WO2012147215A1 - 蛍光体材料の製造方法、蛍光体材料、及び発光装置 - Google Patents
蛍光体材料の製造方法、蛍光体材料、及び発光装置 Download PDFInfo
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- WO2012147215A1 WO2012147215A1 PCT/JP2011/064792 JP2011064792W WO2012147215A1 WO 2012147215 A1 WO2012147215 A1 WO 2012147215A1 JP 2011064792 W JP2011064792 W JP 2011064792W WO 2012147215 A1 WO2012147215 A1 WO 2012147215A1
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- phosphor
- phosphor material
- particles
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- fine particles
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 239000000463 material Substances 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 103
- 239000010419 fine particle Substances 0.000 claims abstract description 50
- 239000000919 ceramic Substances 0.000 claims abstract description 49
- 239000002002 slurry Substances 0.000 claims abstract description 42
- 238000001035 drying Methods 0.000 claims abstract description 35
- 239000011247 coating layer Substances 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 239000012298 atmosphere Substances 0.000 claims abstract description 17
- 239000011261 inert gas Substances 0.000 claims abstract description 10
- 238000007738 vacuum evaporation Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052727 yttrium Inorganic materials 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 6
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical class [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 235000014692 zinc oxide Nutrition 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 238000000034 method Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 230000006866 deterioration Effects 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052688 Gadolinium Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007602 hot air drying Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 229910015999 BaAl Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 238000010030 laminating Methods 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
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—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
- C09K11/02—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
-
- 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
-
- 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
- H01L33/02—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 bodies
- H01L33/20—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 bodies with a particular shape, e.g. curved or truncated substrate
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—Shape
- H01L2224/4809—Loop shape
- H01L2224/48091—Arched
-
- 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 method for producing a phosphor material having a coating layer on the surface of phosphor particles, a phosphor material obtained thereby, and a light emitting device using the same.
- LED lamps are attracting attention as backlights for LCD TVs or next-generation lighting.
- the light emitted from the LED element itself is passed through a fluorescent material such as red, blue, or green or a kneaded lens, and the white light is obtained by superimposing the light emitted from the fluorescent material.
- a fluorescent material such as red, blue, or green or a kneaded lens
- the white light is obtained by superimposing the light emitted from the fluorescent material.
- phosphors have a weak point in that their light emission characteristics deteriorate when exposed to moisture, heat, or ultraviolet rays.
- the phosphor particles are coated with ceramics to prevent deterioration of characteristics and extend the life (see, for example, Patent Document 1).
- Ceramic fine particles As a raw material for coating because high characteristics can be obtained.
- a method is known in which phosphor particles, ceramic fine particles, and liquid are mixed to form a slurry, which is dried by spray drying, hot air drying, or natural drying (for example, Patent Document 2). reference).
- the specific surface area in contact with the drying gas is significantly smaller than that of spray drying or hot air drying, so that drying takes a long time, and moisture in the atmosphere is adsorbed during drying.
- the phosphor particles are deteriorated.
- a method of controlling the atmosphere and drying in a dehydrated atmosphere there is the use of a glove box or the like, but the dehydrated atmosphere gas must be introduced while constantly evacuating, which is very costly and time consuming. is not.
- the present invention has been made on the basis of such problems, and it is possible to efficiently form a coating layer on the surface of phosphor particles, and to obtain a phosphor material capable of obtaining high characteristics and a high yield. It is an object of the present invention to provide a manufacturing method, a phosphor material obtained thereby, and a light emitting device using the same.
- the method for producing a phosphor material according to the present invention is a method for producing a phosphor material having a coating layer on the surface of the phosphor particles, and a slurry containing the phosphor particles, ceramic fine particles, and a liquid is vacuum-evaporated and dried. A coating layer is formed on the surface of the phosphor particles by drying by the method and removing the liquid.
- the phosphor material of the present invention is manufactured by the method for manufacturing a phosphor material of the present invention, and the light emitting device of the present invention includes the phosphor material manufactured thereby.
- the method for producing a phosphor material of the present invention since the slurry containing phosphor particles, ceramic fine particles, and liquid is dried by a vacuum evaporation drying method, the amount of gas exhausted is extremely small, The amount of body particles and ceramic fine particles discharged out of the processing apparatus can be extremely reduced. Therefore, the yield of the phosphor particles can be increased, the change in the particle size distribution of the phosphor particles can be prevented, and the quality of the phosphor material can be maintained. Further, it is possible to reduce the amount of ceramic fine particles that are dried by themselves without adhering to the phosphor particles, and it is possible to increase the film forming efficiency. Further, the drying time is short and the production can be efficiently performed, and the influence of moisture is small, and the deterioration of characteristics can be prevented.
