WO2012074105A1 - Luminophore jaune et son procédé de fabrication - Google Patents
Luminophore jaune et son procédé de fabrication Download PDFInfo
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- WO2012074105A1 WO2012074105A1 PCT/JP2011/077952 JP2011077952W WO2012074105A1 WO 2012074105 A1 WO2012074105 A1 WO 2012074105A1 JP 2011077952 W JP2011077952 W JP 2011077952W WO 2012074105 A1 WO2012074105 A1 WO 2012074105A1
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- phosphor
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- raw material
- yellow phosphor
- production method
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 43
- 238000010304 firing Methods 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims description 51
- 229910052712 strontium Inorganic materials 0.000 claims description 14
- 229910052791 calcium Inorganic materials 0.000 claims description 11
- 229910052788 barium Inorganic materials 0.000 claims description 8
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 239000000126 substance Substances 0.000 description 13
- 239000012298 atmosphere Substances 0.000 description 12
- 239000011575 calcium Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000001354 calcination Methods 0.000 description 8
- 239000011261 inert gas Substances 0.000 description 7
- 150000002736 metal compounds Chemical class 0.000 description 7
- 229910052693 Europium Inorganic materials 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- -1 more particularly Substances 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910001940 europium oxide Inorganic materials 0.000 description 4
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 229910004283 SiO 4 Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 238000002253 near-edge X-ray absorption fine structure spectrum Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910000018 strontium carbonate Inorganic materials 0.000 description 3
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- 229910001508 alkali metal halide Inorganic materials 0.000 description 2
- 150000008045 alkali metal halides Chemical class 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910018514 Al—O—N Inorganic materials 0.000 description 1
- 229910015999 BaAl Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910006360 Si—O—N Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 125000005618 boron oxoacid group Chemical group 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- SULCVUWEGVSCPF-UHFFFAOYSA-L europium(2+);carbonate Chemical compound [Eu+2].[O-]C([O-])=O SULCVUWEGVSCPF-UHFFFAOYSA-L 0.000 description 1
- CQQZFSZWNXAJQN-UHFFFAOYSA-K europium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Eu+3] CQQZFSZWNXAJQN-UHFFFAOYSA-K 0.000 description 1
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 description 1
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical group Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- MOWNZPNSYMGTMD-UHFFFAOYSA-N oxidoboron Chemical class O=[B] MOWNZPNSYMGTMD-UHFFFAOYSA-N 0.000 description 1
- UFQXGXDIJMBKTC-UHFFFAOYSA-N oxostrontium Chemical compound [Sr]=O UFQXGXDIJMBKTC-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7767—Chalcogenides
- C09K11/7769—Oxides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7736—Vanadates; Chromates; Molybdates; Tungstates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7741—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7784—Chalcogenides
- C09K11/7787—Oxides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7784—Chalcogenides
- C09K11/7787—Oxides
- C09K11/7789—Oxysulfides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7794—Vanadates; Chromates; Molybdates; Tungstates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
Definitions
- the present invention relates to a yellow phosphor and a method for producing the same.
- the white LED is composed of a combination of an LED chip that emits light in the ultraviolet to blue region (wavelength of about 380 to 500 nm) and a phosphor that emits light when excited by the light emitted from the LED chip.
- White colors having various color temperatures can be realized based on the combination of the LED chip and the phosphor.
- Patent Document 1 discloses a phosphor represented by Y 3 Al 5 O 12 : Ce (YAG: Ce).
- Y 3 Al 5 O 12 is a host crystal of the phosphor
- Ce is a luminescent ion activated by the host crystal.
- Patent Documents 2 and 3 disclose phosphors represented by Li 2 SrSiO 4 : Eu.
- the phosphor represented by Li 2 SrSiO 4 : Eu is excellent in emission color.
- the phosphor represented by Li 2 SrSiO 4 : Eu efficiently absorbs blue light emitted from a blue LED and exhibits a broad yellow light emission having a peak near 570 nm.
- the phosphor represented by Li 2 SrSiO 4 : Eu can sufficiently maintain the emission intensity even when exposed to high temperatures.
- a phosphor such as Li 2 SrSiO 4 : Eu is required to further improve the emission intensity.
- An object of the present invention is to obtain a yellow phosphor having higher emission intensity (high luminance).
