WO2018056447A1 - Phosphore, dispositif électroluminescent, dispositif d'éclairage, et dispositif d'affichage d'images - Google Patents
Phosphore, dispositif électroluminescent, dispositif d'éclairage, et dispositif d'affichage d'images Download PDFInfo
- Publication number
- WO2018056447A1 WO2018056447A1 PCT/JP2017/034593 JP2017034593W WO2018056447A1 WO 2018056447 A1 WO2018056447 A1 WO 2018056447A1 JP 2017034593 W JP2017034593 W JP 2017034593W WO 2018056447 A1 WO2018056447 A1 WO 2018056447A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- phosphor
- light
- less
- crystal
- emitting device
- Prior art date
Links
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 167
- 238000005286 illumination Methods 0.000 title claims description 8
- 239000013078 crystal Substances 0.000 claims abstract description 53
- 230000005284 excitation Effects 0.000 claims description 12
- 230000004913 activation Effects 0.000 claims description 7
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 description 39
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 34
- 239000001301 oxygen Substances 0.000 description 34
- 238000010304 firing Methods 0.000 description 33
- 238000000295 emission spectrum Methods 0.000 description 28
- 239000000203 mixture Substances 0.000 description 28
- 238000000034 method Methods 0.000 description 22
- 229910052791 calcium Inorganic materials 0.000 description 19
- 239000012071 phase Substances 0.000 description 17
- 239000011777 magnesium Substances 0.000 description 16
- 229910052712 strontium Inorganic materials 0.000 description 16
- 229910052684 Cerium Inorganic materials 0.000 description 15
- 239000000126 substance Substances 0.000 description 15
- 229910052693 Europium Inorganic materials 0.000 description 14
- 229910052749 magnesium Inorganic materials 0.000 description 14
- 239000002994 raw material Substances 0.000 description 14
- 229910052788 barium Inorganic materials 0.000 description 12
- 229910052710 silicon Inorganic materials 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 10
- 238000001514 detection method Methods 0.000 description 10
- 238000004453 electron probe microanalysis Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000002609 medium Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000000921 elemental analysis Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 229910052746 lanthanum Inorganic materials 0.000 description 7
- 230000007547 defect Effects 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 150000004767 nitrides Chemical class 0.000 description 6
- 238000000634 powder X-ray diffraction Methods 0.000 description 6
- 229910052727 yttrium Inorganic materials 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 230000004907 flux Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000001771 impaired effect Effects 0.000 description 5
- 238000009616 inductively coupled plasma Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 229910052688 Gadolinium Inorganic materials 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 238000000695 excitation spectrum Methods 0.000 description 4
- 229910052733 gallium Inorganic materials 0.000 description 4
- 239000002223 garnet Substances 0.000 description 4
- -1 imide compounds Chemical class 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 229910052582 BN Inorganic materials 0.000 description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 3
- 229910052779 Neodymium Inorganic materials 0.000 description 3
- 229910052772 Samarium Inorganic materials 0.000 description 3
- 229910004283 SiO 4 Inorganic materials 0.000 description 3
- 229910052771 Terbium Inorganic materials 0.000 description 3
- 229910052769 Ytterbium Inorganic materials 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 229910052706 scandium Inorganic materials 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910000789 Aluminium-silicon alloy Inorganic materials 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XPIIDKFHGDPTIY-UHFFFAOYSA-N F.F.F.P Chemical class F.F.F.P XPIIDKFHGDPTIY-UHFFFAOYSA-N 0.000 description 2
- 229910052765 Lutetium Inorganic materials 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 229910052775 Thulium Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 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
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000002050 diffraction method Methods 0.000 description 2
- 238000007580 dry-mixing Methods 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000005121 nitriding Methods 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910002706 AlOOH Inorganic materials 0.000 description 1
- 102100032047 Alsin Human genes 0.000 description 1
- 101710187109 Alsin Proteins 0.000 description 1
- 229910015999 BaAl Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910002538 Eu(NO3)3·6H2O Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 238000003991 Rietveld refinement Methods 0.000 description 1
- 229920001800 Shellac Polymers 0.000 description 1
- 229910007991 Si-N Inorganic materials 0.000 description 1
- 229910003564 SiAlON Inorganic materials 0.000 description 1
- 229910006294 Si—N Inorganic materials 0.000 description 1
- 229910003668 SrAl Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- RDYMFSUJUZBWLH-UHFFFAOYSA-N endosulfan Chemical compound C12COS(=O)OCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl RDYMFSUJUZBWLH-UHFFFAOYSA-N 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000002284 excitation--emission spectrum Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000006199 nebulizer Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 238000001683 neutron diffraction Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229940113147 shellac Drugs 0.000 description 1
- 238000010334 sieve classification Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/64—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
Definitions
- the present invention relates to a phosphor, a light emitting device, a lighting device, and an image display device.
- the LED used here is a white light emitting LED in which a phosphor is arranged on an LED chip that emits light of blue or near ultraviolet wavelength.
- a LED using a nitride phosphor that emits red light using blue light from the blue LED chip as an excitation light and a phosphor that emits green light on a blue LED chip has recently been used. It has been.
- green has a particularly high visual sensitivity to human eyes and contributes greatly to the overall brightness of the display.
- phosphors that emit green light include phosphors represented by a composition formula of Sr 2.7 Si 13 Al 3 O 2 N 21 : Eu 0.3 (Patent Document 1), and Si 6-z Al z O. z N 8-z (0 ⁇ z ⁇ 4.2) phosphor represented by the composition of (Patent Document 2), comprising a sialon crystal in which Eu is solid-solved in crystal having a ⁇ -Si 3 N 4 crystal structure A phosphor (Patent Document 3) and the like are disclosed.
- the present invention provides a novel phosphor that has a crystal structure different from that of conventional phosphors, has good light emission characteristics, and is effectively used in LED applications.
- M m Al a O x Si b N d [2] (In the above formula [2], M represents an activation element, 0 ⁇ m ⁇ 0.04 a + b 3 0 ⁇ a ⁇ 0.08 3.6 ⁇ d ⁇ 4.2 x ⁇ a)
- M element in the formula [1] or [2] is a sialon crystal in which Eu is dissolved in a crystal having a ⁇ -type Si 3 N 4 crystal structure. The phosphor described.
