WO2010140411A1 - Method for manufacturing light emitting device, and light emitting device - Google Patents

Method for manufacturing light emitting device, and light emitting device Download PDF

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Publication number
WO2010140411A1
WO2010140411A1 PCT/JP2010/053980 JP2010053980W WO2010140411A1 WO 2010140411 A1 WO2010140411 A1 WO 2010140411A1 JP 2010053980 W JP2010053980 W JP 2010053980W WO 2010140411 A1 WO2010140411 A1 WO 2010140411A1
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Prior art keywords
emitting device
light emitting
phosphor layer
light
led chip
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PCT/JP2010/053980
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French (fr)
Japanese (ja)
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仁 安達
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コニカミノルタオプト株式会社
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Priority to JP2011518336A priority Critical patent/JPWO2010140411A1/en
Publication of WO2010140411A1 publication Critical patent/WO2010140411A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—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
    • H01L33/507—Wavelength conversion elements the elements being in intimate contact with parts other than the semiconductor body or integrated with parts other than the semiconductor body
    • 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
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
    • H01L2224/13—Structure, shape, material or disposition of the bump connectors prior to the connecting process of an individual bump connector
    • 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
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
    • H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
    • H01L2224/161—Disposition
    • H01L2224/16151—Disposition the bump connector 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
    • H01L2224/16221—Disposition the bump connector 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
    • H01L2224/16225—Disposition the bump connector 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 non-metallic, e.g. insulating substrate with or without metallisation
    • 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
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/00011—Not relevant to the scope of the group, the symbol of which is combined with the symbol of this group
    • 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
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/00014—Technical content checked by a classifier the subject-matter covered by the group, the symbol of which is combined with the symbol of this group, being disclosed without further technical details
    • 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
    • H01L33/44—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 coatings, e.g. passivation layer or anti-reflective coating

Definitions

  • the present invention relates to a method for manufacturing a light emitting device and a light emitting device.
  • the present invention relates to a method for manufacturing a light-emitting device and a light-emitting device that are excellent in durability and color rendering while having high emission intensity.
  • white light emitting devices using LEDs have recently attracted attention as highly efficient and highly reliable white illumination light sources, and some of them have already been put into practical use as small power small light sources.
  • This type of white light emitting device is generally a blue LED element (also referred to as an LED chip) covered with a mixture of a phosphor that is excited by blue light and emits yellow light and a transparent resin.
  • a method of combining an ultraviolet LED element with a blue phosphor, a green phosphor, a red phosphor and the like has been developed, and white light emitting devices of these various methods are disclosed.
  • the phosphor layer is formed by dispersing the phosphor in the glass material
  • the phosphor particles are dispersed in the glass melted at a high temperature when the phosphor particles are dispersed in the glass.
  • the phosphor is deactivated by heat, the brightness at the beginning of use is lowered, or the color tone changes when used for a long time.
  • a method for obtaining a phosphor without a binder a method for obtaining a phosphor film having a filling rate of 60 to 97% by an aerosol deposition method is known (for example, see Patent Document 2). Since this method does not require a high vacuum, it is excellent in that the apparatus cost is relatively low and the phosphor can be recovered and reused.
  • the phosphor particles are subjected to a strong impact when colliding with the surface on which the phosphor layer is formed, so that defects are not introduced into the crystal lattice, and the phosphor emits light. There was a problem that efficiency decreased.
  • An object of the present invention is to provide a light-emitting device having excellent durability, little deterioration with time, and preventing a decrease in light emission efficiency to provide a high luminance, and a method for manufacturing the light-emitting device.
  • an LED chip a phosphor layer that absorbs at least a portion of light emitted from the LED chip, emits light after wavelength conversion, and the phosphor layer on the surface of the phosphor layer.
  • a method for manufacturing a light emitting device comprising at least one inorganic layer provided so as to cover The phosphor is produced by colliding and depositing phosphor particles against the light emitting surface of the LED chip or the surface of the base material provided separately from the LED chip and facing the light emitting surface of the LED chip.
  • a method for manufacturing a light emitting device wherein a layer is formed, and then at least one inorganic layer is provided on the surface of the phosphor layer so as to cover the phosphor layer.
  • an LED chip a phosphor layer that absorbs at least a part of light emitted from the LED chip, emits light after wavelength conversion, and the phosphor on the surface of the phosphor layer.
  • a light emitting device comprising: at least one inorganic layer provided to cover the layer.
  • the phosphor particles are placed on the surface on which the phosphor layer is formed at a low speed. Even when the phosphor layer is formed by colliding, the phosphor layer is covered with the inorganic layer, so that the adhesion strength of the phosphor layer to the substrate can be increased.
  • the phosphor layer is formed by colliding and depositing the phosphor particles on the surface on which the phosphor layer is formed, and further provided with an inorganic layer. Deterioration can be suppressed even when the light source has high luminance.
  • the light emitting device 100 of the present invention is provided on the LED chip 1, the base material 2, and one surface 2 a of the base material 2, and converts part of the light emission of the LED chip 1 to a different wavelength.
  • a phosphor layer 3 and a lens 4 that is provided on the other surface 2b of the substrate 2 and collects light emitted from the LED chip 1 and the phosphor layer 3 and emits the light in a desired direction are provided.
  • the phosphor layer 3 is provided on the base 2 provided separately from the LED chip 1, but the same effect can be obtained even if the phosphor layer 3 is provided on the light emitting surface of the LED chip 1. It is done.
  • the configuration in which the phosphor layer 3 is provided on the base 2 provided separately from the LED chip 1 suppresses heat generated in the LED chip 1 from being transmitted to the phosphor. And higher durability can be obtained.
  • the substrate 2 has a flat plate shape and is disposed to face the LED chip 1.
  • a material of the base material 2 The resin material, glass material, translucent ceramic (translucent alumina etc.) which consists of oxide particles, etc. are mentioned. From the viewpoint of preventing deterioration of the light source due to heat or light, the substrate preferably has high heat resistance and light resistance, and a glass material or a translucent ceramic material is preferably used.
  • resin it is preferable to use curable resin with high heat resistance.
  • the substrate 2 is fixed to the support 5. Instead of using the support 5, a material having the same composition as that of the substrate 2 may be used to form an integral structure.
  • the support 5 is fixed to the top of the mount 6.
  • the phosphor layer 3 is provided on the surface 2a (the lower surface in FIG. 1) 2a of the base material 2 through the base layer 7, and the surface opposite to the phosphor layer 3 is provided.
  • a lens 4 is provided on the upper surface 2b (in FIG. 1).
  • the lens 4 has a dome shape that is convex upward, and is made of a known resin material. Further, the lens 4 and the base material 2 may be integrated with the base material 2 using a material having the same composition as the lens 4.
  • An inorganic layer 8 is provided on the surface of the phosphor layer 3 so as to cover the phosphor layer 3, and the inorganic layer 8 has a function of protecting the phosphor layer 3 and increasing the adhesive strength of the phosphor layer 3. is doing.
  • the LED chip 1 has the transparent substrate 9 side facing the phosphor layer 3, and the LED chip 1 receives a signal from the lead wire 11 via the bump electrode 10 on the surface of the semiconductor layer.
  • the LED chip 1 is fixed by a transparent mold resin 12, and the outside is protected by a mount 6.
  • the phosphor layer 3, the inorganic layer 8, the base layer 7, and the LED chip 1 will be described in detail.
  • a phosphor that is a raw material of the phosphor layer an oxide or a compound that easily becomes an oxide at a high temperature is used as a raw material of Y, Gd, Ce, Sm, Al, La, and Ga, and these are stoichiometrically. The raw materials are obtained by thoroughly mixing in the ratio.
  • a coprecipitated oxide obtained by firing a solution obtained by coprecipitation of a solution obtained by dissolving a rare earth element of Y, Gd, Ce, or Sm in an acid at a stoichiometric ratio with oxalic acid, and aluminum oxide or gallium oxide.
  • An appropriate amount of fluoride such as ammonium fluoride is mixed with this as a flux and packed in a crucible and fired in air at a temperature range of 1350 to 1450 ° C. for 2 to 5 hours to obtain a fired product.
  • the desired phosphor can be obtained by ball-milling the fired product in water, washing, separating, drying, and finally passing through a sieve.
  • the phosphor particles are collided with the substrate to form a film.
  • the aerosol deposition method is preferably used.
  • FIG. 2 is a schematic configuration diagram of an aerosol deposition film forming apparatus 200 used in the present invention.
  • the aerosol deposition film forming apparatus 200 includes a holder 21 for holding a substrate 20, an XYZ ⁇ stage 22 for operating the holder 21 in three dimensions with XYZ ⁇ , a nozzle 23 having a narrow opening for ejecting a raw material onto the substrate 20, and a nozzle 23.
  • the chamber 26 includes a pipe 25 connected to the aerosol generation chamber 24, a high-pressure gas cylinder 27 for storing the carrier gas, an aerosol generation chamber 24 in which the fine particle raw material and the carrier gas are stirred and mixed, and a pipe 28 connecting these.
  • a temperature control mechanism using a Peltier element is installed on the back surface of the stage 22 so that the substrate 20 can be maintained at an optimum temperature.
  • the phosphor fine particle raw material in the aerosolization chamber is formed on the substrate surface by the following procedure.
  • the aerosolized particulate material passes through the pipe and is sprayed with a carrier gas from a nozzle having a narrow opening in the chamber together with a carrier gas to form a coating film.
  • the chamber is evacuated by a vacuum pump or the like, and the degree of vacuum in the chamber is adjusted as necessary.
  • the degree of vacuum is preferably 0.01 to 10000 Pa, more preferably 0.1 to 1000 Pa.
  • the substrate holder can be moved three-dimensionally by the XYZ ⁇ stage, a phosphor layer having a necessary thickness can be formed on a predetermined portion of the substrate.
  • the aerosolized raw material particles are preferably transported by a carrier gas having a flow rate of 50 to 400 m / sec and can be deposited by colliding with the substrate.
  • the particles transported by the carrier gas are bonded to each other by impact of collision to form a film.
  • the nitrogen gas is preferably an inert gas such as He gas.
  • nitrogen gas can be preferably used.
  • the specific function of the protective layer is not particularly limited as long as it has a function of increasing the adhesive strength of the phosphor layer, and preferably has a function of protecting the phosphor layer from damage such as scratching or chemical adhesion. Have.
  • the material constituting the inorganic layer is not particularly limited, but is preferably formed of an inorganic oxide film, and particularly preferably contains inorganic oxide particles.
  • the light from the LED chip is scattered by the inorganic oxide particles by forming the inorganic layer with an inorganic oxide film containing inorganic oxide particles.
  • the color shift between the scattered light of the LED chip and the light emitted from the phosphor excited by the scattered light is reduced, and the color mixing property is improved.
  • an inorganic layer can be firmly formed by containing an inorganic oxide particle.
  • the composition of the inorganic oxide particles according to the present invention is not particularly limited, but is preferably at least one of silicon oxide, aluminum oxide, zinc oxide, titanium oxide and zirconium oxide.
  • the average particle diameter of the inorganic oxide particles is from 100 nm to 1 ⁇ m, preferably from 200 to 800 nm, more preferably from 300 to 700 nm, from the viewpoint of the strength of the inorganic layer and the prevention of lowering the incident efficiency of light emitted from the LED chip.
  • a coating film obtained from a dispersion of inorganic oxide particles on the order of ⁇ m cannot be obtained simply by heat treatment, but the specific surface area is reduced because the inorganic oxide particles used are on the order of nm.
  • a robust inorganic oxide film can be formed by heat treatment.
  • the average particle diameters of the inorganic oxide particles and the phosphor fine particles in the present invention are the points at which the cumulative curve becomes 50% when the cumulative curve is obtained by setting the total volume of one group of particle bodies to 100%.
  • particle diameter cumulative average diameter
  • volume average particle diameter or median diameter means one that is generally used as one of parameters for evaluating particle size distribution.
  • the particle size of the inorganic oxide particles and phosphor particles used in the present invention can be measured using a general laser diffraction particle size measuring device, specifically, HELOS (manufactured by JEOL), MicrotracHRA (manufactured by Nikkiso Co., Ltd.), SALD-1100 (manufactured by Shimadzu Corp.), Coulter counter (manufactured by Coulter Corp.) and the like can be mentioned, and SALD-1100 (manufactured by Shimadzu Corp.) is particularly preferable.
