WO2013001685A1 - Composite phosphor and light-emitting device - Google Patents

Composite phosphor and light-emitting device Download PDF

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Publication number
WO2013001685A1
WO2013001685A1 PCT/JP2012/001674 JP2012001674W WO2013001685A1 WO 2013001685 A1 WO2013001685 A1 WO 2013001685A1 JP 2012001674 W JP2012001674 W JP 2012001674W WO 2013001685 A1 WO2013001685 A1 WO 2013001685A1
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phosphor
phosphor particles
composite
particles
light emitting
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PCT/JP2012/001674
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French (fr)
Japanese (ja)
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山中　一彦
瀧川　信一
琢磨 片山
真治 吉田
中西　秀行
田中　毅
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パナソニック株式会社
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    • 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
    • C09K11/7736—Vanadates; Chromates; Molybdates; Tungstates
    • 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
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7774—Aluminates
    • 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
    • C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
    • C09K11/562—Chalcogenides
    • C09K11/565—Chalcogenides with zinc cadmium
    • 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
    • C09K11/57—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing manganese or rhenium
    • C09K11/572—Chalcogenides
    • C09K11/574—Chalcogenides with zinc or cadmium
    • 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
    • H01L2224/01—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
    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
    • 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
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/85—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a wire connector
    • H01L2224/85909—Post-treatment of the connector or wire bonding area
    • H01L2224/8592—Applying permanent coating, e.g. protective coating
    • 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 with at least one potential-jump barrier or surface barrier 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 with at least one potential-jump barrier or surface barrier 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

Definitions

  • the present invention relates to a phosphor used in a light emitting device that emits white light in combination with a semiconductor light emitting element, and more particularly to a composite phosphor and a light emitting device for emitting light with high color rendering and color reproducibility. is there.
  • the light emitted from the light emitting device is pseudo white light which is a combination of blue light and yellow light, and has a problem of poor color rendering.
  • FIG. 10 is a diagram illustrating a configuration of a conventional light emitting device.
  • the first phosphor is an yttrium-aluminum-garnet-based phosphor particle
  • the second phosphor is a phosphor particle made of CaAlSiN 3 crystal to which europium (Eu) is added.
  • a light-emitting device 1001 shown in FIG. 10 is a shell-type white light-emitting diode lamp, and has two lead wires 1002 and 1003. Specifically, the light emitting device 1001 includes two lead wires 1002 and 1003, a blue semiconductor light emitting element 1004, a thin gold wire 1005, a first resin 1006, a phosphor mixture 1007, and a second resin 1008. It consists of and.
  • the lead wire 1002 has a recess, and the blue semiconductor light emitting element 1004 is placed in the recess.
  • the lower electrode and the bottom surface of the recess of the lead wire 1002 are electrically connected by a conductive paste, and the upper electrode and the lead wire 1003 are electrically connected by a gold wire 1005. Yes.
  • the phosphor mixture 1007 is a mixture of the first phosphor and the second phosphor, and is dispersed in the first resin 1006 and mounted in the vicinity of the blue semiconductor light emitting element 1004.
  • the first resin 1006 is transparent and covers the entire blue semiconductor light emitting element 1004.
  • the second resin 1008 is transparent and seals the lead resin 1006 including the lead wire 1003 and the tip of the lead wire 1002 including the recess, the blue semiconductor light emitting element 1004 and the phosphor mixture 1007.
  • the second resin 1008 is formed in a substantially cylindrical shape as a whole, and the tip portion thereof is a lens-shaped curved surface.
  • This second resin 1008 is commonly referred to as a shell type because of this shape.
  • the first phosphor and the second phosphor are mixed at a predetermined mixing ratio, and the mixed powder is mixed with the epoxy resin at a predetermined weight% concentration, and this is dispensed using a dispenser. By dropping an appropriate amount, the first resin 1006 containing the phosphor mixture 1007 dispersed therein is formed.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composite phosphor and a light-emitting device in which distribution does not occur in the concentration of the plurality of phosphors in the phosphor-containing resin even if time elapses.
  • a composite phosphor according to an embodiment of the present invention is a composite phosphor composed of at least two kinds of phosphor particles having different particle diameters, and the first phosphor particles are And having a plurality of second phosphor particles in close contact with the surface, wherein the first phosphor particles are larger than the second phosphor particles.
  • the particle diameter of the first phosphor particles is 100 times or more than the particle diameter of the second phosphor particles.
  • the surface area of the first phosphor particles can be sufficiently increased with respect to the second phosphor particles having characteristics different from those of the first phosphor particles. Thereby, in this composite fluorescent substance, it becomes easy to adjust the quantity of the 2nd fluorescent substance particle with respect to the 1st fluorescent substance particle.
  • the particle diameter of the first phosphor particles is 1 ⁇ m to 100 ⁇ m.
  • the second phosphor particles are composed of quantum dot phosphors.
  • the phosphor particles are configured as nano-sized quantum dot phosphors, the phosphor particles can be made sufficiently small compared to the first phosphor particles. Thereby, a composite phosphor can be easily configured.
  • the center wavelength of the fluorescence spectrum of the first phosphor particles is shorter than the center wavelength of the fluorescence spectrum of the second phosphor particles.
  • the light absorbed by the first phosphor particles generates excitons inside the first phosphor particles, and in the recombination process, the light is non-radiatively recombined at the surface level. Luminous efficiency can be improved by recombining the light emission with the second phosphor particles.
  • the first phosphor particles are composed of a rare earth element activated phosphor.
  • the first phosphor particles are (Y, Gd) 3 Al 4 O 12 : Ce, Y 3 (Al, Ga) 4 O 12 : Ce, Tb 3 Al 5 O 12 : Ce, (Sr, Ca, Ba) 2 SiO 4 : Eu, Ca- ⁇ -sialon: Eu, (Ba, Sr) 2 SiO 4 : Eu, Ca 3 Sc 2 Si 3 O 12: Ce, CaSc 2 O 4 : Ce, ⁇ -sialon: Eu, (Sr, Ba) Si 2 O 2 N 2 : Eu, Ba 3 Si 6 O 12 N 2 : Eu, CaAlSiN 3 : Eu, (Ca, Sr) 2 Si 5 N 8 : Eu, CaAlSiN 3 : Eu, (Sr, Ca) S: Eu, Ba 3 Si 6 O 12 N 2: Eu, BaMgAl10O17: (Eu, Mn), SrAl 2 O 4: Eu, (Sr, Ca, Ba, Mg) 10 (PO 4) 6 Cl
  • the first fluorescent particles can be easily configured.
  • the second phosphor particle is a quantum dot phosphor
  • the quantum dot phosphor is a non-doped quantum dot phosphor or a doped quantum dot phosphor. Consists of.
  • the second phosphor particles can be easily made smaller than the first phosphor particles.
  • the material constituting the non-doped quantum dots is a group III-V compound semiconductor InN, InP, InAs, InSb, GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb and BN, II- It may be configured to be selected from the group consisting of HgS, HgSe, HgTe, CdS, CdSe, CdTe, ZnS, ZnSe and ZnTe, which are group VI compound semiconductors, and mixed crystal thereof.
  • the second phosphor particles can be easily made smaller than the first phosphor particles.
  • the material constituting the doped quantum dot phosphor is composed of ZnS: Mn 2+ , CdS: Mn 2+, and YVO 4: Eu 3+ .
  • the second phosphor particles can be easily made smaller than the first phosphor particles.
  • a light emitting device includes at least the composite phosphor of any of the above aspects and a semiconductor light emitting element.
  • the present invention it is possible to realize a composite phosphor and a light emitting device in which distribution does not occur in the concentration of a plurality of phosphors in the phosphor-containing resin even if time passes.
  • the concentration ratio hardly changes with time even when time passes, and a light emitting device having high color rendering properties and color reproducibility can be stably provided.
  • FIG. 1 is a diagram showing the configuration of the composite phosphor according to Embodiment 1 of the present invention.
  • FIG. 2 is a diagram showing a configuration of a light emitting device using the composite phosphor according to Embodiment 1 of the present invention.
  • FIG. 3A is a diagram showing a design example of the composite phosphor according to Embodiment 1 of the present invention.
  • FIG. 3B is a diagram showing a design example of the composite phosphor according to Embodiment 1 of the present invention.
  • FIG. 4A is a diagram showing an example of designing a spectrum of a light emitting device in which the composite phosphor according to Embodiment 1 of the present invention and a semiconductor light emitting element are combined.
  • FIG. 4A is a diagram showing an example of designing a spectrum of a light emitting device in which the composite phosphor according to Embodiment 1 of the present invention and a semiconductor light emitting element are combined.
  • FIG. 4B is a diagram showing an example of designing a spectrum of a light emitting device in which the composite phosphor according to Embodiment 1 of the present invention and a semiconductor light emitting element are combined.
  • FIG. 4C is a diagram showing an example of designing chromaticity coordinates of a light emitting device in which the composite phosphor according to Embodiment 1 of the present invention and a semiconductor light emitting element are combined.
  • FIG. 5A is a diagram for explaining the method for manufacturing the composite phosphor according to Embodiment 1 of the present invention.
  • FIG. 5B is a diagram for explaining the method for manufacturing the composite phosphor according to Embodiment 1 of the present invention.
  • FIG. 5A is a diagram for explaining the method for manufacturing the composite phosphor according to Embodiment 1 of the present invention.
  • FIG. 5B is a diagram for explaining the method for manufacturing the composite phosphor according to Embodiment 1 of the present invention.
  • FIG. 5C is a diagram for explaining the method for manufacturing the composite phosphor according to Embodiment 1 of the present invention.
  • FIG. 6A is a diagram for explaining the effect of the composite phosphor according to Embodiment 1 of the present invention.
  • FIG. 6B is a diagram for explaining the effect of the composite phosphor according to Embodiment 1 of the present invention.
  • FIG. 7A is a diagram for explaining the effect of the composite phosphor according to Embodiment 1 of the present invention.
  • FIG. 7B is a diagram for explaining the effect of the composite phosphor according to Embodiment 1 of the present invention.
  • FIG. 8 is a diagram showing a configuration of the composite phosphor according to Embodiment 2 of the present invention.
  • FIG. 9 is a diagram showing a configuration of a modification of the composite phosphor according to Embodiment 2 of the present invention.
  • FIG. 10 is a diagram illustrating a configuration of a conventional light emitting device.
  • FIG. 1 is a diagram showing a configuration of a composite phosphor according to Embodiment 1 of the present invention.
  • the composite phosphor 1 includes a first phosphor particle 2 and a second phosphor particle 3.
  • second phosphor particles 3 having a diameter of, for example, 1 nm to 100 nm are attached so as to cover with a predetermined density.
  • the first phosphor particles 2 are dispersed in a base material 2a composed of a material such as yttrium / aluminum / garnet (YAG) in a fluorescence generating portion 2b composed of an activator such as cerium (Ce). Ce-doped YAG phosphor (Ce-activated YAG phosphor).
  • the second phosphor particles 3 are, for example, non-doped quantum dot phosphors, particularly quantum dot phosphors having a core / shell structure.
  • the core material is a compound semiconductor such as InP
  • the shell material is a compound semiconductor such as ZnS.
  • the first phosphor particles 2 generate fluorescence due to the transition between excitation levels of electrons in the activator, and the second phosphor particles 3 are excited in the core material quantized by the size of 100 nm or less. Fluorescence is generated by recombination of the generated electron-hole pairs.
  • the composite phosphor of the present embodiment is configured by combining phosphors having different fluorescence generation principles in different sizes.
  • the material of the first phosphor particles As the material of the first phosphor particles 2, other rare earth element activation such as Eu activated ⁇ sialon crystal, Ce activated CaSc 2 O 4 and Eu activated strontium barium silicate ((Sr, Ba) 2 SiO 4 ) is used. A phosphor may be used. Further, as the material of the second phosphor particles 3, other compound semiconductor materials such as CdSe, CdS, ZnO, ZnSe, AlAs, AlP, AlN, GaAs, GaP, and GaN may be used.
  • the first phosphor particles 2 contain rare earth elements at a predetermined density, and these function as the fluorescence generating part 2b.
  • FIG. 2 is a diagram showing a configuration of a light emitting device using the composite phosphor according to Embodiment 1 of the present invention.
  • a light emitting device 50 shown in FIG. 2 includes a package 10, a semiconductor light emitting element 11, a resin 13, and a composite phosphor 1.
  • the package 10 is configured by, for example, ceramic having predetermined wiring or molding a resin on a metal frame.
