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Abnormal Eu3+ → Eu2+ Reduction in Ca9-xMnxEu(PO4)7 Phosphors: Structure and Luminescent Properties.

ABSTRACT: β-Ca3(PO4)2-type phosphors Ca9-xMnxEu(PO4)7 have been synthesized by high-temperature solid-phase reactions. The crystal structure of Ca8MnEu(PO4)7 was characterized by synchrotron X-ray diffraction. The phase transitions, magnetic and photoluminescence (PL) properties were studied. The abnormal reduction Eu3+ → Eu2+ in air was observed in Ca9-xMnxEu(PO4)7 according to PL spectra study and confirmed by X-ray photoelectron spectroscopy (XPS). Eu3+ shows partial reduction and coexistence of Eu2+/3+ states. It reflects in combination of a broad band from the Eu2+ 4f65d1 → 4f7 transition and a series of sharp lines attributed to 5D0 → 7FJ transitions of Eu3+. Eu2+/Eu3+ ions are redistributed among two crystal sites, M1 and M3, while Mn2+ fully occupies octahedral site M5 in Ca8MnEu(PO4)7. The main emission band was attributed to the 5D0 → 7F2 electric dipole transition of Eu3+ at 395 nm excitation. The abnormal quenching of Eu3+ emission was observed in Ca9-xMnxEu(PO4)7 phosphors with doping of the host by Mn2+ ions. The phenomena of abnormal reduction and quenching were discussed in detail.

SUBMITTER: Sipina EV 

PROVIDER: S-EPMC9962388 | biostudies-literature | 2023 Feb

REPOSITORIES: biostudies-literature

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Abnormal Eu<sup>3+</sup> → Eu<sup>2+</sup> Reduction in Ca<sub>9-<i>x</i></sub>Mn<i><sub>x</sub></i>Eu(PO<sub>4</sub>)<sub>7</sub> Phosphors: Structure and Luminescent Properties.

Sipina Elena V EV   Spassky Dmitry A DA   Krutyak Nataliya R NR   Morozov Vladimir A VA   Zhukovskaya Evgenia S ES   Belik Alexei A AA   Manylov Mikhail S MS   Lazoryak Bogdan I BI   Deyneko Dina V DV  

Materials (Basel, Switzerland) 20230207 4

β-Ca<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub>-type phosphors Ca<sub>9-<i>x</i></sub>Mn<i><sub>x</sub></i>Eu(PO<sub>4</sub>)<sub>7</sub> have been synthesized by high-temperature solid-phase reactions. The crystal structure of Ca<sub>8</sub>MnEu(PO<sub>4</sub>)<sub>7</sub> was characterized by synchrotron X-ray diffraction. The phase transitions, magnetic and photoluminescence (PL) properties were studied. The abnormal reduction Eu<sup>3+</sup> → Eu<sup>2+</sup> in air was observed in Ca<sub>9-<i>  ...[more]

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