WO2007129713A1 - サイアロン蛍光体及びその製造方法並びにそれを用いた照明器具及び発光素子 - Google Patents
サイアロン蛍光体及びその製造方法並びにそれを用いた照明器具及び発光素子 Download PDFInfo
- Publication number
- WO2007129713A1 WO2007129713A1 PCT/JP2007/059527 JP2007059527W WO2007129713A1 WO 2007129713 A1 WO2007129713 A1 WO 2007129713A1 JP 2007059527 W JP2007059527 W JP 2007059527W WO 2007129713 A1 WO2007129713 A1 WO 2007129713A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- sialon
- phosphor
- sialon phosphor
- light
- powder
- Prior art date
Links
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 248
- 238000000034 method Methods 0.000 title description 36
- 230000008569 process Effects 0.000 title description 10
- 239000000843 powder Substances 0.000 claims abstract description 138
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 25
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 19
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 17
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 15
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 11
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 11
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 11
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 11
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 11
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 11
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 11
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 10
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 9
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims description 142
- 239000002994 raw material Substances 0.000 claims description 62
- 238000009826 distribution Methods 0.000 claims description 39
- 229910052751 metal Inorganic materials 0.000 claims description 36
- 239000002184 metal Substances 0.000 claims description 36
- 238000004519 manufacturing process Methods 0.000 claims description 31
- 239000008187 granular material Substances 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 28
- 239000013078 crystal Substances 0.000 claims description 22
- 239000007858 starting material Substances 0.000 claims description 21
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 20
- 230000005284 excitation Effects 0.000 claims description 18
- -1 lanthanide metals Chemical class 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 16
- 229910052582 BN Inorganic materials 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000470 constituent Substances 0.000 claims description 11
- 229910003460 diamond Inorganic materials 0.000 claims description 11
- 239000010432 diamond Substances 0.000 claims description 11
- 230000002093 peripheral effect Effects 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- 238000010304 firing Methods 0.000 claims description 9
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 6
- 238000002441 X-ray diffraction Methods 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 238000005121 nitriding Methods 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 30
- 238000002189 fluorescence spectrum Methods 0.000 description 28
- 239000011163 secondary particle Substances 0.000 description 23
- 239000012071 phase Substances 0.000 description 19
- 239000011575 calcium Substances 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 17
- 239000011164 primary particle Substances 0.000 description 15
- 238000010298 pulverizing process Methods 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 150000004767 nitrides Chemical class 0.000 description 14
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- 229910052581 Si3N4 Inorganic materials 0.000 description 11
- 230000007423 decrease Effects 0.000 description 11
- 239000006104 solid solution Substances 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 238000005259 measurement Methods 0.000 description 10
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 241000254158 Lampyridae Species 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000007921 spray Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 235000019557 luminance Nutrition 0.000 description 7
- 239000011812 mixed powder Substances 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000000149 argon plasma sintering Methods 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 229910052761 rare earth metal Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 4
- 229910001634 calcium fluoride Inorganic materials 0.000 description 4
- 229910001940 europium oxide Inorganic materials 0.000 description 4
- 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 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910007991 Si-N Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910006294 Si—N Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000000790 scattering method Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 229910002601 GaN Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910003564 SiAlON Inorganic materials 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000009499 grossing Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- MVXMNHYVCLMLDD-UHFFFAOYSA-N 4-methoxynaphthalene-1-carbaldehyde Chemical compound C1=CC=C2C(OC)=CC=C(C=O)C2=C1 MVXMNHYVCLMLDD-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910016523 CuKa Inorganic materials 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- 235000005135 Micromeria juliana Nutrition 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241000246354 Satureja Species 0.000 description 1
- 235000007315 Satureja hortensis Nutrition 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- OOJQNBIDYDPHHE-UHFFFAOYSA-N barium silicon Chemical compound [Si].[Ba] OOJQNBIDYDPHHE-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000012611 container material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- QNDQILQPPKQROV-UHFFFAOYSA-N dizinc Chemical compound [Zn]=[Zn] QNDQILQPPKQROV-UHFFFAOYSA-N 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 238000004452 microanalysis Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- SBOJXQVPLKSXOG-UHFFFAOYSA-N o-amino-hydroxylamine Chemical compound NON SBOJXQVPLKSXOG-UHFFFAOYSA-N 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001709 polysilazane Chemical group 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 210000002637 putamen Anatomy 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Chemical group 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
-
- 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
- C09K11/7729—Chalcogenides
- C09K11/7731—Chalcogenides with alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/597—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon oxynitride, e.g. SIALONS
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/6261—Milling
- C04B35/6262—Milling of calcined, sintered clinker or ceramics
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/0883—Arsenides; Nitrides; Phosphides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/64—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/64—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing aluminium
- C09K11/646—Silicates
-
- 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
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/38—Non-oxide ceramic constituents or additives
- C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
- C04B2235/3865—Aluminium nitrides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/38—Non-oxide ceramic constituents or additives
- C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
- C04B2235/3873—Silicon nitrides, e.g. silicon carbonitride, silicon oxynitride
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/442—Carbonates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/444—Halide containing anions, e.g. bromide, iodate, chlorite
- C04B2235/445—Fluoride containing anions, e.g. fluosilicate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5409—Particle size related information expressed by specific surface values
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/76—Crystal structural characteristics, e.g. symmetry
- C04B2235/761—Unit-cell parameters, e.g. lattice constants
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/76—Crystal structural characteristics, e.g. symmetry
- C04B2235/766—Trigonal symmetry, e.g. alpha-Si3N4 or alpha-Sialon
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/76—Crystal structural characteristics, e.g. symmetry
- C04B2235/767—Hexagonal symmetry, e.g. beta-Si3N4, beta-Sialon, alpha-SiC or hexa-ferrites
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Definitions
- Sialon phosphor method for producing the same, lighting apparatus using the same, and light emitting device
- the present invention relates to a sialon phosphor that is excited by ultraviolet or blue light and emits visible light, a method for producing the same, and a lighting fixture and a light emitting device using the sialon phosphor. More specifically, the present invention relates to a phosphor that can be used for a blue light emitting diode (blue LED) or an ultraviolet light emitting diode (ultraviolet LED), a method for producing the same, a lighting fixture and a light emitting device using the phosphor, and particularly a white light emitting diode ( White LED).
- blue LED blue LED
- ultraviolet light emitting diode ultraviolet light emitting diode
- White LED white light emitting diode
- Phosphors using a silicate, phosphate, aluminate, or sulfide as a base material and using a transition metal or a rare earth metal in the light emission center are widely known.
- nitrides and oxynitride phosphors which are materials that have a stable crystal structure and can shift excitation light and light emission to the long wavelength side.
- the ⁇ -type silicon nitride crystal is partially composed of A1— ⁇ bonds and A1
- the a-type sialon is composed of silicon nitride, aluminum nitride, aluminum oxide as necessary, In addition, it is obtained by firing a mixed powder composed of oxides of elements that enter and dissolve in solid at a high temperature in nitrogen.
- Various fluorescence characteristics can be obtained depending on the ratio of the nitride nitride and aluminum compound, the type of element that enters and dissolves, and the ratio of the element that becomes the emission center.
- a diamond sialon in which Ca and the emission center Eu as a penetrating solid solution element are dissolved in a wide range of wavelengths from the ultraviolet to the blue region, and emits yellow to orange light. For this reason, it is expected to be used in white LED applications by combining with blue light emitting LEDs that have complementary colors.
- nitrides such as aluminum nitride, silicon magnesium nitride, calcium calcium nitride, barium silicon nitride, gallium nitride, and zinc zinc nitride, and phosphors of oxynitride (hereinafter referred to as nitride phosphor, Oxynitride phosphors) have been proposed.
- Non-Patent Documents 4 to 6 are characterized in that the raw material powder is inexpensive and can be synthesized at a relatively low temperature of around 1500 ° C. Since gas components such as SiO and CO are generated through the product, it is difficult to obtain a single-phase material, and it is difficult to strictly control the composition and control the particle size.
- nitride containing a constituent element and a compound containing an activator are simply mixed and heated, or a mixture of oxides of the constituent elements is returned with carbon or the like.
- a nitride phosphor or oxynitride phosphor having sufficient characteristics cannot be obtained only by the original nitriding.
- a raw material containing no oxygen for example, a raw material such as calcium fluoride or calcium cyanamide, or a mixing method of raw materials used for firing.
- a manufacturing method requiring almost no pulverization treatment was proposed, and the emission intensity was improved (see Patent Documents 8 and 9).
- White requires a combination of multiple colors different from monochromatic light
- a general white LED is a combination of an ultraviolet LED or blue LED and a phosphor that emits visible light using those light as an excitation source.
- Patent Documents 10 and 11 See, for example, Patent Documents 10 and 11. Therefore, in order to improve the efficiency of the white LED, the luminous efficiency of the LED of the ultraviolet LED or the blue LED itself is improved, the efficiency of the phosphor used in the LED is improved, and the emitted light is further improved. It is necessary to improve the efficiency of taking out the outside. All of these efficiencies need to be improved in order to expand the use of white LEDs for general lighting.
- Patent Document 1 Japanese Patent No. 3668770
- Patent Document 2 Japanese Patent Laid-Open No. 2003-336059
- Patent Document 3 Japanese Patent Laid-Open No. 2003-124527
- Patent Document 4 Japanese Unexamined Patent Application Publication No. 2003-206481
- Patent Document 5 Japanese Unexamined Patent Application Publication No. 2004-186278
- Patent Document 6 Japanese Patent Application Laid-Open No. 2004-244560
- Patent Document 7 Japanese Unexamined Patent Publication No. 2005-255895
- Patent Document 8 Japanese Unexamined Patent Application Publication No. 2008-45271
- Patent Document 9 Special Publication 2005-123876
- Patent Document 10 JP-A-5-152609
- Patent Document 11 JP-A-7-099345
- Non-Patent Document 1 JWH van Krebel "On New Rare-Earth Doped M- Si- A ⁇ O- N Mate rials", TU Eindhoven, The Netherlands, 145-161 (1998)
- Non-Patent Document 2 Proceedings of the 52nd Joint Conference on Applied Physics (March 2005, Saitama University) p. 1614-1615
- Non-Patent Document 3 Proceedings of the 65th JSAP Scientific Meeting (September 2004, Tohoku Gakuin University) No. 3 p. 1282-1284
- Non-Patent Document 5 J. W. T. van Rutten et al., Carbothermal Preparation and Characterization of Ca-a-SiAlON ", J. Eur. Ceram. So, 15, 599-604 (1995)
- Non-Patent Document 6 K. Komeya et al., Hollow Beads Composed of Nanosize Ca-SiAlO N Grains ", J. Am. Ceram. So, 83, 995-997 (2000)
- the phosphor for white LED is generally used by being dispersed as micron-sized particles in a sealing material such as epoxy resin or silicone resin.
