WO2012157604A1 - 赤色蛍光体の製造方法 - Google Patents
赤色蛍光体の製造方法 Download PDFInfo
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- WO2012157604A1 WO2012157604A1 PCT/JP2012/062291 JP2012062291W WO2012157604A1 WO 2012157604 A1 WO2012157604 A1 WO 2012157604A1 JP 2012062291 W JP2012062291 W JP 2012062291W WO 2012157604 A1 WO2012157604 A1 WO 2012157604A1
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- Prior art keywords
- red phosphor
- firing
- europium
- composition formula
- intensity
- Prior art date
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 259
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000010304 firing Methods 0.000 claims abstract description 164
- 239000000203 mixture Substances 0.000 claims abstract description 147
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 72
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 70
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims abstract description 70
- 150000001875 compounds Chemical class 0.000 claims abstract description 47
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 46
- 238000002156 mixing Methods 0.000 claims abstract description 43
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 33
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000010703 silicon Substances 0.000 claims abstract description 31
- 239000011575 calcium Substances 0.000 claims abstract description 25
- 238000010298 pulverizing process Methods 0.000 claims abstract description 25
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 23
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 22
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 18
- 239000011777 magnesium Substances 0.000 claims abstract description 17
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 16
- 239000002210 silicon-based material Substances 0.000 claims abstract description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052788 barium Inorganic materials 0.000 claims abstract description 8
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 75
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 75
- 238000004519 manufacturing process Methods 0.000 claims description 54
- 238000001228 spectrum Methods 0.000 claims description 44
- 238000002441 X-ray diffraction Methods 0.000 claims description 38
- 229910001940 europium oxide Inorganic materials 0.000 claims description 26
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 26
- 230000005284 excitation Effects 0.000 claims description 18
- 239000012298 atmosphere Substances 0.000 claims description 15
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 14
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 14
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 13
- SULCVUWEGVSCPF-UHFFFAOYSA-L europium(2+);carbonate Chemical compound [Eu+2].[O-]C([O-])=O SULCVUWEGVSCPF-UHFFFAOYSA-L 0.000 claims description 12
- 238000005286 illumination Methods 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- LNYNHRRKSYMFHF-UHFFFAOYSA-K europium(3+);triacetate Chemical compound [Eu+3].CC([O-])=O.CC([O-])=O.CC([O-])=O LNYNHRRKSYMFHF-UHFFFAOYSA-K 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 7
- -1 carbonate compound Chemical class 0.000 claims description 5
- 238000005424 photoluminescence Methods 0.000 claims description 4
- 150000001722 carbon compounds Chemical class 0.000 claims 1
- 238000004020 luminiscence type Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 42
- 239000007789 gas Substances 0.000 description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 33
- 238000010438 heat treatment Methods 0.000 description 28
- 238000009616 inductively coupled plasma Methods 0.000 description 27
- 238000010586 diagram Methods 0.000 description 26
- 239000000047 product Substances 0.000 description 25
- 229910052760 oxygen Inorganic materials 0.000 description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 22
- 239000001301 oxygen Substances 0.000 description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 19
- 239000004570 mortar (masonry) Substances 0.000 description 17
- 239000000843 powder Substances 0.000 description 17
- PSBUJOCDKOWAGJ-UHFFFAOYSA-N azanylidyneeuropium Chemical compound [Eu]#N PSBUJOCDKOWAGJ-UHFFFAOYSA-N 0.000 description 15
- 238000000295 emission spectrum Methods 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 238000002485 combustion reaction Methods 0.000 description 13
- 238000007580 dry-mixing Methods 0.000 description 13
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 13
- 239000002243 precursor Substances 0.000 description 13
- 229910000018 strontium carbonate Inorganic materials 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000001514 detection method Methods 0.000 description 12
- 238000001745 non-dispersive infrared spectroscopy Methods 0.000 description 12
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 11
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 230000004907 flux Effects 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 241001085205 Prenanthella exigua Species 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000002411 adverse Effects 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000000695 excitation spectrum Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
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- 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
- C09K11/64—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7729—Chalcogenides
- C09K11/7731—Chalcogenides with alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
- F21V9/00—Elements for modifying spectral properties, polarisation or intensity of the light emitted, e.g. filters
- F21V9/08—Elements for modifying spectral properties, polarisation or intensity of the light emitted, e.g. filters for producing coloured light, e.g. monochromatic; for reducing intensity of light
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/1336—Illuminating devices
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/93—Batch processes
- H01L24/95—Batch processes at chip-level, i.e. with connecting carried out on a plurality of singulated devices, i.e. on diced chips
- H01L24/97—Batch processes at chip-level, i.e. with connecting carried out on a plurality of singulated devices, i.e. on diced chips the devices being connected to a common substrate, e.g. interposer, said common substrate being separable into individual assemblies after connecting
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/10—Details of semiconductor or other solid state devices to be connected
- H01L2924/11—Device type
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Definitions
- the present invention relates to a method for producing a red phosphor having an emission peak wavelength in a red wavelength band (for example, a wavelength band of 620 nm to 770 nm).
