CN108779394A - Fluorophor, light-emitting component and light-emitting device - Google Patents
Fluorophor, light-emitting component and light-emitting device Download PDFInfo
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- CN108779394A CN108779394A CN201780016758.6A CN201780016758A CN108779394A CN 108779394 A CN108779394 A CN 108779394A CN 201780016758 A CN201780016758 A CN 201780016758A CN 108779394 A CN108779394 A CN 108779394A
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- fluorophor
- light
- mass
- grand
- emitting component
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- 239000013078 crystal Substances 0.000 claims abstract description 26
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 19
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 18
- 230000004913 activation Effects 0.000 claims abstract description 10
- 230000004907 flux Effects 0.000 claims description 17
- 239000011164 primary particle Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 description 37
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- 230000000052 comparative effect Effects 0.000 description 35
- 238000004519 manufacturing process Methods 0.000 description 26
- 239000000843 powder Substances 0.000 description 23
- 239000011734 sodium Substances 0.000 description 17
- 239000002994 raw material Substances 0.000 description 15
- 239000012535 impurity Substances 0.000 description 14
- 238000004140 cleaning Methods 0.000 description 13
- 238000005245 sintering Methods 0.000 description 13
- 229910052731 fluorine Inorganic materials 0.000 description 11
- 238000012545 processing Methods 0.000 description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 10
- 238000010306 acid treatment Methods 0.000 description 10
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 8
- 229910052581 Si3N4 Inorganic materials 0.000 description 8
- 239000011737 fluorine Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 229910017083 AlN Inorganic materials 0.000 description 7
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 6
- 239000003566 sealing material Substances 0.000 description 6
- 239000011812 mixed powder Substances 0.000 description 5
- 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 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 4
- BHZCMUVGYXEBMY-UHFFFAOYSA-N trilithium;azanide Chemical compound [Li+].[Li+].[Li+].[NH2-] BHZCMUVGYXEBMY-UHFFFAOYSA-N 0.000 description 4
- 238000010333 wet classification Methods 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 229910052693 Europium Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910001940 europium oxide Inorganic materials 0.000 description 3
- 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 3
- 239000012530 fluid Substances 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910018509 Al—N Inorganic materials 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
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- 239000003595 mist Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 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 2
- 238000007789 sealing Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910007991 Si-N Inorganic materials 0.000 description 1
- 229910006294 Si—N Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 239000012700 ceramic precursor Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- -1 siloxanes Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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
- C09K11/77348—Silicon Aluminium Nitrides or Silicon Aluminium Oxynitrides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Luminescent Compositions (AREA)
- Led Device Packages (AREA)
Abstract
The present invention provides the light-emitting device that fluorescence intensity is high, few long-time is reduced using luminous efficiency and to reach the fluorophor of the purpose.The present invention provides Eu activation Li- α and matches grand system's fluorophor and have the light-emitting device of the fluorophor, wherein, which is that the total content that F contents are 20 mass ppm or less, P and Na is 10 mass ppm or less and α matches grand crystal phase for fluorophor that the ratio of holocrystalline phase is 95 mass % or more.
Description
Technical field
The present invention relates to fluorophor.Moreover, it relates to have the light-emitting component of fluorophor.In turn, the present invention relates to
Has the light-emitting device of light-emitting component.
Background technology
In the past, as the fluorophor for sending out orange-colored light, with general formula：CaxEuySi12-(m+n)Al(m+n)OnN16-nShown in, use
Ca2+Ca- α Sialon phosphors as the metal ion constructed to stable crystal are known, and light efficiency occurred frequently can be obtained
Rate (referring to patent document 1).Ca is used for having this2+α Sialon phosphors light-emitting device, long-time use the case where
Under, not generating the luminous efficiency of light-emitting device reduces this problem.
In contrast, being studied in recent years the short wavelengthization for improving brightness, fluorescence spectrum, it is proposed that use Li+
As making the Li- α Sialon phosphors (with reference to patent document 2 to 4) of the stabilized metal ion of crystal structure.Phase as a result,
Compared with the light-emitting device for using Ca- α Sialon phosphors, though improve the bright of light-emitting device by having Li- α Sialon phosphors
It spends, carry out short wavelengthization, but in the case of long-time use, the resin deterioration of the sealing material as LED encapsulation is former
Cause is considered as the ionization of the impurity element contained by fluorophor, and because above-mentioned resin deteriorates, there is shining for light-emitting device
Efficiency reduces such new problem (with reference to patent document 5).