  • the semiconductor light emitting element 11 is made of, for example, a nitride semiconductor (Al, In, Ga) N on a sapphire substrate (not shown), mounted on the package 10, and wired with a gold wiring or a bump electrode (not shown).
  • Resin 13 is made of, for example, a silicone resin or an epoxy resin, and the composite phosphor 1 is mixed therein.
  • the resin 13 is applied so as to cover the upper part of the semiconductor light emitting element 11.
  • FIG. 3A is a diagram showing an example of the design of the first phosphor particles 2 and the second phosphor particles 3 in the composite phosphor 1. More specifically, in FIG. 3A, 1) the density of the fluorescence generating portion per unit volume in the first phosphor particle 2 and 2) the second per unit area on the surface of the first phosphor particle 2 are shown. An example of values when the density of the phosphor particles 3 and 3) the light emitting portion of the first phosphor particles 2 and the light emission recombination rate ratio of the second phosphor particles 3 are used as parameters is shown. In the calculation using the above design example, the size of the second phosphor particles 3 is 1 nm to 100 nm, which is negligibly small compared to the size of the first phosphor particles 2. .
  • FIG. 3B is a diagram showing an example of the relationship between the diameter of the first phosphor particle 2 and the light emitting portion of the second phosphor particle 3 and the first phosphor particle 2 in the composite phosphor 1. More specifically, FIG. 3B shows the particle diameter of the first phosphor particles 2 in FIG. 3A and the amount of the second phosphor particles 3 in the composite phosphor 1 / the light emission of the first phosphor particles 2. An example of the relationship with the ratio of parts is shown.
  • the surface area / volume ratio of the phosphor particles decreases as the particle diameter of the first phosphor particles 2 increases, the amount of the second phosphor particles 3 / the first The ratio of the light emission part amount of the phosphor particles 2 becomes small. Further, the light emission part of the first phosphor particle 2 and the second phosphor particle 3 have different fluorescence lifetimes.
  • the combination in FIG. 3B for example, if there is a difference of 1000 times in the fluorescence lifetime between the light emitting part of the first phosphor particle 2 and the second phosphor particle 3 (for example, in the case of the combination 2 in FIG. 3A), the combination in FIG. 3B.
  • FIG. 3B As shown in FIG.
  • the ratio of the amount of the second phosphor particles 3 / the amount of the light emitting part of the first phosphor particles 2 is 1. / 10 times to 10 times can be adjusted.
  • FIGS. 4A to 4C are diagrams showing an example of designing a spectrum of a light emitting device in which a composite phosphor and a semiconductor light emitting element are combined.
  • FIG. 4A shows an example of a combination of ratios of the first phosphor particles 2 and the second phosphor particles 3 of the composite phosphor.
  • FIG. 4B shows a calculated spectrum of the light emitting device 50 based on the design of FIG. 4A.
  • FIG. 4C shows an example of chromaticity coordinates obtained from the spectrum of FIG. 4B.
  • FIG. 4A shows an example in which the first phosphor particles 2 are Ce-activated YAG phosphors, and the second phosphor particles 3 are non-doped quantum dot phosphors having an InP / ZnS core-shell structure. .
  • the second phosphor particles 3 are designed to have a peak wavelength of 600 nm and a half width of 50 nm.
  • the spectrum can be freely changed as shown in FIG. 4B. be able to.
  • the chromaticity coordinates calculated based on the spectrum of FIG. 4B are shown in FIG. 4C.
  • the chromaticity coordinates and the color temperature can be freely changed by changing the excitation light absorption amount ratio (total number of second phosphor particles 3 / total number of first phosphor particles 2). Can do.
  • the second phosphor particles 3 are, for example, quantum dot phosphors, and there are various methods for producing quantum dot phosphors, such as a sol-gel method (complex polymerization method), a reverse micelle method, and a colloid deposition method.
  • FIG. 5A is a diagram schematically showing a method for producing a quantum dot phosphor.
  • a container 60 that is a flask is held in a vacuum, and for example, trioctylphosphine oxide (TOPO) is placed in the container 60. Keep at 300 ° C with heater. Subsequently, a mixed solution of trisdimethylaminophosphine [P (NMe2) 3], indium chloride (InCl3), trioctylphosphine (TOP), and TOPO is injected. After that, the InP nanoparticles are formed by adjusting to a predetermined temperature and keeping it for a predetermined time.
  • TOPO trioctylphosphine oxide
  • the mixed solution is combined with a centrifuge and replaced with TOPO, thereby generating a colloidal solution in which InP nanoparticles are mixed with TOPO.
  • a mixed solution of zinc diethyldithiocarbamate ([(C2H5) 2NCS2] 2Zn) and TOP / TOPO into this solution, second phosphor particles that are InP / ZnS core-shell quantum dot phosphors A colloidal solution in which 3 is dispersed is produced.
  • the colloidal solution 61 in which the second phosphor particles 3 are dispersed in TOPO is produced by replacing the colloidal solution with TOPO again using a centrifuge.
  • the first phosphor particles 2 such as Ce-activated YAG phosphor particles having a hydrophobic group added to the surface are dropped into the colloid solution 61 and stirred.
  • a predetermined amount of the second phosphor particle 3 is adsorbed on the surface of the first phosphor particle 2, but the second phosphor particle 3 of a predetermined amount or more is the second phosphor particle 3. They are not attracted by the repulsive force 65 between them.
  • the composite phosphor 1 which is the first phosphor particle 2 having a predetermined amount of the second phosphor particles 3 attached to the surface and the unnecessary second phosphor particles 3.
  • a mixed liquid 62 is generated.
  • a solution having a high concentration of the composite phosphor 1 is extracted from the solution in which the composite phosphor 1 and the second phosphor particles 3 are mixed, and a solvent free of impurities is added thereto.
  • the second mixed solution 63 in which the high-purity composite phosphor 1 is dispersed in a solution of, for example, TOPO can be produced.
  • a composite phosphor-containing resin (resin 13) in which the composite phosphor 1 is contained in the resin. ) Can be manufactured.
  • 6A and 6B are diagrams for explaining the effect of the composite phosphor according to Embodiment 1 of the present invention.
  • FIG. 6A schematically shows an example of a mounting method of the resin 66 in which the first phosphor particles 2 and the second phosphor particles 3 are simply mixed
  • FIG. 6B shows the present invention.
  • An example of a mounting method of the resin 13 mixed with the composite phosphor 1 is schematically shown.
  • the semiconductor light emitting element 11 which is a light emitting diode made of a nitride semiconductor having an InGaN light emitting layer, for example, has a concave portion of the package 10 in which a concave shape is formed on the uppermost surface.
  • a step of forming the light emitting device 50 by dropping the phosphor-containing resin onto the one mounted on the bottom surface is shown.
  • the phosphor-containing resin is placed in, for example, the syringe 20 and dropped from the upper part of the semiconductor light emitting element 11.
  • the syringe 20 contains a resin 66 (phosphor-containing resin) in which a plurality of phosphor particles are mixed in order to improve color rendering.
  • a resin 66 phosphor-containing resin
  • first phosphor particles 2 and second phosphor particles 3 having greatly different particle diameters are mixed.
  • the concentration ratio between the first phosphor particles 2 and the second phosphor particles 3 is shifted between the syringe upper portion 20a and the syringe lower portion 20b as time passes. This suggests that the variation cannot be reduced only by adjusting the amount of the phosphor-containing resin dropped into the package 10.
  • the concentration of the composite phosphor 1 is distributed over time.
  • the ratio between the first phosphor particles 2 and the second phosphor particles 3 constituting the composite phosphor 1 does not change. This suggests that variations in the chromaticity coordinates of the light emitting device 50 can be reduced by adjusting the amount of the phosphor-containing resin dropped.
  • FIG. 7A and 7B are diagrams for explaining the effect of the composite phosphor according to Embodiment 1 of the present invention. More specifically, FIG. 7A is an enlarged view of the first phosphor particles 2, and in the case where only the first phosphor particles 2 are included, excitation absorbed by the first phosphor particles 2 The process by which light is extracted as fluorescence is schematically shown. FIG. 7B is an enlarged view of the composite phosphor 1 and schematically shows a process in which excitation light absorbed by the composite phosphor 1 is extracted as fluorescence.
  • the non-radiative recombination via the surface defect 2c is more effective.
  • the emission recombination of the second phosphor particles 3 is prioritized and emitted as fluorescence 77. Thereby, the loss by the surface defect 2c can be reduced.
  • the semiconductor light emitting element 11 is a light emitting diode, but a light emitting element such as a semiconductor laser or super luminescent may be used.
  • the present invention is not limited thereto.
  • the second phosphor particle 3 is a non-doped quantum dot, and a part of the constituent material has been described.
  • the present invention is not limited to this.
  • group III-V compound semiconductors such as InN, InP, InAs, InSb, GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb and BN, and II-VI group compound semiconductors. It can be selected from the group consisting of HgS, HgSe, HgTe, CdS, CdSe, CdTe, ZnS, ZnSe and ZnTe, and mixed crystal crystals thereof.
  • the second phosphor particles 3 need not be non-doped quantum dot phosphors.
  • doped quantum dot phosphors such as ZnS: Mn 2+ , CdS: Mn 2+ and YVO 4: Eu 3+ may be used. it can.
  • the rare earth element serving as the light emitting portion is influenced by quantization due to the quantum dot structure, and can realize a fluorescence lifetime different from that of the light emitting portion of the rare earth activated phosphor, and thus the composite phosphor of the present invention can be realized.
  • both the first phosphor particles 2 and the second phosphor particles 3 can be composed of rare earth activated phosphors.
  • Ce 3+ that makes 4f-5d transition with a trivalent ion as an activator of one phosphor
  • Eu 2+ or Yb 2+ that makes a 4f-5d transition with a divalent ion as an activator of the other phosphor.
  • a combination of phosphors having different fluorescence lifetimes can be realized.
  • an activator of different phosphors it is possible to comprise any one of Eu 3+ , Pr 3+ , Nd 3+ and Sm 3+ that perform 4f-4f transition.
  • FIG. 8 is a diagram showing a configuration of the composite phosphor according to the second embodiment of the present invention. Elements similar to those in FIG. 1 are denoted by the same reference numerals, and detailed description thereof is omitted.
  • the composite phosphor 100 shown in FIG. 8 includes the first phosphor particles 2, the second phosphor particles 3, and the cover layer 9. More specifically, the composite phosphor 100 includes the base material 2a of the first phosphor particles 2 having a plurality of fluorescence generating portions 2b, and the surface of the composite phosphor 1 (base material 2a) Second phosphor particles 3 are arranged.
  • the cover layer 9 is made of a material having a high gas barrier property.
  • the cover layer 9 can be coated with the first phosphor particles 2 and the second phosphor particles 3 so that the quantum dot phosphors can be used even if, for example, the quantum dot phosphors are used for the second phosphor particles 3. There is an effect that there is little deterioration.
  • the cover layer 9 is coated on the surface of the first phosphor particles 2 having the second phosphor particles 3 by, for example, a sol-gel method. Specifically, a silicon alkoxide is first added to an organic solvent containing the composite phosphor 1, and then the silicon alkoxide is partially hydrolyzed to obtain a solution in which the surface of the composite phosphor 1 is coated with a hydrolyzate. Make it. Subsequently, the surface of the composite phosphor 1 is covered with silicon alkoxide by mixing with an aqueous solution containing partially hydrolyzed silicon alkoxide and the above solution.
  • a sol-gel method Specifically, a silicon alkoxide is first added to an organic solvent containing the composite phosphor 1, and then the silicon alkoxide is partially hydrolyzed to obtain a solution in which the surface of the composite phosphor 1 is coated with a hydrolyzate. Make it. Subsequently, the surface of the composite phosphor 1 is covered with silicon alkoxide by
  • the composite phosphor 100 produced in this way can be taken out by centrifugation and purification or dispersed in a resin.
  • FIG. 9 is a diagram showing a configuration of a modification of the composite phosphor according to Embodiment 2 of the present invention. Elements similar to those in FIG. 1 are denoted by the same reference numerals, and detailed description thereof is omitted.
  • the composite phosphor 101 in this modification is different from the second embodiment in that the shape of the first phosphor particles 2 is indefinite.
  • the amount of the second phosphor particles 3 can be adjusted by using an effective surface. Further, the surface can be easily covered with a film having a high gas barrier property by a sol-gel method or the like.
  • the present invention it is possible to realize a composite phosphor and a light-emitting device in which distribution does not occur in the concentration of a plurality of phosphors in the phosphor-containing resin even if time passes.
