WO2012074103A1 - 結晶性物質、並びにそれを用いた発光装置及び白色led - Google Patents
結晶性物質、並びにそれを用いた発光装置及び白色led Download PDFInfo
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- WO2012074103A1 WO2012074103A1 PCT/JP2011/077950 JP2011077950W WO2012074103A1 WO 2012074103 A1 WO2012074103 A1 WO 2012074103A1 JP 2011077950 W JP2011077950 W JP 2011077950W WO 2012074103 A1 WO2012074103 A1 WO 2012074103A1
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- purity
- crystalline
- crystalline substance
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- phosphor
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- 239000002178 crystalline material Substances 0.000 title claims abstract description 22
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 24
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 17
- 229910052788 barium Inorganic materials 0.000 claims abstract description 12
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 9
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 65
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 34
- 239000000203 mixture Substances 0.000 description 49
- 239000002994 raw material Substances 0.000 description 37
- 238000010304 firing Methods 0.000 description 30
- 239000007789 gas Substances 0.000 description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 24
- 150000002736 metal compounds Chemical class 0.000 description 23
- 239000011575 calcium Substances 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 16
- 229910001940 europium oxide Inorganic materials 0.000 description 13
- 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 13
- -1 nitrogen-containing compounds Chemical class 0.000 description 13
- 235000012239 silicon dioxide Nutrition 0.000 description 13
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 12
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 12
- 238000005121 nitriding Methods 0.000 description 12
- 239000000377 silicon dioxide Substances 0.000 description 12
- 229910000018 strontium carbonate Inorganic materials 0.000 description 12
- 229910002012 Aerosil® Inorganic materials 0.000 description 11
- 229910052808 lithium carbonate Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 229910052693 Europium Inorganic materials 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000000695 excitation spectrum Methods 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 150000004767 nitrides Chemical class 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000005284 excitation Effects 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 238000002253 near-edge X-ray absorption fine structure spectrum Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 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
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001590 oxidative effect Effects 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 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
- 150000001450 anions Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- PSBUJOCDKOWAGJ-UHFFFAOYSA-N azanylidyneeuropium Chemical compound [Eu]#N PSBUJOCDKOWAGJ-UHFFFAOYSA-N 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
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 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
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 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
- 230000002250 progressing effect Effects 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
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 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
- BHZCMUVGYXEBMY-UHFFFAOYSA-N trilithium;azanide Chemical compound [Li+].[Li+].[Li+].[NH2-] BHZCMUVGYXEBMY-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/0821—Oxynitrides of metals, boron or silicon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/0821—Oxynitrides of metals, boron or silicon
- C01B21/0823—Silicon oxynitrides
-
- 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
-
- 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
- C09K11/0883—Arsenides; Nitrides; Phosphides
-
- 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
- C09K11/59—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing silicon
-
- 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
- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
-
- 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
- C09K11/77347—Silicon Nitrides or Silicon Oxynitrides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
Definitions
- the present invention relates to a crystalline substance, and more particularly to a crystalline substance that is a phosphor.
- a 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. Based on the combination of the LED chip and the phosphor, white having various color temperatures can be realized.
- Patent Documents 1 and 2 disclose phosphors represented by Li 2 SrSiO 4 : Eu.
- a phosphor such as Li 2 SrSiO 4 : Eu is required to further improve the emission intensity.
- a phosphor is excited by blue light emitted from a blue LED to emit light, thereby obtaining white light.
- the wavelength peak of the blue light emitted from the blue LED shifts due to the deterioration of the blue LED.
- the color shift of the white LED can be suppressed.
- the excitation spectrum of the phosphor for white LED is as wide as 400 to 500 nm, for example, it is possible to suppress the color shift of the white LED.
- An object of the present invention is to provide a crystalline substance and a phosphor exhibiting high emission intensity (high luminance) and having a wide excitation spectrum. Another object of the present invention is to provide a high-luminance light-emitting device.
- M 1 is an element of at least one selected from alkali metal
- M 2 is at least one element selected Ca, Sr and Ba
- M 3 is at least one selected from Si and Ge L is at least one element selected from rare earth elements
- Bi and Mn a is 0.9 to 1.5 (0.9 or more and 1.5 or less)
- b is 0.8 to 1.2 (0.8 or more and 1.2 or less)
- c is 0.005 to 0.2 (0.005 or more and 0.2 or less)
- d is 0.8.
- the crystalline material of the present invention is usually a phosphor.
- y may be 4-3x / 2.
- L may be at least one element including Eu selected from rare earth elements, Bi and Mn, and this Eu can include divalent Eu.
- the M 1, M 2, M 3 , M 1 is Li, M 3 may be Si.
- M 2 may be only Sr, Sr and Ca, or Sr and Ba.
- Another aspect of the present invention provides a light emitting device including a light emitting element and the phosphor.
- the light emitting element may be an LED.
- another aspect of the present invention provides a white LED comprising an LED and the phosphor.
