New type of symmetry inhomogeneity in β-TCP-type phosphors: symmetrical features of mixed oxysalts

New type of symmetry inhomogeneity in β-TCP-type phosphors: symmetrical features of mixed oxysalts

This study shows the modification of photoluminescent properties (PL) of red-emitting β-Ca3(PO4)2-type (β-TCP) phosphor through anionic sublattice substitution. A new series of Eu3+-activated Ca9La(PO4)7(1–x)(VO4)7x were synthesized using the solid-state method. X-ray powder diffraction study shows...

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Bibliographic Details
Main Authors: I.V. Nikiforov, V.V. Titkov, E.S. Zhukovskaya, M.M. Klimenko, E.A. Pankrushina, А.А. Vasin, D.V. Deyneko
Format: Article
Language:English
Published: Elsevier 2025-07-01
Series:Optical Materials: X
Subjects:
Luminescent materials
Eu doping
Phosphate phosphors
Vanadate
Whitlockite
b-TCP
Online Access:http://www.sciencedirect.com/science/article/pii/S2590147825000233
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Summary:This study shows the modification of photoluminescent properties (PL) of red-emitting β-Ca3(PO4)2-type (β-TCP) phosphor through anionic sublattice substitution. A new series of Eu3+-activated Ca9La(PO4)7(1–x)(VO4)7x were synthesized using the solid-state method. X-ray powder diffraction study shows that all sample have β-TCP structure, however the differences in symmetry between the samples was found by second harmonic generation method. The unusual centrosymmetric structure appeared at 0.2 ≤ x ≤ 0.5 in Ca9La(PO4)7(1–x)(VO4)7x:Eu3+. Study of the series' photoluminescence properties revealed significant improvement in Eu3+-emission intensity for centrosymmetric samples. The PO4 ↔ VO4 substitution at 0.2 ≤ x ≤ 0.5 resulted in a 1.6-fold enhancement of Eu3+ photoluminescent properties. The emission intensity changes correspond to variations in the anionic part of the structure while maintaining constant activator concentration. The optical band-gap of the synthesized phosphors was estimated at ∼3 eV. Characteristic lifetimes decreased from 1.796 to 0.538 ms with increasing VO4 content. Quantum yields reached 34 % with just 1 mol.% of Eu3+. The crystal structure variation proposed here serves as an effective tool for improving photoluminescence properties of rare-earth ions.
ISSN:2590-1478

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