On the other hand, about with a kind of α as red light-emitting phosphor match grand identical nitrogen oxides system fluorophor,
That is CASN systems fluorophor, as reported in patent document 6 to 7, by the halogen for containing the non-element for constituting crystalline phase
Prime element, and obtain high-luminous-efficiency, also it can be seen that the element other than constituting the element of crystalline phase not necessarily bring it is bad
Influence.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2002-363554 bulletins
Patent document 2：International Publication No. 2007/004493
Patent document 3：International Publication No. 2010/018873
Patent document 4：Japanese Unexamined Patent Publication 2010-202738 bulletins
Patent document 5：Japanese Unexamined Patent Publication 2009-224754 bulletins
Patent document 6：Japanese Unexamined Patent Publication 2010-18771 bulletins
Patent document 7：Japanese Unexamined Patent Application Publication 2012-512307 bulletins
Invention content
Problems to be solved by the invention
The characteristic improvement that grand system's fluorophor is matched as described previously for Li- α has carried out various researchs, but for because for a long time
Using and caused by luminous efficiency reduce, still there are improved spaces.The object of the present invention is to provide a kind of fluorescence intensities
High, few long-time is reduced using luminous efficiency light-emitting device and to reach the fluorophor of this purpose.
The solution to the problem
The scheme of the present invention is a kind of fluorophor, is that Eu activation Li- α match grand system's fluorophor, wherein F contents are
20 mass ppm are hereinafter, and the total content of P and Na is 10 mass ppm hereinafter, α matches grand crystal phase is for the ratio of holocrystalline phase
95 mass % or more.
In one embodiment of the fluorophor of the present invention, the total content of P and Na are 5 mass ppm or less.
In another embodiment of the fluorophor of the present invention, Li contents are 1.8 mass % or more and 3 mass % or less.
In another embodiment of the fluorophor of the present invention, Eu contents are 0.1 mass % or more and 1.5 mass % or less.
In another embodiment of the fluorophor of the present invention, O content is 0.4 mass % or more and 1.3 mass % or less.
In another embodiment of the fluorophor of the present invention, average primary particle diameter is 7 μm or more and 35 μm or less.
Another program of the present invention is a kind of light-emitting component, is had：The present invention fluorophor and to the fluorophor irradiate
The illuminating source of exciting light.
In one embodiment of the light-emitting component of the present invention, which is light emitting diode or laser diode.
In another embodiment of the light-emitting component of the present invention, under conditions of 85 DEG C of temperature and relative humidity 85%, lead to
Electric 150mA and place 1000 hours when luminous flux sustainment rate be 95% or more.
Another program of the present invention is a kind of light-emitting device, has the light-emitting component of the present invention.
The effect of invention
In the present invention, grand system's fluorophor is matched for Eu activation Li- α, α is improved and matches ratio of the grand crystal phase for holocrystalline phase
Example, and reduce the content of F, Na and P.By using the fluorophor of the present invention, can be obtained can obtain high fluorescent and i.e.
Make to reduce also few light-emitting device using luminous efficiency for a long time.
Specific implementation mode
The present invention in an arrangement, is related to Eu activation Li- α and matches grand system's fluorophor.Eu activates Li- α and matches grand system's fluorophor
In general, being with following formula：LixEuySi12-(m+n)Alm+nOnN16-n(x+y≤2, m=x+2y) compound represented it is glimmering
Body of light.In the fluorophor, a part for the Si-N keys of alpha silicon nitride crystal is replaced into Al-N keys and Al-O keys, in order to keep electricity
Neutrality, Li and Eu intrusions are solid-solution in the gap in crystal；M values, n values correspond respectively to the replacement rate to Al-N keys, Al-O keys.
Li is used in the present invention+, purpose be not be previous short wavelengthization, but compared to Ca2+The case where obtain more
High fluorescence intensity.α types match grand solid solution compositing range and are not only dissolved limiting for bit number of points by the stabilisation cation
System, also by thermodynamically stable limitation corresponding with cation is stabilized.Li+The case where, α types can be maintained to match the m of grand structure
It is worth range 0.5 or more and 2 hereinafter, n values range is 0 or more and 0.5 or less.If the Li contents in the fluorophor of the present invention are too
Few, then the Grain growth in fluorophor sintering step become very slowly, and with being difficult to obtain high fluorescent
The tendency of bulky grain；If excessive, have and generate LiSi2N3Deng the tendency of other phases, therefore preferably 1.8 mass % or more and 3 matter
Measure % or less.Li contents can be adjusted by being compounded the raw material of fluorophor.Specifically, raw material containing Li can be used as by increase and decrease
Lithium nitride, lithia mix ratio be adjusted.
