WO2012098932A1 - 半導体発光装置 - Google Patents
半導体発光装置 Download PDFInfo
- Publication number
- WO2012098932A1 WO2012098932A1 PCT/JP2012/050065 JP2012050065W WO2012098932A1 WO 2012098932 A1 WO2012098932 A1 WO 2012098932A1 JP 2012050065 W JP2012050065 W JP 2012050065W WO 2012098932 A1 WO2012098932 A1 WO 2012098932A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- phosphor
- emitting device
- light emitting
- activated
- semiconductor light
- Prior art date
Links
- 239000004065 semiconductor Substances 0.000 title claims abstract description 101
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 307
- 238000000295 emission spectrum Methods 0.000 claims abstract description 110
- 239000000203 mixture Substances 0.000 claims description 40
- 239000002245 particle Substances 0.000 claims description 29
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- 238000009877 rendering Methods 0.000 abstract description 30
- 229910003564 SiAlON Inorganic materials 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 125
- 230000000052 comparative effect Effects 0.000 description 56
- 238000004519 manufacturing process Methods 0.000 description 51
- 238000005259 measurement Methods 0.000 description 23
- 229920005989 resin Polymers 0.000 description 23
- 239000011347 resin Substances 0.000 description 23
- 239000011575 calcium Substances 0.000 description 21
- 239000004570 mortar (masonry) Substances 0.000 description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 229910052581 Si3N4 Inorganic materials 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 14
- 238000000695 excitation spectrum Methods 0.000 description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 12
- 239000013078 crystal Substances 0.000 description 10
- 230000005284 excitation Effects 0.000 description 10
- 229920002050 silicone resin Polymers 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 9
- 229910002804 graphite Inorganic materials 0.000 description 9
- 239000010439 graphite Substances 0.000 description 9
- 230000001678 irradiating effect Effects 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 229910052582 BN Inorganic materials 0.000 description 8
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 238000000634 powder X-ray diffraction Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 150000004767 nitrides Chemical class 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 230000005855 radiation Effects 0.000 description 6
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 229910001940 europium oxide Inorganic materials 0.000 description 5
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229910052693 Europium Inorganic materials 0.000 description 4
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 4
- 238000010306 acid treatment Methods 0.000 description 4
- PSBUJOCDKOWAGJ-UHFFFAOYSA-N azanylidyneeuropium Chemical compound [Eu]#N PSBUJOCDKOWAGJ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- -1 calcium nitride Chemical class 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 3
- 238000002284 excitation--emission spectrum Methods 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 238000005121 nitriding Methods 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 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
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000002223 garnet Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910016036 BaF 2 Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 230000036760 body temperature Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/26—Materials of the light emitting region
-
- 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
- C09K11/77—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
-
- 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
- H01L33/504—Elements with two or more wavelength conversion materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—Shape
- H01L2224/4809—Loop shape
- H01L2224/48091—Arched
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
- H01L2224/732—Location after the connecting process
- H01L2224/73251—Location after the connecting process on different surfaces
- H01L2224/73265—Layer and wire connectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
- H01L2924/181—Encapsulation
-
- 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
Definitions
- the present invention relates to a semiconductor light emitting device including a phosphor and a semiconductor light emitting element.
- LEDs light emitting diodes
- Semiconductor light emitting devices such as light emitting diodes (LEDs) have the advantage of being small in size, consuming little power and being able to stably emit light with high brightness.
- the movement to replace with lighting fixtures using light emitting devices composed of LEDs is proceeding.
- the LED that emits white light include a combination of a blue LED and a Ce-activated YAG phosphor represented by a composition formula of (Y, Gd) 3 (Al, Ga) 5 O 12 : Ce.
- white light is realized by mixing the blue light of the LED and the yellow light emitted from the Ce-activated YAG phosphor of the phosphor.
- the red component is insufficient due to the light emission characteristics of the Ce-activated YAG phosphor, and when used in a home lighting device, for example, the human skin color looks unnatural.
- the average color rendering index (hereinafter referred to as Ra) is about 70 to 75 in the color temperature range defined by the daylight white color or the light bulb color used in the lighting fixture, and particularly the red color.
- the special color rendering index (hereinafter referred to as R9) indicating the appearance of the light is about ⁇ 40 to ⁇ 5, and the red appearance becomes extremely worse when used as a lighting fixture.
- Patent Document 1 discloses a white combination of a blue LED as an excitation light source and an orange phosphor having a light emission wavelength of 560 to 590 nm and a green phosphor. A light emitting device is disclosed.
- an ⁇ sialon phosphor and a ⁇ sialon phosphor are disclosed as examples of an orange phosphor and a green phosphor, respectively, although they are not specifically examples of white light emitting devices in which phosphors are combined.
- Patent Document 2 discloses and proposes a combination using Eu-activated ⁇ sialon phosphor as a yellow phosphor, Eu-activated ⁇ sialon phosphor as a green phosphor, and Eu-activated CaAlSiN 3 phosphor as a red phosphor.
- Non-Patent Document 1 has a relationship between the Ra of a white LED that combines a phosphor and a blue LED and the theoretical limit of luminous efficiency that indicates the theoretical limit of the light emission efficiency of the light emitting device (Theoretical Limit of Luminous Efficiency). It is shown.
- Non-Patent Document 2 discloses a method for measuring the internal quantum efficiency of a phosphor described in Non-Patent Document 1, and Non-Patent Document 3 describes a phosphor disclosed in the present application. As an example of another type of phosphor having a different composition, Eu-activated SrAlSiN 3 is disclosed.
- JP 2007-227928 A published September 6, 2007
- JP 2006-261512 A published on September 28, 2006
- Non-Patent Document 1 in the configuration in which Ra is 80 or more, the theoretical limit luminous efficiency is remarkably lowered, and the light emitting device has a practically useful color rendering property. The luminous efficiency is not sufficient.
- Patent Document 2 since the wavelength of the emission spectrum of the red phosphor is a long wavelength, the matching between the human visibility curve and the emission spectrum is poor, and the red light emitted by the red phosphor is human eyes. It looks dark.
- the red light emitted by the red phosphor has a large wavelength shift with the blue light that is the excitation light, so in addition to the large Stokes loss, the red phosphor absorbs the light of the phosphor emitting at a shorter wavelength than the red light. Therefore, using a red phosphor in a semiconductor light-emitting device reduces the light emission efficiency.
- Patent Documents 1 and 2 cause inconveniences when applied to a semiconductor light-emitting device aiming for both high luminance and high color rendering.
- the present invention has been made in view of the above-described problems, and an object thereof is to provide a light-emitting device that has a sufficiently high color rendering property in practical use and does not use a red phosphor and has high luminous efficiency. To do.
- the present inventors have realized a phosphor and a phosphor using a phosphor and a semiconductor light emitting element in order to realize a sufficiently high color rendering property in practical use and to provide a light emitting device with higher luminous efficiency.
- the prototype was repeated.
- the inventors have found that a light-emitting device that can solve the above problems can be provided by the combinations shown below, and have completed the present invention. The detailed contents of the present invention will be described below.
- a semiconductor light emitting device includes a semiconductor light emitting element that emits blue light, a green phosphor that absorbs the blue light and emits green light, and an orange phosphor that absorbs the blue light and emits orange light.
- the orange phosphor is an Eu-activated ⁇ sialon phosphor having an emission spectrum peak wavelength in the range of 595 to 620 nm.
- the Eu activated ⁇ sialon is General formula (Ca x Eu y ) (Si 12- (m + n) Al m + n ) (O n N 16-n ) Eu activated ⁇ sialon indicated by 1.1 ⁇ x ⁇ 2.0 (1) 0 ⁇ y ⁇ 0.4 (2) 1.5 ⁇ x + y ⁇ 2.0 (3) 3.0 ⁇ m ⁇ 4.0 (4) 0 ⁇ n ⁇ y (5) It is designed with the composition which satisfy
- the Eu activated ⁇ sialon is General formula (Ca x Eu y ) (Si 12- (m + n) Al m + n ) (O n N 16-n ) Eu activated ⁇ sialon indicated by 1.1 ⁇ x ⁇ 1.85 (1 ′) 0.15 ⁇ y ⁇ 0.4 (2 ') 1.5 ⁇ x + y ⁇ 2.0 (3 ') 3.0 ⁇ m ⁇ 4.0 (4 ′) 0 ⁇ n ⁇ y (5 ') It is designed with the composition which satisfy
- the semiconductor light emitting device is characterized in that the peak wavelength of the emission spectrum of the Eu activated ⁇ sialon is 605 to 620 nm. According to the above configuration, a light emitting device having higher color rendering properties can be realized.
- the semiconductor light emitting device according to the present invention is characterized in that an average particle diameter of the Eu activated ⁇ sialon phosphor is 15 ⁇ m or more. According to the above configuration, a light emitting device having higher color rendering properties can be realized.
- the semiconductor light emitting device is characterized in that a specific surface area of the Eu-activated ⁇ sialon phosphor is 0.4 m 2 / g or less. According to the above configuration, a light emitting device with higher luminous efficiency and higher color rendering can be realized.
- the semiconductor light emitting device is characterized in that the peak wavelength of the emission spectrum of the green phosphor is in the range of 520 nm to 550 nm. According to the above configuration, when a light emitting device that emits white light is combined with the orange phosphor and the semiconductor light emitting element that emits blue light, the emission spectrum of the light emitting device matches the human visibility curve. A light emitting device with high luminous efficiency can be realized.
- the semiconductor light emitting device is characterized in that the half width of the emission spectrum of the green phosphor is 55 nm or less. According to the above configuration, since mutual absorption between the orange phosphor and the green phosphor is suppressed, a light emitting device with higher luminous efficiency and high color rendering can be realized.
- the semiconductor light-emitting device is characterized in that the green phosphor has an absorptance at 600 nm of 10% or less. According to the above configuration, unnecessary absorption of orange light by the green phosphor is reduced, and a light emitting device with higher luminous efficiency can be realized.
- the semiconductor light emitting device is characterized in that the green phosphor is Eu-activated ⁇ sialon phosphor. According to the above configuration, since the internal fluorescent efficiency of the green phosphor is high and the chemical and physical stability is good, it is possible to realize a light emitting device with higher luminous efficiency, higher stability and reliability.
- the semiconductor light emitting device is characterized in that the oxygen concentration of the Eu-activated ⁇ sialon phosphor is in the range of 0.1 to 0.6% by weight. According to the above configuration, since the emission spectrum of Eu-activated ⁇ sialon has a shorter wavelength, a light emitting device with higher color rendering can be realized.
- the semiconductor light-emitting device is configured using an Eu-activated ⁇ -sialon phosphor having an emission spectrum peak wavelength in the range of 595 to 620 nm as an orange phosphor. And a semiconductor light-emitting device with high luminous efficiency can be provided.
- FIG. 6 is a graph showing an emission spectrum of the phosphor obtained in Production Example 1-1.
- 6 is a graph showing an excitation spectrum of the phosphor obtained in Production Example 1-1.
- 6 is a graph showing an emission spectrum of the phosphor obtained in Production Example 1-2.
- 6 is a graph showing an excitation spectrum of the phosphor obtained in Production Example 1-2.
- 6 is a graph showing an emission spectrum of the phosphor obtained in Production Example 2-1. It is a graph which shows the emission spectrum of the fluorescent substance obtained in manufacture example 2-2.
- 6 is a graph showing an emission spectrum of the phosphor obtained in Production Example 2-3.
- 6 is a graph showing an emission spectrum of the phosphor obtained in Production Example 2-4. 6 is a graph showing an emission spectrum of the phosphor obtained in Comparative Production Example 1. 6 is a graph showing an excitation spectrum of a phosphor obtained in Comparative Production Example 1. 6 is a graph showing an emission spectrum of a phosphor obtained in Comparative Production Example 2. 3 is a graph showing an emission spectrum of the light emitting device created in Example 1. 6 is a graph showing an emission spectrum of the light emitting device created in Example 2. 6 is a graph showing an emission spectrum of the light emitting device created in Example 3. 6 is a graph showing an emission spectrum of the light emitting device created in Example 4. 6 is a graph showing an emission spectrum of the light emitting device created in Example 5.