- the crystalline substance of the present invention can exhibit the properties of a phosphor, has a broad excitation spectrum, and can exhibit high emission intensity. Therefore, by applying this crystalline substance to a light-emitting device, a light-emitting device with high emission intensity (high luminance) can be realized.
- the present embodiment relates to a crystalline substance.
- This crystalline substance usually exhibits the properties of a phosphor and can emit yellow light (peak wavelength is about 560 to 590 nm) when excited by light in a blue region (peak wavelength is about 380 to 500 nm).
- the crystalline substance of this embodiment is represented by the formula: M 1 2a (M 2 b L c ) M 3 d O y N x .
- M 1 represents at least one element selected from alkali metals
- M 2 represents at least one element selected from Ca, Sr and Ba
- M 3 represents at least selected from Si and Ge.
- L represents a rare earth element, at least one element selected from Bi and Mn
- a represents 0.9 to 1.5 (0.9 or more and 1.5 or less)
- b Is 0.8 to 1.2 (0.8 or more and 1.2 or less)
- c is 0.005 to 0.2 (0.005 or more and 0.2 or less)
- d is 0.8 to 1.2 (0.8 or more and 1.2 or less)
- x is 0.001 to 1.0 (0.001 or more and 1.0 or less)
- y is 3. 0 to 4.0 (3.0 or more and 4.0 or less).
- M 1 is preferably one or more (particularly one) element selected from Li, Na, and K, and more preferably Li.
- M 2 is preferably only Sr (Sr alone) or a combination of Sr and other M 2 elements, particularly preferably Sr alone, a combination of Sr and Ca, or Sr and Ba It is a combination.
- the Sr, Ca, and Ba contents with respect to the total amount of Sr, Ca, and Ba each have an atomic ratio of Sr of 0.5 to 1.0 (0.5 ⁇ Sr ⁇ 1.0).
- Ca is preferably 0 to 0.5 (0 ⁇ Ca ⁇ 0.5)
- Ba is preferably 0 to 0.5 (0 ⁇ Ba ⁇ 0.5)
- Sr is 0.7.
- M 3 is preferably Si.
- M 1 is preferably Li.
- L is an element activated as luminescent ions, and preferably contains at least Eu.
- L can be Eu alone, a combination with a rare earth element other than Eu and Eu, a combination of Eu and Bi, and a combination of Eu and Mn.
- Eu as L preferably contains at least divalent Eu (Eu 2+ ), that is, only divalent Eu (Eu 2+ ), or divalent Eu (Eu 2+ ) and trivalent Eu (Eu 3+ ) is preferred.
- Eu as L contains divalent Eu (Eu 2+ )
- the crystalline substance can be excited by blue light and emit yellow light.
- the phosphor of Li 2 SrSiO 4 : Eu disclosed in Patent Document 1 has only Eu with L being trivalent Eu (Eu 3+ ) and emits red light.
- the lower limit of a is 0.9 or more, preferably 0.95 or more.
- the upper limit of a is 1.5 or less, preferably 1.2 or less, more preferably 1.1 or less, and particularly preferably 1.05 or less.
- B has a lower limit of 0.8 or more, preferably 0.9 or more.
- the upper limit of b is 1.2 or less, preferably 1.1 or less, and more preferably 1.05 or less.
- the lower limit of c is 0.005 or more, preferably 0.01 or more, and more preferably 0.015 or more.
- the upper limit of c is 0.2 or less, preferably 0.1 or less, and more preferably 0.05 or less.
- 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 still more preferably 1 It is.
- 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 lower limit of x is 0.001 or more, preferably 0.01 or more.
- the upper limit of x is 1.0 or less, preferably 0.5 or less, more preferably 0.1 or less, and still more preferably 0.08 or less.
- the lower limit of y is 3.0 or more, preferably 3.5 or more, more preferably 3.7 or more.
- the upper limit of y is 4.0 or less, preferably 3.95 or less, and more preferably 3.9 or less.
- y is preferably 4-3x / 2.
- the values of a, b + c, and d are all preferably in the range of 1 ⁇ 0.03, and particularly preferably 1. It is preferable that y is 4-3x / 2, M 1 is Li, M 3 is Si, and M 2 is Sr alone, or Sr and Ca. Specifically, as a preferable composition of the crystalline substance of the present embodiment, for example, Li 1.96 Sr 0.98 Eu 0.02 SiO 3.88 N 0.08 can be given.
- the crystal system of the crystalline substance of this embodiment is usually a trigonal or hexagonal crystal.
- the crystalline material of this embodiment contains a halogen element (one or more elements selected from F, Cl, Br, and I) derived from a raw material mixture described later (for example, when a halogen compound is used as a raw material). Also good.
- the amount of the halogen element in the crystalline substance is usually equal to or less than the total amount of halogen elements contained in the metal compound used as a raw material, preferably 50% or less, more preferably 25% or less.