- a red wavelength band for example, a wavelength band of 620 nm to 770 nm.
- This application includes Japanese Patent Application No. 2011-108870 filed on May 14, 2011 in Japan and Japanese Patent Application No. 2011-263327 filed on December 1, 2011 in Japan. On the basis of the above, and is incorporated into the present application by reference to this application.
- red phosphors that emit red light when excited by blue LEDs in applications such as high color gamut backlights and high color rendering LEDs (Light Emitting Diodes). Phosphors are being developed.
- Patent Document 1 discloses red fluorescence containing europium (Eu), silicon (Si), oxygen (O), and nitrogen (N) using europium nitride (EuN) as a source of europium (Eu). Making a body is described.
- Another object of the present invention is to provide a red phosphor having good light emission characteristics, and a white light source, an illumination device, and a liquid crystal display device using the red phosphor.
- the method for producing a red phosphor according to the present invention includes an element A, europium (Eu), silicon (Si), aluminum (Al), and carbon (C) represented by the following composition formula (1 ),
- the carbonic acid compound of element A, nitrogen-free europium, silicon nitride, aluminum nitride, and a carbon-containing reducing agent are mixed to form a mixture, and the mixture is fired and obtained by the firing.
- the fired product obtained is pulverized.
- the element A in the composition formula (1) is at least one of magnesium (Mg), calcium (Ca), strontium (Sr), or barium (Ba), and m, x in the composition formula (1) , Z, n satisfy the relations 3 ⁇ m ⁇ 5, 0 ⁇ y ⁇ 2, 0 ⁇ x ⁇ 1, 0 ⁇ z ⁇ 1, 0 ⁇ n ⁇ 10.
- the element (A), europium (Eu), silicon (Si), aluminum (Al), and carbon (C) have an atomic ratio of the composition formula (1).
- element (A), nitrogen-free europium, silicon-containing compound, aluminum-containing compound and carbon-containing reducing agent are mixed to form a mixture. The mixture is fired, and the fired product obtained by the firing is ground.
- the intensity of the peak existing at the diffraction angle of 36 ° to 36.6 ° is the intensity of the peak existing at the diffraction angle of 35 ° to 36 °. It is characterized by showing 0.65 times or more.
- the white light source according to the present invention includes a blue light emitting diode formed on an element substrate, and a red phosphor and a green phosphor or a yellow phosphor disposed on the blue light emitting diode and kneaded in a transparent resin.
- the red phosphor is composed of an element (A), europium (Eu), silicon (Si), aluminum (Al), and carbon (C) having an atomic ratio of the composition formula (1).
- the element (A), nitrogen-free europium, silicon-containing compound, aluminum-containing compound and carbon-containing reducing agent are mixed to form a mixture, and the mixture is fired and the fired product obtained by the firing is obtained.
- FIG. 6 is a flowchart showing a specific example (normal pressure two-stage firing) of a method for producing a red phosphor.
- FIG. 7 is a flowchart showing a specific example (pressure two-stage firing) of the method for producing a red phosphor.
- FIG. 8 shows the peak intensity of each red phosphor produced using Eu 2 O 3 , Eu (CH 3 COO) 3 .nH 2 O, Eu 2 (CO 3 ) 3 , or EuN as a source of europium. It is a graph which shows ratio (YAG reference
- FIG. 14 is a graph showing the peak intensity ratio of each red phosphor when the H 2 gas concentration during primary firing is 4%, 50%, or 75%, respectively.
- FIG. 15 is a flowchart showing a specific example (normal pressure one-step firing) of a method for producing a red phosphor.
- FIG. 16 is a graph showing the peak intensity ratio (YAG standard) of each red phosphor produced by pressure two-step firing, normal pressure two-step firing, or normal pressure one-step firing.
- FIG. 17 is a graph showing the internal quantum efficiency of each red phosphor produced by pressure two-stage firing, normal pressure two-stage firing, or normal pressure one-stage firing.
- FIG. 15 is a flowchart showing a specific example (normal pressure one-step firing) of a method for producing a red phosphor.
- FIG. 16 is a graph showing the peak intensity ratio (YAG standard) of each red phosphor produced by pressure two-step firing, normal pressure two-step firing, or normal pressure one-step firing.
- FIG. 18 is a graph showing the peak intensity ratio (YAG standard) of each red phosphor produced at a firing temperature of 1500 ° C., 1600 ° C., 1700 ° C., 1750 ° C., or 1800 ° C., respectively.
- FIG. 19 is a graph showing the maximum peak intensity ratio (YAG standard) for each red phosphor produced at a firing temperature of 1500 ° C., 1600 ° C., 1700 ° C., 1750 ° C., or 1800 ° C., respectively.