- heat treatment is performed in an inert gas atmosphere, for example, in an inert gas atmosphere containing at least one of the group consisting of nitrogen and Group 18 elements of the long period table. Adhesiveness of the coating layer can be improved while preventing deterioration of the characteristics of the phosphor particles.
- the drying time can be further shortened.
- the average particle size of the ceramic fine particles is set to 40 nm or less, or the ceramic fine particles are rare earth oxide, zirconium oxide, titanium oxide, zinc oxide, aluminum oxide, yttrium and aluminum composite oxide, magnesium oxide
- the ceramic fine particles are rare earth oxide, zirconium oxide, titanium oxide, zinc oxide, aluminum oxide, yttrium and aluminum composite oxide, magnesium oxide
- at least one metal oxide selected from the group consisting of aluminum and magnesium complex oxides is included, characteristics such as water resistance and ultraviolet light resistance can be further improved.
- FIG. 1 shows steps of a method for manufacturing a phosphor material according to an embodiment of the present invention
- FIG. 2 schematically shows a phosphor material 10 produced thereby.
- the method for manufacturing the phosphor material 10 according to the present embodiment is to manufacture the phosphor material 10 having the coating layer 12 on the surface of the phosphor particles 11, and the phosphor material 10 according to the present embodiment is The phosphor material 10 is obtained by the manufacturing method.
- step S101 a slurry containing the phosphor particles 11, the ceramic fine particles 12A, and a liquid is prepared (step S101).
- Any phosphor particles 11 may be used.
- blue type such as BaMgAl 10 O 17 : Eu, ZnS: Ag, Cl, BaAl 2 S 4 : Eu or CaMgSi 2 O 6 : Eu.
- examples include green phosphors such as O 3 : Mn, and red phosphors such as (Y, Gd) BO 3 : Eu, Y 2 O 2 S: Eu or YPVO 4 : Eu.
- the particle diameter of the phosphor particles 11 is basically not limited, but it is preferable that the average particle diameter is about 5 ⁇ m to 20 ⁇ m and the particle diameters are as uniform as possible. This is because the characteristics can be stabilized.
- the ceramic fine particles 12A are for forming the coating layer 12, and include, for example, rare earth oxides, zirconium oxides, titanium oxides, zinc oxides, aluminum oxides, yttrium / aluminum / garnet composite oxides such as yttrium and aluminum, It is preferable to contain as a main component at least one metal oxide of the group consisting of magnesium oxide and a composite oxide of aluminum and magnesium such as MgAl 2 O 4 . This is because characteristics such as water resistance and ultraviolet light resistance can be improved. Among these, rare earth oxides are preferred, rare earth oxides containing at least one element from the group consisting of yttrium, gadolinium, cerium and lanthanum are more preferred, and Y 2 O 3 is particularly desirable.
- the ceramic fine particles 12A may be used singly or in combination of two or more. Further, ceramic fine particles 12A made of one kind of metal oxide may be used, but ceramic fine particles 12A containing two or more kinds of metal oxides may be used.
- the average particle size of the ceramic fine particles 12A is preferably 40 nm or less, more preferably 30 nm or less, and even more preferably 25 nm or less. This is because when the average particle size is smaller, the ceramic fine particles 12A are more likely to adhere to the phosphor particles 11 and can be deposited in a state in which there are very few gaps between the particles, so that a good coating layer 12 can be formed. .
- the average particle size of the ceramic fine particles 12A is preferably 10 nm or more, and more preferably 15 nm or more. This is because if the average particle size of the ceramic fine particles 12A is too small, coarse secondary aggregate particles are likely to be generated, and it becomes difficult to uniformly coat the phosphor particles 11.
- the average particle diameter of the ceramic fine particles 12 ⁇ / b> A is preferably about 1/100 to 1/500 of the average particle diameter of the phosphor particles 11. This is because the coating layer 12 can be formed more stably.
- the average particle size is the average particle size of primary particles.
- the maximum particle size of the ceramic fine particles 12A is preferably 50 nm or less, for example. This is because the presence of large particles tends to cause defects in which the phosphor particles 11 are exposed.
- the maximum particle size of the fine particles 12A is more preferably 40 nm or less, and further preferably 30 nm or less.
