Luminescence, structure and antiferroelectric-type phase transition in Ca8ZnEu(PO4)7
Highlights: • Thermal, dielectric and luminescence properties were obtained for Ca{sub 8}ZnEu(PO{sub 4}){sub 7}. • Ca{sub 8}ZnEu(PO{sub 4}){sub 7} belongs to antiferroelectric with T{sub c} = 836 K. • First-order antiferroelectric/paraelectric phase transitions have been found. • Influence of composition on the luminescence properties has been shown. • Structure of Ca{sub 8}ZnEu(PO{sub 4}){sub 7} was refined by the Rietveld method. - Abstract: Photoluminescence excitation and emission spectra of new phosphate Ca{sub 8}ZnEu(PO{sub 4}){sub 7} have been investigated. The influence of the composition on the luminescence intensity has been shown. The substitution of Zn{sup 2+} for Ca{sup 2+} in Ca{sub 9}Eu(PO{sub 4}){sub 7} with the formation of Ca{sub 8}ZnEu(PO{sub 4}){sub 7} leads to the increased emission intensity {sup 5}D{sub 0} → {sup 7}F{sub 2} by about 1.5 times and to decreased number of bands from three to one in the range of {sup 5}D{sub 0} → {sup 7}F{sub 0} transition. Conditions of preparation do not influence the luminescent properties and distribution of Eu{sup 3+} cations in the structure. DSC, SHG data and dielectric spectroscopy reveal that Ca{sub 8}ZnEu(PO{sub 4}){sub 7} belongs to antiferroelectrics (T{sub c} = 836 K). The first-order antiferroelectric/paraelectric transformations are accompanied by a changing symmetry (R3-barC to R3-barm). The structure of Ca{sub 8}ZnEu(PO{sub 4}){sub 7} (sp. gr. R3-barc) was refined by the Rietveld method. The Zn{sup 2+} cations occupy the M5 site. The Eu{sup 3+} and Ca{sup 2+} ions are located in the M1 and M3 sites of β-Ca{sub 3}(PO{sub 4}){sub 2}-type structure.