Phaseformation in triple systems phosphates Sr–M2+–Ln3+ (M2+ = Zn2+, Mg2+, Mn2+; Ln3+ = Eu3+, Tb3+)

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Аннотация

The phase formation in a system of triple phosphates Sr–M2+–Ln3+ (M2+ = Zn2+, Mg2+, Mn2+; Ln3+ = Eu3+, Tb3+) has been investigated. The crystallization of strontiowhitlockite like structure and isomorphism in a series Sr9–xMnxTb(PO4)7, Sr9–xMgxEu(PO4)7 and Sr9–xZnxEu(PO4)7 (0 ≤ x ≤ 1.0) was described. The species were synthesized through solid-state reaction. It was shown that unlimited series of solid solutions can not be formed. The formation of a strontiowhitlockite-like structure was observed for only stoichiometric compositions Sr8MgEu(PO4)7 and Sr8ZnEu(PO4)7. Crystal chemical aspects of the formation of the strontiowhitlockite structure in the series were analysed. Samples with the strontiowhitlockite structure are crystallized in centrosymmetric space group (sp. gr. R3m) compared to a mother structure, mineral whitlockite, and its synthetic modifications based on calcium phosphate. The conditions for the formation of phosphates with the structure of stronciowhitlockite are indicated. The photoluminescence properties were described, and it was shown that samples exhibit intense emission in the red-orange region, due to the presence of Eu3+ ions. A quenching effect in Sr9–xMnxTb(PO4)7 was detected.

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Авторлар туралы

I. Nikiforov

Lomonosov Moscow State University

Хат алмасуға жауапты Автор.
Email: nikiforoviv@my.msu.ru
Ресей, Moscow

K. Yashina

Lomonosov Moscow State University

Email: nikiforoviv@my.msu.ru
Ресей, Moscow

E. Zhukovskaya

Lomonosov Moscow State University

Email: nikiforoviv@my.msu.ru
Ресей, Moscow

S. Gutnikov

Lomonosov Moscow State University

Email: nikiforoviv@my.msu.ru
Ресей, Moscow

S. Aksenov

Kola Science Centre, Russian Academy of Sciences

Email: nikiforoviv@my.msu.ru

Geological Institute; Laboratory of Arctic Mineralogy and Material Sciences

Ресей, Apatity

D. Deyneko

Lomonosov Moscow State University; Kola Science Centre, Russian Academy of Sciences

Email: nikiforoviv@my.msu.ru

Laboratory of Arctic Mineralogy and Material Sciences, Kola Science Centre, Russian Academy of Sciences

Ресей, Moscow; Apatity

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2. Fig. 1. Diffraction patterns of Sr9–xMgxEu(PO4)7 and bar diffraction patterns of the phases Sr9Fe1.5(PO4)7 (PDF-2 51-427) (1), Sr3Eu(PO4)3 (PDF-2 48-410) (2), Sr3(PO4)2 (PDF-2 80-1614) (3) (a); percentage content of the phases Sr9–xM2+xEu(PO4)7, M2+ = Mg2+ (b), Zn2+ (c).

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3. Fig. 2. Diffraction patterns of Sr9–xMnxTb(PO4)7 and bar diffraction patterns of the Sr9Fe1.5(PO4)7 (PDF-2 51-427) (1) and Sr3(PO4)2 (PDF-2 80-1614) (2) phases (reflexes of the Tb7O12 (PDF-2 34-518) phase are indicated by an asterisk) (a); percentage content of the Sr9–xMnxTb(PO4)7 phases (b).

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4. Fig. 3. XPS spectra of Mn2p (a) and Mn3s (b) of Sr9–xMnxTb(PO4)7 at x = 0.2 (1), 1.0 (2).

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5. Fig. 4. Roseboom concentration triangle for the Sr3(PO4)2–Mg3(PO4)2–EuPO4 (a) and Sr3(PO4)2–Mn3(PO4)2–TbPO4 (b) systems: e – eulytine phase Sr3Eu(PO4)3 (Sr3Tb(PO4)3); s – SrMg2(PO4)2 (SrMn2(PO4)2); m – Mg3(PO4)2:0.5Eu3+; w1 – (Sr0.86Mg0.14)3(PO4)2, w2 – (Sr0.95Mg0.04)3(PO4)2, w3 – Sr9Mn1.5(PO4)7 [39]; the compositions obtained in the present work are marked with an asterisk (the asterisk in a circle is a single-phase composition).

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6. Fig. 5. Structure of palmierite Sr3(PO4)2 (a) and comparison of octahedral positions of Sr1O6+6 in palmierite (b) and M5O6 in strontiovitlockite (c) with indication of average distances between the central atom and oxygen.

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7. Fig. 6. Excitation (λemitted = 615 nm) (a) and emission (λexcited = 395 nm) (b) spectra of PL of Sr8MgEu(PO4)7 (1) and Sr8ZnEu(PO4)7 (2).

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8. Fig. 7. Excitation (λemitted = 547 nm) (a) and emission (λexcited = 375 nm) (b) spectra of PL Sr9–xMnxTb(PO4)7.

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