WO2022209178A1 - ユウロピウム賦活β型サイアロン蛍光体、及び発光装置 - Google Patents
ユウロピウム賦活β型サイアロン蛍光体、及び発光装置 Download PDFInfo
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- WO2022209178A1 WO2022209178A1 PCT/JP2022/001816 JP2022001816W WO2022209178A1 WO 2022209178 A1 WO2022209178 A1 WO 2022209178A1 JP 2022001816 W JP2022001816 W JP 2022001816W WO 2022209178 A1 WO2022209178 A1 WO 2022209178A1
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- europium
- light
- activated
- phosphor
- sialon
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- 229910052693 Europium Inorganic materials 0.000 claims abstract description 79
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229910052796 boron Inorganic materials 0.000 claims abstract description 36
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 35
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 91
- 238000000137 annealing Methods 0.000 description 62
- 238000010438 heat treatment Methods 0.000 description 56
- 238000000034 method Methods 0.000 description 39
- 239000000203 mixture Substances 0.000 description 33
- 229910003564 SiAlON Inorganic materials 0.000 description 29
- 238000010304 firing Methods 0.000 description 28
- 238000011156 evaluation Methods 0.000 description 26
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- 150000001875 compounds Chemical class 0.000 description 19
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- 230000005284 excitation Effects 0.000 description 15
- 239000002994 raw material Substances 0.000 description 14
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- 239000012298 atmosphere Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 229910052581 Si3N4 Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 11
- 239000013078 crystal Substances 0.000 description 10
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- 239000000047 product Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 6
- -1 aluminum compound Chemical class 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 6
- 150000002178 europium compounds Chemical class 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 150000004767 nitrides Chemical class 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 229910052582 BN Inorganic materials 0.000 description 5
- 238000010306 acid treatment Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 229910001940 europium oxide Inorganic materials 0.000 description 5
- 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 5
- 230000004907 flux Effects 0.000 description 5
- 238000004020 luminiscence type Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
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- 238000003756 stirring Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- 230000001186 cumulative effect Effects 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
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- 239000012299 nitrogen atmosphere Substances 0.000 description 3
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- 150000003377 silicon compounds Chemical class 0.000 description 3
- 229920002050 silicone resin Polymers 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229920000995 Spectralon Polymers 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- PSBUJOCDKOWAGJ-UHFFFAOYSA-N azanylidyneeuropium Chemical compound [Eu]#N PSBUJOCDKOWAGJ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
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- 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
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
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- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
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- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
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- 239000012153 distilled water Substances 0.000 description 1
- 238000010332 dry classification Methods 0.000 description 1
- DPYXWFUVSMSNNV-UHFFFAOYSA-L europium(2+);diiodide Chemical compound [I-].[I-].[Eu+2] DPYXWFUVSMSNNV-UHFFFAOYSA-L 0.000 description 1
- QEDFUJZRPHEBFG-UHFFFAOYSA-K europium(3+);tribromide Chemical compound Br[Eu](Br)Br QEDFUJZRPHEBFG-UHFFFAOYSA-K 0.000 description 1
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
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- 150000004679 hydroxides Chemical class 0.000 description 1
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- 238000000691 measurement method Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
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- 230000003595 spectral effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- HPNURIVGONRLQI-UHFFFAOYSA-K trifluoroeuropium Chemical compound F[Eu](F)F HPNURIVGONRLQI-UHFFFAOYSA-K 0.000 description 1
- 238000005303 weighing 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
- C09K11/08—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
- C09K11/7734—Aluminates
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
-
- 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
-
- 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 disclosure relates to europium-activated ⁇ -sialon phosphors and light-emitting devices.
- Oxynitride phosphors are known as phosphors with excellent durability, with a small decrease in brightness due to temperature rise.
- europium-activated ⁇ -sialon is known as a green phosphor that can be excited by ultraviolet light, visible light, or the like.
- a ⁇ -sialon phosphor can be obtained, for example, by heating a raw material mixture containing silicon nitride powder, aluminum nitride powder, and europium oxide powder in a nitrogen atmosphere.
- the improvement of brightness is also being studied.
- Patent Document 1 a first heat treatment step of obtaining a first heat-treated product by heat-treating a mixture containing an aluminum compound, a first europium compound, and silicon nitride, and a first heat-treated product and a second europium and a second heat treatment step of heat-treating the compound in a noble gas atmosphere to obtain a second heat-treated product.
- Patent Document 2 discloses a firing process for obtaining a fired product by firing a raw material mixture of a ⁇ -sialon phosphor at a temperature of 1820° C. to 2200° C. in a nitrogen atmosphere, and a firing process in which the fired product is heated to 1100° C.
- a method for producing a ⁇ -sialon phosphor has been proposed, which includes an annealing step of annealing at the above temperature.
- the optical performance of phosphors is evaluated mainly based on the absorption of irradiated light, quantum efficiency, etc., but these are mainly evaluations of powder.
- phosphors used in light-emitting devices and the like are in a state of being dispersed in a transparent sealing resin or the like, and the environments and densities in which the phosphors are placed are different. Therefore, there may be cases where the two evaluations do not match, such as when the effect expected from the evaluation of the phosphor, which is performed on powder, is not sufficiently exhibited when the phosphor is dispersed in the cured resin.
