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Crystal structure and luminescent properties of R2-xEux(MoO4)(3) (R = Gd, Sm) red phosphors

(2014) CHEMISTRY OF MATERIALS. 26(24). p.7124-7136
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Center for nano- and biophotonics (NB-Photonics)
Abstract
The R2(MoO4)3 (R = rare earth elements) molybdates doped with Eu3+ cations are interesting red-emitting materials for display and solid-state lighting applications. The structure and luminescent properties of the R2−xEux(MoO4)3 (R = Gd, Sm) solid solutions have been investigated as a function of chemical composition and preparation conditions. Monoclinic (α) and orthorhombic (β′) R2−xEux(MoO4)3 (R = Gd, Sm; 0 ≤ x ≤ 2) modifications were prepared by solid-state reaction, and their structures were investigated using synchrotron powder X-ray diffraction and transmission electron microscopy. The pure orthorhombic β′-phases could be synthesized only by quenching from high temperature to room temperature for Gd2−xEux(MoO4)3 in the Eu3+-rich part (x > 1) and for all Sm2−xEux(MoO4)3 solid solutions. The transformation from the α-phase to the β′-phase results in a notable increase (∼24%) of the unit cell volume for all R2−xEux(MoO4)3 (R = Sm, Gd) solid solutions. The luminescent properties of all R2−xEux(MoO4)3 (R = Gd, Sm; 0 ≤ x ≤ 2) solid solutions were measured, and their optical properties were related to their structural properties. All R2−xEux(MoO4)3 (R = Gd, Sm; 0 ≤ x ≤ 2) phosphors emit intense red light dominated by the 5D0→7F2 transition at ∼616 nm. However, a change in the multiplet splitting is observed when switching from the monoclinic to the orthorhombic structure, as a consequence of the change in coordination polyhedron of the luminescent ion from RO8 to RO7 for the α- and β′-modification, respectively. The Gd2−xEux(MoO4)3 solid solutions are the most efficient emitters in the range of 0 < x < 1.5, but their emission intensity is comparable to or even significantly lower than that of Sm2−xEux(MoO4)3 for higher Eu3+ concentrations (1.5 ≤ x ≤ 1.75). Electron energy loss spectroscopy (EELS) measurements revealed the influence of the structure and element content on the number and positions of bands in the ultraviolet−visible−infrared regions of the EELS spectrum.
Keywords
ENERGY-TRANSFER, X-RAY, PHOTOLUMINESCENCE PROPERTIES, DOMAIN-STRUCTURE, EU3+, SOL-GEL METHOD, LIGHT-EMITTING-DIODES, TRANSITION-METAL MOLYBDATES, RARE-EARTH MOLYBDATES, DEFECT SCHEELITE-TYPE