  • the concentration ratio hardly changes with time even when time passes, and a light emitting device having high color rendering properties and color reproducibility can be stably provided.
  • the present invention can realize a phosphor having a stable color rendering property even in a resin, for example, not only home lighting equipment but also display lighting equipment for displaying foodstuffs, or a clear display image. It is useful as a backlight light source for large-screen LCD TVs that require high performance.

Abstract

This composite phosphor (1) is configured from two or more types of phosphor particles with at least different diameters, wherein multiple second phosphor particles (3) adhere on the surface of first phosphor particles (2), and the first phosphor particles (2) are larger than the second phosphor particles (3). By mixing these composite phosphors (1) in a resin (13), the ratio of the first phosphor particles (2) and the second phosphor particles (3) does not change even over time, thus effecting that the chromaticity coordinates of the light emitting device when mounted are not prone to shift.

Description

複合蛍光体および発光装置Composite phosphor and light emitting device
　本発明は、半導体発光素子と組み合わせて白色の光を出射する発光装置に用いられる蛍光体に関し、特に、演色性、色再現性の高い光を放射するための複合蛍光体および発光装置に関するものである。 The present invention relates to a phosphor used in a light emitting device that emits white light in combination with a semiconductor light emitting element, and more particularly to a composite phosphor and a light emitting device for emitting light with high color rendering and color reproducibility. is there.
　青色半導体発光素子と黄色蛍光を放射する黄色蛍光体とを組み合わせた白色発光ダイオードなどの発光装置がある。近年、急速に既存の白熱電球や蛍光灯からこの発光装置に置き換えられている。 There are light emitting devices such as white light emitting diodes that combine a blue semiconductor light emitting element and a yellow phosphor that emits yellow fluorescence. In recent years, the existing incandescent bulbs and fluorescent lamps have been rapidly replaced by this light emitting device.
　しかし、この発光装置から出射される光は、青色光と黄色光との組み合わせである擬似白色光であり、演色性が悪いという課題を有する。 However, the light emitted from the light emitting device is pseudo white light which is a combination of blue light and yellow light, and has a problem of poor color rendering.
　この課題を解決するため、青色光を発光する青色半導体発光素子と黄色光を発する第１の蛍光体の他に、赤色の光を発する第２の蛍光体を第１の蛍光体とを混ぜて青色半導体発光素子上に塗布する発光装置が提案されている（例えば、特許文献１）。 In order to solve this problem, in addition to a blue semiconductor light emitting element that emits blue light and a first phosphor that emits yellow light, a second phosphor that emits red light is mixed with the first phosphor. There has been proposed a light emitting device for coating on a blue semiconductor light emitting element (for example, Patent Document 1).
　以下、特許文献１（従来）の発光装置について説明する。図１０は、従来技術の発光装置の構成を示す図である。 Hereinafter, the light emitting device of Patent Document 1 (conventional) will be described. FIG. 10 is a diagram illustrating a configuration of a conventional light emitting device.
　ここでは、第１の蛍光体は、イットリウム・アルミニウム・ガーネット系の蛍光体粒子であり、第２の蛍光体はユーロピウム（Ｅｕ）が添加されたＣａＡｌＳｉＮ３結晶からなる蛍光体粒子である。 Here, the first phosphor is an yttrium-aluminum-garnet-based phosphor particle, and the second phosphor is a phosphor particle made of CaAlSiN 3 crystal to which europium (Eu) is added.
　図１０に示す発光装置１００１は、砲弾型白色発光ダイオードランプであり、２本のリードワイヤ１００２および１００３を有している。具体的には、発光装置１００１は、２本のリードワイヤ１００２および１００３と、青色半導体発光素子１００４と、金細線１００５と、第１の樹脂１００６と、蛍光体混合物１００７と、第２の樹脂１００８とで構成されている。 A light-emitting device 1001 shown in FIG. 10 is a shell-type white light-emitting diode lamp, and has two lead wires 1002 and 1003. Specifically, the light emitting device 1001 includes two lead wires 1002 and 1003, a blue semiconductor light emitting element 1004, a thin gold wire 1005, a first resin 1006, a phosphor mixture 1007, and a second resin 1008. It consists of and.
　リードワイヤ１００２は、凹部が形成されており、凹部に青色半導体発光素子１００４が載置されている。 The lead wire 1002 has a recess, and the blue semiconductor light emitting element 1004 is placed in the recess.
　青色半導体発光素子１００４は、その下部電極とリードワイヤ１００２の凹部の底面とが導電性ペーストによって電気的に接続されており、上部電極とリードワイヤ１００３とが金細線１００５によって電気的に接続されている。 In the blue semiconductor light emitting device 1004, the lower electrode and the bottom surface of the recess of the lead wire 1002 are electrically connected by a conductive paste, and the upper electrode and the lead wire 1003 are electrically connected by a gold wire 1005. Yes.
　蛍光体混合物１００７は第１の蛍光体と第２の蛍光体とを混合したものであり、第１の樹脂１００６に分散されて、青色半導体発光素子１００４近傍に実装されている。 The phosphor mixture 1007 is a mixture of the first phosphor and the second phosphor, and is dispersed in the first resin 1006 and mounted in the vicinity of the blue semiconductor light emitting element 1004.
　第１の樹脂１００６は、透明であり、青色半導体発光素子１００４の全体を被覆している。 The first resin 1006 is transparent and covers the entire blue semiconductor light emitting element 1004.
　第２の樹脂１００８は、透明であり、リードワイヤ１００３および凹部を含むリードワイヤ１００２の先端部、青色半導体発光素子１００４および蛍光体混合物１００７を含む第１の樹脂１００６を、封止している。言い換えると、第２の樹脂１００８は、全体が略円柱形状で形成されており、その先端部がレンズ形状の曲面となっている。この第２の樹脂１００８は、この形状から砲弾型と通称されている。 The second resin 1008 is transparent and seals the lead resin 1006 including the lead wire 1003 and the tip of the lead wire 1002 including the recess, the blue semiconductor light emitting element 1004 and the phosphor mixture 1007. In other words, the second resin 1008 is formed in a substantially cylindrical shape as a whole, and the tip portion thereof is a lens-shaped curved surface. This second resin 1008 is commonly referred to as a shell type because of this shape.
　上記従来例の場合では、第１の蛍光体と第２の蛍光体とを所定の混合割合で混ぜ、その混合粉末を所定の重量％の濃度でエポキシ樹脂に混ぜ、これを、ディスペンサを用いて適量滴下することで、蛍光体混合物１００７が分散されて含まれる第１の樹脂１００６を形成している。 In the case of the above conventional example, the first phosphor and the second phosphor are mixed at a predetermined mixing ratio, and the mixed powder is mixed with the epoxy resin at a predetermined weight% concentration, and this is dispensed using a dispenser. By dropping an appropriate amount, the first resin 1006 containing the phosphor mixture 1007 dispersed therein is formed.
特開２００５－２３５９３４号公報JP 2005-235934 A
　しかしながら、上記従来例の場合のようにディスペンサを用いて複数の蛍光体粒子を樹脂に混合して半導体発光素子上に滴下したものを用いて実装する方法では、時間とともに蛍光体含有樹脂中の蛍光体の濃度に分布が生じるという課題が生じる。 However, as in the case of the above-described conventional example, in the method of mounting using a dispenser mixed with a plurality of phosphor particles and dropped on a semiconductor light emitting element, the fluorescence in the phosphor-containing resin with time There arises a problem that distribution occurs in the concentration of the body.
　具体的には、重量もしくは／および比重の異なる２種類以上の蛍光体粒子を混合した樹脂においては、時間とともに、比重の重い方の蛍光体粒子が沈下していくため、樹脂中の濃度比がディスペンサ内で変化してしまうという課題を生じる。 Specifically, in a resin in which two or more types of phosphor particles having different weights and / or specific gravities are mixed, the phosphor particles having a heavier specific gravity sink with time, so the concentration ratio in the resin The problem of changing within the dispenser arises.
　その結果、上記従来の発光装置を製造する際に、時間とともにその色度座標が変化してしまう。つまり、安定的に色度座標が同じ発光装置を提供するという目的を達成することができなくなる。 As a result, when the conventional light emitting device is manufactured, the chromaticity coordinates change with time. That is, the object of stably providing a light emitting device having the same chromaticity coordinates cannot be achieved.
　本発明は、上述の事情を鑑みてなされたもので、時間が経過しても蛍光体含有樹脂中の複数の蛍光体の濃度に分布が生じない複合蛍光体および発光装置を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composite phosphor and a light-emitting device in which distribution does not occur in the concentration of the plurality of phosphors in the phosphor-containing resin even if time elapses. And
　上記目的を達成するために、本発明の一形態に係る複合蛍光体は、少なくとも粒径の異なる２種類以上の蛍光体粒子で構成される複合蛍光体であって、第１の蛍光体粒子は、表面に密着された複数の第２の蛍光体粒子を有し、前記第１の蛍光体粒子は、前記第２の蛍光体粒子よりも大きい。 In order to achieve the above object, a composite phosphor according to an embodiment of the present invention is a composite phosphor composed of at least two kinds of phosphor particles having different particle diameters, and the first phosphor particles are And having a plurality of second phosphor particles in close contact with the surface, wherein the first phosphor particles are larger than the second phosphor particles.
　この構成により、第１の蛍光体粒子に対する第２の蛍光体粒子の比率がほぼ等しい複合蛍光体を同時に大量に構成することができる。それにより、複合蛍光体を用いることで第１の蛍光体粒子からの蛍光と第２の蛍光体粒子からの蛍光がほぼ等しい蛍光体を作製することが可能となる。 With this configuration, a large number of composite phosphors having substantially the same ratio of the second phosphor particles to the first phosphor particles can be formed at the same time. Thereby, it becomes possible to produce a phosphor in which the fluorescence from the first phosphor particles and the fluorescence from the second phosphor particles are substantially equal by using the composite phosphor.
　また、本発明の一形態に係る複合蛍光体では、前記第１の蛍光体粒子の粒径は、前記第２の蛍光体粒子の粒径の１００倍以上である。 Further, in the composite phosphor according to an aspect of the present invention, the particle diameter of the first phosphor particles is 100 times or more than the particle diameter of the second phosphor particles.
　この構成により、第１の蛍光体粒子と特性が異なる第２の蛍光体粒子に対して、第１の蛍光体粒子の表面積を十分大きくすることができる。それにより、本複合蛍光体において、第１の蛍光体粒子に対する第２の蛍光体粒子の量を調整することが容易となる。 With this configuration, the surface area of the first phosphor particles can be sufficiently increased with respect to the second phosphor particles having characteristics different from those of the first phosphor particles. Thereby, in this composite fluorescent substance, it becomes easy to adjust the quantity of the 2nd fluorescent substance particle with respect to the 1st fluorescent substance particle.
　また、本発明の一形態に係る複合蛍光体では、前記第１の蛍光体粒子の粒径は、１μｍ～１００μｍである。 In the composite phosphor according to one embodiment of the present invention, the particle diameter of the first phosphor particles is 1 μm to 100 μm.
　この構成により、第１の蛍光体粒子に含有される発光部の量と第１の蛍光粒子の表面積の比を調整することが容易となるとともに、第１の蛍光体粒子の表面積に対する体積比を大きくすることができる。それにより、第１の蛍光体粒子表面で欠陥を介した非発光再結合量を低減させることが可能となる。 With this configuration, it becomes easy to adjust the ratio of the amount of the light emitting portion contained in the first phosphor particles and the surface area of the first phosphor particles, and the volume ratio to the surface area of the first phosphor particles can be adjusted. Can be bigger. Thereby, it is possible to reduce the amount of non-radiative recombination via defects on the surface of the first phosphor particles.
　また、本発明の一形態に係る複合蛍光体では、前記第２の蛍光体粒子は、量子ドット蛍光体で構成される。 Further, in the composite phosphor according to one aspect of the present invention, the second phosphor particles are composed of quantum dot phosphors.
　この構成により、第２の蛍光体粒子をナノサイズの量子ドット蛍光体として構成するので、第１の蛍光体粒子と比較し、十分小さい蛍光体粒子とすることができる。それにより、容易に複合蛍光体を構成することが可能となる。 With this configuration, since the second phosphor particles are configured as nano-sized quantum dot phosphors, the phosphor particles can be made sufficiently small compared to the first phosphor particles. Thereby, a composite phosphor can be easily configured.