- FIG. 20 is a flowchart showing a specific example (a nitrogen atmosphere and normal pressure two-step firing) of a method for producing a red phosphor.
- FIG. 21 is an emission / excitation spectrum of a red phosphor.
- FIG. 22 is a graph showing the peak intensity ratio (YAG standard) of the red phosphor with respect to the melamine amount.
- FIG. 23 is a graph showing the internal quantum efficiency of the red phosphor with respect to the melamine amount.
- FIG. 24 is a diagram showing an emission spectrum of each red phosphor (sample 1) when the amount of melamine added is changed.
- FIG. 25 is a diagram showing a spectrum normalized with a peak intensity existing at a diffraction angle of 35 ° to 36 ° with respect to the XRD spectrum of each red phosphor (sample 1) when the amount of melamine added is changed. is there.
- FIG. 26 shows the XRD spectrum of each red phosphor (sample 1) when the melamine addition amount is changed, at each diffraction angle with respect to the peak intensity existing at a position where the diffraction angle is 35.0 ° to 36.0 °. It is a graph which shows the intensity ratio of the diffraction peak of peak intensity.
- FIG. 27 shows that the XRD spectrum of each red phosphor (sample 1) when the melamine addition amount is changed has a diffraction angle of 36 with respect to the peak intensity existing at a position where the diffraction angle is 35.0 ° to 36.0 °.
- FIG. 4 is a diagram showing the relationship between the intensity ratio of diffraction peaks of peak intensities existing at positions of 0.0 ° to 36.6 ° and the intensity ratio of emission peaks (YAG standard).
- FIG. 28 is a diagram showing an emission spectrum of each red phosphor (sample 2) when the amount of melamine added is changed.
- FIG. 29 is a diagram showing a spectrum normalized with the peak intensity existing at a diffraction angle of 35 ° to 36 ° for the XRD spectrum of each red phosphor (sample 2) when the melamine addition amount is changed. is there.
- FIG. 28 is a diagram showing an emission spectrum of each red phosphor (sample 2) when the amount of melamine added is changed.
- FIG. 29 is a diagram showing a spectrum normalized with the peak intensity existing at a diffraction angle of 35 ° to 36 ° for the XRD spectrum of each red phosphor (sample 2) when the melamine addition amount is changed. is there.
- FIG. 30 shows the XRD spectrum of each red phosphor (sample 2) when the amount of melamine added is changed at each diffraction angle with respect to the peak intensity existing at a diffraction angle of 35.0 ° to 36.0 °. It is a graph which shows the intensity ratio of the diffraction peak of peak intensity.
- FIG. 31 shows that the XRD spectrum of each red phosphor (sample 2) when the melamine addition amount is changed has a diffraction angle of 36 with respect to the peak intensity existing at a position where the diffraction angle is 35.0 ° to 36.0 °.
- FIG. 4 is a diagram showing the relationship between the intensity ratio of diffraction peaks of peak intensities existing at positions of 0.0 ° to 36.6 ° and the intensity ratio of emission peaks (YAG standard).
- FIG. 32 is a diagram showing an emission spectrum of each red phosphor (sample 3) when the amount of melamine added is changed.
- FIG. 33 is a diagram showing a spectrum normalized with the peak intensity existing at a diffraction angle of 35 ° to 36 ° for the XRD spectrum of each red phosphor (sample 3) when the melamine addition amount is changed. is there.
- FIG. 32 is a diagram showing an emission spectrum of each red phosphor (sample 3) when the amount of melamine added is changed.
- FIG. 33 is a diagram showing a spectrum normalized with the peak intensity existing at a diffraction angle of 35 ° to 36 ° for the XRD spectrum of each red phosphor (sample 3) when the melamine addition amount is changed.
- FIG. 34 shows the XRD spectrum of each red phosphor (sample 3) when the melamine addition amount is changed, at each diffraction angle with respect to the peak intensity existing at a position where the diffraction angle is 35.0 ° to 36.0 °. It is a graph which shows the intensity ratio of the diffraction peak of peak intensity.
- FIG. 35 shows the XRD spectrum of each red phosphor (sample 3) when the melamine addition amount is changed, with a diffraction angle of 36 for the peak intensity existing at a position where the diffraction angle is 35.0 ° to 36.0 °.
- FIG. 35 shows the XRD spectrum of each red phosphor (sample 3) when the melamine addition amount is changed, with a diffraction angle of 36 for the peak intensity existing at a position where the diffraction angle is 35.0 ° to 36.0 °.
- FIG. 4 is a diagram showing the relationship between the intensity ratio of diffraction peaks of peak intensities existing at positions of 0.0 ° to 36.6 ° and the intensity ratio of emission peaks (YAG standard).