- a sealing material such as epoxy resin or silicone resin.
- these particles are secondary particles obtained by sintering a plurality of fine primary particles. The force that is being studied for its size, distribution, etc. The surface properties of the secondary particles have not been noticed.
- the average particle size of general raw materials such as silicon nitride and aluminum nitride is 1 ⁇ m or less, and nitrides and oxynitride phosphors are synthesized by a conventional method using them as raw materials.
- the obtained powder necessarily has a wide particle size distribution, and in particular, there are many powders with a particle size of several ⁇ m or less that strongly scatter visible light. there were.
- the white LED obtained up to now has a luminous efficiency that does not reach that of a fluorescent lamp.
- White LEDs which use oxynitrides and nitride phosphors such as sialon phosphors, are more efficient than incandescent bulbs. It is essential and improving the luminous efficiency of the phosphor is an important industrial issue.
- the first purpose was to provide a white LED with a peak in the wavelength range of 600 nm and excellent luminous efficiency, in particular, a white LED with excellent luminous efficiency using a blue LED or an ultraviolet LED as a light source.
- the second object of the present invention is to solve the above-mentioned problems of the prior art and provide an LED having excellent luminous efficiency, for example, a white LED, particularly a white LED having a blue LED or an ultraviolet LED as a light source.
- the object is to stably provide phosphors having excellent fluorescence characteristics on an industrial scale.
- the inventors of the present invention have studied a phosphor having a template sialon as a base material, and have determined that the intrusion solid solution element of the template sialon is a specific one, and the crystal lattice size is within an appropriate range.
- a phosphor with a peak in the wavelength range of 540 to 600 nm and excellent luminous efficiency can be obtained, and this can be used to obtain a lighting device with excellent luminous characteristics.
- the present invention has been achieved.
- the inventors of the present invention have made it possible to smooth the surface of the secondary particles by adding seed particles that are the core of grain growth to the raw material powder and using a dense boron nitride crucible in the synthesis process.
- the present invention has been found to improve the properties.
- the sialon phosphor of the present invention has a general formula: (Ml)
- M2 is one or more elements selected from the group consisting of Ce, Pr, Eu, Tb, Yb and Er, and 0.3 ⁇ X + Y ⁇ 1.5 and 0 It is characterized by being a powder having ⁇ -sialon represented by ⁇ Y ⁇ 0 ⁇ 7) as its main component and a specific surface area of 0 ⁇ 2 to 0.5 ⁇ 5m 2 / g.
- the ⁇ -type sialon phosphor is characterized in that the lattice constant a is in the range of 0.780-0.788 nm and the lattice constant c is in the range of 0.565 to 0.573 nm.
- the diffraction intensity of the crystal phase other than the template sialon is (10
- Ml contains at least Ca
- M2 contains at least Eu
- ultraviolet or visible light having a wavelength of 250 to 500 nm is used as an excitation source.
- the emission characteristics having a peak in the wavelength range of 540 to 600 nm are exhibited.
- the method for producing a model sialon phosphor represented by the above general formula of the present invention is characterized in that the starting material contains 5 to 30% by mass of ⁇ -sialon.
- the specific surface area of ⁇ -sialon contained in the starting material is preferably 0.5 to 2 m 2 / g.
- Another method for producing the above-described sialon phosphor of the present invention is characterized in that the starting material is filled in a crucible made of a boron nitride material having a density of 1.75 g / cm 3 or more and fired in a nitriding atmosphere.
- the boron nitride is preferably made of pyrolytic boron nitride (P—BN).
- the lighting fixture of the present invention includes a light emitting light source and a phosphor, and uses at least the sialon phosphor or the sialon phosphor obtained by the manufacturing method.
- sialon phosphors composed of sialon (hereinafter, simply referred to as sialon phosphors)
- the present inventors have conducted characteristics and composition analysis on various powders and conducted experimental verification. As a result, the inventors have found that control of the particle shape, particle size, composition distribution, and the like of the phosphor particles is effective for improving the light emission intensity, leading to the present invention.
- the second sialon phosphor of the present invention has an average circularity of the constituent particles of the phosphor of not less than 0.75, and a particle size distribution of the phosphor D force S5 It is ⁇ 30 zm, and D is 2. O xm or more.
- Another configuration of the sialon phosphor of the present invention is characterized in that the concentration of an element involved in light emission contained in the phosphor particles is high in the outer peripheral portion of the particle, which is low inside the particle.
- the concentration of the element involved in the light emission at the outer peripheral portion of the sialon phosphor particle is 1.2 times or more the concentration of the element involved in the light emission inside the particle.
- the phosphor is preferably represented by the general formula: (Ml) (M2) (Si) (Al)
- Ml is Ca and M2 is Eu.
- the method for producing the template sialon phosphor of the present invention includes a silicon-containing material, an aluminum-containing material, Ml (Li, Mg, Ca, Sr, Y, and lanthanide metal (excluding La and Ce) forces, And a raw material containing one or more elements selected from the group consisting of M2 (one or more elements selected from Ce, Pr, Eu, Tb, Yb, Er)
- M2 one or more elements selected from Ce, Pr, Eu, Tb, Yb, Er
- the granule is subjected to caloric heating in a nitrogen gas atmosphere at a temperature of 1500 to 2100 ° C. to obtain an ⁇ -type sialon phosphor.
- the ⁇ -sialon phosphor synthesized in advance is added to the raw material and mixed.
- the method for producing a ⁇ -sialon phosphor of the present invention comprises mixing a silicon-containing material, an aluminum-containing material, and a raw material containing M3 (one or more elements selected from Mn, Ce, Eu). A granule is prepared, and the granule is heated at a temperature of 1500 to 2100 ° C. in a nitrogen gas atmosphere to obtain a type sialon phosphor. Preferably, a ⁇ -sialon phosphor synthesized in advance is added to the raw material and mixed.
- M3 one or more elements selected from Mn, Ce, Eu
- the light emitting device of the present invention includes the sialon phosphor described above and a light emitting diode having a maximum emission wavelength in the range of 240 to 480 nm as constituent elements.
- the invention's effect is the following:
- the first sialon phosphor of the present invention is more efficient than the conventional one because the primary particles are larger without changing the secondary particle size and the surface of the particles is smoother. It can be absorbed in the grains and has excellent light emission characteristics. Moreover, since the luminaire of the present invention uses the phosphor, good light emission characteristics can be obtained. [0040] Since the second sialon phosphor of the present invention has a specific particle shape and composition distribution, the second sialon phosphor has a feature that the emission intensity and the emission efficiency are high even when the phosphor alone is measured. Furthermore, when dispersed in a sealing resin, the LED element is well dispersed in the resin, and the LED element sealed using it is less likely to cause unnecessary light scattering and absorption in the sealing resin layer. Luminous efficiency is improved.
- the sialon phosphor of the present invention since it has the above-described characteristics, it can be preferably applied to various LEDs, and in particular, a white LED is provided in combination with an LED having a maximum emission intensity at an emission wavelength of 240 to 480 nm. be able to.
- Intrusive elements such as Li, Mg, Ca, Y, and lanthanide metals (excluding La and Ce).
- the solid solution Z value of M is a numerical value determined by the A1-N bond substitution rate of the Si—N bond.
- a range of 7 is preferable.
- ⁇ -sialon is obtained by heating and reacting a mixed powder composed of silicon nitride, aluminum nitride, aluminum oxide, and an interstitial solid solution element in a high-temperature nitrogen atmosphere.
- a mixed powder composed of silicon nitride, aluminum nitride, aluminum oxide, and an interstitial solid solution element in a high-temperature nitrogen atmosphere.
- some of the components form a liquid phase, and the substance moves through it to form ⁇ -sialon solid solution. Therefore, ⁇ form after synthesis Sialon sinters a plurality of primary particles to form secondary particles and further agglomerates, which are pulverized to form a powder.
- the present inventors have obtained the knowledge that the specific surface area of the particles is closely related to the light emission characteristics, and have reached the present invention.
- the specific surface area of the particles shows the smoothness of the particles and is a parameter sensitive to the presence of fine powder.
- the specific surface area of the phosphor powder is preferably 0.2 to 0.5 m 2 Zg. If the specific surface area is more than 0.5 m 2 / g, light scattering by the particle surface and the fine particles will reduce the efficiency with which the excitation light is taken into the particles and the light emission characteristics will deteriorate, which is not preferable. Particles with a specific surface area of less than 0.2 m 2 / g can only be realized with densely sintered particles that are difficult to obtain with isolated primary particles. Since it deviates greatly from suitable size as a fluorescent substance, it is not preferable.
- the phosphor of the present invention forms ⁇ -sialon as a main component, but forms a grain boundary phase having a different composition at the particle interface, and easily forms a crystalline or amorphous second phase. Therefore, the total composition of the phosphor powder does not necessarily correspond to the solid solution composition of ⁇ -sialon. In ⁇ -type sialon crystals, the crystal lattice size increases as the solid solution amount of aluminum and oxygen increases.
- the ⁇ -sialon crystal phase contains as much purity and as much as possible, and is preferably composed of a single phase. Even a mixture containing a phase and other crystalline phases may be in a range where the properties do not deteriorate.
- the diffraction intensity of the crystal phase other than the diamond sialon does not exceed the diffraction ray intensity of the (102) plane of the diamond sialon. Is preferably 10% or less. If a crystal phase exceeding 10% is present, the light emission characteristics deteriorate.
- the atomic weight ratio of Eu serving as the emission center is preferably in the range of 0 and Y ⁇ 0.1. If Y exceeds 0.1, the emission brightness will decrease due to concentration quenching caused by interference between the dissolved Eu ions.
- a powder of silicon nitride, aluminum nitride, calcium-containing compound and europium oxide is used as a raw material.
- the phosphor production method of the present invention is characterized in that 5-30% by mass of a pre-synthesized ⁇ -sialon powder is contained in the raw material powder blended so as to have a predetermined composition. To do.
- the a-type sialon powder previously blended with the raw material powder selectively becomes the starting point for grain formation during the heat treatment, promotes the growth of primary particles, improves the coarsening of the primary particles and improves the surface smoothness.
- ⁇ -sialon powder when added to the raw material powder in advance, it has the effect of suppressing sintering during the synthesis process, and easily savory sialon can be produced.
- This sialon does not require excessive pulverization, and a powder having a desired particle size can be obtained by a simple pulverization process, and has the effect of suppressing the generation of fine particles due to the powder process that lowers the light emission characteristics.