- Example 7 is a graph showing an emission spectrum of the light emitting device created in Example 6.
- 10 is a graph showing an emission spectrum of the light emitting device created in Example 7.
- 10 is a graph showing an emission spectrum of the light emitting device created in Example 8.
- 10 is a graph showing an emission spectrum of the light emitting device created in Example 9.
- 10 is a graph showing an emission spectrum of the light emitting device created in Example 10.
- 10 is a graph showing an emission spectrum of the light emitting device created in Example 11.
- 14 is a graph showing an emission spectrum of the light emitting device created in Example 12.
- 14 is a graph showing an emission spectrum of the light emitting device created in Example 13.
- 6 is a graph showing an emission spectrum of the light emitting device created in Comparative Example 1.
- 10 is a graph showing an emission spectrum of the light emitting device created in Comparative Example 2.
- 10 is a graph showing an emission spectrum of the light emitting device created in Comparative Example 3.
- 10 is a graph showing an emission spectrum of the light emitting device created in Comparative Example 4.
- 10 is a graph showing an emission spectrum of the light emitting device created in Comparative Example 5.
- 14 is a graph showing an emission spectrum of the light emitting device created in Comparative Example 6.
- 6 is a graph showing the relationship between Ra and theoretical limit efficiency of the semiconductor light emitting devices prepared in Examples 1 to 8 and Comparative Examples 1 to 3.
- 6 is a graph showing the relationship between Ra and theoretical limit efficiency of the semiconductor light emitting devices prepared in Examples 9 to 15 and Comparative Examples 4 to 6.
- 10 is a graph showing an emission spectrum of the light emitting device created in Comparative Example 7.
- 10 is a graph showing an emission spectrum of the light emitting device created in Comparative Example 8.
- 10 is a graph showing an emission spectrum of the light emitting device created in Comparative Example 9.
- 10 is a graph showing an emission spectrum of the light emitting device created in Comparative Example 10.
- 6 is a graph showing the relationship between the emission peak wavelength of an orange phosphor and Ra in the semiconductor light emitting devices prepared in Examples 1 to 8 and Comparative Examples 1 and 7 to 9.
- 6 is a graph showing the relationship between Ra and theoretical limit efficiency of the semiconductor light emitting devices prepared in Examples 1 to 8 and Comparative Examples 1 and 7 to 10.
- FIG. 1 is a cross-sectional view showing a schematic configuration of a semiconductor device according to the present embodiment.
- a semiconductor light emitting device 1 according to the present embodiment includes a semiconductor light emitting element 2 that emits blue light, an orange phosphor 13 that absorbs the blue light and emits orange light, and absorbs the blue light and emits green light.
- blue light means light having a peak wavelength of an emission spectrum at a wavelength of 420 to 480 nm
- green light means light having a peak wavelength of an emission spectrum at a wavelength of 500 to 550 nm, orange light.
- the green phosphor is a substance that emits the green light when excited by the blue light
- the orange phosphor is a substance that emits the orange light when excited by the blue light.
- the body means a substance that emits the red light when excited by the blue light.
- the orange phosphor 13 is an Eu-activated ⁇ sialon phosphor having an emission spectrum peak wavelength of 595 nm or more.
- Ra and R9 satisfy practically preferable values.
- a practically useful light-emitting device having a theoretical limit luminous efficiency much higher than that of conventionally known ones can be realized.
- the present inventors have studied to improve the color rendering performance by adjusting the emission spectrum of the Eu-activated ⁇ -sialon phosphor, which is an orange phosphor combined with the green phosphor, based on the design guideline that no red phosphor is used. It was.
- Eu-activated ⁇ sialon a material having an emission spectrum having a longer wavelength than that shown in Non-patent Document 1, Patent Document 1 and 2, it is practically sufficient color rendering without using a red phosphor. It has been found that a light-emitting device having a property can be realized, and a preferable range of the emission peak wavelength of the Eu-activated ⁇ -sialon phosphor is 595 nm or more.
- Ra and R9 are assumed to replace indoor lighting such as a fluorescent lamp with a semiconductor light emitting device.
- JISZ9125 2007, lighting fixtures with Ra of 80 or more work or are long. Recommended for use in rooms where people stay for hours.
- the theoretical limit efficiency is defined in Non-Patent Document 1, and the theoretical limit of the luminous efficiency (lumen per watt: lm / W) of the light emitting device is calculated from the emission spectrum of the light emitting device. It is a thing. When calculating the theoretical limit luminous efficiency, it is assumed that the conversion efficiency from the power of the semiconductor light emitting device to blue light is 100%, and the internal quantum efficiency (IQE) of the phosphor is also 100%. Only Stokes shift loss due to the wavelength conversion is considered as loss.
- Non-Patent Document 2 Korean Patent Document 2 (Kazuaki Okubo et al. “Quantity Efficiency Measurement of NBS Standard Phosphor”, Illuminating Society Journal, Vol. 83, No. 2, p. 87 (1999)). Can be measured by simple methods.
- a semiconductor light emitting device 1 has a semiconductor light emitting element 2 mounted on a printed wiring board 3 as a base, and the orange fluorescent light is placed inside a resin frame 4 that is also mounted on the printed wiring board 3.
- the semiconductor light emitting element 2 is sealed by being filled with a mold resin 5 made of a translucent resin in which the body 13 and the green phosphor 14 are dispersed.
- the semiconductor light emitting device 2 has an InGaN layer 6 as an active layer, and has a p-side electrode 7 and an n-side electrode 8 sandwiching the InGaN layer 6, and the n-side electrode 8 is connected to the printed wiring board 3.
- a p-side electrode 7 and an n-side electrode 8 sandwiching the InGaN layer 6, and the n-side electrode 8 is connected to the printed wiring board 3.
- the p-side electrode 7 of the semiconductor light emitting element 2 is electrically connected to a p-electrode portion 11 provided from the top surface to the back surface of the printed wiring board 3 separately from the n-electrode portion 9 described above via a metal wire 12. ing.
- the semiconductor light emitting device 1 according to the present embodiment is not limited to the structure shown in FIG. 1, and a conventionally known general semiconductor light emitting device structure can be adopted.
- the semiconductor light emitting element 2 is a light emitting diode (LED).
- the semiconductor light emitting element 2 is not limited to a light emitting diode (LED), but a semiconductor laser, an inorganic EL (A conventionally known element that emits blue light, such as an electroluminescence element, can be used.
- a commercially available product such as manufactured by Cree can be used.
- the emission peak wavelength of the semiconductor light emitting device 2 is not particularly limited, but from the viewpoint of increasing the light emission efficiency of the semiconductor light emitting device, it is preferably in the range of 440 nm to 470 nm, and from the viewpoint of increasing the Ra and R9 values. More preferably, it is within the range of 450 nm to 465 nm.
- orange phosphor 13 is an Eu-activated ⁇ sialon phosphor having an emission spectrum peak wavelength in the range of 595 nm to 620 nm. If the emission peak wavelength exceeds 620 nm, the internal quantum efficiency and temperature characteristics of the Eu-activated ⁇ -sialon phosphor tend to be deteriorated, so the wavelength was set to 620 nm.
- Eu-activated ⁇ -sialon phosphor for example, as shown in Japanese Patent Application Laid-Open No. 2005-307012, a material designed with a low oxygen concentration by using a nitride material as a starting material can be suitably used. This is because ⁇ sialon designed with a low oxygen concentration has a high solid solution limit of elements other than Si, Al, O, N, such as Ca and Eu, and these elements are easily incorporated into crystals.
- composition formula for the Eu-activated ⁇ sialon phosphor is: General formula (Ca x Eu y ) (Si 12- (m + n) Al m + n ) (O n N 16-n ) Indicated by 1.1 ⁇ x ⁇ 2.0 (1) 0 ⁇ y ⁇ 0.4 (2) 1.5 ⁇ x + y ⁇ 2.0 (3) 3.0 ⁇ m ⁇ 4.0 (4) 0 ⁇ n ⁇ y (5) Designed with a composition that satisfies
- the Eu-activated ⁇ sialon having the composition as described in (1) to (5) above uses, for example, Ca 3 N 2 as a Ca source, AlN as an Al source, and Si 3 N 4 as an Si source. , Eu 2 O 3 and EuN can be used together as the Eu source.
- the compositions shown in the above (1) to (5) are characterized in that 0 ⁇ n ⁇ y and 1.5 ⁇ x + y ⁇ 2.0. 0 ⁇ n ⁇ y means that the oxygen concentration is designed to be lower than the Eu concentration. The fact that 1.5 ⁇ x + y ⁇ 2.0 means that the Ca concentration and Eu concentration are designed around the upper limit concentration at which an ⁇ -sialon single phase is obtained.
- an Eu-activated ⁇ sialon phosphor having an emission spectrum peak wavelength of 605 nm to 620 nm can be more suitably used, and such Eu-activated ⁇ sialon fluorescence can be used.
- composition formula for the body is General formula (Ca x Eu y ) (Si 12- (m + n) Al m + n ) (O n N 16-n ) Indicated by 1.1 ⁇ x ⁇ 1.85 (1 ′) 0.15 ⁇ y ⁇ 0.4 (2 ') 1.5 ⁇ x + y ⁇ 2.0 (3 ') 3.0 ⁇ m ⁇ 4.0 (4 ′) 0 ⁇ n ⁇ y (5 ') Designed with a composition that satisfies
- the Eu-activated ⁇ sialon having the composition as described in (1 ′) to (5 ′) above uses, for example, Ca 3 N 2 as a Ca source, AlN as an Al source, and Si 3 N 4 as an Si source. And Eu 2 O 3 and EuN can be used together as the Eu source.
- the compositions (1 ′) to (5 ′) are characterized in that the y value is larger than those of (1) to (5).
- a large y value means that the Eu concentration is designed to be high, and the compositions of (1 ′) to (5 ′) have a higher Eu concentration than that of (1) to (5).
- the peak wavelength of the emission spectrum is realized to be 605 nm to 620 nm.
- a seed particle addition step of adding ⁇ sialon powder as seed particles can be suitably used as disclosed in, for example, JP-A-2009-96882. This is because the ⁇ sialon phosphor designed to have a low oxygen concentration has a low oxygen concentration at the time of firing, so that grain growth through the liquid phase hardly occurs.
- a cleaning process by acid treatment as disclosed in JP-A-2005-255855 can be suitably applied to the process for producing the Eu-activated ⁇ sialon.
- the particle size of the orange phosphor 14 is preferably 1 ⁇ m to 50 ⁇ m, and more preferably 5 ⁇ m to 20 ⁇ m.
- the particle shape is preferably a single particle rather than an aggregate, and specifically, the specific surface area measured by the air permeation method is 1 m 2 / g or less, more preferably 0.4 m 2. / G or less is preferable.
- the air permeation method refers to a method generally referred to as the leaner method, and the specific surface area can be obtained from the measurement of the flow velocity and pressure drop of the air that has permeated the sample packed bed.
- Non-Patent Document 3 as another nitride-based orange phosphor having an emission spectrum peak wavelength of 620 nm or less, it has an emission spectrum peak wavelength at 610 nm and becomes orange with high internal quantum efficiency in blue excitation. It is disclosed with respect to Eu-activated SrAlSiN 3 , which is a phosphor material that emits light and is chemically stable, but the Eu-activated SrAlSiN 3 has an absorptance in the green wavelength range compared to Eu-activated ⁇ -sialon phosphor. In other words, it is preferable to use Eu-activated ⁇ -sialon phosphor as the orange phosphor because it absorbs green light emitted from the green phosphor.
