Optical non-linearity tuning in Ca8-xPbxMBi(VO4)7 whitlockite-type systems

Daria A. Beskorovaynaya, Dina V. Deyneko, Oksana V. Baryshnikova, Sergey Yu Stefanovich, Bogdan I. Lazoryak

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17 Citations (Scopus)


Ca8-xPbxMBi(VO4)7, M2+ = Mg2+, Zn2+ (0 ≤ x ≤ 1.5) and M2+ = Ca2+, Cd2+ (0 ≤ x ≤ 2) solid solutions with whitlockite-type structure have been prepared by solid state reactions in the form of powders and ceramics. Ferroelectric phase transitions (FPT) are revealed in the cause of dielectric, calorimetric and temperature second harmonic generation (SHG) investigations. It is found that ferroelectric Curie points in solid solutions decrease with x from 1000-1070 K to 730-800 K. The intensity of SHG firstly increases with x and then decreases, the highest SHG signal belongs to Ca7PbCdBi(VO4)7 and Ca6.5Pb1.5CdBi(VO4)7. Variation of Pb2+ concentration is shown to have a minor influence on the coherence length, therefore the SHG augmentation in solid solutions is attributed to optical nonlinear coefficient <d>. The structure of Ca6.5Pb1.5MgBi(VO4)7 is resolved and crystal structure changes in solid solutions are analyzed. The results are interpreted in view of site occupancy by two- A nd trivalent cations and their influence on formation of spare space essential for Pb2+ and Bi3+ non-bonded electrons stereo-activity in whitlockite-type crystal structures. For the first time contribution to optical nonlinearity from VO4 3- anionic groups in different positions is also discussed.

Original languageEnglish
Pages (from-to)323-330
Number of pages8
JournalJournal of Alloys and Compounds
Publication statusPublished - 25 Jul 2016
Externally publishedYes


  • Crystal structure
  • Nonlinear optics
  • Phase transitions
  • X-ray diffraction


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