- the crystalline substance of the present embodiment includes (i) an atmosphere containing NH 3 gas at least once. And / or (ii) the raw material mixture contains a nitride or an oxynitride, and the nitride or oxynitride is one or more of M 1 , M 2 , M 3 , and L Can be produced by using one or more compounds selected from those containing the above (hereinafter referred to as “nitrogen-containing compounds”).
- the raw material mixture includes a substance containing the element M 1 (first raw material), a substance containing the element M 2 (second raw material), a substance containing the element L (third raw material), and an element M 3.
- the first to fourth raw materials may be referred to as metal compounds in this specification, and the mixture thereof is referred to as a metal compound mixture.
- the term “metal element” is used to include a semi-metal element such as Si and Ge.
- the metal compound may be an oxide of each metal M 1 , M 2 , L, or M 3 , or may be a substance that decomposes or oxidizes at a high temperature (particularly the firing temperature) to form an oxide.
- Substances that form this oxide include hydroxides, nitrides, halides, oxynitrides, acid derivatives, salts (such as carbonates, nitrates, and oxalates).
- the first raw material is preferably selected from hydroxides, oxides, carbonates and nitrides of metal M 1 (particularly lithium).
- Particularly preferred first raw materials include lithium hydroxide (LiOH), lithium oxide (Li 2 O), lithium carbonate (Li 2 CO 3 ), or lithium nitride (Li 3 N). These 1st raw materials may be used individually by 1 type, and may combine multiple.
- the second raw material contains a hydroxide, oxide, carbonate or nitride of metal M 2 (especially strontium, barium, calcium, etc.). More specifically, the second raw materials are strontium hydroxide (Sr (OH) 2 ), strontium oxide (SrO), strontium carbonate (SrCO 3 ), strontium nitride (Sr 3 N 2 ), and calcium carbonate (CaCO 3 ). Chosen from. 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, chloride or nitride 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 ), europium nitrate (Eu (NO 3 ) 2 , Eu (NO 3 ) 3 ) and europium nitride (Eu 3 N 2 , EuN). These third raw materials may be used alone or in combination.
- the fourth raw material is preferably an oxide, acid derivative, salt, or nitride of metal M 3 (particularly silicon).
- Preferable fourth raw materials include, for example, silicon dioxide, silicic acid, silicate, or silicon nitride.
- the mixing of the first raw material to the fourth raw material may be performed by either a wet method or a dry method.
- a normal apparatus can be used for mixing. Examples of such an apparatus include a ball mill, a V-type mixer, and a stirrer.
- the firing conditions can be appropriately changed as long as the crystalline material is obtained.
- the number of firings can be one or more, preferably two or more.
- the firing atmosphere is, for example, an inert gas atmosphere (nitrogen, argon, etc.), an oxidizing gas atmosphere (air, oxygen, a mixed gas of oxygen and inert gas, etc.), or a reducing gas atmosphere (0.1-10 volume) % Of hydrogen and inert gas, NH 3 gas, 10 to less than 100% by volume of NH 3 gas and inert gas).
- the firing atmosphere may be pressurized as necessary. It is also possible to change the atmosphere for each firing. However, it is preferable to perform at least one firing in a nitriding atmosphere.
- the first firing is performed in a non-nitriding atmosphere
- the second and subsequent firings are performed in a nitriding atmosphere.
- the non-nitriding atmosphere is, for example, an atmosphere that does not contain NH 3 gas, or an atmosphere that does not contain high pressure (about 0.1 to 5.0 MPa) N 2 .
- the silicate or germanate represented by M 1 2a (M 2 b L c ) M 3 d O w is obtained in the first firing. Can be formed.
- nitrogen is introduced into the silicate or germanate represented by M 1 2a (M 2 b L c ) M 3 d O w , and M 1 2a ( A crystalline material represented by M 2 b L c ) M 3 d O y N x can be formed.
- the compound represented by M 1 2a (M 2 b L c ) M 3 d O w N z is formed in the first firing by performing the above. Can do.
- the compound represented by M 1 2a (M 2 b L c ) M 3 d O w N z is converted to M 1 2a (M 2 b L c ) M.
- Nitrogen can be introduced so as to have a composition represented by 3 d O y N x .
- w 4 ⁇ 3 / 2 ⁇ z.
- the raw material mixture includes a nitrogen-containing compound
- firing in a nitriding atmosphere is not necessarily performed, and only firing in a non-nitriding atmosphere may be performed.
- the amount of nitrogen of the crystalline substance represented by M 1 2a (M 2 b L c ) M 3 d O y N x is controlled by adjusting the amount of the nitrogen-containing compound in the raw material mixture, Good.
- the gas for forming the nitriding atmosphere is, for example, NH 3 gas (100% by volume), a mixed gas of 10% by volume or more and less than 100% by volume of NH 3 gas and an inert gas, and high pressure (about 0.1 to 5.0 MPa) ) Nitrogen gas.