- a light emitting device comprising the phosphor described above.
- An illumination device comprising the light-emitting device according to [5] as a light source.
- An image display device comprising the light-emitting device according to [5] as a light source.
- the novel phosphor of the present invention has a crystal structure different from that of conventional phosphors and is excellent in light emission characteristics, so that it is effectively used for LED applications. Therefore, the light emitting device using the novel phosphor of the present invention is excellent in color rendering. Furthermore, the illumination device and the image display device including the light emitting device of the present invention are of high quality.
- FIG. 3 is a diagram showing excitation / emission spectra of the phosphor obtained in Example 1.
- the broken line represents the excitation spectrum, and the solid line represents the emission spectrum.
- a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
- each composition formula is delimited by a punctuation mark (,).
- commas when a plurality of elements are listed separated by commas (,), one or two or more of the listed elements may be included in any combination and composition.
- composition formula “(Ca, Sr, Ba) Al 2 O 4 : Eu” has “CaAl 2 O 4 : Eu”, “SrAl 2 O 4 : Eu”, and “BaAl 2 O 4 : Eu”. “Ca 1-x Sr x Al 2 O 4 : Eu”, “Sr 1-x Ba x Al 2 O 4 : Eu”, “Ca 1-x Ba x Al 2 O 4 : Eu”, “Ca 1-x-y Sr x Ba y Al 2 O 4: Eu " (. in the formula, 0 ⁇ x ⁇ 1,0 ⁇ y ⁇ 1,0 ⁇ a x + y ⁇ 1) all the comprehensive It shall be shown in the formula, 0 ⁇ x ⁇ 1,0 ⁇ y ⁇ 1,0 ⁇ a x + y ⁇ 1) all the comprehensive It shall be shown in
- the present invention includes the phosphor according to the first embodiment, the light emitting device according to the second embodiment, the illumination device according to the third embodiment, and the image display device according to the fourth embodiment.
- the phosphor according to the first embodiment of the present invention includes a crystal phase represented by the following formula [1].
- M elements are europium (Eu), manganese (Mn), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium It represents one or more elements selected from the group consisting of (Er), thulium (Tm) and ytterbium (Yb).
- M preferably contains at least Eu, and more preferably Eu.
- a part of Eu may be substituted with at least one element selected from the group consisting of Ce, Pr, Sm, Tb, and Yb, and Ce is more preferable in terms of emission quantum efficiency. That is, M is more preferably Eu and / or Ce, and more preferably Eu.
- the ratio of Eu with respect to the entire activation element is preferably 50 mol% or more, more preferably 70 mol% or more, and particularly preferably 90 mol% or more.
- Al represents aluminum.
- Al is another trivalent element that is chemically similar, for example, boron (B), gallium (Ga), indium (In), scandium (Sc), yttrium (Y), lanthanum (La), gadolinium (Gd ), Lutetium (Lu) or the like.
- Si represents silicon. Si may be partially substituted with other chemically similar tetravalent elements such as germanium (Ge), tin (Sn), titanium (Ti), zirconium (Zr), and hafnium (Hf). Good.
- N represents a nitrogen element. N may be partially substituted with other elements such as oxygen (O), halogen atoms (fluorine (F), chlorine (Cl), bromine (Br), iodine (I)) and the like.
- oxygen O
- halogen atoms fluorine (F)
- chlorine Cl
- bromine Br
- iodine I
- oxygen when oxygen is mixed as an impurity in the raw material metal, it may be introduced during a manufacturing process such as a pulverization process or a nitriding process, and is inevitably mixed in the phosphor of this embodiment. It is.
- halogen atoms when included, it may be mixed as an impurity in the raw material metal or introduced during a manufacturing process such as a pulverization process or a nitriding process.
- a phosphor May be included.
- m represents the content of the activating element M, the range is usually 0 ⁇ m ⁇ 0.04, and the lower limit is preferably 0.0001, more preferably 0.0005, and still more preferably 0.00. 001, more preferably 0.005, and the upper limit thereof is preferably 0.02, more preferably 0.01, and particularly preferably 0.005.
- a represents the content of Al, the range is usually 0 ⁇ a ⁇ 0.08, and the lower limit is preferably 0.0001, more preferably 0.001, and still more preferably 0.005.
- the upper limit is preferably 0.06, more preferably 0.04.
- b represents the content of Si element.
- d represents the content of N, and the range thereof is generally 3.6 ⁇ d ⁇ 4.2, and the lower limit is preferably 3.8, more preferably 3.9, and particularly preferably 3.95.
- the upper limit is preferably 4.1, more preferably 4.05.
- Any content is in the above-described range, which is preferable in terms of good light emission characteristics of the obtained phosphor, particularly light emission luminance.
- the crystal structure can be maintained by partially replacing Si—N in the crystal structure with Al—O.
- Al is increased relative to Si, O can be introduced into the N site while maintaining the charge compensation relationship.
- the phosphor of the present embodiment is characterized in that the composition contains no or very little oxygen.
- the absence of oxygen contained in the composition means that oxygen is below the detection limit when the phosphor powder is subjected to elemental analysis using an EPMA or oxygen-nitrogen / hydrogen analyzer described later. It is synonymous with.
- Al / Eu is preferably 0.05 or more, more preferably 0.10 or more, further preferably 0.2 or more, still more preferably 0.5 or more, and particularly preferably 1.0 or more.
- Another aspect of the phosphor of the present embodiment includes a phosphor characterized by including a crystal phase represented by the following formula [2].
- x represents the content of oxygen (O), and the range thereof is not particularly limited, but it is preferable that x ⁇ a. That is, it is preferable that the content of O is smaller than that of Al. As described above, this means that a phosphor with reduced oxygen can be obtained by introducing Al into the crystal structure in a form other than Al—O.
- x is preferably 0.05 or less, more preferably 0.04 or less, further preferably 0.03 or less, still more preferably 0.01 or less, and particularly preferably an element using an EPMA or an oxygen-nitrogen / hydrogen analyzer.
- x / a is preferably 1.0 or less, more preferably 0.8 or less, still more preferably 0.6 or less, still more preferably 0.4 or less, particularly preferably 0.2 or less, and particularly preferably
- x + d is preferably 3.6 or more, more preferably 3.7 or more, still more preferably 3.8 or more, still more preferably 3.9 or more, and particularly preferably 3.95 or more.
