WO2013183620A1 - 蛍光体の表面処理方法、蛍光体、発光装置及び照明装置 - Google Patents
蛍光体の表面処理方法、蛍光体、発光装置及び照明装置 Download PDFInfo
- Publication number
- WO2013183620A1 WO2013183620A1 PCT/JP2013/065443 JP2013065443W WO2013183620A1 WO 2013183620 A1 WO2013183620 A1 WO 2013183620A1 JP 2013065443 W JP2013065443 W JP 2013065443W WO 2013183620 A1 WO2013183620 A1 WO 2013183620A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- phosphor
- surface treatment
- crystal
- mass
- heat treatment
- Prior art date
Links
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 189
- 238000000034 method Methods 0.000 title claims abstract description 69
- 238000005286 illumination Methods 0.000 title abstract description 5
- 239000013078 crystal Substances 0.000 claims abstract description 45
- 238000010438 heat treatment Methods 0.000 claims abstract description 31
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims abstract description 24
- 239000004254 Ammonium phosphate Substances 0.000 claims abstract description 23
- 235000019289 ammonium phosphates Nutrition 0.000 claims abstract description 23
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 20
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 20
- 238000007598 dipping method Methods 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 238000004381 surface treatment Methods 0.000 claims description 52
- 229910052698 phosphorus Inorganic materials 0.000 claims description 27
- 239000011574 phosphorus Substances 0.000 claims description 27
- 102100032047 Alsin Human genes 0.000 claims description 16
- 101710187109 Alsin Proteins 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 14
- 238000007654 immersion Methods 0.000 claims description 9
- 230000003287 optical effect Effects 0.000 abstract description 9
- 150000004767 nitrides Chemical class 0.000 abstract description 6
- 230000002411 adverse Effects 0.000 abstract 1
- 239000011575 calcium Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 11
- 239000002994 raw material Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- -1 strontium nitride Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- DDXPLCBTGWFAIG-UHFFFAOYSA-N triazanium;phosphate;trihydrate Chemical compound [NH4+].[NH4+].[NH4+].O.O.O.[O-]P([O-])([O-])=O DDXPLCBTGWFAIG-UHFFFAOYSA-N 0.000 description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002335 surface treatment layer Substances 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910001940 europium oxide Inorganic materials 0.000 description 1
- 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 1
- 230000005284 excitation Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Images
Classifications
-
- 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
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
-
- 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
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
-
- 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
- C09K11/64—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing aluminium
-
- 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
- C09K11/64—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing aluminium
- C09K11/641—Chalcogenides
- C09K11/643—Chalcogenides with alkaline earth metals
-
- 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
- C09K11/77348—Silicon Aluminium Nitrides or Silicon Aluminium Oxynitrides
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/02—Heat treatment
-
- 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 phosphor surface treatment method, a phosphor treated by this method, and a light emitting device and an illumination device using the phosphor. More specifically, the present invention relates to a phosphor surface treatment technique in which a base crystal has substantially the same crystal structure as a (Sr, Ca) AlSiN 3 crystal.
- the nitride phosphor containing Sr is liable to be deteriorated by oxygen, heat, moisture, etc., and there is a particular problem in moisture resistance reliability.
- the reason why the moisture resistance reliability of the nitride phosphor containing Sr is inferior is that, for example, the surface of the phosphor containing Sr contains hydroxylated Sr by a reaction with moisture in the atmosphere or a step of contacting with water. It is thought that the hydrolyzed layer containing is easy to be formed.
- Methods for improving the moisture resistance of the phosphor include a method of treating the phosphor surface with a metal alkoxide or a derivative thereof (see Patent Document 1), and a method of forming a surface treatment layer containing fluorine on the phosphor surface (Patent Document). 2).
- Patent Document 1 a method of treating the phosphor surface with a metal alkoxide or a derivative thereof
- Patent Document 3 a method of treating a phosphor made of a nitride-based fluorescent material with a compound containing phosphorus.
- the method of treating the phosphor with a metal alkoxide or a derivative thereof has a problem that the phosphors aggregate.
- the method of forming a surface treatment layer containing fluorine on the phosphor surface has a problem that the resin or phosphor used in combination when LED (Light Emitting Diode) is mounted is deteriorated by fluorine.
- the surface treatment method described in Patent Document 3 since a metal salt of phosphoric acid is used as a compound containing phosphorus, there is a problem that optical properties are deteriorated by lanthanum contained therein.
- the present invention provides a phosphor surface treatment method, phosphor, light emitting device, and illumination capable of improving moisture resistance reliability without degrading optical characteristics in (Sr, Ca) AlSiN 3 nitride phosphor.
- the main purpose is to provide a device.
- the phosphor surface treatment method according to the present invention includes a dipping step of immersing a phosphor having a host crystal having substantially the same crystal structure as the (Sr, Ca) AlSiN 3 crystal in an aqueous solution containing ammonium phosphate; A heat treatment step of holding the phosphor after the immersion step in a temperature environment of 250 to 550 ° C. for 2 to 24 hours.