- the purpose of the present disclosure is to provide a europium-activated ⁇ -SiAlON phosphor that is excellent in external quantum efficiency in powder evaluation and in luminescence properties when dispersed in a curable resin and molded into a sheet.
- One aspect of the present disclosure provides a europium-activated ⁇ -sialon phosphor containing boron and having a boron content of 60 to 500 ppm.
- the above europium-activated ⁇ -sialon phosphor exhibits excellent external quantum efficiency as a powder by containing a predetermined amount of boron, and exhibits excellent luminous properties when dispersed in a cured resin and formed into a sheet. can be demonstrated.
- the boron content may be 100-350 ppm.
- the europium-activated ⁇ -sialon phosphor may have an absorptance of 6.0% or less for light with a wavelength of 600 nm.
- the europium-activated ⁇ -SiAlON phosphor is a green phosphor, and its external quantum efficiency can be further improved by suppressing absorption on the longer wavelength side than the green fluorescence of about 525 nm.
- One aspect of the present disclosure is a light-emitting device that includes a light-emitting element that emits primary light, and a wavelength converter that absorbs part of the primary light and emits secondary light having a longer wavelength than the primary light. and the wavelength converter includes the europium-activated ⁇ -SiAlON phosphor described above.
- the light-emitting device has excellent luminous efficiency because it contains the europium-activated ⁇ -sialon phosphor as a wavelength converter.
- a europium-activated ⁇ -SiAlON phosphor that is excellent in external quantum efficiency in powder evaluation and in luminescence properties when dispersed in a curable resin and molded into a sheet.
- FIG. 1 is a schematic diagram for explaining a measuring method for sheet evaluation.
- each component in the composition means the total amount of the multiple substances present in the composition unless otherwise specified when there are multiple substances corresponding to each component in the composition. .
- the europium-activated ⁇ -sialon phosphor contains boron.
- the europium-activated ⁇ -sialon phosphor may contain ⁇ -sialon as a main crystal, or may be composed of ⁇ -sialon.
- the europium-activated ⁇ -SiAlON phosphor may contain a heterophase within the scope of the present disclosure.
- the europium-activated ⁇ -SiAlON phosphor may have a composition represented by the composition formula Si 6-Z AlZO ZN 8-Z : Eu. In the above composition formula, z may be 0.0 ⁇ z ⁇ 4.2 or 0.0 ⁇ z ⁇ 0.5.
- the composition of the europium-activated ⁇ -SiAlON phosphor can be adjusted by changing the components and composition ratios of the raw material composition when producing the phosphor.
- the contents of nitrogen atoms (N) and oxygen atoms (O) can be quantified by an oxygen-nitrogen analyzer. ), and the content of boron (B) can be quantitatively analyzed using an ICP emission spectrometer.
- the content of boron in the europium-activated ⁇ -sialon phosphor is 60 to 500 ppm.
- the europium-activated ⁇ -SiAlON phosphor according to the present disclosure is excellent in both external quantum efficiency in powder evaluation and luminescence properties when dispersed in a cured resin and formed into a sheet. Although the reason why such an effect is obtained is not necessarily clear, the present inventors presume as follows. That is, in the europium-activated ⁇ -SiAlON phosphor according to the present disclosure, the defects are eliminated by filling the vacancies that become defects in the phosphor generated in the production of the phosphor with a predetermined amount of boron ions. In the sheet evaluation, it is presumed that the energy loss due to absorption that does not contribute to the conversion of light is reduced, resulting in excellent luminescence properties.
- the lower limit of the boron content may be, for example, 80 ppm or more, 90 ppm or more, or 100 ppm or more based on the total amount of the europium-activated ⁇ -sialon phosphor.
- the upper limit of the boron content may be, for example, 450 ppm or less, 400 ppm or less, or 350 ppm or less based on the total amount of the europium-activated ⁇ -sialon phosphor.
- the upper limit of the boron content is within the above range, it is possible to suppress the generation of a heterogeneous phase derived from excessively added boron and suppress the generation of non-light-emitting components, so that the europium-activated ⁇ -sialon phosphor emits light A decrease in characteristics can be suppressed.
- the boron content may be adjusted within the above range, and may be, for example, 100 to 350 ppm based on the total amount of the europium-activated ⁇ -sialon phosphor.
- the boron content in the obtained phosphor is less than 60 ppm when a separate boron source is not added. Typically, it is often around 50 ppm.
- the 50% cumulative diameter (D50) in the volume-based cumulative particle size distribution of the europium-activated ⁇ -sialon phosphor may be adjusted according to the use of the phosphor.
- the 50% cumulative diameter (D50) in volume-based cumulative particle size distribution of the europium-activated ⁇ -SiAlON phosphor may be, for example, 0.1 to 50 ⁇ m, 3 to 40 ⁇ m, or 6 to 30 ⁇ m.
- D50 can be controlled, for example, by adjusting conditions such as heating temperature and heating time during phosphor production, and by classification.
- D50 in this specification refers to the particle diameter when the integrated value from the small particle diameter reaches 50% of the total in the volume-based particle diameter distribution curve measured by the laser diffraction/scattering method.