　また、本発明の一形態に係る複合蛍光体では、前記第１の蛍光体粒子の蛍光スペクトルの中心波長は、前記第２の蛍光体粒子の蛍光スペクトルの中心波長よりも短い。 In the composite phosphor according to one embodiment of the present invention, the center wavelength of the fluorescence spectrum of the first phosphor particles is shorter than the center wavelength of the fluorescence spectrum of the second phosphor particles.
　この構成により、第１の蛍光体粒子に吸収された光が、第１の蛍光体粒子内部で励起子を生成し、その再結合過程において、表面準位で非発光再結合される分の一部を第２の蛍光体粒子で発光再結合させることにより発光効率を向上させることができる。 With this configuration, the light absorbed by the first phosphor particles generates excitons inside the first phosphor particles, and in the recombination process, the light is non-radiatively recombined at the surface level. Luminous efficiency can be improved by recombining the light emission with the second phosphor particles.
　また、本発明の一形態に係る複合蛍光体では、前記第１の蛍光体粒子は、希土類元素賦活蛍光体で構成される。 Further, in the composite phosphor according to one embodiment of the present invention, the first phosphor particles are composed of a rare earth element activated phosphor.
　この構成により、第１の蛍光体粒子の大きさを容易に調整することができるとともに、第１の蛍光粒子内部の発光部である希土類元素の含有量を調整することができる。それにより、容易に発光部の量を調整することができる。 With this configuration, it is possible to easily adjust the size of the first phosphor particles, and it is possible to adjust the content of the rare earth element that is the light emitting portion inside the first phosphor particles. Thereby, the amount of the light emitting part can be easily adjusted.
　ここで、前記第１の蛍光体粒子は、（Ｙ，Ｇｄ）３Ａｌ４Ｏ１２：Ｃｅ、Ｙ３（Ａｌ，Ｇａ）４Ｏ１２：Ｃｅ、Ｔｂ３Ａｌ５Ｏ１２：Ｃｅ、（Ｓｒ，Ｃａ，Ｂａ）２ＳｉＯ４：Ｅｕ、Ｃａ－α－サイアロン：Ｅｕ、（Ｂａ，Ｓｒ）２ＳｉＯ４：Ｅｕ、Ｃａ３Ｓｃ２Ｓｉ３Ｏ１２：Ｃｅ，ＣａＳｃ２Ｏ４：Ｃｅ、β－サイアロン：Ｅｕ、（Ｓｒ，Ｂａ）Ｓｉ２Ｏ２Ｎ２：Ｅｕ、Ｂａ３Ｓｉ６Ｏ１２Ｎ２：Ｅｕ、ＣａＡｌＳｉＮ３：Ｅｕ、（Ｃａ，Ｓｒ）２Ｓｉ５Ｎ８：Ｅｕ、ＣａＡｌＳｉＮ３：Ｅｕ、（Ｓｒ，Ｃａ）Ｓ：Ｅｕ、Ｂａ３Ｓｉ６Ｏ１２Ｎ２：Ｅｕ，ＢａＭｇＡｌ１０Ｏ１７：（Ｅｕ，Ｍｎ）、ＳｒＡｌ２Ｏ４：Ｅｕ、（Ｓｒ，Ｃａ，Ｂａ，Ｍｇ）１０（ＰＯ４）６Ｃｌ２：Ｅｕ、および、（Ｂａ、Ｓｒ）ＭｇＡｌ１０Ｏ１７：Ｅｕのいずれかで構成されるとしてもよい。 Here, the first phosphor particles are (Y, Gd) 3 Al 4 O 12 : Ce, Y 3 (Al, Ga) 4 O 12 : Ce, Tb 3 Al 5 O 12 : Ce, (Sr, Ca, Ba) 2 SiO 4 : Eu, Ca-α-sialon: Eu, (Ba, Sr) 2 SiO 4 : Eu, Ca 3 Sc 2 Si 3 O 12: Ce, CaSc 2 O 4 : Ce, β-sialon: Eu, (Sr, Ba) Si 2 O 2 N 2 : Eu, Ba 3 Si 6 O 12 N 2 : Eu, CaAlSiN 3 : Eu, (Ca, Sr) 2 Si 5 N 8 : Eu, CaAlSiN 3 : Eu, (Sr, Ca) S: Eu, Ba 3 Si 6 O 12 N 2: Eu, BaMgAl10O17: (Eu, Mn), SrAl 2 O 4: Eu, (Sr, Ca, Ba, Mg) 10 (PO 4) 6 Cl 2: Eu, and (Ba, Sr) MgAl 10 O 17: may be composed of any of Eu.
　この構成により、前記第１の蛍光粒子を容易に構成することができる。 With this configuration, the first fluorescent particles can be easily configured.
　また、本発明の一形態に係る複合蛍光体では、前記第２の蛍光体粒子は、量子ドット蛍光体であり、前記量子ドット蛍光体は、ノンドープ型量子ドット蛍光体またはドープ型量子ドット蛍光体で構成される。 In the composite phosphor according to an aspect of the present invention, the second phosphor particle is a quantum dot phosphor, and the quantum dot phosphor is a non-doped quantum dot phosphor or a doped quantum dot phosphor. Consists of.
　この構造により、第２の蛍光体粒子を容易に第１の蛍光体粒子と比較し、小さくすることができる。 With this structure, the second phosphor particles can be easily made smaller than the first phosphor particles.
　ここで、前記ノンドープ型量子ドットを構成する材料は、ＩＩＩ－Ｖ族化合物半導体であるＩｎＮ、ＩｎＰ、ＩｎＡｓ、ＩｎＳｂ、ＧａＮ、ＧａＰ、ＧａＡｓ、ＧａＳｂ、ＡｌＮ、ＡｌＰ、ＡｌＡｓ、ＡｌＳｂおよびＢＮ、ＩＩ－ＶＩ族化合物半導体であるＨｇＳ、ＨｇＳｅ、ＨｇＴｅ、ＣｄＳ、ＣｄＳｅ、ＣｄＴｅ、ＺｎＳ、ＺｎＳｅおよびＺｎＴｅ、並びにこれらの混晶結晶よりなる群から選択されて構成されるとしてもよい。 Here, the material constituting the non-doped quantum dots is a group III-V compound semiconductor InN, InP, InAs, InSb, GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb and BN, II- It may be configured to be selected from the group consisting of HgS, HgSe, HgTe, CdS, CdSe, CdTe, ZnS, ZnSe and ZnTe, which are group VI compound semiconductors, and mixed crystal thereof.
　この構成により、第２の蛍光体粒子を容易に第１の蛍光体粒子と比較し、小さくすることができる。 With this configuration, the second phosphor particles can be easily made smaller than the first phosphor particles.
　また、本発明の一形態に係る複合蛍光体では、前記ドープ型量子ドット蛍光体を構成する材料は、ＺｎＳ：Ｍｎ２＋、ＣｄＳ：Ｍｎ２＋およびＹＶＯ４：Ｅｕ３＋により構成される。 In the composite phosphor according to an aspect of the present invention, the material constituting the doped quantum dot phosphor is composed of ZnS: Mn 2+ , CdS: Mn 2+, and YVO 4: Eu 3+ .
　この構成により、第２の蛍光体粒子を容易に第１の蛍光体粒子と比較し、小さくすることができる。 With this configuration, the second phosphor particles can be easily made smaller than the first phosphor particles.
　また、上記目的を達成するために、本発明の一形態に係る発光装置は、上記形態のいずれかの複合蛍光体と半導体発光素子とを少なくとも有する。 In order to achieve the above object, a light emitting device according to an aspect of the present invention includes at least the composite phosphor of any of the above aspects and a semiconductor light emitting element.
　この構成により、第１の蛍光体粒子と第２の蛍光体粒子との比率がほぼ等しい複合蛍光体を用いて、蛍光体と半導体発光素子を組み合わせた発光装置を実現できる。それにより、大量に製造しても色度が安定している発光装置を実現することができる。 With this configuration, it is possible to realize a light emitting device in which a phosphor and a semiconductor light emitting element are combined using a composite phosphor in which the ratio of the first phosphor particles and the second phosphor particles is substantially equal. Thereby, a light emitting device having stable chromaticity even when manufactured in large quantities can be realized.
　本発明によれば、時間が経過しても蛍光体含有樹脂中の複数の蛍光体の濃度に分布が生じない複合蛍光体および発光装置を実現することができる。それにより、樹脂中において、時間が経過してもその濃度比が時間とともにほとんど変化せずに、高い演色性・色再現性の発光装置を安定的に提供することができる。 According to the present invention, it is possible to realize a composite phosphor and a light emitting device in which distribution does not occur in the concentration of a plurality of phosphors in the phosphor-containing resin even if time passes. As a result, in the resin, the concentration ratio hardly changes with time even when time passes, and a light emitting device having high color rendering properties and color reproducibility can be stably provided.
図１は、本発明の実施の形態１に係る複合蛍光体の構成を示す図である。FIG. 1 is a diagram showing the configuration of the composite phosphor according to Embodiment 1 of the present invention. 図２は、本発明の実施の形態１に係る複合蛍光体を用いた発光装置の構成を示す図である。FIG. 2 is a diagram showing a configuration of a light emitting device using the composite phosphor according to Embodiment 1 of the present invention. 図３Ａは、本発明の実施の形態１に係る複合蛍光体の設計例を示す図である。FIG. 3A is a diagram showing a design example of the composite phosphor according to Embodiment 1 of the present invention. 図３Ｂは、本発明の実施の形態１に係る複合蛍光体の設計例を示す図である。FIG. 3B is a diagram showing a design example of the composite phosphor according to Embodiment 1 of the present invention. 図４Ａは、本発明の実施の形態１に係る複合蛍光体と半導体発光素子を組み合わせた発光装置のスペクトルを設計した例を示す図である。FIG. 4A is a diagram showing an example of designing a spectrum of a light emitting device in which the composite phosphor according to Embodiment 1 of the present invention and a semiconductor light emitting element are combined. 図４Ｂは、本発明の実施の形態１に係る複合蛍光体と半導体発光素子を組み合わせた発光装置のスペクトルを設計した例を示す図である。FIG. 4B is a diagram showing an example of designing a spectrum of a light emitting device in which the composite phosphor according to Embodiment 1 of the present invention and a semiconductor light emitting element are combined. 図４Ｃは、本発明の実施の形態１に係る複合蛍光体と半導体発光素子を組み合わせた発光装置の色度座標を設計した例を示す図である。FIG. 4C is a diagram showing an example of designing chromaticity coordinates of a light emitting device in which the composite phosphor according to Embodiment 1 of the present invention and a semiconductor light emitting element are combined. 図５Ａは、本発明の実施の形態１に係る複合蛍光体の製造方法を説明するための図である。FIG. 5A is a diagram for explaining the method for manufacturing the composite phosphor according to Embodiment 1 of the present invention. 図５Ｂは、本発明の実施の形態１に係る複合蛍光体の製造方法を説明するための図である。FIG. 5B is a diagram for explaining the method for manufacturing the composite phosphor according to Embodiment 1 of the present invention. 図５Ｃは、本発明の実施の形態１に係る複合蛍光体の製造方法を説明するための図である。FIG. 5C is a diagram for explaining the method for manufacturing the composite phosphor according to Embodiment 1 of the present invention. 図６Ａは、本発明の実施の形態１に係る複合蛍光体の効果を説明するための図である。FIG. 6A is a diagram for explaining the effect of the composite phosphor according to Embodiment 1 of the present invention. 図６Ｂは、本発明の実施の形態１に係る複合蛍光体の効果を説明するための図である。FIG. 6B is a diagram for explaining the effect of the composite phosphor according to Embodiment 1 of the present invention. 図７Ａは、本発明の実施の形態１に係る複合蛍光体の効果を説明するための図である。FIG. 7A is a diagram for explaining the effect of the composite phosphor according to Embodiment 1 of the present invention. 図７Ｂは、本発明の実施の形態１に係る複合蛍光体の効果を説明するための図である。FIG. 7B is a diagram for explaining the effect of the composite phosphor according to Embodiment 1 of the present invention. 図８は、本発明の実施の形態２に係る複合蛍光体の構成を示す図である。FIG. 8 is a diagram showing a configuration of the composite phosphor according to Embodiment 2 of the present invention. 図９は、本発明の実施の形態２に係る複合蛍光体の変形例の構成を示す図である。FIG. 9 is a diagram showing a configuration of a modification of the composite phosphor according to Embodiment 2 of the present invention. 図１０は、従来技術の発光装置の構成を示す図である。FIG. 10 is a diagram illustrating a configuration of a conventional light emitting device.
　以下に、本発明の各実施形態について図面を参照しながら説明する。 Hereinafter, embodiments of the present invention will be described with reference to the drawings.