- the phosphorus content in the ammonium phosphate is preferably 0.1 to 2.0 mass%.
- the phosphor according to the present invention includes a dipping process in which a host crystal has substantially the same crystal structure as a (Sr, Ca) AlSiN 3 crystal, and the phosphor is immersed in an aqueous solution containing ammonium phosphate, and the dipping process.
- a surface treatment for performing a heat treatment step of holding the subsequent phosphor in a temperature environment of 250 to 550 ° C. for 2 to 24 hours is performed.
- the phosphorus content of the ammonium phosphate used for the surface treatment is preferably 0.1 to 2.0% by mass.
- the phosphor content of the phosphor according to the present invention is preferably 0.003 to 1% by mass.
- the light emitting device according to the present invention has the phosphor described above.
- the illuminating device of this invention is provided with the said light-emitting device.
- the moisture resistance reliability of the phosphor can be improved without degrading the optical characteristics as compared with the conventional (Sr, Ca) AlSiN 3 nitride phosphor.
- FIG. 1 is a flowchart of a phosphor surface treatment method according to an embodiment of the present invention.
- ammonium phosphate is applied to a phosphor whose base crystal has substantially the same crystal structure as the (Sr, Ca) AlSiN 3 crystal.
- An immersion process (step 1) for immersing in the aqueous solution containing the heat treatment process (step 2) for holding the phosphor after the immersion process in a temperature environment of 250 to 550 ° C. for 2 to 24 hours is performed.
- the water washing process (step 3) described in FIG. 1 can be performed as necessary for the phosphor after the heat treatment process.
- Step 1 Ammonium phosphate forms a phosphoric acid Sr layer having low solubility in water on the surface of the phosphor, and this phosphoric acid Sr layer functions as a barrier layer against water. Since ammonium phosphate does not contain a metal element, unlike the surface treatment method described in Patent Document 3 described above, there is no possibility of deteriorating the optical properties of the phosphor. Examples of the ammonium phosphate used in the dipping step include triammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate alone, a mixture thereof, or a hydrate thereof.
- the ammonium phosphate used in the dipping process preferably has a phosphorus content of 0.1 to 2.0% by mass. Thereby, moisture resistance can be further improved without deteriorating the optical characteristics. If ammonium phosphate having too little phosphorus content is used, the effect of improving moisture resistance by phosphorus treatment may be insufficient. If ammonium phosphate having a too high phosphorus content is used, a phosphorous layer is formed thick on the phosphor surface, which impedes light transmission and lowers the fluorescence intensity of the phosphor.
- the time for immersing the phosphor in the aqueous solution containing ammonium phosphate is preferably 30 minutes or more and 2 hours or less. If the soaking time is too short, unreacted substances tend to remain, and if the soaking time is too long, the effect of the impregnation step causes not only a peak but also a decrease in productivity. In the dipping step, it is preferable to stir the aqueous solution containing ammonium phosphate together with the phosphor, whereby the phosphor can be surface-treated more uniformly.
- Heat treatment process Step 2
- the heat treatment step by adding a heat treatment step to the phosphor after the immersion step, the ammonia component on the surface is volatilized, and phosphoric acid Sr having low solubility in water is more firmly formed on the phosphor surface.
- the moisture resistance reliability of the phosphor can be improved.
- the heat treatment temperature is less than 250 ° C. or when the holding time is less than 2 hours, unreacted sites are generated, and the moisture resistance improving effect cannot be sufficiently obtained.
- the heat treatment temperature exceeds 550 ° C. or the holding time exceeds 24 hours, the crystal structure of the phosphor changes and the fluorescence characteristics deteriorate. Therefore, the heat treatment temperature is 250 to 550 ° C., and the holding time is 2 to 24 hours.
- the heat treatment temperature is preferably 300 to 500 ° C., which can further improve the moisture resistance reliability.
- This heat treatment step can be performed in an inert gas such as argon or nitrogen or in the air.
- the phosphor obtained by the phosphor surface treatment method of the present embodiment preferably has a phosphorus content of 0.003 to 1% by mass. Thereby, moisture resistance reliability can be further improved while maintaining good optical characteristics. If the phosphor content after the surface treatment is too low, improvement in moisture resistance reliability may be insufficient, and if the phosphor content after the surface treatment is too large, the phosphor characteristics will be low. May decrease.
- the phosphorus content of the phosphor can be confirmed by inductively coupled plasma emission spectroscopy (ICP).
- the humidity resistance reliability of the phosphor obtained by the phosphor surface treatment method of the present embodiment can be confirmed by the maintenance rate of the fluorescence intensity after the humidity resistance test that is left for 1000 hours in an environment of a temperature of 85 ° C. and a humidity of 85%. . And in order to use a fluorescent substance stably for a long period of time, it is desirable that the maintenance rate of the fluorescence intensity after 1000 hours is 95% or more.
- the phosphor is immersed in an aqueous solution containing ammonium phosphate and then heat-treated under specific conditions, so that optical characteristics are not deteriorated.
- the humidity resistance reliability of the phosphor can be improved.