- the gas for forming the nitriding atmosphere is preferably NH 3 gas (100% by volume) or a mixed gas of 50% by volume to less than 100% by volume of NH 3 gas and an inert gas.
- the firing 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 metal compound when a hydroxide, carbonate, nitrate, halide or oxalate is used as a metal compound, before firing the raw material mixture or before mixing the metal compound,
- These metal compounds can be calcined.
- the metal compound may be calcined by holding the metal compound at 500 to 800 ° C. for about 1 to 100 hours (preferably 10 to 90 hours).
- a reaction accelerator can be added to the metal compound or a mixture thereof. That is, calcination or baking may be performed in the presence of a reaction accelerator. By adding a reaction accelerator, the emission intensity of the crystalline substance can be increased.
- the 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 calcined product or the fired product after each firing 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.
- the mixing ratio of the metal compound is (M 1 element) :( M 2 element) :( L element) the ratio of (M 3 element) is 2a: b: c: with adjusted so that d, may be adjusted firing time in the nitriding atmosphere.
- the amount of nitrogen used in the crystalline substance should be adjusted by adjusting the amount used and the firing conditions (firing time, etc.) in the nitriding atmosphere. That's fine.
- the oxygen content (value of y) in the crystalline material is adjusted for the firing conditions in the O 2 -containing atmosphere (such as the O 2 concentration in the firing atmosphere and the firing time in the O 2 -containing atmosphere). It is also possible to control by.
- the crystalline material of this embodiment can exhibit the properties of a phosphor.
- the crystalline material has a broad excitation spectrum suitable for white LEDs.
- the crystalline substance can exhibit higher emission intensity than Li 2 SrSiO 4 : Eu when excited by blue light.
- / Luminescence intensity (1)) is 80% or more, preferably 85% or more, and more preferably 90% or more. Therefore, the crystalline substance of this embodiment can be suitably used in a light emitting device (for example, a white LED).
- the light emitting device of this embodiment includes a light emitting element (excitation source) and a phosphor.
- the white LED according to this embodiment includes an LED and a phosphor.
- the phosphor is the crystalline substance of this embodiment.
- the light emitting element is preferably an LED.
- a white LED is usually composed of a light emitting element (LED chip) that emits ultraviolet to blue light (having a wavelength of about 200 to 500 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.
- FIG. 1 is a cross-sectional view showing an embodiment of a light emitting device.
- the light emitting device 1 shown in FIG. 1 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. 1 and can be appropriately modified without departing from the gist of the present invention.
- the crystalline substance of 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 : Ce and Li— (Ca, Mg) —Ln—Al—O—N: Eu (Ca
- Examples of the light emitting element that emits light having a wavelength of 200 nm to 500 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 crystalline substance of this embodiment is a light emitting device other than a white LED, for example, a light emitting device (for example, PDP) whose phosphor excitation source is vacuum ultraviolet light; a light emitting device (for example, a liquid crystal display) whose phosphor excitation source is ultraviolet light Backlight, three-wavelength fluorescent lamp); and 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, PDP
- a light emitting device for example, a liquid crystal display
- phosphor excitation source is ultraviolet light Backlight, three-wavelength fluorescent lamp
- a light emitting device for example, CRT or FED
- the emission intensity of the crystalline material obtained in the following examples was determined using a fluorescence spectrometer (FP-6500 manufactured by JASCO Corporation).
- a fluorescence spectrometer FP-6500 manufactured by JASCO Corporation
- XRD X-ray diffraction
- RINT2000 manufactured by Rigaku X-ray diffractometer
- the valence ratio of Eu in the crystalline material 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 (REX2000 manufactured by Rigaku Corporation). 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 contents of oxygen and nitrogen in the crystalline material were measured using EMGA-920 manufactured by Horiba.
- the non-dispersive infrared absorption method was used for the oxygen content.
- the thermal conductivity method was used for the nitrogen content.
- 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%) was weighed so that the atomic ratio of Li: Sr: Eu: Si was 1.96: 0.98: 0.02: 1.0, and these were dry ball mills. Was mixed for 6 hours to obtain a metal compound mixture.
- the mixture was baked in the atmosphere at 750 ° C. for 10 hours, and then gradually cooled to room temperature.
- the obtained fired product is pulverized, fired at 800 ° C. for 3 hours in an NH 3 gas atmosphere, and represented by the formula Li 1.96 Sr 0.98 Eu 0.02 SiO 3.99 N 0.005.
- a crystalline compound (crystalline substance) was obtained.
- 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%) was weighed so that the atomic ratio of Li: Sr: Eu: Si was 1.96: 0.98: 0.02: 1.0, and these were dry ball mills. Was mixed for 6 hours to obtain a metal compound mixture.
- the mixture was baked in the atmosphere at 750 ° C. for 10 hours, and then gradually cooled to room temperature.
