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Title: Analysis of the Local Structure around Eu and Mn Ions in Alkaline-Earth Silicate Phosphors for White Light Illumination

Abstract

M2SiO4-based phosphors (M: alkaline-earth metal) that emit red to blue light are expected to offer high color rendering to white light-emitting diodes (LEDs) in combination with blue or near-UV excitation sources. It is very important for the complete control of the emission color to understand the crystal field around the active elements (rare-earth and transition metals). XAFS spectroscopy is applied to a (Ba,Ca)2SiO4:Eu,Mn phosphor at Eu L3- and Ba, Ca, Eu, Mn K-edges to elucidate the local environments of Eu and Mn. Eu L3- and Mn K-edge XANES spectra showed that Eu and Mn are both divalent, like Ba and Ca. K-edge EXAFS spectra indicated that the local structures of Eu and Mn are similar to those of Ba and Ca, respectively. However, the curve-fitting analysis showed that the first coordination shell of Eu has two Eu-O bonds that are both shorter than the Ba-O bond. FEFF calculations were also performed based on a BaCaSiO4 model constructed from the crystal structure of KNaSO4. They suggested that Eu substitutes both of Ba and Ca sites with some structural modification while Mn is clearly at the octahedral Ca site that is the smallest of the substitution sites.

Authors:
; ; ; ; ;  [1];  [2];  [3]
  1. Mitsubishi Chemical Group Science and Technology Research Center, Inc., 1000 Kamoshida-cho, Aoba-ku, Yokohama, 227-8502 (Japan)
  2. Japan Synchrotron Radiation Research Institute, 1-1-1, Kouto, Sayo-cho, Sayo-gun, Hyogo, 679-5198 (Japan)
  3. High Energy Accelerator Research Organization, 1-1 Oho, Tsukuba, Ibaraki, 305-0801 (Japan)
Publication Date:
OSTI Identifier:
21054671
Resource Type:
Journal Article
Resource Relation:
Journal Name: AIP Conference Proceedings; Journal Volume: 882; Journal Issue: 1; Conference: XAFS13: 13. international conference on X-ray absorption fine structure, Stanford, CA (United States), 9-14 Jul 2006; Other Information: DOI: 10.1063/1.2644579; (c) 2007 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; ABSORPTION SPECTRA; ABSORPTION SPECTROSCOPY; ALKALINE EARTH METALS; BARIUM SILICATES; CALCIUM SILICATES; COLOR; CRYSTAL FIELD; CRYSTAL STRUCTURE; EUROPIUM; EXCITATION; FINE STRUCTURE; LIGHT EMITTING DIODES; MANGANESE; MANGANESE IONS; MODIFICATIONS; PHOSPHORS; X-RAY SPECTRA; X-RAY SPECTROSCOPY