- the distribution curve for the particle size of the phosphor conforms to the particle size distribution measurement method by the laser diffraction/scattering method described in JIS R 1629: 1997 "Method for measuring particle size distribution of fine ceramic raw materials by laser diffraction/scattering method". conduct.
- a particle size distribution analyzer can be used for the measurement.
- 0.1 g of the phosphor to be measured is put into 100 mL of ion-exchanged water, a small amount of sodium hexametaphosphate is added, and dispersion treatment is performed for 3 minutes using an ultrasonic homogenizer.
- a sample is used, and the particle size is measured using a particle size distribution analyzer, and D50 is determined from the obtained particle size distribution.
- D50 also called median diameter, means the average particle size of the particles of interest.
- the particle size distribution measuring device for example, "Microtrac MT3300EX II" (product name) manufactured by Microtrac Bell Co., Ltd. can be used.
- ultrasonic homogenizer for example, "Ultrasonic Homogenizer US-150E” manufactured by Nippon Seiki Co., Ltd. (product name, chip size: ⁇ 20, amplitude: 100%, oscillation frequency: 19.5 kHz, amplitude: about 31 ⁇ m) is used. can.
- the europium-activated ⁇ -sialon has a suppressed absorptivity for light with a wavelength of 600 nm.
- the absorption of europium in the phosphor with respect to light with a wavelength of 600 nm is small, and the wavelength is less affected by fluorescence generated from the phosphor. Therefore, when the absorptance for light with a wavelength of 600 nm is high, it is considered that the absorption is due to defects or a different phase that is a non-light-emitting component.
- the absorptivity for light with a wavelength of 600 nm can be 6.0% or less.
- the europium-activated ⁇ -SiAlON phosphor has suppressed absorption of light with a wavelength of 600 nm, and is less affected by defects and heterogeneous phases that are non-light-emitting components, and thus can be superior in external quantum efficiency.
- the external quantum efficiency of the europium-activated ⁇ -SiAlON phosphor can be, for example, 63% or more, or 64% or more.
- the light absorptance and quantum efficiency in this specification mean the quantum efficiency obtained when a phosphor is excited with blue light having a wavelength of 455 nm.
- the external quantum efficiency is specifically measured by the method described in the examples of this specification.
- the europium-activated ⁇ -SiAlON phosphor not only has excellent external quantum efficiency in powder evaluation, but also has excellent light-emitting properties when dispersed in a cured resin and molded into a sheet. More specifically, when the sheet containing the europium-activated ⁇ -SiAlON phosphor and the curable resin is irradiated with light having a wavelength of 455 nm, a larger amount of light than the conventional europium-activated ⁇ -SiAlON phosphor A luminous flux (unit: lm) can be produced. Therefore, when the europium-activated ⁇ -SiAlON phosphor according to the present disclosure is used, it is possible to prepare a light-emitting device that is brighter than a conventional phosphor, which is practically useful.
- the europium-activated ⁇ -SiAlON phosphor may be used alone or in combination with other phosphors. Since the europium-activated ⁇ -sialon phosphor is excellent in internal quantum efficiency, it can be suitably used for light-emitting devices such as LEDs.
- the phosphor may be dispersed in the cured resin and used.
- the curable resin is not particularly limited, and for example, a resin used as a sealing resin for light emitting devices or the like can be used.
- An embodiment of a light-emitting device includes a light-emitting element that emits primary light, and a wavelength converter that absorbs part of the primary light and emits secondary light having a longer wavelength than the primary light. It is a device.
- the wavelength converter contains the europium-activated ⁇ -SiAlON phosphor described above.
- a light-emitting element that emits primary light may be, for example, an InGaN blue LED or the like.
- the light emitting element and the wavelength converter may be dispersed in a sealing resin or the like.
- the encapsulating resin is desirably colorless per se, and one having excellent transparency to visible light wavelengths can be used.
- a sealing resin that is generally recognized to be transparent can be used. Examples of the resin as described above include silicone resin and acrylic resin.
- the europium-activated ⁇ -sialon phosphor according to the present disclosure can be produced, for example, by the following method.
- a method for producing a europium-activated ⁇ -SiAlON phosphor a raw material composition containing a silicon source, an aluminum source, and a europium source, and containing at least one of them as a nitride, is subjected to one or more heat treatments.
- a step of obtaining a sintered body containing ⁇ -sialon from (hereinafter also referred to as a sintering step);
- the method may include a step (hereinafter also referred to as an annealing step) of obtaining an annealed body from a mixture containing the fired body and a compound containing boron as a constituent element by annealing. This example will be described below.
- the raw material composition contains a compound having elements that are constituent elements of the europium-activated ⁇ -sialon, and contains at least a silicon source, an aluminum source, and a europium source. At least one of the silicon source, aluminum source, and europium source in the raw material composition is a nitride.
- the nitride is also a nitrogen source because it contains nitrogen which is a constituent element of the europium-activated ⁇ -sialon.
- the silicon source means a compound or element containing silicon as a constituent element
- the aluminum source means a compound or element containing aluminum as a constituent element
- the europium source means a compound or element containing europium as a constituent element.