- FIG. 36 is a diagram showing an emission spectrum of each red phosphor (sample 4) when the amount of melamine added is changed.
- FIG. 37 is a diagram showing a spectrum normalized by the peak intensity existing at a diffraction angle of 35 ° to 36 ° with respect to the XRD spectrum of each red phosphor (sample 4) when the amount of melamine added is changed. is there.
- FIG. 36 is a diagram showing an emission spectrum of each red phosphor (sample 4) when the amount of melamine added is changed.
- FIG. 37 is a diagram showing a spectrum normalized by the peak intensity existing at a diffraction angle of 35 ° to 36 ° with respect to the XRD spectrum of each red phosphor (sample 4) when the amount of
- FIG. 38 shows the XRD spectrum of each red phosphor (sample 4) when the melamine addition amount is changed, at each diffraction angle with respect to the peak intensity existing at a position where the diffraction angle is 35.0 ° to 36.0 °. It is a graph which shows the intensity ratio of the diffraction peak of peak intensity.
- FIG. 39 shows that the XRD spectrum of each red phosphor (sample 4) when the melamine addition amount is changed has a diffraction angle of 36 relative to the peak intensity existing at a diffraction angle of 35.0 ° to 36.0 °.
- FIG. 4 is a diagram showing the relationship between the intensity ratio of diffraction peaks of peak intensities existing at positions of 0.0 ° to 36.6 ° and the intensity ratio of emission peaks (YAG standard).
- FIG. 40 is a diagram showing a spectrum obtained by normalizing the XRD spectrum of the red phosphor of Example 1 with a peak intensity existing at a diffraction angle of 35 ° to 36 °.
- FIG. 41 is a diagram showing a spectrum normalized by the peak intensity existing at a diffraction angle of 35 ° to 36 ° with respect to the XRD spectrum of the red phosphor produced by the conventional manufacturing method.
- FIG. 42 is a graph showing the relationship between the emission intensity at the excitation wavelength of 550 nm and the external quantum efficiency when the emission intensity at the excitation wavelength of 400 nm of the red phosphor is 1.
- the red phosphor represented by the composition formula (1) is composed of a crystal structure belonging to the orthorhombic space point group Pmn21, and contains carbon (C) as one of constituent elements. Carbon functions to remove excess oxygen (O) in the production process and adjust the amount of oxygen.
- melamine having a melting point of 250 ° C. or lower is thermally decomposed.
- the pyrolyzed carbon (C) and hydrogen (H) combine with part of oxygen (O) contained in strontium carbonate to form carbon dioxide (CO or CO 2 ) or H 2 O. Since carbon dioxide gas and H 2 O are vaporized, a part of oxygen is removed from the strontium carbonate of the first fired product. Reduction and nitridation are promoted by nitrogen (N) contained in the decomposed melamine.
- the first crushing step S103 is performed.
- the first fired product is pulverized to produce a first powder.
- the first fired product is pulverized using an agate mortar in a glow box in a nitrogen atmosphere, and then passed through, for example, # 100 mesh (aperture is about 200 ⁇ m) to obtain the first powder. obtain.
- the secondary firing step S104 is performed.
- the first powder is heat treated to produce a second fired product.
- the first powder is put in a boron nitride (BN) crucible, pressurized to 0.85 MPa in a nitrogen (N 2 ) atmosphere, the heat treatment temperature is set to 1800 ° C., and the heat treatment is performed for 2 hours. I do.
- BN boron nitride
- N 2 nitrogen
- the secondary firing step S104 pressurization is performed under high temperature conditions, so that the soaking zone of the heat treatment furnace becomes narrow (about ⁇ 100), and the firing amount is limited.
- the primary firing step S102 it is essential to install a safety device in order to perform heat treatment in a strong reducing atmosphere in which the hydrogen concentration exceeds 4% of the explosion limit value.
- pressurization is performed under high temperature conditions. Therefore, since a heat treatment furnace that can withstand high temperature and pressure is essential, expensive special equipment is required.
- the carbon-containing reducing agent is melamine
- the melamine amount By setting the melamine amount to 65% or less, the maximum peak intensity ratio and the internal quantum efficiency can be obtained under normal pressure conditions or in a low concentration atmosphere of H 2 gas.
- a firing step S12 is performed in which the precursor mixture is filled in a heat treatment furnace and fired.
- This firing step S12 is preferably performed at normal pressure (atmospheric pressure). Thereby, the soaking zone of the heat treatment furnace is narrowed (about ⁇ 100), and it is possible to prevent the firing amount from being limited.
- composition irregularity of the red phosphor can be prevented by performing the first pulverization step after the primary firing step.
- this firing step S12 for example, when melamine is used as the carbon-containing reducing agent and strontium carbonate is used as the element A compound, melamine is thermally decomposed and carbon (C) and hydrogen (H) are contained in strontium carbonate. Combined with part of oxygen (O), carbon dioxide (CO or CO 2 ) or H 2 O is formed. Since carbon dioxide gas and H 2 O are vaporized, a part of oxygen is removed from the strontium carbonate of the fired product. Reduction and nitridation are promoted by nitrogen (N) contained in the decomposed melamine.
