WO2012157604A1 - 赤色蛍光体の製造方法 - Google Patents

赤色蛍光体の製造方法 Download PDF

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Publication number
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
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PCT/JP2012/062291
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English (en)
French (fr)
Japanese (ja)
Inventor
正輝 菅野
孝昌 伊澤
楠木　常夫
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Dexerials Corp
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Sony Chemical and Information Device Corp
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Priority to CN201280023261.4A priority Critical patent/CN103534334B/zh
Priority to EP12785348.9A priority patent/EP2711409B1/en
Priority to US14/110,853 priority patent/US9318658B2/en
Priority to KR1020137032738A priority patent/KR101985555B1/ko
Publication of WO2012157604A1 publication Critical patent/WO2012157604A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/81—Bodies
    • H10H20/822—Materials of the light-emitting regions
    • 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
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    • 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
    • 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
    • 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
    • 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
    • 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
    • H01L2924/12—Passive devices, e.g. 2 terminal devices
    • H01L2924/1204—Optical Diode
    • H01L2924/12041—LED
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/85—Packages
    • H10H20/851—Wavelength conversion means
    • H10H20/8511—Wavelength conversion means characterised by their material, e.g. binder
    • H10H20/8512—Wavelength conversion materials
    • H10H20/8513—Wavelength conversion materials having two or more wavelength conversion materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

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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WO2015029305A1 (ja) * 2013-09-02 2015-03-05 パナソニックＩｐマネジメント株式会社 蛍光体
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US10600604B2 (en) * 2017-06-23 2020-03-24 Current Lighting Solutions, Llc Phosphor compositions and lighting apparatus thereof
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KR20140039223A (ko) 2014-04-01
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US9318658B2 (en) 2016-04-19
CN106987249A (zh) 2017-07-28
US20140036201A1 (en) 2014-02-06
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KR101985555B1 (ko) 2019-06-03
TWI671383B (zh) 2019-09-11
EP2711409B1 (en) 2016-10-12

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