- a raw material mixture containing M 1 , M 2 , and L and SiO are mixed and fired, and yellow fluorescence represented by M 1 2a (M 2 b L c ) M 3 d O 4
- a method for producing a yellow phosphor comprising a step of generating a body.
- another aspect of the present invention is a method for producing a yellow phosphor represented by M 1 2a (M 2 b L c ) M 3 d O 4 , wherein the yellow phosphor comprises at least M 1 , It is manufactured by firing a mixture of a raw material mixture containing M 2 and L and SiO.
- the raw material mixture further contains an M 3 -containing raw material different from SiO, and the ratio of the Si element derived from the SiO to the total amount of the element M 3 in the yellow phosphor is 0.00. It may be from 001 to 50 atomic%. That is, the raw material mixture containing a substance different from SiO as an M 3 -containing raw material may be mixed with SiO and fired. In this case, 0.001 atomic% or more and 50 atomic% of the element M 3 in the phosphor The following may be derived from SiO.
- the L may be at least one element including Eu selected from rare earth elements, Bi and Mn, and the Eu may include divalent Eu.
- M 1 may be Li and M 3 may be Si.
- M 2 may be only Sr, Sr and Ba, or Sr and Ca.
- the a may be 0.9 to 1.1 (0.9 or more and 1.1 or less).
- Another aspect of the present invention provides a yellow phosphor that can be produced by the above production method, and a light emitting device or a white LED having the yellow phosphor.
- the emission intensity (luminance) of the obtained yellow phosphor can be further increased.
- the present embodiment relates to a phosphor that emits yellow light (yellow phosphor).
- Yellow light emission refers to light emission having a peak in the vicinity of a wavelength of 560 nm to 590 nm.
- the yellow phosphor that is the target of the present embodiment is represented by the formula M 1 2a (M 2 b L c ) M 3 d O 4 (wherein M 1 represents at least one element selected from alkali metals, and M 2 Represents at least one element selected from alkaline earth metals (Ca, Sr, Ba), M 3 represents at least one element selected from Si and Ge, and L comprises a rare earth element, Bi and Mn. Represents at least one element selected from the group, a is from 0.1 to 1.5, b is from 0.8 to 1.2, and c is from 0.005 to 0.2. , D is 0.8 to 1.2).
- the M 1 is preferably one or more (particularly one) element selected from Li, Na, and K, and more preferably Li.
- M 2 is preferably one or more (especially one) element selected from Ca, Sr and Ba, and more preferably Sr.
- M 2 preferably further contains Ba and / or Ca, and more preferably contains Ca.
- L is an element that is activated in the host crystal as a luminescent ion, and preferably contains at least Eu.
- L is Eu alone or a combination with one or more elements of L elements (rare earth elements, Bi, Mn) other than Eu and Eu.
- Particularly preferred L is Eu.
- Eu as L preferably contains at least divalent Eu (Eu 2+ ).
- M 3 is preferably Si.
- M 1 is Li.
- the lower limit of a is preferably 0.5 or more, more preferably 0.8 or more, still more preferably 0.9 or more, and particularly preferably 0.95 or more.
- the upper limit of a is preferably 1.2 or less, more preferably 1.1 or less, and particularly preferably 1.05 or less.
- the lower limit of b is preferably 0.8 or more, and more preferably 0.9 or more.
- the upper limit of b is preferably 1.1 or less, and more preferably 1.05 or less. In other words, the b is preferably 0.8 to 1.1, more preferably 0.9 to 1.05.
- the lower limit of c is preferably 0.01 or more, and more preferably 0.015 or more.
- the upper limit of c is preferably 0.1 or less, more preferably 0.05 or less. In other words, the c is preferably 0.01 to 0.1, and more preferably 0.015 to 0.05.
- the value of b + c and the lower limit of d may be the same or different, and are preferably 0.9 or more, more preferably 0.95 or more.
- the value of b + c and the upper limit of d may be the same or different, and are preferably 1.1 or less, more preferably 1.05 or less. In other words, the value of b + c and d may be the same or different, preferably 0.9 to 1.1, more preferably 0.95 to 1.05, and even more preferably. 1.
- the ratio of a to b + c (a / (b + c)), the ratio of a to d (a / d), and the ratio of b + c to d ((b + c) / d) may be the same or different. For example, it is 0.9 to 1.1, preferably 0.95 to 1.05.