- N nitrogen
- the element (A), europium (Eu), silicon (Si), aluminum (Al), and carbon (C) have an atomic ratio of the composition formula (1).
- the element (A), nitrogen-free europium, silicon-containing compound, aluminum-containing compound and carbon-containing reducing agent are mixed to form a mixture, and the mixture is fired and the fired product obtained by the firing is pulverized.
- the intensity of the peak existing at the diffraction angle of 36 ° to 36.6 ° is the intensity of the peak existing at the diffraction angle of 35 ° to 36 °. It indicates 0.65 times or more.
- the red phosphor in the present embodiment preferably satisfies 0.05 ⁇ x ⁇ 0.15 in the composition formula (1).
- the peak of the emission intensity varies depending on the Eu (europium) concentration (x).
- the Eu concentration (x) By setting the Eu concentration (x) in this range, a high external quantum can be obtained. Efficiency can be obtained.
- a resin layer 31 is provided around the blue light emitting diode 21, and an opening 32 that opens on the blue light emitting diode 21 is formed in the resin layer 31.
- the opening 32 is formed on an inclined surface whose opening area is widened in the light emitting direction of the blue light emitting diode 21, and a reflective film 33 is formed on the inclined surface. That is, the resin layer 31 having the mortar-shaped opening 32 is covered with the wall reflecting film 33 of the opening 32 and the blue light emitting diode 21 is disposed on the bottom surface of the opening 32.
- the white light source 1 is configured by embedding a kneaded material 43 in which the red phosphor and the green phosphor are mixed in a transparent resin so as to cover the blue light emitting diode 21 in the opening 32.
- the arrangement may be shifted every other column, for example, by 1/2 pitch.
- the shifting pitch is not limited to 1/2, and may be 1/3 pitch or 1/4 pitch. Further, it may be shifted every line or every plural lines (for example, 2 lines). That is, how to shift the white light source 1 is not limited.
- the white light source 1 has the same configuration as described with reference to FIG. That is, the white light source 1 has a kneaded material 43 obtained by kneading a red phosphor and a green phosphor in a transparent resin on the blue light emitting diode 21.
- the red phosphor the red phosphor represented by the composition formula (1) described above is used.
- FIG. 6 is a flowchart showing a specific example of a method for manufacturing a red phosphor.
- europium oxide (Eu 2 O 3 ) was used as a Eu supply source.
- melamine was added as a flux at a predetermined ratio with respect to the total number of moles of europium oxide, strontium carbonate, silicon nitride, and aluminum nitride.
- step S21 In the raw material mixing step of step S21, a liquid phase method (wet method) was used, ethanol was used as a solvent, each raw material compound was stirred for 30 minutes, and suction filtered. The precipitate was dried at 80 ° C. for 8 hours, and then passed through # 110 mesh to obtain a precursor mixture.
- wet method wet method
- Step S22 a predetermined amount of the precursor mixture is weighed and filled into a boron nitride (BN) crucible, the H 2 gas concentration is set to 4%, the heat treatment temperature is set to 1400 ° C., and the firing is performed for 2 hours. Went.
- BN boron nitride
- the red phosphor represented by the composition formula (2) was obtained by the above two-stage firing at normal pressure.
- ICP Inductively Coupled Plasma
- strontium, europium, aluminum and silicon constituting the composition formula (2) contained in the raw material compound are almost in the same molar ratio (atom (Number ratio), it was confirmed to be contained in the red phosphor.
- the carbon content (z) of each red phosphor was analyzed using an ICP emission analyzer and combustion in oxygen stream-NDIR detection method (apparatus: EMIA-U511 (manufactured by Horiba)). (Z) was confirmed to be in the range of 0 ⁇ z ⁇ 1.
- step S32 a predetermined amount of the precursor mixture is weighed and filled into a boron nitride (BN) crucible, the H 2 gas concentration is set to 75%, the heat treatment temperature is set to 1400 ° C., and the firing is performed for 2 hours. Went.
- BN boron nitride
- 12 and 13 are graphs showing the peak intensity ratio (YAG standard) and internal quantum efficiency of each red phosphor produced by pressure firing or atmospheric pressure firing, respectively.
