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Title: Synthesis and VUV-UV spectroscopic properties of rare earth borosilicate oxyapatite: RE {sub 5}Si{sub 2}BO{sub 13}:Ln {sup 3+} (RE=La, Gd, Y; Ln=Eu, Tb)

Abstract

Three rare earth borosilicate oxyapatites, RE {sub 5}Si{sub 2}BO{sub 13} (RE=La, Gd, Y), were synthesized via wet chemical method, of which RE {sub 5}Si{sub 2}BO{sub 13} (RE=Gd, Y) were first reported in this work. In the three oxyapatites, [BO{sub 4}] and [SiO{sub 4}] share the [TO{sub 4}] tetrahedral oxyanion site, and RE {sup 3+} ions occupy all metal sites. The differential scanning calorimetry-thermo gravimetry measurements and high temperature powder X-ray diffraction pattern revealed a vitrification process within 300-1200 deg. C, which was due to the glass-forming nature of borosilicates. From the VUV excitation spectra of Eu{sup 3+} and Tb{sup 3+} in RE {sub 5}Si{sub 2}BO{sub 13}, the optical band gaps were found to be 6.31, 6.54 and 6.72 eV for RE {sub 5}Si{sub 2}BO{sub 13} (RE=La, Gd, Y), respectively. The emission and excitation bands of Eu{sup 3+} and Tb{sup 3+} are discussed relating with their coordination environments. Among the three hosts, Y{sub 5}Si{sub 2}BO{sub 13} would be the best for Eu{sup 3+} and Tb{sup 3+}-doped phosphors. - Graphical abstract: The perspective view of RE {sub 5}Si{sub 2}BO{sub 13} (RE=La, Gd, Y) oxyapatite along [001] direction. All non-tetrahedral metal sites are occupied by RE {sup 3+}, and the tetrahedral sites bymore » SiO{sub 4} and BO{sub 4} groups. Y{sub 5}Si{sub 2}BO{sub 13} is a good host for both Eu{sup 3+} and Tb{sup 3+} activated phosphors.« less

Authors:
 [1];  [2];  [1];  [2];  [1];  [2];  [1];  [3];  [4];  [4]
  1. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050 (China)
  2. (China)
  3. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050 (China), E-mail: jtzhao@mail.sic.ac.cn
  4. NSRL, University of Science and Technology of China, Hefei 230027 (China)
Publication Date:
OSTI Identifier:
21015785
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 180; Journal Issue: 4; Other Information: DOI: 10.1016/j.jssc.2007.01.033; PII: S0022-4596(07)00066-7; Copyright (c) 2007 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; APATITES; BORATES; BORON SILICATES; BOROSILICATE GLASS; CALORIMETRY; DOPED MATERIALS; EUROPIUM IONS; EV RANGE 01-10; FAR ULTRAVIOLET RADIATION; GRAVIMETRY; PHOSPHORS; RARE EARTH COMPOUNDS; SILICON OXIDES; SPECTRA; SPECTROSCOPY; SYNTHESIS; TEMPERATURE RANGE 0400-1000 K; TEMPERATURE RANGE 1000-4000 K; TERBIUM IONS; VITRIFICATION; X-RAY DIFFRACTION

