Synthesis features of LiRF4 (R = Er–Lu) nanoparticles by the high-temperature co-precipitation method and their photoluminescent properties

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Abstract

Nanoparticles of LiRF4 (R = Y, Yb, Lu), activated with Yb3+/Er3+ and Yb3+/Tm3+ ions, were obtained by the high-temperature co-precipitation method. The influence of the precursor molar ratio and the cationic composition of matrices on their dimensionality and morphology was studied. A method for the heterogeneous crystallization of these compounds using LiYF4 nanoseeds was optimized, which opens up opportunities for controlled synthesis of LiRF4 nanoparticles with controllable characteristics. Among the studied objects, LiYF4@LiYbF4:Tm3+@LiYF4 nanoparticles demonstrate the most intense anti-Stokes photoluminescence in the UV (λ = 362 nm) and blue (λ = 450 nm) ranges, exceeding similar indicators for β-NaYF4:Yb3+/Tm3+@NaYF4 particles. LiYF4@LiLuF4:Yb3+/Er3+@LiYF4 nanoparticles are the most efficient converters of IR radiation in the λ = 1530 nm range among the investigated isostructural matrices and exhibit similar spectral-luminescent properties to the β-NaYF4:Yb3+/Er3+@NaYF4 compound with an equivalent degree of codoping. The obtained results allow considering LiYF4@LiYbF4:Tm3+@LiYF4 and LiYF4@LiLuF4:Yb3+/Er3+@LiYF4 nanoparticles as a real alternative to the most widely used phosphors based on the hexagonal matrix β-NaYF4 for photonics and biotechnology applications.

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About the authors

A. V. Koshelev

Shubnikov Institute of Crystallography of Kurchatov Complex of Crystallography and Photonics of NRC “Kurchatov Institute”

Author for correspondence.
Email: avkoshelev03@gmail.com
Russian Federation, Moscow

V. V. Artemov

Shubnikov Institute of Crystallography of Kurchatov Complex of Crystallography and Photonics of NRC “Kurchatov Institute”

Email: avkoshelev03@gmail.com
Russian Federation, Moscow

N. A. Arkharova

Shubnikov Institute of Crystallography of Kurchatov Complex of Crystallography and Photonics of NRC “Kurchatov Institute”

Email: avkoshelev03@gmail.com
Russian Federation, Moscow

M. S. Seyed Dorraji

University of Zanjan

Email: avkoshelev03@gmail.com
Iran, Islamic Republic of, Zanjan

D. N. Karimov

Shubnikov Institute of Crystallography of Kurchatov Complex of Crystallography and Photonics of NRC “Kurchatov Institute”

Email: avkoshelev03@gmail.com
Russian Federation, Moscow

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Supplementary files

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2. Fig. 1. Phase diagram of the LiF–YF3 binary system [18]

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3. Fig. 2. Radiographs of LiRF4 LPS synthesized with a different ratio of precursors n(Li+):n(R3+):n(F-) (a): 1:1:4 (1), 1.75:1:4 (2), 2.5:1:4 (3); the cationic composition of the crystal matrix (b): R = Y (1), Yb (2), Lu (3) and the precursor ratio 1.75:1:4

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4. Fig. 3. SEM and TEM images of LiRF4 LPS with corresponding histograms of the dimensional distribution obtained with different ratios of precursors: a – 1:1:4, b – 1.75:1:4, c – 2.5:1:4, and the cationic composition of the matrix: R = Y (d), Yb (E), Lu (E)

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5. Fig. 4. X-ray images of LiYF4 (1) nanotubes and structures obtained after applying one (2), three (3) and five (4) epitaxial LiYF4 shells:Yb3+/Er3+ (a); a TEM image of LiYF4 primers is shown in the box. Dependence of the LF dimension LiYF4:Yb3+/Er3+ on the ratio nprek:nzatr (b)

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6. Fig. 5. Low frequency radiographs LiYF4@LiYF4:Yb3+/Tm3+@LiYF4 (nΣprek:pp = 20) (1), LiYF4@LiLuF4:Yb3+/Er3+@LiYF4 (NΣPRECK:psatr = 160) (2) with a seed/core/shell structure and reference woofers β-NaYF4:Yb3+/Tm3+@NaYF4 (a). Low frequency SAM images LiYF4@LiYF4:Yb3+/Tm3+@LiYF4 (b), LiYF4@LiLuF4:Yb3+/Er3+@LiYF4 (c), β-NaYF4:Yb3+/Tm3+@NaYF4 (d), β-NaYF4:Yb3+/Er3+@NaYF4 (e) with corresponding histograms of the dimensional distribution

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7. Fig. 6. Spectra of LF FL LiYF4 (1), LiYbF4 (2), LiLuF4 (3), β-NaYF4 (4) doped with Yb3+/Tm3+ (a) and Yb3+/Er3+ (b) ions. Appearance and observed LF of LF colloids LiYF4@LiYF4:Yb3+/Tm3+@LiYF4 and LiYF4@LiLuF4:Yb3+/Er3+@LiLuF4 , obtained by excitation by radiation λ = 975 nm, shown in the inserts

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