  • HELOS manufactured by JEOL
  • MicrotracHRA manufactured by Nikkiso Co., Ltd.
  • SALD-1100 manufactured by Shimadzu Corp.
  • Coulter counter manufactured by Coulter Corp.
  • SALD-1100 manufactured by Shimadzu Corp.
  • the “inorganic oxide film” is a film containing an inorganic oxide, and includes at least the above-mentioned inorganic oxide particles and a compound having a polysiloxane structure for forming a silica-based film described later.
  • a film containing as a constituent element is preferably used.
  • the content of the inorganic oxide particles is preferably 30 to 99 vol%, more preferably 50 to 80 vol% of the inorganic oxide film.
  • the cross section of the film is observed with a transmission electron microscope, and the ratio of the total area of the inorganic fine particles contained in the total cross-sectional area of the inorganic oxide film Indicated. Since the original particle interface of the inorganic fine particles is observed in the film, the area where the inorganic fine particles are present can be quantified.
  • Inorganic oxide films can be formed by vapor deposition, dry processes, and wet processes such as sol-gel methods, but they all have crystal grain interfaces, so they do not have sufficient barrier properties against gases and water vapor.
  • the inclusion of inorganic oxide particles in the inorganic oxide film according to the present invention can minimize the occurrence of cracks that impair the barrier property, thereby improving the barrier property. Became possible.
  • Method for forming silica-based film As a method for forming a silica-based coating, first, a composition for forming a silica-based coating is applied on a substrate. As a method for applying the composition for forming a silica-based film on the substrate, for example, any method such as a spray method, a spin coating method, a dip coating method, a roll coating method can be used. Used.
  • the silica-based film forming composition applied on the substrate is heat-treated.
  • the means, temperature, time, etc. of the heat treatment are not particularly limited, but in general, it may be heated for about 1 to 6 minutes on a hot plate at about 80 to 300 ° C.
  • an acid or a base is generated by heating with a heat treatment. Hydrolysis is promoted by the generated acid or base, so that the alkoxy group becomes a hydroxyl group and alcohol is generated. Thereafter, a hydroxyl group is polycondensed between two molecules to form a Si—O—Si network, and thus a dense silica-based film can be obtained by heat treatment.
  • the heat treatment is preferably performed in three or more steps in a stepwise manner. Specifically, after the first heat treatment is performed for 30 seconds to 2 minutes on a hot plate of about 60 to 150 ° C. in an air or an inert gas atmosphere such as nitrogen, the temperature is about 100 to 220 ° C. The second heat treatment is performed for about 30 seconds to 2 minutes, and the third heat treatment is performed at about 150 to 300 ° C. for about 30 seconds to 2 minutes.
  • stepwise heat treatment of three or more steps preferably about 3 to 6 steps, a silica-based film can be formed at a lower temperature.
  • the above-described inorganic layer may be a single layer or a plurality of layers.
  • the underlayer is an inorganic oxide layer provided between the phosphor layer and the surface on which the phosphor layer is provided, and is an inorganic oxide film containing the same inorganic oxide particles as the inorganic layer. It is preferable.
  • the underlayer may be a single layer or a plurality of layers.
  • the adhesive strength of the phosphor layer to the surface on which the phosphor layer is provided can be increased. Further, the amount of light emitted from the phosphor layer can be increased by the underlayer.
  • LED chip Various known LED chips can be used as the LED chip. In particular, when obtaining white light, a blue LED chip or an ultraviolet LED chip can be preferably used. As the blue LED chip, any existing one including In x Ga 1-x N system can be used. The emission peak wavelength of the blue LED chip is preferably 440 to 480 nm. Any existing UV LED chip can be used. The emission peak wavelength of the ultraviolet LED chip is preferably 140 to 420 nm.
  • the LED chip can be mounted on a substrate and radiated upward or sideward, or a blue LED chip is mounted on a transparent substrate such as a sapphire substrate, and bumps are formed on the surface.
  • a blue LED chip is mounted on a transparent substrate such as a sapphire substrate, and bumps are formed on the surface.
  • it can be applied to any form of LED chip, such as flip chip connection type that flips over and connects to the electrode on the substrate, but it is suitable for manufacturing method of high brightness type or lens type Is more preferable.
  • the phosphor particles collide with the surface on which the phosphor layer is formed at a low speed. Even when the phosphor layer is formed by depositing, the phosphor layer is covered with an inorganic layer, so that the adhesive strength of the phosphor layer can be increased and it also functions as a protective layer. Therefore, a light-emitting device that has excellent durability and little deterioration with time can be obtained. Further, since it is not necessary to increase the collision speed of the phosphor particles to the surface on which the phosphor layer is formed, no defects occur in the crystal lattice due to the impact applied when the phosphor particles collide. As a result, a reduction in luminous efficiency of the phosphor can be prevented and high luminance can be achieved.
  • LED chip an In 0.2 Ga 0.8 N semiconductor having a main emission peak of 460 nm was used.
  • the LED chip is formed by flowing a TMG (trimethylgallium) gas, a TMI (trimethylindium) gas, a nitrogen gas and a dopant gas together with a carrier gas on a cleaned sapphire substrate, and forming a gallium nitride compound semiconductor film by MOCVD. Formed.
  • N-type conductivity gallium nitride semiconductor and P-type conductivity can be obtained.
  • a gallium nitride based semiconductor was formed, and a PN junction was formed.
  • the semiconductor light emitting device includes a contact layer that is a gallium nitride semiconductor having N-type conductivity, a cladding layer that is a gallium aluminum nitride semiconductor having P-type conductivity, and a contact layer that is a gallium nitride semiconductor having P-type conductivity. Formed.
  • a non-doped InGaN active layer having a single quantum well structure having a thickness of about 3 nm was formed between the contact layer having N-type conductivity and the cladding layer having P-type conductivity.
  • a gallium nitride semiconductor was formed on the sapphire substrate at a low temperature to form a buffer layer.
  • the semiconductor having P-type conductivity was annealed at 400 ° C. or higher after film formation.
  • each PN semiconductor on the sapphire substrate was exposed by etching. Further, there are a plurality of portions where the surface of each PN semiconductor is exposed for each LED chip to be finally formed. Further, the semiconductor layer is partially removed up to the sapphire substrate so that it can be divided into rectangles for each LED chip size and electrically separated.
  • a resist was formed in advance on the pad electrode forming surface for attaching a gold wire to be a conductive wire to form a semiconductor wafer. Thereafter, the resist was removed by lift-off.
  • a scribe line was formed with a scriber. Pressing with a roller along the scribe line from the side of the sapphire substrate, the LED chips were formed by dividing them individually.
  • a chip type LED package was formed using polycarbonate resin by insert molding.
  • the chip type LED package includes an opening in which the LED chip is disposed.
  • a silver-plated copper plate is disposed as an external electrode.
  • a gold wire as a conductive wire is wire-bonded and electrically connected to each electrode of the LED chip and each external electrode provided in the package.
  • 1000 blue light emitting LED chips were formed.
  • Method for producing phosphor A >> Phosphor A ...
  • the phosphor A was dispersed in an epoxy resin so as to be 10% by mass with respect to the resin, and coated on the surface of a flat glass having a thickness of 0.5 mm so that the dry film thickness was 7 ⁇ m. The coating surface was directed to the LED chip side, and was fixed and adhered to the upper part of the package to produce a white light emitting device of Comparative Example 1.
  • Comparative Example 3 A film was formed on the glass by the same method as Comparative Example 2 except that the flow rate of the carrier gas was changed to 100 m / s on the surface of a flat glass having a thickness of 0.5 mm. The surface on which the phosphor layer was formed was directed to the LED chip side, and was fixed and adhered to the upper part of the package to produce a white light emitting device of Comparative Example 3.
  • Example 1 In order to prepare a sol solution using an organometallic compound as a raw material, 0.04 mol of tetraethoxysilane (manufactured by Wako Pure Chemical Industries, Ltd.) was weighed in a polypropylene beaker. While stirring, 0.25 mol of ethyl alcohol was added and stirred for 10 minutes with a magnetic stirrer. Further, 0.24 mol of pure water was added and stirred for 10 minutes, and then 1 ml of 1 mol / L HCL was added to prepare sol solution-1.
  • tetraethoxysilane manufactured by Wako Pure Chemical Industries, Ltd.
  • Example 1 The sample of Example 1 was produced by coating with a spin coater and drying by heating in a dry oven at 150 ° C. for 30 minutes.
  • Example 2 400 g of pure water is put into a 1 L stainless steel pot, and 600 g of silicon oxide (trade name: SFP-20M average particle size: 300 nm) manufactured by Denki Kagaku Kogyo Co., Ltd. is used at 6000 rpm using an Ultra Turrax T25 Digital (IKA). It was added over 5 minutes and then dispersed for 30 minutes.
  • the acidic solution was neutralized with triethylamine ((C 2 H 5 ) 3 N) to obtain a neutralized solution.
  • the solvent of the neutralized solution was replaced with methyl ethyl ketone to obtain a resin solution-1 having a resin nonvolatile content concentration of 60% and a viscosity of 400 cp.
  • 30 g of Dispersion-1 and 70 g of Resin Solution-1 were mixed to obtain 100 g of inorganic oxide particle coating solution-1.
  • Example 3 Sample of Example 3 in the same manner as in Example 2 except that the silicon oxide was changed to trade name: SFP-30M manufactured by Denki Kagaku Kogyo Co., Ltd. (inorganic oxide particle coating solution-2). Was made.
  • Example 4 The sample of Example 4 was prepared in the same manner as in Example 3, except that the silicon oxide was changed to alumina particles (Nippon Light Metal Fine Alumina, trade name: A33F, average particle size 700 nm) (inorganic oxide particle coating solution-3). Was made.
  • Example 5 The sample of Example 5 was prepared in the same manner as in Example 3 except that the silicon oxide was changed to zirconia particles (zirconia powder product name: 3YB average particle size 700 nm, manufactured by Toray Industries, Inc.) (inorganic oxide particle coating solution-4). Produced.
  • Example 6 The surface of a flat glass having a thickness of 0.5 mm was coated with the inorganic oxide particle coating solution-3 so that the thickness after drying was 500 nm. Subsequently, phosphor A was formed on the coating surface by the same method as in Comparative Example 3. Further, the inorganic oxide particle coating solution-2 was coated on the phosphor layer in the same manner as in Example 3, and further dried by heating in a dry oven at 150 ° C. for 30 minutes to prepare a sample of Example 6. [Example 7] A sample of Example 7 was produced in the same manner as in Example 6 except that a dome-shaped glass lens was used instead of the flat glass having a thickness of 0.5 mm in Example 6.
  • White light can be emitted by supplying power to the obtained light-emitting device.
  • the emission intensity was measured from the front of the light emitting device. That is, by supplying power and performing continuous lighting, using a spectral radiance meter CS-1000 manufactured by Konica Minolta Sensing Co., Ltd., the integrated value in the wavelength region of 400 nm to 800 nm with respect to the emission luminance (cd / m 2 ) at the start of lighting.
  • Example 1 Expressed in (Relative value where the integral value of Example 1 is 100) Further, the emission peak intensities at 460 nm and 560 nm were measured at the same time, and expressed as relative values with the intensity at each wavelength in the white light emitting device of Example 1 as 100.
  • the color temperature and color rendering were measured from the front of the light emitting device, and the variation was measured as the area on the chromaticity coordinate. That is, the luminescent color of each light emitting device was measured at a viewing angle of 2 degrees using the spectral radiance meter CS-1000 (manufactured by Konica Minolta Sensing Co., Ltd.), and the color when this data was applied to chromaticity coordinates was determined as CIE1931. The X and Y chromaticity coordinates in the color system were obtained, and the variations of these 50 samples were plotted on the chromaticity coordinates to obtain the area on the chromaticity coordinates.
  • Example 1 was expressed as a relative value with 100 as the value.
  • Examples 1 to 7 provided with the inorganic layer have higher white light intensity than Comparative Examples 1 to 3 provided with no inorganic layer.
  • variations in color temperature and color rendering are small, and it is recognized that the environmental test evaluation and vibration test have high luminance, excellent durability, and little deterioration with time.