- the phosphor is preferably hexagonal or trigonal.
- the phosphor can be manufactured by firing a mixture of a raw material mixture containing at least M 1 , M 2 , and L and SiO. That is, the phosphor is a yellow fluorescent material represented by M 1 2a (M 2 b L c ) M 3 d O 4 by mixing and baking a raw material mixture containing M 1 , M 2 , and L and SiO. It can be manufactured by a method including a step of generating a body.
- SiO 2 is generally used as a raw material for the Si component of the silicate phosphor.
- the manufacturing method according to the present embodiment is different from a normal method in that SiO is used as a raw material for the Si component.
- SiO acts as a source of M 3 components.
- SiO has an action of efficiently reducing the L component (especially europium). Therefore, the L component can be sufficiently reduced, and the luminance of the yellow phosphor can be increased.
- the SiO is preferably powdered SiO.
- the metal element-containing substance may be an oxide of each metal M 1 , M 2 , L, or M 3 , or a substance that decomposes or oxidizes at a high temperature (particularly the firing temperature) to form an oxide. May be.
- Substances that form this oxide include hydroxides, nitrides, oxynitrides, acid derivatives, salts (such as carbonates, nitrates, and oxalates).
- the first raw material is preferably selected from hydroxides, oxides and carbonates of metal M 1 (particularly lithium).
- a particularly preferable first raw material contains lithium hydroxide (LiOH), lithium oxide (Li 2 O), or lithium carbonate (Li 2 CO 3 ). These 1st raw materials may be used individually by 1 type, and may combine multiple.
- the second raw material include a hydroxide, oxide or carbonate of metal M 2 (especially strontium, barium, calcium, etc.). More specifically, the second raw material is selected from, for example, strontium hydroxide (Sr (OH) 2 ), strontium oxide (SrO), and strontium carbonate (SrCO 3 ). These 2nd raw materials may be used individually by 1 type, and may combine multiple.
- the third raw material is preferably a hydroxide, oxide, carbonate or chloride of metal L (especially europium).
- the third raw material includes, for example, europium hydroxide (Eu (OH) 2 , Eu (OH) 3 ), europium oxide (EuO, Eu 2 O 3 ), europium carbonate (EuCO 3 , Eu 2 (CO 3 ) 3 ), It is selected from europium chloride (EuCl 2 , EuCl 3 ) and europium nitrate (Eu (NO 3 ) 2 , Eu (NO 3 ) 3 ). These third raw materials may be used alone or in combination.
- Preferred examples of the fourth raw material include oxides, acid derivatives, and salts of metal M 3 (particularly silicon).
- a preferable fourth raw material includes, for example, silicon dioxide, silicic acid, or silicate.
- the atomic ratio of the elements M 1 , M 2 , L, and M 3 supplied from each raw material is expressed by the formula M 1 2a (M 2 b L c ) M 3 d O 4.
- M 1 2a (M 2 b L c ) M 3 d O 4. Are mixed within a range satisfying the relationship of a, b, c and d.
- the amount is preferably such that That is, of the element M 3 in the phosphor, 0.001 atomic% or more and 50 atomic% or less, preferably 0.005 atomic% or more and 20 atomic% or less of SiO is used in such an amount. It is recommended.
- Li 1.96 Sr 0.98 Eu 0.02 SiO 4 which is one of the preferred compositions of the phosphor obtained by the manufacturing method according to the present embodiment, the following may be performed.
- SiO is used so that the usage ratio is 1.0 atomic% with respect to the total Si-containing material.
- the mixing ratio of SrCO 3 , Li 2 CO 3 , SiO 2 and Eu 2 O 3 contained in the raw material mixture (metal compound mixture) is such that the molar ratio of Li: Sr: Eu: Si is 1.96: 0.98: 0. .02: 1.0 may be set.
- the first to third raw materials (preferably the first to fourth raw materials) and SiO may be mixed by a wet method or a dry method.
- general-purpose devices such as a ball mill, a V-type mixer and a stirrer can be used.
- the firing chamber atmosphere that is, the firing atmosphere
- the firing atmosphere may be any of an inert gas atmosphere, an oxidizing gas atmosphere, and a reducing gas atmosphere.