- Green phosphor From the viewpoint of increasing the light emission efficiency of the semiconductor light emitting device, a green phosphor having a peak wavelength in the range of 520 nm to 550 nm can be preferably used. If the peak wavelength of the emission spectrum of the green phosphor 14 is within the above range, when the light emitting device 1 that emits white light is configured by combining the orange phosphor 13 and the semiconductor light emitting element 2 that emits blue light, An emission spectrum that matches the visual sensitivity curve can be obtained. For this reason, a light emitting device with high luminous efficiency can be realized.
- the green phosphor 14 preferably has a half-value width of its emission spectrum of 70 nm or less, more preferably 55 nm or less.
- the lower limit of the half-value width of the emission spectrum of the green phosphor 14 is not particularly limited, but is preferably 15 nm or more.
- the half-value width of the emission spectrum of the green phosphor 14 is in the above range, the overlap between the absorption spectrum of the orange phosphor 13 and the emission spectrum of the green phosphor 14 is sufficiently small, so that the green phosphor 13 absorbs green light. Is suppressed, and a light emitting device with higher luminous efficiency can be realized.
- the green phosphor 14 as described above is not particularly limited.
- Eu-activated oxynitride phosphor is preferably used because of its high stability and excellent temperature characteristics.
- the Eu-activated BSON phosphor disclosed in Japanese Patent Application Laid-Open No. 2008-138156 and the Eu-activated ⁇ sialon fluorescent material disclosed in Japanese Patent Application Laid-Open No. 2005-255895 are excellent.
- the body is preferably used.
- the Eu-activated ⁇ sialon phosphor is excellent in stability and temperature characteristics, and has a particularly narrow emission spectrum with a particularly narrow half-value width.
- the composition according to the Eu activated BSON phosphor is: Bay ' Eu x' Si u ' O v' N w ' (However, 0 ⁇ y ′ ⁇ 3, 1.6 ⁇ y ′ + x ′ ⁇ 3, 5 ⁇ u ′ ⁇ 7, 9 ⁇ v ′ ⁇ 15, 0 ⁇ w ′ ⁇ 4) And more preferable ranges of y ′, x ′, u ′, v ′, and w ′ are 1.5 ⁇ y ′ ⁇ 3, 2 ⁇ y ′ + x ′ ⁇ 3, and 5.5 ⁇ u. ' ⁇ 7, 10 ⁇ v ′ ⁇ 13, 1.5 ⁇ w ′ ⁇ 4.
- the composition of the Eu-activated ⁇ sialon phosphor is: Si 6-z ′ Al z ′ O z ′ N 8-z ′ (However, 0 ⁇ z ′ ⁇ 4.2) It is preferable that a more preferable range of z ′ is 0 ⁇ z ′ ⁇ 0.5.
- the Eu-activated ⁇ sialon preferably has an oxygen concentration in the range of 0.1 to 0.6% by weight, more preferably an Al concentration of 0.13 to 0.8% by weight. If the Eu-activated ⁇ sialon phosphor is within these ranges, the half-value width of the emission spectrum tends to be narrower.
- the Eu-activated ⁇ sialon phosphor disclosed in International Publication No. WO2008 / 062781 has high emission efficiency due to less unnecessary absorption because the damaged phase of the phosphor is removed by post-treatment such as acid treatment after firing. . Furthermore, the Eu-activated ⁇ sialon phosphor exemplified in Japanese Patent Application Laid-Open No. 2008-303331 is preferable because the oxygen concentration is 0.1 to 0.6% by weight, and the half-value width of the emission spectrum becomes narrower.
- the green phosphor 14 as described above has a light absorption rate of 10 at 600 nm which is a wavelength region which does not contribute to the light emission of the ⁇ sialon phosphor at all and is near the peak wavelength of the orange phosphor. % Or less can be suitably used.
- the particle size of the green phosphor 14 is preferably 1 ⁇ m to 50 ⁇ m, and more preferably 5 ⁇ m to 20 ⁇ m.
- the shape of the particles is preferably a single particle rather than an aggregate, and specifically, the specific surface area is 1 m 2 / g or less, more preferably 0.4 m 2 / g or less. preferable.
- techniques such as mechanical pulverization, grain boundary phase removal by acid treatment, annealing treatment, and the like can be used as appropriate.
- the green phosphor 14 used in the present embodiment is an Eu-activated oxynitride phosphor
- the green phosphor 14 and the orange phosphor 13 are both nitride-based, so two types of fluorescence are used.
- the body temperature dependency, specific gravity, particle size, etc. are close to each other.
- nitride-based phosphors have high stability and reliability that are not affected by the surrounding environment because they are highly temperature-dependent and resistant to chemical and physical damage due to the strong covalent bonding of the host crystal. It becomes a light emitting element.
- the mold resin 5 used for sealing the semiconductor light emitting element 2 is made of a translucent resin such as a silicone resin or an epoxy resin, for example, the orange phosphor 13 and the green phosphor 14. Are dispersed.
- the dispersion method is not particularly limited, and a conventionally known method can be employed.
- the mixing ratio of the orange phosphor 13 and the green phosphor 14 to be dispersed is not particularly limited and can be appropriately determined so that a spectrum showing a desired white point can be obtained.
- the mass ratio of the translucent resin to the orange phosphor 13 and the green phosphor 14 (the mass of the translucent resin / (the orange phosphor 13 + the green phosphor 14)) can be within a range of 1 to 15. .
- the mass ratio of the green phosphor 14 to the orange phosphor 13 (the mass ratio of the green phosphor 14 / the orange phosphor 13) can be in the range of 0.5 to 4.
- the printed wiring board 3 the adhesive 10, the metal wire 12, etc. other than the semiconductor light emitting element 2, the orange phosphor 13, the green phosphor 14, and the mold resin 5.
- a configuration similar to that of the prior art for example, Japanese Patent Application Laid-Open No. 2003-321675, Japanese Patent Application Laid-Open No. 2006-8721, etc.
- ⁇ -type silicon nitride powder As a raw material powder, 59.8% by mass of ⁇ -type silicon nitride powder, 24.3% by mass of aluminum nitride powder, 13.9% by mass of calcium nitride powder, 0.9% by mass of europium oxide powder, and nitriding It weighed so that it might become a composition of 1.1 mass% of europium powder, and it mixed for 10 minutes or more using the mortar and pestle made from a silicon nitride sintered compact, and obtained the powder aggregate.
- the europium nitride used was synthesized by nitriding metal europium in ammonia.
- the obtained powder aggregate was passed through a sieve having an opening of 250 ⁇ m and filled into a boron nitride crucible having a diameter of 20 mm and a height of 20 mm.
- the powder weighing, mixing and molding steps were all performed in a glove box capable of maintaining a nitrogen atmosphere with a moisture content of 1 ppm or less and oxygen of 1 ppm or less.
- the crucible is set in a graphite resistance heating type pressure electric furnace, nitrogen having a purity of 99.999% by volume is introduced to a pressure of 1 MPa, the temperature is raised to 1800 ° C. at 500 ° C. per hour, Heat treatment was performed by holding at 1800 ° C. for 2 hours.
- the product obtained by the heat treatment was pulverized in an agate mortar and further treated at 60 ° C. in a 1: 1 mixed acid of 50% hydrofluoric acid and 96% concentrated sulfuric acid to obtain a phosphor powder.
- XRD powder X-ray diffraction measurement
- FIG. 2A is a graph showing an emission spectrum of the obtained phosphor powder, where the vertical axis represents relative emission intensity (arbitrary unit) and the horizontal axis represents wavelength (nm).
- FIG. 2B is a graph showing an excitation spectrum of the obtained phosphor powder, where the vertical axis represents relative emission intensity (arbitrary unit) and the horizontal axis represents wavelength (nm).
- the excitation spectrum and emission spectrum of the phosphor powder shown in FIGS. 2A and 2B are the results of measurement using F-4500 (manufactured by Hitachi, Ltd.).
- the emission spectrum was measured by excitation with 450 nm light, and the excitation spectrum was measured by scanning the intensity of the emission peak.
- the specific surface area of the obtained phosphor powder was measured by LEA-NURSE manufactured by Tsutsui Rikagaku Kogyo, it was 0.36 m 2 / g, and the average particle size was measured from an SEM image observed by VE-manufactured by Keyence. 16.2 ⁇ m.
- the obtained powder aggregate was passed through a sieve having an opening of 250 ⁇ m and filled into a boron nitride crucible having a diameter of 20 mm and a height of 20 mm.
- the powder weighing, mixing and molding steps were all performed in a glove box capable of maintaining a nitrogen atmosphere with a moisture content of 1 ppm or less and oxygen of 1 ppm or less.
- the crucible is set in a graphite resistance heating type pressure electric furnace, nitrogen having a purity of 99.999% by volume is introduced to a pressure of 1 MPa, the temperature is raised to 1800 ° C. at 500 ° C. per hour, Heat treatment was performed by holding at 1800 ° C. for 2 hours.
- the product obtained by the heat treatment was pulverized in an agate mortar and further treated at 60 ° C. in a 1: 1 mixed acid of 50% hydrofluoric acid and 96% concentrated sulfuric acid to obtain a phosphor powder.
- XRD powder X-ray diffraction measurement
- FIG. 3A is a graph showing an emission spectrum of the obtained phosphor powder, where the vertical axis represents relative emission intensity (arbitrary unit) and the horizontal axis represents wavelength (nm).
- FIG. 3B is a graph showing an excitation spectrum of the obtained phosphor powder, where the vertical axis represents relative emission intensity (arbitrary unit) and the horizontal axis represents wavelength (nm).
- the excitation spectrum and emission spectrum of the phosphor powder shown in FIGS. 3A and 3B are the results of measurement using F-4500 (manufactured by Hitachi, Ltd.).
- the emission spectrum was measured by excitation with 450 nm light, and the excitation spectrum was measured by scanning the intensity of the emission peak.
- the specific surface area of the obtained phosphor powder was measured by LEA-NURSE manufactured by Tsutsui Rikagaku Kogyo, it was 0.38 m 2 / g, and the average particle diameter was measured from the SEM image observed by VE- manufactured by Keyence. , 15.3 ⁇ m.
- the obtained powder aggregate was passed through a sieve having an opening of 250 ⁇ m and filled into a boron nitride crucible having a diameter of 20 mm and a height of 20 mm.
- the powder weighing, mixing and molding steps were all performed in a glove box capable of maintaining a nitrogen atmosphere with a moisture content of 1 ppm or less and oxygen of 1 ppm or less.
- the crucible is set in a graphite resistance heating type pressure electric furnace, nitrogen having a purity of 99.999% by volume is introduced to a pressure of 1 MPa, and the temperature is raised to 1700 ° C. at 500 ° C. per hour, Heat treatment was performed by holding at 1700 ° C. for 2 hours.
- the product obtained by the heat treatment was pulverized in an agate mortar and further treated at 60 ° C. in a 1: 1 mixed acid of 50% hydrofluoric acid and 96% concentrated sulfuric acid to obtain a phosphor powder.
- XRD powder X-ray diffraction measurement
- the phosphor powder emits orange light.
- the emission characteristics of the obtained powder such as the emission spectrum and excitation spectrum, were equivalent to those of the orange phosphor obtained in Production Example 1-2.
- the specific surface area of the obtained phosphor powder was measured by LEA-NURSE manufactured by Tsutsui Chemical Co., Ltd., it was 0.78 m 2 / g, and the average particle diameter was measured from an SEM image observed by VE-manufactured by Keyence. 11.2 ⁇ m.
- the crucible is set in a graphite resistance heating type pressure electric furnace, the firing atmosphere is evacuated by a diffusion pump, heated from room temperature to 800 ° C. at a rate of 500 ° C. per hour, and the purity is 99.800 at 800 ° C.
- the temperature was raised to 1900 ° C. at 500 ° C. per hour, and further maintained at that temperature for 8 hours to obtain a phosphor sample.