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  • Manufacturing & Machinery (AREA)
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Abstract

Disclosed is a method for manufacturing a light emitting device (100) which is provided with: an LED chip (1); a phosphor layer (3), which absorbs light emitted from the LED chip (1), converts the wavelength and emits light; and at least one inorganic layer (8) provided on the surface of the phosphor layer (3) so as to cover the phosphor layer (3). In the method, phosphor particles are made to collide with the light outgoing surface of the LED chip (1) or with the surface (2a) of a base material (2) separately provided from the LED chip, said surface (2a) facing the light outgoing surface of the LED chip (1), the particles are accumulated on the surface, and the phosphor layer (3) is formed. Then, on the surface of the phosphor layer (3), at least one inorganic layer is provided so as to cover the phosphor layer. The light emitting device has improved adhesion strength of the phosphor layer (3) even when the speed of the collision of the phosphor particles with the surface on which the phosphor layer (3) is to be formed is reduced. The light emitting device also has excellent durability, less deterioration with time, and furthermore, a high luminance by eliminating deterioration of light emitting efficiency.

Description

発光装置の製造方法及び発光装置Light emitting device manufacturing method and light emitting device
　本発明は、発光装置の製造方法及び発光装置に関する。特に、高い発光強度を有していながら、耐久性、演色性に優れた発光装置の製造方法及び発光装置に関する。 The present invention relates to a method for manufacturing a light emitting device and a light emitting device. In particular, the present invention relates to a method for manufacturing a light-emitting device and a light-emitting device that are excellent in durability and color rendering while having high emission intensity.
　ＬＥＤチップを使用し、その発光の一部を異なる波長に変換することによって、ＬＥＤチップの発光とは異なる所望の波長の光を得る技術が知られている。 2. Description of the Related Art A technique for obtaining light having a desired wavelength different from light emission of an LED chip by using an LED chip and converting a part of the light emission to a different wavelength is known.
　特にＬＥＤを用いた白色発光装置は、近年、高効率、高信頼性の白色照明光源として注目され、一部が微小電力小型光源として既に実用化されている。この種の白色発光装置は、青色ＬＥＤ素子（ＬＥＤチップともいう）を、青色光で励起されて黄色光を出射する蛍光体と透明樹脂との混合物で被覆したものが一般的である。さらに、紫外線ＬＥＤ素子を青色蛍光体、緑色蛍光体、赤色蛍光体などと組み合わせる方式も開発され、これら様々な方式の白色発光装置が開示されている。 In particular, white light emitting devices using LEDs have recently attracted attention as highly efficient and highly reliable white illumination light sources, and some of them have already been put into practical use as small power small light sources. This type of white light emitting device is generally a blue LED element (also referred to as an LED chip) covered with a mixture of a phosphor that is excited by blue light and emits yellow light and a transparent resin. Furthermore, a method of combining an ultraviolet LED element with a blue phosphor, a green phosphor, a red phosphor and the like has been developed, and white light emitting devices of these various methods are disclosed.
　しかしながら、樹脂やガラスに蛍光体粒子を分散させて蛍光体層を形成する方法においては、基材中で、蛍光体粒子が凝集し、均一な発光が得られないという問題が発生する場合があった。 However, in the method of forming the phosphor layer by dispersing the phosphor particles in resin or glass, there is a case where the phosphor particles aggregate in the base material and uniform light emission cannot be obtained. It was.
　また、基材として樹脂を用いた場合には、青色光や紫外線などの短波長の光はエネルギーが強いので樹脂を劣化させやすいという性質がある。また、ＬＥＤ光源の熱による劣化が生じる場合もある。そのため、このような構造の白色発光装置は、長時間使用していると樹脂が劣化して色調が変化する。また最近では、高出力ＬＥＤ素子を使用して白色発光装置を開発する動きがあるが、この場合限られた部分にきわめて強い青色光（または紫外線）が照射されるので樹脂の劣化が著しく、発光色の変化がきわめて短期間に起こる。また、樹脂モールドされた素子からの放熱性が悪いため、温度が上昇しやすく、温度上昇に伴って発光色の色調が黄色側にシフトするという問題があった。 In addition, when a resin is used as the base material, light having a short wavelength such as blue light or ultraviolet light has a strong energy, and thus has a property of easily deteriorating the resin. In addition, the LED light source may be deteriorated due to heat. Therefore, when the white light emitting device having such a structure is used for a long time, the resin deteriorates and the color tone changes. Recently, there has been a movement to develop a white light emitting device using a high-power LED element. In this case, a very strong blue light (or ultraviolet light) is irradiated to a limited part, so that the resin is significantly deteriorated and the light emission The color change occurs in a very short time. Moreover, since the heat dissipation from the resin-molded element is poor, there is a problem that the temperature is likely to rise and the color tone of the emitted color shifts to the yellow side as the temperature rises.
　また、蛍光体をガラス材料に分散させることで蛍光体層を形成した場合には、ガラス中に蛍光体粒子を分散される際には高温で溶融されたガラス中に蛍光体粒子を分散させるため、熱により蛍光体が失活してしまい、使用当初の輝度が低下したり、長時間使用した場合の色調の変化が問題となる場合があった。 In addition, when the phosphor layer is formed by dispersing the phosphor in the glass material, the phosphor particles are dispersed in the glass melted at a high temperature when the phosphor particles are dispersed in the glass. In some cases, the phosphor is deactivated by heat, the brightness at the beginning of use is lowered, or the color tone changes when used for a long time.
　この問題に対して、スパッタリングを用いて非粒子状性蛍光体膜を用いる方法が知られている（例えば、特許文献１参照）。しかしながら、この方法では、高真空を必要とするため、装置が高価である上、ターゲットとなる蛍光体の利用効率が低いとった問題があった。 For this problem, a method using a non-particulate phosphor film by sputtering is known (for example, see Patent Document 1). However, since this method requires a high vacuum, there are problems that the apparatus is expensive and the utilization efficiency of the target phosphor is low.
　また、バインダレスで蛍光体を得る方法として、エアロゾル・デポジション法により充填率が６０～９７％の蛍光体膜を得る方法が知られている（例えば、特許文献２参照）。この方法では高真空を必要としないため、比較的装置コストが安価である点や、蛍光体を回収し再利用できる点などが優れている。 In addition, as a method for obtaining a phosphor without a binder, a method for obtaining a phosphor film having a filling rate of 60 to 97% by an aerosol deposition method is known (for example, see Patent Document 2). Since this method does not require a high vacuum, it is excellent in that the apparatus cost is relatively low and the phosphor can be recovered and reused.
特開平１１－４６０１５号公報Japanese Patent Laid-Open No. 11-46015 特開２００６－３０３００１号公報JP 2006-303001 A
　しかしながら、上記エアロゾル・デポジション法においては、蛍光体粒子が、蛍光体層が形成される面と衝突する際に強い衝撃が加わることで、結晶格子に欠陥が導入されていまい、蛍光体の発光効率が低下するという問題があった。 However, in the above-described aerosol deposition method, the phosphor particles are subjected to a strong impact when colliding with the surface on which the phosphor layer is formed, so that defects are not introduced into the crystal lattice, and the phosphor emits light. There was a problem that efficiency decreased.
　そこで、蛍光体粒子の基材への衝突速度を低下させる方法があるが、衝突速度を低下させると、膜強度が低下し剥離しやすいという問題が生じる。 Therefore, there is a method of reducing the collision speed of the phosphor particles to the base material. However, when the collision speed is reduced, there arises a problem that the film strength is lowered and the film is easily peeled off.
　本発明は、上記事情に鑑みてなされたもので、蛍光体粒子の蛍光体層が形成される面への衝突速度を下げた場合であっても、蛍光体層の接着強度を上げることができ、耐久性に優れ、経時劣化が少なく、しかも、発光効率の低下を防いで高輝度の発光装置を提供すること及び当該発光装置の製造方法を提供することを目的としている。 The present invention has been made in view of the above circumstances, and even when the collision speed of the phosphor particles to the surface on which the phosphor layer is formed is lowered, the adhesion strength of the phosphor layer can be increased. An object of the present invention is to provide a light-emitting device having excellent durability, little deterioration with time, and preventing a decrease in light emission efficiency to provide a high luminance, and a method for manufacturing the light-emitting device.
　本発明の一態様によれば、ＬＥＤチップと、前記ＬＥＤチップからの発光の少なくとも一部を吸収し、波長変換して発光する蛍光体層と、前記蛍光体層の表面に、前記蛍光体層を被覆するように設けられた少なくとも１層の無機層とを備えた発光装置の製造方法において、
　前記ＬＥＤチップの光出射面または、前記ＬＥＤチップとは別個に設けられた基材の前記ＬＥＤチップの光出射面に対向する面に対して蛍光体粒子を衝突させて堆積することによって前記蛍光体層を成膜し、次いで、前記蛍光体層の表面に、前記蛍光体層を被覆するように少なくとも１層の無機層を設けることを特徴とする発光装置の製造方法が提供される。 According to one aspect of the present invention, an LED chip, a phosphor layer that absorbs at least a portion of light emitted from the LED chip, emits light after wavelength conversion, and the phosphor layer on the surface of the phosphor layer. In a method for manufacturing a light emitting device comprising at least one inorganic layer provided so as to cover
The phosphor is produced by colliding and depositing phosphor particles against the light emitting surface of the LED chip or the surface of the base material provided separately from the LED chip and facing the light emitting surface of the LED chip. There is provided a method for manufacturing a light emitting device, wherein a layer is formed, and then at least one inorganic layer is provided on the surface of the phosphor layer so as to cover the phosphor layer.
　本発明の他の態様によれば、ＬＥＤチップと、前記ＬＥＤチップからの発光の少なくとも一部を吸収し、波長変換して発光する蛍光体層と、前記蛍光体層の表面に、前記蛍光体層を被覆するように設けられた少なくとも１層の無機層とを備えることを特徴とする発光装置が提供される。 According to another aspect of the present invention, an LED chip, a phosphor layer that absorbs at least a part of light emitted from the LED chip, emits light after wavelength conversion, and the phosphor on the surface of the phosphor layer. There is provided a light emitting device comprising: at least one inorganic layer provided to cover the layer.
　本発明によれば、蛍光体層の表面には、蛍光体層を被覆するように少なくとも１層の無機層が設けられているので、蛍光体粒子を蛍光体層が形成される面に低速で衝突させて堆積することによって蛍光体層を形成した場合であっても、蛍光体層が無機層で被覆されるため、基材に対する蛍光体層の接着強度を上げることができる。また、蛍光体粒子を蛍光体層が形成される面に低速で衝突させて堆積させることで蛍光体層を形成し、さらに無機層を設ける構成であるため、樹脂材料を用いる必要がなく、ＬＥＤ光源が高輝度であっても劣化を抑制できる。したがって、耐久性に優れ、経時劣化の少ない発光装置とすることができる。また、蛍光体粒子の基材への衝突速度を上げる必要がなくなるので、蛍光体粒子が基材に衝突する際に加わる衝撃によって結晶格子に欠陥が生じることも無い。その結果、蛍光体の発光効率の低下を防いでより高輝度とすることができる。 According to the present invention, since at least one inorganic layer is provided on the surface of the phosphor layer so as to cover the phosphor layer, the phosphor particles are placed on the surface on which the phosphor layer is formed at a low speed. Even when the phosphor layer is formed by colliding, the phosphor layer is covered with the inorganic layer, so that the adhesion strength of the phosphor layer to the substrate can be increased. In addition, the phosphor layer is formed by colliding and depositing the phosphor particles on the surface on which the phosphor layer is formed, and further provided with an inorganic layer. Deterioration can be suppressed even when the light source has high luminance. Therefore, a light-emitting device that has excellent durability and little deterioration with time can be obtained. In addition, since it is not necessary to increase the collision speed of the phosphor particles to the base material, no defects are generated in the crystal lattice due to the impact applied when the phosphor particles collide with the base material. As a result, the luminance efficiency of the phosphor can be prevented from being lowered and the luminance can be increased.
本発明の発光装置の基本的構成を示す断面図である。It is sectional drawing which shows the basic composition of the light-emitting device of this invention. 本発明の発光装置の製造方法に用いられる成膜装置の例であるエアロゾル・デポジション成膜装置の概略構成図である。It is a schematic block diagram of the aerosol deposition film-forming apparatus which is an example of the film-forming apparatus used for the manufacturing method of the light-emitting device of this invention.
　以下、図面を参照しながら本発明の好ましい実施形態について説明する。 Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings.