- the obtained fired product is pulverized, fired at 800 ° C. for 6 hours in an NH 3 gas atmosphere, and expressed by the formula Li 1.96 Sr 0.98 Eu 0.02 SiO 3.98 N 0.010.
- a crystalline compound (crystalline substance) was obtained.
- Example 3 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%) was weighed so that the atomic ratio of Li: Sr: Eu: Si was 1.96: 0.98: 0.02: 1.0, and these were dry ball mills. Was mixed for 6 hours to obtain a metal compound mixture.
- the mixture was baked in the atmosphere at 750 ° C. for 10 hours, and then gradually cooled to room temperature.
- the obtained fired product was pulverized and fired at 800 ° C. for 12 hours in an NH 3 gas atmosphere to obtain a crystal represented by the formula Li 1.96 Sr 0.98 Eu 0.02 SiO 3.92 N 0.053.
- Compound (crystalline substance) was obtained.
- Example 4 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%) was weighed so that the atomic ratio of Li: Sr: Eu: Si was 1.96: 0.98: 0.02: 1.0, and these were dry ball mills. Was mixed for 6 hours to obtain a metal compound mixture.
- the mixture was baked in the atmosphere at 750 ° C. for 10 hours, and then gradually cooled to room temperature.
- the obtained fired product was pulverized and fired at 800 ° C. for 24 hours in an NH 3 gas atmosphere to obtain a crystal represented by the formula Li 1.96 Sr 0.98 Eu 0.02 SiO 3.88 N 0.082.
- Compound (crystalline substance) was obtained.
- Example 5 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%) was weighed so that the atomic ratio of Li: Sr: Eu: Si was 1.96: 0.98: 0.02: 1.0, and these were dry ball mills. Was mixed for 6 hours to obtain a metal compound mixture.
- the mixture was calcined at 800 ° C. for 12 hours in an NH 3 gas atmosphere, and a crystalline compound represented by the formula Li 1.96 Sr 0.98 Eu 0.02 SiO 3.97 N 0.022 (crystalline substance) )
- Example 6 Lithium carbonate (manufactured by Kanto Chemical Co., Inc., purity 99%), strontium carbonate (manufactured by Sakai Chemical Industry Co., Ltd., purity 99% or higher), calcium carbonate (manufactured by Ube Materials Co., Ltd., purity 99.99% or higher), europium oxide (Shin-Etsu Chemical Co., Ltd., purity 99.99%) and silicon dioxide (Nippon Aerosil Co., Ltd .: purity 99.99%) have a Li: Sr: Ca: Eu: Si atomic ratio of 1.96: 0. It weighed so that it might be set to 97: 0.01: 0.02: 1.0, and these were mixed for 6 hours with the dry-type ball mill, and the metal compound mixture was obtained.
- the mixture was baked in the atmosphere at 750 ° C. for 10 hours, and then gradually cooled to room temperature.
- the obtained fired product was pulverized and calcined at 800 ° C. for 12 hours in an NH 3 gas atmosphere, and the formula Li 1.96 Sr 0.97 Ca 0.01 Eu 0.02 SiO 3.93 N 0.046
- the crystalline compound (crystalline substance) represented was obtained.
- Example 7 Lithium carbonate (Kanto Chemical Co., Ltd., purity 99%), strontium carbonate (Sakai Chemical Industry Co., Ltd., purity 99% or more), Barium carbonate (Kanto Chemical Co., Ltd., purity 99.9%), Europium oxide (Shin-Etsu) Chemical Industry Co., Ltd., purity 99.99%) and silicon dioxide (Nippon Aerosil Co., Ltd .: purity 99.99%) Li: Sr: Ba: Eu: Si atomic ratio 1.96: 0.97: These were weighed so as to be 0.01: 0.02: 1.0, and these were mixed for 6 hours by a dry ball mill to obtain a metal compound mixture.
- the mixture was baked in the atmosphere at 750 ° C. for 10 hours, and then gradually cooled to room temperature.
- the obtained fired product was pulverized, calcined at 800 ° C. for 12 hours in an NH 3 gas atmosphere, and the formula Li 1.96 Sr 0.97 Ba 0.01 Eu 0.02 SiO 3.94 N 0.040
- the crystalline compound (crystalline substance) represented was obtained.
- Crystalline materials of Examples 8 to 10 were obtained in the same manner as Example 3 except that the ratio (atomic ratio) of Eu and Sr in the raw material was changed so as to have the composition formula shown in Table 1 below.
- Crystalline materials of Examples 11 to 13 were obtained in the same manner as in Example 3 except that the ratio (atomic ratio) of Li in the raw material was changed so that the composition formula shown in Table 1 below was obtained.
- Crystalline materials of Examples 14 to 16 were obtained in the same manner as in Example 6 except that the ratio (atomic ratio) of Ca and Sr in the raw material was changed so as to have the composition formula shown in Table 1 below.