If the Eu contents in the fluorophor of the present invention are very little, have for luminous contribution becomes smaller, fluorescence intensity is lower
Tendency；If too many, there is Eu2+Between energy transmission cause fluorescence intensity to be quenched and then cause what fluorescence intensity was lower to incline
To, therefore preferably 0.1 mass % or more and 1.5 mass % or less.Eu contents can be adjusted by being compounded the raw material of fluorophor.
Specifically, can be adjusted by the europium oxide that increases and decreases the raw material containing Eu, the mix ratio for nitrogenizing europium.
Oxygen (O) content in the fluorophor of the present invention is preferably 0.4 mass % or more and 1.3 mass % or less.This be because
For the very little fluorophor of oxygen content is in manufacturing step, and crystal grain-growth is few and is unable to get high fluorescent, if oxygen content is too
It is more, then fluorescence spectrum wide cut, and it is unable to get sufficient fluorescence intensity.
In order to obtain even if long-time using the fluorophor few reduction of luminous efficiency, in the impurity element of fluorophor
In, F contents are preferably in 20 mass ppm hereinafter, more preferably in 10 mass ppm hereinafter, in turn more preferably in 5 mass ppm hereinafter, example
Such as can be 1~20 mass ppm.As described in back segment, the α in order to improve fluorophor matches grand crystal percentage and promotes the characteristics of luminescence, right
It is effective that fluorophor, which carries out acid processing, but F is to be easy mixed element when acid is handled.Acid processing is only carried out to be difficult to fully carry
The characteristics of luminescence is risen, removal F is important for being continuously obtained for excellent luminous efficiency after carrying out sour processing.
In addition, in order to inhibit the luminous efficiency for the light-emitting device for having fluorophor to reduce and reduce electricity when long-time uses
The undesirable generation of performance, it is expected that the further total content of control P and Na.Specifically, the total content of P and Na is preferably 10 mass
Ppm hereinafter, more preferably 5 mass ppm hereinafter, even more preferably be 2 mass ppm hereinafter, for example, can be 1~5 mass ppm.
As described later, the characteristics of luminescence is promoted in order to improve the grand crystal percentage of α matches of fluorophor, the micro- of fluorophor is removed by being classified
Powder is effective.Classification can be used wet classification using calgon as dispersant, but such method be easy to be mixed into P and
Na.Therefore, it is difficult to fully promote the characteristics of luminescence in this case, only carrying out classification, Na and P is removed after being classified for continuing
Excellent luminous efficiency is obtained to be important.Mitigate the cleaning after classification step to further control P content and Na contents
The burden of process, the wet classification using basic solvent may be used in classification process, alternatively, it is also possible to be dry classification.
The fluorophor of the present invention, can be while keeping electroneutral for the purpose of finely tuning fluorescent characteristic, will be in the general formula
Part Li is replaced into selected from one or more of the group being made of Mg, Ca, Y and lanthanide series (not including La, Ce, Eu) displacement member
Element.Therefore, Eu is activated in the embodiment that Li- α match grand system's fluorophor, is replaced by a kind or more of above-mentioned substitutional element
Partial Li.
As long as the fluorophor of the present invention does not influence fluorescent characteristic, then as the crystalline phase being present in fluorophor, not only may be used
Including α matches are grand single-phase, it also may include the crystalline phase of silicon nitride, aluminium nitride, silicon nitride lithium and their solid solution etc..However, one
As for, it is preferably 95 mass % or more that the α in fluorophor, which matches grand ratio, more preferably 97 mass % or more, further more
Preferably 98 mass % or more, for example, can be 95~99 mass %.
If the average primary particle diameter of the fluorophor of the present invention is too small, the tendency being lower with fluorescence intensity, if too big
Coloration with the illuminant colour when fluorophor to be equipped on to the light-emitting surface of LED generates the tendency that uneven or illuminant colour generates color spot,
Therefore preferably 7 μm or more and 35 μm or less.Average primary particle diameter herein refers to the body obtained based on laser diffraction scattering method
The median particle diameter (D50) of product benchmark.
The fluorophor of the present invention can be carried out via the mixed processes of raw material, sintering circuit, acid treatment process and cleaning process
Manufacture.It is preferred that after acid treatment process, before or after cleaning process or front and back all implementation is classified process, is more preferably cleaning
Before process or front and back all implementation is classified process.
