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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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
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Online Access:http://www.sciencedirect.com/science/article/pii/S2590147825000233
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author I.V. Nikiforov
V.V. Titkov
E.S. Zhukovskaya
M.M. Klimenko
E.A. Pankrushina
А.А. Vasin
D.V. Deyneko
author_facet I.V. Nikiforov
V.V. Titkov
E.S. Zhukovskaya
M.M. Klimenko
E.A. Pankrushina
А.А. Vasin
D.V. Deyneko
author_sort I.V. Nikiforov
collection DOAJ
description 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.
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spelling doaj-art-98960848fe6740b5a5b9b8e7522f377e2025-08-23T04:49:03ZengElsevierOptical Materials: X2590-14782025-07-012710042110.1016/j.omx.2025.100421New type of symmetry inhomogeneity in β-TCP-type phosphors: symmetrical features of mixed oxysaltsI.V. Nikiforov0V.V. Titkov1E.S. Zhukovskaya2M.M. Klimenko3E.A. Pankrushina4А.А. Vasin5D.V. Deyneko6Chemistry Department, Lomonosov Moscow State University, 119991, Moscow, RussiaChemistry Department, Lomonosov Moscow State University, 119991, Moscow, RussiaChemistry Department, Lomonosov Moscow State University, 119991, Moscow, RussiaChemistry Department, Lomonosov Moscow State University, 119991, Moscow, RussiaZavaritsky Institute of Geology and Geochemistry UB of RAS, 15 Vonsovsky Str., 620110, Ekaterinburg, RussiaInstitute of Solid State Chemistry, UB of RAS, 91, Pervomayskaya, 620990, Ekaterinburg, RussiaLaboratory of Arctic Mineralogy and Material Sciences, Kola Science Centre RAS, 14 Fersman Str., 184209, Apatity, Russia; Chemistry Department, Lomonosov Moscow State University, 119991, Moscow, Russia; Corresponding author. Chemistry Department, Lomonosov Moscow State University, 119991, Moscow, Russia.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.http://www.sciencedirect.com/science/article/pii/S2590147825000233Luminescent materialsEu dopingPhosphate phosphorsVanadateWhitlockiteb-TCP
spellingShingle I.V. Nikiforov
V.V. Titkov
E.S. Zhukovskaya
M.M. Klimenko
E.A. Pankrushina
А.А. Vasin
D.V. Deyneko
New type of symmetry inhomogeneity in β-TCP-type phosphors: symmetrical features of mixed oxysalts
Optical Materials: X
Luminescent materials
Eu doping
Phosphate phosphors
Vanadate
Whitlockite
b-TCP
title New type of symmetry inhomogeneity in β-TCP-type phosphors: symmetrical features of mixed oxysalts
title_full New type of symmetry inhomogeneity in β-TCP-type phosphors: symmetrical features of mixed oxysalts
title_fullStr New type of symmetry inhomogeneity in β-TCP-type phosphors: symmetrical features of mixed oxysalts
title_full_unstemmed New type of symmetry inhomogeneity in β-TCP-type phosphors: symmetrical features of mixed oxysalts
title_short New type of symmetry inhomogeneity in β-TCP-type phosphors: symmetrical features of mixed oxysalts
title_sort new type of symmetry inhomogeneity in β tcp type phosphors symmetrical features of mixed oxysalts
topic Luminescent materials
Eu doping
Phosphate phosphors
Vanadate
Whitlockite
b-TCP
url http://www.sciencedirect.com/science/article/pii/S2590147825000233
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