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Abstract
Description
1.赤色蛍光体の構成
2.従来における赤色蛍光体の製造方法
3.本発明の一実施形態における赤色蛍光体の製造方法
4.発光特性が良好な赤色蛍光体の構成
5.白色光源の構成例
6.照明装置の構成例
7.液晶表示装置の構成例
8.実施例
本発明の一実施の形態に係る赤色蛍光体は、元素A、ユーロピウム(Eu)、シリコン(Si)、アルミニウム(Al)及び炭素(C)を、下記組成式(1)の原子数比で含有する。
次に、赤色蛍光体の従来における製造方法について、図1に示すフローチャートを用いて説明する。
次に、本発明の一実施の形態に係る赤色蛍光体の製造方法を、図2に示すフローチャートを用いて説明する。本発明の一実施の形態に係る赤色蛍光体の製造方法では、賦活剤であるユーロピウムの供給源として、酸化ユーロピウム(Eu2O3)、酢酸ユーロピウム(Eu(CH3COO)3・nH2O)、炭酸ユーロピウム(Eu2(CO3)3)などの窒素非含有ユーロピウムを用いる。これにより、湿式法による混合が可能となり、混合物の組成ムラを防ぎ、生産性を向上させることができる。
本件発明者らは、前述したユーロピウム(Eu)、シリコン(Si)、アルミニウム(Al)、炭素(C)、酸素(O)、及び窒素(N)を含有する赤色蛍光体において、X線回折(XRD)スペクトルにおいて、特定の回折パターンを示すことにより、良好な発光強度が得られることを見出した。
次に、本発明の一実施の形態に係る白色光源を、図3に示す概略断面図を用いて説明する。
次に、本発明の一実施の形態に係る照明装置を、図4の概略平面図を用いて説明する。
さらに、1行ごとに、もしくは複数行(例えば2行)ごとにずらしてもよい。すなわち、白色光源1のずらし方は、限定されるものではない。
次に、本発明の一実施の形態に係る液晶表示装置を、図5の概略構成図を用いて説明する。
以下、実施例を挙げて、本発明を具体的に説明するが、本発明は、これらの実施例に限定されるものではない。
賦活剤であるユーロピウムの供給源として、酸化ユーロピウム(Eu2O3)、酢酸ユーロピウム(Eu(CH3COO)3・nH2O)、炭酸ユーロピウム(Eu2(CO3)3)、又は窒化ユーロピウム(EuN)を用いて、各赤色蛍光体を作製し、発光特性を評価した。
図6は、赤色蛍光体の製造方法の具体例を示すフローチャートである。この製造方法では、Euの供給源として、酸化ユーロピウム(Eu2O3)を用いた。また、フラックスとしてメラミンを、酸化ユーロピウム、炭酸ストロンチウム、窒化シリコン、及び窒化アルミニウムの全モル数の合計に対して所定割合で添加した。
Euの供給源として、酢酸ユーロピウム(Eu(CH3COO)3・nH2O)を用いた以外は、前述の酸化ユーロピウムを用いた赤色蛍光体の製造方法と同様に、図6に示すフローチャート(常圧2段階焼成)によって、組成式(2)で表される赤色蛍光体(m=3.79、x=0.0663、y=0.474)を得た。
図7は、赤色蛍光体の製造方法の具体例を示すフローチャートである。この製造方法では、Euの供給源として、炭酸ユーロピウム(Eu2(CO3)3)を用いた。また、フラックスとしてメラミンを、炭酸ユーロピウム、炭酸ストロンチウム、窒化シリコン、及び窒化アルミニウムの全モル数の合計に対して所定割合で添加した。
Euの供給源として、窒化ユーロピウム(EuN)を用いた場合、湿式混合が困難なため、図1に示す従来の製造方法で赤色蛍光体を製造した。
図8及び図9は、それぞれユーロピウムの供給源として、酸化ユーロピウム(Eu2O3)、酢酸ユーロピウム(Eu(CH3COO)3・nH2O)、炭酸ユーロピウム(Eu2(CO3)3)、又は窒化ユーロピウム(EuN)を用いて作製された各赤色蛍光体のピーク強度比(YAG基準)及び内部量子効率を示すグラフである。なお、赤色蛍光体のピーク強度比は、日本分光社製分光蛍光光度計FP-6500を用い、専用セルに蛍光体粉末を充填し、波長450nmの青色励起光を照射させて測定した。また、内部量子効率は、日本分光社製分光蛍光光度計FP-6500を用いて測定した。赤色蛍光体の内部量子効率は、蛍光スペクトルの結果から分光蛍光光度計付属の量子効率測定ソフトを用いて算出した。
次に、ユーロピウムの供給源として、酸化ユーロピウム(Eu2O3)を用い、湿式混合と乾式混合の比較を行った。湿式混合では、溶媒にエタノールを使用し、各原料化合物を30分間撹拌し、吸引ろ過し、沈殿物を80℃、8hの条件で乾燥後、#110メッシュに通して前駆体混合物を得た。また、乾式混合では、各原料化合物を乳鉢により粉砕混合し、混合物を得た。その後、図6に示すフローチャートと同様の常圧2段階焼成を行うことにより、組成式(2)で表される赤色蛍光体(m=3.79、x=0.0663、y=0.474)が得られた。