　図１に示す通り、本発明の発光装置１００は、ＬＥＤチップ１と、基材２と、基材２の一方の面２ａに設けられてＬＥＤチップ１の発光の一部を異なる波長に変換する蛍光体層３と、基材２の他方の面２ｂに設けられてＬＥＤチップ１及び蛍光体層３の発光を集光し所望の方向に放射するレンズ４と、を備えている。ここでは、蛍光体層３をＬＥＤチップ１とは別個に設けられた基材２上に設ける構成としたが、蛍光体層３をＬＥＤチップ１の発光面上に設けても同様の効果が得られる。ただし、耐久性の観点では、蛍光体層３をＬＥＤチップ１とは別個に設けられた基材２上に設ける構成の方が、ＬＥＤチップ１で発生した熱が蛍光体に伝わることを抑制することが可能となり、より高い耐久性が得られる。 As shown in FIG. 1, the light emitting device 100 of the present invention is provided on the LED chip 1, the base material 2, and one surface 2 a of the base material 2, and converts part of the light emission of the LED chip 1 to a different wavelength. A phosphor layer 3 and a lens 4 that is provided on the other surface 2b of the substrate 2 and collects light emitted from the LED chip 1 and the phosphor layer 3 and emits the light in a desired direction are provided. Here, the phosphor layer 3 is provided on the base 2 provided separately from the LED chip 1, but the same effect can be obtained even if the phosphor layer 3 is provided on the light emitting surface of the LED chip 1. It is done. However, from the viewpoint of durability, the configuration in which the phosphor layer 3 is provided on the base 2 provided separately from the LED chip 1 suppresses heat generated in the LED chip 1 from being transmitted to the phosphor. And higher durability can be obtained.
　基材２は、平板状をなしＬＥＤチップ１に対向して配置されている。基材２の材料としては、特に制限はなく、樹脂材料、ガラス材料、酸化物粒子からなる透光性セラミック（透光性アルミナ等）等が挙げられる。光源の熱や光による劣化を防止する観点で、基材は高い耐熱、耐光性を有することが好ましく、ガラス材料や透光性セラミック材料が好ましく用いられる。樹脂を用いる場合には、耐熱性の高い硬化性樹脂を用いることが好ましい。基材２は支持体５に固定されている。支持体５を用いることなく、基材２と同一組成の材料を用いて一体構成にしても良い。支持体５はマウント６の上部に固定されている。 The substrate 2 has a flat plate shape and is disposed to face the LED chip 1. There is no restriction | limiting in particular as a material of the base material 2, The resin material, glass material, translucent ceramic (translucent alumina etc.) which consists of oxide particles, etc. are mentioned. From the viewpoint of preventing deterioration of the light source due to heat or light, the substrate preferably has high heat resistance and light resistance, and a glass material or a translucent ceramic material is preferably used. When using resin, it is preferable to use curable resin with high heat resistance. The substrate 2 is fixed to the support 5. Instead of using the support 5, a material having the same composition as that of the substrate 2 may be used to form an integral structure. The support 5 is fixed to the top of the mount 6.
　ここでは、基材２のＬＥＤチップ１に対向する面（図１中、下面）２ａに、下地層７を介して蛍光体層３が設けられており、蛍光体層３とは反対側の面（図１中、上面）２ｂにレンズ４が設けられている。 Here, the phosphor layer 3 is provided on the surface 2a (the lower surface in FIG. 1) 2a of the base material 2 through the base layer 7, and the surface opposite to the phosphor layer 3 is provided. A lens 4 is provided on the upper surface 2b (in FIG. 1).
　レンズ４は、上向きに凸となるドーム状をなし、公知の樹脂素材からなる。また、基材２をレンズ４と同一組成の材料を用いてレンズ４と基材２とを一体構成にしても良い。 The lens 4 has a dome shape that is convex upward, and is made of a known resin material. Further, the lens 4 and the base material 2 may be integrated with the base material 2 using a material having the same composition as the lens 4.
　なお、基材２と蛍光体層３との間の下地層７は、少なくとも１層以上設けることが好ましい。 In addition, it is preferable to provide at least one base layer 7 between the base material 2 and the phosphor layer 3.
　蛍光体層３の表面には、蛍光体層３を被覆するように無機層８が設けられ、無機層８は蛍光体層３を保護するとともに、蛍光体層３の接着強度を高める機能を有している。 An inorganic layer 8 is provided on the surface of the phosphor layer 3 so as to cover the phosphor layer 3, and the inorganic layer 8 has a function of protecting the phosphor layer 3 and increasing the adhesive strength of the phosphor layer 3. is doing.
　ＬＥＤチップ１は透明基板９側を蛍光体層３と対向させ、ＬＥＤチップ１は半導体層の表面にバンプ電極１０を介してリード線１１から信号を受ける。ＬＥＤチップ１は透明なモールド樹脂１２により固定され、さらに外部をマウント６で保護されている。 The LED chip 1 has the transparent substrate 9 side facing the phosphor layer 3, and the LED chip 1 receives a signal from the lead wire 11 via the bump electrode 10 on the surface of the semiconductor layer. The LED chip 1 is fixed by a transparent mold resin 12, and the outside is protected by a mount 6.
　以下、蛍光体層３、無機層８、下地層７、ＬＥＤチップ１について詳細に説明する。
［蛍光体層］
　蛍光体層の原料である蛍光体としては、Ｙ、Ｇｄ、Ｃｅ、Ｓｍ、Ａｌ、Ｌａ及びＧａの原料として酸化物、または高温で容易に酸化物になる化合物を使用し、それらを化学量論比で十分に混合して原料を得る。または、Ｙ、Ｇｄ、Ｃｅ、Ｓｍの希土類元素を化学量論比で酸に溶解した溶解液を蓚酸で共沈したものを焼成して得られる共沈酸化物と、酸化アルミニウム、酸化ガリウムとを混合して混合原料を得る。これにフラックスとしてフッ化アンモニウム等のフッ化物を適量混合して坩堝に詰め、空気中１３５０～１４５０℃の温度範囲で２～５時間焼成して焼成品を得る。次に、焼成品を水中でボールミルして、洗浄、分離、乾燥、最後に篩いを通すことで所望の蛍光体を得ることができる。 Hereinafter, the phosphor layer 3, the inorganic layer 8, the base layer 7, and the LED chip 1 will be described in detail.
[Phosphor layer]
As a phosphor that is a raw material of the phosphor layer, an oxide or a compound that easily becomes an oxide at a high temperature is used as a raw material of Y, Gd, Ce, Sm, Al, La, and Ga, and these are stoichiometrically. The raw materials are obtained by thoroughly mixing in the ratio. Alternatively, a coprecipitated oxide obtained by firing a solution obtained by coprecipitation of a solution obtained by dissolving a rare earth element of Y, Gd, Ce, or Sm in an acid at a stoichiometric ratio with oxalic acid, and aluminum oxide or gallium oxide. Mix to obtain a mixed raw material. An appropriate amount of fluoride such as ammonium fluoride is mixed with this as a flux and packed in a crucible and fired in air at a temperature range of 1350 to 1450 ° C. for 2 to 5 hours to obtain a fired product. Next, the desired phosphor can be obtained by ball-milling the fired product in water, washing, separating, drying, and finally passing through a sieve.
　蛍光体層の形成には、蛍光体の微粒子を基材に衝突させて成膜する。具体的には、エアロゾル・デポジション法が好ましく用いられる。 In forming the phosphor layer, the phosphor particles are collided with the substrate to form a film. Specifically, the aerosol deposition method is preferably used.
　エアロゾル・デポジション法による成膜装置としては、「応用物理」誌６８巻１号４４ページ、特開２００３－２１５２５６号公報等に開示されている構成などを利用することができる。 As a film forming apparatus using the aerosol deposition method, a configuration disclosed in “Applied Physics”, Vol. 68, No. 1, page 44, Japanese Patent Laid-Open No. 2003-215256, and the like can be used.
　図２は、本発明に用いられるエアロゾル・デポジション成膜装置２００の概略構成図である。エアロゾル・デポジション成膜装置２００は、基板２０を保持するホルダー２１、ホルダー２１をＸＹＺθで３次元に作動させるＸＹＺθステージ２２、基板２０に原料を噴出させる細い開口を備えたノズル２３、ノズル２３をエアロゾル化室２４と繋ぐ配管２５を備えたチャンバー２６、さらに、搬送ガスを貯留する高圧ガスボンベ２７、微粒子原料とキャリアガスが攪拌・混合されるエアロゾル化室２４及びこれらを繋ぐ配管２８によって構成される。ステージ２２の裏面にはペルチェ素子による温度制御機構が設置され、基板２０を最適な温度に保つことができる。 FIG. 2 is a schematic configuration diagram of an aerosol deposition film forming apparatus 200 used in the present invention. The aerosol deposition film forming apparatus 200 includes a holder 21 for holding a substrate 20, an XYZθ stage 22 for operating the holder 21 in three dimensions with XYZθ, a nozzle 23 having a narrow opening for ejecting a raw material onto the substrate 20, and a nozzle 23. The chamber 26 includes a pipe 25 connected to the aerosol generation chamber 24, a high-pressure gas cylinder 27 for storing the carrier gas, an aerosol generation chamber 24 in which the fine particle raw material and the carrier gas are stirred and mixed, and a pipe 28 connecting these. . A temperature control mechanism using a Peltier element is installed on the back surface of the stage 22 so that the substrate 20 can be maintained at an optimum temperature.
　さらに、エアロゾル化室内の蛍光体微粒子原料は、以下のような手順によって基材表面に形成される。 Furthermore, the phosphor fine particle raw material in the aerosolization chamber is formed on the substrate surface by the following procedure.
　エアロゾル化室内に充填された、好ましくは０．０２～５μｍ、より好ましくは０．１～２μｍの粒径の蛍光体微粒子原料は、キャリアガスを貯留する高圧ガスボンベより配管を通ってエアロゾル化室に導入されキャリアガスとともに、振動・攪拌されてエアロゾル化される。 The phosphor fine particle raw material having a particle size of preferably 0.02 to 5 μm, more preferably 0.1 to 2 μm, which is filled in the aerosolization chamber, passes from the high-pressure gas cylinder storing the carrier gas through the pipe to the aerosolization chamber. Introduced and agitated with carrier gas to be aerosolized.
　エアロゾル化された微粒子原料は配管を通り、チャンバー内の細い開口を備えたノズルから基板にキャリアガスとともに吹き付けられ塗膜を形成する。チャンバーは真空ポンプ等で排気され、チャンバー内の真空度は必要に応じて調整されている。本発明では真空度は、好ましくは０．０１～１００００Ｐａであり、さらに好ましくは０．１～１０００Ｐａである。さらに、基板のホルダーはＸＹＺθステージにより３次元に動くことができるため、基板の所定の部分に必要な厚みの蛍光体層が形成できる。 The aerosolized particulate material passes through the pipe and is sprayed with a carrier gas from a nozzle having a narrow opening in the chamber together with a carrier gas to form a coating film. The chamber is evacuated by a vacuum pump or the like, and the degree of vacuum in the chamber is adjusted as necessary. In the present invention, the degree of vacuum is preferably 0.01 to 10000 Pa, more preferably 0.1 to 1000 Pa. Further, since the substrate holder can be moved three-dimensionally by the XYZθ stage, a phosphor layer having a necessary thickness can be formed on a predetermined portion of the substrate.
　エアロゾル化された原料粒子は、好ましくは流速５０～４００ｍ／ｓｅｃのキャリアガスによって搬送され、基材上に衝突することによって堆積することができる。キャリアガスによって搬送された粒子は、互いに衝突の衝撃によって接合し、膜を形成する。本発明においては、高い蛍光体強度を得る目的から、流速５０～１８０ｍ／ｓｅｃで成膜することが特に好ましい。 The aerosolized raw material particles are preferably transported by a carrier gas having a flow rate of 50 to 400 m / sec and can be deposited by colliding with the substrate. The particles transported by the carrier gas are bonded to each other by impact of collision to form a film. In the present invention, it is particularly preferable to form a film at a flow rate of 50 to 180 m / sec for the purpose of obtaining a high phosphor intensity.
　本発明の製造方法において、原料粒子を加速・噴出するためのキャリアガスとしては、窒素ガスはＨｅガスなどの不活性ガスが好ましい。特に窒素ガスを好ましく用いることができる。
［無機層］
　保護層の具体的な機能は特に限定されず、蛍光体層の接着強度を高める機能を有していればよく、好ましくは、蛍光体層を傷つきや薬品付着などの損傷から保護しうる機能を有する。無機層を構成する材料についても、特に限定はないが、無機酸化物膜で形成されていることが好ましく、特に無機酸化物粒子を含有することが好ましい。 In the production method of the present invention, as the carrier gas for accelerating and ejecting the raw material particles, the nitrogen gas is preferably an inert gas such as He gas. In particular, nitrogen gas can be preferably used.