- the crystal structure of the phosphor according to the present embodiment is preferably a crystal structure of a sialon crystal in which Eu is dissolved in a crystal having a ⁇ -type Si 3 N 4 crystal structure.
- Si 3 N 4 crystal structure it is generally known that there are ⁇ -type and ⁇ -type, but the phosphor of this embodiment has a desired emission wavelength and half-value width due to being ⁇ -type. Since an emission peak is obtained, it is preferable.
- the lattice constant of the phosphor of this embodiment varies depending on the type of elements constituting the crystal, but is in the following range.
- the a-axis lattice constant (lattice constant La) is usually in the range of 7.600 ⁇ ⁇ La ⁇ 7.630 ⁇ , and the lower limit thereof is preferably 7.601 ⁇ , more preferably 7.602 ⁇ , and even more preferably 7.60 ⁇ .
- the upper limit is preferably 603 ⁇ , and more preferably 7.615 ⁇ ⁇ .
- the b-axis lattice constant (lattice constant Lb) is the same as the a-axis lattice constant.
- the c-axis lattice constant (lattice constant Lc) is usually in the range of 2.90 ⁇ ⁇ Lc ⁇ 2.91 ⁇ , and the lower limit is preferably 2.903 ⁇ , more preferably 2.906 ⁇ , and the upper limit is It is preferably 2.909 mm, more preferably 2.908 mm, and even more preferably 2.907 mm.
- the phosphor according to the present embodiment is stably generated, and the generation of the impurity phase is suppressed, so that the emission luminance of the obtained phosphor is good.
- the unit cell volume calculated from the lattice constant (V) is preferably, 145.30A 3 or more, more preferably 145.35A 3 or more, more preferably 145.40A 3 or more, preferably 146.50A 3 or less, more preferably 146.30A 3 or less, further preferably 146.10A 3 or less. If the unit cell volume is too large or the unit cell volume is too small, the skeletal structure becomes unstable and impurities of another structure are produced as a by-product, which tends to cause a decrease in emission intensity and color purity.
- the crystal system in the phosphor according to this embodiment is a hexagonal system.
- the space group in the phosphor of the present embodiment is not particularly limited as long as the average structure statistically considered within a range that can be distinguished by single crystal X-ray diffraction shows a repetition period of the above length, but “International It is preferable to belong to No. 173 (P6 3 ) or No. 176 (P6 3 / m) based on “Tables for Crystallography (Third, Revised Edition), Volume A SPACE-GROUP SYMMETRY”.
- the lattice constant and the space group can be obtained according to a conventional method. If it is a lattice constant, the results of X-ray diffraction and neutron diffraction can be obtained by Rietveld analysis, and if it is a space group, it can be obtained by electron beam diffraction.
- the emission color of the phosphor of this embodiment is excited by light in the near ultraviolet region to the blue region having a wavelength of 300 nm to 500 nm by adjusting the chemical composition and the like, and is blue, blue green, green, yellow green, yellow, orange , Red, etc., and a desired emission color can be obtained.
- the phosphor of this embodiment preferably has the following characteristics when an emission spectrum is measured when excited with light having a wavelength of 300 nm or more and 460 nm or less (in particular, a wavelength of 400 nm or 450 nm).
- the phosphor of this embodiment has a peak wavelength in the above-described emission spectrum of usually 500 nm or more, preferably 510 nm or more, more preferably 520 nm or more. Moreover, it is 560 nm or less normally, Preferably it is 550 nm or less, More preferably, it is 545 nm or less. It is preferable for it to be in the above-mentioned range since the obtained phosphor exhibits a good green color.
- the half-value width of the emission peak in the above-mentioned emission spectrum is usually 70 nm or less, preferably 60 nm or less, and usually 25 nm or more, preferably 30 nm or more. By being within the above range, it can be used for an image display device such as a liquid crystal display.
- the half-value width of the emission peak is preferably 50 nm or less, more preferably 48 nm or less, further preferably 45 nm or less, and 43 nm or less. Is particularly preferred.
- the peak ratio of the emission spectrum is as follows in addition to the above-described half-value width range. It is good to be in the range.
- the value of P1 / P2 is usually 0.1 or more, preferably 0.3 or more, more preferably 0.5 or more, and further preferably It is 0.7 or more, more preferably 0.9 or more, particularly preferably 1.1 or more, and particularly preferably 1.3 or more, usually 3.0 or less, preferably 2.5 or less.
- a GaN-based LED in order to excite the phosphor of this embodiment with light having a wavelength of 400 nm, for example, a GaN-based LED can be used.
- the measurement of the emission spectrum of the phosphor of this embodiment and the calculation of the emission peak wavelength, peak relative intensity, and peak half width are, for example, a 150 W xenon lamp as an excitation light source and a multi-channel CCD detector as a spectrum measurement device. It can be performed using a fluorescence measuring apparatus (manufactured by JASCO Corporation) equipped with C7041 (manufactured by Hamamatsu Photonics).
- the x value of the CIE chromaticity coordinate of the phosphor of this embodiment is usually 0.240 or more, preferably 0.250 or more, more preferably 0.260 or more, and usually 0.420 or less, preferably 0.400. In the following, it is more preferably 0.380 or less, further preferably 0.360 or less, and still more preferably 0.340 or less.
- the y value of the CIE chromaticity coordinates of the phosphor of the present embodiment is usually 0.575 or more, preferably 0.580 or more, more preferably 0.620 or more, and further preferably 0.640 or more. It is 0.700 or less, preferably 0.690 or less.
- the phosphor of this embodiment is also excellent in temperature characteristics. Specifically, the ratio of the emission peak intensity value in the emission spectrum at 150 ° C. to the emission peak intensity value in the emission spectrum at 25 ° C. when irradiated with light having a wavelength of 450 nm is usually 50%. Or more, preferably 60% or more, particularly preferably 70% or more. In addition, since the emission intensity of ordinary phosphors decreases with increasing temperature, it is unlikely that the ratio exceeds 100%, but it may exceed 100% for some reason. However, if it exceeds 100%, there is a tendency to cause a color shift due to a temperature change. Incidentally, when measuring the temperature characteristics, a conventional method may be followed, for example, a method described in JP-A-2008-138156.