- Crystalline materials of Examples 17 to 19 were obtained in the same manner as in Example 7 except that the ratio (atomic ratio) of Ba and Sr in the raw material was changed so as to satisfy the composition formula shown in Table 1 below.
- the ratio (atomic ratio) of the M 1 element, M 2 element, L element, and M 3 element in the raw material is the same as the atomic ratio of these elements in the composition formula shown in Table 1. It is.
- 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%) was weighed so that the atomic ratio of Li: Sr: Eu: Si was 1.96: 0.98: 0.02: 1.0, and these were dry ball mills. Was mixed for 6 hours to obtain a metal compound mixture.
- the mixture was calcined at 800 ° C. for 24 hours in a mixed gas atmosphere of N 2 and 5% by volume of H 2, and then gradually cooled to room temperature to obtain the formula Li 1.96 (Sr 0.98 Eu 0.02 ).
- a crystalline compound represented by SiO 4.00 was obtained.
- 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%) was weighed so that the atomic ratio of Li: Sr: Eu: Si was 1.96: 0.98: 0.02: 1.0, and these were dry ball mills. Was mixed for 6 hours to obtain a metal compound mixture.
- the mixture was baked at 800 ° C. for 24 hours in a mixed gas atmosphere of N 2 and 5% by volume of H 2 and then gradually cooled to room temperature.
- the obtained fired product was pulverized and fired at 800 ° C. for 24 hours in a mixed gas atmosphere of N 2 and 5% by volume of H 2 to obtain the formula Li 1.96 (Sr 0.98 Eu 0.02 ) SiO 2.
- a crystalline compound represented by 4.00 was obtained.
- Comparative Example 3 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%) was weighed so that the atomic ratio of Li: Sr: Eu: Si was 1.96: 0.98: 0.02: 1.0, and these were dry ball mills. Was mixed for 6 hours to obtain a metal compound mixture.
- the mixture was baked in the atmosphere at 750 ° C. for 10 hours, and then gradually cooled to room temperature.
- the obtained fired product was pulverized and fired at 800 ° C. for 24 hours in a mixed gas atmosphere of N 2 and 5% by volume of H 2 to obtain the formula Li 1.96 (Sr 0.98 Eu 0.02 ) SiO 2.
- a crystalline compound represented by 4.00 was obtained.
- Comparative Example 4 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%) was weighed so that the atomic ratio of Li: Sr: Eu: Si was 2.00: 0.98: 0.02: 1.0, and these were dry ball mills Was mixed for 6 hours to obtain a metal compound mixture.
- the mixture was baked in the atmosphere at 750 ° C. for 10 hours, and then gradually cooled to room temperature.
- the obtained fired product was pulverized and fired at 800 ° C. for 24 hours in a mixed gas atmosphere of N 2 and 5% by volume of H 2 to obtain the formula Li 2.00 (Sr 0.98 Eu 0.02 ) SiO 2.
- a compound represented by 4.00 was obtained.
- Table 1 shows the characteristics of the crystalline compounds obtained in Examples 1 to 19 and Comparative Examples 1 to 4.
- the emission intensity (1) represents the peak intensity of the emission spectrum when the crystalline substance is excited with light having a wavelength of 450 nm
- the emission intensity (2) is the excitation of the crystalline substance with light having a wavelength of 500 nm. Represents the peak intensity of the emission spectrum. Both the emission intensities (1) and (2) are expressed as relative values when the emission intensity (1) of Comparative Example 1 is 100.
- the emission spectra of Example 4 and Comparative Example 1 are shown in FIG.
- the crystalline materials obtained in Examples 1 to 19 had higher emission intensity (1) and (2) than the crystalline materials obtained in Comparative Examples 1 to 4. Further, in the crystalline materials obtained in Comparative Examples 1 to 4, the emission intensity (2) is reduced to less than about 75% with respect to the emission intensity (1), whereas in Examples 1 to 19, it is the same. Or even if it decreased, it was 75% or more (preferably 80% or more). That is, it was found that the crystalline substances obtained in Examples 1 to 19 can suppress the decrease in emission intensity even when the excitation wavelength is shifted.
- the crystalline substance of the present invention can exhibit the properties of a phosphor, has a broad excitation spectrum in the blue region, and exhibits high emission intensity when excited with blue light, it is represented by a white LED. It is suitably used for a phosphor part of a light emitting device.
