WO2011096074A1 - Dispositif émetteur de lumière - Google Patents

Dispositif émetteur de lumière Download PDF

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Publication number
WO2011096074A1
WO2011096074A1 PCT/JP2010/051748 JP2010051748W WO2011096074A1 WO 2011096074 A1 WO2011096074 A1 WO 2011096074A1 JP 2010051748 W JP2010051748 W JP 2010051748W WO 2011096074 A1 WO2011096074 A1 WO 2011096074A1
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WO
WIPO (PCT)
Prior art keywords
phosphor
light
layer
ceramic layer
led
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Application number
PCT/JP2010/051748
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English (en)
Japanese (ja)
Inventor
貴志 鷲巣
Original Assignee
コニカミノルタオプト株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by コニカミノルタオプト株式会社 filed Critical コニカミノルタオプト株式会社
Priority to JP2011552625A priority Critical patent/JP5304905B2/ja
Priority to PCT/JP2010/051748 priority patent/WO2011096074A1/fr
Publication of WO2011096074A1 publication Critical patent/WO2011096074A1/fr

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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
    • H01L33/505—Wavelength conversion elements characterised by the shape, e.g. plate or foil
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder

Definitions

  • the present invention relates to a light emitting device.
  • a light emitting device that obtains white light by emitting light from a phosphor using light from an LED element as excitation light in applications such as lighting has been developed.
  • a light emitting device for example, a phosphor that emits yellow light by blue light emitted from an LED element is used, and a light emitting device that produces white light by mixing each light, or emitted from an LED element.
  • a light emitting device that produces white light by mixing three colors of light emitted from a phosphor using a phosphor that emits blue, green, and red light by ultraviolet light.
  • a light-emitting device As a configuration of such a light-emitting device, a light-emitting device has been developed by directly sealing an LED chip with a curable resin in which a phosphor is dispersed.
  • the white LED has been increased in output and the LED chip is generating heat, which is dispersed in the sealing material as described above.
  • the phosphor When the LED element is directly provided on the LED element, the phosphor may be thermally deteriorated due to heat generated by the LED element.
  • phosphor degradation due to moisture is also a problem.
  • a technique has been proposed in which a phosphor is dispersed not in a resin but in a ceramic and the LED is sealed to prevent deterioration of the sealant (for example, see Patent Document 1). .
  • the present invention has been made in view of the above circumstances, and an object thereof is to provide a light emitting device capable of obtaining a sufficient moisture permeation preventing effect and preventing generation of cracks and deterioration of light emission intensity. It is said.
  • an LED element that emits light of a specific wavelength;
  • the light emitted from the LED element is incident, and a wavelength conversion part that converts the incident light into light of a specific wavelength, and
  • the wavelength conversion site is formed from a ceramic layer prepared using polysilazane containing a phosphor as a raw material,
  • a surface layer portion includes a layer that does not include a phosphor, and the thickness of the layer that does not include the phosphor is 0.05 ⁇ m or more and 20 ⁇ m or less.
  • a sufficient moisture permeation preventing effect can be obtained, and generation of cracks and deterioration of light emission intensity can be prevented.
  • FIG. 1 is a cross-sectional view illustrating a schematic configuration of a light emitting device.
  • the light emitting device 100 of the present invention includes an LED chip (light emitting element) 1 that emits light of a specific wavelength, an LED storage portion 2 that stores the LED chip 1, and a condensing lens (optical) provided above the LED chip 1.