Citation Formats

Okamoto, Kaoru, Yoshino, Masahiko, Shigeiwa, Motoyuki, Mikami, Masayoshi, Akai, Toshio, Kijima, Naoto, Honma, Tetsuo, and Nomura, Masaharu. Analysis of the Local Structure around Eu and Mn Ions in Alkaline-Earth Silicate Phosphors for White Light Illumination. United States: N. p., 2007. Web. doi:10.1063/1.2644579.
Okamoto, Kaoru, Yoshino, Masahiko, Shigeiwa, Motoyuki, Mikami, Masayoshi, Akai, Toshio, Kijima, Naoto, Honma, Tetsuo, & Nomura, Masaharu. Analysis of the Local Structure around Eu and Mn Ions in Alkaline-Earth Silicate Phosphors for White Light Illumination. United States. doi:10.1063/1.2644579.
Okamoto, Kaoru, Yoshino, Masahiko, Shigeiwa, Motoyuki, Mikami, Masayoshi, Akai, Toshio, Kijima, Naoto, Honma, Tetsuo, and Nomura, Masaharu. Fri . "Analysis of the Local Structure around Eu and Mn Ions in Alkaline-Earth Silicate Phosphors for White Light Illumination". United States. doi:10.1063/1.2644579.
@article{osti_21054671,
title = {Analysis of the Local Structure around Eu and Mn Ions in Alkaline-Earth Silicate Phosphors for White Light Illumination},
author = {Okamoto, Kaoru and Yoshino, Masahiko and Shigeiwa, Motoyuki and Mikami, Masayoshi and Akai, Toshio and Kijima, Naoto and Honma, Tetsuo and Nomura, Masaharu},
abstractNote = {M2SiO4-based phosphors (M: alkaline-earth metal) that emit red to blue light are expected to offer high color rendering to white light-emitting diodes (LEDs) in combination with blue or near-UV excitation sources. It is very important for the complete control of the emission color to understand the crystal field around the active elements (rare-earth and transition metals). XAFS spectroscopy is applied to a (Ba,Ca)2SiO4:Eu,Mn phosphor at Eu L3- and Ba, Ca, Eu, Mn K-edges to elucidate the local environments of Eu and Mn. Eu L3- and Mn K-edge XANES spectra showed that Eu and Mn are both divalent, like Ba and Ca. K-edge EXAFS spectra indicated that the local structures of Eu and Mn are similar to those of Ba and Ca, respectively. However, the curve-fitting analysis showed that the first coordination shell of Eu has two Eu-O bonds that are both shorter than the Ba-O bond. FEFF calculations were also performed based on a BaCaSiO4 model constructed from the crystal structure of KNaSO4. They suggested that Eu substitutes both of Ba and Ca sites with some structural modification while Mn is clearly at the octahedral Ca site that is the smallest of the substitution sites.},
doi = {10.1063/1.2644579},
journal = {AIP Conference Proceedings},
number = 1,
volume = 882,
place = {United States},
year = {Fri Feb 02 00:00:00 EST 2007},
month = {Fri Feb 02 00:00:00 EST 2007}
}
  • Highlights: • A novel yellow-emitting alkaline and alkaline-earth silicate Na{sub 2}Ca{sub 3}Si{sub 6}O{sub 16}:Eu{sup 2+} was first developed. • Under excitation with UV or near UV light the silicate presents broad emission band centered at 580 nm. - Abstract: Yellow-emitting phosphors of Na{sub 2}Ca{sub 3}Si{sub 6}O{sub 16}:Eu{sup 2+} was prepared by wet chemistry sol–gel method. X-ray powder diffraction and SEM measurements were applied to characterize the structure and morphology, respectively. The luminescence properties were investigated by the photoluminescence excitation and emission spectra, decay curve (lifetimes), CIE coordinates and the internal quantum efficiencies. The excitation spectra can match well with themore » emission light of near UV-LED chips (360–400 nm). Na{sub 2}Ca{sub 3}Si{sub 6}O{sub 16}:Eu{sup 2+} presents a symmetric emission band from 4f{sup 6}5d{sup 1} ⟶ 4f{sup 7}({sup 8}S{sub 7/2}) transitions of Eu{sup 2+} ions on doping below 3.0 mol%. On increasing Eu-doping levels, the sample contains two kinds of emission centers, i.e., Eu{sup 2+} and Eu{sup 3+} ions, which present the characteristic broad band (5d ⟶ 4f) and narrower (4f ⟶ 4f) luminescence lines, respectively. The energy transfer, the luminescence thermal stability (activation energy ΔE for thermal quenching) and luminescence mechanism of Na{sub 2}Ca{sub 3}Si{sub 6}O{sub 16}:Eu{sup 2+} phosphors were discussed by analyzing the relationship between the luminescence characteristics and the crystal structure.« less