- the added amount of the a-type sialon powder is 5% by mass or more, the formation, sintering, and grain growth of new template sialon particles may proceed in a portion other than the added template sialon particles. A powder having a small specific surface area can be obtained. If the added amount of the model sialon powder is 30% by mass or less, it is possible to prevent the grain growth base point from being excessively large and individual particle growth to be slight, making it difficult to obtain a sufficiently smooth particle surface. preferable.
- the constituent elements and composition of the model sialon powder previously contained in the raw material are not limited.
- the fluorescence characteristics are emitted mainly in the region close to the powder surface. This is to make it appear.
- the use of ⁇ -sialon powder that contains different luminescent center elements or contains an impurity element such as iron that inhibits light emission greatly affects the characteristics of the ⁇ -sialon phosphor layer formed on the surface. It is not preferable because it affects.
- the specific surface area of the diamond sialon powder added in advance is 0.5 to 2 m 2 / g. If the specific surface area is 2 m 2 / g or less, the effect on grain growth is sufficiently achieved. On the other hand, if the specific surface area is 0.5 m 2 Zg or more, the secondary particle size of the synthetic powder becomes remarkably large. Since the final specific surface area of 0.2 to 0.5 m 2 Zg can be easily obtained without finally requiring a pulverization treatment or the like, it is preferable.
- a method of dry mixing a method of removing the solvent after wet mixing in an inert solvent that does not substantially react with each component of the raw material, etc. are adopted. can do.
- a V-type mixer a mouth mixer, a ball mill, a vibration mill and the like are preferably used.
- Powder obtained by mixing so as to have a desired composition (hereinafter referred to as raw material powder) is filled in a container such as a crucible made of boron nitride at least on the surface in contact with the raw material powder.
- a container such as a crucible made of boron nitride at least on the surface in contact with the raw material powder.
- ⁇ -sialon is obtained by heating in the atmosphere at a temperature range of 1600-1800 ° C for a predetermined time.
- the reason why boron nitride is used for the container material is that the reactivity with each component of the raw material is very low, but the present inventors have increased the density of boron nitride used in the crucible.
- ⁇ -sialon powder we found that it has the effect of increasing the primary particles and smoothing the surface.
- the density of boron nitride used in the crucible is preferably 1.75 g / cm 3 or more. When the density is less than 1.75 g / cm 3 , gas permeation through the crucible easily occurs, volatilization of the components contained in the raw material powder filled in the crucible is promoted, and compositional deviation only occurs. Carbon monoxide gas, cyan gas, etc. existing in the crucible penetrate into the crucible and cause reaction with the raw material powder and inhibition of grain growth.
- the density of the crucible is preferably as high as possible.
- pyrolytic boron nitride (P—BN) produced by a vapor phase method is very dense and is preferably used.
- the filling of the raw material powder into the container is preferably as bulky as possible from the viewpoint of suppressing interparticle sintering during heating.
- the bulk density when filling the raw material powder into the synthesis container is preferably 1. Og / cm 3 or less.
- the heating time in the heat treatment a time range in which there are no inconveniences such as many unreacted substances, insufficient growth of primary particles, or sintering between particles is selected. According to the study by the present inventors, about 2 to 24 hours is a preferable range.
- the model sialon obtained by the above-described operation is in the form of a lump, it can be used in various applications by combining it with pulverization, pulverization and, in some cases, classification treatment, to obtain a powder of a predetermined size. In the form of a phosphor.
- the average particle size of secondary particles is set to 3 to 30 ⁇ m. If the average particle size of the secondary particles is 3 ⁇ m or more, the emission intensity will be low. If the average particle size is 30 ⁇ m or less, uniform dispersion in the resin that seals the LED is easy, and light emission. It can be used practically without causing variations in strength and color tone.
- the agglomerate made of a-type sialon obtained by the above-described production method is relatively easy to grind and has a feature that it can be easily ground to a predetermined particle size with a mortar or the like.
- a ball mill, vibration mill, jet mill, etc. it is also acceptable to use a general dusting machine such as the above.
- the sialon phosphor of the present invention has a wide excitation range from ultraviolet to visible light and emits visible light, and thus is suitable for a lighting fixture.
- the phosphor obtained by selecting Ca and Eu as the intrusion elements into the crystal lattice of ⁇ -sialon has a peak wavelength due to the substitution rate of Si-N bonds to A1-N bonds and Al_O bonds. Can be controlled to yellow to orange light of 540 to 600 nm and has high luminance emission characteristics. Therefore, white light can be easily obtained in combination with a blue LED.
- the model sialon does not deteriorate even when exposed to high temperatures, has excellent heat resistance, and has excellent long-term stability in an oxidizing atmosphere and moisture environment.
- the lighting fixture of the present invention is configured using at least a light emitting light source and the phosphor of the present invention.
- the lighting fixture of the present invention include LED lighting fixtures and fluorescent lamps.
- LED lighting using the phosphor of the present invention is performed by a known method as disclosed in Patent Documents 10 and 11, etc.
- An instrument can be manufactured.
- the light emitting source is preferably an ultraviolet LED or a blue LED emitting light with a wavelength of 350 to 500 nm, and these light emitting elements are made of nitride semiconductors such as GaN and InGaN, and the composition is adjusted. By doing so, it can be a light emitting light source that emits light at a predetermined wavelength.
- a lighting fixture that emits a desired color can be configured by using in combination with a phosphor having other light emission characteristics.
- the average circularity of the constituent particles of the phosphor is 0.75 or more, and the particle size distribution of the phosphor has a 50% diameter in a volume-based integrated fraction.
- D force ⁇ 30 ⁇ , D is 2 ⁇ 0 / im or more.
- the average circularity of the sialon phosphor particles of the present invention is 0.75 or more, preferably 0.8 or more, more preferably 0.85 or more.
- the average circularity is the average value of circularity defined by (circumference length of circle equal to particle area) ⁇ (particle circumference), and is a particle shape measuring device, for example, flow particle image analyzer ( It can be measured by FPIA-3000) manufactured by Sysmetas.
- the number of particles to be measured is the number average value of the circularity that is desired to be 500 or more so that the variation in the measured value becomes small.
- the size of the particles to be measured should be in the range of 0.5 to 100 x m in terms of area circle equivalent diameter.
- the 50% diameter (D) in the volume-based integrated fraction is 5 to 30 x m, preferably 10 to 25 x m. D force ⁇ m or less
- the emission intensity of the sialon phosphor measured with a fluorescence spectrophotometer decreases.
- the LED when the LED is assembled, light scattering within the layer containing the phosphor becomes significant, which reduces the light extraction efficiency. If the LED light emission efficiency decreases, there will be no disadvantages.
- D is 30 / m or less, the emission intensity of the phosphor measured with a spectrofluorometer
- the LED's luminous efficiency is large enough, and the particle size is too large.For example, if mixed with resin, it will be difficult to use because it will settle in the resin, and the chromaticity of the LED It does not cause variations or uneven color on the irradiated surface.
- the 10% diameter (0) in the volume-based integrated fraction is 2 zm or more, preferably 4.5 zm or more, more preferably 7.0. ⁇ m or less
- the D force is less than 3 ⁇ 4 z m, the reason is unknown, but it is measured with a fluorescence spectrophotometer.
- the emission intensity of the phosphor decreases. Also, when assembled into an LED, the number of particles with a small particle size close to the wavelength of visible light is large, so light is strongly scattered within the layer containing the phosphor, and the LED light emission efficiency (light extraction efficiency) decreases. To do. Since these values are also related to the refractive index of the phosphor, the optimum value is a force type sialon that differs depending on the phosphor material, and the type sialon has a different density and refractive index, although the crystal structure is different. Since it is not different, it can be specified with the same numerical value. In addition, since the refractive index is higher than that of oxide and sulfide phosphors that have been widely used in the past, these optimum values in the particle size distribution of sialon phosphors are increased.
- the particle size distribution measurement methods include laser diffraction scattering method, centrifugal sedimentation light transmission method, X-ray transmission method, light shielding method, electrical detection band method, etc., but the reproducibility is good and the operation is relatively
- the laser diffraction scattering method was adopted because of its simplicity.
- a pretreatment for the measurement of sampnore a small amount of sampnore is taken in water in which a dispersing agent such as sodium phosphate aqueous solution is dropped, and dispersed by applying ultrasonic waves.
- the sialon phosphor of the present invention is characterized in that the concentration of elements involved in light emission contained in the phosphor particles is high in the outer peripheral portion where the inside of the particles is low. Preferably, the concentration at the outer periphery of the phosphor particles is 1.2 times or more the concentration inside the particles.
- the present inventors have experimentally confirmed that the luminous efficiency of an LED when assembled in an LED is improved by controlling the concentration of elements involved in the light emission in the phosphor in this way.
- the element involved in light emission contained in the sialon phosphor is generally an emission center. It refers to a metal ion called.
- many rare earth ions such as Ce, Pr, Eu, Tb, Yb, Er, and transition metal element ions, such as Mn ions, can be included as the emission center.
- these elements In order for a phosphor to absorb excitation light and emit sufficient intensity of fluorescence, these elements must be contained in a concentration above a certain level. However, if the concentration is too high, concentration quenching generally occurs and light emission occurs. Since the intensity decreases, the concentration of elements involved in light emission in the phosphor must be controlled to an appropriate value. This concentration range is different for each phosphor.
- the concentration of the elements involved in the light emission in the outer peripheral portion and inside of the phosphor powder can be measured as follows.
- the phosphor powder is encapsulated with epoxy resin and cut with an argon ion beam cross-section preparation device.
- Look for cut phosphor particles by observing the cut surface with an electron microscope, and analyze the elements on the cut surface of the phosphor by line analysis using energy dispersive X-ray analysis (EDX) or surface analysis using electron beam micro analysis (EPMA). I do. Since the number of counts obtained by EDX or EPMA is proportional to the number of elements present, if the ratio of count numbers is measured under the same analysis conditions, the ratio of count numbers becomes the ratio of concentration. The ratio of the density at the outer periphery can be measured.
- the interior of the sialon phosphor particles in the present invention is defined as follows. In the particle cross section obtained as described above, the maximum value of the particle length in the vertical direction from the tangent of the particle outer peripheral portion (hereinafter referred to as the maximum length in the tangential vertical direction of the particle). Ask.
- the inside of the sialon phosphor particles refers to the portion inside the line that is 20% inside this maximum value.
- the outer periphery refers to the portion outside the 20% inner line.
- the state in which the concentration of the element involved in light emission is low in the particle outer periphery where the particle interior is low is high in the particle cross section having a particle size near D, which means that the entire interior is lower than the entire outer periphery. This means that the average concentration within the dimension of about 1 ⁇ m inside the particle is lower than the average concentration within the dimension of about 1 ⁇ m around the particle.