- a light emitting device and a lighting device with high moisture resistance reliability can be realized.
- the phosphor to be subjected to the surface treatment method of the phosphor of the examples and comparative examples is a phosphor in which the base crystal has substantially the same crystal structure as the (Sr, Ca) AlSiN 3 crystal. It is manufactured by the following Example 1 in Table 1.
- the raw materials for the phosphor were 52.2% by mass of ⁇ -type silicon nitride powder (SN-E10 grade made by Ube Industries), 45.8% by mass of aluminum nitride powder (E grade made by Tokuyama Corp.), europium oxide (Shin-Etsu) Chemical Industry Co., Ltd. RU grade) 2.0 mass% was used. These raw materials were mixed by a ball mill to obtain mixed raw materials. For ball mill mixing, nylon pots and silicon nitride balls were used, and ethanol was used as the solvent. The mixed raw material was dried to remove the solvent, and then classified with a sieve having an opening of 75 ⁇ m, and the material passed through the sieve was collected.
- the mixed raw material after classification, strontium nitride powder (Matterion, purity 99%), and calcium nitride powder (Matterion, purity 99%) are carried into a nitrogen-substituted glove box, and these are put in a mortar.
- the obtained raw material mixed powder was filled in a cylindrical boron nitride container with a lid (N-1 grade, manufactured by Denki Kagaku Kogyo Co., Ltd.) in a glove box.
- the raw material mixed powder after filling was taken out of the glove box together with the container and immediately set in an electric furnace of a carbon heater. Thereafter, the inside of the electric furnace was sufficiently evacuated to 0.1 Pa or less. Then, heating was started in an exhausted state, nitrogen gas was introduced at 600 ° C., and the atmospheric pressure in the electric furnace was set to 0.9 MPa. Even after introducing nitrogen gas, the temperature was raised to 1800 ° C. as it was, followed by firing at 1800 ° C. for 4 hours to obtain a phosphor.
- the fired phosphor was cooled and recovered from the electric furnace. Since the obtained phosphor was a red lump, it was crushed with a ball mill and classified with a vibrating sieve having an opening of 45 ⁇ m. Thereafter, the classified phosphor that passed through the vibrating sieve was washed with water, and the fine powder that floated on the surface of the liquid during washing was removed to obtain a phosphor.
- this phosphor was analyzed with an X-ray diffractometer (Ultima IV, manufactured by Rigaku Corporation), the host crystal was a phosphor having substantially the same crystal structure as the (Sr, Ca) AlSiN 3 crystal.
- Example 1 In the phosphor surface treatment method of Example 1, the above-described host crystal is immersed in an aqueous solution containing ammonium phosphate with respect to the phosphor having substantially the same crystal structure as the (Sr, Ca) AlSiN 3 crystal. An immersion process and a heat treatment process of holding the phosphor after the immersion process in a temperature environment of 500 ° C. for 2 hours were performed. In the dipping process, the phosphor produced by the method described above and triammonium phosphate trihydrate (manufactured by Kanto Chemical Co., Inc., purity 95% or more) are suspended in pure water with a mass ratio of 7 times, Stir for 2 hours. At that time, the amount of triammonium phosphate trihydrate added to the phosphor was 2.80 mass%, and the phosphorus content relative to the phosphor was 0.43 mass%.
- triammonium phosphate trihydrate manufactured by Kanto Chemical Co., Inc., purity 95% or more
- the phosphor after the dipping process was dried and recovered, and the recovered phosphor was filled in an alumina crucible and placed in a muffle furnace together with the alumina crucible and left in the atmosphere at a temperature of 500 ° C. for 2 hours.
- the phosphors are classified by a 45 ⁇ m sieve, and only those passing through the sieve are collected, and the phosphors surface-treated by the phosphor surface treatment method of Example 1 Got.
- Table 1 shows the evaluation results of the phosphor obtained by the phosphor surface treatment method of Example 1 described above.
- “Relative fluorescence intensity with respect to Reference Example 1” in Table 1 is obtained by using a spectrofluorometer (F-7000 manufactured by Hitachi High-Technologies Corporation) obtained by correcting the phosphor according to Reference Example 1 with Rhodamine B and a sub-standard light source. It was measured. For the measurement, a solid sample holder attached to the photometer was used, and a fluorescence spectrum at an excitation wavelength of 455 nm was obtained.
- “relative fluorescence intensity with respect to Reference Example 1” is shown as a relative value when the peak intensity of the fluorescence spectrum is used as an index and Reference Example 1 is set to 100%. In the evaluation, a value of “relative fluorescence intensity with respect to Reference Example 1” of 90% or more was regarded as acceptable.
- the “phosphor relative peak intensity” in Table 1 is a value obtained by dividing the fluorescence intensity after the moisture resistance test by the fluorescence intensity before the moisture resistance test.
- the environment in the moisture resistance test was set to a temperature of 85 ° C., a humidity of 85%, and 1000 hours. In the evaluation, a value of “phosphor relative peak intensity” of 90% or more was regarded as acceptable.