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Abstract
Description
前記原料混合物は、より詳細には、元素M1を含む物質(第1原料)、元素M2を含む物質(第2原料)、元素Lを含む物質(第3原料)、元素M3を含む物質(第4原料)の混合物である。元素M1、M2、L、及びM3はいずれも金属元素であるため、本明細書では前記第1~第4原料を金属化合物と称する場合があり、それらの混合物を金属化合物混合物と称する場合がある。なお、本明細書において「金属元素」とは、Si及びGeのような半金属元素も含む意味で用いる。前記金属化合物は、各金属M1、M2、L、又はM3の酸化物であってもよいし、高温(特に焼成温度)で分解又は酸化して酸化物を形成する物質であってもよい。この酸化物を形成する物質には、水酸化物、窒化物、ハロゲン化物、酸窒化物、酸誘導体、塩(炭酸塩、硝酸塩、シュウ酸塩など)などが含まれる。
焼成条件は、結晶性物質が得られる条件であれば適宜変更できる。焼成回数は1回又は2回以上とすることができ、好ましくは2回以上である。焼成の雰囲気は、例えば、不活性ガス雰囲気(窒素、アルゴンなど)、酸化性ガス雰囲気(空気、酸素、酸素と不活性ガスの混合ガスなど)、又は還元性ガス雰囲気(0.1~10体積%の水素と不活性ガスとの混合ガス、NH3ガス、10~100体積%未満のNH3ガスと不活性ガスとの混合ガス)とすることができる。焼成の雰囲気は、必要に応じて加圧してもよい。焼成ごとに雰囲気を変更することも可能である。ただし、焼成の少なくとも1回を窒化雰囲気下で行うことが好ましい。
炭酸リチウム(関東化学株式会社製、純度99%)、炭酸ストロンチウム(堺化学工業株式会社製、純度99%以上)、酸化ユウロピウム(信越化学工業株式会社製、純度99.99%)及び二酸化珪素(日本アエロジル株式会社製:純度99.99%)をLi:Sr:Eu:Siの原子比が1.96:0.98:0.02:1.0となるように秤量し、これらを乾式ボールミルにより6時間混合して金属化合物混合物を得た。
炭酸リチウム(関東化学株式会社製、純度99%)、炭酸ストロンチウム(堺化学工業株式会社製、純度99%以上)、酸化ユウロピウム(信越化学工業株式会社製、純度99.99%)及び二酸化珪素(日本アエロジル株式会社製:純度99.99%)をLi:Sr:Eu:Siの原子比が1.96:0.98:0.02:1.0となるように秤量し、これらを乾式ボールミルにより6時間混合して金属化合物混合物を得た。
炭酸リチウム(関東化学株式会社製、純度99%)、炭酸ストロンチウム(堺化学工業株式会社製、純度99%以上)、酸化ユウロピウム(信越化学工業株式会社製、純度99.99%)及び二酸化珪素(日本アエロジル株式会社製:純度99.99%)をLi:Sr:Eu:Siの原子比が1.96:0.98:0.02:1.0となるように秤量し、これらを乾式ボールミルにより6時間混合して金属化合物混合物を得た。
炭酸リチウム(関東化学株式会社製、純度99%)、炭酸ストロンチウム(堺化学工業株式会社製、純度99%以上)、酸化ユウロピウム(信越化学工業株式会社製、純度99.99%)及び二酸化珪素(日本アエロジル株式会社製:純度99.99%)をLi:Sr:Eu:Siの原子比が1.96:0.98:0.02:1.0となるように秤量し、これらを乾式ボールミルにより6時間混合して金属化合物混合物を得た。
炭酸リチウム(関東化学株式会社製、純度99%)、炭酸ストロンチウム(堺化学工業株式会社製、純度99%以上)、酸化ユウロピウム(信越化学工業株式会社製、純度99.99%)及び二酸化珪素(日本アエロジル株式会社製:純度99.99%)をLi:Sr:Eu:Siの原子比が1.96:0.98:0.02:1.0となるように秤量し、これらを乾式ボールミルにより6時間混合して金属化合物混合物を得た。
炭酸リチウム(関東化学株式会社製、純度99%)、炭酸ストロンチウム(堺化学工業株式会社製、純度99%以上)、炭酸カルシウム(宇部マテリアルズ株式会社製、純度99.99%以上)、酸化ユウロピウム(信越化学工業株式会社製、純度99.99%)及び二酸化珪素(日本アエロジル株式会社製:純度99.99%)をLi:Sr:Ca:Eu:Siの原子比が1.96:0.97:0.01:0.02:1.0となるように秤量し、これらを乾式ボールミルにより6時間混合して金属化合物混合物を得た。
炭酸リチウム(関東化学株式会社製、純度99%)、炭酸ストロンチウム(堺化学工業株式会社製、純度99%以上)、炭酸バリウム(関東化学株式会社製、純度99.9%)、酸化ユウロピウム(信越化学工業株式会社製、純度99.99%)及び二酸化珪素(日本アエロジル株式会社製:純度99.99%)をLi:Sr:Ba:Eu:Siの原子比が1.96:0.97:0.01:0.02:1.0となるように秤量し、これらを乾式ボールミルにより6時間混合して金属化合物混合物を得た。
炭酸リチウム(関東化学株式会社製、純度99%)、炭酸ストロンチウム(堺化学工業株式会社製、純度99%以上)、酸化ユウロピウム(信越化学工業株式会社製、純度99.99%)及び二酸化珪素(日本アエロジル株式会社製:純度99.99%)をLi:Sr:Eu:Siの原子比が1.96:0.98:0.02:1.0となるように秤量し、これらを乾式ボールミルにより6時間混合して金属化合物混合物を得た。
炭酸リチウム(関東化学株式会社製、純度99%)、炭酸ストロンチウム(堺化学工業株式会社製、純度99%以上)、酸化ユウロピウム(信越化学工業株式会社製、純度99.99%)及び二酸化珪素(日本アエロジル株式会社製:純度99.99%)をLi:Sr:Eu:Siの原子比が1.96:0.98:0.02:1.0となるように秤量し、これらを乾式ボールミルにより6時間混合して金属化合物混合物を得た。