First, alpha-silicon nitride powders, aluminium nitride powder, europium oxide etc. are nitrogenized with desired ratio glimmering other than lithium powder
Body of light raw material mixes.If in view of the productivity of industry, preferably mixed by wet mixed.After wet mixed, pass through
Solvent, drying and crushing are removed, and obtains premixing powder.By this premixing powder and lithium powder is nitrogenized with desired ratio
Mixing, this makes it possible to obtain raw material mixed powder ends.In order to inhibit to hydrolyze, preferably mixed under nitrogen atmosphere etc..
By the way that the raw material mixed powder end to be sintered, it is grand that Eu activation Li- α matches can be obtained.As the crucible used in sintering,
It is preferred that being made of the material stablized under the atmosphere of high temperature, the preferred refractory metals system such as boron nitride system, carbon system, molybdenum or tantalum
Deng.As sintering atmosphere, there is no particular restriction, but is usually carried out under non-active gas atmosphere or reducing atmosphere.Non-active gas
Or reducibility gas can be used only a kind, can also in any combination and ratio combine use two or more.As non-active gas
Or reducibility gas, hydrogen, nitrogen, argon gas, ammonia etc. can be enumerated, wherein preferably in a nitrogen atmosphere.The pressure of sintering atmosphere
It can be selected according to sintering temperature.Atmosphere pressures are higher, and the decomposition temperature of fluorophor is higher, if but in view of the production of industry
Rate then preferably carries out under the pressurization of gauge pressure (gauge pressure) 0.02~1.0MPa or so.If sintering temperature is less than
1650 DEG C, then the crystal defect of parent crystal, unreacted residues quantitative change are more, and parent decomposes if more than 1900 DEG C, because without excellent
Choosing.Therefore, sintering temperature is preferably 1650~1900 DEG C.If sintering time is short, crystal defect, the unreacted of parent crystal are residual
Allowance is more, if sintering time is elongated, it is contemplated that when industrial productivity, then not preferably.It is therefore preferable that being 2~24 hours.Gained
Eu activation Li- α matches grand can be classified as desired granularity as needed.
For by be sintered obtained Eu activate Li- α match it is grand, it is however generally that, it is relatively low that α matches grand crystal area proportion, therefore is difficult to
Excellent fluorescence intensity is presented.It is therefore preferable that carry out sour processing with mixed liquor of hydrofluoric acid and nitric acid etc., with improve α match it is grand
Crystal area proportion.
As previously mentioned, if the grain size of fluorophor is too small, there is the tendency that fluorescence intensity is lower, it is therefore, high in order to obtain
The fluorophor of brightness is implemented preferably after acid treatment process to remove the classification process of micro mist.Wet type can be used in classification process
And dry type is any, but preferably elutriation (elutriation) classification or dry classification, elutriation classification is to stand fluorophor
In ion exchange water and the in the mixed solvent of the calgon as dispersant or the mixed base of ion exchange water and ammonium hydroxide
In property solvent.
By through peracid treatment and classification process, α can be improved and match grand crystal area proportion, if but with the mixed of hydrofluoric acid and nitric acid
Liquid etc. is closed to carry out sour processing, carry out elutriation classification processing with calgon, then the impurity such as F, Na and P are attached to fluorophor, it
Become impurity instead, become for a long time using rear luminous efficiency reduce the reason of.Therefore, by carrying out sour processing, elutriation
After classification processing, fluorophor is disperseed and cleaned with ultrasonic homogenizer in ion exchange water equal solvent, can so be had
Effect removal impurity.
Another program of the present invention is the light-emitting component with illuminating source and fluorophor, and the fluorophor is above-mentioned fluorescence
Body.As the illuminating source, preferably the peak strength of emission wavelength in 240nm or more and 480nm monochromatic LED below or
LD.This is because the peak wavelength of light source is to be used in actual use in 240nm or more and 480nm monochromatic light below
If the wavelength region of most blue leds can carry out having high fluorescence in addition, grand with the excitation Li- α matches of the wavelength of the range
Intensity shines.
The present invention light-emitting component in one embodiment, 85 DEG C of temperature and 85% relative humidity under conditions of,
Luminous flux sustainment rate when can make energization 150mA and place 1000 hours, can preferably 97% or more 95% or more
More preferably 98% or more, for example, can be 95~99%.