[Inorganic layer]
The specific function of the protective layer is not particularly limited as long as it has a function of increasing the adhesive strength of the phosphor layer, and preferably has a function of protecting the phosphor layer from damage such as scratching or chemical adhesion. Have. The material constituting the inorganic layer is not particularly limited, but is preferably formed of an inorganic oxide film, and particularly preferably contains inorganic oxide particles.
　無機層を、無機酸化物粒子を含有する無機酸化物膜で形成することによって、ＬＥＤチップからの光が無機酸化物粒子により散乱される。その結果、このＬＥＤチップの散乱光と、散乱光により励起される蛍光体から発する光との色ズレが低減され、混色性が向上する。また、無機酸化物粒子を含有することで、無機層を強固に形成することができる。 The light from the LED chip is scattered by the inorganic oxide particles by forming the inorganic layer with an inorganic oxide film containing inorganic oxide particles. As a result, the color shift between the scattered light of the LED chip and the light emitted from the phosphor excited by the scattered light is reduced, and the color mixing property is improved. Moreover, an inorganic layer can be firmly formed by containing an inorganic oxide particle.
　（無機酸化物粒子）
　本発明に係る無機酸化物粒子の組成は特に制限は無いが、酸化珪素、酸化アルミニウム、酸化亜鉛、酸化チタン及び酸化ジルコニウムの少なくともいずれかであることが好ましい。 (Inorganic oxide particles)
The composition of the inorganic oxide particles according to the present invention is not particularly limited, but is preferably at least one of silicon oxide, aluminum oxide, zinc oxide, titanium oxide and zirconium oxide.
　無機酸化物粒子の平均粒径は、無機層の強度の面およびＬＥＤチップからの発光の入射効率低下防止の面から、１００ｎｍ～１μｍ、好ましくは２００～８００ｎｍ、さらに好ましくは３００～７００ｎｍである。 The average particle diameter of the inorganic oxide particles is from 100 nm to 1 μm, preferably from 200 to 800 nm, more preferably from 300 to 700 nm, from the viewpoint of the strength of the inorganic layer and the prevention of lowering the incident efficiency of light emitted from the LED chip.
　つまりμｍオーダーの無機酸化物粒子の分散液より得られた塗膜を加熱処理するだけでは強固な塗膜は得られないが、使用する無機酸化物粒子がｎｍオーダーであることにより、比表面積が増大することで反応性が向上し、加熱処理によって強固な無機酸化物膜を形成できる。 In other words, a coating film obtained from a dispersion of inorganic oxide particles on the order of μm cannot be obtained simply by heat treatment, but the specific surface area is reduced because the inorganic oxide particles used are on the order of nm. By increasing the reactivity, a robust inorganic oxide film can be formed by heat treatment.
　ここで、本発明における無機酸化物粒子及び蛍光体微粒子の平均粒径とは、粒子体の一つの集団の全体積を１００％として累積曲線を求めた時、累積曲線が５０％となる点の粒子径（累積平均径）を意味しており、体積平均粒径、メジアン径とも呼ばれ、粒度分布を評価するパラメータの一つとして、一般的に利用されているものを意味する。 Here, the average particle diameters of the inorganic oxide particles and the phosphor fine particles in the present invention are the points at which the cumulative curve becomes 50% when the cumulative curve is obtained by setting the total volume of one group of particle bodies to 100%. This means particle diameter (cumulative average diameter), which is also called volume average particle diameter or median diameter, and means one that is generally used as one of parameters for evaluating particle size distribution.
　なお、本発明で用いられる無機酸化物粒子及び蛍光体粒子の粒径は、一般的なレーザー回折式粒径測定装置を用いて測定可能であり、具体的には、HELOS(JEOL社製)、MicrotracHRA(日機装社製)、SALD-1100(島津製作所社製)、コールターカウンター（コールター社製）などが挙げられ、特に好ましくはSALD-1100(島津製作所社製)である。 The particle size of the inorganic oxide particles and phosphor particles used in the present invention can be measured using a general laser diffraction particle size measuring device, specifically, HELOS (manufactured by JEOL), MicrotracHRA (manufactured by Nikkiso Co., Ltd.), SALD-1100 (manufactured by Shimadzu Corp.), Coulter counter (manufactured by Coulter Corp.) and the like can be mentioned, and SALD-1100 (manufactured by Shimadzu Corp.) is particularly preferable.
　（無機酸化物膜）
　本発明に係る「無機酸化物膜」とは、無機酸化物を含有する膜であり、少なくとも上記の無機酸化物粒子と後述するシリカ系被膜を形成するためのポリシロキサン構造を有する化合物とをその構成要素として含有する膜が、好ましく用いられる。 (Inorganic oxide film)
The “inorganic oxide film” according to the present invention is a film containing an inorganic oxide, and includes at least the above-mentioned inorganic oxide particles and a compound having a polysiloxane structure for forming a silica-based film described later. A film containing as a constituent element is preferably used.
　無機酸化物粒子の含有率は、無機酸化物膜の３０～９９ｖｏｌ％が好ましく、５０～８０ｖｏｌ％がさらに好ましい。 The content of the inorganic oxide particles is preferably 30 to 99 vol%, more preferably 50 to 80 vol% of the inorganic oxide film.
　無機酸化物膜中の無機酸化物粒子の含有率については、フィルムの断面を透過型電子顕微鏡で観察を行い、無機酸化物膜の全断面積中に含まれる無機微粒子の面積の合計の割合で示される。無機微粒子は膜中で元の粒子界面が観察されることから、無機微粒子の存在する面積を定量することが可能である。無機酸化物膜は蒸着などとドライプロセスや、ゾルゲル法といったウェットプロセスにて成膜可能であるが、いずれも結晶の粒界面が存在するため、ガスや水蒸気に対してのバリア性が十分ではなかったが、本発明に係る無機酸化物膜中に無機酸化物粒子が含有されていることにより、バリア性を損なう原因となるクラックの発生を極小化することができるため、バリア性を向上することが可能となった。 Regarding the content of the inorganic oxide particles in the inorganic oxide film, the cross section of the film is observed with a transmission electron microscope, and the ratio of the total area of the inorganic fine particles contained in the total cross-sectional area of the inorganic oxide film Indicated. Since the original particle interface of the inorganic fine particles is observed in the film, the area where the inorganic fine particles are present can be quantified. Inorganic oxide films can be formed by vapor deposition, dry processes, and wet processes such as sol-gel methods, but they all have crystal grain interfaces, so they do not have sufficient barrier properties against gases and water vapor. However, the inclusion of inorganic oxide particles in the inorganic oxide film according to the present invention can minimize the occurrence of cracks that impair the barrier property, thereby improving the barrier property. Became possible.
　（シリカ系被膜の形成方法）
　シリカ系被膜の形成方法としては、まず、シリカ系被膜形成用組成物を基板上に塗布する。基板上にシリカ系被膜形成用組成物を塗布する方法としては、例えば、スプレー法、スピンコート法、ディップコート法、ロールコート法など、任意の方法を用いることができるが、通常スピンコート法が用いられる。 (Method for forming silica-based film)
As a method for forming a silica-based coating, first, a composition for forming a silica-based coating is applied on a substrate. As a method for applying the composition for forming a silica-based film on the substrate, for example, any method such as a spray method, a spin coating method, a dip coating method, a roll coating method can be used. Used.
　次に、基板上に塗布されたシリカ系被膜形成用組成物を加熱処理する。加熱処理は、その手段、温度、時間などについては特に制限されないが、一般的には、８０～３００℃程度のホットプレート上で１～６分間程度加熱すればよい。 Next, the silica-based film forming composition applied on the substrate is heat-treated. The means, temperature, time, etc. of the heat treatment are not particularly limited, but in general, it may be heated for about 1 to 6 minutes on a hot plate at about 80 to 300 ° C.
　上記シリカ系被膜形成用組成物によれば、加熱処理により加熱することで、酸または塩基が発生する。この発生した酸または塩基により加水分解が促進されるため、アルコキシ基が水酸基となり、アルコールが生成する。その後、２分子間で水酸基が重縮合することにより、Ｓｉ－Ｏ－Ｓｉのネットワークが形成されるため、加熱処理により、緻密なシリカ系被膜を得ることができる。 According to the composition for forming a silica-based film, an acid or a base is generated by heating with a heat treatment. Hydrolysis is promoted by the generated acid or base, so that the alkoxy group becomes a hydroxyl group and alcohol is generated. Thereafter, a hydroxyl group is polycondensed between two molecules to form a Si—O—Si network, and thus a dense silica-based film can be obtained by heat treatment.
　また、加熱処理は、好ましくは、３段階以上、段階的に昇温することが好ましい。具体的には、大気中または窒素などの不活性ガス雰囲気下、６０～１５０℃程度のホットプレート上で３０秒～２分間程度第１回目の加熱処理を行ったのち、１００～２２０℃程度で３０秒～２分間程度第２回目の加熱処理を行い、さらに１５０～３００℃程度で３０秒～２分間程度第３回目の加熱処理を行う。このように３段階以上、好ましくは３～６段階程度の段階的な加熱処理を行うことにより、より低い温度で、シリカ系被膜の形成をすることができる。 In addition, the heat treatment is preferably performed in three or more steps in a stepwise manner. Specifically, after the first heat treatment is performed for 30 seconds to 2 minutes on a hot plate of about 60 to 150 ° C. in an air or an inert gas atmosphere such as nitrogen, the temperature is about 100 to 220 ° C. The second heat treatment is performed for about 30 seconds to 2 minutes, and the third heat treatment is performed at about 150 to 300 ° C. for about 30 seconds to 2 minutes. Thus, by performing stepwise heat treatment of three or more steps, preferably about 3 to 6 steps, a silica-based film can be formed at a lower temperature.
　なお、上述の無機層は１層でも良いし、複数層設けても良い。
［下地層］
　下地層は、蛍光体層と、蛍光体層が設けられる面との間に設けられた無機酸化物層であって、上記無機層と同様の無機酸化物粒子を含有する無機酸化物膜とすることが好ましい。下地層は１層でも良いし、複数層設けても良い。 Note that the above-described inorganic layer may be a single layer or a plurality of layers.
[Underlayer]
The underlayer is an inorganic oxide layer provided between the phosphor layer and the surface on which the phosphor layer is provided, and is an inorganic oxide film containing the same inorganic oxide particles as the inorganic layer. It is preferable. The underlayer may be a single layer or a plurality of layers.
　下地層を設けることによって、蛍光体層が設けられる面に対する蛍光体層の接着強度を上げることができる。また、蛍光体層から発する光量を下地層によって増加させることができる。
［ＬＥＤチップ］
　ＬＥＤチップとしては、公知の様々なＬＥＤチップを用いることが可能である。特に白色光を得る場合は青色ＬＥＤチップや紫外線ＬＥＤチップを好ましく用いることができる。青色ＬＥＤチップとしては、ＩｎｘＧａ１－ｘＮ系をはじめ既存のあらゆるものを使用することができる。青色ＬＥＤチップの発光ピーク波長は４４０～４８０ｎｍのものが好ましい。紫外線ＬＥＤチップとしては、既存のあらゆるものを使用することができる。紫外線ＬＥＤチップの発光ピーク波長は１４０～４２０ｎｍのものが好ましい。また、ＬＥＤチップの形態としては、基板上にＬＥＤチップを実装し、そのまま上方または側方に放射させるタイプ、またはサファイア基板等の透明基板上に青色ＬＥＤチップを実装し、その表面にバンプを形成した後、裏返して基板上の電極と接続する、いわゆるフリップチップ接続タイプなど、どのような形態のＬＥＤチップでも適用することが可能だが、高輝度タイプやレンズ使用タイプの製造方法により適するフリップチップタイプがより好ましい。 By providing the base layer, the adhesive strength of the phosphor layer to the surface on which the phosphor layer is provided can be increased. Further, the amount of light emitted from the phosphor layer can be increased by the underlayer.
