O. V. Baryshnikova

Ca10.5 − xPbx(PO4)7 and Ca9.5 − xPbxM(PO4)7 ferroelectrics with the whitlockite structure

We have prepared Ca9.5 − xPbxM(PO4)7 (M = Mg, Zn, Cd) and Ca10.5 − xPbx(PO4)7 solid solutions. A polar whitlockite-like (sp. gr. R3c) crystal structure exists in the range 0 ≤ x ≤ 1.5 for all of the M cations in Ca9.5 − xPbxM(PO4)7 and in the range 0 ≤ x ≤ 2.5 for Ca10.5 − xPbx(PO4)7. X-ray powder diffraction profile analysis results for Ca8.5PbCd(PO4)7 powder demonstrate that the small divalent M cations reside predominantly on the octahedral site M5 of the whitlockite structure, the calcium cation occupy the M1–M3 sites, and the lead cations are located primarily on the M4 site. Differential scanning calorimetry, second-harmonic generation, and dielectric permittivity data indicate that all of the synthesized phosphates are high-temperature ferroelectrics. The highest Curie temperatures are offered by the x = 0.5 materials, in which most of the lead resides in the spacious oxygen polyhedra M4 and only a small amount of lead is incorporated into the smaller polyhedra around M1–M3. The nonlinear optical activity has a maximum in the middle of the solid-solution series and is an order of magnitude higher than that of the parent, lead-free phases.

Structure and properties of Ca9 − xPbxR(PO4)7 (R = Sc, Cr, Fe, Ga, In) whitlockite-like solid solutions

We have prepared solid solutions based on whitlockite-structure ferroelectrics, Ca9 − xPbxR(PO4)7 (R = Sc, Cr, Fe, Ga, In), through Pb substitution for Ca. Single-phase Ca9 − xPbxR(PO4)7 materials with a polar whitlockite-like structure (sp. gr. R3c) exist in the range 0 ≤ x ≤ 1.5 for all of the R metals studied. X-ray powder diffraction profile analysis results for R = In (x = 0.5, 0.8, and 1.0) demonstrate that the trivalent cations reside on the octahedral site M5 of the whitlockite structure, the calcium cation occupy the M1–M3 sites, and the lead cations are located predominantly on the M3 site. Differential scanning calorimetry, dielectric permittivity, and second-harmonic generation data attest to a ferroelectric phase transition, whose temperature is 580–610°C in Ca9R(PO4)7 and decreases monotonically to 480–520°C as x increases to 1.5.

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

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 Rc. 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 Rc to Rm. 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.

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

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.