  • a layer (wavelength conversion site) 4 4.
  • the LED chip 1 emits light having a first predetermined wavelength.
  • the LED chip 1 emits blue light.
  • the wavelength of the LED chip 1 of the present invention and the wavelength of the emitted light from the phosphor are not limited, and the wavelength of the emitted light from the LED chip 1 and the synthesized light with the wavelength of the emitted light from the phosphor being in a complementary color relationship.
  • the wavelengths of the emitted light from the LED chip 1 and the emitted light from the phosphor are preferably visible light.
  • a known blue LED chip can be used.
  • the blue LED chip any existing one including In x Ga 1-x N can be used.
  • the emission peak wavelength of the blue LED chip is preferably 440 to 480 nm.
  • the LED chip is mounted on the substrate and directly radiated upward or sideward, or the blue LED chip is mounted on a transparent substrate such as a sapphire substrate, and bumps are formed on the surface thereof. It can be applied to any form of LED chip, such as the so-called flip chip connection type, which is flipped over and connected to the electrode on the substrate, but it is suitable for the manufacturing method of high brightness type or lens type A type is more preferable.
  • the LED storage portion 2 has a substantially box shape, and the LED chip 1 is fixed to the center of the bottom surface.
  • the inner wall surface 2a of the LED storage unit 2 is preferably provided with a mirror member such as Al or Ag.
  • the LED housing portion 2 is not particularly limited, but it is preferable to use a material that is excellent in light reflectivity and hardly deteriorates with respect to light from the LED chip 1.
  • a condensing lens 3 having a ceramic layer 4 formed thereon is provided above the LED chip 1 on the upper end surface of the LED housing portion 2.
  • the condensing lens 3 is for condensing the first predetermined wavelength light (blue light) emitted from the LED chip 1 and the second predetermined wavelength light (yellow light) emitted from the phosphor. is there.
  • the condenser lens 3 has a substantially flat plate shape and is provided so as to cover the upper end opening of the LED storage portion 2.
  • the condenser lens 3 is made of low melting point glass, metal glass, resin, or the like.
  • a ceramic layer 4 made of polysilazane containing a phosphor as a raw material is provided on the lower surface of such a condenser lens 3.
  • a layer 41 not containing a phosphor exists in the surface layer portion (the upper layer portion in FIG. 4A) in the ceramic layer 4, and the thickness of the layer 41 not containing the phosphor is 0.05 ⁇ m or more. 20 ⁇ m or less.
  • the reason why the thickness of the layer 41 not containing the phosphor is set to 0.05 ⁇ m or more and 20 ⁇ m or less is that if it is thinner than 0.05 ⁇ m, a sufficient moisture penetration preventing effect cannot be obtained, and if it is thicker than 20 ⁇ m, cracks This is because of this.
  • FIG. 4B shows a case where the thickness of the layer 41 not containing the phosphor is thicker than 20 ⁇ m
  • FIG. 4C shows a case where the layer not containing the phosphor is thinner than 0.05 ⁇ m.
  • the polysilazane used in the present invention is represented by the following general formula (1).
  • R 1 R 2 SiNR 3 n
  • each of R1, R2, and R3 independently represents a hydrogen atom, an alkyl group, an aryl group, a vinyl group, or a cycloalkyl group, and at least one of R1, R2, and R3 is a hydrogen atom, preferably All are hydrogen atoms, and n represents an integer of 1 to 60.
  • the molecular shape of polysilazane may be any shape, for example, linear or cyclic.
  • the polysilazane represented by the above formula (1) and a reaction accelerator according to need are dissolved in an appropriate solvent and cured by heating, excimer light treatment, UV light treatment, and excellent heat resistance and light resistance.
  • a ceramic film can be made.
  • the effect of preventing penetration of moisture can be further improved by heat curing after irradiation with UVU radiation (eg, excimer light) containing a wavelength component in the range of 170 to 230 nm.