- the average of line analysis values with a length of about 1 ⁇ m can be compared.
- the measurement location can be determined by taking the portion with the lowest concentration inside the particle and the portion with the highest concentration at the outer periphery and measuring the concentration to obtain a ratio.
- the concentration ratio is 1.2 or more Toyoyore. If it is smaller than 1, the difference in density becomes small, and the difference in light emission between the outer periphery and the inside becomes small, so that the effects of the present invention may not be sufficiently obtained. The reason why the effect of the present invention is obtained is estimated as follows.
- the particle size tends to be larger and the emission intensity tends to be higher.
- the LED is actually assembled and its emission efficiency is measured, If a phosphor having a large diameter is used, the light emission efficiency may decrease.
- the difference is that in the measurement using a fluorescence spectrophotometer, in the case of a force LED in which the incident direction of excitation light and the measurement direction of fluorescence are on the same side of one surface of the measurement cell filled with the phosphor, This may be due to the measurement of light transmitted through the dispersed layer.
- Phosphors with a large particle size have a higher rate of absorption without transmitting light, especially in the case of secondary particles in which primary particles are aggregated, light scattering or absorption is likely to occur at the interface inside the secondary particles. Even if light is emitted immediately inside the secondary particles, it becomes difficult to extract the light out of the phosphor particles, and the luminous efficiency of the LED is considered to be reduced.
- the number of interfaces in the secondary particles that cause light scattering and absorption is reduced as much as possible, that is, the number of primary particles constituting the secondary particles is reduced, It is considered important to minimize crystal phases and foreign substances other than sialon in the particles.
- the light is easily taken out of the phosphor, and it is considered that the extra light absorption inside the secondary particles can be reduced.
- the concentration quenching of the concentration of the element involved in the light emission at the outer peripheral portion does not occur. If it is limited to a certain extent, the absorption and emission of excitation light occur more strongly in the outer periphery than in the interior, and the light can be easily taken out of the phosphor particles, so that the above object can be achieved.
- Ml is one or more elements selected from the group consisting of Li, Mg, Ca, Y and lanthanide metals (excluding La and Ce), and M2 is from Ce, Pr, Eu, Tb, Yb, Er. Forces known to be represented by one or more selected elements)
- M2 is from Ce, Pr, Eu, Tb, Yb, Er. Forces known to be represented by one or more selected elements
- 0.3 ⁇ X + Y ⁇ 1.5, 0 ⁇ ⁇ 0.7, 0.6 6 ⁇ m ⁇ 3.0, 0 ⁇ n ⁇ 2.5, X + Y mZ
- the a-type silon having the relationship of (valence number) is selected.
- Ml may take 1 to 3 valences and M2 may take 2 to 4 valences
- the above average valence is calculated from the valence and content of each element.
- 60% of Ml is Li +
- 40% of Ml is Ca 2 M2 force SCe 3+
- the average valence is 1.72.
- Y has a lower limit of X + Y of 0.01 or more, preferably 0.02 or more, and an upper limit of 0.5 or less, preferably 0.3 or less. If Y exceeds the upper limit, so-called concentration quenching occurs and the phosphor emission intensity decreases, and M2 is generally expensive, leading to an increase in cost.
- the Ml is Ca and M2 is Eu. In this case, it absorbs visible light to ultraviolet light and emits light having a peak at 565 to 610 nm, and the light emission intensity and light emission wavelength change due to the operating temperature with high light emission efficiency is small.
- High phosphor This is suitably used as a phosphor for white LEDs using blue to ultraviolet LEDs.
- the present invention relates to a type sier represented by the general formula: Si Al ON (provided that 0.01 ⁇ z ⁇ 4.2).
- a sialon phosphor characterized by containing Ron as a base material and containing a metal element M3 (wherein M3 is one or more elements selected from Mn, Ce, Eu) from 0 ⁇ 01 to 10 atm% .
- M3 is one or more elements selected from Mn, Ce, Eu
- High emission intensity can be obtained in this range.
- M3 is Eu
- the Eu content is 0.05 ⁇ 0.25 to 0.25 atm%.
- the present invention creates a granule by mixing raw materials containing silicon-containing material, aluminum-containing material and, if necessary, Ml, M2, M3, and heated in a nitrogen gas atmosphere at 1500-2100 ° C This is a method for producing a sialon phosphor.
- the present inventors have obtained the knowledge that the secondary particle shape after the firing reaction reflects the granule shape if the condylar particles are formed at the raw material stage and then appropriately processed, leading to the present invention. is there.
- the silicon-containing material it is common to use a nitride nitride powder. However, a part of the silicon-containing material may be replaced with silicon oxide, zeolite, polysilazane, metal silicon, etc., or two or more kinds may be mixed. It may be used.
- the aluminum-containing material an aluminum nitride, an amino oxide, an aminoalane, an iminoalane, a metallic aluminum, or the like can be used, or a mixture of two or more types can be used.
- Ml-containing, M2-containing, M3-containing M2, M3 nitrides, oxides, carbonates, nitrates, oxalates, fluorides, carbides, hydroxides, metals, etc. can be used, or a mixture of two or more may be used.
- a spray having a suitable particle size can be formed by using a spray drier among the forces that can employ various methods.
- the granule is prepared using a spray dryer as follows. First, a ball mill pot containing balls is prepared, and a solvent such as ethanol, raw materials and a small amount of binder, and a predetermined amount of a dispersing agent, if necessary, are weighed and mixed to prepare a slurry. .
- the spray dryer is heated by blowing hot air in advance. The slurry is supplied to the spray nozzle provided at the top of this spray dryer, and the granule made of the cyclone provided downstream of the hot air is collected.
- the ball mill pot is preferably made of a material or a material having little influence even if it is worn and mixed, for example, a product made of polyamide resin.
- the ball can be made of a material mainly composed of a metal constituting a sialon such as silicon or aluminum such as a nitride nitride ball or a high-purity aluminum ball.
- a metal constituting a sialon such as silicon or aluminum
- a nitride nitride ball or a high-purity aluminum ball As the binder, polyvinyl alcohol, polyvinyl butyral, polyacrylic acid, methyl cellulose, or the like can be used.
- As the solvent methanol, isopropanol, acetone or the like can be used in addition to ethanol. A small amount of butanol, toluene, xylene, etc.
- the binder solubility and slurry properties may be mixed to adjust the binder solubility and slurry properties.
- water can be used as a solvent when a slurry can be made by mixing in a short time using a binder that is soluble in water.
- the hydrolyzed screen powder used as a raw material can be surface-treated by a known method.
- the shape of the granule affects the secondary particle shape of the phosphor obtained by subsequent firing, it is necessary to set the granule shape, sphericity, particle size distribution, granule hardness, etc. to appropriate values. is there.
- the shape and particle size of the granule can be controlled by the raw material composition, the nozzle method of spraying fluid such as spray dryer fluid or rotary nozzle, fluid flow rate, slurry supply rate, hot air inlet temperature, etc. It is necessary to examine the granule production conditions in advance and ensure that the resulting granule does not become hollow or rupture.
- the average particle size of the phosphor obtained after firing is 5-30 ⁇
- the conditions should be selected so that the particle size of the granules is about 10 to 35 / im. Further, when the particle size distribution width of the granules is narrowed, the characteristics of the obtained sialon phosphor are improved.
- the obtained granule is put into a crucible made of boron nitride, silicon nitride, aluminum nitride, or a composite material thereof and debindered.
- the binder removal temperature is approximately 600 ° C or less, and the heating device can be selected as appropriate, such as a resistance heating furnace or gas furnace, and the atmosphere during binder removal can be selected as appropriate, such as nitrogen, air, combustion gas, or vacuum. do it. Since the granules may be destroyed by the gas generated during debinding, it is necessary to adjust the temperature rise profile and the degree of vacuum so that the granules do not break.
- the temperature rise rate and vacuum are set so that the granules do not break down due to the generated gas. Need to control the degree.
- an atmosphere control electric furnace using alumina fiber as a heat insulating material, a graphite heater heating electric furnace using a carbon heat insulating material, or the like can be used depending on the firing temperature condition. Debinding may be performed in the same furnace. Bake at 1500-2100 ° C until synthesis of sialon. In the case of model sialon, it is synthesized at ⁇ MA 1500 ⁇ : 1850 ° C, preferably ⁇ MA 1600 ⁇ : 1800 ° C, in the case of model sialon, ⁇ MA, 1800-2100 ° C, preferably ⁇ 1900-2050 ° C.
- each sialon is formed, but the luminescence center element is not sufficiently dissolved in the sialon crystal, so that the emission intensity is lowered. If this temperature is exceeded, the cause is not known, but the light emission intensity may decrease.
- the firing time is appropriately selected between 4 and 36 hours.
- the nitrogen gas pressure in the atmosphere is set higher than the decomposition pressure of the nitride nitride to prevent the formation of silicon metal.
- the circularity of the obtained phosphor particles is improved, and the average particle size and particle size distribution can be controlled.
- the luminous efficiency of the LED used can be improved.
- the distribution of the elements involved in the light emission in the inner and outer peripheral parts of the obtained sialon phosphor can be generated by adjusting the conditions. When the concentration at the outer periphery is higher than the inside, the phosphor And the luminous efficiency of the LED using it is improved.
- the present invention is a method for producing a sialon phosphor, characterized in that sialon powder synthesized in advance is added to the raw material powder and mixed. According to this method, the phosphor particles to be added are grown larger, and the concentration of the elements involved in the light emission at the outer peripheral portion of the phosphor particles is high at the outer peripheral portion of the particle where the concentration is low inside the particle. I can make it. As a result, the emission intensity of the phosphor can be further increased, and the luminous efficiency of the LED using the phosphor can be increased.
- the sialon powder to be added preferably has a high degree of circularity, for example, particles of 0.75 or more, and sialon crystals grow on the outer periphery of the sialon powder. Can be made. As a result, secondary particles with a small number of primary particles are formed, so that unnecessary dispersion and absorption of light inside the phosphor particles can be reduced, and the emission intensity of the phosphor is further increased. The luminous efficiency of the LED used can be increased.
- sialon powder added to the raw material ⁇ -type sialon is used when synthesizing ⁇ -type sialon, and type-sialon is used when synthesizing type sialon.
- other sialons and other nitrides or oxynitrides may contain 10% by mass or less. If it is contained in an amount of more than 10% by mass, it is preferable because it can make the ⁇ -sialon single phase during the synthesis reaction if it is less than the force that may deteriorate the fluorescence characteristics.
- the amount added is 5-50% by mass with respect to 100% by mass of the total amount of raw material powder. The emission intensity can be improved at 5% or more, and the productivity is sufficiently good at 50% or less.