　（実施の形態１）
　以下に、本発明の実施の形態１に係る複合蛍光体について、図を参照しながら説明する。 (Embodiment 1)
Hereinafter, the composite phosphor according to Embodiment 1 of the present invention will be described with reference to the drawings.
　図１は、本発明の実施の形態１に係る複合蛍光体の構成を示す図である。 FIG. 1 is a diagram showing a configuration of a composite phosphor according to Embodiment 1 of the present invention.
　図１に示す複合蛍光体１は、第１の蛍光体粒子２と第２の蛍光体粒子３とで構成されている。より具体的には、複合蛍光体１の中心部には、直径が例えば１μｍ～１００μｍの第１の蛍光体粒子２の母材２ａが構成されており、その母材２ａは、分散された複数の蛍光発生部２ｂを有する。複合蛍光体１（母材２ａ）の表面には、直径が例えば１ｎｍ～１００ｎｍの第２の蛍光体粒子３が所定の密度で覆うように付着している。 1 includes a first phosphor particle 2 and a second phosphor particle 3. The composite phosphor 1 shown in FIG. More specifically, a base material 2a of first phosphor particles 2 having a diameter of, for example, 1 μm to 100 μm is formed in the central portion of the composite phosphor 1, and the base material 2a includes a plurality of dispersed base materials 2a. The fluorescence generation part 2b. On the surface of the composite phosphor 1 (base material 2a), second phosphor particles 3 having a diameter of, for example, 1 nm to 100 nm are attached so as to cover with a predetermined density.
　ここで、第１の蛍光体粒子２は、例えばセリウム（Ｃｅ）などの賦活剤で構成された蛍光発生部２ｂがイットリウム・アルミニウム・ガーネット（ＹＡＧ）などの材料で構成された母材２ａに分散されているＣｅドープＹＡＧ蛍光体（Ｃｅ賦活ＹＡＧ蛍光体）である。一方、第２の蛍光体粒子３は、例えばノンドープ型の量子ドット蛍光体、特にコア・シェル構造を有する量子ドット蛍光体である。このコア材料は、例えばＩｎＰなどの化合物半導体であり、シェル材料は例えばＺｎＳなどの化合物半導体である。 Here, the first phosphor particles 2 are dispersed in a base material 2a composed of a material such as yttrium / aluminum / garnet (YAG) in a fluorescence generating portion 2b composed of an activator such as cerium (Ce). Ce-doped YAG phosphor (Ce-activated YAG phosphor). On the other hand, the second phosphor particles 3 are, for example, non-doped quantum dot phosphors, particularly quantum dot phosphors having a core / shell structure. The core material is a compound semiconductor such as InP, and the shell material is a compound semiconductor such as ZnS.
　第１の蛍光体粒子２は賦活剤における電子の励起準位間の遷移により蛍光が発生し、第２の蛍光体粒子３は大きさ１００ｎｍ以下にすることで量子化されたコア材料において、励起された電子－正孔対が再結合するによって蛍光が発生する。 The first phosphor particles 2 generate fluorescence due to the transition between excitation levels of electrons in the activator, and the second phosphor particles 3 are excited in the core material quantized by the size of 100 nm or less. Fluorescence is generated by recombination of the generated electron-hole pairs.
　このように、本実施の形態の複合蛍光体は、蛍光発生原理が異なる蛍光体を異なる大きさで組み合わせて構成される。 Thus, the composite phosphor of the present embodiment is configured by combining phosphors having different fluorescence generation principles in different sizes.
　なお、第１の蛍光体粒子２の材料として、Ｅｕ賦活βサイアロン結晶、Ｃｅ賦活ＣａＳｃ２Ｏ４やＥｕ賦活ストロンチウム・バリウム・シリケート（（Ｓｒ，Ｂａ）２ＳｉＯ４）等の他の希土類元素賦活蛍光体を用いるとしてもよい。また、第２の蛍光体粒子３の材料として、ＣｄＳｅ、ＣｄＳ、ＺｎＯ、ＺｎＳｅ、ＡｌＡｓ、ＡｌＰ、ＡｌＮ、ＧａＡｓ、ＧａＰ、ＧａＮ等の他の化合物半導体材料を用いるとしてもよい。 As the material of the first phosphor particles 2, other rare earth element activation such as Eu activated β sialon crystal, Ce activated CaSc 2 O 4 and Eu activated strontium barium silicate ((Sr, Ba) 2 SiO 4 ) is used. A phosphor may be used. Further, as the material of the second phosphor particles 3, other compound semiconductor materials such as CdSe, CdS, ZnO, ZnSe, AlAs, AlP, AlN, GaAs, GaP, and GaN may be used.
　また、第１の蛍光体粒子２には、所定の密度で、希土類元素が含まれており、それらが蛍光発生部２ｂとして機能する。 Moreover, the first phosphor particles 2 contain rare earth elements at a predetermined density, and these function as the fluorescence generating part 2b.
　続いて図２を用いて、本実施の形態の複合蛍光体１を用いた発光装置５０について説明する。 Subsequently, a light emitting device 50 using the composite phosphor 1 of the present embodiment will be described with reference to FIG.
　図２は、本発明の実施の形態１に係る複合蛍光体を用いた発光装置の構成を示す図である。図２に示す発光装置５０は、パッケージ１０と、半導体発光素子１１と、樹脂１３と、複合蛍光体１とで構成される。 FIG. 2 is a diagram showing a configuration of a light emitting device using the composite phosphor according to Embodiment 1 of the present invention. A light emitting device 50 shown in FIG. 2 includes a package 10, a semiconductor light emitting element 11, a resin 13, and a composite phosphor 1.
　パッケージ１０は、例えばセラミックに所定の配線をしたものや、金属フレームに樹脂をモールドすることで構成される。 The package 10 is configured by, for example, ceramic having predetermined wiring or molding a resin on a metal frame.
　半導体発光素子１１は、例えば図示しないサファイア基板上に窒化物半導体（Ａｌ、Ｉｎ、Ｇａ）Ｎで構成され、パッケージ１０上に実装され、図示しない金配線もしくはバンプ電極等で配線される。 The semiconductor light emitting element 11 is made of, for example, a nitride semiconductor (Al, In, Ga) N on a sapphire substrate (not shown), mounted on the package 10, and wired with a gold wiring or a bump electrode (not shown).
　樹脂１３は、例えばシリコーン樹脂、エポキシ樹脂等からなり、複合蛍光体１が混合されている。樹脂１３は、半導体発光素子１１の上部を覆うように塗布さている。 Resin 13 is made of, for example, a silicone resin or an epoxy resin, and the composite phosphor 1 is mixed therein. The resin 13 is applied so as to cover the upper part of the semiconductor light emitting element 11.
　続いて図３Ａおよび図３Ｂを用いて本実施の形態の複合蛍光体１の設計例について説明する。 Subsequently, a design example of the composite phosphor 1 of the present embodiment will be described with reference to FIGS. 3A and 3B.
　具体的には、図３Ａは、複合蛍光体１における第１の蛍光体粒子２と第２の蛍光体粒子３の設計の一例を示す図である。より具体的には、図３Ａには、１）第１の蛍光体粒子２における単位体積あたりの蛍光発生部の密度、２）第１の蛍光体粒子２の表面における単位面積あたりの第２の蛍光体粒子３の密度、３）第１の蛍光体粒子２の発光部と第２の蛍光体粒子３の発光再結合速度比とをパラメータとした場合の値の一例が示されている。なお、上記設計例を用いて計算する際には、第２の蛍光体粒子３の大きさは１ｎｍ～１００ｎｍであり、第１の蛍光体粒子２の大きさと比較し、無視できるほど小さいとする。 Specifically, FIG. 3A is a diagram showing an example of the design of the first phosphor particles 2 and the second phosphor particles 3 in the composite phosphor 1. More specifically, in FIG. 3A, 1) the density of the fluorescence generating portion per unit volume in the first phosphor particle 2 and 2) the second per unit area on the surface of the first phosphor particle 2 are shown. An example of values when the density of the phosphor particles 3 and 3) the light emitting portion of the first phosphor particles 2 and the light emission recombination rate ratio of the second phosphor particles 3 are used as parameters is shown. In the calculation using the above design example, the size of the second phosphor particles 3 is 1 nm to 100 nm, which is negligibly small compared to the size of the first phosphor particles 2. .
　本実施の形態の第１の蛍光体粒子２の蛍光寿命と第２の蛍光体粒子３の蛍光寿命は、上記に述べたように、異なる蛍光発生原理を用いることができる。そのため、例えば一方がマイクロ秒オーダー、もう一方がナノ秒オーダーと非常に大きな差を実現できる。 As described above, different fluorescence generation principles can be used for the fluorescence lifetime of the first phosphor particles 2 and the fluorescence lifetime of the second phosphor particles 3 of the present embodiment. Therefore, for example, a very large difference can be realized in which one is on the microsecond order and the other is on the nanosecond order.
　図３Ｂは、第１の蛍光体粒子２の直径と、複合蛍光体１における第２の蛍光体粒子３と第１の蛍光体粒子２の発光部の関係の一例を示す図である。より具体的には、図３Ｂには、図３Ａにおける第１の蛍光体粒子２の粒径と、複合蛍光体１における第２の蛍光体粒子３の量／第１の蛍光体粒子２の発光部量の比との関係の一例が示されている。 FIG. 3B is a diagram showing an example of the relationship between the diameter of the first phosphor particle 2 and the light emitting portion of the second phosphor particle 3 and the first phosphor particle 2 in the composite phosphor 1. More specifically, FIG. 3B shows the particle diameter of the first phosphor particles 2 in FIG. 3A and the amount of the second phosphor particles 3 in the composite phosphor 1 / the light emission of the first phosphor particles 2. An example of the relationship with the ratio of parts is shown.
　図３Ｂに示されるように、第１の蛍光体粒子２の粒径が大きくなるにしたがい、蛍光体粒子の表面積／体積比が小さくなるため、第２の蛍光体粒子３の量／第１の蛍光体粒子２の発光部量の比が小さくなる。また、第１の蛍光体粒子２の発光部と第２の蛍光体粒子３においては、蛍光寿命が異なる。ここで、例えば、第１の蛍光体粒子２の発光部と第２の蛍光体粒子３の蛍光寿命に１０００倍の差があるとすると（例えば図３Ａの組み合せ２の場合）、図３Ｂの組み合わせ２に示されるように、第１の蛍光体粒子２の粒径が１μｍ～１００μｍの範囲において、第２の蛍光体粒子３の量／第１の蛍光体粒子２の発光部量の比を１／１０倍～１０倍程度まで調整することが可能である。 As shown in FIG. 3B, since the surface area / volume ratio of the phosphor particles decreases as the particle diameter of the first phosphor particles 2 increases, the amount of the second phosphor particles 3 / the first The ratio of the light emission part amount of the phosphor particles 2 becomes small. Further, the light emission part of the first phosphor particle 2 and the second phosphor particle 3 have different fluorescence lifetimes. Here, for example, if there is a difference of 1000 times in the fluorescence lifetime between the light emitting part of the first phosphor particle 2 and the second phosphor particle 3 (for example, in the case of the combination 2 in FIG. 3A), the combination in FIG. 3B. As shown in FIG. 2, when the particle diameter of the first phosphor particles 2 is in the range of 1 μm to 100 μm, the ratio of the amount of the second phosphor particles 3 / the amount of the light emitting part of the first phosphor particles 2 is 1. / 10 times to 10 times can be adjusted.
　図４Ａ～図４Ｃは、複合蛍光体と半導体発光素子を組み合わせた発光装置のスペクトルを設計した例を示す図である。具体的には、図４Ａは、複合蛍光体の第１の蛍光体粒子２と第２の蛍光体粒子３との比率の組み合わせの一例を示している。図４Ｂは、図４Ａの設計に基づいて、計算した発光装置５０のスペクトル例を示している。図４Ｃは、図４Ｂのスペクトルより得られる色度座標の例を示している。 4A to 4C are diagrams showing an example of designing a spectrum of a light emitting device in which a composite phosphor and a semiconductor light emitting element are combined. Specifically, FIG. 4A shows an example of a combination of ratios of the first phosphor particles 2 and the second phosphor particles 3 of the composite phosphor. FIG. 4B shows a calculated spectrum of the light emitting device 50 based on the design of FIG. 4A. FIG. 4C shows an example of chromaticity coordinates obtained from the spectrum of FIG. 4B.
