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Author Morozov, V.A.; Lazoryak, B.I.; Shmurak, S.Z.; Kiselev, A.P.; Lebedev, O.I.; Gauquelin, N.; Verbeeck, J.; Hadermann, J.; Van Tendeloo, G.
Title Influence of the structure on the properties of NaxEuy(MoO4)z red phosphors Type A1 Journal article
Year 2014 Publication Chemistry of materials Abbreviated Journal Chem Mater
Volume 26 Issue 10 Pages 3238-3248
Keywords A1 Journal article; Electron microscopy for materials research (EMAT)
Abstract Scheelite related compounds (A',A '')(n)[(B',B '')O-4](m) with B', B '' = W and/or Mo are promising new materials for red phosphors in pc-WLEDs (phosphor-converted white-light-emitting-diode) and solid-state lasers. Cation substitution in CaMoO4 of Ca2+ by the combination of Na+ and Eu3+, with the creation of A cation vacancies, has been investigated as a factor for controlling the scheelite-type structure and the luminescent properties. Na5Eu(MoO4)(4) and NaxEu(2-x)/33+square(2-x)/3MoO4 (0.138 <= x <= 0.5) phases with a scheelite-type structure were synthesized by the solid state method; their structural characteristics were investigated using transmission electron microscopy. Contrary to powder synchrotron X-ray diffraction before, the study by electron diffraction and high resolution transmission electron microscopy in this paper revealed that Na0.286Eu0.571MoO4 has a (3 + 2)D incommensurately modulated structure and that (3 + 2)D incommensurately modulated domains are present in Na0.200Eu0.600MoO4. It also confirmed the (3 + 1)D incommensurately modulated character of Na(0.138)Eu(0.621)Mo04. The luminescent properties of all phases under near-ultraviolet (n-UV) light have been investigated. The excitation spectra of these phosphors show the strongest absorption at about 395 nm, which matches well with the commercially available n-UV-emitting GaN-based LED chip. The emission spectra indicate an intense red emission due to the D-5(0) -> F-7(2) transition of Eu3+, with local minima in the intensity at Na0.286Eu0.571MoO4 and Na0.200Eu0.600MoO4 for similar to 613 nm and similar to 616 nm bands. The phosphor Na5Eu(MoO4)(4) shows the brightest red light emission among the phosphors in the Na2MoO4-Eu2/3MoO4 system and the maximum luminescence intensity of Na5Eu(MoO4)(4) (lambda(ex) = 395 nm) in the D-5(0) -> F-7(2) transition region is close to that of the commercially used red phosphor YVO4:Eu3+ (lambda(ex) = 326 nm). Electron energy loss spectroscopy measurements revealed the influence of the structure and Na/Eu cation distribution on the number and positions of bands in the UV-optical-infrared regions of the EELS spectrum.
Address
Corporate Author Thesis
Publisher Place of Publication Editor
Language Wos 000336637000028 Publication Date 2014-05-01
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 0897-4756;1520-5002; ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor 9.466 Times cited (up) 53 Open Access
Notes Fwo G039211n; Fwo G004413n; 278510 Vortex ECASJO_; Approved Most recent IF: 9.466; 2014 IF: 8.354
Call Number UA @ lucian @ c:irua:117765UA @ admin @ c:irua:117765 Serial 1652
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Author Morozov, V.A.; Belik, A.A.; Stefanovich, S.Y.; Grebenev, V.V.; Lebedev, O.I.; Van Tendeloo, G.; Lazoryak, B.I.
Title High-temperature phase transition in the whitlockite-type phosphate Ca9In(PO4)7 Type A1 Journal article
Year 2002 Publication Journal of solid state chemistry Abbreviated Journal J Solid State Chem
Volume 165 Issue 2 Pages 278-288
Keywords A1 Journal article; Electron microscopy for materials research (EMAT)
Abstract The double phosphate Ca9In(PO4)(7) was obtained by solid-state reaction and was studied by room and high-temperature Xray powder diffraction, electron diffraction, high-resolution electron microscopy, second-harmonic generation (SHG) technique, differential scanning calorimetry, dielectric and conductivity measurements. The beta-Ca9In(PO4)(7) room-temperature phase is related to the mineral whitlockite and is similar to beta-Ca-3(PO4)(2). It has space group R (3) over barc, with unit cell parameters: a = 10.4008(1) Angstrom, c = 37.272(1) Angstrom, Z = 6. The structure was refined by the Rietveld method (R-wp = 4.69, R-I = 1.81). A reversible first-order beta <----> beta' phase transition of the ferroelectric type with T-c = 902 K is revealed by SHG, differential scanning calorimetry and dielectric measurements. The centrosymmetric beta'-Ca9In(PO4)(7) (973 K) has space group R (3) over barc, a = 10.4611(2) Angstrom, c = 37.874 (1) Angstrom (R-wp = 4.27, R-I = 4.11). Compared to the low-temperature beta-Ca9In(PO4)(7) structure, beta'-Ca9In(PO4)(7) can be described as an orientational disordering of the P1O(4) tetrahedra together with a calcium disordering on the M3 site. (C) 2002 Elsevier Science (USA).