  • UVU radiation eg, excimer light
  • an acid, a base, or the like is preferably used, but it may not be used.
  • reaction accelerators include triethylamine, diethylamine, N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, hydrochloric acid, oxalic acid, fumaric acid, sulfonic acid, acetic acid, nickel, iron, palladium , Metal carboxylates including iridium, platinum, titanium, and aluminum, but are not limited thereto. Particularly preferred when a reaction accelerator is used is a metal carboxylate, and the addition amount is preferably 0.01 to 5 mol% based on polysilazane.
  • the solvent aliphatic hydrocarbons, aromatic hydrocarbons, halogen hydrocarbons, ethers, and esters can be used.
  • methyl ethyl ketone Preferred are methyl ethyl ketone, tetrahydrofuran, benzene, toluene, xylene, dimethyl fluoride, chloroform, carbon tetrachloride, ethyl ether, isopropyl ether, dibutyl ether, and ethyl butyl ether.
  • the polysilazane concentration is preferably higher, but since the increase in concentration leads to a shortening of the polysilazane storage period, the polysilazane is preferably dissolved in the solvent at 5 wt% or more and 50 wt% or less.
  • the phosphor has a phosphor that converts light having a first predetermined wavelength emitted from the LED chip 1 into a second predetermined wavelength.
  • blue light emitted from the LED chip 1 is converted into yellow light.
  • Such phosphors use oxides or compounds that easily become oxides at high temperatures as raw materials for Y, Gd, Ce, Sm, Al, La and Ga, and mix them well in a stoichiometric ratio.
  • a coprecipitated oxide obtained by calcining a solution obtained by coprecipitation of oxalic acid with a solution obtained by dissolving a rare earth element of Y, Gd, Ce, and Sm in an acid at a stoichiometric ratio, and aluminum oxide and gallium oxide.
  • An appropriate amount of fluoride such as ammonium fluoride is mixed with this as a flux and pressed to obtain a molded body.
  • the compact can be 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 sintered body having the phosphor emission characteristics.
  • the phosphor obtained in this manner was used as a binder with polysilazane dissolved in a solvent, and a mixed material of the binder and the phosphor was applied to one surface of the condenser lens 3 and allowed to stand to fluoresce.
  • the surface layer portion 41 not containing the phosphor is extracted with a micropipette, and then baked and cured. Thereby, it can be set as the ceramic layer 4 which has the layer 41 which does not contain fluorescent substance in a surface layer part.
  • Such a ceramic layer 4 preferably contains a phosphor having a center particle size of 5 ⁇ m or more and 50 ⁇ m or less in a concentration of 40 wt% or more and 95 wt% or less.
  • the maximum thickness of the ceramic layer is preferably 5 ⁇ m or more and 500 ⁇ m or less.
  • the lower limit value of the maximum thickness of the ceramic layer is not limited, but the thickness of the ceramic layer is larger than that of the phosphor particles, so that the moisture permeation preventing effect can be obtained and the phosphor particles are deteriorated. Can be suppressed.
  • the thickness of the ceramic layer is preferably 500 ⁇ m or less from the viewpoint of preventing the occurrence of cracks.
  • the condensing lens 3 and the LED housing 2 are sealed in a state where the ceramic layer 4 on the lower surface of the condensing lens 3 and the upper end surface of the LED housing 2 are in close contact with each other, as shown in FIG. It is joined by materials. Then, a space 5 is formed between the ceramic layer 4 and the bottom surface of the LED storage unit 3, and the LED chip 1 is sealed inside the space 5, and deterioration due to oxygen and humidity of the outside air can be suppressed.
  • the space 5 is preferably a low refractive index layer lower than the refractive index of the condenser lens 3.
  • the low refractive index layer for example, a gas layer filled with gas, an air layer, or a resin layer is preferable.