- a compound containing silicon as a constituent element is also called a silicon compound
- a compound containing aluminum as a constituent element is also called an aluminum compound
- a compound containing europium as a constituent element is also called a europium compound.
- Silicon compounds, aluminum compounds and europium compounds can each be nitrides, oxides, oxynitrides and hydroxides.
- the raw material composition may further contain ⁇ -sialon or europium-activated ⁇ -sialon.
- the ⁇ -sialon or the europium-activated ⁇ -sialon is an aggregate or core material.
- silicon compounds include silicon nitride (Si 3 N 4 ) and silicon oxide (SiO 2 ).
- Silicon nitride having a high ⁇ fraction is preferably used.
- the ⁇ fraction of silicon nitride may be, for example, 80% by mass or more, 90% by mass or more, or 95% by mass or more.
- primary grain growth can be promoted.
- Silicon nitride having a low oxygen content is preferably used.
- the oxygen content of silicon nitride may be, for example, 3.0% by weight or less, or 1.3% by weight or less. When the oxygen content of silicon nitride is within the above range, the occurrence of defects in the crystal of ⁇ -sialon can be suppressed.
- aluminum compounds examples include aluminum nitride (AlN), aluminum oxide (Al 2 O 3 ), and aluminum hydroxide (Al(OH) 3 ).
- Europium compounds include, for example, europium oxide (europium oxide), europium nitride (europium nitride), and europium halide.
- europium halides include europium fluoride, europium chloride, europium bromide, and europium iodide.
- the europium compound preferably comprises europium oxide.
- the valence of europium in the europium compound may be divalent or trivalent, preferably divalent.
- the raw material mixture can be prepared by weighing and mixing each compound. Dry mixing or wet mixing may be used for mixing.
- the dry mixing method may be, for example, a method of mixing each component using a V-type mixer or the like.
- the wet mixing method may be, for example, a method of adding a solvent such as water or a dispersion medium to prepare a solution or slurry, mixing the components, and then removing the solvent or dispersion medium.
- the heating temperature in the firing step may be, for example, 1800-2500°C, 1800-2400°C, 1850-2100°C, 1900-2100°C, 1900-2050°C, or 1920-2050°C.
- the heating temperature in the firing step may be, for example, 1800-2500°C, 1800-2400°C, 1850-2100°C, 1900-2100°C, 1900-2050°C, or 1920-2050°C.
- the heating time in the firing step is preferably long from the viewpoint of promoting the growth of primary particles of ⁇ -sialon, but if the heating time is too long, crystal defects may increase. , or 5 to 20 hours.
- the raw material mixture in the firing step may be heated, for example, under a nitrogen atmosphere. Decomposition of silicon nitride at high temperatures can be suppressed by heating under conditions of high nitrogen partial pressure. Moreover, grain growth can be accelerated by processing at a high temperature.
- the raw material mixture in the firing step may be heated under pressure, for example.
- the pressure at this time is, for example, 0.01 to 200 MPaG, 0.02 to 200 MPaG, 0.1 to 200 MPaG, 0.1 to 100 MPaG, 0.1 to 50 MPaG, 0.1 to 15 MPaG, or 0.1 to 5 MPaG. can be
- the number of heat treatments in the firing step may be one, but may be, for example, two or more, two to five, or two to four.
- a europium-activated ⁇ -sialon phosphor with more excellent emission intensity can be obtained by performing the heat treatment a plurality of times.
- the firing step one or more heat treatments are performed, but when heat treatments are performed multiple times, they are called first heat treatment, second heat treatment, etc., and the steps of performing each heat treatment are sequentially referred to as the first firing step. , the second firing step, and the like.
- the firing step includes a step of first heat-treating a raw material composition containing a nitride to obtain a first heat-treated body; It is also said to include a second firing step of obtaining a second heat-treated body by subjecting the first heat-treated body to a second heat-treatment.
- the second heat-treated body corresponds to the fired body containing ⁇ -sialon.
- the silicon source, the aluminum source, and the europium source may be further mixed and heat-treated before heat-treating multiple times.
- the heating temperature, heating time, atmosphere during heating, and pressure during heating in the first firing step are the same as the heating temperature, heating time, and heating time in the above-described heating step. atmosphere and pressure during heating can be applied.
- the heating temperature, heating time, atmosphere during heating, and pressure during heating in and after the second firing step may be the same as or different from those in the first firing step. However, even if the heating temperature, heating time, atmosphere during heating, and pressure during heating in the second and subsequent firing steps are different from those in the first firing step, they are within the range of the conditions shown for the above heating step. shall be
- the sintered body obtained in the sintering process has crystals of ⁇ -sialon, and is a solid solution in which an element that serves as a luminescence center is dissolved in a part of the crystal, and itself can emit fluorescence.
- the sintered body obtained by the sintering step may be lumpy, and the particle size may be adjusted by pulverization or the like prior to the annealing step.
- the annealing step in the manufacturing method of this example means a step of annealing a mixture containing the fired body obtained in the above-described firing step and a compound having boron as a constituent element.
- an annealed body is obtained from the mixture by one or more heat treatments.
- Compounds containing boron as a constituent element may be, for example, oxides, nitrides, oxoacids, etc., preferably oxoacids.