- the phosphor of this embodiment has an excitation peak in a wavelength range of usually 300 nm or more, preferably 320 nm or more, more preferably 400 nm or more, and usually 480 nm or less, preferably 470 nm or less, more preferably 460 nm or less. That is, it is excited by light in the near ultraviolet to blue region.
- the raw materials, the phosphor production method, and the like for obtaining the phosphor of this embodiment are as follows.
- the method for producing the phosphor of the present embodiment is not particularly limited.
- the element M as an activator hereinafter referred to as “M source” and the element Al (hereinafter referred to as “Al source” as appropriate).
- a raw material of elemental Si hereinafter referred to as “Si source” as appropriate
- Si source A raw material of elemental Si (hereinafter referred to as “Si source” as appropriate) is mixed so as to have a stoichiometric ratio of the formula [1] (mixing step), and the resulting mixture is fired (firing step).
- the raw material of the element Eu may be referred to as “Eu source”.
- Phosphor raw materials that is, M source, Al source, and Si source
- Phosphor raw materials include metals, alloys, imide compounds, and acids of each element of M element, Al element, and Si element.
- Examples thereof include nitrides, nitrides, oxides, hydroxides, carbonates, nitrates, sulfates, oxalates, carboxylates, and halides. From these compounds, the reactivity to the composite oxynitride and the low generation amount of NOx, SOx, etc. during firing may be selected as appropriate.
- M source Of the M sources, specific examples of Eu sources include Eu 2 O 3 , Eu 2 (SO 4 ) 3 , Eu 2 (C 2 O 4 ) 3 ⁇ 10H 2 O, EuCl 2 , EuCl 3 , Eu (NO 3 ) 3 ⁇ 6H 2 O, EuN , EuNH and the like. Of these, Eu 2 O 3 , EuN and the like are preferable, and EuN is particularly preferable.
- raw materials of other activating elements such as Sm source, Tm source, Yb source, etc., compounds in which Eu is replaced with Sm, Tm, Yb, etc. in the respective compounds listed as specific examples of Eu source Is mentioned.
- Al source Specific examples of the Al source include AlN, Al 2 O 3 , Al (OH) 3 , AlOOH, Al (NO 3 ) 3 and the like. Among these, AlN and Al 2 O 3 are preferable, and AlN is particularly preferable. Moreover, as AlN, the thing with a small particle size from a reactive point and a high purity from the point of luminous efficiency is preferable.
- the amount of oxygen contained in Al metal or AlN is usually 100 ppm or less, more preferably 50 ppm or less, and still more preferably 20 ppm or less.
- Specific examples of other trivalent element materials include compounds in which Al is replaced with B, Ga, In, Sc, Y, La, Gd, Lu, etc. in each of the compounds listed as specific examples of the Al source. Can be mentioned.
- the Al source may be single Al.
- Si source Specific examples of the Si source include SiO 2 , ⁇ -type Si 3 N 4 , and ⁇ -type Si 3 N 4 , and ⁇ -type Si 3 N 4 and ⁇ -type Si 3 N 4 are preferable. It is also possible to use a compound as a SiO 2. Specific examples of such a compound include SiO 2 , H 4 SiO 4 , Si (OCOCH 3 ) 4 and the like. Further, ⁇ -type Si 3 N 4 is preferably one having a small particle diameter and high purity from the viewpoint of light emission efficiency from the viewpoint of reactivity. Furthermore, the thing with few content rates of the carbon element which is an impurity is preferable.
- Si source having a lower oxygen content Si metal may be used, or Si 3 N 4 having a low oxygen content may be used.
- the oxygen content in ⁇ -type Si 3 N 4 and ⁇ -type Si 3 N 4 is usually 100 ppm or less, preferably 80 ppm or less, more preferably 60 ppm or less, still more preferably 40 ppm or less, and particularly preferably 20 ppm or less. It is more preferable to use ⁇ -type Si 3 N 4 having a high oxygen content after performing heat treatment at 1.0 MPa or lower and 1600 ° C. or higher to obtain ⁇ -type Si 3 N 4 having a low oxygen content.
- Specific examples of other raw materials for tetravalent elements include compounds in which Si is replaced by Ge, Ti, Zr, Hf, etc. in the respective compounds listed as specific examples of the Si source.
- the Si source may be single Si.
- each of the above-described M source, Al source, and Si source may be used alone or in combination of two or more in any combination and ratio.
- the mixing method is not particularly limited, and may be either a dry mixing method or a wet mixing method.
- the dry mixing method include a ball mill.
- a solvent or dispersion medium such as water is added to the above-described phosphor raw material, mixed using a mortar and pestle, and in a solution or slurry state, spray drying, heat drying, Alternatively, it is a method of drying by natural drying or the like.
- the obtained mixture is filled in a heat-resistant container such as a crucible or a tray made of a material having low reactivity with each phosphor raw material.
- a heat-resistant container such as a crucible or a tray made of a material having low reactivity with each phosphor raw material.
- the material of the heat-resistant container used at the time of firing is not particularly limited as long as the effects of the present embodiment are not impaired, and examples thereof include a crucible such as boron nitride.
- the firing temperature varies depending on other conditions such as pressure, the firing can be usually performed in a temperature range of 1700 ° C. or higher and 2150 ° C. or lower.
- the maximum temperature reached in the firing step is usually 1700 ° C. or higher, preferably 1750 ° C. or higher, and usually 2150 ° C. or lower, preferably 2100 ° C. or lower. If the calcination temperature is too high, nitrogen will fly and tend to produce defects in the host crystal and color, while if it is too low, the progress of the solid phase reaction will tend to be slow, making it difficult to obtain the target phase as the main phase. .
- the firing is preferably performed at a maximum attained temperature of 1800 ° C. or higher, more preferably 1900 ° C. or higher, and particularly preferably 2000 ° C. or higher.
- the highest temperature reached during firing is usually 1800 ° C. or higher, preferably 1900 ° C. or higher, and usually 2150 ° C. or lower, more preferably 2100 ° C. or lower.
- the firing temperature is less than 1800 ° C., the solid phase reaction does not proceed, so that only the impurity phase or the unreacted phase appears, and it may be difficult to obtain the target phase as the main phase.