- the sialon with a high concentration at the outer periphery and a low inside is advantageous because it allows the powder to be synthesized.
- a sialon phosphor with high emission intensity can be obtained as it is after being taken out of the heating furnace through each step.
- an appropriate solution can be obtained.
- a phosphor that falls within the scope of the present invention can be obtained by pulverization, pulverization, and classification.
- a general pulverizer such as a ball mill, a rough mill, a jet mill or the like can be used.
- pulverization with high strength is not preferable because a large amount of powder having a fine particle diameter is produced.
- moderate pulverization has the effect of adjusting the shape of the phosphor particles and increasing the circularity.
- a process for removing the produced fine powder may be required.
- general classifiers such as air classifier, water classifier, sieve, etc. can be used, but air classifier and water classifier are suitable for removing fine powder.
- the present invention is a light-emitting element including the sialon phosphor described above and an LED having a maximum emission wavelength of 240 to 480 nm as constituent elements.
- the phosphor of the present invention has high luminous efficiency of itself, and can also increase the luminous efficiency (light extraction efficiency) of the LED using the phosphor. Therefore, the LED of the present invention is high. The luminous efficiency is shown.
- the sialon phosphor of the present invention may form a transparent film having an antireflection function on the surface, or may be treated with a silane coupling agent to form a resin and phosphor used for LED assembly. Adhesion is improved, and the dispersibility of the phosphor in the resin is improved. As a result, the LED characteristics can be improved.
- a-type sialon powder (hereinafter referred to as arsenic powder) to be contained in the raw material powder:
- arsenic powder As the composition of the raw material powder, 75.4% by weight of the nitride nitride powder, 14% by weight of the aluminum nitride powder, carbonic acid The calcium powder was 5.5% by mass, the calcium fluoride powder was 4.3% by mass, and the europium oxide powder was 0.8% by mass.
- This raw material powder was mixed in a ethanol solvent with a wet nitrided pot and a ball for 3 hours by wet ball milling, filtered and dried to obtain a mixed powder.
- the mixed powder was passed through a sieve having a mesh size of 75 zm, and then filled into a boron nitride crucible (N1 grade, manufactured by Denki Kagaku Kogyo). Heat treatment was performed at 170 0 ° C. for 5 hours. The obtained product was lightly crushed and passed through a sieve with a mesh opening of 45 / im to obtain ⁇ core powder.
- Part of the ⁇ -nuclear powder A is further subjected to a nitrided carbon in an ethanol solvent. Wet ball milling with a pot and balls was performed for 24 hours, filtered and dried to obtain ⁇ core powder B.
- the specific surface area of the ⁇ -type sialon powder and ⁇ -type sialon fine powder was measured using a constant volume gas adsorption method with a specific surface area measuring device (BELS ⁇ RP_mini) manufactured by Nippon Bell Co., Ltd. Calculated. Note that the sample should be stored in advance at 305 ° C in an atmospheric pressure N flow.
- the arsenic powder A or arsenic powder B, the silicon nitride powder, the aluminum nitride powder, the calcium carbonate powder, and the europium oxide powder are used so as to be a single-phase sialon phase after synthesis.
- the composition shown in Table 1 was adopted.
- the mixed composition (mass%) of the raw material powder of Example 1 was sucrose powder A 5.
- the mixed composition of the raw material powder of Example 2 is as follows: nucleated powder A 15.0%, Si N 63.8%, A1N
- the mixing composition of the raw material powder of Example 3 is as follows: ⁇ core powder A 40%, Si N 29.8%, A1N 5.5%, CaCO 4.3%, Eu
- the mixing composition of the raw material powder of Comparative Example 1 is that no ⁇ -nuclear powder is added, Si N is 74.5%, A1N
- the mixed composition of the raw material powder of Comparative Example 2 is as follows: ⁇ core powder 15. 15.0%, Si ⁇ 63.3%, A1N 11.8%, CaCO 9.2
- the blended raw material powder is wet ball milled using ethanol as a solvent in a plastic pot and a nitrided nitride ball, and the solvent is removed by a rotary evaporator and passed through a sieve with a mesh opening of 75 ⁇ m. To obtain a mixed powder.
- the specific surface area was measured by the method described above.
- Fluorescence characteristics were measured using a spectrofluorimeter (F4500, manufactured by Hitachi High-Technologies Corp.) calibrated using the rhodamine B method and a standard light source, and the fluorescence wavelength was measured at 455 nm excitation light, and the peak wavelength, peak intensity, and luminance were measured. Asked. Both the peak intensity and luminance are shown as relative values when Example 1 is 100. Further, CIE1931 chromaticity coordinate values (x, y) were determined from the fluorescence spectrum. The evaluation results are shown in Tables 2 and 3.
- Example 2 a specific surface area of ⁇ 3, respectively, 0. 47m 2 / g, 0. 31m 2 / g, a 0. 36MVg, in the case of Comparative Examples 1 and 2, respectively, 0. 72m 2 / g, 0.61 m 2 / g.
- the peak wavelengths of the fluorescence spectra obtained with the phosphors of Examples 1 to 3 were 585 nm, 588 nm, and 589 nm, respectively. Was also 587 nm.
- the relative peak intensities of the fluorescence spectra obtained with the phosphors of Examples 1 to 3 are 100%, 118% and 110%, respectively. In Comparative Examples 1 and 2, 85 %, 95%.
- the relative luminances of the fluorescence spectra obtained with the phosphors of Examples 1 to 3 are 100%, 1 16%, and 107%, respectively, and in the case of Comparative Examples 1 and 2, 85%, 95%.
- the chromaticity coordinate values (x, y) of the fluorescence spectra obtained with the phosphors of Examples 1 to 3 are (0. 518, 0.474), (0. 524, 0. 469), In the case of Comparative Examples 1 and 2, they were (0. 517, 0.475) and (0. 519, 0. 473), respectively.
- the ratio of A1N strongest peak intensity to (102) plane diffraction line intensity of a-type sialon is They were 32% and 6%, respectively.
- the peak wavelength of the fluorescence spectrum was 576 nm, and the relative peak intensity was a low 38%.
- Examples 4 and 5 As shown in Table 4, the passing rates of the phosphor powders of Examples 4 and 5 were 38% and 34%, respectively.
- the specific surface areas of Examples 4 and 5 were 0.47 mVg and 0.42 mVg, respectively. From X-ray diffraction, the crystal phases of Examples 4 and 5 were all ct type sialon only.
- the lattice constants a were 0.77839A and 0.77838A, respectively, and the lattice constants c were 0.5690A and 0.5688A, respectively.
- the peak wavelengths of the fluorescence spectra obtained with the phosphors of Examples 4 and 5 were 585 nm and 584 nm, respectively.
- the relative peak intensities of the fluorescence spectra obtained with the phosphors of Examples 4 and 5 were 101% and 108%, respectively.
- the relative luminances of the fluorescence spectra obtained with the phosphors of Examples 1 to 3 were 100% and 108%, respectively.
- the chromaticity coordinate values (x, y) of the fluorescent spectrum obtained by the phosphors of Examples 4 and 5 are (0. 518, 0. 474), (0. 517, 0. 475), respectively. there were.
- the composition of the raw material powder is 150 parts by mass of nitride nitride powder (Ube Industries, E10), 28 parts by mass of aluminum nitride powder (Tokuyama, F grade), europium oxide powder (Shin-Etsu Chemical Co., Ltd., RU grade) was 1.6 parts by mass, and calcium fluoride powder (manufactured by Wako Pure Chemical Industries, Ltd.) was 13 parts by mass.
- the above raw material powder was put into a nylon pot with an internal volume of 21 together with 470 ml of ethanol, 1.4 kg of nitrided silicon balls and 10 g of butyral (manufactured by Electrochemical Co., 3000K), and mixed with a wet Bonole mill. Went for hours.
- the obtained slurry was sprayed with a spray dryer (manufactured by Fujisaki Denki, Mikuguchi Mist Dryer MDL-050B) to prepare granules.
- the granules were observed with an electron microscope and found to have a particle size of 10-30 / im.
- the average circularity of the powder was measured with a flow particle image measuring device (FPIA3000) manufactured by Sysmetas.
- the measurement sample was prepared by adding the powder to be measured to water whose viscosity was adjusted by adding propylene glycol and dispersing with ultrasonic waves.
- an average value of 500 or more data having an area circle equivalent diameter in the range of 0.5 to 100 zm was taken.
- the particle size distribution of the obtained powder was measured by a laser diffraction scattering method (using a “LS_230 type” particle size distribution measuring device manufactured by Coulter).
- the preparation of the sample for particle size distribution measurement was in accordance with the measurement conditions for silicon nitride in Table 1 of JIS R 1629-1997.
- the concentration of the element involved in the light emission in the particles was determined as follows.
- the obtained phosphor powder was embedded in an epoxy resin and cut using a cross section polisher (SM-9010) manufactured by JEOL to prepare a sample for electron microscope observation of the particle cross section. It, day Using this electron beam microanalyzer CIXA-8200), the elements involved in the light emission of the cross section of the particles (Eu in this case) were mapped.
- the particles for element mapping particles having a particle size in the vicinity of the average particle size measured in advance were appropriately selected.
- compositions X, ⁇ , m, and n of the ⁇ -type sialon phosphor of Example 6 were 0.87, 0.034, 1.80, and 0.23, respectively.
- the average circularity of the ⁇ -type sialon phosphor was 0.86, and the particle size distributions D and D were 11 ⁇ 6 / im and 4.2 / im, respectively.
- Examples 7 to 13 The starting material powder of 13 is calcium oxide instead of the calcium fluoride of Example 6, except that the same raw material powder composition as in Example 6 is used. Finally, the ⁇ -sialon phosphor powder synthesized in Example 6 was added at a blending ratio as shown in Table 6. Using this raw material powder, ⁇ -sialon phosphors of Examples 7 to 13 were synthesized in the same manner as in Example 6. As shown in Table 6, measured values and calculated values were obtained in the same manner as in Example 6. Asked.
- Example 6 As shown in Table 6, the amount of the above-mentioned diamond sialon phosphor powder contained in the starting material of Example 7 was 2% by mass. The average circularity of the model sialon phosphor synthesized in Example 7 was 0.79, and D and D in the particle size distribution were 1 1. ⁇ ⁇ ⁇ and 4.2 x m, respectively.
- the amount of the model sialon phosphor powder contained in the starting material of Example 8 was 5% by mass.
- the average circularity of the model sialon phosphor synthesized in Example 8 was 0.84, and D and D of the particle size distribution were 13 2 / im and 5. ⁇ , respectively.
- Example 9 The amount of the ⁇ -sialon phosphor powder contained in the starting material of Example 9 was 10% by mass.