- Compounds containing boron as a constituent element may be, for example, boron oxide (B 2 O 3 ), boron nitride (BN), and boric acid (H 3 BO 3 ).
- the compounding amount of the compound having boron as a constituent element is, for example, 0.05 to 0.70% by mass, 0.07 to 0.65% by mass, or 0.08 to 0.60% with respect to the total amount of the mixture. % by mass.
- the amount By setting the amount to be 0.05% by mass or more, boron can be more easily introduced into the phosphor, and the external quantum efficiency of the obtained europium-activated ⁇ -SiAlON phosphor can be further improved.
- By setting the blending amount to 0.70% by mass or less it is possible to suppress deterioration in the emission characteristics of the resulting europium-activated ⁇ -sialon phosphor. Since the composition ratio of boron varies depending on the type of compound containing boron as a constituent element, the preferred blending amount can be adjusted within the above range.
- the annealing process is performed in an atmosphere containing at least one selected from the group consisting of rare gases, reducing gases, and inert gases.
- an atmosphere containing a rare gas, a reducing gas, or an inert gas By performing the annealing treatment in an atmosphere containing a rare gas, a reducing gas, or an inert gas, the proportion of divalent europium in europium in the solid solution can be increased.
- the rare gas may contain, for example, argon and helium, may contain argon, or may consist of argon.
- the reducing gas may contain, for example, ammonia, hydrocarbons, carbon monoxide, hydrogen, or the like, and may contain or consist of hydrogen.
- the inert gas may contain, for example, nitrogen or may consist of nitrogen.
- the atmosphere of the annealing step may be a mixed gas of two or more of the rare gas, the reducing gas, and the inert gas. When the atmosphere of the annealing step is the mixed gas, the content of the reducing gas may be, for example, 1 to 50% by volume, or 4 to 20% by volume based on the total volume of the mixed gas.
- the content of the inert gas may be, for example, 1 to 50% by volume, or 4 to 20% by volume, based on the total volume of the mixed gas.
- the volumes of the reducing gas, the inert gas and the mixed gas mentioned above are values based on the volume under standard conditions.
- the pressure during the annealing treatment may be the same as the pressure in the firing process, but is preferably lower than the pressure conditions in the firing process, more preferably atmospheric pressure.
- the temperature of the annealing treatment must be set lower than the heating temperature in the firing process.
- the upper limit of the annealing temperature may be, for example, 1700° C. or lower, or 1680° C. or lower. By setting the upper limit of the annealing temperature within the above range, it is possible to prevent further grain growth in the sintered body, aggregation between the solid solutions, formation of secondary particles, and coarsening of the grains.
- the lower limit of the annealing temperature may be, for example, 1000° C. or higher, 1100° C. or higher, 1200° C. or higher, 1300° C. or higher, or 1400° C. or higher.
- the crystal defect density of the ⁇ -sialon contained in the annealed body can be reduced, and the quantum efficiency can be further improved.
- the temperature of the annealing treatment can be adjusted within the above range, and can be, for example, 1000-1700°C, or 1100-1680°C.
- the heating time in the annealing treatment may be, for example, 1 to 30 hours, 2 to 25 hours, or 3 to 20 hours from the viewpoint of further reducing crystal defects in the phosphor contained in the annealed body.
- the annealing step one or more annealing treatments are performed. When multiple annealing treatments are performed, they are called first annealing treatment, second annealing treatment, etc., and the steps of performing each annealing treatment are sequentially referred to as the first annealing step. , a second annealing step, and the like.
- the annealing step includes a step of first annealing the fired body to obtain a first annealed body, and the first annealing It is also said to include a second annealing step of obtaining a second annealed body by second annealing the processed body.
- the second annealed body corresponds to the annealed body described above.
- the annealing temperature, heating time, and heating pressure in the first annealing step are set to the annealing temperature, heating time, and heating pressure in the annealing step described above. Each pressure can be applied.
- the annealing temperature, heating time, and heating pressure in and after the second annealing step may be the same as or different from those in the first annealing step. However, even if the annealing temperature, heating time, and pressure during heating after the second annealing step are different from those in the first annealing step, they are within the range of the conditions shown for the annealing step above. do.
- the number of annealing treatments in the annealing step may be one time, but may be, for example, two or more times, two to five times, or two to four times. By performing multiple annealing treatments, it is possible to reduce the crystal defect density of the ⁇ -sialon contained in the annealed body and obtain a europium-activated ⁇ -sialon phosphor with more excellent quantum efficiency.
- the compound having boron as a constituent element may be mixed in the first annealing process all at once, or may be divided into multiple annealing processes and mixed. Good, but preferably combined together in the first annealing step.
- the explanation regarding the total blending amount of the compound having boron as a constituent element is applied by replacing it with the total amount of the compound having boron as a constituent element to be blended in a plurality of annealing steps. It shall be.
- the method for producing the europium-activated ⁇ -sialon phosphor may have other steps in addition to the firing step and the annealing step.
- Other steps include, for example, a step of treating the annealed body obtained in the annealing step with at least one of acid and alkali, a classification step of adjusting the particle size of the annealed body or the annealed body that has undergone acid treatment, etc. may have A process of treating the annealed body with an acid is called an acid treatment process, and a process of treating the annealed body with an alkali is called an alkali treatment process.
