Preparation of rare-earth doped NaYF4 luminescent nanoparticles by a high-energy ball milling process

A possible fabrication of photoluminescent fluoride nanoparticles NaYF4 doped with rare-earth ions employing high-energy ball milling is demonstrated. The melt-grown bulk cubic crystal Na0.40Y0.480Yb0.108Er0.012F2.2 and composite Na0.55Y0.360Yb0.081Er0.009F2.10 comprising hexagonal β-NaYF4 modificat...

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Bibliographic Details
Published in:CrystEngComm 2023-08, Vol.25 (33), p.4745-4754
Main Authors: Koshelev, Aleksandr V, Grebenev, Vadim V, Arkharova, Natalia A, Shiryaev, Andrey A, Karimov, Denis N
Format: Article
Language:English
Subjects:
Ball milling
Crystal growth
Erbium
Fluorides
Heat treatment
High temperature
Mechanical alloying
Mechanical milling
Nanoparticles
Oleic acid
Phase transitions
Photoluminescence
Rare earth elements
Raw materials
Sodium compounds
X-ray diffraction
Ytterbium
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Summary:A possible fabrication of photoluminescent fluoride nanoparticles NaYF4 doped with rare-earth ions employing high-energy ball milling is demonstrated. The melt-grown bulk cubic crystal Na0.40Y0.480Yb0.108Er0.012F2.2 and composite Na0.55Y0.360Yb0.081Er0.009F2.10 comprising hexagonal β-NaYF4 modification were used as raw materials. The samples were analyzed using X-ray diffraction analysis, differential scanning calorimetry, transmission electron microscopy, and optical spectroscopy after the milling. Pure single-phase NaYF4 was not obtained even after 14 hours of mechanochemical treatment of individual components. However, high-energy ball milling of the crystals in the presence of oleic acid as a surfactant for 16 hours allowed production of single-phase β-NaYF4:Yb,Er nanoparticles with an average size of 20–30 nm. The milled β-NaYF4:Yb,Er nanoparticles demonstrate intense green fluorescence upon excitation at λ = 980 nm and can potentially be used in biomedicine and nanophotonics. The optimized methodology of high-energy milling has great potential for scalable and reproducible production of β-NaYF4 nanoparticles for industrial and scientific applications. High-temperature X-ray diffraction confirmed the phase transformation of melt-grown α-NaYF4 crystals into the hexagonal β-modification both during mechanical (4 hours) and thermal treatment in the 653–823 K range. The long duration of the process precludes the possibilities of large scale preparation of the cubic α-NaYF4 by mechanical milling.
ISSN:1466-8033
DOI:10.1039/d3ce00642e