  • Melt quenching of B{sub 2}O{sub 3} with less than 25 mol. % rare-earth oxide (RE{sub 2}O{sub 3}) at ambient pressure results in a milky white glass because of liquid-liquid phase separation into B{sub 2}O{sub 3} and RE{sub 2}O{sub 3}{center_dot}3B{sub 2}O phases. In contrast, we have found that melt quenching under GPa-order pressure realizes a transparent RE-doped B{sub 2}O{sub 3} glass. This study investigates the local structure around the RE ions in the B{sub 2}O{sub 3} glass prepared at 3 GPa using optical measurements and electron-spin-echo envelope modulation spectroscopy. It is shown that the RE-rich microparticles disappear and the RE ionsmore » are isolated from each other in a highly symmetric crystal field formed by triangular and tetrahedral boron units. This result is consistent with that extrapolated from the data for RE-doped sodium borate glasses.« less
  • We have studied the local structure around Ce atom in Ca3Sc2Si3O12 host crystal, which has been developed as a new green phosphor for white light emitting diodes (LEDs). As the local structure and chemical environment of the dopant atom are very important to improve the performance of the phosphor, we have used XAFS to get chemical and structural information around the Ce dopant. The XANES spectrum of the Ce LIII-edge reveals that the Ce atom is trivalent in Ca3Sc2Si3O12. There are two kinds of possible Ce substitution sites, Ca site and Sc site, in garnet type Ca3Sc2Si3O12 crystal structure. Themore » Ce atom is found to be at the Ca site in the host crystal by the comparison of the Fourier transform of Ce K-edge EXAFS spectrum with those of Ca and Sc K-edge EXAFS spectra. The theoretical analysis with FEFF also clarified the Ce substitution at the Ca site. Furthermore, the result of the analysis indicates the structural disorder around Ca and Si atoms at 3.75 A. It is possible that there are some defects around the Ca and Si atoms at 3.75 A to compensate the excess positive charge by introduced Ce3+ at the Ca2+ site.« less
  • We investigated the luminescence properties of (Ca{sub 1-x}Zn{sub x})Ga{sub 2}S{sub 4}:Eu{sup 2+} phosphor as a function of Zn{sup 2+} and Eu{sup 2+} concentrations. The luminescence intensity was markedly enhanced by increasing the mole fraction of Zn{sup 2+} at Ca{sup 2+} sites. Lacking any Zn{sup 2+} ions, CaGa{sub 2}S{sub 4}:0.01Eu{sup 2+} converted only 18.1% of the absorbed blue light into luminescence. As the Zn{sup 2+} concentration increased, the quantum yield increased and reached a maximum of 24.4% at x = 0.1. Furthermore, to fabricate the device, the optimized green-yellow (Ca{sub 0.9}Zn{sub 0.1})Ga{sub 2}S{sub 4}:Eu{sup 2+} phosphor was coated with MgO. Whitemore » light was generated by combining the MgO-coated phosphor and the blue emission from a GaN chip.« less
  • Highlights: • BaLa{sub 2}WO{sub 7}:Dy{sup 3+}, Eu{sup 3+} phosphors were synthesized by solid-state reaction. • Eu{sup 3+} compensated the red emission component of the BaLa{sub 2}WO{sub 7}:Dy{sup 3+} phosphor. • The observed emission lifetimes indicates the energy transfer from Dy{sup 3+} to Eu{sup 3+}. • BaLa{sub 2}WO{sub 7}:Dy{sup 3+}, Eu{sup 3+} are potential phosphors used in n-UV pumped white LEDs. - Abstract: Tunable full color emissive BaLa{sub 1.75−x}WO{sub 7}:0.25Dy{sup 3+}, xEu{sup 3+} phosphors which peaked at 484 nm (blue), 572 nm (yellow), 593 nm (orange), and 617 nm (red) were synthesized by the traditional solid-state reaction method. The as-synthesized phosphorsmore » were characterized by X-ray power diffraction, diffused reflectance spectra, photoluminescence decay curves, photoluminescence excitation and emission spectra. The photoluminescence excitation spectra range from 200 to 500 nm, including an O{sup 2−}⟶W{sup 6+} charge transfer band and several 4f–4f transition peaks of Dy{sup 3+} and Eu{sup 3+}. Co-doping with Eu{sup 3+} compensated the red emission component of the BaLa{sub 2}WO{sub 7}:Dy{sup 3+} phosphor. Furthermore, the energy transfer from Dy{sup 3+} to Eu{sup 3+} was confirmed based on the luminescence spectra and decay curves. The intense white light emissions are suggestive exploration for the potential phosphor for optical materials applications used in the ultraviolet excited white light emitting diodes.« less