　図４Ａでは、第１の蛍光体粒子２はＣｅ賦活ＹＡＧ蛍光体、第２の蛍光体粒子３はＩｎＰ／ＺｎＳのコア・シェル構造のノンドープ型量子ドット蛍光体とした場合の例を示している。また第２の蛍光体粒子３は、ピーク波長６００ｎｍ、半値幅５０ｎｍに設計されている。 FIG. 4A shows an example in which the first phosphor particles 2 are Ce-activated YAG phosphors, and the second phosphor particles 3 are non-doped quantum dot phosphors having an InP / ZnS core-shell structure. . The second phosphor particles 3 are designed to have a peak wavelength of 600 nm and a half width of 50 nm.
　図４Ａに示すように励起光吸収量比（第２の蛍光体粒子３の総数／第１の蛍光体粒子２の総数）を変化させることで、図４Ｂに示すようにスペクトルを自由に変化させることができる。図４Ｂのスペクトルを元に計算した色度座標は図４Ｃに示されている。図４Ｃに示すように、励起光吸収量比（第２の蛍光体粒子３の総数／第１の蛍光体粒子２の総数）を変化させることで色度座標および色温度を自在に変化させることができる。 By changing the excitation light absorption ratio (total number of second phosphor particles 3 / total number of first phosphor particles 2) as shown in FIG. 4A, the spectrum can be freely changed as shown in FIG. 4B. be able to. The chromaticity coordinates calculated based on the spectrum of FIG. 4B are shown in FIG. 4C. As shown in FIG. 4C, the chromaticity coordinates and the color temperature can be freely changed by changing the excitation light absorption amount ratio (total number of second phosphor particles 3 / total number of first phosphor particles 2). Can do.
　続いて、本実施の形態の複合蛍光体１の製造方法について説明する。 Then, the manufacturing method of the composite fluorescent substance 1 of this Embodiment is demonstrated.
　図５Ａ～図５Ｃは、本発明の実施の形態１に係る複合蛍光体の製造方法を示す図である。第２の蛍光体粒子３は、例えば量子ドット蛍光体であるが、量子ドット蛍光体の製造方法は、ゾル・ゲル法（錯体重合法）、逆ミセル法、コロイド析出法、等さまざまある。 5A to 5C are diagrams showing a method for manufacturing the composite phosphor according to Embodiment 1 of the present invention. The second phosphor particles 3 are, for example, quantum dot phosphors, and there are various methods for producing quantum dot phosphors, such as a sol-gel method (complex polymerization method), a reverse micelle method, and a colloid deposition method.
　本実施の形態では、ホットソープ法を用いたコア・シェル型量子ドット蛍光体の製造方法について説明する。 In the present embodiment, a method for manufacturing a core-shell type quantum dot phosphor using a hot soap method will be described.
　図５Ａは、量子ドット蛍光体の製造方法を模式的に示した図であり、例えばフラスコである容器６０を真空中に保持し、例えばトリオクチルホスフフィンオキサイド（ＴＯＰＯ）を、容器６０を入れてヒーターにより３００℃に保つ。続いて、トリスジメチルアミノホスフィン［Ｐ（ＮＭｅ２）３］と塩化インジウム（ＩｎＣｌ３）とトリオクチルホスフフィン（ＴＯＰ）、ＴＯＰＯとの混合溶液を注入する。その後、所定の温度に調整し、所定の時間保つことでＩｎＰのナノ粒子が形成される。続いて、上記混合溶液を遠心分離機と組み合わせ、ＴＯＰＯで置換することによりＩｎＰナノ粒子がＴＯＰＯに混合されたコロイド溶液が生成される。続いてこの溶液にジエチルジチオカルバミン酸亜鉛（［（Ｃ２Ｈ５）２ＮＣＳ２］２Ｚｎ）とＴＯＰ／ＴＯＰＯとの混合溶液を注入することによりＩｎＰ／ＺｎＳコア・シェル型量子ドット蛍光体である第２の蛍光体粒子３が分散されたコロイド溶液が生成される。続いて、再び、このコロイド溶液を、遠心分離機を用いてＴＯＰＯで置換することにより第２の蛍光体粒子３がＴＯＰＯに分散したコロイド溶液６１が作製される。 FIG. 5A is a diagram schematically showing a method for producing a quantum dot phosphor. For example, a container 60 that is a flask is held in a vacuum, and for example, trioctylphosphine oxide (TOPO) is placed in the container 60. Keep at 300 ° C with heater. Subsequently, a mixed solution of trisdimethylaminophosphine [P (NMe2) 3], indium chloride (InCl3), trioctylphosphine (TOP), and TOPO is injected. After that, the InP nanoparticles are formed by adjusting to a predetermined temperature and keeping it for a predetermined time. Subsequently, the mixed solution is combined with a centrifuge and replaced with TOPO, thereby generating a colloidal solution in which InP nanoparticles are mixed with TOPO. Subsequently, by injecting a mixed solution of zinc diethyldithiocarbamate ([(C2H5) 2NCS2] 2Zn) and TOP / TOPO into this solution, second phosphor particles that are InP / ZnS core-shell quantum dot phosphors A colloidal solution in which 3 is dispersed is produced. Subsequently, the colloidal solution 61 in which the second phosphor particles 3 are dispersed in TOPO is produced by replacing the colloidal solution with TOPO again using a centrifuge.
　次に、このコロイド溶液６１に、表面に疎水性の基を付加した例えばＣｅ賦活ＹＡＧ蛍光体粒子などの第１の蛍光体粒子２をコロイド溶液６１中に滴下し、攪拌する。このとき、所定の量の第２の蛍光体粒子３が第１の蛍光体粒子２の表面に吸着されるが、所定量以上の第２の蛍光体粒子３は、第２の蛍光体粒子３同士の反発力６５により吸着されない。この結果、図５Ｂに示すように、所定の量の第２の蛍光体粒子３が表面に付着した第１の蛍光体粒子２である複合蛍光体１と、不要な第２の蛍光体粒子３が混合した混合液６２が生成される。 Next, the first phosphor particles 2 such as Ce-activated YAG phosphor particles having a hydrophobic group added to the surface are dropped into the colloid solution 61 and stirred. At this time, a predetermined amount of the second phosphor particle 3 is adsorbed on the surface of the first phosphor particle 2, but the second phosphor particle 3 of a predetermined amount or more is the second phosphor particle 3. They are not attracted by the repulsive force 65 between them. As a result, as shown in FIG. 5B, the composite phosphor 1 which is the first phosphor particle 2 having a predetermined amount of the second phosphor particles 3 attached to the surface and the unnecessary second phosphor particles 3. A mixed liquid 62 is generated.
　次に、このようにして形成された複合蛍光体１から不要な第２の蛍光体粒子３を除去するため、以下の作業を行う。まず、遠心分離機により、複合蛍光体１と第２の蛍光体粒子３が混合した溶液から複合蛍光体１の濃度が濃い溶液を抽出し、そこに不純物のない溶媒を追加する。この作業を複数回繰り返すことで、純度の高い複合蛍光体１が例えばＴＯＰＯである溶液中に分散された第二の混合液６３を製造することができる。このようにして製造した第二の混合液６３の溶媒を所定の樹脂に置換することで、図５Ｃに示すように、樹脂中に複合蛍光体１が含有された複合蛍光体含有樹脂（樹脂１３）を製造することができる。 Next, in order to remove unnecessary second phosphor particles 3 from the composite phosphor 1 thus formed, the following operation is performed. First, a solution having a high concentration of the composite phosphor 1 is extracted from the solution in which the composite phosphor 1 and the second phosphor particles 3 are mixed, and a solvent free of impurities is added thereto. By repeating this operation a plurality of times, the second mixed solution 63 in which the high-purity composite phosphor 1 is dispersed in a solution of, for example, TOPO can be produced. By replacing the solvent of the second mixed solution 63 thus manufactured with a predetermined resin, as shown in FIG. 5C, a composite phosphor-containing resin (resin 13) in which the composite phosphor 1 is contained in the resin. ) Can be manufactured.
　次に、本実施の形態の効果について説明する。 Next, the effect of this embodiment will be described.
　図６Ａおよび図６Ｂは、本発明の実施の形態１に係る複合蛍光体の効果を説明するための図である。 6A and 6B are diagrams for explaining the effect of the composite phosphor according to Embodiment 1 of the present invention.
　具体的には、図６Ａでは、第１の蛍光体粒子２と第２の蛍光体粒子３を単純に混合した樹脂６６の実装方法の一例を模式的に示しており、図６Ｂでは、本発明の複合蛍光体１を混合した樹脂１３の実装方法の一例を模式的に示している。 Specifically, FIG. 6A schematically shows an example of a mounting method of the resin 66 in which the first phosphor particles 2 and the second phosphor particles 3 are simply mixed, and FIG. 6B shows the present invention. An example of a mounting method of the resin 13 mixed with the composite phosphor 1 is schematically shown.
　より具体的には、図６Ａおよび図６Ｂでは、例えばＩｎＧａＮ発光層を有する窒化物半導体で構成された発光ダイオードである半導体発光素子１１が、最上面に凹型の形状が形成されたパッケージ１０の凹部底面に実装されたものに、蛍光体含有樹脂を滴下して発光装置５０を形成する工程を示す。 More specifically, in FIG. 6A and FIG. 6B, the semiconductor light emitting element 11 which is a light emitting diode made of a nitride semiconductor having an InGaN light emitting layer, for example, has a concave portion of the package 10 in which a concave shape is formed on the uppermost surface. A step of forming the light emitting device 50 by dropping the phosphor-containing resin onto the one mounted on the bottom surface is shown.
　蛍光体含有樹脂は、例えばシリンジ２０に入れられて、半導体発光素子１１の上部より滴下される。 The phosphor-containing resin is placed in, for example, the syringe 20 and dropped from the upper part of the semiconductor light emitting element 11.
　図６Ａに示すように、シリンジ２０内には、演色性を高めるために、複数の蛍光体粒子が混合された樹脂６６（蛍光体含有樹脂）が入っている。この樹脂６６（蛍光体含有樹脂）には、粒径の大きく異なる複数の蛍光体粒子（第１の蛍光体粒子２と第２の蛍光体粒子３）が混合されている。しかし、これら蛍光体粒子の比重は異なるので、時間の経過とともに、シリンジ上部２０ａとシリンジ下部２０ｂでは、第１の蛍光体粒子２と第２の蛍光体粒子３との濃度比がずれてしまう。これはパッケージ１０内に滴下する蛍光体含有樹脂の量を調整することだけでは、ばらつきを低減させることができないことを示唆する。 As shown in FIG. 6A, the syringe 20 contains a resin 66 (phosphor-containing resin) in which a plurality of phosphor particles are mixed in order to improve color rendering. In the resin 66 (phosphor-containing resin), a plurality of phosphor particles (first phosphor particles 2 and second phosphor particles 3) having greatly different particle diameters are mixed. However, since the specific gravity of these phosphor particles is different, the concentration ratio between the first phosphor particles 2 and the second phosphor particles 3 is shifted between the syringe upper portion 20a and the syringe lower portion 20b as time passes. This suggests that the variation cannot be reduced only by adjusting the amount of the phosphor-containing resin dropped into the package 10.
　一方、図６Ｂに示すように、本実施の形態の複合蛍光体１が含有された蛍光体含有樹脂（樹脂１３）を用いると、時間の経過とともに、複合蛍光体１の濃度は分布が生じる。しかし、複合蛍光体１を構成する第１の蛍光体粒子２と第２の蛍光体粒子３との比率は変化することがない。これは、蛍光体含有樹脂の滴下量を調整することで、発光装置５０の色度座標のばらつきを低減させることができることを示唆する。 On the other hand, as shown in FIG. 6B, when the phosphor-containing resin (resin 13) containing the composite phosphor 1 of the present embodiment is used, the concentration of the composite phosphor 1 is distributed over time. However, the ratio between the first phosphor particles 2 and the second phosphor particles 3 constituting the composite phosphor 1 does not change. This suggests that variations in the chromaticity coordinates of the light emitting device 50 can be reduced by adjusting the amount of the phosphor-containing resin dropped.
　次に、更なる効果について説明する。 Next, further effects will be described.