- the obtained phosphor sample was pulverized using an agate mortar and further treated at 60 ° C. in a 1: 1 mixed acid of 50% hydrofluoric acid and 70% nitric acid to obtain a phosphor powder.
- the phosphor powder When the phosphor powder was subjected to powder X-ray diffraction measurement (XRD) using Cu K ⁇ radiation, the phosphor powder was found to have a ⁇ -type sialon structure. Further, as a result of irradiating the phosphor powder with a lamp emitting light having a wavelength of 365 nm, it was confirmed that the phosphor powder emitted green light.
- XRD powder X-ray diffraction measurement
- the emission spectrum shown in FIG. 4 was obtained.
- the vertical axis represents emission intensity (arbitrary unit), and the horizontal axis represents wavelength (nm).
- the specific surface area of the obtained phosphor powder was measured by LEA-NURSE manufactured by Tsutsui Rikagaku Kogyo, it was 0.80 m 2 / g, and the average particle diameter was measured from the SEM image observed by VE-manufactured by Keyence. 9.2 ⁇ m.
- the crucible is set in a graphite resistance heating type pressure electric furnace, and the firing atmosphere is evacuated by a diffusion pump, and is heated from room temperature to 800 ° C. at a rate of 500 ° C. per hour.
- 999 vol% nitrogen was introduced to adjust the pressure to 0.5 MPa, the temperature was raised to 1300 ° C. at 500 ° C. per hour, then raised to 1600 ° C. at 1 ° C. per minute, and held at that temperature for 8 hours.
- the synthesized sample was pulverized into powder with an agate mortar to obtain a powder sample.
- the powder fired at 1600 ° C. was pulverized using a silicon nitride mortar and pestle and then naturally dropped into a boron nitride crucible having a diameter of 20 mm and a height of 20 mm.
- the crucible is set in a graphite resistance heating type pressure electric furnace, and the firing atmosphere is evacuated by a diffusion pump, heated from room temperature to 800 ° C. at a rate of 500 ° C. per hour, and the purity is 99.999% by volume at 800 ° C. Then, the pressure was adjusted to 1 MPa, and then the temperature was increased to 1900 ° C. at 500 ° C. per hour, and the temperature was further maintained for 8 hours to obtain a phosphor sample. The obtained phosphor sample was pulverized with an agate mortar and further treated at 60 ° C. in a 1: 1 mixed acid of 50% hydrofluoric acid and 70% nitric acid to obtain a phosphor powder.
- the emission spectrum shown in FIG. 5 was obtained.
- the vertical axis represents emission intensity (arbitrary unit), and the horizontal axis represents wavelength (nm).
- oxygen content contained in these synthetic powders was measured using the oxygen-nitrogen analyzer by a combustion method (TC436 type
- the absorptance of light having a wavelength of 600 nm was measured using MCPD-7000 (manufactured by Otsuka Electronics Co., Ltd.) and found to be 12.5%.
- the obtained slurry was oven-dried at 100 ° C., and the obtained powder aggregate was pulverized by a dry rolling ball mill using an agate ball and a nylon pot to obtain fine particles having a particle size of about 10 ⁇ m. After filling the obtained fine particles into an alumina crucible and applying compression molding with light weight, it is fired in air at 1100 ° C. for 3 hours, and the resulting fired body is pulverized with an agate mortar to produce a precursor sample Got.
- the crucible is set in a graphite resistance heating type pressure electric furnace, the firing atmosphere is evacuated by a diffusion pump, heated from room temperature to 800 ° C. at a rate of 500 ° C. per hour, and the purity is 99.800 at 800 ° C.
- the temperature was raised to 1300 ° C. at 500 ° C. per hour and further maintained at that temperature for 2 hours to obtain a phosphor sample.
- the fired product obtained was pulverized using an agate mortar, filled again into an alumina crucible, lightly loaded and compression molded, and then fired in a nitrogen atmosphere at 1300 ° C. for 48 hours. Was pulverized with an agate mortar to obtain phosphor powder.
- the powder was subjected to powder X-ray diffraction measurement (XRD) using Cu K ⁇ radiation, and all charts obtained from the phosphor powder showed a BSON structure. Further, as a result of irradiating the phosphor powder with a lamp emitting light having a wavelength of 365 nm, it was confirmed that the phosphor powder emitted green light.
- XRD powder X-ray diffraction measurement
- the emission spectrum shown in FIG. 6 was obtained.
- the vertical axis represents emission intensity (arbitrary unit), and the horizontal axis represents wavelength (nm).
- the absorptance of light having a wavelength of 600 nm was measured by using MCPD-7000 (manufactured by Otsuka Electronics Co., Ltd.) and found to be 8.2%.
- the obtained mixture was filled in a quartz crucible, fired in a reducing atmosphere of N 2 (95%) + H 2 (5%) at 1400 ° C. for 5 hours, and the obtained fired body was pulverized with an agate mortar. Thus, a phosphor powder was obtained.
- the vertical axis represents emission intensity (arbitrary unit), and the horizontal axis represents wavelength (nm).
- the obtained powder aggregate was passed through a sieve having an opening of 250 ⁇ m and filled into a boron nitride crucible having a diameter of 20 mm and a height of 20 mm.
- the powder weighing, mixing and molding steps were all performed in a glove box capable of maintaining a nitrogen atmosphere with a moisture content of 1 ppm or less and oxygen of 1 ppm or less.
- the crucible is set in a graphite resistance heating type pressure electric furnace, nitrogen having a purity of 99.999% by volume is introduced to a pressure of 1 MPa, the temperature is raised to 1800 ° C. at 500 ° C. per hour, Heat treatment was performed by holding at 1800 ° C. for 2 hours.
- the product obtained by the heat treatment was pulverized in an agate mortar and further treated in a 1: 1 mixed acid of 50% hydrofluoric acid and 96% concentrated sulfuric acid to obtain a phosphor powder.
- XRD powder X-ray diffraction measurement
- FIG. 8A is a graph showing an emission spectrum of the obtained phosphor powder, where the vertical axis represents relative emission intensity (arbitrary unit) and the horizontal axis represents wavelength (nm).
- FIG. 8B is a graph showing an excitation spectrum of the obtained phosphor powder, where the vertical axis represents relative emission intensity (arbitrary unit) and the horizontal axis represents wavelength (nm).
- the excitation spectrum and emission spectrum of the phosphor powder shown in FIGS. 8A and 8B are the results of measurement using F-4500 (manufactured by Hitachi, Ltd.).
- the emission spectrum was measured by excitation with 450 nm light, and the excitation spectrum was measured by scanning the intensity of the emission peak.
- Europium nitride was synthesized by nitriding metal europium in ammonia.
- the powder aggregate was naturally dropped into a boron nitride crucible having a diameter of 20 mm and a height of 20 mm.
- the powder weighing, mixing, and forming steps were all performed in a glove box capable of maintaining a nitrogen atmosphere with a moisture content of 1 ppm or less and oxygen of 1 ppm or less.
- the crucible is set in a graphite resistance heating type pressure electric furnace, nitrogen having a purity of 99.999% by volume is introduced to a pressure of 1 MPa, and the temperature is raised to 1800 ° C. at 500 ° C. per hour.
- a phosphor sample was obtained by holding at 1800 ° C. for 2 hours.
- the obtained phosphor sample was pulverized using an agate mortar to obtain phosphor powder.
- XRD X-ray diffraction measurement
- FIG. 9 is a graph showing an emission spectrum of the obtained phosphor powder, where the vertical axis represents relative emission intensity (arbitrary unit) and the horizontal axis represents wavelength (nm).
- the emission spectrum of the phosphor powder shown in FIG. 9 is a result of measurement using F-4500 (manufactured by Hitachi, Ltd.), and is obtained when excited with light of 450 nm.
- an LED having a light emission peak wavelength shown in Table 2 (trade name: EZR, manufactured by Cree) is used. It adjusted suitably so that it might become.
- FIGS. 10 to 24 show emission spectra of the semiconductor light emitting devices of Examples 1 to 15.
- the emission spectra shown in FIGS. 10 to 24 were measured using MCPD-7000 (manufactured by Otsuka Electronics).
- Example 16 Using a silicone resin (trade name: KER2500, manufactured by Shin-Etsu Silicone Co., Ltd.), the phosphor shown in Table 4 is mixed and dispersed with the silicone resin at a mass ratio shown in Table 4 to produce a mold resin, and the structure shown in FIG.
- a semiconductor light-emitting device of Example 16 having:
- Example 16 an LED having an emission peak wavelength at 450 nm (trade name: EZR, manufactured by Cree) was used as the semiconductor light emitting element, and the resin / phosphor ratio was a black body locus when the color temperature of the light emitting device was around 5000K. The chromaticity point was appropriately adjusted so as to be asymptotic.
- Table 5 shows the light emission characteristics of the light emitting devices produced in Example 16 and Example 9, and Table 6 shows the characteristics of the Eu activated ⁇ sialon phosphor used. Each index shown in Table 5 was calculated from the spectrum measured by MCPD-7000.
- Example 9 has improved color rendering properties compared to Example 16, although the light emission characteristics of the phosphors used were the same. As shown in Table 6, this is considered to be due to the difference in the particle shape such as the average particle diameter and specific surface area of the Eu-activated ⁇ -sialon phosphor, which is an orange phosphor.
- the Eu-activated ⁇ -sialon phosphor produced in Production Example 1-3 used in Example 16 was used in the Eu-activated ⁇ -sialon phosphor produced in Production Example 1-2 used in Example 9.
- the average particle size is large and the specific surface area is small.
- the Eu-activated ⁇ -sialon phosphor produced in Production Example 1-2 has an average particle size of 15.3 ⁇ m and a specific surface area of 0.38 m 2 / g, whereas Production Example 1-3.
- the Eu-activated ⁇ sialon phosphor produced in 1) has an average particle size of 11.2 ⁇ m and a specific surface area of 0.78 m 2 / g. Therefore, it is considered that the Eu activated ⁇ sialon phosphor produced in Production Example 1-2 is different from the Eu activated ⁇ sialon phosphor produced in Production Example 1-3 in the dispersion state in the mold resin.
- the dispersion state of the Eu-activated ⁇ sialon phosphor in the mold resin is different, the scattering and absorption states of blue light and green light by the orange phosphor change. This change is considered to affect the emission spectrum of the light-emitting device and improve the color rendering properties of the semiconductor light-emitting device shown in Example 9.
- the average particle diameter of the Eu-activated ⁇ sialon phosphor is preferably 15 ⁇ m or more, and the specific surface area is preferably 0.4 m 2 / g or less.
- the specific surface area is small indicates that the particle size of the individual particles constituting the phosphor is large and the crystal uniformity is high. If the crystal uniformity is high, Luminous efficiency is increased. Therefore, by reducing the specific surface area to 0.4 m 2 / g or less, it contributes to the improvement of luminous efficiency.
- an LED (trade name: EZR, manufactured by Cree) having an emission peak wavelength shown in Table 2 is used, and the ratios of resin, orange phosphor, green phosphor, and red phosphor are the ratios of the light emitting device.
- the color temperature was appropriately adjusted so as to be around 5000K.
- Comparative Examples 1 and 4 do not include a red phosphor
- Comparative Examples 3 and 6 do not include an orange phosphor.
- Comparative Examples 2 and 5 correspond to the examples disclosed in Patent Document 2.
- Comparative Examples 2 and 5 correspond to the examples disclosed in Patent Document 3.
- FIGS. 25 to 30 show emission spectra of the semiconductor light emitting devices of Comparative Examples 1 to 6, respectively.
- the emission spectra shown in FIGS. 25 to 30 were measured using MCPD-7000 (manufactured by Otsuka Electronics).
- Table 7 shows the light emission characteristics of the light emitting devices manufactured in the above examples and comparative examples. Each index shown in Table 7 was calculated from the emission spectra of FIGS.