- an organic solvent is preferably used as the liquid in which the ceramic fine particles 12A are dispersed.
- the material of the liquid is basically not limited, but it is preferable to use ethanol or IPA (isopropyl alcohol) as a material that is inexpensive and easily evaporates at normal temperature and pressure and has low toxicity.
- ethanol or IPA isopropyl alcohol
- water and a material containing a large amount of water are not preferable.
- a material that does not easily evaporate at normal temperature and pressure is also not preferable.
- the reduced-pressure evaporation drying method is a method in which evaporation of a liquid is promoted by a reduced-pressure atmosphere to dry.
- the slurry temperature may be raised by heating from the outside of the container in order to promote drying.
- Stirring may be performed, for example, by rotating a container containing the slurry, or by a stirring device such as a rotary blade provided in the container storing the slurry.
- a stirring device such as a rotary blade provided in the container storing the slurry.
- the phosphor particles 11 to which the ceramic fine particles 12A are attached are heat-treated in an inert gas atmosphere (step S103).
- an inert gas what contains at least 1 sort (s) of the group which consists of nitrogen and a long periodic table group 18 element is mentioned, for example.
- the heat treatment temperature is preferably set to 450 ° C. or lower, for example. This is because deterioration of characteristics can be prevented.
- each process of preparation of a slurry may be performed once, but may be repeated a plurality of times.
- slurry step S101), drying (step S102), and heat treatment (step S103) are performed, and the phosphor particles 11 on which the coating layer 12 is formed are prepared again with the ceramic fine particles 12A and the liquid (step).
- S101), drying (step S102), and heat treatment step S103 may be performed. This is because the phosphor particles 11 can be more reliably coated.
- the coating layer 12 is preferably formed by laminating three or more ceramic fine particles 12A in the thickness direction, and the thickness of the coating layer 12 is preferably 10 nm or more and 1 ⁇ m or less. If the number of ceramic fine particles 12A is small, or if the coating layer 12 is thin, the effect of preventing characteristic deterioration is small. If the thickness is thick, the light transmittance is lowered and the light emission efficiency is lowered. It is. Thereby, the phosphor material 10 which coat
- FIG. 3 shows a configuration example of the light emitting device 20 using the phosphor material 10.
- a light emitting element 22 is mounted on a substrate 21, and the light emitting element 22 is electrically connected to a wiring 23 formed on the substrate 21 by a wire 24.
- a reflector frame 25 is formed around the light emitting element 22, and a sealing layer 26 is formed on the light emitting element 22 so as to cover the light emitting element 22.
- the sealing layer 26 is made of, for example, a resin in which the phosphor material 10 is dispersed.
- the light emitting element 22 is, for example, one that emits ultraviolet light, blue light, or green light as excitation light.
- the phosphor material 10 for example, one that emits red light by excitation light emitted from the light emitting element 22, one that emits blue light, one that emits green light, one that emits yellow light, or the like is necessary. Accordingly, two or more kinds are used in combination.
- the slurry containing the phosphor particles 11, the ceramic fine particles 12A, and the liquid is dried by the reduced pressure evaporation drying method.
- the amount of the body particles 11 and the ceramic fine particles 12A discharged to the outside of the processing apparatus can be extremely reduced. Therefore, the yield of the phosphor particles 11 can be increased, the change in the particle size distribution of the phosphor particles 11 can be prevented, and the quality of the phosphor material 10 can be maintained. Further, the amount of the ceramic fine particles 12A that are dried alone without adhering to the phosphor particles 11 can be reduced, and the film formation efficiency can be increased. Furthermore, the drying time is short and the production can be performed efficiently, and the influence of moisture is small, so that the characteristic deterioration can be prevented.
- heat treatment is performed in an inert gas atmosphere, for example, in an inert gas atmosphere containing at least one of the group consisting of nitrogen and Group 18 elements of the long period table.
- the adhesion of the coating layer 12 can be improved while preventing the deterioration of the characteristics of the phosphor particles 11.
- the drying time can be further shortened.
- the average particle size of the ceramic fine particles 12A is set to 40 nm or less, or the ceramic fine particles are rare earth oxide, zirconium oxide, titanium oxide, zinc oxide, aluminum oxide, composite oxide of yttrium and aluminum, oxidation
- the ceramic fine particles are rare earth oxide, zirconium oxide, titanium oxide, zinc oxide, aluminum oxide, composite oxide of yttrium and aluminum, oxidation
- at least one metal oxide of the group consisting of magnesium and a composite oxide of aluminum and magnesium characteristics such as water resistance and ultraviolet light resistance can be further improved.