　図７Ａおよび図７Ｂは、本発明の実施の形態１に係る複合蛍光体の効果を説明するための図である。より具体的には、図７Ａは、第１の蛍光体粒子２の拡大図であり、第１の蛍光体粒子２のみで構成される場合において、第１の蛍光体粒子２によって吸収された励起光が蛍光として、取り出される過程を模式的に示している。図７Ｂは、複合蛍光体１の拡大図であり、複合蛍光体１によって吸収された励起光が蛍光として、取り出される過程を模式的に示している。 7A and 7B are diagrams for explaining the effect of the composite phosphor according to Embodiment 1 of the present invention. More specifically, FIG. 7A is an enlarged view of the first phosphor particles 2, and in the case where only the first phosphor particles 2 are included, excitation absorbed by the first phosphor particles 2 The process by which light is extracted as fluorescence is schematically shown. FIG. 7B is an enlarged view of the composite phosphor 1 and schematically shows a process in which excitation light absorbed by the composite phosphor 1 is extracted as fluorescence.
　図７Ａに示すように、第１の蛍光体粒子２で吸収された励起光７０は、大部分が蛍光発生部２ｂにおいて、準位間遷移により蛍光７５となり出射される。しかし、一部のエネルギー７３は表面欠陥２ｃにおいて非発光再結合となり、ロスとなる。 As shown in FIG. 7A, most of the excitation light 70 absorbed by the first phosphor particles 2 is emitted as fluorescence 75 due to transition between levels in the fluorescence generation section 2b. However, a part of the energy 73 becomes non-radiative recombination at the surface defect 2c and becomes a loss.
　一方、図７Ｂに示すように、本発明の複合蛍光体１では、表面欠陥２ｃに近接して、第２の蛍光体粒子３が存在するため、表面欠陥２ｃを介した非発光再結合よりも第２の蛍光体粒子３の発光再結合が優先され蛍光７７として出射される。それにより、表面欠陥２ｃによるロスを低減させることができる。 On the other hand, as shown in FIG. 7B, in the composite phosphor 1 of the present invention, since the second phosphor particles 3 are present in the vicinity of the surface defect 2c, the non-radiative recombination via the surface defect 2c is more effective. The emission recombination of the second phosphor particles 3 is prioritized and emitted as fluorescence 77. Thereby, the loss by the surface defect 2c can be reduced.
　なお、上記において、半導体発光素子１１を発光ダイオードとしたが半導体レーザやスーパールミネッセントのような発光素子でもよい。 In the above description, the semiconductor light emitting element 11 is a light emitting diode, but a light emitting element such as a semiconductor laser or super luminescent may be used.
　また、上記において、第１の蛍光体粒子２を希土類賦活蛍光体として一部の材料について説明したが、上記の限りではない。発光波長に合わせて、例えば、（Ｙ，Ｇｄ）３Ａｌ４Ｏ１２：Ｃｅ、Ｙ３（Ａｌ，Ｇａ）４Ｏ１２：Ｃｅ、Ｔｂ３Ａｌ５Ｏ１２：Ｃｅ、（Ｓｒ，Ｃａ，Ｂａ）２ＳｉＯ４：Ｅｕ、Ｃａ－α－サイアロン：Ｅｕ、（Ｂａ，Ｓｒ）２ＳｉＯ４：Ｅｕ、Ｃａ３Ｓｃ２Ｓｉ３Ｏ１２：Ｃｅ，ＣａＳｃ２Ｏ４：Ｃｅ、β－サイアロン：Ｅｕ、（Ｓｒ，Ｂａ）Ｓｉ２Ｏ２Ｎ２：Ｅｕ、Ｂａ３Ｓｉ６Ｏ１２Ｎ２：Ｅｕ、ＣａＡｌＳｉＮ３：Ｅｕ、（Ｃａ，Ｓｒ）２Ｓｉ５Ｎ８：Ｅｕ、ＣａＡｌＳｉＮ３：Ｅｕ、（Ｓｒ，Ｃａ）Ｓ：Ｅｕ、Ｂａ３Ｓｉ６Ｏ１２Ｎ２：Ｅｕ，ＢａＭｇＡｌ１０Ｏ１７：（Ｅｕ，Ｍｎ）、ＳｒＡｌ２Ｏ４：Ｅｕ、（Ｓｒ，Ｃａ，Ｂａ，Ｍｇ）１０（ＰＯ４）６Ｃｌ２：Ｅｕ、および、（Ｂａ、Ｓｒ）ＭｇＡｌ１０Ｏ１７：Ｅｕなどが選択できる。 In the above description, some materials have been described using the first phosphor particles 2 as rare earth activated phosphors, but the present invention is not limited thereto. According to the emission wavelength, for example, (Y, Gd) 3 Al 4 O 12 : Ce, Y3 (Al, Ga) 4 O 12 : Ce, Tb 3 Al 5 O 12 : Ce, (Sr, Ca, Ba) 2 SiO 4 : Eu, Ca— α-sialon: Eu, (Ba, Sr) 2 SiO 4 : Eu, Ca 3 Sc 2 Si 3 O 12: Ce, CaSc 2 O 4 : Ce, β-sialon: Eu, (Sr, Ba) Si 2 O 2 N 2 : Eu, Ba 3 Si 6 O 12 N 2: Eu , CaAlSiN 3: Eu, (Ca, Sr) 2 Si 5 N 8: Eu, CaAlSiN 3: Eu, (Sr, Ca) S: Eu, Ba 3 Si 6 O 12 N 2: Eu, BaMgAl10O17: (Eu, Mn ), SrAl 2 O 4: Eu, (Sr, Ca, Ba, Mg) 10 (PO 4) 6 Cl 2: Eu, and ( a, Sr) MgAl 10 O 17 : Eu , and the like can be selected.
　また、上記において、第２の蛍光体粒子３をノンドープ型量子ドットとして、その構成材料の一部を説明したが、それに限られない。発光波長に合わせて、例えば、ＩＩＩ－Ｖ族化合物半導体であるＩｎＮ、ＩｎＰ、ＩｎＡｓ、ＩｎＳｂ、ＧａＮ、ＧａＰ、ＧａＡｓ、ＧａＳｂ、ＡｌＮ、ＡｌＰ、ＡｌＡｓ、ＡｌＳｂおよびＢＮ、ＩＩ－ＶＩ族化合物半導体であるＨｇＳ、ＨｇＳｅ、ＨｇＴｅ、ＣｄＳ、ＣｄＳｅ、ＣｄＴｅ、ＺｎＳ、ＺｎＳｅおよびＺｎＴｅ、並びにこれらの混晶結晶よりなる群から選択することができる。 In the above description, the second phosphor particle 3 is a non-doped quantum dot, and a part of the constituent material has been described. However, the present invention is not limited to this. According to the emission wavelength, for example, group III-V compound semiconductors such as InN, InP, InAs, InSb, GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb and BN, and II-VI group compound semiconductors. It can be selected from the group consisting of HgS, HgSe, HgTe, CdS, CdSe, CdTe, ZnS, ZnSe and ZnTe, and mixed crystal crystals thereof.
　また、第２の蛍光体粒子３はノンドープ型量子ドット蛍光体である必要はなく、例えばＺｎＳ：Ｍｎ２＋、ＣｄＳ：Ｍｎ２＋およびＹＶＯ４：Ｅｕ３＋のようなドープ型量子ドット蛍光体を用いることもできる。この場合、発光部となる希土類元素は、量子ドット構造により量子化の影響を受けており、希土類賦活蛍光体の発光部と異なる蛍光寿命を実現できるため、本発明の複合蛍光体を実現できる。 The second phosphor particles 3 need not be non-doped quantum dot phosphors. For example, doped quantum dot phosphors such as ZnS: Mn 2+ , CdS: Mn 2+ and YVO 4: Eu 3+ may be used. it can. In this case, the rare earth element serving as the light emitting portion is influenced by quantization due to the quantum dot structure, and can realize a fluorescence lifetime different from that of the light emitting portion of the rare earth activated phosphor, and thus the composite phosphor of the present invention can be realized.
　また、賦活剤も上記例に限られない。賦活剤を選ぶことで、第１の蛍光体粒子２および第２の蛍光体粒子３を共に希土類賦活蛍光体で構成することも可能である。例えば、一方の蛍光体の賦活剤を３価イオンで４ｆ－５ｄ遷移するＣｅ３＋、もう一方の蛍光体の賦活剤を、２価イオンで４ｆ－５ｄ遷移するＥｕ２＋もしくはＹｂ２＋を用いることで異なる蛍光寿命をもつ蛍光体の組み合わせを実現できる。さらには、異なる蛍光体の賦活剤として、４ｆ－４ｆ遷移を行うＥｕ３＋、Ｐｒ３＋、Ｎｄ３＋，Ｓｍ３＋のいずれか一つで構成することも可能である。 Moreover, an activator is not restricted to the said example. By selecting an activator, both the first phosphor particles 2 and the second phosphor particles 3 can be composed of rare earth activated phosphors. For example, by using Ce 3+ that makes 4f-5d transition with a trivalent ion as an activator of one phosphor and Eu 2+ or Yb 2+ that makes a 4f-5d transition with a divalent ion as an activator of the other phosphor. A combination of phosphors having different fluorescence lifetimes can be realized. Furthermore, as an activator of different phosphors, it is possible to comprise any one of Eu 3+ , Pr 3+ , Nd 3+ and Sm 3+ that perform 4f-4f transition.
　（実施の形態２）
　以下、実施の形態２の複合蛍光体について説明する。 (Embodiment 2)
Hereinafter, the composite phosphor of the second embodiment will be described.
　図８は、本発明の実施の形態２に係る複合蛍光体の構成を示す図である。図１と同様の要素には同一の符号を付しており、詳細な説明は省略する。 FIG. 8 is a diagram showing a configuration of the composite phosphor according to the second embodiment of the present invention. Elements similar to those in FIG. 1 are denoted by the same reference numerals, and detailed description thereof is omitted.
　本実施の形態において、図８に示す複合蛍光体１００は、第１の蛍光体粒子２と第２の蛍光体粒子３とカバー層９とで構成されている。より具体的には、複合蛍光体１００は、複数の蛍光発生部２ｂを有する第１の蛍光体粒子２の母材２ａが構成されており、複合蛍光体１（母材２ａ）の表面に、第２の蛍光体粒子３が配置されている。そして、第１の蛍光体粒子２と第２の蛍光体粒子３とを覆うように、例えば膜厚が０．１μｍ～５μｍのＳｉＯ２もしくはＳｉＮであるカバー層９が形成されている。 In the present embodiment, the composite phosphor 100 shown in FIG. 8 includes the first phosphor particles 2, the second phosphor particles 3, and the cover layer 9. More specifically, the composite phosphor 100 includes the base material 2a of the first phosphor particles 2 having a plurality of fluorescence generating portions 2b, and the surface of the composite phosphor 1 (base material 2a) Second phosphor particles 3 are arranged. A cover layer 9 made of, for example, SiO 2 or SiN having a thickness of 0.1 μm to 5 μm is formed so as to cover the first phosphor particles 2 and the second phosphor particles 3.
　カバー層９は、ガスバリア性の高い材料からなる。そして、カバー層９は、第１の蛍光体粒子２と第２の蛍光体粒子３とコートすることにより例えば第２の蛍光体粒子３に量子ドット蛍光体を用いても、量子ドット蛍光体が劣化することが少ないという効果を奏する。 The cover layer 9 is made of a material having a high gas barrier property. The cover layer 9 can be coated with the first phosphor particles 2 and the second phosphor particles 3 so that the quantum dot phosphors can be used even if, for example, the quantum dot phosphors are used for the second phosphor particles 3. There is an effect that there is little deterioration.
　ここで、カバー層９は例えば、ゾル・ゲル法により、第２の蛍光体粒子３を有する第１の蛍光体粒子２の表面にコートされる。具体的には、まず複合蛍光体１を含む有機溶媒にケイ素アルコキシドを添加した後、ケイ素アルコキシドを部分的に加水分解させることで、複合蛍光体１の表面が加水分解物で被覆された溶液を作製する。続いて　部分的に加水分解したケイ素アルコキシドを含む水溶液と、上記の溶液と混合することで、複合蛍光体１の表面をケイ素アルコキシドで覆う。続いて、エタノールを加えたアルカリ性水溶液を加えることで、ケイ素アルコキシドを反応させてカバー層９であるシリカ（ガラス）層を堆積させる。このようにして作製した複合蛍光体１００は、遠心分離と純化により取り出すことや樹脂中に分散させることが可能となる。 Here, the cover layer 9 is coated on the surface of the first phosphor particles 2 having the second phosphor particles 3 by, for example, a sol-gel method. Specifically, a silicon alkoxide is first added to an organic solvent containing the composite phosphor 1, and then the silicon alkoxide is partially hydrolyzed to obtain a solution in which the surface of the composite phosphor 1 is coated with a hydrolyzate. Make it. Subsequently, the surface of the composite phosphor 1 is covered with silicon alkoxide by mixing with an aqueous solution containing partially hydrolyzed silicon alkoxide and the above solution. Subsequently, by adding an alkaline aqueous solution to which ethanol is added, the silicon alkoxide is reacted to deposit a silica (glass) layer as the cover layer 9. The composite phosphor 100 produced in this way can be taken out by centrifugation and purification or dispersed in a resin.