- the ⁇ -sialon phosphor synthesized in Example 9 had an average circularity of 0.86, and D and D in the particle size distribution were 18 ⁇ O / im and 6.3 ⁇ , respectively.
- the amount of the ⁇ -sialon phosphor powder contained in the starting material of Example 10 was 20% by mass.
- the average circularity of the model sialon phosphor synthesized in Example 10 was 0.91, and D and D of the particle size distribution were 19. 19. ⁇ -m and 8. respectively.
- the amount of the above-mentioned template sialon phosphor powder contained in the starting material of Example 1 was 30% by mass.
- the average circularity of the model sialon phosphor synthesized in Example 11 was 0.92, and D and D of the particle size distribution were 19. ⁇ ⁇ -m and 8. respectively.
- Model sialon firefly The internal and external concentrations of Eu, an M2 metal added to the light body, were 4 and 8, respectively.
- the emission peak intensity of the fluorescence spectrum was 134.
- the amount of the ⁇ -sialon phosphor powder contained in the starting material of Example 12 was 40% by mass.
- the average circularity of the model sialon phosphor synthesized in Example 12 was 0.92, and D and D of the particle size distribution were 17.5 zm and 7. respectively.
- model sialon phosphor powder contained in the starting material of Example 13 was 80% by mass.
- the average circularity of the model sialon phosphor synthesized in Example 13 was 0.88, and D and D of the particle size distribution were 13. ⁇ ⁇ -m and 6. respectively.
- the ⁇ -sialon phosphor of Comparative Example 4 has an average circularity of 0.73, and the particle size distributions D and D
- the internal and external concentrations of the bimetallic Eu were 6 and 6, respectively.
- the emission peak intensity of the fluorescence spectrum was 100. If the granulation process is not performed, it can be seen that the average circularity decreases and the emission intensity is low.
- Nitride Ube Industries, E10, 91 parts by weight, aluminum nitride (Tokuyama, F Dale) 6.8 parts by weight, Alumina (Daimei Chemical, TM—DAR grade) 0.2 parts by weight, oxide Piaum (manufactured by Shin-Etsu Chemical Co., Ltd., RU grade) 2.0 parts by weight was synthesized and sialon was synthesized in the same manner as in Example 6 except that 12 hours of baking was performed at 20000 ° C. A j3-type sialon phosphor was obtained, and the average circularity, particle size distribution, Eu concentration, and luminescence were the same as in Example 6. The strength and composition were determined.
- the composition Z of the type sialon phosphor of Example 14 was 0.27, and the content of Eu as an M3 metal was 0.14 atm%.
- the average circularity of the type sialon phosphor was 0.77, and D and D of the particle size distribution were 12.5 zm and 4.
- Example 14 In addition to the raw material powder of Example 14, the type phosphor powder obtained in Example 14 was added at the blending ratio shown in Table 7, and the ⁇ -type sialon fluorescence of Example 15 21 was obtained in the same manner as Example 14. The body was synthesized, and measured values and calculated values were obtained in the same manner as in Example 14 as shown in Table 7.
- Example 15 As shown in Table 7, the amount of the ⁇ -sialon phosphor powder contained in the starting material of Example 15 was 2% by mass. The average circularity of the ⁇ -sialon phosphor synthesized in Example 15 was 0 ⁇ 78, and D and D of the particle size distribution were 13 ⁇ 2 / im and 4.8 ⁇ , respectively.
- the amount of the above [Type 3 sialon phosphor powder contained in the starting material of Example 16 was 5% by mass.
- the average circularity of the j3 type sialon phosphor synthesized in Example 16 was 0.80, and D and D of the particle size distribution were 14.9 zm and 5.9 xm, respectively.
- j3 type sialon firefly The internal and external concentrations of Eu, an M3 metal added to the light body, were 7 and 8, respectively.
- the emission peak intensity of the fluorescence spectrum was 121.
- the amount of the ⁇ -type sialon phosphor powder contained in the starting material of Example 17 is 10% by mass, and the composition ⁇ of the j3-type sialon phosphor synthesized in Example 17 is 0.27, and M3 The content of Eu, which is a metal, was 0.14 atm%.
- the average circularity of the / 3 type sialon phosphor was 0.84, and D and D of the particle size distribution were 17. ⁇ ⁇ ⁇ and 7.6 x m, respectively. ⁇
- the amount of the [3-type sialon phosphor powder contained in the starting material of Example 18 was 20% by mass.
- the average circularity of the j3 type sialon phosphor synthesized in Example 18 was 0.88, and D and D of the particle size distribution were 20.7 zm and 9. respectively.
- the amount of the ⁇ -type sialon phosphor powder contained in the starting material of Example 19 is 30% by mass, the composition is 0.27, and the content of Eu, which is the three metals, is 0.14 atm%. there were.
- the ⁇ -sialon phosphor synthesized in Example 19 has an average circularity of 0.90 and a particle size distribution of D
- the amount of the ⁇ -sialon phosphor powder contained in the starting material of Example 20 was 40% by mass.
- the average sphericity of the type sialon phosphor synthesized in Example 20 was 0.90, and D and D of the particle size distribution were 21. ⁇ and 8.7 x m, respectively.
- the amount of the [type 3 sialon phosphor powder contained in the starting material of Example 21 was 80% by mass.
- the average circularity of the j3 type sialon phosphor synthesized in Example 21 was 0.82, and the particle size distributions D and D were 14. ⁇ ⁇ and 6. respectively.
- the internal and external concentrations of Eu, an M3 metal added to the light body, are 6 and 8, respectively. It was.
- the emission peak intensity of the fluorescence spectrum was 118.
- a [Type 3 sialon phosphor of Comparative Example 5 was synthesized in the same manner as Example 14 except that the raw material powder was mixed with a ball mill, placed in a boron nitride crucible, and fired without a debinding step.
- the composition ⁇ of the ⁇ -type sialon phosphor of Comparative Example 5 was 0.27, and the content of Eu, which is ⁇ 3 metal, was 0.14 atm%.
- the average circularity of the j3 type sialon phosphor of Comparative Example 5 is 0.69, and the particle size distributions D and D are 8.5 ⁇ and 1.4 ⁇ m, respectively.
- Each of the phosphor powders obtained in Examples 6 and 10 and Comparative Example 4 was added to 100 g of water with an epoxy-based silane coupling agent (manufactured by Shin-Etsu Silicone, KBE402) 1. With Og, left overnight with stirring. . After that, the sialon phosphor treated with the filtered and dried silane coupling agent was kneaded with 5 g of epoxy resin (NLD-SL-2101 made by SUNREC), and the emission wavelength 460 nm was electrically connected in advance into the surface mount package for LED. This kneaded product was potted on a blue LED, vacuum degassed, and heat-cured at 120 ° C to produce a surface-mounted LED. Table 8 shows the luminous efficiency obtained by measuring the emission spectrum of light generated by applying a current of 20 mA to this surface-mounted LED.
- an epoxy-based silane coupling agent manufactured by Shin-Etsu Silicone, KBE402
- the luminous efficiencies of the LEDs of Examples 22 and 23 and Comparative Example 6 were 4 llm / W, 511 m / W, and 361 m / W, respectively.
- epoxy-based silane coupling agent (KBE402, manufactured by Shin-Etsu Silicone) in 100 g of water 1. Hold it with Og and leave it overnight with stirring. . After that, the sialon phosphor treated with the filtered and dried silane coupling agent is kneaded with 5 g of epoxy resin (NLD_SL_ 2101 made by SUNREC), and blue light with an emission wavelength of 460 nm that is electrically connected to the surface mount package for LED in advance. The kneaded product was potted on the LED, vacuum degassed, and heated and cured at 120 ° C to produce a surface-mounted LED. Table 9 shows the light emission efficiency obtained by measuring the emission spectrum of light generated by applying a current of 20 mA to this surface-mounted LED.
- a phosphor having excellent light emission characteristics can be produced with good reproducibility and mass productivity.
- the template sialon phosphor of the present invention exhibits a light emission characteristic having a peak in the region of 540 to 600 nm by excitation light of ultraviolet to blue light. It is suitable as a phosphor for white LEDs using a blue LED as the light source, and is very useful in industry.
- the luminaire of the present invention uses the phosphor, it has excellent light emission characteristics and is extremely useful in industry where energy efficiency is high.
- the second sialon phosphor of the present invention is remarkably superior in fluorescence properties as compared with conventional products, it can be suitably used for various light emitting applications including LEDs.
- a white LED can be provided in combination with an LED having a maximum emission wavelength of 240 to 480 nm, it can be applied to various applications by replacing the fluorescent lamp that has been used conventionally.
