WO2015025526A1 - Dispositif à del, et procédé de fabrication associé - Google Patents

Dispositif à del, et procédé de fabrication associé Download PDF

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Publication number
WO2015025526A1
WO2015025526A1 PCT/JP2014/004335 JP2014004335W WO2015025526A1 WO 2015025526 A1 WO2015025526 A1 WO 2015025526A1 JP 2014004335 W JP2014004335 W JP 2014004335W WO 2015025526 A1 WO2015025526 A1 WO 2015025526A1
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light
layer
mass
led device
component
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PCT/JP2014/004335
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English (en)
Japanese (ja)
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有由見 米崎
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コニカミノルタ株式会社
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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
    • H01L33/52—Encapsulations
    • H01L33/56—Materials, e.g. epoxy or silicone resin
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/85—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a wire connector
    • H01L2224/85909—Post-treatment of the connector or wire bonding area
    • H01L2224/8592—Applying permanent coating, e.g. protective coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181—Encapsulation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/44—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 an LED device having a light-emitting element and a light-transmitting layer that seals the substrate surface, and a method for manufacturing the LED device.
  • a white LED device in which a phosphor such as a YAG phosphor is arranged in the vicinity of a gallium nitride (GaN) blue LED (Light Emitting Diode) chip has been developed.
  • the blue light emitted from the blue LED chip and the yellow light emitted from the phosphor in response to the blue light are mixed to obtain white light.
  • a white LED device in which various phosphors are arranged in the vicinity of the blue LED chip has also been developed.
  • white LED device white light is obtained by mixing blue light emitted from the blue LED chip with red light and green light emitted from the phosphor upon receiving the blue light.
  • Such white LED devices are widely applied as alternatives to conventional fluorescent lamps and incandescent lamps, and further improvement in light extraction efficiency and longer life are required.
  • the LED element may be deteriorated by the humidity in the environment, or the lead electrode or the metal reflective layer on the substrate may be corroded by the hydrogen sulfide gas in the environment.
  • the light extraction efficiency of the LED device decreases. Therefore, a general LED device employs a method in which an LED element, an electrode on a substrate, and the like are directly sealed with an epoxy resin or a silicone resin (see Patent Documents 1 to 3).
  • epoxy resin is easily deteriorated by heat and light, and is deteriorated and colored by short wavelength light (for example, blue light).
  • short wavelength light for example, blue light
  • the LED element that is a light source and a heat source and the epoxy resin are close to each other, so that the influence of deterioration and coloring increases. Therefore, there has been a problem that the light transmittance of the sealing resin gradually decreases, and the light extraction efficiency from the LED device decreases.
  • the silicone resin has a low barrier property against water vapor and hydrogen sulfide gas, and there is a problem that the deterioration of the LED element and the corrosion of the metal cannot be sufficiently suppressed only by sealing with the silicone resin.
  • an LED element or the like is sealed with a layer made of an amorphous solid mainly containing ZrO.
  • An amorphous solid mainly containing ZrO has a very high refractive index and is close to the refractive index of the surface of the LED element. Therefore, in this technique, reflection of light at the interface between the sealing layer and the LED element is suppressed to increase the light extraction efficiency from the LED device.
  • Japanese Patent No. 2927279 Japanese Patent No. 3349111 U.S. Pat. No. 7,629,621 Japanese Patent No. 5059251
  • the zirconium alkoxide which is the material of the sealing layer of Patent Document 4
  • the polycondensation reaction of the alkoxide proceeds very fast.
  • the film obtained by polycondensation of the alkoxide is likely to be distorted and cracks are likely to occur. That is, the sealing layer of Patent Document 4 cannot sufficiently suppress deterioration of the LED element, metal corrosion, and the like. For this reason, it has been difficult to maintain the light extraction efficiency of the LED device over a long period of time.
  • an object of the present invention is to provide an LED device that has excellent barrier properties against humidity and hydrogen sulfide gas, and has high light extraction efficiency over a long period of time, and a method for manufacturing the same.
  • the present invention provides the following LED device.
  • An LED device having a substrate having a lead electrode, an LED element electrically connected to the lead electrode, and a light-transmitting layer covering the LED element and the lead electrode, wherein the light-transmitting layer There comprises SiO 2 component less than 50 wt% to 90 wt%, and containing ZrO component less than 10 wt% to 50 wt%, LED device.
  • An LED device having a substrate and an LED element mounted on the substrate, wherein the LED device has a light-transmitting layer covering at least one of the LED element and the substrate, and the light-transmitting layer is SiO 2.
  • the LED device which contains 50 mass% or more and less than 90 mass% of components, and contains ZrO component 10 mass% or more and less than 50 mass%.
  • At least a part of the SiO 2 component is a component derived from one or more silane compounds selected from the group consisting of a bifunctional silane compound, a trifunctional silane compound, and a tetrafunctional silane compound.
  • LED device [4] The LED device according to any one of [1] to [3], wherein the light transmitting layer includes a cyclic ether compound. [5] The LED device according to any one of [1] to [4], wherein the light transmitting layer has a thickness of 0.1 ⁇ m or more and 10 ⁇ m or less.
  • the light transmitting layer composition is selected from the group consisting of a bifunctional silane compound, a trifunctional silane compound, and a tetrafunctional silane compound.
  • a method for producing an LED device comprising at least one silane compound or a polymer thereof and a metal chelate or metal alkoxide of zirconium.
  • the light-transmitting layer composition is formed of a bifunctional silane compound, a trifunctional silane compound, and a tetrafunctional silane compound.
  • a method for producing an LED device comprising one or more silane compounds or polymers thereof selected from the group consisting of a metal chelate or metal alkoxide of zirconium.
  • the composition for light transmissive layer further includes a silane coupling agent, and the amount of the silane coupling agent is 0.1% by mass or more based on the total solid content of the composition for light transmissive layer.
  • the translucent layer of the LED device of the present invention has a high barrier property against humidity and hydrogen sulfide gas. Moreover, the LED device which can maintain high light extraction efficiency over a long period of time can be obtained.
  • the LED device 100 of the present invention includes a substrate 1, an LED element 2, and a translucent layer 3 that covers at least one of the substrate 1 and the LED element 2. .
  • the LED device 100 may further include a wavelength conversion layer 4 that covers the LED element 2 and the translucent layer 3.
  • the translucent layer 3 contains a SiO 2 component and a ZrO component.
  • the SiO 2 component refers to silicon and oxygen that are siloxane-bonded in the light-transmitting layer
  • the ZrO component refers to zirconium and oxygen that are metalloxane-bonded in the light-transmitting layer.
  • the layer containing ZrO as a main component is likely to crack during the film formation, and it is difficult to increase the barrier property against humidity and hydrogen sulfide. Furthermore, the layer containing ZrO as a main component has a large refractive index difference from the wavelength conversion layer and the like, and light is likely to be reflected at these interfaces. Therefore, it is difficult to sufficiently improve the light extraction from the LED device.
  • the light-transmitting layer 3 of the LED device 100 of the present invention contains 50% by mass or more of SiO 2 component and 10% by mass or more and less than 50% by mass of ZrO component.
  • the SiO 2 component can be obtained by polymerizing, for example, alkoxysilane or aryloxysilane (a bifunctional silane compound, a trifunctional silane compound, or a tetrafunctional silane compound). Proceed relatively slowly. Therefore, the light-transmitting layer 3 having a SiO 2 component of 50% by mass or more has few cracks, and the moisture resistance and hydrogen sulfide gas resistance of the light-transmitting layer 3 are likely to increase. Therefore, it is possible to maintain high light extraction efficiency over a long period of time.
  • the refractive index of the light-transmitting layer 3 does not increase excessively. Therefore, in the LED device 100 of the present invention, when the light transmissive layer 3 covers the LED element 2, the refractive index gradually decreases in the order of LED element 2 / light transmissive layer 3 / wavelength conversion layer 4. As a result, the reflection of light at the interface of each member is suppressed, and the light extraction efficiency from the LED device 100 is likely to increase.
  • zirconium forms a strong metalloxane bond with an OH group or the like present on the surface of the substrate 1 or the LED element 2. Therefore, in the translucent layer containing 10% by mass or more of the ZrO component, the adhesion between the substrate 1 or the LED element 2 and the translucent layer 3 is likely to increase.