- an appropriate amount of carbon may be added to the raw material mixture (metal compound mixture) and fired.
- FIG. 1 is a schematic view showing an embodiment of a firing processing apparatus for firing a raw material mixture. The firing is performed by, for example, putting the mixture 5 of the raw material mixture and SiO in the firing chamber 30 and heating.
- Examples of the inert gas include nitrogen and argon.
- Examples of the oxidizing gas include oxygen, oxygen-containing inert gas (nitrogen, argon, etc.), and air.
- Examples of the reducing gas include a mixed gas of 0.1 to 10% by volume of hydrogen and an inert gas (nitrogen, argon, etc.), or 10 to 100% by volume (preferably 50 to 100% by volume) of NH. 3 and an inert gas (nitrogen, argon, etc.). These gases may be pressurized as necessary.
- a preferable firing atmosphere is a mixed gas of 0.1 to 10% by volume (more preferably 2 to 8% by volume, particularly preferably 4 to 6% by volume) hydrogen and an inert gas (particularly nitrogen).
- Calcination may be repeated a plurality of times.
- the firing atmosphere may be changed between the first firing and the second firing, and the firing atmosphere may be changed in the third and subsequent firings.
- calcination when calcination is performed in an inert gas atmosphere or an oxidizing gas atmosphere, it is preferable to perform calcination in a reducing gas atmosphere thereafter.
- Calcination temperature is usually 700 to 1000 ° C., preferably 750 to 950 ° C., more preferably 800 to 900 ° C.
- the firing time is usually 1 to 100 hours, preferably 10 to 90 hours, and more preferably 20 to 80 hours.
- the method according to the present embodiment includes a raw material mixture, if necessary, at a temperature lower than the calcination (eg, 500 to 800 ° C.) for a predetermined time (eg, 1 to 100 hours, preferably 10 to 90 hours). And a step of calcining the raw material mixture may be further included.
- a temperature lower than the calcination eg, 500 to 800 ° C.
- a predetermined time eg, 1 to 100 hours, preferably 10 to 90 hours.
- reaction accelerator is selected from, for example, alkali metal halides, alkali metal carbonates, alkali metal hydrogen carbonates, ammonium halides, boron oxides (B 2 O 3 ), and boron oxo acids (H 3 BO 3 ).
- the alkali metal halide is preferably an alkali metal fluoride or an alkali metal chloride, such as LiF, NaF, KF, LiCl, NaCl, or KCl.
- the alkali metal carbonate is, for example, Li 2 CO 3 , Na 2 CO 3 or K 2 CO 3 .
- the alkali metal bicarbonate is, for example, NaHCO 3 .
- the ammonium halide is, for example, NH 4 Cl or NH 4 I.
- the phosphor obtained by the manufacturing method according to the present embodiment may contain a halogen element derived from the raw material mixture, that is, one or more elements of F, Cl, Br, or I.
- the total content of halogen elements may be equal to or less than the total content of halogen elements contained in the raw material, preferably 50% or less, and more preferably 25% or less.
- the calcined product or the fired product may be subjected to any one or more of pulverization, mixing, washing, and classification.
- pulverization and mixing for example, a ball mill, a V-type mixer, a stirrer, a jet mill or the like can be used.
- a high-luminance phosphor can be obtained.
- a phosphor is a yellow phosphor represented by M 1 2a (M 2 b L c ) M 3 d O 4 . Since the yellow phosphor obtained by the above production method has high emission intensity, it can be suitably used in a light emitting device (for example, white LED).
- a white LED is composed of a light emitting element (LED chip) that emits ultraviolet to blue light (having a wavelength of about 200 to 550 nm, preferably about 380 to 500 nm), and a fluorescent layer containing a phosphor.
- This white LED can be manufactured by a method disclosed in, for example, Japanese Patent Application Laid-Open Nos. 11-31845 and 2002-226846. That is, for example, a white LED can be manufactured by a method in which the light emitting element is sealed with a translucent resin such as an epoxy resin or a silicone resin, and the surface thereof is covered with a phosphor. If the amount of the phosphor is appropriately set, the white LED emits a desired white color.
- a translucent resin such as an epoxy resin or a silicone resin
- FIG. 2 is a cross-sectional view showing an embodiment of a light emitting device.
- the light emitting device 1 illustrated in FIG. 2 includes a light emitting element 10 and a fluorescent layer 20 provided on the light emitting element 10.