- the acid treatment step or the alkali treatment step for example, the crystal defect density in the phosphor contained in the annealed body is further reduced, the silicon present on the surface of the solid solution generated by thermal decomposition of ⁇ -sialon, etc. is removed, and the first It is possible to remove AlN polytypoid, which is a pseudo-polymorph of aluminum nitride (AlN), and the like, which is by-produced during the preparation of the sintered body.
- Acids may include, for example, hydrofluoric acid and nitric acid.
- the acid may be a mixed acid of hydrofluoric acid and nitric acid.
- Alkali may include, for example, sodium hydroxide and the like.
- the classification process may be performed, for example, by either a wet classification method or a dry classification method.
- wet classification for example, the annealed body is added to a mixed solvent containing ion-exchanged water and a dispersant (e.g., sodium hexametaphosphate, etc.), or a mixed solvent containing ion-exchanged water and aqueous ammonia, stirred, and then allowed to stand.
- a dispersant e.g., sodium hexametaphosphate, etc.
- An elutriation classification method for removing particles having a small particle size can be mentioned.
- a cylindrical boron nitride container with a lid (manufactured by Denka Co., Ltd., a molded product mainly composed of boron nitride (trade name: Denka Boron Nitride N-1), inner diameter: 10 cm, height: 10 cm) was prepared as described above. 200 g of the raw material composition was weighed. After that, the container was placed in an electric furnace equipped with a carbon heater, heated to 2020°C in a nitrogen gas atmosphere (pressure: 0.90 MPaG), and heated at a heating temperature of 2020°C for 8 hours ( firing process). After heating, loosely agglomerated masses in the container were taken in a mortar and crushed. After pulverization, it was passed through a sieve with an opening of 250 ⁇ m to obtain a powdery first fired body.
- the first fired body was filled in a cylindrical boron nitride container, and this container was placed in an electric furnace equipped with a carbon heater.
- the temperature was raised to 1450° C. in an argon gas atmosphere (pressure: 0.025 MPaG), and heating was performed at the heating temperature of 1450° C. for 3 hours (annealing step).
- argon gas atmosphere pressure: 0.025 MPaG
- heating was performed at the heating temperature of 1450° C. for 3 hours (annealing step).
- loosely aggregated masses of particles in the container were pulverized with a mortar and passed through a 250 ⁇ m sieve to obtain a powder.
- the obtained powder was mixed with a mixed acid of hydrofluoric acid (concentration: 50% by mass) and nitric acid (concentration: 70% by mass) (so that the volume ratio of hydrofluoric acid and nitric acid was 1:1). ) and acid-treated for 30 minutes while stirring at a temperature of 75°C. After the acid treatment, stirring was terminated and the powder was allowed to settle, and the supernatant and fine powder refined by the acid treatment were removed. After that, distilled water was further added and stirred again. Stirring was terminated, the powder was precipitated, and the supernatant and fine powder were removed. This operation was repeated until the pH of the aqueous solution was 8 or less and the supernatant liquid became transparent, and the resulting precipitate was filtered and dried to obtain a europium-activated ⁇ -SiAlON phosphor.
- Example 1 In the annealing step, boric acid is blended so that the blending amount of boric acid is 0.1% by mass with respect to the total amount of 100% by mass of the first fired body and boric acid (H 3 BO 3 ), and the mixture is was prepared, and a europium-activated ⁇ -SiAlON phosphor was obtained in the same manner as in Comparative Example 1, except that this was heated in a hydrogen gas atmosphere.
- Example 2 A europium-activated ⁇ -sialon phosphor was obtained in the same manner as in Example 1, except that the amount of boric acid was changed to 0.5% by mass.
- Comparative Example 3 A standard sample of ⁇ -SiAlON phosphor (NIMS Standard Green lot No. NSG1301 manufactured by SiAlON Co., Ltd.) was used as the phosphor of Comparative Example 3.
- the europium-activated ⁇ -SiAlON phosphor was dissolved by the pressure acid decomposition method to prepare a sample solution.
- Constituent elements including boron were measured by quantitatively analyzing the elements of the obtained sample solution using an ICP emission spectrometer (manufactured by Shimadzu Corporation, model: ICPE-9000).
- the absorptance (excitation light absorptivity), internal quantum efficiency and external quantum efficiency of the phosphor when irradiated with excitation light having a wavelength of 455 nm were calculated by the following procedure.
- the fluorescent substance to be measured was filled in a concave cell so as to have a smooth surface, and was attached to the opening of an integrating sphere.
- a monochromatic light having a wavelength of 455 nm from a Xe lamp as a light emission source was introduced into the integrating sphere as excitation light for the phosphor using an optical fiber.
- the fluorescent substance to be measured was irradiated with the monochromatic light, which is the excitation light, and the fluorescence spectrum was measured.
- a spectrophotometer manufactured by Otsuka Electronics Co., Ltd., model: MCPD-7000 was used for the measurement.
