Issue 9, 2017

Ferroelectric crystal Ca9Yb(VO4)7 in the series of Ca9R(VO4)7 non-linear optical materials (R = REE, Bi, Y)

Abstract

The crystal structure, thermal, dielectric and second harmonic generation (SHG), and nonlinear optical activity data for whitlockite-type Ca9Yb(VO4)7 single crystals were obtained on one and the same sample produced by means of the Czochralski method. The crystal structure refinement has revealed that Yb3+ cations substitute for Ca2+ ions only in the M1, M2 and M5 positions of the whitlockite-type structure. Dielectric, differential thermal analysis and SHG data have shown that Ca9Yb(VO4)7 belongs to the family of high-temperature Ca3(VO4)2 ferroelectrics with Curie temperature Tc = 1221 K, where the symmetry changes from R3c to R[3 with combining macron]c. At higher temperatures a previously unknown complementary phase transition is discovered at T2 = 1276 K and is associated with the symmetry change during heating from R[3 with combining macron]c to R[3 with combining macron]m. Unlike other whitlockites, two phase transitions in Ca9Yb(VO4)7 are separated by a broad interval (ΔT = 55 K) which allows one to register two phase transitions by DSC and dielectric measurements. According to the thermal type both transitions are classified as first-order transformations and their structural mechanisms are considered. Inhomogeneity in the cation distribution is argued to have a crucial influence on the optical quality and ferroelectric domain structures of Ca9Yb(VO4)7 and other whitlockite-type laser crystals.

Graphical abstract: Ferroelectric crystal Ca9Yb(VO4)7 in the series of Ca9R(VO4)7 non-linear optical materials (R = REE, Bi, Y)

Supplementary files

Article information

Article type
Paper
Submitted
10 Jan 2017
Accepted
30 Jan 2017
First published
14 Feb 2017

J. Mater. Chem. C, 2017,5, 2301-2310

Ferroelectric crystal Ca9Yb(VO4)7 in the series of Ca9R(VO4)7 non-linear optical materials (R = REE, Bi, Y)

B. I. Lazoryak, S. M. Aksenov, S. Yu. Stefanovich, N. G. Dorbakov, D. A. Belov, O. V. Baryshnikova, V. A. Morozov, M. S. Manylov and Z. Lin, J. Mater. Chem. C, 2017, 5, 2301 DOI: 10.1039/C7TC00124J

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