- the “ammonium phosphate content (% by mass)” with respect to the phosphor in Table 1 is the content of ammonium phosphate with respect to the phosphor when the phosphor surface treatment method is performed. In Reference Example 1, there is no value because the phosphor surface treatment method is not performed.
- the temperature in the heat treatment process” in Table 1 is a set temperature in the heat treatment process in the surface treatment process of the phosphor.
- the “phosphorus content in the phosphor after the surface treatment” in Table 1 is a value obtained by inductively coupled plasma measurement (CIROS-120 manufactured by SPECTRO).
- Example 2 In the phosphor surface treatment method of Example 2, the above-mentioned host crystal was substantially the same as the (Sr, Ca) AlSiN 3 crystal in the same method and conditions as in Example 1 except that the temperature in the heat treatment step was 300 ° C. Surface treatment was performed on the phosphors having the same crystal structure.
- Example 3 In the phosphor surface treatment method of Example 3, the amount of triammonium phosphate trihydrate added to the phosphor was 0.70% by mass (the phosphorus content relative to the phosphor was 0.11% by mass). In the same manner and conditions as in Example 1, surface treatment was performed on a phosphor in which the above-mentioned base crystal had substantially the same crystal structure as the (Sr, Ca) AlSiN 3 crystal.
- Example 4 The phosphor surface treatment method of Example 4 is obtained by adding a water washing step (Step 3) to the phosphor surface treatment method of Example 3 described above. In the water washing step, the phosphor obtained in Example 3 was suspended in pure water having a mass ratio of 7 times, stirred for 2 hours, washed with water and dried.
- Example 5 In the phosphor surface treatment method of Example 5, the addition amount of triammonium phosphate trihydrate in Example 1 to the phosphor was 7.00% by mass (the phosphorus content relative to the phosphor was 1.10% by mass). The phosphor was such that the host crystal had substantially the same crystal structure as the (Sr, Ca) AlSiN 3 crystal under the same method and conditions as in Example 1 except that the surface treatment was performed.
- the host crystal was substantially the same as the (Sr, Ca) AlSiN 3 crystal under the same method and conditions as in Example 1 except that the temperature of the heat treatment step was 600 ° C. Surface treatment was performed on the phosphors having the same crystal structure.
- Table 1 shows the evaluation results of the phosphors of Examples 1 to 5, Reference Example 1 and Comparative Examples 1 and 2.
- the phosphor of Example 1 has a relative fluorescence intensity of 99% with respect to Reference Example 1 and a phosphor relative peak intensity of 100%. Obtained.
- the phosphor content in the phosphor after the surface treatment was 0.38% by mass.
- the phosphor of Example 2 was good with little deterioration due to fluorescence characteristics and moisture resistance test.
- the phosphor of Example 3 had a relative fluorescence intensity of 94% with respect to Reference Example 1, and a phosphor relative peak intensity in a moisture resistance test of 95%.
- the phosphorus content in the phosphor of Example 4 was 0.01% by mass.
- the phosphor of Example 4 had a relative fluorescence intensity of 94% with respect to Reference Example 1, and the fluorescence characteristics were maintained at 94% even after the subsequent moisture resistance test. From Examples 3 and 4, it can be said that the phosphorus content with respect to the phosphor is preferably 0.1% by mass or more and the phosphorus content after the surface treatment is preferably 0.003% by mass or more.
- the phosphorus content in the phosphor of Example 5 was 0.89% by mass. Moreover, although the relative fluorescence intensity with respect to the reference example 1 was 93%, even if it passed through the subsequent moisture resistance test, 93% and the fluorescence characteristic were maintained. In addition, it can be said that the phosphorus content with respect to the phosphor is preferably 2% by mass or less, and the phosphorus content after the surface treatment is preferably 1% by mass or less.
- the phosphor of Reference Example 1 had a phosphor relative peak intensity of 78%, and the emission intensity after the moisture resistance test was deteriorated.
- the relative fluorescence intensity with respect to Reference Example 1 after the surface treatment process was not changed from 100%, but the phosphor relative peak intensity was 79%.
- the phosphor of Comparative Example 2 had a relative fluorescence intensity of 72% with respect to Reference Example 1 and a phosphor relative peak intensity of 70%.
- Example 6 As Example 6, the phosphor of Example 1 described above was mixed in a silicon sealing resin and mounted on the light emitting surface of the LED to produce a light emitting device. Since this light emitting device uses a phosphor with high moisture resistance reliability, the long-term reliability is high.