- the emission intensity of the phosphor was determined from the obtained fluorescence spectrum data. Also, the number of excitation reflected light photons (Qref) and the number of fluorescence photons (Qem) were calculated from the obtained fluorescence spectrum data. The number of reflected excitation light photons was calculated in the same wavelength range as the number of excitation light photons, and the number of fluorescence photons was calculated in the range of 465 to 800 nm. Using the same apparatus, a standard reflector plate with a reflectance of 99% (Spectralon (registered trademark) manufactured by Labsphere) was attached to the aperture of the integrating sphere, and the spectrum of excitation light with a wavelength of 455 nm was measured. At that time, the number of excitation light photons (Qex) was calculated from the spectrum in the wavelength range of 450 to 465 nm.
- the absorptivity of excitation light at 455 nm and the internal quantum efficiency of the fluorescent substance to be measured were obtained based on the following calculation formulas.
- Absorption rate of excitation light at 455 nm ((Qex-Qref)/Qex) x 100
- Internal quantum efficiency (Qem/(Qex-Qref)) x
- External quantum efficiency (Qem/Qex) x 100
- the relational expressions among the external quantum efficiency, the absorptance of excitation light at 455 nm, and the internal quantum efficiency can be expressed as follows.
- External quantum efficiency 455 nm light absorption rate x internal quantum efficiency
- Chromaticity X is defined by JIS Z 8781-3:2016 "Colorimetry-Part 3: CIE tristimulus values” from spectral data in the wavelength range of 465 to 780 nm of the fluorescence spectrum.
- the CIE chromaticity coordinate x value was determined by measuring and calculating according to the method described in JIS Z 8724:2015 “Color measurement method-light source color”.
- ⁇ 600 nm light absorption rate> A standard reflector (Spectralon (registered trademark) manufactured by Labsphere) with a reflectance of 99% was set in the side opening of the integrating sphere.
- a monochromatic light having a wavelength of 600 nm from a light emission source (Xe lamp) was introduced into this integrating sphere through an optical fiber, and the reflected light spectrum was measured with a spectrophotometer (MCPD-7000 manufactured by Otsuka Electronics Co., Ltd.). At that time, the number of incident light photons (Qex(600)) was calculated from the spectrum in the wavelength range of 590 to 610 nm.
- the measured values for the absorptivity of the phosphor, internal quantum efficiency, external quantum efficiency, and chromaticity X may vary depending on the manufacturer of the measuring device, production lot number, etc. Therefore, as various measured values, values measured by the measuring method described in this specification are adopted. However, when the manufacturer of the measuring device, production lot number, etc. are changed, each measured value can be corrected using the measured value of the standard sample of the ⁇ -SiAlON phosphor described above as a reference value. As a standard sample for obtaining the reference value, the standard sample of the ⁇ -sialon phosphor given as Comparative Example 3 can be used.
- an evaluation sample was prepared according to the following procedure. 40 parts by mass of the europium-activated ⁇ -sialon phosphor and 60 parts by mass of silicone resin (manufactured by Dow Corning Toray Co., Ltd., trade name: OE-6630) are weighed into a container, and a rotation / revolution mixer (manufactured by Thinky Corporation , model: ARE-310) was used to prepare the mixture by stirring and defoaming. Stirring was performed at a rotation speed of 2000 rpm for 2 minutes and 30 seconds, and defoaming treatment was performed at a rotation speed of 2200 rpm for 2 minutes and 30 seconds.
- a rotation / revolution mixer manufactured by Thinky Corporation , model: ARE-310
- the mixture prepared as described above is dropped onto a transparent fluororesin film (trade name: NR5100-003:100P manufactured by Fron Chemical Co., Ltd.), and another fluororesin film is placed on top of the drop.
- a laminate was obtained in which a liquid film was formed between two fluororesin films.
- the thickness of the liquid film between the fluororesin films was adjusted by passing the laminate between two rollers provided with a predetermined gap.
- the gap between the rollers was set to a value obtained by adding 40 ⁇ m to twice the thickness of the fluororesin film.
- the laminate was heated at 150°C for 60 minutes to cure the silicone resin. After that, the two fluororesin films were peeled off to obtain a cured sheet as an evaluation sample.
- the resulting cured sheet had a thickness of 40 ⁇ 4 ⁇ m.
- FIG. 1 shows a schematic diagram for explaining a measuring method for sheet evaluation.
- the evaluation apparatus 200 includes a base 10, a light emitting element 30 provided in the center of the base 10, and a mounting table 20 provided on the base 10 so as to surround the light emitting element and for mounting an evaluation sample.
- An evaluation sample 100 was placed on the evaluation device 200 .
- a blue light emitting diode was used as the light emitting element 30, and the distance t between the blue light emitting diode and the lower surface of the evaluation sample was set to 2 mm.
- Excitation light with a wavelength of 455 nm is irradiated from below the evaluation sample 100, and the luminous flux Ig of light with a wavelength of 500 to 800 nm emitted from the upper surface (the main surface opposite to the light emitting element side) of the evaluation sample 100 is measured.
- a total luminous flux measurement system (model: HM-9030) manufactured by Otsuka Electronics Co., Ltd. was used to measure the luminous flux.
- the blue light emitting diode used for the measurement has a peak wavelength of 455 nm, a chromaticity x of 0.145 to 0.165, and a chromaticity y of 0.023 to 0.037 (product number: SMT type , PLCC-6, 0.2 W, SMD 5050 LED) was used.