炭酸リチウム(関東化学株式会社製、純度99%)、炭酸ストロンチウム(堺化学工業株式会社製、純度99%以上)、酸化ユウロピウム(信越化学工業株式会社製、純度99.99%)及び二酸化珪素(日本アエロジル株式会社製:純度99.99%)をLi:Sr:Eu:Siの原子比が1.96:0.98:0.02:1.0となるように秤量し、これらを乾式ボールミルにより6時間混合して金属化合物混合物を得た。
炭酸リチウム(関東化学株式会社製、純度99%)、炭酸ストロンチウム(堺化学工業株式会社製、純度99%以上)、酸化ユウロピウム(信越化学工業株式会社製、純度99.99%)及び二酸化珪素(日本アエロジル株式会社製:純度99.99%)をLi:Sr:Eu:Siの原子比が2.00:0.98:0.02:1.0となるように秤量し、これらを乾式ボールミルにより6時間混合して金属化合物混合物を得た。
Claims (10)
- M1 2a(M2 bLc)M3 dOyNxで表され、
M1はアルカリ金属から選択される少なくとも一種の元素であり、
M2はCa、Sr及びBaから選択される少なくとも一種の元素であり、
M3はSiおよびGeから選択される少なくとも一種の元素であり、
Lは希土類元素、BiおよびMnから選択される少なくとも一種の元素であり、
aは、0.9~1.5であり、
bは、0.8~1.2であり、
cは、0.005~0.2であり、
dは、0.8~1.2であり、
xは、0.001~1.0であり、
yは、3.0~4.0以下である、
結晶性物質。 - Lが、希土類元素、BiおよびMnから選択される、Euを含む少なくとも一種の元素である、請求項1に記載の結晶性物質。
- Lが、希土類元素、Bi及びMnから選択される、2価のEuを含む少なくとも一種の元素である、請求項2に記載の結晶性物質。
- M1がLiであり、M3がSiである、請求項1~3のいずれか一項に記載の結晶性物質。
- M2がSrのみである、Sr及びCaである、又はSr及びBaである、請求項1~4のいずれか一項に記載の結晶性物質。
- yが4-3x/2である、請求項1~5のいずれか一項に記載の結晶性物質。
- 蛍光体である、請求項1~6のいずれか一項に記載の結晶性物質。
- 発光素子と、
請求項7に記載の蛍光体と、
を備える、発光装置。 - 前記発光素子がLEDである、請求項8に記載の発光装置。
- LEDと、
請求項7に記載の蛍光体と、
を備える、白色LED。
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CN2011800579269A CN103237759A (zh) | 2010-12-02 | 2011-12-02 | 结晶性物质,以及使用其的发光装置及白色led |
US13/990,839 US20130292733A1 (en) | 2010-12-02 | 2011-12-02 | Crystalline material, and light-emitting device and white led using same |
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JP2006232906A (ja) * | 2005-02-23 | 2006-09-07 | Sumitomo Chemical Co Ltd | 蛍光体およびそれを用いた発光装置 |
WO2008004640A1 (fr) * | 2006-07-05 | 2008-01-10 | Ube Industries, Ltd. | Phosphores d'oxynitrure à base de sialon et procédé de production de ceux-ci |
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CN100572498C (zh) * | 2007-04-03 | 2009-12-23 | 北京宇极科技发展有限公司 | 一种氮氧化合物发光材料及其制法以及由其制成的照明或显示光源 |
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JP2006232906A (ja) * | 2005-02-23 | 2006-09-07 | Sumitomo Chemical Co Ltd | 蛍光体およびそれを用いた発光装置 |
WO2008004640A1 (fr) * | 2006-07-05 | 2008-01-10 | Ube Industries, Ltd. | Phosphores d'oxynitrure à base de sialon et procédé de production de ceux-ci |
JP2009179662A (ja) * | 2008-01-29 | 2009-08-13 | Toshiba Corp | 蛍光体および発光装置 |
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TOMOYUKI NAKANO ET AL.: "Novel Ba-Sc-Si-oxide and oxynitride phosphors for a white LED", RARE EARTHS, 21 May 2009 (2009-05-21), pages 146 - 147 * |
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TW201235449A (en) | 2012-09-01 |
US20130292733A1 (en) | 2013-11-07 |
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