  • the gas layer for example, a gas such as nitrogen is preferably purged.
  • the gas layer As the gas layer, for example, a gas such as nitrogen is preferably purged.
  • the operation of the light emitting device 100 will be described.
  • the LED chip 1 emits blue light toward the outside, the blue light enters the phosphor of the ceramic layer 4. Then, yellow light is emitted from the phosphor excited by the blue light. As a result, the blue light and the yellow light generated by the phosphor are superimposed and emitted as white light to the outside of the LED storage unit 2.
  • the above light-emitting device 100 can be used suitably as a headlight etc. for motor vehicles.
  • the configuration of the light-emitting device 100 of the present invention is not limited to the configuration shown in FIG. 1, and may be, for example, the light-emitting devices 100A and 100B having the configurations shown in FIGS.
  • the ceramic layer 4A is provided on the curved surface that is the inner surface of the dome-shaped condenser lens 3A.
  • the condensing lens 3A is provided above the LED chip 1 fixed at the center of the upper surface of the substantially flat substrate 2A.
  • a ceramic layer 4A containing a phosphor and made of polysilazane is formed on the lower surface of the condenser lens 3A.
  • the ceramic layer 4A has the layer 41A that does not contain a phosphor in the surface layer portion (the lower layer portion in FIG. 2).
  • the condensing lens 3A and the substrate 2A are joined by a sealing material or the like in a state where the lower surfaces of the condensing lens 3A and the ceramic layer 4A and the upper surface of the substrate 2A are in close contact with each other.
  • the space 5A between the ceramic layer 4A and the upper surface of the substrate 2A is preferably a layer having a lower refractive index than the refractive index of the condenser lens 3A, as in FIG.
  • the shape of the exit surface and the entrance surface of the condensing lenses 3 and 3A is not limited to the flat plate shape and the dome shape, but a light collecting property such as an aspherical shape or a cylindrical shape, light distribution properties, etc. are taken into consideration. Any desired shape can be used.
  • the exit surface has a Fresnel structure with light condensing property
  • the condensing lens can be thinned, and the light emitting device can be further miniaturized.
  • the ceramic layer 4B is provided in the LED housing part 2 shown in FIG. 1, a polysilazane solution containing a phosphor is applied to the LED chip 1 side and allowed to stand. After the phosphor is precipitated, in FIG. 3, the upper layer portion 41B not containing the phosphor is extracted with a micropipette and then cured and sealed.
  • a layer that does not contain a phosphor is provided on the surface layer portion in the ceramic layer, thereby creating a layer that prevents moisture from penetrating outside the portion containing the phosphor.
  • the thickness of the layer not including the phosphor is 0.05 ⁇ m or more and 20 ⁇ m or less, it is possible to obtain a sufficient moisture penetration preventing effect and to prevent generation of cracks.
  • the phosphor can be cured at a low temperature of about 500 ° C. without being deteriorated.
  • heat curing is performed after excimer irradiation in the curing step, the effect of preventing moisture penetration can be further improved.
  • the blue LED used for all samples was mounted in a flip chip type using a size of 1000 ⁇ m ⁇ 1000 ⁇ m ⁇ 100 ⁇ m.
  • Yellow fluorescent particles prepared by the following method were used. A mixture in which the following phosphor raw materials are sufficiently mixed is filled in an aluminum crucible, mixed with an appropriate amount of fluoride such as ammonium fluoride as a flux, and 1350 ° C to 1450 ° C in a reducing atmosphere in which hydrogen-containing nitrogen gas is circulated.
  • a fired product ((Y 0.72 Gd 0.24 ) 3 Al 5 O 12 : Ce 0.04 ) was obtained by firing for 2 to 5 hours in the temperature range of ° C.
  • the fired product obtained was pulverized, washed, separated, and dried to obtain a desired phosphor.