Citation Formats

Yuan Junlin, Graduate School of Chinese Academy of Sciences, Beijing, Zhang Zhijun, Graduate School of Chinese Academy of Sciences, Beijing, Wang Xiaojun, Graduate School of Chinese Academy of Sciences, Beijing, Chen Haohong, Zhao Jingtai, Zhang Guobin, and Shi Chaoshu. Synthesis and VUV-UV spectroscopic properties of rare earth borosilicate oxyapatite: RE {sub 5}Si{sub 2}BO{sub 13}:Ln {sup 3+} (RE=La, Gd, Y; Ln=Eu, Tb). United States: N. p., 2007. Web. doi:10.1016/j.jssc.2007.01.033.
Yuan Junlin, Graduate School of Chinese Academy of Sciences, Beijing, Zhang Zhijun, Graduate School of Chinese Academy of Sciences, Beijing, Wang Xiaojun, Graduate School of Chinese Academy of Sciences, Beijing, Chen Haohong, Zhao Jingtai, Zhang Guobin, & Shi Chaoshu. Synthesis and VUV-UV spectroscopic properties of rare earth borosilicate oxyapatite: RE {sub 5}Si{sub 2}BO{sub 13}:Ln {sup 3+} (RE=La, Gd, Y; Ln=Eu, Tb). United States. doi:10.1016/j.jssc.2007.01.033.
Yuan Junlin, Graduate School of Chinese Academy of Sciences, Beijing, Zhang Zhijun, Graduate School of Chinese Academy of Sciences, Beijing, Wang Xiaojun, Graduate School of Chinese Academy of Sciences, Beijing, Chen Haohong, Zhao Jingtai, Zhang Guobin, and Shi Chaoshu. Sun . "Synthesis and VUV-UV spectroscopic properties of rare earth borosilicate oxyapatite: RE {sub 5}Si{sub 2}BO{sub 13}:Ln {sup 3+} (RE=La, Gd, Y; Ln=Eu, Tb)". United States. doi:10.1016/j.jssc.2007.01.033.
@article{osti_21015785,
title = {Synthesis and VUV-UV spectroscopic properties of rare earth borosilicate oxyapatite: RE {sub 5}Si{sub 2}BO{sub 13}:Ln {sup 3+} (RE=La, Gd, Y; Ln=Eu, Tb)},
author = {Yuan Junlin and Graduate School of Chinese Academy of Sciences, Beijing and Zhang Zhijun and Graduate School of Chinese Academy of Sciences, Beijing and Wang Xiaojun and Graduate School of Chinese Academy of Sciences, Beijing and Chen Haohong and Zhao Jingtai and Zhang Guobin and Shi Chaoshu},
abstractNote = {Three rare earth borosilicate oxyapatites, RE {sub 5}Si{sub 2}BO{sub 13} (RE=La, Gd, Y), were synthesized via wet chemical method, of which RE {sub 5}Si{sub 2}BO{sub 13} (RE=Gd, Y) were first reported in this work. In the three oxyapatites, [BO{sub 4}] and [SiO{sub 4}] share the [TO{sub 4}] tetrahedral oxyanion site, and RE {sup 3+} ions occupy all metal sites. The differential scanning calorimetry-thermo gravimetry measurements and high temperature powder X-ray diffraction pattern revealed a vitrification process within 300-1200 deg. C, which was due to the glass-forming nature of borosilicates. From the VUV excitation spectra of Eu{sup 3+} and Tb{sup 3+} in RE {sub 5}Si{sub 2}BO{sub 13}, the optical band gaps were found to be 6.31, 6.54 and 6.72 eV for RE {sub 5}Si{sub 2}BO{sub 13} (RE=La, Gd, Y), respectively. The emission and excitation bands of Eu{sup 3+} and Tb{sup 3+} are discussed relating with their coordination environments. Among the three hosts, Y{sub 5}Si{sub 2}BO{sub 13} would be the best for Eu{sup 3+} and Tb{sup 3+}-doped phosphors. - Graphical abstract: The perspective view of RE {sub 5}Si{sub 2}BO{sub 13} (RE=La, Gd, Y) oxyapatite along [001] direction. All non-tetrahedral metal sites are occupied by RE {sup 3+}, and the tetrahedral sites by SiO{sub 4} and BO{sub 4} groups. Y{sub 5}Si{sub 2}BO{sub 13} is a good host for both Eu{sup 3+} and Tb{sup 3+} activated phosphors.},
doi = {10.1016/j.jssc.2007.01.033},
journal = {Journal of Solid State Chemistry},
number = 4,
volume = 180,
place = {United States},
year = {Sun Apr 15 00:00:00 EDT 2007},
month = {Sun Apr 15 00:00:00 EDT 2007}
}
  • Graphical abstract: Display Omitted Highlights: ► We report the VUV spectroscopic properties of rare-earth ions in K{sub 2}LnZr(PO{sub 4}){sub 3}. ► The O{sup 2−}-Eu{sup 3+} charge transfer bands at about 220 nm have been observed. ► The 4f–5d spin-allowed and spin-forbidden transitions of Tb{sup 3+} have been observed. ► There is energy transfer between the host and rare-earth activators. -- Abstract: Rare earth (RE = Sm, Eu, Tb, Dy and Tm)-activated K{sub 2}LnZr(PO{sub 4}){sub 3} (Ln = Y, La, Gd and Lu) have been synthesized by solid-state reaction method, and their vacuum ultraviolet (VUV) excitation luminescent characteristics have been investigated.more » The band in the wavelength range of 130–157 nm and the other one range from 155 to 216 nm with the maximum at about 187 nm in the VUV excitation spectra of these compounds are attributed to the host lattice absorption and O–Zr charge transfer transition, respectively. The charge transfer bands (CTB) of O{sup 2−}-Sm{sup 3+}, O{sup 2−}-Dy{sup 3+} and O{sup 2−}-Tm{sup 3+}, in Sm{sup 3+}, Dy{sup 3+} and Tm{sup 3+}-activated samples, have not been obviously observed probably because the 2p electrons of oxygen are tightly bound to the zirconium ion in the host lattice. For Eu{sup 3+}-activated samples, the relatively weak O{sup 2−}-Eu{sup 3+} CTB at about 220 nm is observed. And for Tb{sup 3+}-activated samples, the bands at 223 and 258 nm are related to the 4f-5d spin-allowed and spin-forbidden transitions of Tb{sup 3+}, respectively. It is observed that there is energy transfer between the host lattice and the luminescent activators (e.g. Eu{sup 3+}, Tb{sup 3+}). From the standpoint of luminescent efficiency, color purity and chemical stability, K{sub 2}GdZr(PO{sub 4}){sub 3}:Sm{sup 3+}, Eu{sup 3+}, Tb{sup 3+} are attractive candidates for novel yellow, red, green-emitting PDP phosphors.« less