- FIG. 31 shows the relationship between Ra and theoretical limit luminous efficiency for the semiconductor light emitting devices fabricated in Examples 1 to 8 and Comparative Examples 1 to 3 in which the peak wavelength of the blue LED is 460 nm.
- 32 is a graph showing the relationship between Ra and theoretical limit efficiency for the semiconductor light emitting devices manufactured in Examples 9 to 15 and Comparative Examples 4 to 6 in which the peak wavelength of the blue LED is 450 nm. The relationship between Ra and theoretical limit luminous efficiency is shown for a blue LED having a peak wavelength of 450 nm.
- Table 8 the theoretical limit luminous efficiency and the relative value of the LED luminous intensity of each light emitting device created in the above examples and comparative examples are compared.
- the LED luminous intensity shown in Table 8 was measured with a configuration in which MCPD-7000 and an integrating sphere unit were combined under driving conditions of a voltage of 5 V and a current of 20 mA.
- Comparative Examples 2, 3, 5, and 6 the ratio of relative LED luminous intensity / relative theoretical limit luminous efficiency is lower than in the examples. That is, in the semiconductor light emitting devices created in Comparative Examples 2, 3, 5, and 6, the measured value of the LED luminous intensity is lower than the LED luminous intensity predicted by the theoretical calculation. This is because the red phosphor is used for the semiconductor light emitting devices manufactured in Comparative Examples 2, 3, 5, and 6 in Table 8, and the red phosphor in addition to the green phosphor absorbing orange light. In addition, absorption of green light and orange light causes a two-stage conversion loss, resulting in a decrease in light emission efficiency of the light emitting device.
- Comparative Example 1 and Comparative Example 4 have higher LED luminosity than the Examples, but as shown in Table 7, Comparative Example 1 and Comparative Example 4 have Ra of 70 or less and R9 of ⁇ 40 or less. The color rendering is extremely low. Therefore, although the comparative example 1 and the comparative example 4 have high LED luminous intensity, color rendering property is not preferable practically.
- the light emitting device shown in this example has high light emission efficiency because of less mutual absorption between phosphors than the light emitting device shown in the comparative example. This tendency is particularly noticeable in Examples 1 to 4 and Examples 9 to 11, and in these Examples, the ratio of relative LED luminous intensity / relative theoretical limit luminous efficiency is particularly high at 0.97 or more. . This is because the green phosphors used in Examples 1 to 4 and Examples 9 to 11 are Eu-activated ⁇ sialon phosphors shown in Production Examples 2-1 and 2-2.
- the Eu-activated ⁇ sialon phosphor has a narrow emission spectrum half-width of 70 nm or less, the overlap between the absorption spectrum of the orange phosphor and the emission spectrum of the green phosphor is reduced, and the mutual absorption between the phosphors is particularly suppressed. .
- an LED having a light emission peak wavelength at 460 nm (trade name: EZR, manufactured by Cree) is used, and the ratio of resin, orange phosphor, and green phosphor is such that the color temperature of the light emitting device is around 5000K. It adjusted suitably so that it might become.
- FIGS. 33 to 35 show emission spectra of the semiconductor light emitting devices of Comparative Examples 7 to 9, respectively.
- the emission spectra shown in FIGS. 33 to 35 were measured using MCPD-7000 (manufactured by Otsuka Electronics).
- an LED having a light emission peak wavelength at 460 nm (trade name: EZR, manufactured by Cree) is used, and the resin / phosphor ratio is a chromaticity point on a black body locus when the color temperature of the light emitting device is around 5000K. was adjusted as appropriate to asymptotically.
- FIG. 36 shows emission spectra of the semiconductor light emitting device of Comparative Example 10, respectively.
- the emission spectrum shown in FIG. 36 was measured using MCPD-7000 (manufactured by Otsuka Electronics).
- Table 11 shows the light emission characteristics of the light emitting devices manufactured in the above examples and comparative examples. Each index shown in Table 11 was calculated from the emission spectra of FIGS.
- FIG. 37 shows the relationship between the emission peak wavelength of the orange phosphor and the color rendering properties for Examples 1 to 8 and Comparative Examples 1 and 7 to 9 shown in Table 11.
- FIG. 38 shows the relationship between Ra of the semiconductor light emitting device and the theoretical limit luminous efficiency for Examples 1 to 8 and Comparative Examples 1 and 7 to 10 shown in Table 11.
- the peak wavelength range of the orange phosphor according to the present invention will be described with reference to FIG. From FIG. 37, it can be seen that Ra is improved as the peak wavelength of the orange phosphor is longer, and Ra is rapidly improved particularly at a wavelength of 595 nm or more. That is, it was shown that the inflection point at which the color rendering property is rapidly improved is 595 nm with respect to the peak wavelength of the orange phosphor used in the light emitting device.
- the light-emitting device shown in this embodiment has higher luminous efficiency and color rendering than conventionally known combinations, and is a highly practical light-emitting device.
- Ra> 80 is satisfied with the theoretical limit efficiency almost equivalent to that using the Ce-activated YAG phosphor.
- R9 is not particularly defined in the JIS standard or the like, it is a practically preferable feature that R9> 0 when an orange phosphor of 595 nm or more is used. As described above, if R9 is a negative value such as ⁇ 5 or less, the appearance of red is insufficient, and therefore, when used for household lighting equipment, for example, the color of human skin is unnatural. Inconvenience such as being visible occurs.
- the semiconductor light emitting device has high luminous efficiency and emits white light showing high Ra and R9. For this reason, it can be used suitably for various lighting fixtures such as household lighting and vehicle lamps.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Luminescent Compositions (AREA)
- Led Device Packages (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
Description
そのような状況から、特許文献1に、高い演色性と安定性を兼ね備えた組み合わせとして、青色LEDを励起光源とし、発光波長は560~590nmである橙色蛍光体と緑色蛍光体とを組み合わせた白色発光装置が開示されている。この文献では、具体的に蛍光体を組合せた白色発光装置事例としてではないが、橙色蛍光体、緑色蛍光体の一例としてそれぞれαサイアロン蛍光体、βサイアロン蛍光体が開示されている。
一方、特許文献2に記載の構成では、赤色蛍光体の発光スペクトルの波長が長波長である為、人間の視感度曲線と発光スペクトルのマッチングが悪く、赤色蛍光体の発する赤色光は人間の目には暗くみえてしまう。また、赤色蛍光体の発する赤色光は励起光である青色光との波長シフトが大きい為、ストークス損失が大きいことに加え、赤色蛍光体は赤色光より短波長で発光する蛍光体の光を吸収しやすく、赤色蛍光体を半導体発光装置に用いることは、発光効率を低下させてしまう。
一般式(CaxEuy)(Si12-(m+n)Alm+n)(OnN16-n)
で示されるEu賦活αサイアロンで、
1.1≦x<2.0 ・・・・( 1 )
0<y<0.4 ・・・・・・( 2 )
1.5<x+y<2.0 ・・( 3 )
3.0≦m<4.0 ・・・・( 4 )
0≦n<y ・・・・・( 5 )
を満たす組成で設計されていることを特徴とする。上記構成によれば、Eu賦活αサイアロンの内部量子効率が高くなり、発光効率の高い発光装置が実現可能となる。