- the phosphor forming the fluorescent layer 20 receives the light from the light emitting element 10 and is excited to emit fluorescence.
- White light emission can be obtained by appropriately setting the type, amount, and the like of the phosphor constituting the phosphor layer 20. That is, a white LED can be configured.
- the light emitting device or the white LED according to this embodiment is not limited to the form shown in FIG. 2 and can be appropriately modified without departing from the gist of the present invention.
- the yellow fluorescent substance obtained by the manufacturing method which concerns on this embodiment may be included independently, and the other fluorescent substance may be further included.
- Other phosphors include, for example, BaMgAl 10 O 17 : Eu, (Ba, Sr, Ca) (Al, Ga) 2 S 4 : Eu, BaMgAl 10 O 17 : (Eu, Mn), BaAl 12 O 19 :( Eu, Mn), (Ba, Sr, Ca) S: (Eu, Mn), YBO 3 : (Ce, Tb), Y 2 O 3 : Eu, Y 2 O 2 S: Eu, YVO 4 : Eu, ( Ca, Sr) S: Eu, SrY 2 O 4 : Eu, Ca—Al—Si—O—N: Eu, (Ba, Sr, Ca) Si 2 O 2 N 2 : Eu, ⁇ -sialon, CaSc 2 O 4 : Selected from Ce and Li— (Ca, Mg) —Ln—A
- Examples of the light emitting element that emits light having a wavelength of 200 nm to 550 nm include an ultraviolet LED chip and a blue LED chip.
- GaN, In i Ga 1-i N (0 ⁇ i ⁇ 1), In i Al j Ga 1- jN (0 ⁇ i ⁇ 1, 0 ⁇ j ⁇ 1, i + j) are used as light emitting layers.
- a semiconductor having a layer such as ⁇ 1) is used.
- the emission wavelength can be changed by changing the composition of the light emitting layer.
- the phosphor obtained by the manufacturing method according to the present embodiment is a light emitting device other than a white LED, for example, a light emitting device whose phosphor excitation source is vacuum ultraviolet light (for example, PDP); a light emitting device whose phosphor excitation source is ultraviolet light (For example, a backlight for a liquid crystal display, a three-wavelength fluorescent lamp); It can also be used for a light emitting device (for example, CRT or FED) in which the phosphor excitation source is an electron beam.
- a light emitting device whose phosphor excitation source is vacuum ultraviolet light (for example, PDP); a light emitting device whose phosphor excitation source is ultraviolet light (For example, a backlight for a liquid crystal display, a three-wavelength fluorescent lamp); It can also be used for a light emitting device (for example, CRT or FED) in which the phosphor excitation source is an electron beam.
- a light emitting device for example, a light emitting device
- the emission intensity of the phosphors obtained in the following examples was determined using a fluorescence spectrometer (FP-6500 manufactured by JASCO Corporation).
- An X-ray diffractometer (RINT2000 manufactured by Rigaku) was used for X-ray diffraction (XRD) measurement of the phosphor.
- XRD X-ray diffraction
- the valence ratio of Eu in the phosphor was evaluated by X-ray absorption fine structure (XAFS) measurement.
- XAFS measurement was performed by the transmission method using the beam line BL14B2 at SPring-8.
- BaMgAl 10 O 17 : Eu 2+ (BAM) was used as a standard sample of Eu 2+ (6792 eV).
- Eu 3+ (6980 eV) europium oxide (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.99%) was used.
- the X-ray absorption near edge structure (XANES) spectrum was obtained by processing the XAFS data of each sample based on the background using an analysis program (Rigaku REX2000). Thereafter, pattern fitting of the XANES spectrum of each sample was performed using the XANES spectra of the Eu 2+ standard sample and Eu 3+ standard sample, and the ratio of Eu 2+ in the sample was calculated from the ratio of Eu 2+ peaks.
- the content of oxygen in the crystalline substance was measured using EMGA-920 manufactured by Horiba.
- the non-dispersive infrared absorption method was used for the oxygen content.