  • the ZrO component often forms nano-sized clusters in the light-transmitting layer.
  • Such a cluster exhibits a photocatalytic effect, and converts hydrogen sulfide gas having high metal corrosivity into sulfur dioxide gas having low corrosivity. Therefore, the metal covered with the translucent layer 3 including such clusters is very unlikely to corrode.
  • the substrate 1 is a member for holding the LED element 2 and has a lead electrode 11.
  • the lead electrode 11 is a member that supplies electricity to the LED element 2 from a power source (not shown) arranged outside the substrate 1.
  • the lead electrode 11 may also serve as a reflection layer for reflecting the light from the LED element 2 and the light from the wavelength conversion layer 4 to the light extraction surface side.
  • the shape of the lead electrode 11 is appropriately selected according to the type and application of the light emitting device 100.
  • the substrate 1 may have a cavity (concave portion) as shown in FIG. 1, or may have a flat plate shape as shown in FIG.
  • the shape of the cavity that the substrate 1 has is not particularly limited. For example, it may be a truncated cone shape, and may be a truncated pyramid shape, a cylindrical shape, a prismatic shape, or the like.
  • the substrate 1 preferably has insulating properties and heat resistance, and is preferably made of a ceramic resin or a heat resistant resin.
  • the heat resistant resin include liquid crystal polymer, polyphenylene sulfide, aromatic nylon, epoxy resin, hard silicone resin, polyphthalic acid amide and the like.
  • the substrate 1 may contain an inorganic filler.
  • the inorganic filler can be titanium oxide, zinc oxide, alumina, silica, barium titanate, calcium phosphate, calcium carbonate, white carbon, talc, magnesium carbonate, boron nitride, glass fiber, and the like.
  • the manufacturing method of the substrate 1 having the lead electrode 11 is not particularly limited, and is generally obtained by integrally molding a lead frame having a desired shape and a resin.
  • the LED element 2 is electrically connected to the lead electrode 11 formed on the surface of the substrate 1 and emits light of a specific wavelength.
  • the wavelength of the light emitted from the LED element 2 is not particularly limited.
  • the LED element 2 may be, for example, an element that emits blue light (light of about 420 nm to 485 nm) or an element that emits ultraviolet light.
  • the configuration of the LED element 2 is not particularly limited.
  • the LED element 2 is an element that emits blue light
  • the LED element 2 includes an n-GaN compound semiconductor layer (cladding layer), an InGaN compound semiconductor layer (light emitting layer), and a p-GaN compound semiconductor layer. It may be a laminate of (cladding layer) and a transparent electrode layer.
  • the LED element 2 may have a light emitting surface of 200 to 300 ⁇ m ⁇ 200 to 300 ⁇ m, for example.
  • the height of the LED element 2 is usually about 50 to 200 ⁇ m. In the LED device 100 shown in FIG. 1, only one LED element 2 is disposed on the substrate 1, but a plurality of LED elements 2 may be disposed on the substrate 1.
  • connection method between the LED element 2 and the lead electrode 11 formed on the surface of the substrate 1 is not particularly limited.
  • the LED element 2 and the lead electrode 11 may be connected via a wire 12.
  • the LED element 2 and the lead electrode 11 may be connected via the protruding electrode 13.
  • a mode in which the LED element 3 and the metal wiring (lead electrode) 11 are connected via the wire 12 is referred to as a wire bonding type.
  • a mode in which the LED element 2 and the lead electrode 11 are connected via the protruding electrode 13 is called a flip chip bonding type.
  • the gap between the LED element 2 and the substrate 1 may be filled with an underfill material (not shown).
  • the underfill material can be a silicone resin, an epoxy resin, or the like. Moreover, you may consist of a material similar to the light-transmissive layer 3 mentioned later.
  • the translucent layer 3 is a layer that covers the surface of one or both of the LED element 2 and the substrate 1, and leads formed on the LED element 2 and the substrate 1. This is a layer that protects the electrode 11, the LED element 2, and the like from humidity outside the LED device and hydrogen sulfide gas.
  • the translucent layer 3 may be a layer that covers the surface of the LED element 2 or the substrate 1 on the side where the LED element 2 is disposed, and may be a layer that covers the entire surface of the LED element 2 and the substrate 1. It may be a layer that covers only the LED element 2 or a layer that covers a partial region of the substrate 1. However, the translucent layer 3 is preferably a layer that covers a member made of metal, such as the lead electrode 11 on the substrate 1 or a metal reflection layer, and further the LED element 2.
  • the translucent layer 3 contains a SiO 2 component.
  • the SiO 2 component is derived from an alkoxysilane or aryloxysilane (a bifunctional silane compound, a trifunctional silane compound, or a tetrafunctional silane compound), a component derived from silicon oxide particles or the like, or a silane coupling agent. Although it may be a component or the like, it is preferably a component mainly derived from alkoxysilane or aryloxysilane.
  • the amount of the SiO 2 component contained in the light transmissive layer 3 is 50% by weight or more and less than 90% by weight, preferably 55 to 80% by weight, and more preferably 60% by weight with respect to the total weight of the light transmissive layer 3. -70% by mass.
  • the amount of the SiO 2 component contained in the light transmissive layer 3 is 50% by mass or more, the light transmissive layer 3 is hardly cracked as described above.
  • the amount of the SiO 2 component exceeds 90% by mass, the amount of the ZrO component is relatively decreased, and the adhesion between the light-transmitting layer 3 and the substrate 1 may not be sufficiently increased.
  • the amount of the SiO 2 component contained in the light transmissive layer 3 is adjusted by the amount of the silane compound, the amount of silicon oxide particles, the amount of the silane coupling agent, etc. at the time of forming the light transmissive layer.
  • the translucent layer 3 contains a ZrO component.
  • the ZrO component may be a component derived from zirconium metal alkoxide or metal chelate, a component derived from zirconium oxide particles, or the like, but is preferably mainly a component derived from zirconium metal alkoxide or metal chelate.
  • the amount of the ZrO component contained in the light transmissive layer 3 is 10% by weight or more and less than 50% by weight, preferably 15 to 40% by weight, more preferably 20 to 30%, based on the total weight of the light transmissive layer 3. % By mass. As described above, when the amount of the ZrO component is too large, cracks are likely to occur in the light-transmitting layer 3, and the light-transmitting layer 3 may easily transmit hydrogen sulfide gas. On the other hand, if the amount of the ZrO component contained in the light transmissive layer 3 is too small, the adhesion between the light transmissive layer 3 and the substrate 1 or the like is not sufficiently increased. The amount of the ZrO component contained in the light transmissive layer 3 is adjusted by the amount of zirconium metal alkoxide or metal chelate, the amount of zirconium oxide particles, and the like during film formation of the light transmissive layer.
  • the transparent layer 3 may contain components other than SiO 2 component and the ZrO component but the total of SiO 2 component and the ZrO component, 60 to 99% by weight relative to the total weight of the transparent layer 3 Preferably, it is 70 to 98.5% by mass, and more preferably 80 to 98% by mass. If the light-transmitting layer 3 contains a large amount of components other than the SiO 2 component and the ZrO component, the moisture resistance and hydrogen sulfide gas resistance of the light-transmitting layer 3 are likely to be lowered.
  • the amount of the SiO 2 component and the ZrO component contained in the light transmissive layer 3 is obtained by ICP analysis of the amount of silicon and the amount of zirconium contained in the light transmissive layer 3, and the amount of SiO 2 component calculated from these analysis results, And ZrO component amount.
  • the light-transmitting layer 3 further includes a hydrocarbon component (organic group) bonded to Si or Zr.
  • the hydrocarbon component may be an organic group contained in a bifunctional silane compound or a trifunctional silane compound, a zirconium metal alkoxide, or a metal chelate that is a raw material of the light transmissive layer 3.
  • the crosslink density is not excessively increased when the light transmissive layer 3 is formed, and the light transmissive layer 3 is hardly cracked.
  • the flexibility of the light transmissive layer 3 is likely to increase, and the light transmissive layer 3 can easily follow the deformation of the substrate 1 and the like. Therefore, even when the substrate 1 or the like expands or contracts when the LED device is used, they are difficult to peel off at the interface between the translucent layer 3 and the substrate 1 or the like.