一般式(CaxEuy)(Si12-(m+n)Alm+n)(OnN16-n)
で示されるEu賦活αサイアロンで、
1.1≦x<1.85 ・・・・( 1’ )
0.15<y<0.4 ・・・( 2’ )
1.5<x+y<2.0 ・・( 3’ )
3.0≦m<4.0 ・・・・( 4’ )
0≦n<y ・・・・・( 5’ )
を満たす組成で設計されていることを特徴とする。上記構成によれば、発光スペクトルのピーク波長が605~620nmであるEu賦活αサイアロンの内部量子効率が高くなり、発光効率の高い発光装置が実現可能となる。
本実施の形態では、上記半導体発光素子2は発光ダイオード(LED)であるが、上記半導体発光素子2としては発光ダイオード(LED)に限定されず、半導体レーザ、無機EL(electroluminescence)素子等の青色光を発する従来公知の素子を使用することができる。尚、LEDは、例えば、Cree社製等の市販品を用いることができる。
上記橙色蛍光体13は、発光スペクトルのピーク波長が595nm~620nmの範囲内であるEu賦活αサイアロン蛍光体である。発光ピーク波長が620nmを超えると、Eu賦活αサイアロン蛍光体の内部量子効率、温度特性が悪くなる傾向にあるため、620nmとした。
一般式(CaxEuy)(Si12-(m+n)Alm+n)(OnN16-n)
で示され、
1.1≦x<2.0 ・・・・( 1 )
0<y<0.4 ・・・・・・( 2 )
1.5<x+y<2.0 ・・( 3 )
3.0≦m<4.0 ・・・・( 4 )
0≦n<y ・・・・・( 5 )
を満たす組成で設計される。
一般式(CaxEuy)(Si12-(m+n)Alm+n)(OnN16-n)
で示され、
1.1≦x<1.85 ・・・・( 1’ )
0.15<y<0.4 ・・・( 2’ )
1.5<x+y<2.0 ・・( 3’ )
3.0≦m<4.0 ・・・・( 4’ )
0≦n<y ・・・・・( 5’ )
を満たす組成で設計される。
緑色蛍光体14は、半導体発光装置の発光効率を高くする観点から、ピーク波長が520nm~550nmの範囲にあるものを好適に用いることができる。緑色蛍光体14の発光スペクトルのピーク波長が上記範囲内であれば、上記橙色蛍光体13及び青色を発光する半導体発光素子2と組み合わせることにより白色光を発する発光装置1を構成した際に、ヒトの視感度曲線とマッチングした発光スペクトルを得ることができる。このため、発光効率の高い発光装置が実現可能となる。
Bay’Eux’Siu’Ov’Nw’
(但し、0≦y’≦3、1.6≦y’+x’≦3、5≦u’≦7、9<v’<15、0<w’≦4)
であることが好ましく、上記y’、x’、u’、v’、w’のより好ましい範囲は、1.5≦y’≦3、2≦y’+x’≦3、5.5≦u’≦7、10<v’<13、1.5<w’≦4である。
Si6-z’Alz’Oz’N8-z’
(但し、0<z’<4.2)
であることが好ましく、上記z’のさらに好ましい範囲は、0<z’<0.5である。
(Re1-xGdx)3(Al1-yGay)5O12:Ce(Re=Y,Lu,Tb、0≦x≦1、0≦y≦1)で表されるCe賦活アルミン酸塩ガーネット蛍光体、
(Ca,Mg)3Sc2Si3O12:Ceで表されるCe賦活ケイ酸塩ガーネット蛍光体、MSi2O2N2:Eu(M=Ba,Ca,Sr,Mg)で表されるEu賦活アルカリ土類シリコンオキシナイトライド蛍光体、
M2SiO4:Eu(M=Ba,Ca,Sr,Mg)で表されるEu賦活アルカリ土類シリケート系蛍光体等、従来公知の蛍光体を用いることができる。
上記半導体発光装置1において、半導体発光素子2の封止に用いるモールド樹脂5は、例えば、シリコーン樹脂、エポキシ樹脂等の透光性樹脂に上記橙色蛍光体13及び緑色蛍光体14を分散させたものである。当該分散方法としては、特には限定されず、従来公知の方法を採用することができる。
本実施の形態に係る半導体発光装置において、半導体発光素子2、橙色蛍光体13、緑色蛍光体14、及びモールド樹脂5以外の、プリント配線基板3、接着剤10、金属ワイヤ12等については、従来技術(例えば、特開2003-321675号公報、特開2006-8721号公報等)と同様の構成を採用することができ、従来技術と同様の方法により製造することができる。
以下に実施例、比較例に使用する各蛍光体の製法、特性について示す。また、表1に各蛍光体(製造例1-1~1-3、2-1~2-4、比較製造例1、2)の化学式、蛍光体特性、実施例・比較例適用の内容の一覧を示す。
組成式(CaxEuy)(Si12-(m+n)Alm+n)(OnN16-n)において、x=1.8、y=0.075、m=3.75、n=0.05のものを得るべく、原料粉末として、α型窒化ケイ素粉末59.8質量%、窒化アルミニウム粉末24.3質量%、窒化カルシウム粉末13.9質量%、酸化ユーロピウム粉末0.9質量%、窒化ユーロピウム粉末1.1質量%の組成となるように秤量し、窒化ケイ素焼結体製の乳鉢と乳棒とを用い、10分以上混合し粉体凝集体を得た。尚、窒化ユーロピウムは、金属ユーロピウムをアンモニア中で窒化して合成したものを用いた。
得られた蛍光体粉末について、CuのKα線を用いた粉体X線回折測定(XRD)を行ったところ、当該蛍光体粉末はαサイアロン結晶の構造を有することがわかった。また、当該蛍光体粉末に、波長365nmの光を発するランプで照射した結果、橙色に発光することを確認した。
図2Aに示す発光スペクトルの色度座標は(x,y)=(0.559,0.438)、ピーク波長は597nm、半値幅は93nmであった。
組成式(CaxEuy)(Si12-(m+n)Alm+n)(OnN16-n)において、x=1.7、y=0.2、m=3.8、n=0のものを得るべく、原料粉末として、α型窒化ケイ素粉末58.4質量%、窒化アルミニウム粉末23.7質量%、窒化カルシウム粉末12.8質量%、窒化ユーロピウム粉末5.1質量%の組成となるように秤量し、窒化ケイ素焼結体製の乳鉢と乳棒とを用い、10分以上混合し粉体凝集体を得た。
得られた蛍光体粉末について、CuのKα線を用いた粉体X線回折測定(XRD)を行ったところ、当該蛍光体粉末はαサイアロン結晶の構造を有することがわかった。また、当該蛍光体粉末に、波長365nmの光を発するランプで照射した結果、橙色に発光することを確認した。
図3Aに示す発光スペクトルの色度座標は(x,y)=(0.587,0.411)、ピーク波長は610nm、半値幅は92nmであった。
組成式(CaxEuy)(Si12-(m+n)Alm+n)(OnN16-n)において、x=1.7、y=0.2、m=3.8、n=0と、製造例1-2と同等の設計組成の蛍光体粉末を得るべく、原料粉末を所定量秤量し、窒化ケイ素焼結体製の乳鉢と乳棒とを用い、10分以上混合し粉体凝集体を得た。
Si6-z’Alz’Oz’N8-z’で表される組成式において、z’=0.23のものにEuが0.09at.%賦活されたEu賦活βサイアロン蛍光体を得るべく、α型窒化ケイ素粉末95.82質量%、窒化アルミニウム粉末3.37質量%、及び酸化ユーロピウム粉末0.81質量%の組成となるように秤量し、窒化ケイ素焼結体製の乳鉢と乳棒とを用い、10分以上混合し粉体凝集体を得た。この粉体凝集体を窒化ホウ素製のるつぼに自然落下させて充填した。
Si6-z’Alz’Oz’N8-z’で表される組成式において、z’=0.06のものにEuが0.10at.%賦活されたEu賦活βサイアロン蛍光体を得るべく、45μmの篩を通した金属Si粉末93.59重量%、窒化アルミニウム粉末5.02重量%及び酸化ユーロピウム粉末1.39重量%の組成となるように所定量秤量し、窒化ケイ素焼結体製の乳鉢と乳棒とを用い、10分以上混合し粉体凝集体を得た。この粉体凝集体を直径20mm、高さ20mmの大きさの窒化ホウ素製のるつぼに自然落下させて入れた。
図5に示す発光スペクトルの色度座標は(x,y)=(0.289,0.674)、ピーク波長は528nm、半値幅は51nmであった。また、燃焼法による酸素窒素分析計(LECO社製TC436型)を用いて、これらの合成粉末中に含まれる酸素量を測定したところ、酸素含有量は0.4重量%であった。また、MCPD-7000(大塚電子製)を用いて波長600nmの光の吸収率を測定した結果12.5%であった。
Ba2.07Eu0.13Si7O10.2N4で表される組成式のものを得るべく、β型窒化ケイ素粉末17.12質量%、酸化ケイ素粉末29.32質量%、炭酸バリウム粉末50.75質量%、及び酸化ユーロピウム粉末2.81質量%の組成となるようにメノウ製乳鉢と乳棒を用いて混合し、粉体混合物50gを得た。得られた粉体混合物を150ccのエタノール中でメノウ製ボールとナイロンポットを用いた転動ボールミルにより混合し、スラリーを得た。
Lu2.7Ce0.3Al5O12で表される組成式のものを得るべく、Lu2O3粉末63.7重量%、CeO2粉末6.1重量%、Al2O3粉末30.2重量%を所定の組成となるように空気中で秤量し、更に焼成助剤としてBaF2を所定量添加してメノウ製ボールとナイロンポットとを用いた転動ボールミルにより混合し、粉体混合物を得た。得られた混合物を石英ルツボに充填し、N2(95%)+H2(5%)の還元雰囲気で1400℃、5時間の条件で焼成し、得られた焼成体をメノウ製乳鉢により粉砕して蛍光体粉末を得た。
(比較製造例1:Eu賦活αサイアロン蛍光体の作成)
組成式(CaxEuy)(Si12-(m+n)Alm+n)(OnN16-n)において、x=0.75、y=0.08、m=1.67、n=0.95のものを得るべく、原料粉末として、α型窒化ケイ素粉末69.0質量%、窒化アルミニウム粉末16.9質量%、炭酸カルシウム粉末11.8質量%、酸化ユーロピウム粉末2.3質量%の組成となるように秤量し、窒化ケイ素焼結体製の乳鉢と乳棒とを用い、10分以上混合し粉体凝集体を得た。
得られた蛍光体粉末について、CuのKα線を用いた粉体X線回折測定(XRD)を行ったところ、当該蛍光体粉末はαサイアロン結晶の構造を有することがわかった。また、当該蛍光体粉末に、波長365nmの光を発するランプで照射した結果、橙色に発光することを確認した。
図8Aに示す発光スペクトルの色度座標は(x,y)=(0.509,0.484)、ピーク波長は585nm、半値幅は94nmであった。
(比較製造例2:Eu賦活CaAlSiN3蛍光体の作製)
Ca0.992Eu0.008SiAlN3で表される組成式のものを得るべく、窒化アルミニウム粉末29.7質量%、α型窒化ケイ素粉末33.9質量%、窒化カルシウム粉末35.6質量%及び窒化ユーロピウム粉末0.8質量%を秤量し、窒化ケイ素焼結体製の乳鉢と乳棒とを用い、10分以上混合し粉体凝集体を得た。窒化ユーロピウムは、金属ユーロピウムをアンモニア中で窒化して合成したものを用いた。この粉体凝集体を直径20mm、高さ20mmの大きさの窒化ホウ素製のるつぼに自然落下させて入れた。尚、粉末の秤量、混合、成形の各工程は全て、水分1ppm以下、酸素1ppm以下の窒素雰囲気を保持することができるグローブボックス中で行なった。
<実施例1~15>
シリコーン樹脂(商品名:KER2500、信越シリコーン社製)を用い、表2に示す蛍光体を当該シリコーン樹脂と、表3に示す質量比率でそれぞれ混合分散させモールド樹脂を作製し、図1に示した構造を有する、各実施例の半導体発光装置を作製した。
シリコーン樹脂(商品名:KER2500、信越シリコーン社製)を用い、表4に示す蛍光体を当該シリコーン樹脂と、表4に示す質量比率で混合分散させモールド樹脂を作製し、図1に示した構造を有する、実施例16の半導体発光装置を作製した。
シリコーン樹脂(商品名:KER2500、信越シリコーン社製)を用い、表2に示す蛍光体を当該シリコーン樹脂と、表3に示す質量比率でそれぞれ混合分散させモールド樹脂を作製し、図1に示した構造を有する、比較例1~6の半導体発光装置を作製した。
<比較例7~9>
シリコーン樹脂(商品名:KER2500、信越シリコーン社製)を用い、表9に示す蛍光体を当該シリコーン樹脂と、表10に示す質量比率でそれぞれ混合分散させモールド樹脂を作製し、図1に示した構造を有する、各比較例の半導体発光装置を作製した。
シリコーン樹脂(商品名:KER2500、信越シリコーン社製)を用い、市販のCe賦活YAG蛍光体(商品名:P46-Y3、化成オプトニクス製、発光ピーク波長568nm、半値幅129nm、色度座標(x,y)=(0.613,0.386))を当該シリコーン樹脂と、樹脂/蛍光体=11.7の質量比率で混合分散させモールド樹脂を作製し、図1に示した構造を有する、比較例10の半導体発光装置を作製した。
2 半導体発光素子
3 プリント配線基板
4 樹脂枠
5 モールド樹脂
6 InGaN層
7 p側電極
8 n側電極
9 n電極部
10 接着剤
11 p電極部
12 金属ワイヤ
13 橙色蛍光体
14 緑色蛍光体
Claims (11)
- 青色光を発する半導体発光素子と、前記青色光を吸収して緑色光を発する緑色蛍光体と、前記青色光を吸収して橙色光を発する橙色蛍光体とを備え、該橙色蛍光体は、595~620nmの範囲に発光スペクトルのピーク波長を有したEu賦活αサイアロン蛍光体であることを特徴とする半導体発光装置。
- 前記Eu賦活αサイアロンが、
一般式(CaxEuy)(Si12-(m+n)Alm+n)(OnN16-n)
で示されるEu賦活αサイアロンで、
1.1≦x<2.0 ・・・・( 1 )
0<y<0.4 ・・・・・・( 2 )
1.5<x+y<2.0 ・・( 3 )
3.0≦m<4.0 ・・・・( 4 )
0≦n<y ・・・・・( 5 )
を満たす組成で設計されていることを特徴とする請求項1に記載の半導体発光装置。 - 前記Eu賦活αサイアロンが、
一般式(CaxEuy)(Si12-(m+n)Alm+n)(OnN16-n)
で示されるEu賦活αサイアロンで、
1.1≦x<1.85 ・・・・( 1’ )
0.15<y<0.4 ・・・( 2’ )
1.5<x+y<2.0 ・・( 3’ )
3.0≦m<4.0 ・・・・( 4’ )
0≦n<y ・・・・・( 5’ )
を満たす組成で設計されていることを特徴とする請求項1に記載の半導体発光装置。 - 前記Eu賦活αサイアロンの発光スペクトルのピーク波長が、605~620nmであることを特徴とする請求項3に記載の半導体発光装置。
- 前記Eu賦活αサイアロン蛍光体の平均粒径が15μm以上であることを特徴とする請求項1~4のいずれかに記載の半導体発光装置。
- 前記Eu賦活αサイアロン蛍光体の比表面積が0.4m2/g以下であることを特徴とする1~5のいずれかに記載の半導体発光装置。
- 前記緑色蛍光体の発光スペクトルのピーク波長が、520nm~550nmの範囲にあることを特徴とする請求項1~6のいずれかに記載の半導体発光装置。
- 前記緑色蛍光体として発光スペクトルの半値幅が55nm以下であることを特徴とする請求項7に記載の半導体発光装置。
- 前記緑色蛍光体の600nmにおける吸収率が10%以下であることを特徴とする請求項1~8のいずれかに記載の半導体発光装置。
- 前記緑色蛍光体が、Eu賦活βサイアロン蛍光体であることを特徴とする請求項1~9のいずれかに記載の半導体発光装置。
- 前記Eu賦活βサイアロン蛍光体の酸素濃度が、0.1~0.6重量%の範囲であることを特徴とする請求項10に記載の半導体発光装置。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/979,554 US9570655B2 (en) | 2011-01-18 | 2012-01-05 | Semiconductor light-emitting device |
EP16181473.6A EP3133135B1 (en) | 2011-01-18 | 2012-01-05 | Semiconductor light-emitting device |
JP2012553649A JP5676653B2 (ja) | 2011-01-18 | 2012-01-05 | 半導体発光装置 |
CN201280005648.7A CN103328608B (zh) | 2011-01-18 | 2012-01-05 | 半导体发光装置 |