  • the obtained phosphor was pulverized into phosphor particles having a particle size of about 10 ⁇ m.
  • the composition of the obtained phosphor was examined, it was confirmed that it was a desired phosphor.
  • the emission wavelength of excitation light having a wavelength of 465 nm was examined, it had a peak wavelength of approximately 570 nm.
  • Example 1 Aquamica NL120-20wt% (manufactured by AZ Electronic Materials Co., Ltd.) 0.8 g of the phosphor prepared in 1 g was mixed, dropped into the LED storage part of FIG. 3 and allowed to stand for 1 minute to precipitate the phosphor, The layer containing no phosphor was extracted with a micropipette and then baked at 250 ° C. for 1 hour. The thickness of the layer not containing the phosphor was 10 ⁇ m.
  • Example 2 Aquamica NL120-20wt% (manufactured by AZ Electronic Materials Co., Ltd.) 0.8 g of the phosphor prepared in 1 g was mixed, dropped into the LED storage part of FIG. 3 and allowed to stand for 1 minute to precipitate the phosphor, The layer containing no phosphor was extracted with a micropipette and then baked at 250 ° C. for 1 hour. The thickness of the layer not containing the phosphor was 20 ⁇ m.
  • Example 3 Aquamica NN120-20wt% (manufactured by AZ Electronic Materials Co., Ltd.) 0.8g of the phosphor prepared in 1g was mixed, dropped into the LED storage part of Fig. 3 and allowed to stand for 1 minute to precipitate the phosphor, The layer containing no phosphor was extracted with a micropipette and then baked at 450 ° C. for 1 hour. The thickness of the layer not containing the phosphor was 20 ⁇ m.
  • Example 4 Aquamica NP120-20wt% (manufactured by AZ Electronic Materials Co., Ltd.) 0.8g of phosphor prepared in 1g was mixed, dropped into the LED storage part of Fig. 3 and allowed to stand for 1 minute to precipitate the phosphor, The layer containing no phosphor was extracted with a micropipette, dried at 100 ° C. for 10 minutes, and cured by irradiation with Xe 2 excimer radiation 30 mWcm ⁇ 2 for 1 minute. Then, it baked at 250 degreeC for 10 minutes. The thickness of the layer not containing the phosphor was 20 ⁇ m.
  • Example 5 Aquamica NN120-20wt% (manufactured by AZ Electronic Materials Co., Ltd.) 0.8g of the phosphor prepared in 1g was mixed, dropped into the LED storage part of Fig. 3 and allowed to stand for 1 minute to precipitate the phosphor, The layer containing no phosphor was extracted with a micropipette, dried at 100 ° C. for 10 minutes, and cured by irradiation with Xe 2 excimer radiation 30 mWcm ⁇ 2 for 1 minute. Then, it baked at 450 degreeC for 10 minutes. The thickness of the layer not containing the phosphor was 20 ⁇ m.
  • Example 6 Aquamica NN120-20wt% (manufactured by AZ Electronic Materials Co., Ltd.) 0.8g of the phosphor prepared in 1g is mixed, dip-coated on the 1mm-thick glass substrate in Fig. 1, and allowed to stand for 1 minute for the phosphor. After precipitation, the layer containing no phosphor was extracted with a micropipette and then baked at 450 ° C. for 1 hour. The thickness of the layer not containing the phosphor was 1 ⁇ m.
  • the thickness of the phosphor layer was measured by shaving the measurement part of the phosphor layer and the layer not containing the phosphor, and measuring the difference in height before and after shaving using a measurement microscope MF-A505H manufactured by Mitutoyo.
  • Example 3 since it was cured by excimer irradiation, the barrier property was better than that in Example 2. Moreover, it turned out that an effect is acquired also when a ceramic layer is formed on a glass substrate like Example 4.
  • FIG. 4 As described above, by providing a layer containing no phosphor in the ceramic layer in which the phosphor is dispersed in polysilazane so as to be within the definition of the present invention, there is no crack or inactivation, and the wavelength conversion site has high fluorescence intensity. (Ceramic layer) can be created.
  • LED chip (LED element) 2 LED housing part 3 Condensing lens 4, 4A Ceramic layer (wavelength conversion part) 41, 41A Layer 100, 100A not including phosphor