  • the amount of the hydrocarbon component contained in the translucent layer 3 is preferably 5 to 40% by mass, preferably 15 to 40% by mass, and more preferably 20 to 20% by mass with respect to the total mass of the translucent layer 3. 35% by mass.
  • the amount of the hydrocarbon component contained in the light transmissive layer 3 is adjusted by the type and amount of the silane compound, zirconium metal alkoxide, or metal chelate that is the raw material of the light transmissive layer 3.
  • the amount of the hydrocarbon component contained in the light transmissive layer 3 is determined as follows.
  • the translucent layer 3 is immersed in an organic solvent, and the organic component contained in the translucent layer 3 is removed. And the translucent layer 3 after organic component removal is baked at 500 degreeC for about 1 hour, and let the weight reduction amount by baking be the quantity of the hydrocarbon component (organic group) couple
  • the light-transmitting layer 3 further contains a cyclic ether compound.
  • a cyclic ether compound When the LED device 100 is used in a humid heat environment, metal ions are generated from the lead electrode 11 or the like, and the metal ions may move to the light-transmitting layer 3 and be precipitated (migration). In contrast, when the light transmitting layer 3 contains a cyclic ether compound, the metal ions that have flowed out are captured and corrosion (migration or the like) of the lead electrode 11 or the like is suppressed.
  • the amount of the cyclic ether compound contained in the light transmissive layer 3 is preferably 0.5 to 5% by mass, preferably 1 to 4% by mass, and more preferably, with respect to the total mass of the light transmissive layer 3. 2 to 3% by mass.
  • the cyclic ether compound contained in the light transmissive layer 3 is 0.5% by mass or more, corrosion of the lead electrode 11 and the like is easily suppressed.
  • the amount of the cyclic ether compound exceeds 5% by mass, the amounts of the SiO 2 component and the ZrO component are relatively reduced, and the moisture resistance and hydrogen sulfide gas resistance of the light-transmitting layer 3 are hardly sufficiently increased.
  • the amount of the cyclic ether compound contained in the light transmissive layer 3 is determined as follows.
  • the light transmissive layer 3 is immersed in an organic solvent or the like, and the organic components contained in the light transmissive layer 3 are extracted. And when an organic component is only cyclic ether, let the mass of an extract be the mass of a cyclic ether compound.
  • the mass after isolation is defined as the amount of the cyclic ether compound.
  • the structure of the organic component is confirmed by NMR analysis or the like.
  • the thickness of the light transmitting layer 3 is not particularly limited, but is preferably 0.1 ⁇ m or more and 10 ⁇ m or less, more preferably 0.3 ⁇ m or more and 4 ⁇ m or less, and further preferably 0.5 ⁇ m or more and 1 ⁇ m or less. If the thickness of the light-transmitting layer 3 is excessively thick, distortion is likely to occur when the light-transmitting layer 3 is formed, and cracks may occur. On the other hand, if the thickness of the translucent layer 3 is excessively thin, the translucent layer 3 does not sufficiently protect the LED element 2, the lead electrode 11, etc., and the deterioration with time may not be sufficiently suppressed.
  • the thickness of the light transmissive layer 3 is the maximum thickness of the light transmissive layer 3 disposed on the upper surface of the LED element 2 when the light transmissive layer 3 covers the LED element 2. Moreover, when the translucent layer 3 covers only the substrate 1, the maximum thickness of the translucent layer 3 formed on the substrate 1 is set. The layer thickness is measured using a laser holo gauge.
  • the raw material and the film forming method are not particularly limited, but the light-transmitting layer composition described below; Specifically, a composition containing at least one silane compound selected from the group consisting of a bifunctional silane compound, a trifunctional silane compound, and a tetrafunctional silane compound or a polymer thereof and a metal chelate or metal alkoxide of zirconium is applied. And a layer obtained by curing.
  • the LED device may include the wavelength conversion layer 4.
  • the wavelength conversion layer 4 is a layer that converts light having a specific wavelength emitted from the LED element 2 into light having another specific wavelength.
  • the wavelength conversion layer 4 may be a layer in which phosphor particles are dispersed in a binder.
  • the phosphor particles contained in the wavelength conversion layer 4 may be anything that is excited by light emitted from the LED element 2 and emits fluorescence having a wavelength different from that of the emitted light from the LED element 2.
  • examples of phosphor particles that emit yellow fluorescence include YAG (yttrium, aluminum, garnet) phosphors.
  • the YAG phosphor receives blue light (wavelength 420 nm to 485 nm) emitted from the blue LED element, and emits yellow fluorescence (wavelength 550 nm to 650 nm).
  • the phosphor particles are, for example, 1) An appropriate amount of flux (fluoride such as ammonium fluoride) is mixed with a mixed raw material having a predetermined composition, and pressed to form a molded body. 2) The obtained molded body is 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.
  • flux fluoride such as ammonium fluoride
  • a mixed raw material having a predetermined composition is obtained by sufficiently mixing oxides such as Y, Gd, Ce, Sm, Al, La, and Ga, or compounds that easily become oxides at high temperatures in a stoichiometric ratio. .
  • the mixed raw material which has a predetermined composition mixes the solution which dissolved 1) the rare earth elements of Y, Gd, Ce, and Sm in the acid in stoichiometric ratio, and oxalic acid, and obtains a coprecipitation oxide. 2) It can also be obtained by mixing this coprecipitated oxide with aluminum oxide or gallium oxide.
  • the kind of the phosphor is not limited to the YAG phosphor, and may be another phosphor such as a non-garnet phosphor that does not contain Ce.
  • the average particle diameter of the phosphor particles is preferably 1 ⁇ m to 50 ⁇ m, and more preferably 10 ⁇ m or less.
  • the particle diameter of the phosphor particles is too large, a gap generated at the interface between the phosphor particles and the binder becomes large. Thereby, the intensity
  • the average particle diameter of the phosphor particles refers to the value of D50 measured with a laser diffraction particle size distribution meter. Examples of the laser diffraction particle size distribution measuring device include a laser diffraction particle size distribution measuring device manufactured by Shimadzu Corporation.
  • the binder contained in the wavelength conversion layer 4 can be a transparent resin or a translucent ceramic.
  • the transparent resin can be, for example, a silicone resin and an epoxy resin.
  • the thickness of the wavelength conversion layer 4 is preferably about 25 ⁇ m to 5 mm. If the wavelength conversion layer 4 is too thick, the concentration of the phosphor particles becomes excessively low, and the phosphor particles may not be uniformly dispersed.
  • the thickness of the wavelength conversion layer 4 means the maximum thickness of the wavelength conversion layer 4 formed on the light emitting surface of the LED element 2.
  • the thickness of the wavelength conversion layer 4 can be measured with a laser holo gauge.
  • the binder is a transparent resin, the amount of phosphor particles contained in the wavelength conversion layer 4 is usually 5 to 15% by mass.
  • the translucent ceramic may be a polycondensate of alkoxysilane or aryloxysilane, that is, polysiloxane.
  • the wavelength conversion layer 4 preferably has a thickness of 5 to 200 ⁇ m.
  • the thickness of the wavelength conversion layer 4 means the maximum thickness of the wavelength conversion layer 4 formed on the light emitting surface of the LED element 2. The thickness of the wavelength conversion layer 4 can be measured with a laser holo gauge.
  • the amount of the phosphor particles contained in the wavelength conversion layer 4 is preferably 60 to 95% by mass.
  • the concentration of the phosphor particles is high, the strength of the wavelength conversion layer 4 tends to increase.
  • the content ratio of the translucent ceramic is too small, the phosphor particles may not be sufficiently retained.
  • the translucent layer of the LED device described above may be a layer obtained by applying and curing the following translucent layer composition.
  • the translucent layer composition includes one or more silane compounds selected from the group consisting of a bifunctional silane compound, a trifunctional silane compound, and a tetrafunctional silane compound, or a polymer thereof, and a metal chelate or metal alkoxide of zirconium.
  • a composition for a light transmissive layer is included.
  • the composition for a light transmissive layer further includes inorganic oxide fine particles, a cyclic ether compound, a silane coupling agent, a solvent, and the like as necessary.
  • the light-transmitting layer composition includes at least one silane compound (monomer) selected from the group consisting of a bifunctional silane compound, a trifunctional silane compound, and a tetrafunctional silane compound, Or the polymer (oligomer) is included.