[LED chip]
Various known LED chips can be used as the LED chip. In particular, when obtaining white light, a blue LED chip or an ultraviolet LED chip can be preferably used. As the blue LED chip, any existing one including In x Ga 1-x N system can be used. The emission peak wavelength of the blue LED chip is preferably 440 to 480 nm. Any existing UV LED chip can be used. The emission peak wavelength of the ultraviolet LED chip is preferably 140 to 420 nm. In addition, the LED chip can be mounted on a substrate and radiated upward or sideward, or a blue LED chip is mounted on a transparent substrate such as a sapphire substrate, and bumps are formed on the surface. After that, it can be applied to any form of LED chip, such as flip chip connection type that flips over and connects to the electrode on the substrate, but it is suitable for manufacturing method of high brightness type or lens type Is more preferable.
　以上のように、蛍光体層の表面には、蛍光体層を被覆するように少なくとも１層の無機層が設けられているので、蛍光体粒子を蛍光体層が形成される面に低速で衝突させて堆積することにより蛍光体層を形成した場合であっても、蛍光体層が無機層で被覆されるため、蛍光体層の接着強度を上げることができるとともに保護層としても機能する。したがって、耐久性に優れ、経時劣化の少ない発光装置とすることができる。また、蛍光体粒子の蛍光体層が形成される面への衝突速度を上げる必要がなくなるので、蛍光体粒子が衝突する際に加わる衝撃によって結晶格子に欠陥が生じることも無い。その結果、蛍光体の発光効率の低下を防いで高輝度とすることができる。 As described above, since at least one inorganic layer is provided on the surface of the phosphor layer so as to cover the phosphor layer, the phosphor particles collide with the surface on which the phosphor layer is formed at a low speed. Even when the phosphor layer is formed by depositing, the phosphor layer is covered with an inorganic layer, so that the adhesive strength of the phosphor layer can be increased and it also functions as a protective layer. Therefore, a light-emitting device that has excellent durability and little deterioration with time can be obtained. Further, since it is not necessary to increase the collision speed of the phosphor particles to the surface on which the phosphor layer is formed, no defects occur in the crystal lattice due to the impact applied when the phosphor particles collide. As a result, a reduction in luminous efficiency of the phosphor can be prevented and high luminance can be achieved.
　以下、本発明について実施例及び比較例を用いて具体的に説明する。
《青色発光のＬＥＤチップの製造方法》
　ＬＥＤチップとして主発光ピークが４６０ｎｍのＩｎ０．２Ｇａ０．８Ｎ半導体を用いた。ＬＥＤチップは、洗浄したサファイア基板上にＴＭＧ（トリメチルガリウム）ガス、ＴＭＩ（トリメチルインジュウム）ガス、窒素ガス及びドーパントガスをキャリアガスと共に流し、ＭＯＣＶＤ法で窒化ガリウム系化合物半導体を成膜させることにより形成した。 Hereinafter, the present invention will be specifically described with reference to examples and comparative examples.
<< Production Method of Blue Light-Emitting LED Chip >>
As the LED chip, an In 0.2 Ga 0.8 N semiconductor having a main emission peak of 460 nm was used. The LED chip is formed by flowing a TMG (trimethylgallium) gas, a TMI (trimethylindium) gas, a nitrogen gas and a dopant gas together with a carrier gas on a cleaned sapphire substrate, and forming a gallium nitride compound semiconductor film by MOCVD. Formed.
　ドーパントガスとしては、ＳｉＨ４とＣｐ２Ｍｇ（シクロペンタジエニルマグネシウム、［Ｍｇ（Ｃ５Ｈ５）２］）とを切り替えることによってＮ型導電性を有する窒化ガリウム系半導体とＰ型導電性を有する窒化ガリウム系半導体を形成し、ＰＮ接合を形成した。 As dopant gas, by switching between SiH 4 and Cp 2 Mg (cyclopentadienyl magnesium, [Mg (C 5 H 5 ) 2 ]), N-type conductivity gallium nitride semiconductor and P-type conductivity can be obtained. A gallium nitride based semiconductor was formed, and a PN junction was formed.
　半導体発光素子としては、Ｎ型導電性を有する窒化ガリウム半導体であるコンタクト層と、Ｐ型導電性を有する窒化ガリウムアルミニウム半導体であるクラッド層、Ｐ型導電性を有する窒化ガリウム半導体であるコンタクト層を形成した。 The semiconductor light emitting device includes a contact layer that is a gallium nitride semiconductor having N-type conductivity, a cladding layer that is a gallium aluminum nitride semiconductor having P-type conductivity, and a contact layer that is a gallium nitride semiconductor having P-type conductivity. Formed.
　Ｎ型導電性を有するコンタクト層とＰ型導電性を有するクラッド層との間に厚さ約３ｎｍの、単一量子井戸構造とされるノンドープＩｎＧａＮの活性層を形成した。なお、サファイア基板上には低温で窒化ガリウム半導体を形成しバッファ層とした。また、Ｐ型導電性を有する半導体は、成膜後４００℃以上でアニールした。 A non-doped InGaN active layer having a single quantum well structure having a thickness of about 3 nm was formed between the contact layer having N-type conductivity and the cladding layer having P-type conductivity. A gallium nitride semiconductor was formed on the sapphire substrate at a low temperature to form a buffer layer. The semiconductor having P-type conductivity was annealed at 400 ° C. or higher after film formation.
　その後、エッチングによりサファイア基板上のＰＮ各半導体表面を露出させた。また、ＰＮ各半導体表面が露出された部位は、最終的に形成される各ＬＥＤチップ毎に複数ある。さらに、各ＬＥＤチップの大きさごと矩形に分割できるよう半導体層をサファイア基板まで部分的に除去し電気的にも分離させておく。導電性ワイヤーとなる金線を付着させるためのパッド電極形成面には、レジストを予め形成させ半導体ウエハを形成した。この後、レジストをリフトオフにより除去した。 Thereafter, the surface of each PN semiconductor on the sapphire substrate was exposed by etching. Further, there are a plurality of portions where the surface of each PN semiconductor is exposed for each LED chip to be finally formed. Further, the semiconductor layer is partially removed up to the sapphire substrate so that it can be divided into rectangles for each LED chip size and electrically separated. A resist was formed in advance on the pad electrode forming surface for attaching a gold wire to be a conductive wire to form a semiconductor wafer. Thereafter, the resist was removed by lift-off.
　次いで半導体ウエハをＬＥＤチップに分割させるためのエッチングラインに沿ってダイサーでダイシングした後、スクライバーでスクライブラインを形成した。スクライブラインに沿ってサファイア基板側からローラにより加圧して、個々に分割しＬＥＤチップを形成した。 Then, after dicing with a dicer along an etching line for dividing the semiconductor wafer into LED chips, a scribe line was formed with a scriber. Pressing with a roller along the scribe line from the side of the sapphire substrate, the LED chips were formed by dividing them individually.
　また、インサート成型によりポリカーボネート樹脂を用いてチップタイプＬＥＤのパッケージを形成した。チップタイプＬＥＤのパッケージ内は、ＬＥＤチップが配される開口部を備えている。パッケージ中には、銀メッキした銅板を外部電極として配置させてある。導電性ワイヤーである金線をＬＥＤチップの各電極とパッケージに設けられた各外部電極とにそれぞれワイヤーボンディングさせ電気的に接続させてある。こうして青色発光のＬＥＤチップを１０００個形成した。
《蛍光体Ａの製造方法》
蛍光体Ａ・・・（Ｙ０．７２Ｇｄ０．２４）３Ａｌ５Ｏ１２：Ｃｅ０．０４
Ｙ２Ｏ３　　７．４１ｇ
Ｇｄ２Ｏ３　４．０１ｇ
ＣｅＯ２　　０．６３ｇ
Ａｌ２Ｏ３　７．７７ｇ
　上記蛍光体原料を充分に混合した原料混合物をアルミ坩堝に充填し、これにフラックスとしてフッ化アンモニウム等のフッ化物を適量混合して、水素含有窒素ガスを通気しながら還元雰囲気中において、１３５０～１４５０℃の温度範囲で２～５時間焼成して焼成品を得た。得られた焼成品を粉砕、洗浄、分離、乾燥することで平均粒径０．５μｍの蛍光体Ａを得た。 Further, a chip type LED package was formed using polycarbonate resin by insert molding. The chip type LED package includes an opening in which the LED chip is disposed. In the package, a silver-plated copper plate is disposed as an external electrode. A gold wire as a conductive wire is wire-bonded and electrically connected to each electrode of the LED chip and each external electrode provided in the package. Thus, 1000 blue light emitting LED chips were formed.
<< Method for producing phosphor A >>
Phosphor A ... (Y 0.72 Gd 0.24 ) 3 Al 5 O 12 : Ce 0.04
Y 2 O 3 7.41 g
4.01 g of Gd 2 O 3
CeO 2 0.63 g
Al 2 O 3 7.77 g
A raw material mixture in which the above phosphor raw materials are sufficiently mixed is filled in an aluminum crucible, and an appropriate amount of fluoride such as ammonium fluoride is mixed as a flux into the aluminum crucible. A baked product was obtained by calcination at a temperature range of 1450 ° C. for 2 to 5 hours. The obtained fired product was pulverized, washed, separated, and dried to obtain phosphor A having an average particle size of 0.5 μm.
　さらに得られた蛍光体の組成を調べ、蛍光体組成は（Ｙ０．７２Ｇｄ０．２４）３Ａｌ５Ｏ１２：Ｃｅ０．０４であることを確認した。また４６５ｎｍの励起光における発光波長を調べたところ、おおよそ５７０ｎｍにピーク波長を有していた。
［比較例１］
　エポキシ樹脂中に蛍光体Ａを、樹脂に対して１０質量％となるように分散し、厚さ０．５ｍｍの平板ガラスの表面に、乾燥膜厚が７μｍとなるようにコーティングした。コーティング面をＬＥＤチップ側に向け、パッケージ上部に固定し接着させ、比較例１の白色発光装置を作製した。
［比較例２］
　厚さ０．５ｍｍの平板ガラスの表面に、図２に示すエアロゾル・デポジション成膜装置と上記蛍光体Ａを用いて蛍光体層を形成した。蛍光体Ａをエアロゾル化室に充填し、キャリアガスとして流速３００ｍ／ｓのＮ２ガスを用い、チャンバーの真空度は１００Ｐａ、基板温度を２０℃として、ガラス上に吹きつけて２μｍの成膜を行った。 Furthermore, the composition of the obtained phosphor was examined, and it was confirmed that the phosphor composition was (Y 0.72 Gd 0.24 ) 3 Al 5 O 12 : Ce 0.04 . Further, when the emission wavelength in the excitation light of 465 nm was examined, it had a peak wavelength at about 570 nm.
[Comparative Example 1]
The phosphor A was dispersed in an epoxy resin so as to be 10% by mass with respect to the resin, and coated on the surface of a flat glass having a thickness of 0.5 mm so that the dry film thickness was 7 μm. The coating surface was directed to the LED chip side, and was fixed and adhered to the upper part of the package to produce a white light emitting device of Comparative Example 1.
[Comparative Example 2]
A phosphor layer was formed on the surface of a flat glass plate having a thickness of 0.5 mm using the aerosol deposition film forming apparatus shown in FIG. Phosphor A is filled in an aerosol chamber, N 2 gas with a flow rate of 300 m / s is used as a carrier gas, the chamber is 100 Pa, the substrate temperature is 20 ° C., and sprayed onto glass to form a film of 2 μm. went.
　上記蛍光体層が形成された面をＬＥＤチップ側に向け、パッケージ上部に固定し接着させ、比較例２の白色発光装置を作製した。
［比較例３］
　厚さ０．５ｍｍの平板ガラスの表面に、キャリアガスの流速を１００ｍ／ｓに変えた以外は、全て比較例２と同じ方法により、ガラス上に成膜を行った。上記蛍光体層が形成された面をＬＥＤチップ側に向け、パッケージ上部に固定し接着させ、比較例３の白色発光装置を作製した。
［実施例１］
　有機金属化合物を原料とするゾル溶液を調製するため、テトラエトキシシラン（和光純薬製）０．０４ｍｏｌをポリプロピレンビーカーに秤量した。撹拌しながらエチルアルコール０．２５ｍｏｌを添加し、マグネチックスターラーにより１０分間撹拌した。さらに、純水０．２４ｍｏｌを添加し１０分間撹拌した後、１ｍｏｌ／Ｌ　ＨＣＬ　１ｍｌを添加し、ゾル溶液－１を調製した。 The surface on which the phosphor layer was formed was directed to the LED chip side, and was fixed and adhered to the upper part of the package to produce a white light emitting device of Comparative Example 2.