- the heating rate in the firing step is usually 2 ° C./min or more, preferably 5 ° C./min or more, more preferably 10 ° C./min or more, and usually 30 ° C./min or less, preferably 25 ° C./min or less. It is. If the rate of temperature rise is below this range, the firing time may be long. In addition, if the rate of temperature rise exceeds this range, the firing device, container, etc. may be damaged.
- the firing atmosphere in the firing step is arbitrary as long as the phosphor of this embodiment is obtained, but a nitrogen-containing atmosphere is preferable. Specific examples include a nitrogen atmosphere and a hydrogen-containing nitrogen atmosphere, and a nitrogen atmosphere is particularly preferable.
- the oxygen content in the firing atmosphere is usually 10 ppm or less, preferably 5 ppm or less.
- Calcination time varies depending on the temperature and pressure at the time of calcination, but is usually 10 minutes or more, preferably 30 minutes or more, and usually 72 hours or less, preferably 12 hours or less. If the firing time is too short, grain formation and grain growth cannot be promoted, so that a phosphor with good characteristics cannot be obtained. If the firing time is too long, volatilization of the constituent elements is promoted, so atomic deficiency As a result, defects may be induced in the crystal structure and a phosphor having good characteristics may not be obtained.
- the firing conditions may be the same or different between the first firing and the second firing.
- the phosphor of the present embodiment when manufacturing the phosphor of the present embodiment, during the firing step, for example, Li 3 N, Na 3 N, Mg 3 N 2 , Ca 3 N 2 , Sr 3 N 2 , Ba 3 N 2 and the like are fluxed. It is preferably used as (crystal growth aid).
- constituent elements of the flux such as Li, Na, Mg, Ca, Sr, and Ba may be mixed into the phosphor.
- the flux in this embodiment preferably has an effect of reducing the proportion of oxygen in the obtained phosphor in addition to the effect as the crystal growth aid.
- a member that adsorbs the gas in order to trap a gas containing oxygen in a constituent element such as SiO generated during firing.
- a member made of C (carbon) is good, and a C-made felt or C-cube is preferably arranged in the vicinity of the BN crucible.
- the obtained fired product is pulverized, pulverized, and / or classified into a powder having a predetermined size.
- D 50 is less than about 30 [mu] m.
- Specific examples of the treatment include a method of subjecting the synthesized product to sieve classification with an opening of about 45 ⁇ m, and passing the powder that has passed through the sieve to the next step, or the synthesized product to a general method such as a ball mill, a vibration mill, or a jet mill.
- pulverizing to a predetermined particle size using a grinder is mentioned. In the latter method, excessive pulverization not only generates fine particles that easily scatter light, but also generates crystal defects on the particle surface, which may cause a decrease in luminous efficiency.
- the phosphor of this embodiment may be formed by a so-called alloy method in which a constituent metal element is alloyed in advance and nitrided.
- the phosphor according to the first embodiment of the present invention can be used by mixing with a liquid medium.
- a liquid medium when the phosphor according to the first embodiment of the present invention is used for a light emitting device or the like, it is preferable to use the phosphor in a form dispersed in a liquid medium.
- What dispersed the fluorescent substance which concerns on 1st embodiment of this invention in the liquid medium as one embodiment of this invention is suitably with "the fluorescent substance containing composition which concerns on one embodiment of this invention", etc. Shall be called.
- the phosphor according to the first embodiment of the present invention to be contained in the phosphor-containing composition of the present embodiment may be only one type, or two or more types may be used in combination in any combination and ratio. Also good.
- the phosphor-containing composition of the present embodiment may contain a phosphor other than the phosphor according to the first embodiment of the present invention as long as the effects of the present embodiment are not significantly impaired.
- the liquid medium used in the phosphor-containing composition of the present embodiment is not particularly limited as long as the performance of the phosphor is not impaired within the intended range.
- any inorganic material and any material can be used as long as it exhibits liquid properties under the desired use conditions, suitably disperses the phosphor according to the first embodiment of the present invention, and does not cause an undesirable reaction.
- An organic material can be used, and examples thereof include a silicone resin, an epoxy resin, and a polyimide silicone resin.
- the phosphor and the liquid medium content in the phosphor-containing composition of the present embodiment are arbitrary as long as the effects of the present embodiment are not significantly impaired, but for the liquid medium, the phosphor-containing composition of the present embodiment.
- the total amount is usually 50% by weight or more, preferably 75% by weight or more, and usually 99% by weight or less, preferably 95% by weight or less.
- the fluorescent substance containing composition of this embodiment may contain other components other than a fluorescent substance and a liquid medium, unless the effect of this embodiment is impaired remarkably.
- 1 type may be used for another component and it may use 2 or more types together by arbitrary combinations and a ratio.
- a second embodiment of the present invention is a light-emitting device including a first light emitter (excitation light source) and a second light emitter that emits visible light when irradiated with light from the first light emitter.
- the second luminous body contains the phosphor according to the first embodiment of the present invention.
- any one of the phosphors according to the first embodiment of the present invention may be used alone, or two or more thereof may be used in any combination and ratio.
- the phosphor according to the first embodiment of the present invention for example, a phosphor that emits green region fluorescence under irradiation of light from an excitation light source is used.
- the green phosphor in the first embodiment of the present invention preferably has an emission peak in a wavelength range of 500 nm or more and 560 nm or less.
- the excitation source one having an emission peak in a wavelength range of less than 420 nm may be used.
- the phosphor according to the first embodiment of the present invention has a light emission peak in a wavelength range of 500 nm to 560 nm, and the first light emitter has a light emission peak in a wavelength range of 300 nm to 460 nm.
- this embodiment is not limited thereto.
- the light-emitting device of this embodiment can be set as follows, for example. That is, the first light emitter has a light emission peak in the wavelength range of 300 nm to 460 nm, and the first phosphor of the second light emitter has a light emission peak in the wavelength range of 500 nm to 560 nm.
- An embodiment using (red phosphor) can be employed.
- the following fluorescent substance is used suitably, for example.