　（変形例）
　図９は、本発明の実施の形態２に係る複合蛍光体の変形例の構成を示す図である。図１と同様の要素には同一の符号を付しており、詳細な説明は省略する。 (Modification)
FIG. 9 is a diagram showing a configuration of a modification of the composite phosphor according to Embodiment 2 of the present invention. Elements similar to those in FIG. 1 are denoted by the same reference numerals, and detailed description thereof is omitted.
　本変形における複合蛍光体１０１は、実施の形態２と比較して、第１の蛍光体粒子２の形状が不定形である点が異なる。しかし、この場合においても、実効的な表面を用いることで、第２の蛍光体粒子３の量を調整することができる。また、ゾル・ゲル法等により表面を容易にガスバリア性の高い膜で覆うことが可能である。 The composite phosphor 101 in this modification is different from the second embodiment in that the shape of the first phosphor particles 2 is indefinite. However, even in this case, the amount of the second phosphor particles 3 can be adjusted by using an effective surface. Further, the surface can be easily covered with a film having a high gas barrier property by a sol-gel method or the like.
　以上、本発明によれば、時間が経過しても蛍光体含有樹脂中の複数の蛍光体の濃度に分布が生じない複合蛍光体および発光装置を実現することができる。それにより、樹脂中において、時間が経過してもその濃度比が時間とともにほとんど変化せずに、高い演色性・色再現性の発光装置を安定的に提供することができる。 As described above, according to the present invention, it is possible to realize a composite phosphor and a light-emitting device in which distribution does not occur in the concentration of a plurality of phosphors in the phosphor-containing resin even if time passes. As a result, in the resin, the concentration ratio hardly changes with time even when time passes, and a light emitting device having high color rendering properties and color reproducibility can be stably provided.
　以上、本発明の複合蛍光体および発光装置について、実施の形態に基づいて説明したが、本発明は、この実施の形態に限定されるものではない。本発明の趣旨を逸脱しない限り、当業者が思いつく各種変形を本実施の形態に施したものや、異なる実施の形態における構成要素を組み合わせて構築される形態も、本発明の範囲内に含まれる。 As mentioned above, although the composite fluorescent substance and light-emitting device of this invention were demonstrated based on embodiment, this invention is not limited to this embodiment. Unless it deviates from the meaning of this invention, the form which carried out the various deformation | transformation which those skilled in the art will think to this embodiment, and the form constructed | assembled combining the component in different embodiment are also contained in the scope of the present invention. .
　本発明は、樹脂中においても安定的に演色性の良い蛍光体を実現することができるため、例えば、家庭用照明器具だけでなく、食料品を展示する展示用照明器具、又は表示映像の鮮明性が必要な大画面型液晶テレビのバックライト光源に有用である。 Since the present invention can realize a phosphor having a stable color rendering property even in a resin, for example, not only home lighting equipment but also display lighting equipment for displaying foodstuffs, or a clear display image. It is useful as a backlight light source for large-screen LCD TVs that require high performance.
　１、１００、１０１　　複合蛍光体
　２　　第１の蛍光体粒子
　２ａ　　母材
　２ｂ　　蛍光発生部
　２ｃ　　表面欠陥
　３　　第２の蛍光体粒子
　９　　カバー層
　１０　　パッケージ
　１１　　半導体発光素子
　１３、６６　　樹脂
　２０　　シリンジ
　２０ａ　　シリンジ上部
　２０ｂ　　シリンジ下部
　５０、１００１　　発光装置
　６０　　容器
　６１　　コロイド溶液
　６２　　混合液
　６３　　第二の混合液
　６５　　反発力
　７０　　励起光
　７３　　エネルギー
　７５、７７　　蛍光
　１００２、１００３　　リードワイヤ
　１００４　　青色半導体発光素子
　１００５　　金細線
　１００６　　第１の樹脂
　１００７　　蛍光体混合物
　１００８　　第２の樹脂 DESCRIPTION OF SYMBOLS 1,100,101 Composite fluorescent substance 2 1st fluorescent substance particle 2a Base material 2b Fluorescence generating part 2c Surface defect 3 2nd fluorescent substance particle 9 Cover layer 10 Package 11 Semiconductor light emitting element 13, 66 Resin 20 Syringe 20a Upper part of syringe 20b Lower syringe part 50, 1001 Light emitting device 60 Container 61 Colloidal solution 62 Mixed liquid 63 Second mixed liquid 65 Repulsive force 70 Excitation light 73 Energy 75, 77 Fluorescence 1002, 1003 Lead wire 1004 Blue semiconductor light emitting element 1005 Gold wire 1006 1st Resin 1007 Phosphor mixture 1008 Second resin

Claims (11)

  1. 　少なくとも粒径の異なる２種類以上の蛍光体粒子で構成される複合蛍光体であって、
    　第１の蛍光体粒子は、表面に密着された複数の第２の蛍光体粒子を有し、
    　前記第１の蛍光体粒子は、前記第２の蛍光体粒子よりも大きい
    　複合蛍光体。     A composite phosphor composed of at least two kinds of phosphor particles having different particle diameters,
    The first phosphor particles have a plurality of second phosphor particles adhered to the surface,
    The first phosphor particles are larger than the second phosphor particles.
  2. 　前記第１の蛍光体粒子の粒径は、前記第２の蛍光体粒子の粒径の１００倍以上である
    　請求項１に記載の複合蛍光体。     The composite phosphor according to claim 1, wherein the particle diameter of the first phosphor particles is 100 times or more than the particle diameter of the second phosphor particles.
  3. 　前記第２の蛍光体粒子は、量子ドット蛍光体で構成される
    　請求項１または２に記載の複合蛍光体。     The composite phosphor according to claim 1, wherein the second phosphor particle is configured by a quantum dot phosphor.
  4. 　前記第１の蛍光体粒子の粒径は、１μｍ～１００μｍである
    　請求項１～３のいずれか１項に記載の複合蛍光体。     The composite phosphor according to any one of claims 1 to 3, wherein the particle diameter of the first phosphor particles is 1 袖 m to 100 袖 m.
  5. 　前記第１の蛍光体粒子の蛍光スペクトルの中心波長は、前記第２の蛍光体粒子の蛍光スペクトルの中心波長よりも短い
    　請求項１～４のいずれか１項に記載の複合蛍光体。     The composite phosphor according to any one of claims 1 to 4, wherein a center wavelength of a fluorescence spectrum of the first phosphor particles is shorter than a center wavelength of a fluorescence spectrum of the second phosphor particles.
  6. 　前記第１の蛍光体粒子は、希土類元素賦活蛍光体で構成される
    　請求項１～５のいずれか１項に記載の複合蛍光体。     6. The composite phosphor according to claim 1, wherein the first phosphor particles are made of a rare earth element activated phosphor.
  7. 　前記第１の蛍光体粒子は、
    　（Ｙ，Ｇｄ）３Ａｌ４Ｏ１２：Ｃｅ、Ｙ３（Ａｌ，Ｇａ）４Ｏ１２：Ｃｅ、Ｔｂ３Ａｌ５Ｏ１２：Ｃｅ、（Ｓｒ，Ｃａ，Ｂａ）２ＳｉＯ４：Ｅｕ、Ｃａ－α－サイアロン：Ｅｕ、（Ｂａ，Ｓｒ）２ＳｉＯ４：Ｅｕ、Ｃａ３Ｓｃ２Ｓｉ３Ｏ１２：Ｃｅ，ＣａＳｃ２Ｏ４：Ｃｅ、β－サイアロン：Ｅｕ、（Ｓｒ，Ｂａ）Ｓｉ２Ｏ２Ｎ２：Ｅｕ、Ｂａ３Ｓｉ６Ｏ１２Ｎ２：Ｅｕ、ＣａＡｌＳｉＮ３：Ｅｕ、（Ｃａ，Ｓｒ）２Ｓｉ５Ｎ８：Ｅｕ、ＣａＡｌＳｉＮ３：Ｅｕ、（Ｓｒ，Ｃａ）Ｓ：Ｅｕ、Ｂａ３Ｓｉ６Ｏ１２Ｎ２：Ｅｕ，ＢａＭｇＡｌ１０Ｏ１７：（Ｅｕ，Ｍｎ）、ＳｒＡｌ２Ｏ４：Ｅｕ、（Ｓｒ，Ｃａ，Ｂａ，Ｍｇ）１０（ＰＯ４）６Ｃｌ２：Ｅｕ、および、（Ｂａ、Ｓｒ）ＭｇＡｌ１０Ｏ１７：Ｅｕのうちのいずれかで構成される
    　請求項１～６のいずれか１項に記載の複合蛍光体。     The first phosphor particles are:
    (Y, Gd) 3 Al 4 O 12: Ce, Y3 (Al, Ga) 4O12: Ce, Tb3Al5O12: Ce, (Sr, Ca, Ba) 2 SiO 4: Eu, Ca-α- sialon: Eu, (Ba , Sr) 2 SiO 4 : Eu, Ca 3 Sc 2 Si 3 O 12 : Ce, CaSc 2 O 4 : Ce, β-sialon: Eu, (Sr, Ba) Si 2 O 2 N 2 : Eu, Ba 3 Si 6 O 12 N 2 : Eu CaAlSiN 3 : Eu, (Ca, Sr) 2 Si 5 N 8 : Eu, CaAlSiN 3 : Eu, (Sr, Ca) S: Eu, Ba 3 Si 6 O 12 N 2 : Eu, BaMgAl 10 O 17: (Eu, Mn ), SrAl 2 O 4: Eu , (Sr, Ca, Ba, Mg) 10 (PO 4) 6 Cl 2: Eu, and, (Ba, Sr) MgAl 10 O 7: composite phosphor according to any one of constituted claims 1 to 6, in any of Eu.
  8. 　前記第２の蛍光体粒子は、量子ドット蛍光体であり、
    　前記量子ドット蛍光体は、ノンドープ型量子ドット蛍光体またはドープ型量子ドット蛍光体で構成される
    　請求項７に記載の複合蛍光体。     The second phosphor particles are quantum dot phosphors,
    The composite phosphor according to claim 7, wherein the quantum dot phosphor is composed of a non-doped quantum dot phosphor or a doped quantum dot phosphor.
  9. 　前記ノンドープ型量子ドットを構成する材料は、
    　ＩＩＩ－Ｖ族化合物半導体であるＩｎＮ、ＩｎＰ、ＩｎＡｓ、ＩｎＳｂ、ＧａＮ、ＧａＰ、ＧａＡｓ、ＧａＳｂ、ＡｌＮ、ＡｌＰ、ＡｌＡｓ、ＡｌＳｂおよびＢＮ、ＩＩ－ＶＩ族化合物半導体であるＨｇＳ、ＨｇＳｅ、ＨｇＴｅ、ＣｄＳ、ＣｄＳｅ、ＣｄＴｅ、ＺｎＳ、ＺｎＳｅおよびＺｎＴｅ、並びにこれらの混晶結晶よりなる群から選択されて構成される
    　請求項８に記載の複合蛍光体。     The material constituting the non-doped quantum dots is
    Group III-V compound semiconductors InN, InP, InAs, InSb, GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb and BN, Group II-VI compound semiconductors HgS, HgSe, HgTe, CdS, The composite phosphor according to claim 8, wherein the composite phosphor is selected from the group consisting of CdSe, CdTe, ZnS, ZnSe, ZnTe, and mixed crystal thereof.
  10. 　前記ドープ型量子ドット蛍光体を構成する材料は、ＺｎＳ：Ｍｎ２＋、ＣｄＳ：Ｍｎ２＋およびＹＶＯ４：Ｅｕ３＋により構成される
    　請求項８に記載の複合蛍光体。     The composite phosphor according to claim 8, wherein the material constituting the doped quantum dot phosphor is composed of ZnS: Mn 2+ , CdS: Mn 2+, and YVO 4: Eu 3+ .
  11. 　請求項１～１０のいずれか１項に記載の複合蛍光体と半導体発光装置とを少なくとも有する
    　発光装置。     A light emitting device comprising at least the composite phosphor according to any one of claims 1 to 10 and a semiconductor light emitting device.
PCT/JP2012/001674 2011-06-29 2012-03-09 Composite phosphor and light-emitting device WO2013001685A1 (en)

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