  • the polymer (oligomer) of the silane compound may be a compound in which several to several tens of monomers of the silane compound are polymerized.
  • each R 4 independently represents an alkyl group or a phenyl group, preferably an alkyl group having 1 to 5 carbon atoms, or a phenyl group.
  • R 5 represents a hydrogen atom or an alkyl group.
  • bifunctional silane compound examples include dimethoxysilane, diethoxysilane, dipropoxysilane, dipentyloxysilane, diphenyloxysilane, methoxyethoxysilane, methoxypropoxysilane, methoxypentyloxysilane, methoxyphenyloxysilane, ethoxypropoxy.
  • Examples of the trifunctional silane compound include a compound represented by the following general formula (III).
  • R 1 Si (OR 2 ) 3 (III) R 1 each independently represents an alkyl group or a phenyl group, preferably an alkyl group having 1 to 5 carbon atoms, or a phenyl group.
  • R 2 represents a hydrogen atom or an alkyl group.
  • trifunctional silane compounds include trimethoxysilane, triethoxysilane, tripropoxysilane, tripentyloxysilane, triphenyloxysilane, dimethoxymonoethoxysilane, diethoxymonomethoxysilane, dipropoxymonomethoxysilane, di Propoxymonoethoxysilane, dipentyloxylmonomethoxysilane, dipentyloxymonoethoxysilane, dipentyloxymonopropoxysilane, diphenyloxylmonomethoxysilane, diphenyloxymonoethoxysilane, diphenyloxymonopropoxysilane, methoxyethoxypropoxysilane, monopropoxydimethoxysilane Monopropoxydiethoxysilane, monobutoxydimethoxysilane, monopentyloxydiethoxysilane, monophenyl Monohydrosilane compounds such as ruoxydiethoxy
  • each R 3 independently represents an alkyl group or a phenyl group, preferably an alkyl group having 1 to 5 carbon atoms, or a phenyl group.
  • tetrafunctional silane compounds include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetrapentyloxysilane, tetraphenyloxysilane, trimethoxymonoethoxysilane, dimethoxydiethoxysilane, and triethoxymonomethoxy.
  • Silane trimethoxymonopropoxysilane, monomethoxytributoxysilane, monomethoxytripentyloxysilane, monomethoxytriphenyloxysilane, dimethoxydipropoxysilane, tripropoxymonomethoxysilane, trimethoxymonobutoxysilane, dimethoxydibutoxysilane, Triethoxymonopropoxysilane, diethoxydipropoxysilane, tributoxymonopropoxysilane, dimethoxymonoethoxymonobutoxy Silane, diethoxymonomethoxymonobutoxysilane, diethoxymonopropoxymonobutoxysilane, dipropoxymonomethoxymonoethoxysilane, dipropoxymonomethoxymonobutoxysilane, dipropoxymonoethoxymonobutoxysilane, dipropoxymonoethoxymonobutoxysilane, dipropoxymonoethoxymonobutoxy
  • the oligomer of the silane compound is obtained by mixing the above-mentioned bifunctional silane compound, trifunctional silane compound, and tetrafunctional silane compound in a desired ratio and reacting them in the presence of an acid catalyst, water, and a solvent.
  • the oligomer of the silane compound preferably has a weight average molecular weight measured by GPC (gel permeation chromatograph) of 500 to 20000, more preferably 1000 to 10,000, and still more preferably 1500 to 6000. If the degree of polymerization of the oligomer is too high, the viscosity of the coating solution may increase or the components may precipitate.
  • the molecular weight of the oligomer of the silane compound is adjusted by the reaction time, temperature, water concentration, and the like.
  • the amount of the silane compound or polymer thereof contained in the composition for light transmissive layer is preferably 50 to 95% by mass with respect to the solid content (total mass excluding solvent) of the composition for light transmissive layer. More preferably, it is 55 to 90% by mass, and still more preferably 60 to 80% by mass.
  • the composition for a light transmissive layer contains a silane compound or a polymer thereof in an amount of 50% by mass or more, moisture resistance and hydrogen sulfide gas resistance of the obtained light transmissive layer 3 are likely to be increased.
  • the zirconium metal alkoxide or metal chelate contained in the light-transmitting layer composition may be a compound represented by the following general formula (V). Zr 4+ X n Y 4-n (V) In general formula (V), n represents the number of X groups and is an integer of 2 or more and 4 or less.
  • X represents a hydrolyzable group, and may be a group that is hydrolyzed to generate a hydroxyl group.
  • the hydrolyzable group include a lower alkoxy group having 1 to 5 carbon atoms, an acetoxy group, a butanoxime group, a chloro group and the like.
  • all the groups represented by X may be the same group or different groups.
  • the hydrolyzable group represented by X is hydrolyzed and separated when zirconium forms a metalloxane bond with the hydroxyl group or silane compound on the surface of the substrate 1, but the compound that X is produced after hydrolysis is It is preferable that it is volatile and light boiling. Therefore, the group represented by X is preferably a lower alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group or an ethoxy group.
  • the monovalent organic group represented by Y may be the same group as the monovalent organic group contained in a general silane coupling agent. Specifically, the aliphatic group, alicyclic group, aromatic group, fatty acid having 1 to 1000 carbon atoms, preferably 500 or less, more preferably 100 or less, further preferably 40 or less, and particularly preferably 6 or less. It may be a ring aromatic group.
  • the organic group represented by Y may be an aliphatic group, an alicyclic group, an aromatic group, or a group in which an alicyclic aromatic group is bonded via a linking group.
  • the linking group can be an atom such as O, N, or S, or an atomic group containing these.
  • the organic group represented by Y may have a substituent.
  • substituents include halogen atoms such as F, Cl, Br, and I; vinyl group, methacryloxy group, acryloxy group, styryl group, mercapto group, epoxy group, epoxycyclohexyl group, glycidoxy group, amino group, cyano group, Organic groups such as nitro group, sulfonic acid group, carboxy group, hydroxy group, acyl group, alkoxy group, imino group and phenyl group are included.
  • metal alkoxide or metal chelate of zirconium represented by the general formula (V) include zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetra n-propoxide, zirconium tetra i-propoxide, zirconium tetra n. -Butoxide, zirconium tetra-i-butoxide, zirconium tetra-t-butoxide, zirconium dimethacrylate dibutoxide, dibutoxyzirconium bis (ethylacetoacetate) and the like.
  • the amount of the metal alkoxide or metal chelate of zirconium contained in the composition for light transmissive layer is preferably 5 to 50% by mass with respect to the solid content (total mass excluding the solvent) of the composition for light transmissive layer. More preferably, it is 8 to 40% by mass, and further preferably 10 to 30% by mass.
  • the amount of the metal alkoxide or metal chelate of zirconium is 5% by mass or more, the above-described adhesion improving effect can be sufficiently obtained.
  • the amount of the metal alkoxide or metal chelate of zirconium is 50% by mass or less, the storage stability of the light-transmitting layer composition is improved.
  • the light-transmitting layer composition may contain inorganic oxide fine particles.
  • inorganic oxide fine particles When inorganic oxide fine particles are contained in the composition for light transmissive layer, the strength of the light transmissive layer 3 obtained is likely to increase.
  • fine-particles are contained in the composition for translucent layers, a fine unevenness
  • the inorganic oxide fine particles may be zirconium oxide fine particles, silicon oxide fine particles, titanium oxide fine particles, zinc oxide fine particles and the like.
  • the average primary particle size of the inorganic oxide fine particles is preferably 1 nm or more and 100 nm or less, more preferably 1 nm or more and 50 nm or less.
  • the average primary particle size of the inorganic oxide fine particles is measured, for example, by a Coulter counter method.
  • the inorganic oxide fine particles may be porous, and the specific surface area is preferably 200 m 2 / g or more.
  • the viscosity of the light transmitting layer composition is likely to increase, and the inorganic oxide fine particles and the like are less likely to settle in the light transmitting layer composition.
  • the amount of the inorganic oxide fine particles contained in the light transmissive layer composition is preferably 5 to 50% by weight, more preferably based on the solid content of the light transmissive layer composition (total weight excluding solvent). 10 to 30% by mass.
  • the amount of the inorganic oxide is less than 5% by mass, the strength of the obtained light-transmitting layer 3 is difficult to increase, and the above-described adhesion improving effect is hardly obtained.