- the Mn-activated fluoride phosphor include K 2 (Si, Ti) F 6 : Mn, K 2 Si 1-x Na x Al x F 6 : Mn (0 ⁇ x ⁇ 1)
- sulfide phosphors include (Sr, Ca) S: Eu (CAS phosphor), La 2 O 2 S: Eu (LOS phosphor)
- the garnet phosphor include (Y, Lu, Gd, Tb) 3 Mg 2 AlSi 2 O 12 : Ce
- nanoparticles include CdSe
- Examples of the nitride or oxynitride phosphor include (Sr, Ca) AlSiN 3 : Eu (S / CASN phosphor), (CaAlSiN 3 ) 1-x ⁇ (SiO 2 N 2 ) x : Eu (CASON fluorescence).
- the half-value width of the emission spectrum of the red phosphor in the above embodiment is usually 90 nm or less, preferably 70 nm or less, more preferably 50 nm or less, and still more preferably. Is 30 nm or less, usually 5 nm or more, more preferably 10 nm or more.
- a phosphor having a light emission peak in the range of 550 to 580 nm may be used.
- the following phosphors are preferably used as the yellow phosphor.
- Examples of the garnet phosphor include (Y, Gd, Lu, Tb, La) 3 (Al, Ga) 5 O 12 : (Ce, Eu, Nd),
- Examples of the orthosilicate include (Ba, Sr, Ca, Mg) 2 SiO 4 : (Eu, Ce)
- Examples of (acid) nitride phosphors include (Ba, Ca, Mg) Si 2 O 2 N 2 : Eu (SION phosphor), (Li, Ca) 2 (Si, Al) 12 (O, N 16 : (Ce, Eu) ( ⁇ -sialon phosphor), (Ca, Sr) AlSi 4 (O, N) 7 : (Ce, Eu) (1147 phosphor), (La, Ca, Y) 3 ( Al, Si) 6 N 11 : Ce (LSN phosphor) Etc.
- the phosphor is preferably a garnet phosphor, and most preferably a YAG phosphor represented by Y 3 Al
- the green phosphor may include a phosphor other than the phosphor according to the first embodiment of the present invention.
- the following phosphors are preferably used.
- the garnet phosphor include (Y, Gd, Lu, Tb, La) 3 (Al, Ga) 5 O 12 : (Ce, Eu, Nd), Ca 3 (Sc, Mg) 2 Si 3 O 12. : (Ce, Eu) (CSMS phosphor),
- the silicate phosphor include (Ba, Sr, Ca, Mg) 3 SiO 10 : (Eu, Ce), (Ba, Sr, Ca, Mg) 2 SiO 4 : (Ce, Eu) (BSS phosphor).
- oxide phosphor for example, (Ca, Sr, Ba, Mg) (Sc, Zn) 2 O 4 : (Ce, Eu) (CASO phosphor)
- oxide phosphor for example, (Ca, Sr, Ba, Mg) (Sc, Zn) 2 O 4 : (Ce, Eu) (CASO phosphor)
- (acid) nitride phosphors include (Ba, Sr, Ca, Mg) Si 2 O 2 N 2 : (Eu, Ce), Si 6-z Al z O z N 8-z : (Eu, Ce) ( ⁇ -sialon phosphor) (0 ⁇ z ⁇ 1), (Ba, Sr, Ca, Mg, La) 3 (Si, Al) 6 O 12 N 2 : (Eu, Ce) (BSON phosphor)
- Examples of the aluminate phosphor include (Ba, Sr, Ca, Mg) 2 Al 10 O 17 : (Eu, Mn) (
- the light emitting device of this embodiment has a first light emitter (excitation light source) and uses at least the phosphor according to the first embodiment of the present invention as the second light emitter,
- the configuration is not limited, and a known device configuration can be arbitrarily employed.
- Examples of the device configuration and the light emitting device include those described in Japanese Patent Application Laid-Open No. 2007-291352.
- examples of the form of the light emitting device include a shell type, a cup type, a chip on board, a remote phosphor, and the like.
- the use of the light-emitting device according to the second embodiment of the present invention is not particularly limited and can be used in various fields where a normal light-emitting device is used, but has a wide color reproduction range and color rendering properties. In particular, it is particularly preferably used as a light source for illumination devices and image display devices.
- a third embodiment of the present invention is an illumination device including the light emitting device according to the second embodiment of the present invention as a light source.
- the light-emitting device according to the second embodiment of the present invention is applied to a lighting device, the light-emitting device as described above may be appropriately incorporated into a known lighting device.
- a surface emitting illumination device in which a large number of light emitting devices are arranged on the bottom surface of the holding case can be used.
- an image display device comprising the light emitting device according to the second embodiment of the present invention as a light source.
- the specific configuration of the image display device is not limited, but it is preferably used with a color filter.
- the image display device is a color image display device using color liquid crystal display elements
- the light emitting device is used as a backlight, a light shutter using liquid crystal, and a color filter having red, green, and blue pixels; By combining these, an image display device can be formed.
- Luminescent characteristics The sample was packed in a copper sample holder, and the excitation emission spectrum and emission spectrum were measured using a fluorescence spectrophotometer FP-6500 (manufactured by JASCO). During the measurement, the slit width of the light-receiving side spectroscope was set to 1 nm and the measurement was performed. The emission peak wavelength (hereinafter sometimes referred to as “peak wavelength”) and the half width of the emission peak were read from the obtained emission spectrum.
- peak wavelength The emission peak wavelength (hereinafter sometimes referred to as “peak wavelength”) and the half width of the emission peak were read from the obtained emission spectrum.
- phosphors were prepared as follows. The raw materials were weighed with an electronic balance so as to have the weights shown in Table 1 below, placed in an alumina mortar, and ground and mixed until uniform. Further, 1.00 g of Mg 3 N 2 (manufactured by Shellac Co.) was added as a flux to this mixed powder, and further pulverized and mixed. These operations were performed in a glove box filled with Ar gas.
- Example 1 The result of SEM observation of the phosphor of Example 1 is shown in FIG.
- the single crystal of Example 1 was selected from SEM observation, and elemental analysis (EPMA measurement) was performed in order to examine the constituent elements and their ratios.
- Elements detected in EPMA were Eu, Al, Si, and N, and magnesium and oxygen were below the detection limit.