- Example 7 As Example 7, an illumination device was manufactured using the light-emitting device of Example 6 as a light source. Since this lighting device uses a phosphor with high moisture resistance reliability, the long-term reliability is high.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Metallurgy (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Led Device Packages (AREA)
- Luminescent Compositions (AREA)
Abstract
Description
本発明の蛍光体の表面処理方法では、前記リン酸アンモニウムにおけるリン含有率を0.1~2.0質量%とすることが好ましい。
本発明の蛍光体の表面処理方法では、前記熱処理工程後の蛍光体を水洗する水洗工程を行うことが好ましい。
本発明に係る蛍光体は、前記表面処理に用いるリン酸アンモニウムのリン含有率を0.1~2.0質量%とすることが好ましい。
前記表面処理において、前記熱処理工程後の蛍光体を水洗する水洗工程を行うことが好ましい。
本発明に係る蛍光体のリン含有率は、0.003~1質量%が好ましい。
本発明の照明装置は、前記発光装置を備えるものである。
リン酸アンモニウムは、蛍光体の表面に水への溶解度が低いリン酸Sr層を形成し、このリン酸Sr層が水に対するバリア層として機能する。リン酸アンモニウムは金属元素を含有しないため、前述した特許文献3に記載の表面処理方法のように、蛍光体の光学特性を低下させるおそれがない。浸漬工程で使用するリン酸アンモニウムとしては、リン酸三アンモニウム、リン酸水素二アンモニウム、リン酸二水素アンモニウムの単体、これらの混合体、又はこれらの水和物がある。
熱処理工程では、浸漬工程後の蛍光体に熱処理工程を加えることによって、表面のアンモニア成分を揮発させ、水に対する溶解度の低いリン酸Srをより強固に蛍光体表面に形成する。これにより、蛍光体の耐湿信頼性を向上させることができる。ただし、熱処理温度が250℃未満の場合又は保持時間が2時間未満の場合、未反応部位が発生し、耐湿性向上効果が十分に得られない。一方、熱処理温度が550℃を超えるか又は保持時間が24時間を超えると、蛍光体の結晶構造が変化し、蛍光特性が低下する。よって、熱処理温度は250~550℃、保持時間は2~24時間である。
熱処理工程によって、蛍光体表面に「余剰なリンを含む水溶性化合物」が残存する場合がある。この「余剰なリンを含む水溶性化合物」は、蛍光体の光透過性を妨げ蛍光強度低下を引き起こすことがある。このため、本実施形態の蛍光体の表面処理方法においては、水洗工程を行い、蛍光体表面に存在する余剰なリンを含む水溶性化合物を除去することが好ましい。これにより、光学特性の低下を更に抑制することができる。
本実施形態の蛍光体の表面処理方法により得られる蛍光体は、リン含有率が0.003~1質量%であることが好ましい。これにより、良好な光学特性を保ちつつ、耐湿信頼性を更に向上させることができる。なお、表面処理後の蛍光体のリン含有率があまりに低いと、耐湿信頼性の向上が不十分になることがあり、また、表面処理後の蛍光体のリン含有率があまりに多いと蛍光特性が低下することがある。蛍光体のリンの含有率は、誘導結合プラズマ発光分光分析(ICP)によって確認することができる。
蛍光体の原料には、α型窒化ケイ素粉末(宇部興産株式会社製 SN-E10グレード)52.2質量%、窒化アルミニウム粉末(トクヤマ株式会社製 Eグレード)45.8質量%、酸化ユーロピウム(信越化学工業株式会社製 RUグレード)2.0質量%を用いた。これらの原料を、ボールミルにより混合し、混合原料にした。ボールミル混合にあっては、ナイロン製ポットと窒化ケイ素製ボールを使用し、溶媒にはエタノールを使用した。混合原料を、乾燥させて溶媒を除去した後、目開き75μmの篩で分級し、篩を通過したものを回収した。
実施例1の蛍光体の表面処理方法では、前述の母体結晶が(Sr,Ca)AlSiN3結晶と実質的に同一の結晶構造を有する蛍光体に対して、リン酸アンモニウムを含む水溶液に浸漬する浸漬工程と、前記浸漬工程後の蛍光体を500℃の温度環境下に2時間保持する熱処理工程を行った。浸漬工程では、前述した方法で製造した蛍光体と、リン酸三アンモニウム三水和物(関東化学株式会社製、純度95%以上)を、質量比7倍の純水中に懸濁させて、2時間攪拌した。その際、リン酸三アンモニウム三水和物の蛍光体に対する添加量は2.80質量%とし、蛍光体に対するリン含有率は0.43質量%であった。
実施例2の蛍光体の表面処理方法では、熱処理工程での温度を300℃にした以外は実施例1と同様の方法及び条件で、前述の母体結晶が(Sr,Ca)AlSiN3結晶と実質的に同一の結晶構造を有する蛍光体に対して表面処理を行った。
実施例3の蛍光体の表面処理方法では、リン酸三アンモニウム三水和物の蛍光体に対する添加量を0.70質量%(蛍光体に対するリンの含有率は0.11質量%)とした以外は実施例1と同様の方法及び条件で、前述の母体結晶が(Sr,Ca)AlSiN3結晶と実質的に同一の結晶構造を有する蛍光体に対して表面処理を行った。
実施例4の蛍光体の表面処理方法は、前述した実施例3の蛍光体の表面処理方法に水洗工程(ステップ3)を追加したものである。水洗工程では、実施例3で得た蛍光体を、質量比7倍の純水中に懸濁させ、2時間攪拌した後、水洗し乾燥した。
実施例5の蛍光体の表面処理方法は、実施例1におけるリン酸三アンモニウム三水和物の蛍光体に対する添加量を7.00質量%(蛍光体に対するリンの含有率は1.10質量%)とした以外は実施例1と同様の方法及び条件で、前述の母体結晶が(Sr,Ca)AlSiN3結晶と実質的に同一の結晶構造を有する蛍光体に対して表面処理を行った。
比較例1の蛍光体の表面処理方法では、前述の母体結晶が(Sr,Ca)AlSiN3結晶と実質的に同一の結晶構造を有する蛍光体に対して、浸漬工程のみ行い、熱処理工程を行わなかった。
比較例2の蛍光体の表面処理方法では、熱処理工程の温度を600℃にした以外は、実施例1と同様の方法及び条件で、前述の母体結晶が(Sr,Ca)AlSiN3結晶と実質的に同一の結晶構造を有する蛍光体に対して表面処理を行った。
実施例6として、前述した実施例1の蛍光体をシリコンの封止樹脂に混入させてLEDの発光面に搭載し、発光装置を作製した。この発光装置は、耐湿信頼性の高い蛍光体を用いているため、長期信頼性が高かった。
実施例7として、実施例6の発光装置を光源として用いて照明装置を作製した。この照明装置は、耐湿信頼性の高い蛍光体を用いているため、長期信頼性が高かった。
Claims (9)