  • the amount of the inorganic oxide exceeds 50% by mass, the translucent layer 3 becomes brittle, and the strength of the translucent layer 3 decreases.
  • the surface of the inorganic oxide fine particles may be treated with a silane coupling agent or a titanium coupling agent. By the surface treatment, the compatibility between the inorganic oxide fine particles and the polysiloxane or the solvent is easily increased.
  • the light-transmitting layer composition may contain a cyclic ether compound.
  • the cyclic ether compound traps metal ions generated from the lead electrode and the metal reflection layer of the substrate 1 in the light-transmitting layer 3 obtained by applying the light-transmitting layer composition. Therefore, when a cyclic ether compound is contained in the composition for light transmissive layer, metal migration that occurs when the LED device is used is suppressed.
  • the cyclic ether compound contained in the composition for light transmissive layer may be a cyclic compound represented by the following general formula (A). (—CH 2 —CH 2 —Z—) n (A)
  • Z represents O, NR (R represents hydrogen or an alkylene group having 1 to 1000 carbon atoms), or S.
  • n represents an integer of 1 or more.
  • Z represents O
  • NR represents hydrogen or an alkylene group having 1 to 1000 carbon atoms
  • S represents S.
  • n represents an integer of 1 or more.
  • Z represents O
  • NR represents hydrogen or an alkylene group having 1 to 1000 carbon atoms
  • n represents an integer of 1 or more.
  • Z represents O
  • NR represents hydrogen or an alkylene group having 1 to 1000 carbon atoms
  • n represents an integer of 1 or more.
  • the structure of the cyclic ether compound may contain a benzene ring or the like as shown in the following formula (B).
  • cyclic ether compound contained in the light-transmitting layer 3 include 12-crown-4-ether, 15-crown-5-ether, 18-crown-6-ether, 21-crown-7-ether, and dibenzo-ether. 18-crown-6-ether, diaza-18-crown-6-ether and the like.
  • the cyclic ether compound contained in the light transmitting layer is preferably a 15 to 21-membered ring compound, more preferably an 18-membered ring compound.
  • the amount of the cyclic ether compound contained in the composition for light transmissive layer is preferably 0.1 to 5.0% by mass with respect to the solid content (total mass excluding solvent) of the composition for light transmissive layer. More preferably, it is 0.5 to 3.0% by mass, and still more preferably 1.0 to 2.0% by mass.
  • the cyclic ether compound is contained in an amount of 0.1% by mass or more in the light transmitting layer composition, corrosion of the lead electrode 11 and the like is suppressed.
  • the light transmissive layer composition may contain a silane coupling agent.
  • a silane coupling agent is contained in the composition for light transmissive layer, the adhesion between the obtained light transmissive layer 3 and the substrate 1 or the LED element 2, or the adhesion between the light transmissive layer 3 and the wavelength conversion layer 4 is enhanced. .
  • peeling or the like hardly occurs at the interface of each layer, and the durability of the LED device is increased.
  • the silane coupling agent contained in the light-transmitting layer composition is not particularly limited as long as it has a reactive group capable of binding to silicon or zirconium, and may be a known silane coupling agent.
  • the silane coupling agent include an epoxy group-containing silane coupling agent, an amino group-containing silane coupling agent, a mercapto group-containing silane coupling agent, and an isocyanate group-containing silane coupling agent.
  • silane coupling agent contained in the light-transmitting layer composition examples include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycidoxypropyl.
  • the amount of the silane coupling agent contained in the composition for light transmissive layer is preferably 0.1 to 5% by mass with respect to the solid content (total mass excluding solvent) of the composition for light transmissive layer. More preferably, it is 2 to 3% by mass.
  • the adhesiveness of the translucent layer 3 obtained and the layer (For example, the board
  • the light transmissive layer composition may contain a solvent.
  • the solvent contained in the light-transmitting layer composition is not particularly limited as long as it can dissolve or disperse the above-mentioned silane compound or polymer thereof, zirconium metal alkoxide, metal chelate, and the like.
  • it may be an aqueous solvent having excellent compatibility with water, or may be a non-aqueous solvent having low compatibility with water.
  • Examples of the solvent contained in the light-transmitting layer composition include monoalcohols such as methanol, ethanol, propanol, and butanol; ethylene glycol, propylene glycol, diethylene glycol, glycerin, 1,3-butanediol, and 1,4-butanediol. And other polyhydric alcohols. Moreover, water may be contained in the composition for translucent layers.
  • the solvent contained in the light-transmitting layer composition preferably has a boiling point of 250 ° C. or lower. When the boiling point of the solvent is too high, drying of the composition for a light transmissive layer is delayed.
  • the amount of the solvent contained in the light transmissive layer composition is preferably 5 to 99% by weight, more preferably 20 to 99% by weight, based on the total weight of the light transmissive layer composition. Preferably, it is 50 to 99% by mass.
  • composition for light transmissive layer is not particularly limited, and the aforementioned silane compound or polymer thereof, zirconium metal alkoxide or metal chelate, cyclic ether compound, It may be a method in which inorganic oxide fine particles, a solvent and the like are mixed and prepared by stirring.
  • the method of stirring the mixed solution is not particularly limited, and may be a method of stirring using, for example, a stirring mill, a blade kneading stirring device, a thin film swirl type dispersing machine, or the like. It is preferable to suppress sedimentation of inorganic oxide fine particles by adjusting the stirring conditions.
  • Method for Manufacturing LED Device can be a method having the following two steps. (1) The process of preparing the board
  • a substrate having lead electrodes is prepared. And it may be a step of fixing the LED element to the substrate and connecting the lead electrode of the substrate 1 to the cathode electrode and the anode electrode of the LED element.
  • the method for connecting the LED element and the lead electrode and the method for fixing the LED element to the substrate are not particularly limited, and may be the same as a conventionally known method.
  • the aforementioned translucent layer composition is applied so as to cover the LED element, the lead electrode of the substrate, and the metal reflective layer.
  • the method for applying the light-transmitting layer composition is not particularly limited, and may be blade coating, spin coating coating, dispenser coating, spray coating, or the like. By spray coating, a thin light-transmitting layer can be formed.
  • the composition for light transmissive layers is apply
  • a conventionally known dispenser can be used as the dispenser for applying the light-transmitting layer composition.
  • it may be a jet dispenser that does not have a needle (hollow needle) in the discharge part of the composition for light transmissive layer.
  • a needle-type dispenser having a needle (hollow needle) in the discharge portion of the composition for light transmissive layer is more preferable from the viewpoint of reliably applying the composition for light transmissive layer to a desired region.
  • the coating film After application of the light transmissive layer composition, the coating film is heated to 120 ° C. or higher, preferably 150 to 300 ° C., to dry and cure the light transmissive layer composition.
  • the heating temperature is less than 120 ° C., moisture generated during the dehydration condensation of the silane compound or polymer thereof, zirconium metal alkoxide or metal chelate contained in the composition for the light transmissive layer is not sufficiently removed, and the light transmissive The hydrogen sulfide gas resistance of the layer may be reduced.
  • a wavelength conversion layer composition containing phosphor particles is applied on the above-described light transmitting layer and cured to form a wavelength conversion layer.
  • the composition for wavelength conversion layers may be a composition containing a binder component and phosphor particles.
  • the binder component contained in the composition for wavelength conversion layer may be the aforementioned transparent resin or a precursor thereof, a silane compound, or a polymer (oligomer) thereof.
  • a solvent is contained in the composition for wavelength conversion layers as needed.
  • the solvent contained in the composition for wavelength conversion layers is not particularly limited as long as it can dissolve or disperse the binder component.
  • the solvent is a hydrocarbon such as toluene or xylene; a ketone such as acetone or methyl ethyl ketone; an ether such as diethyl ether or tetrahydrofuran; propylene glycol monomethyl ether acetate, ethyl It may be an ester such as acetate.
  • the binder component is a silane compound
  • the solvent may be the same as the solvent contained in the light-transmitting layer composition.
  • the mixing of the composition for wavelength conversion layer can be performed, for example, with a stirring mill, a blade kneading stirring device, a thin-film swirling disperser or the like.
  • a stirring mill a blade kneading stirring device, a thin-film swirling disperser or the like.