  • Eu{sup 3+} photoluminescence is studied in La{sub 5}Si{sub 2}BO{sub 13} with apatite related structure. La{sub 5-x}Eu{sub x}Si{sub 2}BO{sub 13} [x=0.05, 0.1, 0.3, 0.5, 0.7, 1.0, 2.0] compositions are synthesized. The emission results shows that Eu{sup 3+} ions occupy two different cationic sites viz., La(1) and La(2). The increase in the intensity of {sup 5}D{sub 0}-{sup 7}F{sub 0} line with increasing Eu{sup 3+} content shows the preferential occupancy of Eu{sup 3+} in La(2) site due to the existence of short La(2)-O(4) (free oxide ion) bond. The observation of antiferromagnetic interactions in Gd and Dy analogues supports the structural features elucidates frommore » photoluminescence studies. - Graphical abstract: In La{sub 5}Si{sub 2}BO{sub 13}, the La(1)O{sub 9} polyhedra share faces, the La(2)O{sub 7} polyhedra are connected through corners and La(2)O{sub 7} and La(1)O{sub 9} polyhedra are connected to each other by edge sharing along 'z'-axis.« less
  • The spectroscopic properties in VUV-vis range for phosphors calcium and gadolinium double borate Ca{sub 3}Gd{sub 2}(BO{sub 3}){sub 4} doped with rare-earth ions Ce{sup 3+}, Sm{sup 3+}, Eu{sup 3+} and Tb{sup 3+} were investigated. The host-related absorption, the f-d transitions of Ce{sup 3+} and Tb{sup 3+}, as well as the charge transfer transitions of Sm{sup 3+} and Eu{sup 3+} in the host lattice are assigned and discussed. The CIE chromaticity coordinates for Eu{sup 3+}- and Tb{sup 3+}-activated phosphors are calculated.
  • Spherical SiO{sub 2} particles have been coated with rare earth oxide layers by a Pechini sol-gel process, leading to the formation of core-shell structured SiO{sub 2}-RE{sub 2}O{sub 3} (RE=rare earth elements) and SiO{sub 2}-Gd{sub 2}O{sub 3}:Ln{sup 3+} (Ln=Eu, Tb, Dy, Sm, Er, Ho) particles. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), photoluminescence (PL), and cathodoluminescence spectra as well as lifetimes were used to characterize the resulting SiO{sub 2}-RE{sub 2}O{sub 3} (RE=rare earth elements) and SiO{sub 2}-Gd{sub 2}O{sub 3}:Ln{sup 3+} (Eu{sup 3+}, Tb{sup 3+}, Dy{sup 3+}, Sm{sup 3+}, Er{sup 3+}, Ho{sup 3+}) samples. The obtainedmore » core-shell phosphors have perfect spherical shape with narrow size distribution (average size ca. 380 nm), smooth surface and non-agglomeration. The thickness of shells could be easily controlled by changing the number of deposition cycles (40 nm for two deposition cycles). Under the excitation of ultraviolet, the Ln{sup 3+} ion mainly shows its characteristic emissions in the core-shell particles from Gd{sub 2}O{sub 3}:Ln{sup 3+} (Eu{sup 3+}, Tb{sup 3+}, Sm{sup 3+}, Dy{sup 3+}, Er{sup 3+}, Ho{sup 3+}) shells. - Graphical abstract: The advantages of core-shell phosphors are the easy availability of homogeneous spherical morphology in different size, and its corresponding luminescence color can change from red, yellow to green.« less
  • Highlights: {yields} Orthoborates and their solid solutions were prepared by metathesis reaction. {yields} NaCl (by-product) is the driving force for these metathesis reactions. {yields} Structural refinement for TbBO{sub 3} was carried out. {yields} Spin-Hamiltonian parameters of Gd{sup 3+} were deduced from the ESR spectra of LaBO{sub 3}:Gd. -- Abstract: Lanthanide orthoborates of composition LnBO{sub 3} (Ln = Tb, La, Pr, Nd, Sm, Eu, Gd, Dy, Y) and LaBO{sub 3}:Gd, Tb, Eu have been prepared by metathesis reaction. This method provides a convenient route for the synthesis of orthoborates and its solid solutions at low temperatures. Powder X-ray diffraction and FT-IRmore » spectroscopy were used to characterize these borates. Rare earth borates, (LnBO{sub 3}) are isomorphous with different forms of CaCO{sub 3} depending on the radius of rare earth ion. LaBO{sub 3}, LaBO{sub 3}:Gd, Tb, Eu, PrBO{sub 3}, NdBO{sub 3} crystallized in aragonite structure, SmBO{sub 3} crystallized in H-form and TbBO{sub 3}, EuBO{sub 3}, GdBO{sub 3}, DyBO{sub 3}, YBO{sub 3} crystallized in vaterite structure. The structural analysis of TbBO{sub 3} was carried out. The morphology of these borates was obtained from Scanning electron microscopy. Spin-Hamiltonian parameters for Gd{sup 3+} are deduced from room temperature electron spin resonance spectrum of LaBO{sub 3}:Gd. The luminescence of LaBO{sub 3}:Tb, Eu gave characteristics peaks corresponding to Tb{sup 3+}, Eu{sup 3+} respectively.« less