- 母体結晶が(Sr,Ca)AlSiN3結晶と実質的に同一の結晶構造を有する蛍光体を、リン酸アンモニウムを含む水溶液に浸漬する浸漬工程と、
前記浸漬工程後の蛍光体を250~550℃の温度環境下に2~24時間保持する熱処理工程と、
を有する蛍光体の表面処理方法。 - 前記リン酸アンモニウムにおけるリン含有率が0.1~2.0質量%である請求項1記載の蛍光体の表面処理方法。
- 前記熱処理工程後の蛍光体を水洗する水洗工程を有する請求項1又は2記載の蛍光体の表面処理方法。
- 母体結晶が(Sr,Ca)AlSiN3結晶と実質的に同一の結晶構造を有し、
リン酸アンモニウムを含む水溶液に蛍光体を浸漬する浸漬工程と、該浸漬工程後の蛍光体を250~550℃の温度環境下に2~24時間保持する熱処理工程とを行う表面処理が施された蛍光体。 - 前記リン酸アンモニウムはリン含有率が0.1~2.0質量%である請求項4記載の蛍光体。
- 前記表面処理において、前記熱処理工程後の蛍光体を水洗する水洗工程を行う請求項4又は5に記載の蛍光体。
- リン含有率が0.003~1質量%である請求項4~6のいずれか1項に記載の蛍光体。
- 請求項4~7のいずれか1項に記載の蛍光体を有する発光装置。
- 請求項8に記載の発光装置を備える照明装置。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP13801121.8A EP2860235B1 (en) | 2012-06-08 | 2013-06-04 | Method for treating surface of phosphor, phosphor, light-emitting device, and illumination device |
JP2014519995A JP6175060B2 (ja) | 2012-06-08 | 2013-06-04 | 蛍光体の表面処理方法、蛍光体、発光装置及び照明装置 |
US14/406,141 US20150137037A1 (en) | 2012-06-08 | 2013-06-04 | Method for treating surface of phosphor, phosphor, light-emitting device, and illumination device |
CN201380030222.1A CN104350127B (zh) | 2012-06-08 | 2013-06-04 | 荧光体的表面处理方法、荧光体、发光装置以及照明装置 |
KR1020147036893A KR20150028259A (ko) | 2012-06-08 | 2013-06-04 | 형광체의 표면 처리 방법, 형광체, 발광 장치 및 조명 장치 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012130333 | 2012-06-08 | ||
JP2012-130333 | 2012-06-08 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013183620A1 true WO2013183620A1 (ja) | 2013-12-12 |
Family
ID=49712011
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2013/065443 WO2013183620A1 (ja) | 2012-06-08 | 2013-06-04 | 蛍光体の表面処理方法、蛍光体、発光装置及び照明装置 |
Country Status (7)
Country | Link |
---|---|
US (1) | US20150137037A1 (ja) |
EP (1) | EP2860235B1 (ja) |
JP (1) | JP6175060B2 (ja) |
KR (1) | KR20150028259A (ja) |
CN (1) | CN104350127B (ja) |
TW (1) | TWI582213B (ja) |
WO (1) | WO2013183620A1 (ja) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5729698B1 (ja) * | 2014-10-14 | 2015-06-03 | 株式会社ルミネッサス | 発光体及びその製造方法 |
JP5967787B1 (ja) * | 2016-02-12 | 2016-08-10 | エルティーアイ株式会社 | 蓄光顔料の製造方法 |
JP2017155217A (ja) * | 2016-02-26 | 2017-09-07 | 日亜化学工業株式会社 | 蛍光体、発光装置及び蛍光体の製造方法 |
US10153405B2 (en) | 2016-02-26 | 2018-12-11 | Nichia Corporation | Fluorescent material, light emitting device, and method for producing fluorescent material |
US11773323B2 (en) | 2022-01-27 | 2023-10-03 | Nichia Corporation | Fluorescent material and method for producing same |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63199787A (ja) * | 1987-02-16 | 1988-08-18 | Kasei Optonix Co Ltd | 表面処理螢光体及びその製造法 |
JPH01315485A (ja) * | 1988-03-17 | 1989-12-20 | Sumitomo Chem Co Ltd | El発光体用リン酸塩被覆螢光体及びその製造方法 |
JPH08319483A (ja) * | 1995-05-26 | 1996-12-03 | Nichia Chem Ind Ltd | 真空紫外線励起発光蛍光体およびその製造方法 |
JP2001089761A (ja) * | 1999-09-09 | 2001-04-03 | Osram Sylvania Inc | ホスフェート処理珪酸塩蛍光体 |
JP2002309247A (ja) * | 2001-04-16 | 2002-10-23 | Nichia Chem Ind Ltd | 窒化ガリウム蛍光体及びその製造方法 |
JP2006269938A (ja) | 2005-03-25 | 2006-10-05 | Nichia Chem Ind Ltd | 発光装置、発光素子用蛍光体及びその製造方法 |
JP2008111080A (ja) | 2006-10-31 | 2008-05-15 | Mitsubishi Chemicals Corp | 蛍光体表面処理方法、蛍光体、蛍光体含有組成物、発光装置、画像表示装置、および照明装置 |