  • the method for applying the wavelength conversion layer composition is appropriately selected according to the type of the binder component.
  • the binder component is a transparent resin or a precursor thereof, it can be dispenser application or the like.
  • the binder component is an organosilicon compound, it can be dispenser coating, spray coating, or the like.
  • the composition for wavelength conversion layer After the composition for wavelength conversion layer is applied, it is cured.
  • the curing method and curing conditions of the wavelength conversion layer composition are appropriately selected depending on the type of binder component.
  • An example of the curing method is heat curing.
  • LED device is further provided with other optical components (such as a lens) to form various optical members.
  • other optical components such as a lens
  • the LED device of the present invention is excellent in moisture resistance and hydrogen sulfide gas resistance, it is suitable for lighting for vehicles, lighting for outdoor use, and the like.
  • the obtained fired product was pulverized, washed, separated, and dried to obtain yellow phosphor particles having an average particle diameter of about 10 ⁇ m.
  • the emission wavelength of excitation light with a wavelength of 465 nm was measured, it had a peak wavelength at a wavelength of approximately 570 nm.
  • distributed to silicone resin was prepared.
  • concentration of the fluorescent substance particle contained in the composition for wavelength conversion layers was 8 mass%.
  • the wavelength conversion layer composition was potted in the concave portion of the substrate. And it baked at 150 degreeC for 1 hour, and the LED apparatus of the comparative example 1 was obtained.
  • the thickness of the wavelength conversion layer was 2.5 mm.
  • composition for translucent layer 60.0 g of methyltrimethoxysilane (KBM-13, manufactured by Shin-Etsu Chemical Co., Ltd.), 40.0 g of methanol, and 40.0 g of acetone were mixed and stirred. To the mixture, 54.6 g of water and 4.7 ⁇ L of 60% nitric acid were added, and the mixture was further stirred for 3 hours. Thereafter, it was aged at 26 ° C. for 2 days. The obtained composition was diluted with isopropyl alcohol so that the solid content concentration of the polysiloxane compound was 10% by mass to prepare a polysiloxane solution composed of a trifunctional silane compound.
  • the composition for light transmissive layer was filled in a coating solution tank of a dispenser device (manufactured by Musashi Engineering Co., Ltd., SM200DSS-3A), and coated so as to cover the LED element and the metal reflective layer.
  • a dispenser device manufactured by Musashi Engineering Co., Ltd., SM200DSS-3A
  • the air pressure of the dispenser was 0.1 MPa
  • the vacuum was 0 kPa
  • the coating time was 0.07 seconds.
  • the thickness of the obtained translucent layer was 0.95 ⁇ m.
  • the wavelength conversion layer was formed similarly to the comparative example 1, and the LED device which has an LED element, a translucent layer, and a wavelength conversion layer was obtained.
  • the thickness of the wavelength conversion layer was 2.5 mm.
  • Example 1 To the polysiloxane solution 1.3 g of Comparative Example 2, 0.325 g of Zr chelate (ZC700: Matsumoto Fine Chemical Co., Ltd. (solid content 20 mass%)), SiO 2 fine particles (TECNADIS-SI-230-1KG: TECNAN Co., Ltd.) 0.0722 g, butanol 0.4667 g, and isopropyl alcohol 33.95 g were added and stirred to obtain the light transmissive layer composition of Example 1. Subsequently, a light-transmitting layer and a wavelength conversion layer were formed in the same manner as in Comparative Example 2, and an LED device having an LED element, a light-transmitting layer, and a wavelength conversion layer was obtained. The thickness of the obtained translucent layer was 0.95 ⁇ m, and the thickness of the wavelength conversion layer was 2.5 mm.
  • ZC700 Matsumoto Fine Chemical Co., Ltd. (solid content 20 mass%)
  • SiO 2 fine particles TECNADIS-SI-230-1KG: TECN
  • Example 2 0.04645 g of Zr chelate (ZC700: manufactured by Matsumoto Fine Chemical Co., Ltd. (solid content: 20% by mass)) and ZrO fine particles (TECNADIS-ZR-220-1KG: manufactured by TECNAN) were added to 2.5 g of the polysiloxane solution of Comparative Example 2. 0.09285 g, butanol (0.4341 g) and isopropyl alcohol (28.94 g) were added and stirred to obtain the light transmissive layer composition of Example 2.
  • ZC700 manufactured by Matsumoto Fine Chemical Co., Ltd. (solid content: 20% by mass)
  • TECNADIS-ZR-220-1KG manufactured by TECNAN
  • a light-transmitting layer and a wavelength conversion layer were formed in the same manner as in Comparative Example 2, and an LED device having an LED element, a light-transmitting layer, and a wavelength conversion layer was obtained.
  • the thickness of the obtained translucent layer was 0.95 ⁇ m, and the thickness of the wavelength conversion layer was 2.5 mm.
  • Example 3 To the polysiloxane solution of Comparative Example 2, 0.0929 g of Zr chelate (ZC700: manufactured by Matsumoto Fine Chemical Co., Ltd. (solid content: 20% by mass)) and ZrO fine particles (TECNADIS-ZR-220-1KG: manufactured by TECNAN) were added. 0.1857 g, 0.4341 g of butanol, and 28.94 g of isopropyl alcohol were added and stirred to obtain the composition for light transmissive layer of Example 3. Subsequently, a light-transmitting layer and a wavelength conversion layer were formed in the same manner as in Comparative Example 2, and an LED device having an LED element, a light-transmitting layer, and a wavelength conversion layer was obtained. The thickness of the obtained translucent layer was 0.95 ⁇ m, and the thickness of the wavelength conversion layer was 2.5 mm.
  • ZC700 manufactured by Matsumoto Fine Chemical Co., Ltd. (solid content: 20% by mass)
  • ZrO fine particles TECNADIS-ZR
  • Example 4 To the polysiloxane solution 1.3 g of Comparative Example 2, 0.2167 g of Zr chelate (ZC700: manufactured by Matsumoto Fine Chemical Co., Ltd. (solid content: 20% by mass)) and ZrO fine particles (TECNADIS-ZR-220-1KG: manufactured by TECNAN) were added. 0.2167 g, 0.4767 g of butanol and 33.90 g of isopropyl alcohol were added and stirred to obtain the composition for light transmissive layer of Example 4. Subsequently, a light-transmitting layer and a wavelength conversion layer were formed in the same manner as in Comparative Example 2, and an LED device having an LED element, a light-transmitting layer, and a wavelength conversion layer was obtained. The thickness of the obtained translucent layer was 0.95 ⁇ m, and the thickness of the wavelength conversion layer was 2.5 mm.
  • ZC700 manufactured by Matsumoto Fine Chemical Co., Ltd. (solid content: 20% by mass)
  • ZrO fine particles TECNADIS
  • Example 5 To 1.3 g of the polysiloxane solution of Comparative Example 2, 0.325 g of Zr chelate (ZC700: manufactured by Matsumoto Fine Chemical Co., Ltd. (solid content: 20% by mass)) and ZrO fine particles (TECNADIS-ZR-220-1KG: manufactured by TECNAN) were added. 0.325 g, 0.4767 g of butanol, and 33.90 g of isopropyl alcohol were added and stirred to obtain the composition for light transmissive layer of Example 5.
  • ZC700 manufactured by Matsumoto Fine Chemical Co., Ltd. (solid content: 20% by mass)
  • ZrO fine particles TECNADIS-ZR-220-1KG: manufactured by TECNAN
  • a light-transmitting layer and a wavelength conversion layer were formed in the same manner as in Comparative Example 2, and an LED device having an LED element, a light-transmitting layer, and a wavelength conversion layer was obtained.
  • the thickness of the obtained translucent layer was 0.95 ⁇ m, and the thickness of the wavelength conversion layer was 2.5 mm.
  • Example 7 10.5 g of dimethoxydimethylsilane, 29.7 g of methyltrimethoxysilane, 19.9 g of tetramethoxysilane, 40.0 g of methanol, and 40.0 g of acetone were mixed and stirred. Thereto were added 54.6 g of water and 4.7 ⁇ L of 60% nitric acid, and the mixture was further stirred for 3 hours. Thereafter, it was aged at 26 ° C. for 2 days.