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Chicago
Morozov, Vladimir A, Maria V Raskina, Bogdan I Lazoryak, Katrien Meert, Katleen Korthout, Philippe Smet, Dirk Poelman, et al. 2014. “Crystal Structure and Luminescent Properties of R2-xEux(MoO4)(3) (R = Gd, Sm) Red Phosphors.” Chemistry of Materials 26 (24): 7124–7136.
APA
Morozov, V. A., Raskina, M. V., Lazoryak, B. I., Meert, K., Korthout, K., Smet, P., Poelman, D., et al. (2014). Crystal structure and luminescent properties of R2-xEux(MoO4)(3) (R = Gd, Sm) red phosphors. CHEMISTRY OF MATERIALS, 26(24), 7124–7136.
Vancouver
1.
Morozov VA, Raskina MV, Lazoryak BI, Meert K, Korthout K, Smet P, et al. Crystal structure and luminescent properties of R2-xEux(MoO4)(3) (R = Gd, Sm) red phosphors. CHEMISTRY OF MATERIALS. 2014;26(24):7124–36.
MLA
Morozov, Vladimir A, Maria V Raskina, Bogdan I Lazoryak, et al. “Crystal Structure and Luminescent Properties of R2-xEux(MoO4)(3) (R = Gd, Sm) Red Phosphors.” CHEMISTRY OF MATERIALS 26.24 (2014): 7124–7136. Print.
@article{5929425,
  abstract     = {The R2(MoO4)3 (R = rare earth elements) molybdates doped with Eu3+ cations are interesting red-emitting materials for display and solid-state lighting applications. The structure and luminescent properties of the R2\ensuremath{-}xEux(MoO4)3 (R = Gd, Sm) solid solutions have been investigated as a function of chemical composition and preparation conditions. Monoclinic (\ensuremath{\alpha}) and orthorhombic (\ensuremath{\beta}{\textquotesingle}) R2\ensuremath{-}xEux(MoO4)3 (R = Gd, Sm; 0 \ensuremath{\leq} x \ensuremath{\leq} 2) modifications were prepared by solid-state reaction, and their structures were investigated using synchrotron powder X-ray diffraction and transmission electron microscopy. The pure orthorhombic \ensuremath{\beta}{\textquotesingle}-phases could be synthesized only by quenching from high temperature to room temperature for Gd2\ensuremath{-}xEux(MoO4)3 in the Eu3+-rich part (x {\textrangle} 1) and for all Sm2\ensuremath{-}xEux(MoO4)3 solid solutions. The transformation from the \ensuremath{\alpha}-phase to the \ensuremath{\beta}{\textquotesingle}-phase results in a notable increase (\ensuremath{\sim}24\%) of the unit cell volume for all R2\ensuremath{-}xEux(MoO4)3 (R = Sm, Gd) solid solutions. The luminescent properties of all R2\ensuremath{-}xEux(MoO4)3 (R = Gd, Sm; 0 \ensuremath{\leq} x \ensuremath{\leq} 2) solid solutions were measured, and their optical properties were related to their structural properties. All R2\ensuremath{-}xEux(MoO4)3 (R = Gd, Sm; 0 \ensuremath{\leq} x \ensuremath{\leq} 2) phosphors emit intense red light dominated by the 5D0{\textrightarrow}7F2 transition at \ensuremath{\sim}616 nm. However, a change in the multiplet splitting is observed when switching from the monoclinic to the orthorhombic structure, as a consequence of the change in coordination polyhedron of the luminescent ion from RO8 to RO7 for the \ensuremath{\alpha}- and \ensuremath{\beta}{\textquotesingle}-modification, respectively. The Gd2\ensuremath{-}xEux(MoO4)3 solid solutions are the most efficient emitters in the range of 0 {\textlangle} x {\textlangle} 1.5, but their emission intensity is comparable to or even significantly lower than that of Sm2\ensuremath{-}xEux(MoO4)3 for higher Eu3+ concentrations (1.5 \ensuremath{\leq} x \ensuremath{\leq} 1.75). Electron energy loss spectroscopy (EELS) measurements revealed the influence of the structure and element content on the number and positions of bands in the ultraviolet\ensuremath{-}visible\ensuremath{-}infrared regions of the EELS spectrum.},
  author       = {Morozov, Vladimir A and Raskina, Maria V and Lazoryak, Bogdan I and Meert, Katrien and Korthout, Katleen and Smet, Philippe and Poelman, Dirk and Gauquelin, Nicolas and Verbeeck, Johan and Abakumov, Artem M and Hadermann, Joke},
  issn         = {0897-4756},
  journal      = {CHEMISTRY OF MATERIALS},
  keyword      = {ENERGY-TRANSFER,X-RAY,PHOTOLUMINESCENCE PROPERTIES,DOMAIN-STRUCTURE,EU3+,SOL-GEL METHOD,LIGHT-EMITTING-DIODES,TRANSITION-METAL MOLYBDATES,RARE-EARTH MOLYBDATES,DEFECT SCHEELITE-TYPE},
  language     = {eng},
  number       = {24},
  pages        = {7124--7136},
  title        = {Crystal structure and luminescent properties of R2-xEux(MoO4)(3) (R = Gd, Sm) red phosphors},
  url          = {http://dx.doi.org/10.1021/cm503720s},
  volume       = {26},
  year         = {2014},
}

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