- Comparative Example 1 Lithium carbonate (manufactured by Kanto Chemical Co., Ltd., purity 99%), strontium carbonate (manufactured by Sakai Chemical Industry Co., Ltd., purity 99% or more), europium oxide (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.99%), and silicon dioxide (Nippon Aerosil Co., Ltd .: purity 99.99%) were weighed so that the atomic ratio of Li: Sr: Eu: Si was 1.96: 0.98: 0.02: 1.0. Were mixed by a dry ball mill for 6 hours to obtain a metal compound mixture.
- the metal compound mixture was heated (baked) for 24 hours at a temperature of 800 ° C. in an N 2 atmosphere containing 5% by volume of H 2 . This was gradually cooled to room temperature to obtain a phosphor containing a compound represented by the formula Li 1.96 (Sr 0.98 Eu 0.02 ) SiO 4 .
- the ratio of divalent Eu (Eu 2+ ) in the total Eu of the phosphor was 14%.
- Comparative Example 2 Lithium carbonate (manufactured by Kanto Chemical Co., Ltd., purity 99%), strontium carbonate (manufactured by Sakai Chemical Industry Co., Ltd., purity 99% or more), europium oxide (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.99%), and silicon dioxide (Nippon Aerosil Co., Ltd .: purity 99.99%) were weighed so that the atomic ratio of Li: Sr: Eu: Si was 1.96: 0.98: 0.02: 1.0. Were mixed by a dry ball mill for 6 hours to obtain a metal compound mixture.
- the metal compound mixture was heated (baked) at a temperature of 800 ° C. for 24 hours and gradually cooled to room temperature.
- the obtained fired product is pulverized, and further heated (fired) at a temperature of 800 ° C. for 24 hours in an N 2 atmosphere containing 5% by volume of H 2 to obtain the formula Li 1.96 (Sr 0.98 Eu 0 0.02 )
- a phosphor containing a compound represented by SiO 4 was obtained.
- the ratio of divalent Eu (Eu 2+ ) in the total Eu of the phosphor was 17%.
- SYMBOLS 1 Light-emitting device, 5 ... Mixture of raw material mixture and SiO, 10 ... Light emitting element, 20 ... Fluorescent layer, 30 ... Baking chamber.
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Abstract
La présente invention concerne un procédé de fabrication d'un luminophore jaune, comprenant une étape de génération d'un luminophore jaune représenté par M1
2a(M2
bLc)M3
dO4 par mélange et cuisson de SiO et d'un mélange brut contenant M1, M2 et L.
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JP2010-269353 | 2010-12-02 | ||
JP2010269353A JP2012116980A (ja) | 2010-12-02 | 2010-12-02 | 黄色蛍光体およびその製造方法 |
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WO2012074105A1 true WO2012074105A1 (fr) | 2012-06-07 |
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PCT/JP2011/077952 WO2012074105A1 (fr) | 2010-12-02 | 2011-12-02 | Luminophore jaune et son procédé de fabrication |
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JP (1) | JP2012116980A (fr) |
TW (1) | TW201241153A (fr) |
WO (1) | WO2012074105A1 (fr) |
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NL2014941A (en) | 2014-07-16 | 2016-04-12 | Asml Netherlands Bv | Lithographic apparatus, device manufacturing method and associated data processing apparatus and computer program product. |
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WO2006090865A1 (fr) * | 2005-02-23 | 2006-08-31 | Sumitomo Chemical Company, Limited | Phosphore, dispositif d’emission lumineuse et diode emettant une lumiere blanche |
-
2010
- 2010-12-02 JP JP2010269353A patent/JP2012116980A/ja not_active Withdrawn
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2011
- 2011-12-02 WO PCT/JP2011/077952 patent/WO2012074105A1/fr active Application Filing
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WO2006090865A1 (fr) * | 2005-02-23 | 2006-08-31 | Sumitomo Chemical Company, Limited | Phosphore, dispositif d’emission lumineuse et diode emettant une lumiere blanche |
Non-Patent Citations (1)
Title |
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KENJI TODA ET AL.: "Kitai kara Tsukuru Jisedai Shomeiyo Hakko Zairyo Retort Pack no Hogo Film kara Keikotai ga Dekita!", SHUKI THE JAPAN SOCIETY OF APPLIED PHYSICS GAKUJUTSU KOENKAI NO PREVIEW HAPPYO, 1 September 2010 (2010-09-01), Retrieved from the Internet <URL:http://www.jsap.or.jp/pressrelease/press-100901.html> * |
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