  • Example 7 solid content 20% by mass
  • TECNADIS-ZR-220-1KG manufactured by TECNAN
  • 0.4767 g of butanol and 33.90 g of isopropyl alcohol were added and stirred to obtain a composition for light transmissive layer of Example 7.
  • a light-transmitting layer and a wavelength conversion layer were formed in the same manner as in Comparative Example 2, and an LED device having an LED element, a light-transmitting layer, and a wavelength conversion layer was obtained.
  • the thickness of the obtained translucent layer was 0.95 ⁇ m
  • the thickness of the wavelength conversion layer was 2.5 mm.
  • Example 8 To 1.3 g of the polysiloxane solution of Example 7, 0.2 g of Zr chelate (ZC700: manufactured by Matsumoto Fine Chemical Co., Ltd. (solid content: 20% by mass)) and ZrO fine particles (TECNADIS-ZR-220-1KG: manufactured by TECNAN) were added. 0.2 g, 0.18 g of Al 2 O 3 fine particles (TECNADIS-AL-210-1KG: manufactured by TECNAN), 0.4767 g of butanol and 33.90 g of isopropyl alcohol were added and stirred. A composition for an optical layer was obtained.
  • ZC700 manufactured by Matsumoto Fine Chemical Co., Ltd. (solid content: 20% by mass)
  • TECNADIS-ZR-220-1KG: manufactured by TECNAN ZrO fine particles
  • a light-transmitting layer and a wavelength conversion layer were formed in the same manner as in Comparative Example 2, and an LED device having an LED element, a light-transmitting layer, and a wavelength conversion layer was obtained.
  • the thickness of the obtained translucent layer was 0.95 ⁇ m, and the thickness of the wavelength conversion layer was 2.5 mm.
  • the translucent layer was immersed in acetone and sonicated for 1 hour. Then, the presence or absence of a component (cyclic ether) extracted into acetone was confirmed, and when there was an extract, its weight was measured. Furthermore, the extract was subjected to NMR measurement to identify the chemical structure of the composition.
  • a component cyclic ether
  • the weight of the light transmitting layer was measured again. And it baked at 500 degreeC for 1 hour, and measured the weight after baking. Further, the volatile component during firing was subjected to gas chromatograph mass spectrometry (GC-MS), and it was confirmed that the volatile component was a hydrocarbon component.
  • GC-MS gas chromatograph mass spectrometry
  • ICP analysis was performed on the light-transmitting layer after firing at 500 ° C. Thus, it obtains the weight ratio of Si and Zr, SiO 2 component amount, and to identify the ZrO component amount.
  • ⁇ Crack resistance evaluation> About the translucent layer of the LED device, appearance observation was performed at a magnification of 1000 times by SEM (VE7800, manufactured by Keyence) before forming the wavelength conversion layer. The crack resistance was evaluated according to the following criteria. A: There is no crack with a length of 5 ⁇ m or more in the translucent layer. ⁇ : There is a crack with a length of 5 ⁇ m or more in the translucent layer, but there is no crack with a length of 10 ⁇ m or more. ⁇ : 10 ⁇ m or more in the translucent layer. There are 1 or more and less than 5 cracks in length ⁇ : The light transmitting layer has 5 or more cracks having a length of 10 ⁇ m or more
  • the wet heat resistance of the LED device was evaluated. Specifically, the LED device was continuously energized in a humid heat environment with a temperature of 85 ° C. and a relative humidity of 85% RH. The total luminous flux value was measured every 200 hours from the start of energization, and the total luminous flux decrease rate ((total luminous flux value before test ⁇ total luminous flux value after test) / total luminous flux value before test ⁇ 100) was calculated. The value was evaluated according to the following criteria. Evaluation was performed based on the total luminous flux reduction rate of the LED device of Comparative Example 1.
  • the total luminous flux reduction rate is smaller than the total luminous flux reduction rate after 800 hours of continuous energization in Comparative Example 1, but the total luminous flux reduction rate after 1000 hours of continuous energization is the total luminous flux reduction rate after 1000 hours of continuous energization in Comparative Example 1.
  • X The total luminous flux reduction rate after 600 hours of continuous energization is smaller than the total luminous flux reduction rate after 600 hours of continuous energization in Comparative Example 1, but the total luminous flux reduction rate after 800 hours of continuous energization is Comparative Example 1. 800 hours of continuous energization Is the total luminous flux reduction rate more
  • the LED device was evaluated for hydrogen sulfide gas resistance based on the gas exposure test of JIS standard (JIS C60068-2-43). The LED device was exposed to an environment of 15 ppm hydrogen sulfide gas, a temperature of 25 ° C., and a relative humidity of 75% RH for 1000 hours. The total luminous flux was measured for the LED devices before and after exposure, and the resistance to hydrogen sulfide gas was evaluated according to the following criteria. The total luminous flux was measured with a spectral radiance meter (CS-2000, manufactured by Konica Minolta Sensing).
  • CS-2000 spectral radiance meter
  • Total luminous flux to initial ratio (total luminous flux value after exposure to hydrogen sulfide gas / total luminous flux value before exposure to hydrogen sulfide gas ⁇ 100) is 96% or more
  • total luminous flux to initial ratio (total luminous flux value after exposure to hydrogen sulfide gas) / Total luminous flux value before exposure to hydrogen sulfide gas ⁇ 100) is 92% or more and less than 96%
  • initial luminous flux to initial ratio (total luminous flux value after exposure to hydrogen sulfide gas / total luminous flux value before exposure to hydrogen sulfide gas ⁇ 100) Less than 92%
  • Comparative Example 1 that does not have a light-transmitting layer, it is presumed that the resistance to sulfidation is low and the metal reflective layer or the like is corroded. Moreover, in Comparative Example 2 in which the ZrO component contained in the light transmissive layer was 70% by mass, cracks occurred, and thus the wet heat resistance and hydrogen sulfide gas resistance of the light transmissive layer were reduced.
  • Example 9 The amount of ZrO fine particles (TECNADIS-ZR-220-1KG: manufactured by TECNAN) contained in the composition for light transmissive layer of Example 6 was changed to the value shown in Table 2, and the increase / decrease amount of the ZrO fine particles amount was changed to ZrO.
  • An LED device was produced in the same manner as in Example 6 except that the amount was adjusted by the amount of chelate.
  • the ratio between the SiO 2 component amount and the ZrO component amount in each example was the same as the ratio in Example 6.
  • Comparative Example 3 0.4875 g of Zr chelate (ZC700: manufactured by Matsumoto Fine Chemical Co., Ltd. (solid content 20 mass%)) and ZrO fine particles (TECNADIS-ZR-220-1KG: manufactured by TECNAN) were added to 1.3 g of the polysiloxane solution of Example 6. 2.1125 g, butanol (1.0725 g), and isopropyl alcohol (103.36 g) were added and stirred to obtain a light transmissive layer composition of Comparative Example 3. Subsequently, a light-transmitting layer and a wavelength conversion layer were formed in the same manner as in Comparative Example 2, and an LED device having an LED element, a light-transmitting layer, and a wavelength conversion layer was obtained.
  • ZC700 manufactured by Matsumoto Fine Chemical Co., Ltd. (solid content 20 mass%)
  • TECNADIS-ZR-220-1KG manufactured by TECNAN
  • ⁇ Adhesion evaluation> The adhesion of the light transmissive layer of the LED device was evaluated. Specifically, a cycle of ⁇ 40 ° C. (30 minutes) and 100 ° C. (30 minutes) was repeated using an LED device using a heat shock tester (TSA-42EL; manufactured by Espec Corp.). After this test, the LED device was examined for non-lighting due to peeling of the translucent layer, and the adhesion was evaluated according to the following criteria. ⁇ : No lighting at 1200 cycles of heat shock ⁇ : No lighting at 1000 or more cycles of heat shock ⁇ : No lighting at 700 cycles or more of heat shock, less than 1000 cycles ⁇ : 350 cycles or more of heat shock, 700 cycles Lights out at less than
  • Example 9 in which the SiO 2 component is contained in the light transmissive layer by 50% by mass or more and the ZrO component is contained by 10% by mass or more and less than 50% by mass, The light-transmitting layer did not peel from the substrate even when a heat shock test was performed.
  • Example 9 in which the component amount of the ZrO particles was 3% by mass with respect to the solid content of the composition for light transmissive layer, the adhesion between the substrate and the light transmissive layer was slightly low. If the amount of the inorganic oxide fine particles is small, it is presumed that the adhesion at the interface between the translucent layer and the wavelength conversion layer was difficult to increase.