- the phosphor having the above characteristics can be stably provided in a large amount, which is extremely useful industrially.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Structural Engineering (AREA)
- Luminescent Compositions (AREA)
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020107028742A KR101204573B1 (ko) | 2006-05-10 | 2007-05-08 | 사이알론 형광체 및 그 제조 방법 및 그것을 이용한 조명기구 및 발광소자 |
CN200780016969.6A CN101443432B (zh) | 2006-05-10 | 2007-05-08 | 赛隆荧光粉及其制备方法以及使用该荧光粉的照明器具和发光元件 |
KR1020127018633A KR101221683B1 (ko) | 2006-05-10 | 2007-05-08 | 사이알론 형광체 및 그 제조 방법 및 그것을 이용한 조명기구 및 발광소자 |
EP07742962.9A EP2022835B1 (en) | 2006-05-10 | 2007-05-08 | Sialon phosphor, process for producing the same, and illuminator and luminescent element employing the same |
US12/300,127 US20100237767A1 (en) | 2006-05-10 | 2007-05-08 | Sialon phosphor, process for producing the same, and illuminator and luminescent element employing the same |
KR1020127018634A KR101221691B1 (ko) | 2006-05-10 | 2007-05-08 | 사이알론 형광체 및 그 제조 방법 및 그것을 이용한 조명기구 및 발광소자 |
US13/464,855 US20120270049A1 (en) | 2006-05-10 | 2012-05-04 | Sialon phosphor, process for producing the same, and illuminator and luminescent element employing the same |
US13/791,762 US8685279B2 (en) | 2006-05-10 | 2013-03-08 | Sialon phosphor, process for producing the same, and illuminator and luminescent element employing the same |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2006-131018 | 2006-05-10 | ||
JP2006131018A JP5124101B2 (ja) | 2006-05-10 | 2006-05-10 | α型サイアロン蛍光体及びその製造方法、並びに照明器具 |
JP2006168759A JP2007332324A (ja) | 2006-06-19 | 2006-06-19 | サイアロン蛍光体とその製造方法、およびそれを用いた発光素子 |
JP2006-168759 | 2006-06-19 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/300,127 A-371-Of-International US20100237767A1 (en) | 2006-05-10 | 2007-05-08 | Sialon phosphor, process for producing the same, and illuminator and luminescent element employing the same |
US13/464,855 Division US20120270049A1 (en) | 2006-05-10 | 2012-05-04 | Sialon phosphor, process for producing the same, and illuminator and luminescent element employing the same |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2007129713A1 true WO2007129713A1 (ja) | 2007-11-15 |
Family
ID=38667822
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2007/059527 WO2007129713A1 (ja) | 2006-05-10 | 2007-05-08 | サイアロン蛍光体及びその製造方法並びにそれを用いた照明器具及び発光素子 |
Country Status (5)
Country | Link |
---|---|
US (3) | US20100237767A1 (ja) |
EP (2) | EP2022835B1 (ja) |
KR (5) | KR20110004917A (ja) |
CN (2) | CN102676163B (ja) |
WO (1) | WO2007129713A1 (ja) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011083671A1 (ja) * | 2010-01-08 | 2011-07-14 | シャープ株式会社 | 蛍光体、発光装置およびそれを用いた液晶表示装置 |
CN102300955A (zh) * | 2009-01-27 | 2011-12-28 | 电气化学工业株式会社 | α型赛隆荧光体、其制造方法及发光装置 |
WO2012032818A1 (ja) * | 2010-09-09 | 2012-03-15 | 電気化学工業株式会社 | Eu固溶β型サイアロンの製造方法 |
US9024519B2 (en) | 2011-01-26 | 2015-05-05 | Denki Kagaku Kogyo Kabushiki Kaisha | α-SiAlON, light-emitting device and use thereof |
JP2018109075A (ja) * | 2016-12-28 | 2018-07-12 | デンカ株式会社 | 緑色蛍光体、その製造方法、発光素子及び発光装置 |
JP2019186537A (ja) * | 2018-03-30 | 2019-10-24 | 日亜化学工業株式会社 | 波長変換部材及び発光装置 |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102676163B (zh) | 2006-05-10 | 2014-11-05 | 电气化学工业株式会社 | 赛隆荧光粉及其制备方法以及使用该荧光粉的照明器具和发光元件 |
JP5122765B2 (ja) * | 2006-06-09 | 2013-01-16 | 電気化学工業株式会社 | 蛍光体の製造方法、蛍光体と照明器具 |
US9000664B2 (en) | 2009-04-06 | 2015-04-07 | Sharp Kabushiki Kaisha | Phosphor particle group, light emitting apparatus using the same, and liquid crystal display television |
KR20110082837A (ko) * | 2010-01-12 | 2011-07-20 | 삼성전자주식회사 | 나이트라이드 형광체, 그 제조 방법 및 그것을 사용한 백색 발광 소자 |
KR101455486B1 (ko) * | 2010-03-31 | 2014-10-27 | 우베 고산 가부시키가이샤 | 사이알론계 산질화물 형광체의 제조 방법 및 사이알론계 산질화물 형광체 |
BR112013013485B1 (pt) | 2010-12-01 | 2020-12-29 | Lumileds Holding B.V. | material ba1-x-y-zsrxcayeuz)2si5-a-balan8-a-4boa+4b, estrutura emissora de luz e sistema |
KR101772656B1 (ko) * | 2011-05-19 | 2017-08-29 | 삼성전자주식회사 | 형광체 및 발광장치 |
KR101877416B1 (ko) * | 2011-11-23 | 2018-07-11 | 엘지이노텍 주식회사 | 산질화물 형광체 및 그를 포함한 발광소자 패키지 |
CN103827260B (zh) * | 2012-03-16 | 2015-11-25 | 株式会社东芝 | 荧光体、荧光体的制造方法及发光装置 |
EP2837669B1 (en) * | 2012-03-16 | 2016-08-31 | Kabushiki Kaisha Toshiba | Phosphor, phosphor production method, and light-emitting device |
DE102013100429B4 (de) | 2013-01-16 | 2023-12-07 | Osram Gmbh | Verfahren zur Herstellung eines pulverförmigen Precursormaterials und Verwendung eines mit dem Verfahren hergestellten pulverförmigen Precursormaterials |
AT513747B1 (de) | 2013-02-28 | 2014-07-15 | Mikroelektronik Ges Mit Beschränkter Haftung Ab | Bestückungsverfahren für Schaltungsträger und Schaltungsträger |
US10294419B2 (en) * | 2015-08-28 | 2019-05-21 | Denka Company Limited | Charged particle radiation measuring method and charged particle radiation measuring device |
US11851596B2 (en) | 2016-08-12 | 2023-12-26 | Osram Oled Gmbh | Lighting device |
DE102016121692A1 (de) | 2016-08-12 | 2018-02-15 | Osram Gmbh | Leuchtstoff und Verfahren zur Herstellung eines Leuchtstoffs |
WO2019029849A1 (de) * | 2016-11-11 | 2019-02-14 | Osram Opto Semiconductors Gmbh | Dimmbare lichtquelle |
US10608149B2 (en) | 2018-03-30 | 2020-03-31 | Nichia Corporation | Wavelength converting member and light emitting device |
CN110387231A (zh) * | 2018-04-17 | 2019-10-29 | 中国科学院上海硅酸盐研究所 | 一种β-SiAlON:Eu,M荧光粉及其制备方法 |
EP3726206B1 (en) * | 2019-03-26 | 2022-11-02 | FEI Company | Methods and systems for inclusion analysis |
CN110655920A (zh) * | 2019-09-20 | 2020-01-07 | 北京科技大学 | 一种二价铕掺杂的α-sialon基长余辉发光材料及制备方法 |
Citations (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05152609A (ja) | 1991-11-25 | 1993-06-18 | Nichia Chem Ind Ltd | 発光ダイオード |
JPH0799345A (ja) | 1993-09-28 | 1995-04-11 | Nichia Chem Ind Ltd | 発光ダイオード |
JP2002194347A (ja) * | 2000-12-22 | 2002-07-10 | Toshiba Corp | 蛍光体,その製造方法および発光デバイス |
JP2003124527A (ja) | 2001-07-16 | 2003-04-25 | Patent Treuhand Ges Elektr Gluehlamp Mbh | 光源として少なくとも1つのledを備えた照明ユニット |
JP2003206481A (ja) | 2001-09-25 | 2003-07-22 | Patent Treuhand Ges Elektr Gluehlamp Mbh | 光源として少なくとも1つのledを備えた照明ユニット |
JP2003253260A (ja) * | 2002-03-04 | 2003-09-10 | Kasei Optonix Co Ltd | 硫化亜鉛蛍光体 |
JP2003336059A (ja) | 2002-05-23 | 2003-11-28 | National Institute For Materials Science | サイアロン系蛍光体 |
JP2004186278A (ja) | 2002-11-29 | 2004-07-02 | Toyoda Gosei Co Ltd | 発光装置及び発光方法 |
JP2004244560A (ja) | 2003-02-17 | 2004-09-02 | Nichia Chem Ind Ltd | シリコンナイトライド系蛍光体及びそれを用いた発光装置 |
JP2004277663A (ja) * | 2003-03-18 | 2004-10-07 | National Institute For Materials Science | サイアロン蛍光体とその製造方法 |
JP2005097011A (ja) * | 2003-09-22 | 2005-04-14 | Shoei Chem Ind Co | 酸窒化物の製造方法 |
JP2005105177A (ja) * | 2003-09-30 | 2005-04-21 | Sumitomo Osaka Cement Co Ltd | 蛍光体粒子、及びその製造方法、並びに蛍光体粒子を用いた発光装置 |
JP3668770B2 (ja) | 2001-06-07 | 2005-07-06 | 独立行政法人物質・材料研究機構 | 希土類元素を付活させた酸窒化物蛍光体 |
JP2005255895A (ja) | 2004-03-12 | 2005-09-22 | National Institute For Materials Science | 蛍光体とその製造方法 |
WO2005123876A1 (ja) | 2004-06-18 | 2005-12-29 | National Institute For Materials Science | α型サイアロン及びα型サイアロン蛍光体並びにその製造方法 |
WO2006011542A1 (ja) * | 2004-07-28 | 2006-02-02 | Dowa Electronics Materials Co., Ltd. | 蛍光体およびその製造方法、並びに光源 |
JP2006052337A (ja) * | 2004-08-12 | 2006-02-23 | Fujikura Ltd | サイアロン蛍光体およびその製造方法 |
JP2008045271A (ja) | 2006-08-10 | 2008-02-28 | Aqua Control:Kk | 地下水集水多重管 |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL8400660A (nl) * | 1984-03-01 | 1985-10-01 | Philips Nv | Luminescerend scherm. |
JPH0776129B2 (ja) | 1988-04-14 | 1995-08-16 | 日本特殊陶業株式会社 | 酸窒化珪素焼結体の製造方法 |
US5096864A (en) * | 1990-09-18 | 1992-03-17 | Norton Company | Process of spray drying sialon |
JPH069956A (ja) * | 1991-12-27 | 1994-01-18 | Fuji Photo Film Co Ltd | 球形焼結蛍光体およびその製造法 |
WO2002028800A2 (en) * | 2000-10-02 | 2002-04-11 | Indexable Cutting Tools Of Canada Limited | 'SiAION MATERIAL AND CUTTING TOOLS MADE THEREOF' |
JP4052136B2 (ja) * | 2003-02-06 | 2008-02-27 | 宇部興産株式会社 | サイアロン系酸窒化物蛍光体およびその製造方法 |
JP4143516B2 (ja) | 2003-10-16 | 2008-09-03 | キヤノン株式会社 | 画像処理装置、画像検証方法、プログラムおよび記憶媒体 |
JP4277666B2 (ja) * | 2003-12-01 | 2009-06-10 | 宇部興産株式会社 | サイアロン系蛍光体の製造方法およびサイアロン系蛍光体 |