The yet another aspect of the present invention is the light-emitting device for having the light-emitting component.As light-emitting device, for example, can enumerate：
The device for display of message that signal, outdoor displaying device etc. use outdoors, and substitute automobile head lamp, incandescent lamp, fluorescent lamp
Lighting device.
The light-emitting component of the fluorophor and LED that have the present invention can for example manufacture as follows.First, by the fluorescence of the present invention
Body is mixed with sealing material, prepares slurry.For example, can be relative to 100 mass parts of sealing material with the ratio of 30~50 mass parts
It is mixed, to prepare slurry.As sealing material, for example, thermoplastic resin, thermosetting resin, photo-curable tree can be enumerated
Fat etc..Specifically, for example, can enumerate：The methacrylic resins such as polymethyl methacrylate；Polystyrene, styrene-
The styrene resins such as acrylonitrile copolymer；Polycarbonate resin；Polyester resin；Phenoxy resin；Butyral resin；Polyvinyl alcohol；
The cellulose-based resins such as ethyl cellulose, cellulose ethanoate, cellulose acetate butyrate；Epoxy resin；Phenolic resin；Have
Machine silicones etc..Alternatively, it is also possible to using inorganic based material, such as metal alkoxide, ceramic precursor will be made by sol-gal process
It is inorganic obtained from solution or combination thereof solidification made of solution hydrolysis of the polymer containing metal alkoxide closes
Based material, such as the inorganic based material with siloxanes key.In addition, if the sealing for being not directly contacted with LED chip and can be external
Portion's (for example, external cap, dome-type sealing etc.), then can also be used fusion method glass.It should be noted that sealing material
Can be used a kind, can also in any combination and ratio combine use two or more.
In sealing material, it is preferable to use with Thermocurable and having at normal temperatures the reasons why based on dispersibility, formability
The resin of mobility.As with the Thermocurable and at normal temperatures resin with mobility, such as organic siliconresin can be used.
For example, can enumerate：Dow Corning Toray Co., Ltd.s system, trade name：JCR6175,OE6631,OE6635,
OE6636, OE6650 etc..
Then, for example, being equipped with top view (top view) type in the 460nm blue LED dies with peak wavelength
In packaging body, 3~4 μ L of above-mentioned slurry are injected.This is filled with the top view type packaging body of slurry with the temperature of 140~160 DEG C of ranges
Degree was heated with 2~2.5 hours ranges, so that slurry curing.The range of 420~480nm of absorbing wavelength can so be manufactured
Light and release wavelength be more than 480nm and be 800nm light below light-emitting component.
Embodiment
Compare the embodiment of the present invention and comparative example, and is illustrated using table.
<Embodiment 1>
It is illustrated for the manufacturing method of the fluorophor of embodiment 1.Via the mixed processes of raw material, sintering circuit, system
Make fluorophor.
(mixed processes)
The raw material of the fluorophor of embodiment 1 is Si3N4(the emerging production corporation E10 grades in space portion), AlN (TOKUYAMA corporations
F grades), Eu2O3(chemical industrial company of SHIN-ETSU HANTOTAI RU grades), Li3N powder (99.5 mass % of Materion corporations purity ,-
60mesh).So that molar ratio is Si3N4：AlN：Eu2O3=84.5：14.8：0.64 mode, these raw materials of weighing, and into
Row mixing, and obtain premixing powder.
In a nitrogen environment, with the molal quantity (Si as premixing powder3N4, AlN and Eu2O3Total mole number)：Li3N
Molal quantity=94.1：The mode of 5.9 ratio, mixing premixing powder, obtains raw material mixed powder end.
(sintering circuit)
In glove box, aforementioned raw material mixed-powder is filled to the crucible of boron nitride, and in the electric furnace of carbon heater
It is interior, in the pressurized nitrogen atmosphere of gauge pressure 0.8MPa, sintering in 8 hours is carried out with 1800 DEG C, and it is grand to obtain Eu activation Li- α matches.
This Eu activation Li- α are matched into grand crushing using the Dry-crusher based on roller mill and jet pulverizer, and by its
The sieve of 45 μm of mesh is attached to make it through, it is classified.
(acid treatment process)
The sour processing of grand progress is matched to the Eu activation Li- α after classification with the mixed liquor (80 DEG C) of hydrofluoric acid and nitric acid.
(cleaning process)
Fluorophor after acid treatment process is mixed into ion exchange water equal solvent, its point is made in ultrasonic homogenizer
It dissipates 5 minutes, thus removes impurity.It is filtered later.