  • Comparative Example 3 in which the amount of the SiO 2 component contained in the translucent layer was 30% by mass, all of crack resistance, wet heat resistance, hydrogen sulfide gas resistance, and adhesion were low. Since the amount of the SiO 2 component is small and the SiO 2 network is not sufficiently formed, it is assumed that cracks and the like have occurred. In Comparative Example 3, the light extraction efficiency was also reduced. It is presumed that the light transmittance was lowered due to light scattering caused by cracks and a large amount of ZrO particles contained in the light transmitting layer.
  • Example 12 to 15 An LED device was produced in the same manner as in Example 6 except that the ZrO fine particles contained in the composition for light transmissive layer of Example 6 were changed to ZrO fine particles having an average primary particle size shown in Table 3.
  • ⁇ Pot life evaluation> The composition for translucent layer was left still at room temperature for 3 weeks. Thereafter, precipitates were evaluated with a dynamic light scattering particle size measuring instrument (Desla nano S, manufactured by Beckman Coulter, Inc.), and pot life evaluation was performed according to the following criteria.
  • Example 12 to 15 in which the SiO 2 component is contained in the light transmissive layer by 50% by mass or more and the ZrO component is contained by 10% or more and less than 50% by mass, the light transmissive layer is cracked. The light-transmitting layer did not peel from the substrate even when the heat shock test was performed. Moreover, light extraction efficiency, wet heat resistance, and hydrogen sulfide gas resistance were also good. However, in Example 15 in which the average primary particle size of the inorganic oxide fine particles (ZrO fine particles) was 65 nm, the light extraction efficiency, the wet heat resistance, and the hydrogen sulfide gas resistance were good, but the pot for the composition for the translucent layer Life was easy to fall.
  • ZrO fine particles the average primary particle size of the inorganic oxide fine particles
  • Example 16 To the polysiloxane solution of Example 6 was added 0.2168 g of Zr chelate (ZC700: Matsumoto Fine Chemical Co., Ltd. (solid content: 20% by mass)) and ZrO fine particles (TECNADIS-ZR-220-1KG: TECNAN Co.). 0.2108 g, 0.0108 g of a silane coupling agent (KBM-903: manufactured by Shin-Etsu Chemical Co., Ltd.) diluted to 1% with isopropyl alcohol was added, 0.0108 g, butanol was added 0.4795 g, and isopropyl alcohol was added 33.91 g. The mixture was stirred to obtain a light transmissive layer composition of Example 16. Subsequently, a light-transmitting layer and a wavelength conversion layer were formed in the same manner as in Comparative Example 2, and an LED device having an LED element, a light-transmitting layer, and a wavelength conversion layer was obtained.
  • a silane coupling agent KBM-903
  • Examples 17 to 19 The amount of the silane coupling agent (KBM-903: manufactured by Shin-Etsu Chemical Co., Ltd.) in the composition for light transmissive layer of Example 16 was changed to the value shown in Table 4, and the increased amount of the silane coupling agent An LED device was produced in the same manner as in Example 16 except that the amount was reduced.
  • the ratio between the SiO 2 component amount and the ZrO component amount in each example was the same as that in Example 16.
  • the obtained LED device was evaluated for crack resistance, light extraction efficiency, wet heat resistance, and hydrogen sulfide gas resistance.
  • the evaluation methods for crack resistance, light extraction efficiency, wet heat resistance, and hydrogen sulfide gas resistance were the same as those described above.
  • the evaluation methods for wet heat resistance and hydrogen sulfide gas resistance were the same as those described above.
  • the amount of SiO 2 component and the amount of ZrO component in the light-transmitting layer were also identified by the same method as described above. The results are shown in Table 4.
  • Example 20 0.2243 g of Zr chelate (ZC700: manufactured by Matsumoto Fine Chemical Co., Ltd. (solid content: 20% by mass)) and ZrO fine particles (TECNADIS-ZR-220-1KG: manufactured by TECNAN) were added to 1.3 g of the polysiloxane solution of Example 6.
  • ZC700 manufactured by Matsumoto Fine Chemical Co., Ltd. (solid content: 20% by mass)
  • ZrO fine particles TECNADIS-ZR-220-1KG: manufactured by TECNAN
  • Example 21 to 23 The amount of the cyclic ether compound (B1539: manufactured by Tokyo Chemical Industry Co., Ltd.) in the composition for the light-transmitting layer of Example 20 was changed to the value shown in Table 5, and the increased amount of the cyclic ether compound and the amount of the silane compound were decreased. Produced an LED device in the same manner as in Example 20. The ratio between the SiO 2 component amount and the ZrO component amount in each example was the same as that in Example 20.
  • the obtained LED device was evaluated for crack resistance, light extraction efficiency, wet heat resistance, and hydrogen sulfide gas resistance.
  • the evaluation methods for crack resistance, light extraction efficiency, wet heat resistance, and hydrogen sulfide gas resistance were the same as those described above.
  • the evaluation methods for wet heat resistance and hydrogen sulfide gas resistance were the same as those described above.
  • the amount of SiO 2 component and the amount of ZnO component in the light transmitting layer were also specified. The results are shown in Table 5.
  • Example 24 to 26 An LED device was produced in the same manner as in Example 21 except that the thickness of the light transmitting layer was changed to the thickness shown in Table 6.
  • the obtained LED device was evaluated for crack resistance, light extraction efficiency, wet heat resistance, and hydrogen sulfide gas resistance.
  • the evaluation methods for wet heat resistance, light extraction efficiency, wet heat resistance, and hydrogen sulfide gas resistance were the same as those described above.
  • the evaluation methods for crack resistance and hydrogen sulfide gas resistance were the same as those described above. Further, the amount of SiO 2 component and the amount of ZrO component in the light transmitting layer were also specified. The results are shown in Table 6.
  • the light emitting device of the present invention is excellent in gas barrier properties, heat and humidity resistance, and light resistance. Therefore, it is useful for lighting used outdoors or indoors.

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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 a pour objectif de proposer un dispositif à DEL, présentant d'excellentes caractéristiques de barrière par rapport à l'eau et au sulfure d'hydrogène gazeux, et offrant un rendement d'extraction de lumière élevé sur une longue durée. L'invention concerne en outre un procédé de fabrication de dispositif à DEL. Pour ce faire, un dispositif à DEL selon l'invention comprend un substrat et un élément de DEL monté sur le substrat. Le dispositif à DEL comporte une couche translucide qui recouvre l'élément de DEL et/ou le substrat. La couche translucide contient un composant de SiO2 en une quantité supérieure ou égale à 50 % en masse mais inférieure à 90 % en masse, et un composant de ZrO en une quantité supérieure ou égale à 10 % en masse mais inférieure à 50 % en masse.
PCT/JP2014/004335 2013-08-23 2014-08-22 Dispositif à del, et procédé de fabrication associé WO2015025526A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005309215A (ja) * 2004-04-23 2005-11-04 Hitachi Chemical Dupont Microsystems Ltd 感光性重合体組成物及びそれを用いたレリ−フパターンの製造法、電子部品。
JP2012211235A (ja) * 2011-03-31 2012-11-01 Asahi Kasei Chemicals Corp オルガノポリシロキサン及びそれを用いた熱硬化性樹脂組成物、光半導体用封止材、光半導体用ダイボンド材
WO2013099193A1 (fr) * 2011-12-26 2013-07-04 コニカミノルタ株式会社 Agent de scellement pour un dispositif à del, dispositif à del et procédé de production de dispositif à del

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005309215A (ja) * 2004-04-23 2005-11-04 Hitachi Chemical Dupont Microsystems Ltd 感光性重合体組成物及びそれを用いたレリ−フパターンの製造法、電子部品。
JP2012211235A (ja) * 2011-03-31 2012-11-01 Asahi Kasei Chemicals Corp オルガノポリシロキサン及びそれを用いた熱硬化性樹脂組成物、光半導体用封止材、光半導体用ダイボンド材
WO2013099193A1 (fr) * 2011-12-26 2013-07-04 コニカミノルタ株式会社 Agent de scellement pour un dispositif à del, dispositif à del et procédé de production de dispositif à del

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