次に、ユーロピウムの供給源として、酸化ユーロピウム(Eu2O3)を用い、焼成時の加圧の有無の比較を行った。加圧焼成は、図7に示すフローチャートと同様の加圧2段階焼成により行った。すなわち、1次焼成工程では、H2ガス濃度を75%、熱処理温度を1400℃に設定し、2時間の焼成を行い、2次焼成工程では、0.85MPaの加圧条件の窒素(N2)雰囲気で熱処理温度を1750℃に設定し、2時間の焼成を行った。
これにより、組成式(2)で表される赤色蛍光体(m=3.79、x=0.0663、y=0.474)が得られた。
次に、ユーロピウムの供給源として、酸化ユーロピウム(Eu2O3)を用い、1次焼成時のH2ガス濃度の影響について評価した。1次焼成時のH2ガス濃度をそれぞれ4%、50%、75%とした以外は、図7に示すフローチャートと同様の加圧2段階焼成により、組成式(2)で表される赤色蛍光体(m=3.79、x=0.0663、y=0.474)が得られた。
次に、ユーロピウムの供給源として、酸化ユーロピウム(Eu2O3)を用い、焼成時の焼成回数について評価した。図6に示すフローチャートと同様の常圧2段階焼成、及び図7に示すフローチャートと同様の加圧2段階焼成により、それぞれ組成式(2)で表される赤色蛍光体(m=3.79、x=0.0663、y=0.474)が得られた。
次に、ユーロピウムの供給源として、酸化ユーロピウム(Eu2O3)を用い、2次焼成時における焼成温度の影響について評価した。図6に示すフローチャートと同様の常圧2段階焼成において、前駆体熱処理工程及び1次焼成工程のH2ガス濃度を75%とし、2次焼成工程の焼成温度を1500℃、1600℃、1700℃、1750℃、又は1800℃とすることにより、組成式(2)で表される赤色蛍光体(m=3.79、x=0.0663、y=0.474)が得られた。
次に、図20に示すフローチャートにより、他の組成の赤色蛍光体を作製した。この製造方法では、Euの供給源として、酸化ユーロピウム(Eu2O3)を用いた。また、フラックスとしてメラミンを、酸化ユーロピウム、炭酸ストロンチウム、炭酸カルシウム、窒化シリコン、及び窒化アルミニウムの全モル数の合計に対して所定割合で添加した。
また、本件発明者らは、前述したユーロピウム(Eu)、シリコン(Si)、炭素(C)、酸素(O)、及び窒素(N)を含有する赤色蛍光体において、X線回折(XRD)スペクトルにおいて、特定の回折パターンを示すことにより、良好な発光強度が得られることを見出した。
次に、本製法による赤色蛍光体と従来の製法による赤色蛍光体とを組成を同様にして比較した。実施例1の赤色蛍光体は、ユーロピウムの供給源として酸化ユーロピウム(Eu2O3)を用いて、図6に示すフローチャートと同様の湿式混合を用いた常圧2段階焼成を行って作製した。メラミン仕込量は29mol%とした。また、実施例2の赤色蛍光体は、ユーロピウムの供給源として酸化ユーロピウム(Eu2O3)を用いて、図15に示すフローチャートと同様の湿式混合を用いた常圧1段階焼成を行って作製した。メラミン仕込量は29mol%とした。
図42は、メラミン添加量を変化させたときの各赤色蛍光体の励起波長400nmの発光強度を1としたときにおける励起波長550nmの発光強度(以下、550nmPLE強度/400nmPLE強度と表記する)と外部量子効率の関係を示すグラフである。550nmPLE強度/400nmPLE強度は、各赤色蛍光体のPLEスペクトルにおいて、励起波長400nmの発光強度を1としたときにおける励起波長550nmの発光強度の相対値とした。また、各赤色蛍光体の外部量子効率は、日本分光社製分光蛍光光度計FP-6500を用いて測定した。専用セルに蛍光体粉末を充填し、波長450nmの青色励起光を照射させて、蛍光スペクトルを測定し、その結果を、分光蛍光光度計付属の量子効率測定ソフトを用いて、赤色の外部量子効率を算出した。
Claims (14)
- 元素A、ユーロピウム(Eu)、シリコン(Si)、アルミニウム(Al)及び炭素(C)が、下記組成式(1)の原子数比となるように、元素A含有化合物、窒素非含有ユーロピウム、シリコン含有化合物、アルミニウム含有化合物及び炭素含有還元剤を混合して混合物を生成し、
前記混合物の焼成と、当該焼成によって得られた焼成物の粉砕とを行う
赤色蛍光体の製造方法。