EP12736448.7A EP2666841B1 (en) | 2011-01-18 | 2012-01-05 | Semiconductor light-emitting device |
US15/076,757 US9711686B2 (en) | 2011-01-18 | 2016-03-22 | Lighting device with plural fluorescent materials |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011008069 | 2011-01-18 | ||
JP2011-008069 | 2011-01-18 | ||
JP2011119337 | 2011-05-27 | ||
JP2011-119337 | 2011-05-27 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/979,554 A-371-Of-International US9570655B2 (en) | 2011-01-18 | 2012-01-05 | Semiconductor light-emitting device |
US15/076,757 Continuation US9711686B2 (en) | 2011-01-18 | 2016-03-22 | Lighting device with plural fluorescent materials |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012098932A1 true WO2012098932A1 (ja) | 2012-07-26 |
Family
ID=46515563
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2012/050065 WO2012098932A1 (ja) | 2011-01-18 | 2012-01-05 | 半導体発光装置 |
Country Status (5)
Country | Link |
---|---|
US (2) | US9570655B2 (ja) |
EP (2) | EP3133135B1 (ja) |
JP (1) | JP5676653B2 (ja) |
CN (1) | CN103328608B (ja) |
WO (1) | WO2012098932A1 (ja) |
Cited By (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012224757A (ja) * | 2011-04-20 | 2012-11-15 | Ube Industries Ltd | Ca含有α型サイアロン蛍光体およびその製造方法 |
WO2014061748A1 (ja) * | 2012-10-17 | 2014-04-24 | 宇部興産株式会社 | 波長変換部材及びそれを用いた発光装置 |
JP2014167974A (ja) * | 2013-02-28 | 2014-09-11 | Toyoda Gosei Co Ltd | 蛍光体の選別方法及び発光装置 |
JP2015028983A (ja) * | 2013-07-30 | 2015-02-12 | シャープ株式会社 | 波長変換部材及び発光装置 |
KR20160008443A (ko) * | 2014-11-10 | 2016-01-22 | 엘지전자 주식회사 | 발광 장치 |
JP2016207824A (ja) * | 2015-04-22 | 2016-12-08 | 日亜化学工業株式会社 | 発光装置及びその製造方法 |
JP2017017059A (ja) * | 2015-06-26 | 2017-01-19 | パナソニックIpマネジメント株式会社 | 照明用光源及び照明装置 |
JPWO2016063965A1 (ja) * | 2014-10-23 | 2017-09-07 | 三菱ケミカル株式会社 | 蛍光体、発光装置、照明装置及び画像表示装置 |
WO2020203486A1 (ja) * | 2019-03-29 | 2020-10-08 | デンカ株式会社 | 蛍光体粉末、複合体および発光装置 |
JP2020164798A (ja) * | 2020-02-21 | 2020-10-08 | デンカ株式会社 | 蛍光体粉末、複合体および発光装置 |
WO2020203485A1 (ja) * | 2019-03-29 | 2020-10-08 | デンカ株式会社 | 蛍光体粒子、複合体、発光装置および蛍光体粒子の製造方法 |
WO2020203488A1 (ja) * | 2019-03-29 | 2020-10-08 | デンカ株式会社 | 蛍光体粉末、複合体および発光装置 |
WO2020203487A1 (ja) * | 2019-03-29 | 2020-10-08 | デンカ株式会社 | 蛍光体粉末、複合体および発光装置 |
JP2020529733A (ja) * | 2017-07-31 | 2020-10-08 | カレント・ライティング・ソルーションズ,エルエルシー | 狭帯域緑色蛍光体を有する蛍光体変換白色発光ダイオード |
WO2020203483A1 (ja) * | 2019-03-29 | 2020-10-08 | デンカ株式会社 | 蛍光体粒子、複合体、発光装置および蛍光体粒子の製造方法 |
JP2020164788A (ja) * | 2019-03-29 | 2020-10-08 | デンカ株式会社 | 蛍光体粉末、複合体および発光装置 |
WO2020209148A1 (ja) * | 2019-04-09 | 2020-10-15 | デンカ株式会社 | 表面被覆蛍光体粒子、表面被覆蛍光体粒子の製造方法および発光装置 |
WO2020209147A1 (ja) * | 2019-04-09 | 2020-10-15 | デンカ株式会社 | 表面被覆蛍光体粒子、表面被覆蛍光体粒子の製造方法および発光装置 |
JP2021011586A (ja) * | 2020-10-26 | 2021-02-04 | デンカ株式会社 | 蛍光体粉末、複合体および発光装置 |
WO2021079739A1 (ja) * | 2019-10-23 | 2021-04-29 | デンカ株式会社 | 蛍光体プレート、発光装置および蛍光体プレートの製造方法 |
WO2021157458A1 (ja) * | 2020-02-07 | 2021-08-12 | デンカ株式会社 | 蛍光体プレート、及び発光装置 |
WO2021176912A1 (ja) * | 2020-03-04 | 2021-09-10 | デンカ株式会社 | 蛍光体プレート、及び発光装置 |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015008061A (ja) * | 2013-06-25 | 2015-01-15 | 信越化学工業株式会社 | 屋外照明 |
US10270015B1 (en) | 2017-01-13 | 2019-04-23 | Nichia Corporation | Light-emitting device |
JP6558378B2 (ja) * | 2017-01-13 | 2019-08-14 | 日亜化学工業株式会社 | 発光装置 |
WO2021186970A1 (ja) * | 2020-03-18 | 2021-09-23 | デンカ株式会社 | 蛍光体プレート、及び発光装置 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005307012A (ja) * | 2004-04-22 | 2005-11-04 | National Institute For Materials Science | サイアロン蛍光体とその製造方法 |
JP2006057018A (ja) * | 2004-08-20 | 2006-03-02 | Dowa Mining Co Ltd | 蛍光体およびその製造方法、並びに当該蛍光体を用いた光源 |
JP2006070088A (ja) * | 2004-08-31 | 2006-03-16 | Shoei Chem Ind Co | 酸窒化物蛍光体、酸窒化物蛍光体の製造方法及び白色発光素子 |
JP2006137902A (ja) * | 2004-11-15 | 2006-06-01 | Shoei Chem Ind Co | 窒化物蛍光体、窒化物蛍光体の製造方法及び白色発光素子 |
WO2007066733A1 (ja) * | 2005-12-08 | 2007-06-14 | National Institute For Materials Science | 蛍光体とその製造方法および発光器具 |
JP2007227928A (ja) * | 2006-02-22 | 2007-09-06 | Samsung Electro-Mechanics Co Ltd | 白色発光装置 |
JP2009096882A (ja) * | 2007-10-17 | 2009-05-07 | Denki Kagaku Kogyo Kk | 蛍光体とその製造方法 |
Family Cites Families (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10133352A1 (de) * | 2001-07-16 | 2003-02-06 | Patent Treuhand Ges Fuer Elektrische Gluehlampen Mbh | Beleuchtungseinheit mit mindestens einer LED als Lichtquelle |
JP2003321675A (ja) | 2002-04-26 | 2003-11-14 | Nichia Chem Ind Ltd | 窒化物蛍光体及びその製造方法 |
JP3837588B2 (ja) | 2003-11-26 | 2006-10-25 | 独立行政法人物質・材料研究機構 | 蛍光体と蛍光体を用いた発光器具 |
JP4144877B2 (ja) | 2004-03-11 | 2008-09-03 | ユニケミカル株式会社 | アミン変性リン酸基を含有する固体高分子電解質膜及びその原料単量体組成物、並びにその固体高分子電解質膜の製造方法及び用途 |
JP3921545B2 (ja) | 2004-03-12 | 2007-05-30 | 独立行政法人物質・材料研究機構 | 蛍光体とその製造方法 |
WO2006061778A1 (en) * | 2004-12-06 | 2006-06-15 | Philips Intellectual Property & Standards Gmbh | Illumination system comprising a radiation source and a blue-emitting phospor |
JP4104013B2 (ja) * | 2005-03-18 | 2008-06-18 | 株式会社フジクラ | 発光デバイス及び照明装置 |
EP1892268B1 (en) * | 2005-06-14 | 2015-10-28 | Denki Kagaku Kogyo Kabushiki Kaisha | Resin composition and sheet containing phosphor, and light emitting element using such composition and sheet |
JP5110518B2 (ja) * | 2005-07-01 | 2012-12-26 | 独立行政法人物質・材料研究機構 | 蛍光体とその製造方法および照明器具 |
JP4685627B2 (ja) | 2005-12-28 | 2011-05-18 | 株式会社日立ハイテクノロジーズ | 試料加工方法 |
WO2007088966A1 (ja) | 2006-02-02 | 2007-08-09 | Mitsubishi Chemical Corporation | 複合酸窒化物蛍光体、それを用いた発光装置、画像表示装置、照明装置及び蛍光体含有組成物、並びに、複合酸窒化物 |
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 |
EP2056366B1 (en) * | 2006-08-14 | 2013-04-03 | Fujikura Ltd. | Light emitting device and illumination device |
JP2008120938A (ja) * | 2006-11-14 | 2008-05-29 | Sharp Corp | 蛍光体およびその製造方法、ならびに半導体発光装置および画像表示装置 |
EP2093272B1 (en) | 2006-11-20 | 2016-11-02 | Denka Company Limited | Fluorescent substance and production method thereof, and light emitting device |
JP5367218B2 (ja) * | 2006-11-24 | 2013-12-11 | シャープ株式会社 | 蛍光体の製造方法および発光装置の製造方法 |
WO2008093768A1 (ja) * | 2007-02-01 | 2008-08-07 | Panasonic Corporation | 蛍光ランプ、並びに蛍光ランプを用いた発光装置及び表示装置 |
US9279079B2 (en) * | 2007-05-30 | 2016-03-08 | Sharp Kabushiki Kaisha | Method of manufacturing phosphor, light-emitting device, and image display apparatus |
JP5263722B2 (ja) | 2007-06-08 | 2013-08-14 | シャープ株式会社 | 蛍光体、発光装置および画像表示装置 |
CN101578714B (zh) * | 2007-08-03 | 2011-02-09 | 松下电器产业株式会社 | 发光装置 |
JP5941243B2 (ja) * | 2007-10-17 | 2016-06-29 | スタンレー電気株式会社 | 発光装置、それを用いた車両用灯具、およびヘッドランプ |
JP5000479B2 (ja) * | 2007-12-27 | 2012-08-15 | シャープ株式会社 | 面光源、表示装置及びその製造方法 |
RU2010132369A (ru) * | 2008-01-03 | 2012-02-10 | Конинклейке Филипс Электроникс Н.В. (Nl) | Устройство отображения и осветительное устройство |
US8324798B2 (en) | 2010-03-19 | 2012-12-04 | Nitto Denko Corporation | Light emitting device using orange-red phosphor with co-dopants |
-
2012
- 2012-01-05 EP EP16181473.6A patent/EP3133135B1/en active Active
- 2012-01-05 JP JP2012553649A patent/JP5676653B2/ja not_active Expired - Fee Related
- 2012-01-05 US US13/979,554 patent/US9570655B2/en active Active
- 2012-01-05 WO PCT/JP2012/050065 patent/WO2012098932A1/ja active Application Filing
- 2012-01-05 CN CN201280005648.7A patent/CN103328608B/zh not_active Expired - Fee Related