[Comparative Example 3]
A film was formed on the glass by the same method as Comparative Example 2 except that the flow rate of the carrier gas was changed to 100 m / s on the surface of a flat glass having a thickness of 0.5 mm. The surface on which the phosphor layer was formed was directed to the LED chip side, and was fixed and adhered to the upper part of the package to produce a white light emitting device of Comparative Example 3.
[Example 1]
In order to prepare a sol solution using an organometallic compound as a raw material, 0.04 mol of tetraethoxysilane (manufactured by Wako Pure Chemical Industries, Ltd.) was weighed in a polypropylene beaker. While stirring, 0.25 mol of ethyl alcohol was added and stirred for 10 minutes with a magnetic stirrer. Further, 0.24 mol of pure water was added and stirred for 10 minutes, and then 1 ml of 1 mol / L HCL was added to prepare sol solution-1.
　次に、ゾル溶液－１を、厚さ０．５ｍｍの平板ガラスの表面に、比較例３と同じ方法により成膜した蛍光体層の上に、乾燥後の膜の厚さが１００ｎｍとなるようにスピンコーターによりコーティングし、ドライオーブンにて１５０℃、３０分加熱乾燥し、実施例１のサンプルを作製した。
［実施例２］
　１Ｌのステンレスポットに純水４００ｇを入れ、ウルトラタラックス　Ｔ２５　デジタル　（ＩＫＡ社）を用いて６０００ｒｐｍにて、酸化珪素（電気化学工業株式会社製　商品名：ＳＦＰ－２０Ｍ　平均粒径：３００ｎｍ）６００ｇを５分かけて添加し、その後３０分間分散を行った。その後、１０００ｇのＭＥＫを添加し、バス温４０℃、２．０×１０２ｔｏｒｒ（２．７×１０４Ｐａ）の減圧下にて残質量が８００ｇとなるまでエバポレーターにより溶媒除去する操作を３回繰り返し、最後にＭＥＫを２００ｇ加えて総質量を１０００ｇとし、分散液－１を得た。 Next, the sol solution-1 is formed on the surface of a flat glass having a thickness of 0.5 mm on the phosphor layer formed by the same method as in Comparative Example 3, so that the thickness of the dried film becomes 100 nm. The sample of Example 1 was produced by coating with a spin coater and drying by heating in a dry oven at 150 ° C. for 30 minutes.
[Example 2]
400 g of pure water is put into a 1 L stainless steel pot, and 600 g of silicon oxide (trade name: SFP-20M average particle size: 300 nm) manufactured by Denki Kagaku Kogyo Co., Ltd. is used at 6000 rpm using an Ultra Turrax T25 Digital (IKA). It was added over 5 minutes and then dispersed for 30 minutes. Thereafter, 1000 g of MEK was added, and the operation of removing the solvent with an evaporator until the residual mass reached 800 g under a reduced pressure of bath temperature of 40 ° C. and 2.0 × 10 2 torr (2.7 × 10 4 Pa) was 3 Repeatedly, finally, 200 g of MEK was added to make the total mass 1000 g, and dispersion 1 was obtained.
　次にテトラエトキシシラン（Ｓｉ（Ｃ２Ｈ５Ｏ）４）を２０質量部と、フェニルトリエトキシシラン（Ｃ６Ｈ５Ｓｉ（ＯＣ２Ｈ５）３）を８０質量部とをエチルアルコール１００質量部に混合し、蟻酸を触媒として反応させ、酸性の溶液を得た。 Next, 20 parts by mass of tetraethoxysilane (Si (C 2 H 5 O) 4 ), 80 parts by mass of phenyltriethoxysilane (C 6 H 5 Si (OC 2 H 5 ) 3 ) and 100 parts by mass of ethyl alcohol The formic acid was reacted as a catalyst to obtain an acidic solution.
　次に、その酸性溶液をトリエチルアミン（（Ｃ２Ｈ５）３Ｎ）によって中和し、中和溶液を得た。そして、中和溶液をメチルエチルケトンで溶剤置換し、樹脂不揮発分濃度６０％、粘度４００ｃｐの樹脂溶液－１を得た。分散液－１の３０ｇと樹脂溶液－１の７０ｇを混合し、無機酸化物粒子塗布液－１を１００ｇ得た。 Next, the acidic solution was neutralized with triethylamine ((C 2 H 5 ) 3 N) to obtain a neutralized solution. Then, the solvent of the neutralized solution was replaced with methyl ethyl ketone to obtain a resin solution-1 having a resin nonvolatile content concentration of 60% and a viscosity of 400 cp. 30 g of Dispersion-1 and 70 g of Resin Solution-1 were mixed to obtain 100 g of inorganic oxide particle coating solution-1.
　次に、前述の無機酸化物粒子塗布液－１を、厚さ０．５ｍｍの平板ガラスの表面に、実施例１と同じ方法により成膜した蛍光体層の上に、乾燥後の膜の厚さが１００ｎｍとなるようにスピンコーターによりコーティングし、ドライオーブンにて１５０℃、３０分加熱乾燥し、実施例２のサンプルを作製した。
［実施例３］
　酸化珪素を電気化学工業株式会社製の商品名：ＳＦＰ－３０Ｍ　平均粒径７００ｎｍに変えた（無機酸化物粒子塗布液－２）以外は、全て実施例２と同じ方法により、実施例３のサンプルを作製した。
［実施例４］
　酸化珪素をアルミナ粒子（日本軽金属製　微粒アルミナ　商品名：Ａ３３Ｆ　平均粒径　７００ｎｍ）に変えた（無機酸化物粒子塗布液－３）以外は、全て実施例３と同じ方法により、実施例４のサンプルを作製した。
［実施例５］
　酸化珪素をジルコニア粒子（東レ製ジルコニア粉末　商品名：３ＹＢ　平均粒径　７００ｎｍ）に変えた（無機酸化物粒子塗布液－４）以外は、全て実施例３と同じ方法により、実施例５のサンプルを作製した。
［実施例６］
　厚さ０．５ｍｍの平板ガラスの表面に、上記無機酸化物粒子塗布液－３を乾燥後の膜厚が５００ｎｍとなるようにコーティングした。続いてコーティング面上に、比較例３と同様の方法で蛍光体Ａを成膜した。さらに蛍光体層の上から実施例３と同様に無機酸化物粒子塗布液－２をコーティングし、さらにドライオーブンにて１５０℃、３０分加熱乾燥し、実施例６のサンプルを作製した。
［実施例７］
　実施例６の厚さ０．５ｍｍの平板ガラスに変えて、ドーム形状のガラスレンズとした以外は、全て実施例６と同じ方法により、実施例７のサンプルを作製した。 Next, the above-described inorganic oxide particle coating liquid-1 is dried on the phosphor layer formed by the same method as in Example 1 on the surface of a flat glass having a thickness of 0.5 mm. The sample was coated with a spin coater so that the thickness was 100 nm and dried by heating in a dry oven at 150 ° C. for 30 minutes to prepare a sample of Example 2.
[Example 3]
Sample of Example 3 in the same manner as in Example 2 except that the silicon oxide was changed to trade name: SFP-30M manufactured by Denki Kagaku Kogyo Co., Ltd. (inorganic oxide particle coating solution-2). Was made.
[Example 4]
The sample of Example 4 was prepared in the same manner as in Example 3, except that the silicon oxide was changed to alumina particles (Nippon Light Metal Fine Alumina, trade name: A33F, average particle size 700 nm) (inorganic oxide particle coating solution-3). Was made.
[Example 5]
The sample of Example 5 was prepared in the same manner as in Example 3 except that the silicon oxide was changed to zirconia particles (zirconia powder product name: 3YB average particle size 700 nm, manufactured by Toray Industries, Inc.) (inorganic oxide particle coating solution-4). Produced.
[Example 6]
The surface of a flat glass having a thickness of 0.5 mm was coated with the inorganic oxide particle coating solution-3 so that the thickness after drying was 500 nm. Subsequently, phosphor A was formed on the coating surface by the same method as in Comparative Example 3. Further, the inorganic oxide particle coating solution-2 was coated on the phosphor layer in the same manner as in Example 3, and further dried by heating in a dry oven at 150 ° C. for 30 minutes to prepare a sample of Example 6.
[Example 7]
A sample of Example 7 was produced in the same manner as in Example 6 except that a dome-shaped glass lens was used instead of the flat glass having a thickness of 0.5 mm in Example 6.
　上記作製したサンプルの内容を表－１に示す。 The contents of the sample prepared above are shown in Table-1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
《評価方法》
［白色発光装置の輝度評価］
　得られた発光装置に電力を供給させることによって白色系を発光させることができる。発光装置の正面から発光強度を測定した。即ち、電力を供給し連続点灯を行って、コニカミノルタセンシング社製分光放射輝度計ＣＳ－１０００を用い、点灯開始時の発光輝度（ｃｄ／ｍ２）について、４００ｎｍ～８００ｎｍの波長領域における積分値で表した。（実施例１の積分値を１００とする相対値）
　また、４６０ｎｍ，５６０ｎｍにおける発光ピーク強度を同時に測定し、実施例１の白色発光装置におけるそれぞれの波長での強度を１００とした相対値で表した。 "Evaluation methods"
[Brightness evaluation of white light emitting device]
White light can be emitted by supplying power to the obtained light-emitting device. The emission intensity was measured from the front of the light emitting device. That is, by supplying power and performing continuous lighting, using a spectral radiance meter CS-1000 manufactured by Konica Minolta Sensing Co., Ltd., the integrated value in the wavelength region of 400 nm to 800 nm with respect to the emission luminance (cd / m 2 ) at the start of lighting. Expressed in (Relative value where the integral value of Example 1 is 100)
Further, the emission peak intensities at 460 nm and 560 nm were measured at the same time, and expressed as relative values with the intensity at each wavelength in the white light emitting device of Example 1 as 100.
　また、作製した白色発光装置から無作為に選択した５０個について、発光装置の正面から色温度、演色性をそれぞれ測定し、このバラツキを色度座標上の面積として測定した。即ち、各発光装置の発光色を、前記分光放射輝度計ＣＳ－１０００（コニカミノルタセンシング社製）を用い、２度視野角において測定し、このデータを色度座標に当てはめたときの色をＣＩＥ１９３１表色系におけるＸ、Ｙ色度座標として求め、これらサンプル５０個のバラツキを色度座標上にプロットして色度座標上の面積として求めた。実施例１を１００とした相対値で表した。
［白色発光装置の環境試験評価］
　得られた発光装置を温度５０℃、湿度８０％の環境下で２４００時間発光し、輝度の変化を確認した。当初の輝度を１００として、相対値で表した。輝度は前記同様にしてコニカミノルタセンシング社製分光放射輝度計ＣＳ－１０００を用い測定した。
［白色発光装置の振動試験］
　得られた発光装置を梱包包装試験機「ＢＦ－５０ＵＴ」（アイメックス社製）を使用し、重力加速度２．５Ｇ、振幅０．８ｍｍ、周波数１０Ｈｚ～４０Ｈｚで周期的に変化する振動をｘｙｚ方向に２０分間加える方法で行った。その後、輝度を上記方法で測定し、振動後の輝度を当初の輝度を１００として、相対値で表した。輝度は前記同様にしてコニカミノルタセンシング社製分光放射輝度計ＣＳ－１０００を用い測定した。 Further, for 50 randomly selected white light emitting devices, the color temperature and color rendering were measured from the front of the light emitting device, and the variation was measured as the area on the chromaticity coordinate. That is, the luminescent color of each light emitting device was measured at a viewing angle of 2 degrees using the spectral radiance meter CS-1000 (manufactured by Konica Minolta Sensing Co., Ltd.), and the color when this data was applied to chromaticity coordinates was determined as CIE1931. The X and Y chromaticity coordinates in the color system were obtained, and the variations of these 50 samples were plotted on the chromaticity coordinates to obtain the area on the chromaticity coordinates. Example 1 was expressed as a relative value with 100 as the value.
[Environmental test evaluation of white light emitting devices]
The obtained light-emitting device emitted light for 2400 hours in an environment of a temperature of 50 ° C. and a humidity of 80%, and the change in luminance was confirmed. The initial luminance was set as 100 and expressed as a relative value. The luminance was measured in the same manner as described above using a spectral radiance meter CS-1000 manufactured by Konica Minolta Sensing.