JP2012031425A (ja) | 2010-03-31 | 2012-02-16 | Sekisui Chem Co Ltd | 表面処理蛍光体及び表面処理蛍光体の製造方法 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4395387A (en) * | 1981-10-13 | 1983-07-26 | Pennwalt Corporation | Method for manufacturing water glass cement hardeners |
EP0333053B1 (en) * | 1988-03-17 | 1993-03-03 | Sumitomo Chemical Company, Limited | Phosphate-coated electroluminescent phosphor for electroluminescent lamp and a process for producing the same |
JP2003336046A (ja) * | 2002-05-17 | 2003-11-28 | Konica Minolta Holdings Inc | 無機蛍光体の表面処理方法及びそれを用いたディスプレイ素子 |
EP1935958A4 (en) * | 2005-08-10 | 2010-10-27 | Mitsubishi Chem Corp | PHOSPHOR AND LUMINESCENT DEVICE USING THE SAME |
TWI414583B (zh) * | 2006-09-15 | 2013-11-11 | Mitsubishi Chem Corp | 螢光體及其製造方法,暨含有螢光體之組成物,發光裝置,圖像顯示裝置及照明裝置 |
US8178001B2 (en) * | 2007-04-18 | 2012-05-15 | Mitsubishi Chemical Corporation | Method for producing inorganic compound, phosphor, phosphor-containing composition, light-emitting device, lighting system, and display device |
US8274215B2 (en) * | 2008-12-15 | 2012-09-25 | Intematix Corporation | Nitride-based, red-emitting phosphors |
ES2542524T3 (es) * | 2009-05-27 | 2015-08-06 | Easymining Sweden Ab | Producción de fosfatos de amonio |
JP2010275426A (ja) * | 2009-05-28 | 2010-12-09 | Sumitomo Chemical Co Ltd | 表面処理蛍光体粒子の製造方法及び表面処理蛍光体粒子 |
DE102009044255A1 (de) * | 2009-10-15 | 2011-04-28 | Leuchtstoffwerk Breitungen Gmbh | Erdalkalimetallsilikat-Leuchtstoffe und Verfahren zur Verbesserung ihrer Langzeitstabilität |
US8593062B2 (en) * | 2010-04-29 | 2013-11-26 | General Electric Company | Color stable phosphors for LED lamps and methods for preparing them |
-
2013
- 2013-06-04 EP EP13801121.8A patent/EP2860235B1/en not_active Not-in-force
- 2013-06-04 KR KR1020147036893A patent/KR20150028259A/ko not_active Application Discontinuation
- 2013-06-04 JP JP2014519995A patent/JP6175060B2/ja active Active
- 2013-06-04 WO PCT/JP2013/065443 patent/WO2013183620A1/ja active Application Filing
- 2013-06-04 CN CN201380030222.1A patent/CN104350127B/zh not_active Expired - Fee Related
- 2013-06-04 US US14/406,141 patent/US20150137037A1/en not_active Abandoned
- 2013-06-06 TW TW102120044A patent/TWI582213B/zh not_active IP Right Cessation
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63199787A (ja) * | 1987-02-16 | 1988-08-18 | Kasei Optonix Co Ltd | 表面処理螢光体及びその製造法 |
JPH01315485A (ja) * | 1988-03-17 | 1989-12-20 | Sumitomo Chem Co Ltd | El発光体用リン酸塩被覆螢光体及びその製造方法 |
JPH08319483A (ja) * | 1995-05-26 | 1996-12-03 | Nichia Chem Ind Ltd | 真空紫外線励起発光蛍光体およびその製造方法 |
JP2001089761A (ja) * | 1999-09-09 | 2001-04-03 | Osram Sylvania Inc | ホスフェート処理珪酸塩蛍光体 |
JP2002309247A (ja) * | 2001-04-16 | 2002-10-23 | Nichia Chem Ind Ltd | 窒化ガリウム蛍光体及びその製造方法 |
JP2006269938A (ja) | 2005-03-25 | 2006-10-05 | Nichia Chem Ind Ltd | 発光装置、発光素子用蛍光体及びその製造方法 |
JP2008111080A (ja) | 2006-10-31 | 2008-05-15 | Mitsubishi Chemicals Corp | 蛍光体表面処理方法、蛍光体、蛍光体含有組成物、発光装置、画像表示装置、および照明装置 |
