keywords: crystal structure; ferroelectricity; phase transitions; single crystals; whitlockite
Corresponding author: Dr. Dina V. Deyneko, Chemistry Department, Lomonosov Moscow State University, Moscow 119991, Russia

Acknowledgements

This research was supported by the Russian Science Foundation (Grant 16-13-10340). D.V.D. is grateful for financial support of the Foundation of the President of the Russian Federation (Grant MК-3502.2018.5).

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Supplemental Material:

The online version of this article offers supplementary material (https://doi.org/10.1515/zkri-2017-2132).

Received: 2017-11-18
Accepted: 2017-12-22
Published Online: 2018-3-16
Published in Print: 2018-7-26

©2018 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

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  2. Graphical Synopsis
  3. Review Article
  4. N Donor substituted acetylacetones – versatile ditopic ligands
  5. Inorganic Crystal Structures
  6. Pure, lithium- or magnesium-doped ferroelectric single crystals of Ca9Y(VO4)7: cation arrangements and phase transitions
  7. The crystal structure of nonmetamict Nb-rich zirconolite-3T from the Eifel paleovolcanic region, Germany
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https://doi.org/10.1515/zkri-2017-2132
Keywords for this article
crystal structure; ferroelectricity; phase transitions; single crystals; whitlockite

Articles in the same Issue

  1. Frontmatter
  2. Graphical Synopsis
  3. Review Article
  4. N Donor substituted acetylacetones – versatile ditopic ligands
  5. Inorganic Crystal Structures
  6. Pure, lithium- or magnesium-doped ferroelectric single crystals of Ca9Y(VO4)7: cation arrangements and phase transitions
  7. The crystal structure of nonmetamict Nb-rich zirconolite-3T from the Eifel paleovolcanic region, Germany
  8. Mn-bearing eleonorite from Hagendorf South pegmatite, Germany: crystal structure and crystal-chemical relationships with other beraunite-type phosphates
  9. Na3GaF6 – A crystal chemical and solid state NMR spectroscopic study
  10. Temperature dependent optical properties of red emitting Na3GaF6:Mn4+ as a color converter for warm white LEDs
  11. Organic and Metalorganic Crystal Structures
  12. Hydrogen bonding in hydroxypyridium salts
  13. Synthesis and structural characterization of a series of uranyl-betaine coordination complexes
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