- 2012-01-05 EP EP12736448.7A patent/EP2666841B1/en not_active Not-in-force
-
2016
- 2016-03-22 US US15/076,757 patent/US9711686B2/en not_active Expired - Fee Related
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005307012A (ja) * | 2004-04-22 | 2005-11-04 | National Institute For Materials Science | サイアロン蛍光体とその製造方法 |
JP2006057018A (ja) * | 2004-08-20 | 2006-03-02 | Dowa Mining Co Ltd | 蛍光体およびその製造方法、並びに当該蛍光体を用いた光源 |
JP2006070088A (ja) * | 2004-08-31 | 2006-03-16 | Shoei Chem Ind Co | 酸窒化物蛍光体、酸窒化物蛍光体の製造方法及び白色発光素子 |
JP2006137902A (ja) * | 2004-11-15 | 2006-06-01 | Shoei Chem Ind Co | 窒化物蛍光体、窒化物蛍光体の製造方法及び白色発光素子 |
WO2007066733A1 (ja) * | 2005-12-08 | 2007-06-14 | National Institute For Materials Science | 蛍光体とその製造方法および発光器具 |
JP2007227928A (ja) * | 2006-02-22 | 2007-09-06 | Samsung Electro-Mechanics Co Ltd | 白色発光装置 |
JP2009096882A (ja) * | 2007-10-17 | 2009-05-07 | Denki Kagaku Kogyo Kk | 蛍光体とその製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2666841A4 * |
Cited By (49)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012224757A (ja) * | 2011-04-20 | 2012-11-15 | Ube Industries Ltd | Ca含有α型サイアロン蛍光体およびその製造方法 |
JPWO2014061748A1 (ja) * | 2012-10-17 | 2016-09-05 | 宇部興産株式会社 | 波長変換部材及びそれを用いた発光装置 |
WO2014061748A1 (ja) * | 2012-10-17 | 2014-04-24 | 宇部興産株式会社 | 波長変換部材及びそれを用いた発光装置 |
CN104736664A (zh) * | 2012-10-17 | 2015-06-24 | 宇部兴产株式会社 | 波长转换部件及使用其的发光装置 |
US9708533B2 (en) | 2012-10-17 | 2017-07-18 | Ube Industries, Ltd. | Wavelength conversion member and light-emitting device employing same |
JP5954425B2 (ja) * | 2012-10-17 | 2016-07-20 | 宇部興産株式会社 | 波長変換部材及びそれを用いた発光装置 |
JP2014167974A (ja) * | 2013-02-28 | 2014-09-11 | Toyoda Gosei Co Ltd | 蛍光体の選別方法及び発光装置 |
JP2015028983A (ja) * | 2013-07-30 | 2015-02-12 | シャープ株式会社 | 波長変換部材及び発光装置 |
JPWO2016063965A1 (ja) * | 2014-10-23 | 2017-09-07 | 三菱ケミカル株式会社 | 蛍光体、発光装置、照明装置及び画像表示装置 |
KR20160008443A (ko) * | 2014-11-10 | 2016-01-22 | 엘지전자 주식회사 | 발광 장치 |
KR102100193B1 (ko) | 2014-11-10 | 2020-04-13 | 엘지전자 주식회사 | 발광 장치 |
JP2016207824A (ja) * | 2015-04-22 | 2016-12-08 | 日亜化学工業株式会社 | 発光装置及びその製造方法 |
JP2017017059A (ja) * | 2015-06-26 | 2017-01-19 | パナソニックIpマネジメント株式会社 | 照明用光源及び照明装置 |
JP7332578B2 (ja) | 2017-07-31 | 2023-08-23 | カレント・ライティング・ソルーションズ,エルエルシー | 狭帯域緑色蛍光体を有する蛍光体変換白色発光ダイオード |
JP2020529733A (ja) * | 2017-07-31 | 2020-10-08 | カレント・ライティング・ソルーションズ,エルエルシー | 狭帯域緑色蛍光体を有する蛍光体変換白色発光ダイオード |
US11359139B2 (en) | 2019-03-29 | 2022-06-14 | Denka Company Limited | Phosphor powder, composite, and light-emitting device |
WO2020203486A1 (ja) * | 2019-03-29 | 2020-10-08 | デンカ株式会社 | 蛍光体粉末、複合体および発光装置 |
WO2020203487A1 (ja) * | 2019-03-29 | 2020-10-08 | デンカ株式会社 | 蛍光体粉末、複合体および発光装置 |
WO2020203485A1 (ja) * | 2019-03-29 | 2020-10-08 | デンカ株式会社 | 蛍光体粒子、複合体、発光装置および蛍光体粒子の製造方法 |
WO2020203483A1 (ja) * | 2019-03-29 | 2020-10-08 | デンカ株式会社 | 蛍光体粒子、複合体、発光装置および蛍光体粒子の製造方法 |
JP2020164788A (ja) * | 2019-03-29 | 2020-10-08 | デンカ株式会社 | 蛍光体粉末、複合体および発光装置 |
JP2020164754A (ja) * | 2019-03-29 | 2020-10-08 | デンカ株式会社 | 蛍光体粉末、複合体および発光装置 |
JP7436214B2 (ja) | 2019-03-29 | 2024-02-21 | デンカ株式会社 | 蛍光体粉末、複合体および発光装置 |
US11898079B2 (en) | 2019-03-29 | 2024-02-13 | Denka Company Limited | Phosphor powder, composite, and light-emitting device |
TWI829904B (zh) * | 2019-03-29 | 2024-01-21 | 日商電化股份有限公司 | 螢光體粉末、複合體及發光裝置 |
WO2020203488A1 (ja) * | 2019-03-29 | 2020-10-08 | デンカ株式会社 | 蛍光体粉末、複合体および発光装置 |
US11485906B2 (en) | 2019-03-29 | 2022-11-01 | Denka Company Limited | Phosphor particle, composite, light-emitting device, and method for producing phosphor particle |
US11434422B2 (en) | 2019-03-29 | 2022-09-06 | Denka Company Limited | Phosphor powder, composite, and light-emitting device |
US11339325B2 (en) | 2019-03-29 | 2022-05-24 | Denka Company Limited | Phosphor particle, composite, light-emitting device, and method for producing phosphor particle |
KR20210128007A (ko) * | 2019-03-29 | 2021-10-25 | 덴카 주식회사 | 형광체 분말, 복합체 및 발광 장치 |
KR20210128005A (ko) * | 2019-03-29 | 2021-10-25 | 덴카 주식회사 | 형광체 입자, 복합체, 발광 장치 및 형광체 입자의 제조 방법 |
KR20210128006A (ko) * | 2019-03-29 | 2021-10-25 | 덴카 주식회사 | 형광체 입자, 복합체, 발광 장치 및 형광체 입자의 제조 방법 |
KR102336243B1 (ko) | 2019-03-29 | 2021-12-07 | 덴카 주식회사 | 형광체 입자, 복합체, 발광 장치 및 형광체 입자의 제조 방법 |
KR102336242B1 (ko) | 2019-03-29 | 2021-12-07 | 덴카 주식회사 | 형광체 입자, 복합체, 발광 장치 및 형광체 입자의 제조 방법 |
KR102336244B1 (ko) | 2019-03-29 | 2021-12-07 | 덴카 주식회사 | 형광체 분말, 복합체 및 발광 장치 |
WO2020209147A1 (ja) * | 2019-04-09 | 2020-10-15 | デンカ株式会社 | 表面被覆蛍光体粒子、表面被覆蛍光体粒子の製造方法および発光装置 |
JP7507149B2 (ja) | 2019-04-09 | 2024-06-27 | デンカ株式会社 | 表面被覆蛍光体粒子、表面被覆蛍光体粒子の製造方法および発光装置 |
JP7507150B2 (ja) | 2019-04-09 | 2024-06-27 | デンカ株式会社 | 表面被覆蛍光体粒子、表面被覆蛍光体粒子の製造方法および発光装置 |
WO2020209148A1 (ja) * | 2019-04-09 | 2020-10-15 | デンカ株式会社 | 表面被覆蛍光体粒子、表面被覆蛍光体粒子の製造方法および発光装置 |
TWI829912B (zh) * | 2019-04-09 | 2024-01-21 | 日商電化股份有限公司 | 表面被覆螢光體粒子、表面被覆螢光體粒子之製造方法以及發光裝置 |
JP7519372B2 (ja) | 2019-10-23 | 2024-07-19 | デンカ株式会社 | 蛍光体プレート、発光装置および蛍光体プレートの製造方法 |
WO2021079739A1 (ja) * | 2019-10-23 | 2021-04-29 | デンカ株式会社 | 蛍光体プレート、発光装置および蛍光体プレートの製造方法 |
WO2021157458A1 (ja) * | 2020-02-07 | 2021-08-12 | デンカ株式会社 | 蛍光体プレート、及び発光装置 |
JP2020164798A (ja) * | 2020-02-21 | 2020-10-08 | デンカ株式会社 | 蛍光体粉末、複合体および発光装置 |
JP7432705B2 (ja) | 2020-03-04 | 2024-02-16 | デンカ株式会社 | 蛍光体プレート、及び発光装置 |
JPWO2021176912A1 (ja) * | 2020-03-04 | 2021-09-10 | ||
WO2021176912A1 (ja) * | 2020-03-04 | 2021-09-10 | デンカ株式会社 | 蛍光体プレート、及び発光装置 |
JP2021011586A (ja) * | 2020-10-26 | 2021-02-04 | デンカ株式会社 | 蛍光体粉末、複合体および発光装置 |
JP7252186B2 (ja) | 2020-10-26 | 2023-04-04 | デンカ株式会社 | 蛍光体粉末、複合体および発光装置 |
Also Published As
Publication number | Publication date |
---|---|
EP2666841A4 (en) | 2014-08-20 |
EP2666841A1 (en) | 2013-11-27 |
CN103328608B (zh) | 2015-04-22 |
EP3133135A1 (en) | 2017-02-22 |
JPWO2012098932A1 (ja) | 2014-06-09 |
EP3133135B1 (en) | 2019-03-06 |
US20130285104A1 (en) | 2013-10-31 |
US20160204311A1 (en) | 2016-07-14 |
JP5676653B2 (ja) | 2015-02-25 |
US9570655B2 (en) | 2017-02-14 |
EP2666841B1 (en) | 2016-09-21 |
CN103328608A (zh) | 2013-09-25 |
US9711686B2 (en) | 2017-07-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5676653B2 (ja) | 半導体発光装置 | |
JP5450625B2 (ja) | 発光装置 | |
JP4869317B2 (ja) | 赤色蛍光体およびそれを用いた発光装置 | |
JP5791034B2 (ja) | 発光装置 | |
JP5216330B2 (ja) | 放射線源および発光物質を含む照明系 | |
JP5777032B2 (ja) | 発光装置 | |
JP5511820B2 (ja) | アルファ−サイアロン発光体 | |
WO2007004493A1 (ja) | 蛍光体とその製造方法および照明器具 | |
WO2007004492A1 (ja) | 蛍光体とその製造方法および照明器具 | |
JP4825923B2 (ja) | 赤色蛍光体およびそれを用いた発光装置 | |
JP2006282872A (ja) | 窒化物蛍光体または酸窒化物蛍光体、及びその製造方法、並びに当該蛍光体を用いた発光装置 | |
JP6323177B2 (ja) | 半導体発光装置 | |
JP6287268B2 (ja) | 発光装置 | |
TWI458806B (zh) | β型矽鋁氮氧化物之製造方法、β型矽鋁氮氧化物及發光裝置 | |
WO2012165032A1 (ja) | 発光装置 | |
JP5783512B2 (ja) | 発光装置 | |
JP4948015B2 (ja) | アルミン酸系青色蛍光体およびそれを用いた発光装置 |
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: 12736448 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2012553649 Country of ref document: JP Kind code of ref document: A |
|
REEP | Request for entry into the european phase |
Ref document number: 2012736448 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012736448 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13979554 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |