WO2013001685A1 - Luminophore composite et dispositif émettant de la lumière - Google Patents

Luminophore composite et dispositif émettant de la lumière 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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English (en)
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 having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502—Wavelength conversion materials
    • H01L33/504—Elements with two or more wavelength conversion materials

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.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Luminescent Compositions (AREA)
  • Led Device Packages (AREA)

Abstract

Ce luminophore composite (1) est configuré à partir d'au moins deux types de particules de luminophore ayant au moins des diamètres différents, de multiples secondes particules de luminophore (3) adhérant sur la surface des premières particules de luminophore (2) et les premières particules de luminophore (2) étant plus grandes que les secondes particules de luminophore (3). Par mélange de ces luminophores composites (1) dans une résine (13), le rapport des premières particules de luminophore (2) et des secondes particules de luminophore (3) ne change pas au cours du temps, présentant pour résultat que les coordonnées de chromaticité du dispositif émettant de la lumière, lorsqu'il est monté, ne sont pas sujettes à un déplacement.
PCT/JP2012/001674 2011-06-29 2012-03-09 Luminophore composite et dispositif émettant de la lumière WO2013001685A1 (fr)

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CN103642495A (zh) * 2013-12-13 2014-03-19 中国科学院长春应用化学研究所 一种核壳结构的发光材料及其制备方法
JP2017525832A (ja) * 2014-06-05 2017-09-07 ジョインスター バイオメディカル テクノロジー カンパニー リミテッド 担体粒子およびその製造方法
CN107978014A (zh) * 2017-12-21 2018-05-01 乐蜜有限公司 一种粒子渲染方法、装置、电子设备及存储介质
WO2018163830A1 (fr) * 2017-03-08 2018-09-13 パナソニックＩｐマネジメント株式会社 Dispositif de type source de lumière
WO2019058988A1 (fr) * 2017-09-25 2019-03-28 日本電気硝子株式会社 Élément de conversion de longueur d'onde
JP2019143117A (ja) * 2017-12-08 2019-08-29 奇美實業股▲ふん▼有限公司 ルミネセント材料ならびにそれを用いた発光デバイスおよび表示デバイス
CN110746957A (zh) * 2018-07-24 2020-02-04 Tcl集团股份有限公司 基于量子点的长余辉复合材料及其制备方法和应用
JP2020145240A (ja) * 2019-03-04 2020-09-10 中原大學 発光ダイオードパッケージ構造およびそれを製造する方法

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CN103627399A (zh) * 2013-12-13 2014-03-12 中国科学院长春应用化学研究所 一种半导体/荧光粉异质结构及其制备方法
CN103642495A (zh) * 2013-12-13 2014-03-19 中国科学院长春应用化学研究所 一种核壳结构的发光材料及其制备方法
CN103642495B (zh) * 2013-12-13 2015-05-20 中国科学院长春应用化学研究所 一种核壳结构的发光材料及其制备方法
JP2017525832A (ja) * 2014-06-05 2017-09-07 ジョインスター バイオメディカル テクノロジー カンパニー リミテッド 担体粒子およびその製造方法
KR20170117360A (ko) * 2014-06-05 2017-10-23 조인스타 바이오메디컬 테크놀로지 컴퍼니 리미티드 담체 입자 및 이의 제조 방법
US10421903B2 (en) 2014-06-05 2019-09-24 Joinstar Biomedical Technology Co., Ltd. Carrier particle and preparation method thereof
KR101974571B1 (ko) * 2014-06-05 2019-05-02 조인스타 바이오메디컬 테크놀로지 컴퍼니 리미티드 담체 입자 및 이의 제조 방법
WO2018163830A1 (fr) * 2017-03-08 2018-09-13 パナソニックＩｐマネジメント株式会社 Dispositif de type source de lumière
JP2019059802A (ja) * 2017-09-25 2019-04-18 日本電気硝子株式会社 波長変換部材
WO2019058988A1 (fr) * 2017-09-25 2019-03-28 日本電気硝子株式会社 Élément de conversion de longueur d'onde
JP2019143117A (ja) * 2017-12-08 2019-08-29 奇美實業股▲ふん▼有限公司 ルミネセント材料ならびにそれを用いた発光デバイスおよび表示デバイス
CN107978014A (zh) * 2017-12-21 2018-05-01 乐蜜有限公司 一种粒子渲染方法、装置、电子设备及存储介质
CN107978014B (zh) * 2017-12-21 2021-06-18 卓米私人有限公司 一种粒子渲染方法、装置、电子设备及存储介质
CN110746957A (zh) * 2018-07-24 2020-02-04 Tcl集团股份有限公司 基于量子点的长余辉复合材料及其制备方法和应用
CN110746957B (zh) * 2018-07-24 2021-02-05 Tcl科技集团股份有限公司 基于量子点的长余辉复合材料及其制备方法和应用
JP2020145240A (ja) * 2019-03-04 2020-09-10 中原大學 発光ダイオードパッケージ構造およびそれを製造する方法

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