<Embodiment 2>
Embodiment 2 is in the manufacturing method of embodiment 1, the additional process below before cleaning process.
(wet classification process)
Fluorophor after acid treatment process is statically placed in the mixing of ion exchange water and the calgon as dispersant
10 minutes in solvent, micro mist is removed.By above process, the fluorophor of embodiment 2 is manufactured.
<Embodiment 3>
Embodiment 3 is the fluorophor made as follows：It is cleaned with ultrasonic homogenizer in the manufacturing method of embodiment 2
So that it is disperseed when process 1 hour, in addition to this, fluorophor is made with condition same as Example 2.
<Embodiment 4>
Embodiment 4 is the fluorophor made as follows：It is cleaned with ultrasonic homogenizer in the manufacturing method of embodiment 2
So that it is disperseed when process 2 hours, in addition to this, fluorophor is made with condition same as Example 2.
<Embodiment 5>
Embodiment 5 is the fluorophor made as follows：By in the manufacturing method of embodiment 2 to the fluorescence after acid treatment process
Body starts the cleaning processing in the in the mixed solvent of ion exchange water and the calgon as dispersant and is changed to hand in ion
It changes in the mixed-alkali solvent of water and ammonium hydroxide and starts the cleaning processing, in addition to this, fluorescence is made with condition same as Example 2
Body.
<Embodiment 6>
Embodiment 6 is the fluorophor made as follows：It is carried out before wet classification process in the manufacturing method of embodiment 5
In addition to this cleaning process makes fluorophor with condition same as Example 5.
<Comparative example 1>
Comparative example 1 is the substance made as follows：Acid treatment process and scavenger are omitted in the manufacturing process of embodiment 1
In addition to this sequence is manufactured with identical manufacturing method.
<Comparative example 2>
Comparative example 2 is the substance made as follows：Cleaning process is omitted in the manufacturing process of embodiment 1, in addition to this, with
Identical manufacturing method is manufactured.
<Comparative example 3>
Comparative example 3 is the substance made as follows：Acid treatment process and scavenger are omitted in the manufacturing process of embodiment 2
In addition to this sequence is manufactured with identical manufacturing method.
<Comparative example 4>
Comparative example 4 is the substance made as follows：Cleaning process is omitted in the manufacturing process of embodiment 2, in addition to this, with
Identical manufacturing method is manufactured.
<Comparative example 5>
Comparative example 5 is the substance made as follows：Acid treatment process is omitted in the manufacturing method of embodiment 2, in addition to this,
It is manufactured with identical manufacturing method.
<Comparative example 6>
Comparative example 6 is the substance made as follows：Cleaning process is omitted in the manufacturing method of embodiment 5, in addition to this, with
Identical manufacturing method is manufactured.
<Comparative example 7>
The point different from comparative example 4 of comparative example 7 is：By lithium nitride (Li3N) raw material is changed to nitridation calcium powder
(Ca3N2), manufacture Ca- α match grand system's fluorophor.It should be noted that the ratio of premixed powder is using molar ratio computing as silicon nitride powder
End：Aluminium nitride powder：Europium oxide powder=71.6：25.8：2.6 (molar ratios).The premixing powder is put under nitrogen atmosphere
Glove box in, so that it mix with nitridation calcium powder, and it is last to obtain raw material mixed powder.Mixing ratio is to be pre-mixed the molal quantity of powder
(Si3N4, AlN and Eu2O3Total mole number)：Nitrogenize molal quantity=87.1 of calcium powder：12.9.
(light-emitting component manufacturing process)
Relative to organic siliconresin (Dow Corning Toray Co., Ltd.s system, trade name：JCR6175 etc.) 100
Mass parts, with each fluorophor of the Examples and Comparative Examples after the ratio mixing cleaning process of 30 mass parts, to prepare slurry.It
Afterwards, 3~4 μ L injections of above-mentioned slurry are equipped with the top view type packaging body in the 460nm blue LED dies with peak wavelength.
This is filled with the heating in the range of the top view type packaging body of slurry is carried out 2 hours with 150 DEG C, makes slurry curing, with manufacture
Light-emitting component.
The evaluation of each fluorophor of Examples and Comparative Examples is shown in table 1.Table 1 shows impurity for Examples and Comparative Examples
Content (unit：Quality ppm), median particle diameter (unit：μm), α match ratio (unit of the grand crystal phase for holocrystalline phase：Matter
Measure %), peak wavelength (unit：Nm), fluorescence intensity (unit：%), the luminous flux sustainment rate (unit of LED：%).