JP2012031425A (ja) | 2010-03-31 | 2012-02-16 | Sekisui Chem Co Ltd | 表面処理蛍光体及び表面処理蛍光体の製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2860235A4 |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5729698B1 (ja) * | 2014-10-14 | 2015-06-03 | 株式会社ルミネッサス | 発光体及びその製造方法 |
JP2016079244A (ja) * | 2014-10-14 | 2016-05-16 | 株式会社ルミネッサス | 発光体及びその製造方法 |
JP5967787B1 (ja) * | 2016-02-12 | 2016-08-10 | エルティーアイ株式会社 | 蓄光顔料の製造方法 |
JP2017155217A (ja) * | 2016-02-26 | 2017-09-07 | 日亜化学工業株式会社 | 蛍光体、発光装置及び蛍光体の製造方法 |
US10153405B2 (en) | 2016-02-26 | 2018-12-11 | Nichia Corporation | Fluorescent material, light emitting device, and method for producing fluorescent material |
US11773323B2 (en) | 2022-01-27 | 2023-10-03 | Nichia Corporation | Fluorescent material and method for producing same |
Also Published As
Publication number | Publication date |
---|---|
JP6175060B2 (ja) | 2017-08-02 |
KR20150028259A (ko) | 2015-03-13 |
TW201406925A (zh) | 2014-02-16 |
CN104350127B (zh) | 2017-02-22 |
US20150137037A1 (en) | 2015-05-21 |
CN104350127A (zh) | 2015-02-11 |
EP2860235A1 (en) | 2015-04-15 |
EP2860235B1 (en) | 2017-09-06 |
TWI582213B (zh) | 2017-05-11 |
EP2860235A4 (en) | 2016-02-17 |
JPWO2013183620A1 (ja) | 2016-02-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6175060B2 (ja) | 蛍光体の表面処理方法、蛍光体、発光装置及び照明装置 | |
KR102059385B1 (ko) | 형광체의 제조방법 | |
WO2018092696A1 (ja) | 赤色蛍光体、発光部材、及び発光装置 | |
JPWO2017122800A1 (ja) | 蛍光体および発光装置 | |
TW201508049A (zh) | 螢光體、發光裝置及螢光體之製造方法 | |
US9657223B2 (en) | Method of stabilizing alpha-sialon phosphor raw powder, alpha-sialon phosphor composition obtained therefrom, and method of manufacturing alpha-sialon phosphor | |
KR20210150475A (ko) | 표면 피복 형광체 입자, 표면 피복 형광체 입자의 제조 방법 및 발광 장치 | |
KR20220015417A (ko) | 표면 피복 형광체 입자 및 발광 장치 | |
KR20210150474A (ko) | 표면 피복 형광체 입자, 표면 피복 형광체 입자의 제조 방법 및 발광 장치 | |
JP5912580B2 (ja) | 蛍光体、その製造方法及びその用途 | |
KR20150140281A (ko) | 산질화물 형광체 분말 및 그 제조 방법 | |
JP6869057B2 (ja) | 赤色蛍光体および発光装置 | |
WO2019188632A1 (ja) | 赤色蛍光体及び発光装置 | |
JP2011105532A (ja) | β型サイアロンの製造方法 | |
TWI450947B (zh) | β型矽鋁氮氧化物之製造方法 | |
JP2017186459A (ja) | 窒化物蛍光体粉末およびその製造方法 | |
JP2017125160A (ja) | 赤色蛍光体及び発光装置 | |
WO2018003605A1 (ja) | 赤色蛍光体の製造方法 | |
US11795391B2 (en) | Red phosphor and light emitting device | |
JP6576246B2 (ja) | 蛍光体、発光装置及びその製造方法 | |
JP2013237713A (ja) | β型サイアロン、発光装置及びβ型サイアロンの製造方法 | |
TWI844681B (zh) | 表面被覆螢光體粒子、以及發光裝置 | |
JP2012077182A (ja) | 蛍光体、半導体発光素子及び蛍光体の製造方法 | |
US20140191159A1 (en) | Method of stabilizing alph-sialon phosphor raw powder, alph-sialon phosphor composition obtained therefrom, and method of manufacturing alpha-sialon phosphor |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13801121 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2014519995 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14406141 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REEP | Request for entry into the european phase |
Ref document number: 2013801121 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2013801121 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 20147036893 Country of ref document: KR Kind code of ref document: A |