Address
Corporate Author Thesis
Publisher Place of Publication London Editor
Language Wos 000175916000010 Publication Date 2002-10-06
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 0022-4596; ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor 2.299 Times cited (up) 57 Open Access
Notes Approved Most recent IF: 2.299; 2002 IF: 1.671
Call Number UA @ lucian @ c:irua:94926 Serial 1467
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Author Morozov, V.A.; Bertha, A.; Meert, K.W.; Van Rompaey, S.; Batuk, D.; Martinez, G.T.; Van Aert, S.; Smet, P.F.; Raskina, M.V.; Poelman, D.; Abakumov, A.M.; Hadermann, J.;
Title Incommensurate modulation and luminescence in the CaGd2(1-x)Eu2x(MoO4)4(1-y)(WO)4y (0\leq x\leq1, 0\leq y\leq1) red phosphors Type A1 Journal article
Year 2013 Publication Chemistry of materials Abbreviated Journal Chem Mater
Volume 25 Issue 21 Pages 4387-4395
Keywords A1 Journal article; Electron microscopy for materials research (EMAT)
Abstract Scheelite related compounds (A',A '') [(B',B '')O-4], with B', B '' = W and/or Mo are promising new light-emitting materials for photonic applications, including phosphor converted LEDs (light-emitting diodes). In this paper, the creation and ordering of A-cation vacancies and the effect of cation substitutions in the scheelite-type framework are investigated as a factor for controlling the scheelite-type structure and luminescent properties. CaGd2(1-x)Eu2x(MoO4)(4(1-y))(WO4)(4y) (0 <= x <= 1, 0 <= y <= 1) solid solutions with scheelite-type structure were synthesized by a solid state method, and their structures were investigated using a combination of transmission electron microscopy techniques and powder X-ray diffraction. Within this series all complex molybdenum oxides have (3 + 2)D incommensurately modulated structures with superspace group I4(1)/a(alpha,beta,0)00(-beta,alpha,0)00, while the structures of all tungstates are (3 + 1)D incommensurately modulated with superspace group I2/b(alpha beta 0)00. In both cases the modulation arises because of cation-vacancy ordering at the A site. The prominent structural motif is formed by columns of A-site vacancies running along the c-axis. These vacant columns occur in rows of two or three aligned along the [110] direction of the scheelite subcell. The replacement of the smaller Gd3+ by the larger Eu3+ at the A-sublattice does not affect the nature of the incommensurate modulation, but an increasing replacement of Mo6+ by W6+ switches the modulation from (3 + 2)D to (3 + 1)D regime. Thus, these solid solutions can be considered as a model system where the incommensurate modulation can be monitored as a function of cation nature while the number of cation vacancies at the A sites remain constant upon the isovalent cation replacement. All compounds' luminescent properties were measured, and the optical properties were related to the structural properties of the materials. CaGd2(1-x)(MoO4)(4(1-y))(WO4)(4y) phosphors emit intense red light dominated by the D-5(0)-F-7(2) transition at 612 nm, along with other transitions from the D-5(1) and D-5(0) excited states. The intensity of the 5D0-7F2 transition reaches a maximum at x = 0.5 for y = 0 and 1.
Address
Corporate Author Thesis
Publisher Place of Publication Washington, D.C. Editor
Language Wos 000327045000030 Publication Date 2013-09-24
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 0897-4756;1520-5002; ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor 9.466 Times cited (up) 63 Open Access
Notes Approved Most recent IF: 9.466; 2013 IF: 8.535
Call Number UA @ lucian @ c:irua:112776 Serial 1594
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