[Vibration test of white light emitting device]
Using the packaging and testing machine “BF-50UT” (manufactured by Imex), the obtained light-emitting device is subjected to a vibration that periodically changes in the xyz direction with a gravitational acceleration of 2.5 G, an amplitude of 0.8 mm, and a frequency of 10 Hz to 40 Hz. The method was performed by adding for 20 minutes. Thereafter, the luminance was measured by the above method, and the luminance after vibration was expressed as a relative value with the initial luminance being 100. The luminance was measured in the same manner as described above using a spectral radiance meter CS-1000 manufactured by Konica Minolta Sensing.
　以上の評価について結果を表２に示す。 The results of the above evaluation are shown in Table 2.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表２の結果から明らかなように、無機層を設けた実施例１～７は、無機層を設けなかった比較例１～３に比して白色光強度が強い。また、実施例１～７では色温度、演色性のバラツキも小さく、環境試験評価及び振動試験においても高輝度で、耐久性に優れ、経時劣化が少ないことが認められる。 As is apparent from the results in Table 2, Examples 1 to 7 provided with the inorganic layer have higher white light intensity than Comparative Examples 1 to 3 provided with no inorganic layer. In Examples 1 to 7, variations in color temperature and color rendering are small, and it is recognized that the environmental test evaluation and vibration test have high luminance, excellent durability, and little deterioration with time.
　１　ＬＥＤチップ
　２　基材
　３　蛍光体層
　４　レンズ
　７　下地層
　８　無機層
　１００　発光装置 DESCRIPTION OF SYMBOLS 1 LED chip 2 Base material 3 Phosphor layer 4 Lens 7 Underlayer 8 Inorganic layer 100 Light-emitting device

Claims (17)

  1. 　ＬＥＤチップと、
    　前記ＬＥＤチップからの発光の少なくとも一部を吸収し、波長変換して発光する蛍光体層と、
    　前記蛍光体層の表面に、前記蛍光体層を被覆するように設けられた少なくとも１層の無機層とを備えた発光装置の製造方法において、
    　前記ＬＥＤチップの光出射面または、前記ＬＥＤチップとは別個に設けられた基材の前記ＬＥＤチップの光出射面に対向する面に対して蛍光体粒子を衝突させて堆積することによって前記蛍光体層を成膜し、
    　次いで、前記蛍光体層の表面に、前記蛍光体層を被覆するように少なくとも１層の無機層を設けることを特徴とする発光装置の製造方法。     An LED chip;
    A phosphor layer that absorbs at least part of the light emitted from the LED chip, converts the wavelength, and emits light;
    In a method for manufacturing a light emitting device comprising at least one inorganic layer provided on the surface of the phosphor layer so as to cover the phosphor layer,
    The phosphor is produced by colliding and depositing phosphor particles against the light emitting surface of the LED chip or the surface of the base material provided separately from the LED chip and facing the light emitting surface of the LED chip. Deposit layers,
    Next, at least one inorganic layer is provided on the surface of the phosphor layer so as to cover the phosphor layer.
  2. 　前記無機層が、無機酸化物膜で形成されていることを特徴とする請求項１に記載の発光装置の製造方法。 The method for manufacturing a light emitting device according to claim 1, wherein the inorganic layer is formed of an inorganic oxide film.
  3. 　前記無機酸化物膜は、前記蛍光体層の表面に塗布液を塗布後、乾燥、焼結させることで形成されることを特徴とする請求項２に記載の発光装置の製造方法。 3. The method of manufacturing a light emitting device according to claim 2, wherein the inorganic oxide film is formed by applying a coating solution to the surface of the phosphor layer, followed by drying and sintering.
  4. 　前記塗布液が無機酸化物粒子を含有することを特徴とする請求項３に記載の発光装置の製造方法。 The method for manufacturing a light emitting device according to claim 3, wherein the coating liquid contains inorganic oxide particles.
  5. 　前記無機酸化物粒子が、平均粒径が１００ｎｍ以上１μｍ以下であることを特徴とする請求項４に記載の発光装置の製造方法。 The method for manufacturing a light emitting device according to claim 4, wherein the inorganic oxide particles have an average particle size of 100 nm or more and 1 µm or less.
  6. 　前記発光装置は、前記前記ＬＥＤチップとは別個に設けられた基材を有し、前記基材の前記ＬＥＤチップの光出射面に対向する面に対して蛍光体粒子を衝突させて堆積することによって前記蛍光体層を形成することを特徴とする請求項１から５の何れか１項に記載の発光装置の製造方法。 The light emitting device includes a base material provided separately from the LED chip, and deposits phosphor particles by colliding with a surface of the base material facing a light emitting surface of the LED chip. The method for manufacturing a light emitting device according to claim 1, wherein the phosphor layer is formed by:
  7. 　前記蛍光体層は、前記基材の前記ＬＥＤチップの光出射面に対向する面上に形成された無機酸化物膜からなる下地層上に設けられることを特徴とする請求項６に記載の発光装置の製造方法。 7. The light emitting device according to claim 6, wherein the phosphor layer is provided on a base layer made of an inorganic oxide film formed on a surface of the base material facing a light emitting surface of the LED chip. Device manufacturing method.
  8. 　前記蛍光体層を成膜する工程において、該蛍光体層が前記蛍光体粒子の流速５０～１８０ｍ／ｓ以下で成膜されることを特徴とする請求項１から７の何れか１項に記載の発光装置の製造方法。 8. The method according to claim 1, wherein in the step of forming the phosphor layer, the phosphor layer is formed at a flow rate of the phosphor particles of 50 to 180 m / s or less. Method for manufacturing the light emitting device.
  9. 　ＬＥＤチップと、
    　前記ＬＥＤチップからの発光の少なくとも一部を吸収し、波長変換して発光する蛍光体層と、
    　前記蛍光体層の表面に、前記蛍光体層を被覆するように設けられた少なくとも１層の無機層とを備え、請求項１から８の何れか１項に記載の製造方法により製造されたことを特徴とする発光装置。     An LED chip;
    A phosphor layer that absorbs at least part of the light emitted from the LED chip, converts the wavelength, and emits light;
    It was manufactured by the manufacturing method according to any one of claims 1 to 8, comprising at least one inorganic layer provided on the surface of the phosphor layer so as to cover the phosphor layer. A light emitting device characterized by the above.
  10. 　前記無機層が、無機酸化物膜で形成されていることを特徴とする請求項９に記載の発光装置。 The light emitting device according to claim 9, wherein the inorganic layer is formed of an inorganic oxide film.
  11. 　前記無機層が、無機酸化物粒子を含有する無機酸化物膜で形成されていることを特徴とする請求項９または１０に記載の発光装置。 The light emitting device according to claim 9 or 10, wherein the inorganic layer is formed of an inorganic oxide film containing inorganic oxide particles.
  12. 　前記無機酸化物膜が、粒径が１００ｎｍ以上１μｍ以下の無機酸化物粒子を含有することを特徴とする請求項９から１１の何れか１項に記載の発光装置。 The light emitting device according to any one of claims 9 to 11, wherein the inorganic oxide film contains inorganic oxide particles having a particle size of 100 nm or more and 1 µm or less.
  13. 　前記無機酸化物粒子が、酸化珪素、酸化アルミニウム、酸化亜鉛、酸化チタン及び酸化ジルコニウムのうちの少なくとも一つの化合物を含有することを特徴とする請求項９から１２の何れか１項に記載の発光装置。 The light emission according to any one of claims 9 to 12, wherein the inorganic oxide particles contain at least one compound of silicon oxide, aluminum oxide, zinc oxide, titanium oxide, and zirconium oxide. apparatus.
  14. 　前記発光装置は、前記前記ＬＥＤチップとは別個に設けられた基材を有し、前記基材の前記ＬＥＤチップの光出射面に対向する面に前記蛍光体層が設けられることを特徴とする請求項９から１３に記載の発光装置。 The light-emitting device has a base material provided separately from the LED chip, and the phosphor layer is provided on a surface of the base material facing a light emitting surface of the LED chip. The light emitting device according to claim 9.
  15. 　前記基材と前記蛍光体層との間に、少なくとも１層の無機酸化物膜からなる下地層が設けられていることを特徴とする請求項１４に記載の発光装置。 15. The light emitting device according to claim 14, wherein a base layer made of at least one inorganic oxide film is provided between the substrate and the phosphor layer.
  16. 　前記基材が前記蛍光体層の発光を集光し、所望の方向に放射する光学レンズとしての機能を有することを特徴とする請求項９から１５のいずれか１項に記載の発光装置。 The light-emitting device according to any one of claims 9 to 15, wherein the substrate has a function as an optical lens that collects light emitted from the phosphor layer and emits the light in a desired direction.
  17. 　前記ＬＥＤチップは青色光を出射し、前記蛍光体層は、前記ＬＥＤチップからの青色光の少なくとも一部を吸収して黄色光を出射し、少なくとも一部の青色光を透過させることで、疑似白色光を形成することを特徴とする請求項９から１６の何れか１項に記載の発光装置。 The LED chip emits blue light, and the phosphor layer absorbs at least a part of the blue light from the LED chip, emits yellow light, and transmits at least a part of the blue light. The light-emitting device according to claim 9, wherein the light-emitting device forms white light.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011125646A1 (en) * 2010-03-31 2011-10-13 Jsr株式会社 Curable resin composition and light emitting device
WO2014029642A1 (en) * 2012-08-23 2014-02-27 Osram Opto Semiconductors Gmbh Method for producing a light-emitting semiconductor component and light-emitting semiconductor component
JP2014138081A (en) * 2013-01-17 2014-07-28 Konica Minolta Inc Light emitting device, wavelength conversion-light diffusion element, method for manufacturing the same, and composition for forming light diffusion ceramic layer
JP2016072471A (en) * 2014-09-30 2016-05-09 日亜化学工業株式会社 Translucent member and manufacturing method of the translucent member, and light-emitting device and manufacturing method of the light-emitting device
JP2019050432A (en) * 2018-12-28 2019-03-28 日亜化学工業株式会社 Light transmitting member, method for manufacturing the same, light emitting device, and method for manufacturing the same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006303001A (en) * 2005-04-18 2006-11-02 Konica Minolta Opto Inc Light emitting diode and its manufacturing method
JP2006313829A (en) * 2005-05-09 2006-11-16 Konica Minolta Opto Inc White light emitting diode and its manufacturing method
JP2006332501A (en) * 2005-05-30 2006-12-07 Konica Minolta Opto Inc Light-emitting diode (led) and its manufacturing method
JP2006339217A (en) * 2005-05-31 2006-12-14 Konica Minolta Opto Inc Light emitting diode and its fabrication process

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006303001A (en) * 2005-04-18 2006-11-02 Konica Minolta Opto Inc Light emitting diode and its manufacturing method
JP2006313829A (en) * 2005-05-09 2006-11-16 Konica Minolta Opto Inc White light emitting diode and its manufacturing method
JP2006332501A (en) * 2005-05-30 2006-12-07 Konica Minolta Opto Inc Light-emitting diode (led) and its manufacturing method
JP2006339217A (en) * 2005-05-31 2006-12-14 Konica Minolta Opto Inc Light emitting diode and its fabrication process

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011125646A1 (en) * 2010-03-31 2011-10-13 Jsr株式会社 Curable resin composition and light emitting device
WO2014029642A1 (en) * 2012-08-23 2014-02-27 Osram Opto Semiconductors Gmbh Method for producing a light-emitting semiconductor component and light-emitting semiconductor component
JP2014138081A (en) * 2013-01-17 2014-07-28 Konica Minolta Inc Light emitting device, wavelength conversion-light diffusion element, method for manufacturing the same, and composition for forming light diffusion ceramic layer
JP2016072471A (en) * 2014-09-30 2016-05-09 日亜化学工業株式会社 Translucent member and manufacturing method of the translucent member, and light-emitting device and manufacturing method of the light-emitting device
US10290607B2 (en) 2014-09-30 2019-05-14 Nichia Corporation Method for manufacturing light emitting device including light emitting element and color conversion material layer
US10636764B2 (en) 2014-09-30 2020-04-28 Nichia Corporation Light emitting device
JP2019050432A (en) * 2018-12-28 2019-03-28 日亜化学工業株式会社 Light transmitting member, method for manufacturing the same, light emitting device, and method for manufacturing the same

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