- Example 1 Green phosphor particles 11 having an average particle diameter of about 10 ⁇ m are mixed with ceramic fine particles 12A made of yttrium oxide (Y 2 O 3 ) having an average particle diameter of 20 nm and a maximum particle diameter of 50 nm dispersed in an organic solvent.
- a slurry was prepared (step S101). Next, using a rotary evaporator, this slurry was dried by a vacuum evaporation method, and the organic solvent was removed (step S102). At that time, the slurry was dried while being stirred by rotating the container containing the slurry. Subsequently, the dried powder, that is, the phosphor particles 11 with the ceramic fine particles 12A attached thereto was heat-treated at 400 ° C.
- step S103 For the obtained powder, that is, the phosphor particles 11 on which the coating layer 12 is formed, the slurry preparation (step S101), drying (step S102), and heat treatment (step S103) are repeated once in the same manner.
- a body material 10 was obtained.
- Example 1-1 A phosphor material was produced in the same manner as in Example 1 except that the slurry was dried by spray drying. With respect to the obtained fluorescent material, the yield of the phosphor particles used as a raw material was examined and found to be about 70%.
- Comparative Example 1-2 A phosphor material was produced in the same manner as in Example 1 except that the slurry was dried by natural drying. In Comparative Example 1-2, it took 10 times more time than Example 1 to dry the same amount of slurry as Example 1.
- Table 1 shows the results of Example 1 and Comparative Examples 1-1 and 1-2.
- Example 2-1 Using the phosphor material 10 produced in Example 1, a light emitting device 20 as shown in FIG. 3 was produced.
- the light emitting element 22 used emits ultraviolet light.
- Example 2-2 Except that the heat treatment was performed in an oxidizing atmosphere (in the air atmosphere), the phosphor material 10 was fabricated in the same manner as in Example 1, and the light emitting device 20 was fabricated in the same manner as in Example 2-1. .
- Example 2 A light emitting device was fabricated in the same manner as in Example 2-1, using the phosphor particles as a phosphor material without forming a coating layer on the phosphor particles.
- Example 3-1 the average particle size is 40 nm and the maximum particle size is 50 nm.
- Example 3-2 the average particle size is 30 nm and the maximum particle size is 50 nm.
- Example 3-3 the average particle size is 25 nm and the maximum particle size.
- Ceramic fine particles 12A having a diameter of 50 nm, an average particle diameter of 20 nm and a maximum particle diameter of 40 nm in Example 3-4, and an average particle diameter of 15 nm and a maximum particle diameter of 40 nm were used in Example 3-5.
- the obtained light-emitting device 20 was subjected to a light emission test in the same manner as in Example 2-1, and the change in luminance with time was examined.
- the obtained results are shown in Table 3 together with the results of Example 2-1 and Comparative example 2.
- the luminance maintenance rate after 2000 hours is a relative value when the initial luminance of Comparative Example 2 in which no coating layer is formed is 100%.
- the average particle diameter of the ceramic fine particles 12A is set to 40 nm or less and 10 nm or more. It was also found that higher characteristics can be obtained if the maximum particle size of the fine particles 12A is 50 nm or less.
- It can be used for light emitting devices such as LEDs.