(identification of crystalline phase and α match ratio of the grand crystal phase for holocrystalline phase)
For each fluorophor of Examples and Comparative Examples, X-ray diffraction device (Rigaku limited liability companies system is used
UltimaIV), by using the Alpha-ray powder x-ray diffractions of CuK (XRD), the identification of crystalline phase is carried out.Examples 1 to 6, ratio
It is considered diffraction pattern identical with the α grand crystal of match compared with the X-ray diffraction pattern of the fluorophor of gained in example 1~6, it is thus identified that main
Crystalline phase is that α matches are grand.In addition, matching the diffraction pattern of grand diffraction pattern and impurity crystalline phase based on α, calculates α and match grand crystal phase
For the mass ratio of holocrystalline phase.On the other hand, it in comparative example 7, is considered as α and matches grand diffraction pattern, it is thus identified that main knot
Crystalline phase is that α matches are grand.
(impurity content)
After so that fluorophor 0.5g/ water 25ml is dissolved out and is filtered with 100 DEG C × 12H, filled with ICP ICP Atomic Emission Spectrophotometers
It sets (Rigaku limited liability companies system, CIROS-120), analyzes the content of phosphorus, sodium and fluorine.
(median particle diameter (D50))
The median particle diameter (D50) (average primary particle diameter) of each fluorophor of Examples and Comparative Examples is measured with following main points.
First, with 1：1 mixing hydrofluoric acid (range of 46~48g/100ml of concentration) and nitric acid (concentration 60g/100ml), then with distilled water
4 times are diluted to, treatment fluid is made.The treatment fluid is heated to 80 DEG C, is stirred on one side, on one side with relative to treatment fluid
100ml is the fluorophor that 20g amounts below add embodiment or comparative example, makes its dispersion.It is small that 1 is placed after so that fluorophor is disperseed
When, insoluble powder is recycled by decantation (decantation).The insoluble powder of recycling is washed, is dried.After drying
Insoluble powder, utilize laser diffraction and scattering formula particle size distribution device (BECKMAN COULTER limited liability company LS
320) 13 measure particle diameter distribution, using the grain size of the accumulation 50% of volume reference as median particle diameter (D50).
(chemical composition)
In addition, carrying out fluorescence by ICP emission spectrophotometers (Rigaku limited liability companies system, CIROS-120)
The analysis of body, as a result, the Li contents of the fluorophor of embodiment 1 and comparative example 6 are 1.8 mass % or more and 3 mass % or less
Range, Eu contents be 0.1 mass % or more and 1.5 mass % ranges below, O content be 0.4 mass % or more and 1.3 matter
Measure % ranges below.
(peak wavelength)
For each fluorophor of Examples and Comparative Examples, using by rhodamine (Rhodamine) B and secondary standard light source into
The modified spectrofluorophotometer (Hitachi High-Technologies corporations, F-7000) of row, carries out fluoremetry.
Using the solid sample frame that photometer is subsidiary in measurement, fluorescence spectrum and peak wavelength under excitation wavelength 455nm are measured.
(fluorescence intensity)
By the product of photoluminescence spectrum intensity and CIE standard luminous efficiency, fluorescence intensity is calculated.It should be noted that because
Changed according to measurement device, condition, therefore unit is arbitrary, with the phase of the Examples and Comparative Examples measured under the same conditions
Situation is compared.As benchmark, the fluorescence intensity of embodiment 4 is set as 100%.85% or more is acceptance value.
(the luminous flux sustainment rate (durability evaluation of light-emitting component) of light-emitting component)
Then, for the light-emitting component for the phosphor particle for having Examples and Comparative Examples, light flux variations are measured.For
The measurement of light flux variations, under the high temperature and humidity of 85 DEG C of temperature and 85% relative humidity, to light-emitting component energization 150mA
And after placing the stipulated time, total light flux measurement system (Half Moon are used：Great Zhong electronics limited liability company HH41-
0773-1), the light flux variations for the fluorescence released from light-emitting component are measured.It should be noted that it is powered according to per unit
The light flux values of time, ratio when by being powered after just beginning as 100% are expressed as luminous flux sustainment rate, preferably through
It is 95% or more after 1000 hours.