JP4888624B2 (ja) * | 2004-07-30 | 2012-02-29 | 独立行政法人物質・材料研究機構 | α型サイアロン粉末の製造方法 |
CN101982891A (zh) * | 2005-02-28 | 2011-03-02 | 电气化学工业株式会社 | 荧光体及其制造方法及使用了该荧光体的发光元件 |
US8003011B2 (en) * | 2005-05-12 | 2011-08-23 | National Institute For Materials Science | β type sialon fluorescent substance |
JP2006348139A (ja) * | 2005-06-15 | 2006-12-28 | Fujikura Ltd | アルファサイアロン蛍光体粉末の製造方法 |
WO2007018260A1 (ja) * | 2005-08-10 | 2007-02-15 | Mitsubishi Chemical Corporation | 蛍光体及びそれを用いた発光装置 |
CN102676163B (zh) | 2006-05-10 | 2014-11-05 | 电气化学工业株式会社 | 赛隆荧光粉及其制备方法以及使用该荧光粉的照明器具和发光元件 |
WO2008062781A1 (fr) * | 2006-11-20 | 2008-05-29 | Denki Kagaku Kogyo Kabushiki Kaisha | Substance fluorescente et son procédé de fabrication, et dispositif électroluminescent |
EP2500399B1 (en) | 2009-11-10 | 2018-05-30 | Denka Company Limited | Method for producing beta-sialon and light-emitting device using the same |
-
2007
- 2007-05-08 CN CN201210072617.5A patent/CN102676163B/zh not_active Expired - Fee Related
- 2007-05-08 KR KR1020107028743A patent/KR20110004917A/ko active Search and Examination
- 2007-05-08 KR KR1020127018633A patent/KR101221683B1/ko active IP Right Grant
- 2007-05-08 WO PCT/JP2007/059527 patent/WO2007129713A1/ja active Search and Examination
- 2007-05-08 US US12/300,127 patent/US20100237767A1/en not_active Abandoned
- 2007-05-08 KR KR1020087029585A patent/KR20090018085A/ko active Search and Examination
- 2007-05-08 KR KR1020107028742A patent/KR101204573B1/ko not_active IP Right Cessation
- 2007-05-08 CN CN201210072625.XA patent/CN102643645B/zh not_active Expired - Fee Related
- 2007-05-08 EP EP07742962.9A patent/EP2022835B1/en not_active Expired - Fee Related
- 2007-05-08 EP EP16150385.9A patent/EP3093327A3/en not_active Ceased
- 2007-05-08 KR KR1020127018634A patent/KR101221691B1/ko not_active IP Right Cessation
-
2012
- 2012-05-04 US US13/464,855 patent/US20120270049A1/en not_active Abandoned
-
2013
- 2013-03-08 US US13/791,762 patent/US8685279B2/en not_active Expired - Fee Related
Patent Citations (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05152609A (ja) | 1991-11-25 | 1993-06-18 | Nichia Chem Ind Ltd | 発光ダイオード |
JPH0799345A (ja) | 1993-09-28 | 1995-04-11 | Nichia Chem Ind Ltd | 発光ダイオード |
JP2002194347A (ja) * | 2000-12-22 | 2002-07-10 | Toshiba Corp | 蛍光体,その製造方法および発光デバイス |
JP3668770B2 (ja) | 2001-06-07 | 2005-07-06 | 独立行政法人物質・材料研究機構 | 希土類元素を付活させた酸窒化物蛍光体 |
JP2003124527A (ja) | 2001-07-16 | 2003-04-25 | Patent Treuhand Ges Elektr Gluehlamp Mbh | 光源として少なくとも1つのledを備えた照明ユニット |
JP2003206481A (ja) | 2001-09-25 | 2003-07-22 | Patent Treuhand Ges Elektr Gluehlamp Mbh | 光源として少なくとも1つのledを備えた照明ユニット |
JP2003253260A (ja) * | 2002-03-04 | 2003-09-10 | Kasei Optonix Co Ltd | 硫化亜鉛蛍光体 |
JP2003336059A (ja) | 2002-05-23 | 2003-11-28 | National Institute For Materials Science | サイアロン系蛍光体 |
JP2004186278A (ja) | 2002-11-29 | 2004-07-02 | Toyoda Gosei Co Ltd | 発光装置及び発光方法 |
JP2004244560A (ja) | 2003-02-17 | 2004-09-02 | Nichia Chem Ind Ltd | シリコンナイトライド系蛍光体及びそれを用いた発光装置 |
JP2004277663A (ja) * | 2003-03-18 | 2004-10-07 | National Institute For Materials Science | サイアロン蛍光体とその製造方法 |
JP2005097011A (ja) * | 2003-09-22 | 2005-04-14 | Shoei Chem Ind Co | 酸窒化物の製造方法 |
JP2005105177A (ja) * | 2003-09-30 | 2005-04-21 | Sumitomo Osaka Cement Co Ltd | 蛍光体粒子、及びその製造方法、並びに蛍光体粒子を用いた発光装置 |
JP2005255895A (ja) | 2004-03-12 | 2005-09-22 | National Institute For Materials Science | 蛍光体とその製造方法 |
WO2005123876A1 (ja) | 2004-06-18 | 2005-12-29 | National Institute For Materials Science | α型サイアロン及びα型サイアロン蛍光体並びにその製造方法 |
WO2006011542A1 (ja) * | 2004-07-28 | 2006-02-02 | Dowa Electronics Materials Co., Ltd. | 蛍光体およびその製造方法、並びに光源 |
JP2006063323A (ja) * | 2004-07-28 | 2006-03-09 | Dowa Mining Co Ltd | 蛍光体およびその製造方法、並びに光源 |
JP2006052337A (ja) * | 2004-08-12 | 2006-02-23 | Fujikura Ltd | サイアロン蛍光体およびその製造方法 |
JP2008045271A (ja) | 2006-08-10 | 2008-02-28 | Aqua Control:Kk | 地下水集水多重管 |
Non-Patent Citations (7)
Title |
---|
"Dai 52 kai Ouyou Butsurigaku Kankei Rengou", KOUENKAI KOUEN YOKOUSYU, March 2005 (2005-03-01), pages 1614 - 1615 |
"Dai 65 kai Ouyou Butsurigakkai Gakujyutsu", KOUENKAI KOUEN YOKOUSYU, vol. 3, September 2004 (2004-09-01), pages 1282 - 1284 |
J. W. T. VAN RUTTEN ET AL.: "Carbothermal Preparation and Characterization of Ca-a-SiAlON", J. EUR. CERAM. SOC., vol. 15, 1995, pages 599 - 604 |
J.W.H VAN KREBEL: "On New Rare-Earth Doped M-Si-Al-O-N Materials", TU EINDHOVEN, 1998, pages 145 - 161 |
K. KOMEYA ET AL.: "Hollow Beads Composed of Nanosize Ca a-SiAlON Grains", J. AM. CERAM. SOC., vol. 83, 2000, pages 995 - 997, XP055005784, DOI: doi:10.1111/j.1151-2916.2000.tb01316.x |
M. MITOMO ET AL.: "Preparation of a-SiAlON Powders by Carbothermal Reduction and Nitridation", CERAM. INT., vol. 14, 1988, pages 43 - 48, XP024157845, DOI: doi:10.1016/0272-8842(88)90017-X |
See also references of EP2022835A4 |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102300955A (zh) * | 2009-01-27 | 2011-12-28 | 电气化学工业株式会社 | α型赛隆荧光体、其制造方法及发光装置 |
WO2011083671A1 (ja) * | 2010-01-08 | 2011-07-14 | シャープ株式会社 | 蛍光体、発光装置およびそれを用いた液晶表示装置 |
US8709283B2 (en) | 2010-01-08 | 2014-04-29 | Sharp Kabushiki Kaisha | Phosphor, light emitting apparatus, and liquid crystal display apparatus using the same |
US9496463B2 (en) | 2010-01-08 | 2016-11-15 | Ge Phosphors Technology, Llc | Phosphor, light emitting apparatus, and liquid crystal display apparatus using the same |
WO2012032818A1 (ja) * | 2010-09-09 | 2012-03-15 | 電気化学工業株式会社 | Eu固溶β型サイアロンの製造方法 |
US9024519B2 (en) | 2011-01-26 | 2015-05-05 | Denki Kagaku Kogyo Kabushiki Kaisha | α-SiAlON, light-emitting device and use thereof |
JP2018109075A (ja) * | 2016-12-28 | 2018-07-12 | デンカ株式会社 | 緑色蛍光体、その製造方法、発光素子及び発光装置 |
JP2019186537A (ja) * | 2018-03-30 | 2019-10-24 | 日亜化学工業株式会社 | 波長変換部材及び発光装置 |
Also Published As
Publication number | Publication date |
---|---|
CN102676163B (zh) | 2014-11-05 |
KR101221683B1 (ko) | 2013-01-11 |
KR101221691B1 (ko) | 2013-01-11 |
KR20090018085A (ko) | 2009-02-19 |
KR20110004916A (ko) | 2011-01-14 |
US20130193600A1 (en) | 2013-08-01 |
EP2022835A4 (en) | 2011-10-05 |
KR20110004917A (ko) | 2011-01-14 |
US20100237767A1 (en) | 2010-09-23 |
EP2022835A1 (en) | 2009-02-11 |
US8685279B2 (en) | 2014-04-01 |
CN102676163A (zh) | 2012-09-19 |
KR101204573B1 (ko) | 2012-11-26 |
CN102643645B (zh) | 2014-05-07 |
EP3093327A2 (en) | 2016-11-16 |
EP2022835B1 (en) | 2018-04-11 |
KR20120098885A (ko) | 2012-09-05 |
CN102643645A (zh) | 2012-08-22 |
US20120270049A1 (en) | 2012-10-25 |
EP3093327A3 (en) | 2017-05-03 |
KR20120096576A (ko) | 2012-08-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2007129713A1 (ja) | サイアロン蛍光体及びその製造方法並びにそれを用いた照明器具及び発光素子 | |
KR101732746B1 (ko) | α형 사이알론 형광체, 그의 제조법 및 발광 장치 | |
TWI411660B (zh) | A phosphor and a method for manufacturing the same, and a light-emitting element using the same | |
KR101354896B1 (ko) | 사이알론계 산질화물 형광체 및 그 제조방법 | |
JP5737693B2 (ja) | β型サイアロン、その製造方法及びそれを用いた発光装置 | |
JP2007332324A (ja) | サイアロン蛍光体とその製造方法、およびそれを用いた発光素子 | |
CN101443432B (zh) | 赛隆荧光粉及其制备方法以及使用该荧光粉的照明器具和发光元件 | |
JP2009096882A (ja) | 蛍光体とその製造方法 | |
JP5854051B2 (ja) | 酸窒化物蛍光体粉末及びその製造方法 | |
WO2007142289A1 (ja) | 蛍光体及びその製造方法並びにそれを用いた照明器具 | |
EP3135746B1 (en) | Method for producing nitride fluorescent material |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 07742962 Country of ref document: EP Kind code of ref document: A1 |
|
DPE1 | Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101) | ||
WWE | Wipo information: entry into national phase |
Ref document number: 12300127 Country of ref document: US Ref document number: 200780016969.6 Country of ref document: CN |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2007742962 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020087029585 Country of ref document: KR |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020107028743 Country of ref document: KR Ref document number: 1020107028742 Country of ref document: KR |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020127018634 Country of ref document: KR Ref document number: 1020127018633 Country of ref document: KR |
|
DPE1 | Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101) |