- a europium-activated ⁇ -SiAlON phosphor that is excellent in external quantum efficiency in powder evaluation and in luminescence properties when dispersed in a curable resin and molded into a sheet.
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Abstract
Description
[ユウロピウム賦活β型サイアロン蛍光体の調製]
容器に、窒化ケイ素(Si3N4、α分率:95質量%、酸素含有量:1.3質量%)が96.0質量%、窒化アルミニウム(AlN)が2.8質量%、酸化アルミニウム(Al2O3)が0.5質量%、及び酸化ユウロピウム(Eu2O3)が0.7質量%となるように各原材料を測り取り、V型混合機(筒井理化学機械株式会社製)によって混合し、混合物を得た。得られた混合物を目開き250μmの篩を全通させ凝集物を取り除くことで、原料組成物を得た。篩を通らない凝集物は粉砕し、篩を通るように粒径を調整した。
アニール工程において、第一焼成体とホウ酸(H3BO3)の合計量100質量%に対してホウ酸の配合量が0.1質量%となるように、ホウ酸を配合して、混合物を調製したうえで、これを水素ガス雰囲気下で加熱したこと以外は、比較例1と同様にして、ユウロピウム賦活β型サイアロン蛍光体を得た。
ホウ酸の配合量を0.5質量%に変更したこと以外は、実施例1と同様にして、ユウロピウム賦活β型サイアロン蛍光体を得た。
ホウ酸の配合量を1.0質量%に変更したこと以外は、実施例1と同様にして、ユウロピウム賦活β型サイアロン蛍光体を得た。
β型サイアロン蛍光体の標準試料(株式会社サイアロン製、NIMS Standard Green lot No.NSG1301)を比較例3の蛍光体とした。
実施例1~2、及び比較例1~2で調製した各ユウロピウム賦活β型サイアロン蛍光体、並びに比較例3の蛍光体について、ホウ素の含有量を以下に示す方法で測定した。結果を表1に示す。
実施例1~2、及び比較例1~2で調製した各ユウロピウム賦活β型サイアロン蛍光体、並びに比較例3の蛍光体について、波長455nmの励起光を照射した場合の吸収率、内部量子効率、外部量子効率、色度X、並びに波長600nmの励起光を照射した場合の吸収率を、後述する方法で評価した。結果を表1に示す。
波長455nmの励起光を照射した場合の蛍光体の吸収率(励起光吸収率)、内部量子効率及び外部量子効率は、以下の手順で算出した。まず、測定対象である蛍光体を、凹型セルに表面が平滑になるように充填し、積分球の開口部に取り付けた。発光光源であるXeランプから455nmの波長に分光した単色光を、光ファイバーを用いて蛍光体の励起光として上記積分球内に導入した。この励起光である単色光を測定対象である蛍光体に照射し、蛍光スペクトルを測定した。測定には、分光光度計(大塚電子株式会社製、型式:MCPD-7000)を用いた。
455nmの励起光の吸収率=((Qex-Qref)/Qex)×100
内部量子効率=(Qem/(Qex-Qref))×100
外部量子効率=(Qem/Qex)×100
なお、上記式から外部量子効率と、455nmの励起光の吸収率、及び内部量子効率との関係式は以下のように表すことができる。
外部量子効率=455nm光吸収率×内部量子効率
色度Xは、蛍光スペクトルの465~780nmの範囲の波長域におけるスペクトルデータから、JIS Z 8781-3:2016「測色-第3部:CIE三刺激値」で規定されるXYZ表色系におけるCIE色度座標x値(色度X)をJIS Z 8724:2015「色の測定方法-光源色」に記載の方法に準拠して測定及び算出することで求めた。
積分球の側面開口部に反射率が99%の標準反射板(Labsphere社製スペクトラロン(登録商標))をセットした。この積分球に、発光光源(Xeランプ)から600nmの波長に分光した単色光を光ファイバーにより導入し、反射光スペクトルを分光光度計(大塚電子株式会社製MCPD-7000)により測定した。その際、590~610nmの波長範囲のスペクトルから入射光フォトン数(Qex(600))を算出した。
600nm光吸収率=((Qex(600)-Qref(600))/Qex(600))×100
実施例1~2、及び比較例1~2で調製した各ユウロピウム賦活β型サイアロン蛍光体、並びに比較例3の蛍光体を用いて、後述する方法でシート評価を行った。結果を表1に示す。
Claims (4)
- ホウ素を含有し、前記ホウ素の含有量が60~500ppmである、ユウロピウム賦活β型サイアロン蛍光体。
- 前記ホウ素の含有量が100~350ppmである、請求項1に記載のユウロピウム賦活β型サイアロン蛍光体。
- 波長600nmの光に対する吸収率が6.0%以下である、請求項1又は2に記載のユウロピウム賦活β型サイアロン蛍光体。
- 一次光を発する発光素子と、前記一次光の一部を吸収して、一次光の波長よりも長い波長を有する二次光を発する波長変換体と、を備える発光装置であって、
前記波長変換体が、請求項1~3のいずれか一項に記載のユウロピウム賦活β型サイアロン蛍光体を含む、発光装置。
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