- the atomic ratio of Eu: Al: Si was 0.016 (1): 0.048 (1): 2.95 (2). Numbers in parentheses represent standard deviation. It was confirmed that the mixing of oxygen during firing was almost zero.
- Example 1 the single crystal structure analysis of Example 1 was implemented.
- the unit cell volume of the phosphor of Example 1 was 146.454 3 .
- the excitation / emission spectrum of the phosphor of Example 1 is shown in FIG.
- the excitation spectrum is obtained by monitoring emission at 540 nm.
- the emission spectrum is a measurement result when excited at 450 nm.
- the phosphor of Example 1 showed an emission spectrum with an emission peak wavelength of 540 nm and a half width of 70 nm, and was confirmed to show green emission.
- Examples 2 and 3 For the phosphors of Examples 2 and 3, single crystals of Examples 2 and 3 were selected from SEM observation, and EPMA composition analysis was performed. Elements detected in EPMA were Eu, Al, Si, and N as in Example 1, and magnesium and oxygen were below the detection limit. As a result of quantitative analysis, the atomic ratio of Eu: Al: Si was 0.008 (1): 0.039 (1): 2.96 (2) in Example 2, and was 0.8 in Example 3. 006 (1): 0.030 (1): 2.97 (2). Numbers in parentheses represent standard deviation. It was confirmed that the mixing of oxygen during firing was almost zero.
- the phosphor of Example 4 was subjected to composition analysis by ICP and O / N analysis by an oxygen nitrogen hydrogen analyzer. As a result, oxygen was below the detection limit, and the atomic ratio of Eu: Al: Si was 0.003: 0.04: 2.96.
- Table 2 shows the lattice constants and unit cell volumes of the phosphors of Examples 2 to 7 refined from the obtained powder X-ray diffraction pattern. In Examples 2 to 7, phosphors having a structure similar to that of Example 1 were obtained in a substantially single phase.
- the phosphor obtained according to the first embodiment of the present invention can change the ratio of Eu: Al: Si in the crystal to change the a-axis from 7.604 to 7.6265 and the c-axis from 2.906 to vary from 2.908A, accordingly, the unit cell volume was also found to vary from 145.53A 3 to 146.454 ⁇ 3.
- the emission spectra of the phosphors of Examples 2, 3, 5, and 7 when excited with light having a wavelength of 450 nm are shown in FIG.
- Table 3 shows the emission peak wavelength, the half width, and the chromaticity read from the emission spectrum when excited with light having a wavelength of 450 nm for the phosphors of Examples 2 to 7.
- the phosphor obtained by the first embodiment of the present invention changes the Eu: Al: Si ratio in the crystal to change the emission peak wavelength in the emission spectrum from 513 nm to 540 nm, and the half width from 40 nm. It became clear that it was possible to change to 76 nm. That is, light emission of blue green to yellow green can be obtained by using an arbitrary composition.
- Example 8 A phosphor was prepared as follows using Eu 2 O 3 , Si 3 N 4 , AlN, and Al 2 O 3 as phosphor materials.
- Si 3 N 4 ⁇ -type Si 3 N 4 (manufactured by Ube Industries, Ltd .: SN-E10) was heat-treated at 1950 ° C. for 12 hours in a nitrogen atmosphere at a pressure of 0.92 MPa to make all ⁇ -type Si 3 N 4 It was used.
- the raw materials were weighed with an electronic balance so as to have the respective weights shown in Table 4 below, placed in an alumina mortar, and ground and mixed until uniform in the air.
- magnesium nitride was not used.
- Example 8 was all ⁇ -SiAlON single phase.
- Example 8 The composition analysis by ICP of Example 8 and the O / N analysis by an oxygen nitrogen hydrogen analyzer were performed. As a result, oxygen was detected, and the atomic ratio of Eu: Al: Si: O: N was 0.003: 0.05: 2.95: 0.04: 3.91.
- Table 5 shows the emission peak wavelength, half-value width, and chromaticity read from the emission spectrum when excited with light having a wavelength of 450 nm for the phosphors of Example 4 and Example 8. It has been clarified that by reducing oxygen in the crystal structure, the emission peak wavelength is shortened and the half width is narrowed.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Luminescent Compositions (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Illuminated Signs And Luminous Advertising (AREA)
- Led Device Packages (AREA)
Abstract
L'invention concerne un phosphore caractérisé en ce qu'il inclut une phase cristalline représentée par la formule [2]. [2]: MmAlaOxSibNd (Dans la formule [2], M représente un élément d'activation, 0 < m ≤ 0,04, a + b = 3, 0 < a ≤ 0,08, 3,6 ≤ d ≤ 4,2, et x < a)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201780053292.7A CN109699179B (zh) | 2016-09-26 | 2017-09-25 | 荧光体、发光装置、照明装置以及图像显示装置 |
JP2018540339A JP6985704B2 (ja) | 2016-09-26 | 2017-09-25 | 蛍光体、発光装置、照明装置及び画像表示装置 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016187524 | 2016-09-26 | ||
JP2016-187524 | 2016-09-26 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2018056447A1 true WO2018056447A1 (fr) | 2018-03-29 |
Family
ID=61690564