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Led Device Packages (AREA)

Abstract

L'invention concerne un dispositif émetteur de lumière (100) comprenant : une puce à DEL (1) qui peut émettre une lumière ayant une longueur d'onde spécifique ; et une unité de conversion de longueur d'onde dans laquelle la lumière émise par la puce à DEL (1) pénètre et qui peut convertir la lumière entrante en une lumière ayant une longueur d'onde spécifique. L'unité de conversion de longueur d'onde se compose d'une couche céramique (4) qui est produite en utilisant un polysilazane contenant du phosphore en qualité de matériau de base, la partie couche de surface de la couche céramique (4) comportant une couche sans phosphore (41) ayant une épaisseur de 0,05 à 20 μm compris.
PCT/JP2010/051748 2010-02-08 2010-02-08 Dispositif émetteur de lumière WO2011096074A1 (fr)

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JP2011552625A JP5304905B2 (ja) 2010-02-08 2010-02-08 発光装置
PCT/JP2010/051748 WO2011096074A1 (fr) 2010-02-08 2010-02-08 Dispositif émetteur de lumière

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PCT/JP2010/051748 WO2011096074A1 (fr) 2010-02-08 2010-02-08 Dispositif émetteur de lumière

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Cited By (5)

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JP2013165223A (ja) * 2012-02-13 2013-08-22 Konica Minolta Inc 波長変換素子及びその製造方法、発光装置及びその製造方法、蛍光体分散液
WO2014048997A1 (fr) * 2012-09-28 2014-04-03 Osram Opto Semiconductors Gmbh Procédé de fabrication d'un composant optoélectronique
EP2752897A4 (fr) * 2011-10-07 2015-04-29 Konica Minolta Inc Procédé de fabrication de dispositif à del et solution à matière fluorescente dispersée utilisée dans celui-ci
KR20160068267A (ko) * 2014-12-05 2016-06-15 엘지이노텍 주식회사 발광 모듈
WO2017126440A1 (fr) * 2016-01-22 2017-07-27 日本特殊陶業株式会社 Élément de conversion de longueur d'onde et dispositif d'émission de lumière

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Cited By (12)

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Publication number Priority date Publication date Assignee Title
EP2752897A4 (fr) * 2011-10-07 2015-04-29 Konica Minolta Inc Procédé de fabrication de dispositif à del et solution à matière fluorescente dispersée utilisée dans celui-ci
US9318646B2 (en) 2011-10-07 2016-04-19 Konica Minolta, Inc. LED device manufacturing method and fluorescent material-dispersed solution used in same
JP2013165223A (ja) * 2012-02-13 2013-08-22 Konica Minolta Inc 波長変換素子及びその製造方法、発光装置及びその製造方法、蛍光体分散液
WO2014048997A1 (fr) * 2012-09-28 2014-04-03 Osram Opto Semiconductors Gmbh Procédé de fabrication d'un composant optoélectronique
KR20160068267A (ko) * 2014-12-05 2016-06-15 엘지이노텍 주식회사 발광 모듈
KR102294163B1 (ko) 2014-12-05 2021-08-27 쑤저우 레킨 세미컨덕터 컴퍼니 리미티드 발광 모듈
WO2017126440A1 (fr) * 2016-01-22 2017-07-27 日本特殊陶業株式会社 Élément de conversion de longueur d'onde et dispositif d'émission de lumière
JPWO2017126440A1 (ja) * 2016-01-22 2018-02-01 日本特殊陶業株式会社 波長変換部材および発光装置
KR20180083380A (ko) * 2016-01-22 2018-07-20 니뽄 도쿠슈 도교 가부시키가이샤 파장 변환 부재 및 발광 장치
CN108474543A (zh) * 2016-01-22 2018-08-31 日本特殊陶业株式会社 波长转换构件以及发光装置
KR102078532B1 (ko) * 2016-01-22 2020-02-19 니뽄 도쿠슈 도교 가부시키가이샤 파장 변환 부재 및 발광 장치
US10707385B2 (en) 2016-01-22 2020-07-07 Ngk Spark Plug Co., Ltd. Wavelength conversion member and light-emitting device

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