By table 1, it can be seen that, the Li- α of 1~embodiment of embodiment 6 match grand system's fluorophor compared with comparative example, impurity level content
Few, the ratio that α matches grand crystal is also high.As a result, while obtaining high fluorescent, even using for a long time, luminous efficiency
Reduction it is also few, be the less light-emitting device of electrical property unfavorable condition.Using 1~embodiment of embodiment 6 fluorophor shine
Element is because the content of the impurity element contained by fluorophor is denier, thus is inhibited caused by the impurity element by fluorophor
The generation that resin solidification hinders, therefore cause the possibility of the electrical anomalies such as short circuit minimum, the service life is elongated.
In contrast, in comparative example 1, though fluorine, sodium and phosphorus content are few, because the ratio that α matches grand crystal is low, therefore fluorescence is strong
It spends low.In comparative example 2, though sodium and phosphorus content are few, fluorine content is high, and luminous flux sustainment rate is also low.In comparative example 3, though fluorine content
It is few, but sodium and phosphorus content are high, luminous flux sustainment rate is also low, α match grand crystal ratio it is also low.In comparative example 4, because of phosphorus, sodium, fluorine
Content is high, therefore luminous flux sustainment rate is low.In comparative example 5, phosphorus, sodium, fluorine content are few, and the ratio that α matches grand crystal is low.Therefore, light is logical
It measures sustainment rate and is less than example.In comparative example 6, though sodium and phosphorus content are few, fluorine content is high, and luminous flux sustainment rate is low.Therefore, light
Flux sustainment rate is less than example.In comparative example 7, although fluorine, sodium and phosphorus content are high, luminous flux sustainment rate is still high.That is, impurity
The presence of element might not cause undesirable influence because the presence of impurity element and causing characteristic to reduce such phenomenon is
Phenomenon peculiar in grand system's fluorophor is matched in Li- α.
[table 1]
Claims (10)
1. a kind of fluorophor is that Eu activation Li- α match grand system's fluorophor, wherein F contents are 20 mass ppm hereinafter, and P and Na
Total content be 10 mass ppm hereinafter, it is 95 mass % or more for the ratio of holocrystalline phase that α, which matches grand crystal phase,.
2. fluorophor as described in claim 1, wherein the total content of P and Na is 5 mass ppm or less.
3. fluorophor as claimed in claim 1 or 2, wherein Li contents are 1.8 mass % or more and 3 mass % or less.
4. fluorophor according to any one of claims 1 to 3, wherein Eu contents are 0.1 mass % or more and 1.5 matter
Measure % or less.
5. fluorophor as described in any one of claims 1 to 4, wherein O content is 0.4 mass % or more and 1.3 mass %
Below.
6. such as fluorophor according to any one of claims 1 to 5, average primary particle diameter is 7 μm or more and 35 μm or less.
7. a kind of light-emitting component, has：Fluorophor according to any one of claims 1 to 6 and to the fluorophor irradiate swash
Luminous illuminating source.
8. light-emitting component as claimed in claim 7, wherein the illuminating source is light emitting diode or laser diode.
9. light-emitting component as claimed in claim 7 or 8, wherein under conditions of 85 DEG C of temperature and relative humidity 85%, be powered
150mA and place 1000 hours when luminous flux sustainment rate be 95% or more.
10. a kind of light-emitting device has the light-emitting component described in any one of claim 7 to 9.
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| PCT/JP2017/009792 WO2017155111A1 (en) | 2016-03-11 | 2017-03-10 | Phosphor, light-emitting element, and light-emitting device |
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| CN102753650A (en) * | 2010-03-01 | 2012-10-24 | 宇部兴产株式会社 | Li-containing alpha-sialon fluorescent particles, method for producing same, illumination device, and image display device |
| JP2011213839A (en) * | 2010-03-31 | 2011-10-27 | Ube Industries Ltd | METHOD FOR PRODUCING Li CONTAINING α-SIALON PHOSPHOR |
| CN104797684A (en) * | 2012-11-13 | 2015-07-22 | 电气化学工业株式会社 | Phosphor, light-emitting element and lighting device |
| CN104837954A (en) * | 2012-11-13 | 2015-08-12 | 电气化学工业株式会社 | Phosphor, light-emitting element and lighting device |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP6970658B2 (en) | 2021-11-24 |
| TW201802230A (en) | 2018-01-16 |
| TWI751140B (en) | 2022-01-01 |
| KR102399783B1 (en) | 2022-05-19 |
| JPWO2017155111A1 (en) | 2019-01-17 |
| KR20180118223A (en) | 2018-10-30 |
| WO2017155111A1 (en) | 2017-09-14 |
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