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2017/034593 WO2018056447A1 (fr) | 2016-09-26 | 2017-09-25 | Phosphore, dispositif électroluminescent, dispositif d'éclairage, et dispositif d'affichage d'images |
Country Status (4)
Country | Link |
---|---|
JP (1) | JP6985704B2 (fr) |
CN (1) | CN109699179B (fr) |
TW (1) | TWI808946B (fr) |
WO (1) | WO2018056447A1 (fr) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023153157A1 (fr) * | 2022-02-08 | 2023-08-17 | デンカ株式会社 | LUMINOPHORE À BASE DE SIALON β ACTIVÉ PAR EUROPIUM |
WO2023171504A1 (fr) * | 2022-03-07 | 2023-09-14 | デンカ株式会社 | PARTICULES FLUORESCENTES DE SIALON DE TYPE β ACTIVÉES PAR EU, POUDRE FLUORESCENTE DE SIALON DE TYPE β ET DISPOSITIF ÉLECTROLUMINESCENT |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPWO2022102511A1 (fr) * | 2020-11-13 | 2022-05-19 | ||
EP4293732A4 (fr) | 2022-01-20 | 2024-05-15 | Mitsubishi Chemical Corporation | Luminophore, dispositif électroluminescent, dispositif d'éclairage, dispositif d'affichage d'image et voyant lumineux pour véhicules |
EP4293733A4 (fr) | 2022-01-20 | 2024-04-17 | Mitsubishi Chemical Corporation | Luminophore, dispositif électroluminescent, dispositif d'éclairage, dispositif d'affichage d'image et lampe d'affichage pour poste mobile |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005255895A (ja) * | 2004-03-12 | 2005-09-22 | National Institute For Materials Science | 蛍光体とその製造方法 |
WO2006101095A1 (fr) * | 2005-03-22 | 2006-09-28 | National Institute For Materials Science | Luminophore et procédé servant à produire celui-ci |
WO2007066733A1 (fr) * | 2005-12-08 | 2007-06-14 | National Institute For Materials Science | Phosphore, procede et production correspondant, et dispositif luminescent |
JP2009010315A (ja) * | 2007-05-30 | 2009-01-15 | Sharp Corp | 蛍光体の製造方法、発光装置および画像表示装置 |
JP2013142135A (ja) * | 2012-01-12 | 2013-07-22 | Denki Kagaku Kogyo Kk | 蛍光体及び発光装置 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101613856B (zh) * | 2009-07-16 | 2011-04-27 | 中国科学院上海硅酸盐研究所 | 一种铝掺杂α相氮化硅(α-Si3N4)基材料及其制备方法 |
-
2017
- 2017-09-25 WO PCT/JP2017/034593 patent/WO2018056447A1/fr active Application Filing
- 2017-09-25 CN CN201780053292.7A patent/CN109699179B/zh active Active
- 2017-09-25 JP JP2018540339A patent/JP6985704B2/ja active Active
- 2017-09-26 TW TW106132986A patent/TWI808946B/zh active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005255895A (ja) * | 2004-03-12 | 2005-09-22 | National Institute For Materials Science | 蛍光体とその製造方法 |
WO2006101095A1 (fr) * | 2005-03-22 | 2006-09-28 | National Institute For Materials Science | Luminophore et procédé servant à produire celui-ci |
WO2007066733A1 (fr) * | 2005-12-08 | 2007-06-14 | National Institute For Materials Science | Phosphore, procede et production correspondant, et dispositif luminescent |
JP2009010315A (ja) * | 2007-05-30 | 2009-01-15 | Sharp Corp | 蛍光体の製造方法、発光装置および画像表示装置 |
JP2013142135A (ja) * | 2012-01-12 | 2013-07-22 | Denki Kagaku Kogyo Kk | 蛍光体及び発光装置 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023153157A1 (fr) * | 2022-02-08 | 2023-08-17 | デンカ株式会社 | LUMINOPHORE À BASE DE SIALON β ACTIVÉ PAR EUROPIUM |
WO2023171504A1 (fr) * | 2022-03-07 | 2023-09-14 | デンカ株式会社 | PARTICULES FLUORESCENTES DE SIALON DE TYPE β ACTIVÉES PAR EU, POUDRE FLUORESCENTE DE SIALON DE TYPE β ET DISPOSITIF ÉLECTROLUMINESCENT |
Also Published As
Publication number | Publication date |
---|---|
JPWO2018056447A1 (ja) | 2019-07-04 |
CN109699179A (zh) | 2019-04-30 |
JP6985704B2 (ja) | 2021-12-22 |
CN109699179B (zh) | 2022-03-29 |
TWI808946B (zh) | 2023-07-21 |
TW201817853A (zh) | 2018-05-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2018056447A1 (fr) | Phosphore, dispositif électroluminescent, dispositif d'éclairage, et dispositif d'affichage d'images | |
WO2015002139A1 (fr) | Luminophore et dispositif électroluminescent | |
JP6782427B2 (ja) | 蛍光体、発光装置、照明装置及び画像表示装置 | |
CN106574181B (zh) | 荧光体、发光装置、图像显示装置及照明装置 | |
JP2023107773A (ja) | 蛍光体、発光装置、画像表示装置及び照明装置 | |
WO2016076380A1 (fr) | Phosphore, dispositif électroluminescent, dispositif d'éclairage, et dispositif d'affichage d'images | |
JP7155507B2 (ja) | 蛍光体、発光装置、照明装置及び画像表示装置 | |
JP2017190434A (ja) | 蛍光体、発光装置、照明装置及び画像表示装置 | |
JP6372368B2 (ja) | 蛍光体、発光装置、照明装置及び画像表示装置 | |
JP2016088970A (ja) | 蛍光体、発光装置、照明装置及び画像表示装置 | |
JP2016079213A (ja) | 蛍光体、発光装置、照明装置及び画像表示装置 | |
JP2016124929A (ja) | 蛍光体、発光装置、照明装置及び画像表示装置 | |
JP2016056246A (ja) | 蛍光体、発光装置、照明装置及び画像表示装置 | |
JP2016191011A (ja) | 蛍光体、発光装置、照明装置及び画像表示装置 | |
JP2016124928A (ja) | 蛍光体、発光装置、照明装置及び画像表示装置 | |
JP7310977B2 (ja) | 蛍光体、発光装置、照明装置及び画像表示装置 | |
JP2016094533A (ja) | 蛍光体、発光装置、照明装置及び画像表示装置 | |
JP7144002B2 (ja) | 蛍光体及びこれを用いた蛍光体組成物、並びにこれらを用いた発光装置、照明装置及び画像表示装置 | |
JP2017206599A (ja) | 蛍光体、発光装置、照明装置及び画像表示装置 | |
JP2017088791A (ja) | 蛍光体、発光装置、照明装置及び画像表示装置 | |
JP2016199675A (ja) | 蛍光体、発光装置、照明装置及び画像表示装置 | |
JP2017043728A (ja) | 蛍光体、発光装置、照明装置及び画像表示装置 | |
JP2017014370A (ja) | 蛍光体、発光装置、照明装置及び画像表示装置 | |
JP2023057391A (ja) | 蛍光体 | |
JP2016056329A (ja) | 蛍光体、発光装置、照明装置及び画像表示装置 |
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: 17853214 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2018540339 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 17853214 Country of ref document: EP Kind code of ref document: A1 |