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Abstract
Description
平均粒子径20nm、最大粒子径50nmの酸化イットリウム(Y2O3)よりなるセラミックス微粒子12Aを有機溶媒に分散させたものに、平均粒子径が10μm程度の緑色系の蛍光体粒子11を混合してスラリーを調製した(ステップS101)。次いで、ロータリーエバポレーターを用い、このスラリーを減圧蒸発乾燥法により乾燥させ、有機溶媒を除去した(ステップS102)。その際、スラリーを収納した容器を回転させることによりスラリーを撹拌しながら乾燥させた。続いて、乾燥させた粉末、すなわちセラミックス微粒子12Aを付着させた蛍光体粒子11を窒素雰囲気中において400℃で2時間熱処理した(ステップS103)。そののち、得られた粉末、すなわち被覆層12を形成した蛍光体粒子11について、同様にしてスラリーの調製(ステップS101)、乾燥(ステップS102)、熱処理(ステップS103)をもう1回繰り返し、蛍光体材料10を得た。得られた蛍光体材料10について、原料に用いた蛍光体粒子11の収率を調べたところ、95%以上であった。なお、収率は、収率=処理後の総重量/(処理前の蛍光体粒子重量+セラミックス微粒子の重量)により求めた。
スラリーを噴霧乾燥により乾燥させたことを除き、他は実施例1と同様にして蛍光体材料を作製した。得られた蛍光材料について、原料に用いた蛍光体粒子の収率を調べたところ、約70%であった。
スラリーを自然乾燥により乾燥させたことを除き、他は実施例1と同様にして蛍光体材料を作製した。比較例1-2では、実施例1と同量のスラリーを乾燥させるのに、実施例1の10倍以上の時間がかかった。
実施例1により作製した蛍光体材料10を用い、図3に示したような発光装置20を作製した。発光素子22には紫外光を発するものを用いた。
熱処理を酸化雰囲気中(大気雰囲気中)において行ったことを除き、他は実施例1と同様にして蛍光体材料10を作製し、実施例2-1と同様にして、発光装置20を作製した。
蛍光体粒子に被覆層を形成せずに、そのまま蛍光体材料として用い、実施例2-1と同様にして発光装置を作製した。
実施例2-1,2-2及び比較例2の各発光装置20について、発光試験を行い、輝度の経時変化を調べた。得られた結果を表2に示す。表2において、相対輝度というのは、被覆層を形成していない比較例2の初期輝度を100%とした場合の相対値である。
セラミックス微粒子12Aの平均粒子径及び最大粒子径を変化させたことを除き、他は実施例1と同様にして蛍光体材料10を作製し、実施例2-1と同様にして発光装置20を作製した。実施例3-1では平均粒子径が40nm、最大粒子径が50nm、実施例3-2では平均粒子径が30nm、最大粒子径が50nm、実施例3-3では平均粒子径が25nm、最大粒子径が50nm、実施例3-4では平均粒子径が20nm、最大粒子径が40nm、実施例3-5では平均粒子径が15nm、最大粒子径が40nmのセラミックス微粒子12Aを用いた。得られた発光装置20について実施例2-1と同様にして発光試験を行い、輝度の経時変化を調べた。得られた結果を実施例2-1及び比較例2の結果と共に表3に示す。表3において、2000時間後の輝度維持率というのは、被覆層を形成していない比較例2の初期輝度を100%とした場合の相対値である。
Claims (9)
- 蛍光体粒子の表面に被覆層を有する蛍光体材料の製造方法であって、
蛍光体粒子と、セラミックス微粒子と、液体とを含むスラリーを減圧蒸発乾燥法により乾燥させ、液体を除去することにより、蛍光体粒子の表面に被覆層を形成することを特徴とする蛍光体材料の製造方法。 - 前記スラリーを乾燥させたのち、不活性ガス雰囲気中において熱処理することを特徴とする請求項1記載の蛍光体材料の製造方法。
- 前記熱処理は、窒素及び長周期表第18族元素からなる群のうちの少なくとも1種を含む不活性ガス雰囲気中において行うことを特徴とする請求項2記載の蛍光体材料の製造方法。
- 前記スラリーを乾燥させる際に、スラリーを撹拌することを特徴とする請求項1記載の蛍光体材料の製造方法。
- 前記スラリーを乾燥させる際に、ロータリーエバポレーター又はフラッシュエバポレーターを用いることを特徴とする請求項1記載の蛍光体材料の製造方法。
- 前記セラミックス微粒子の平均粒径を40nm以下とすることを特徴とする請求項1記載の蛍光体材料の製造方法。
- 前記セラミックス微粒子は、希土類酸化物,酸化ジルコニウム,酸化チタン,酸化亜鉛,酸化アルミニウム,イットリウムとアルミニウムの複合酸化物,酸化マグネシウム及びアルミニウムとマグネシウムの複合酸化物からなる群のうちの少なくとも1種の金属酸化物を含むことを特徴とする請求項1記載の蛍光体材料の製造方法。
- 蛍光体粒子の表面に被覆層を有する蛍光体材料であって、
蛍光体粒子と、セラミックス微粒子と、液体とを含むスラリーを減圧蒸発乾燥法により乾燥させ、液体を除去することにより、蛍光体粒子の表面に被覆層が形成されたことを特徴とする蛍光体材料。 - 蛍光体材料を含む発光装置であって、
前記蛍光体材料は、蛍光体粒子の表面に被覆層を有し、
前記被覆層は、蛍光体粒子と、セラミックス微粒子と、液体とを含むスラリーを減圧蒸発乾燥法により乾燥させ、液体を除去することにより、蛍光体粒子の表面に形成された
ことを特徴とする発光装置。
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