- 前記窒素非含有ユーロピウムは、酸化ユーロピウム、酢酸ユーロピウム、又は炭酸ユーロピウムの少なくとも1つであり、
元素Aの炭酸化合物、窒素非含有ユーロピウム、窒化シリコン、窒化アルミニウム及び炭素含有還元剤を混合して混合物を生成する請求項1記載の赤色蛍光体の製造方法。 - 前記混合物を湿式法により生成する請求項2記載の赤色蛍光体の製造方法。
- 前記炭素含有還元剤は、メラミンであり、
元素Aの炭酸化合物、窒素非含有ユーロピウム、窒化シリコン、及び窒化アルミニウムの全モル数に対して、前記メラミンを65%以下添加する請求項3記載の赤色蛍光体の製造方法。 - 前記焼成は、常圧で行われる請求項4記載の赤色蛍光体の製造方法。
- 前記焼成は、H2ガス濃度が4%以下の雰囲気で行われる請求項5記載の赤色蛍光体の製造方法。
- 前記焼成は、1400℃以上1800℃以下の温度範囲で行われる請求項6記載の赤色蛍光体の製造方法。
- 元素(A)、ユーロピウム(Eu)、シリコン(Si)、アルミニウム(Al)及び炭素(C)が、下記組成式(1)の原子数比となるように、元素(A)、窒素非含有ユーロピウム、シリコン含有化合物、アルミニウム含有化合物及び炭素含有還元剤を混合して混合物を生成し、
前記混合物の焼成と、該焼成によって得られた焼成物の粉砕とを行うことで得られ、
X線回折パターンにおいて、回折角が36°~36.6°の位置に存在するピークの強度が、回折角が35°~36°の位置に存在するピークの強度の0.65倍以上を示す赤色蛍光体。
- 前記組成式(1)中、z≦0.072を満たす請求項8記載の赤色蛍光体。
- PLE(Photoluminescence Excitation)スペクトルにおいて、励起波長400nmの発光強度を1としたときにおける励起波長550nmの発光強度の相対値が0.48以上である請求項8又は9に記載の赤色蛍光体。
- 前記組成式(1)中、0.05≦x≦0.15を満たす請求項8乃至10のいずれか1項に記載の赤色蛍光体。
- 素子基板上に形成された青色発光ダイオードと、
前記青色発光ダイオード上に配置されていて赤色蛍光体と緑色蛍光体もしくは黄色蛍光体とを透明樹脂に混練した混練物とを有し、
前記赤色蛍光体は、
元素(A)、ユーロピウム(Eu)、シリコン(Si)、アルミニウム(Al)及び炭素(C)が、下記組成式(1)の原子数比となるように、元素(A)、窒素非含有ユーロピウム、シリコン含有化合物、アルミニウム含有化合物及び炭素含有還元剤を混合して混合物を生成し、
前記混合物の焼成と、該焼成によって得られた焼成物の粉砕とを行うことで得られ、
X線回折パターンにおいて、回折角が36°~36.6°の位置に存在するピークの強度が、回折角が35°~36°の位置に存在するピークの強度の0.65倍以上を示す白色光源。
- 照明基板上に複数の白色光源が配置され、
前記白色光源は、
素子基板上に形成された青色発光ダイオードと、
前記青色発光ダイオード上に配置されていて赤色蛍光体と緑色蛍光体もしくは黄色蛍光体を透明樹脂に混練した混練物を有し、
前記赤色蛍光体は、
元素(A)、ユーロピウム(Eu)、シリコン(Si)、アルミニウム(Al)及び炭素(C)が、下記組成式(1)の原子数比となるように、元素(A)、窒素非含有ユーロピウム、シリコン含有化合物、アルミニウム含有化合物及び炭素含有還元剤を混合して混合物を生成し、
前記混合物の焼成と、該焼成によって得られた焼成物の粉砕とを行うことで得られ、
X線回折パターンにおいて、回折角が36°~36.6°の位置に存在するピークの強度が、回折角が35°~36°の位置に存在するピークの強度の0.65倍以上を示す照明装置。
- 液晶表示パネルと、
前記液晶表示パネルを照明する複数の白色光源を用いたバックライトとを有し、
前記白色光源は、
素子基板上に形成された青色発光ダイオードと、
前記青色発光ダイオード上に配置されていて赤色蛍光体と緑色蛍光体もしくは黄色蛍光体を透明樹脂に混練した混練物を有し、
前記赤色蛍光体は、
元素(A)、ユーロピウム(Eu)、シリコン(Si)、アルミニウム(Al)及び炭素(C)が、下記組成式(1)の原子数比となるように、元素(A)、窒素非含有ユーロピウム、シリコン含有化合物、アルミニウム含有化合物及び炭素含有還元剤を混合して混合物を生成し、
前記混合物の焼成と、該焼成によって得られた焼成物の粉砕とを行うことで得られ、
X線回折パターンにおいて、回折角が36°~36.6°の位置に存在するピークの強度が、回折角が35°~36°の位置に存在するピークの強度の0.65倍以上を示す液晶表示装置。
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