WO2018008539A1 - 紫外線発光半導体装置およびその製造方法 - Google Patents

紫外線発光半導体装置およびその製造方法 Download PDF

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Publication number
WO2018008539A1
WO2018008539A1 PCT/JP2017/024107 JP2017024107W WO2018008539A1 WO 2018008539 A1 WO2018008539 A1 WO 2018008539A1 JP 2017024107 W JP2017024107 W JP 2017024107W WO 2018008539 A1 WO2018008539 A1 WO 2018008539A1
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Prior art keywords
sealing material
light emitting
ultraviolet light
material layer
semiconductor device
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PCT/JP2017/024107
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English (en)
French (fr)
Japanese (ja)
Inventor
翔平 堀田
高島　正之
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住友化学株式会社
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Application filed by 住友化学株式会社 filed Critical 住友化学株式会社
Priority to KR1020197003571A priority Critical patent/KR20190030702A/ko
Priority to CN201780034189.8A priority patent/CN109219892A/zh
Publication of WO2018008539A1 publication Critical patent/WO2018008539A1/ja

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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
    • H01L33/54—Encapsulations having a particular shape
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • 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
    • H01L33/005—Processes
    • 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
    • H01L33/58—Optical field-shaping elements

Definitions

  • the present invention relates to an ultraviolet light emitting semiconductor device and a manufacturing method thereof.
  • a method of manufacturing a semiconductor light emitting device for example, a step of installing a semiconductor light emitting element on a substrate, a step of potting a polycondensation type silicone sealing material before curing so as to cover the semiconductor light emitting element on the substrate, And a step of curing the potted polycondensation type silicone sealing material before curing.
  • the manufacturing method includes a step of forming a sealing material layer.
  • Patent Document 1 discloses an addition polymerization type silicone sealing material so as to cover a semiconductor light emitting element placed on a substrate in order to improve the thermal shock resistance of a sealing material layer of a semiconductor light emitting device.
  • a method for manufacturing a semiconductor light emitting device which includes a step of forming a sealing material layer (ii) using a polycondensation type silicone sealing material (ii). In the semiconductor light emitting device manufactured by the manufacturing method, two layers of the sealing material layer (i) and the sealing material layer (ii) are formed on the semiconductor light emitting element.
  • an object of the present invention is to provide an ultraviolet light emitting semiconductor device that is unlikely to cause cracking or coloring (that is, an ultraviolet light emitting semiconductor device having high ultraviolet durability) and a method for manufacturing the ultraviolet light emitting semiconductor device.
  • the present invention provides the following [1] to [15].
  • An ultraviolet light-emitting semiconductor device comprising a base material, an ultraviolet light-emitting element disposed on the base material, and a sealing material layer that seals at least a part of the ultraviolet light-emitting element,
  • the sealing material layer has a first sealing material layer and a second sealing material layer,
  • the first sealing material layer includes an addition polymerization type silicone sealing material or a polycondensation type silicone sealing material containing a resin having a dialkylsiloxane structure;
  • the second sealing material layer includes a polycondensation type silicone sealing material containing a resin having an organopolysiloxane structure represented by the following general formula (2A-1) or (3A-1):
  • An ultraviolet light emitting semiconductor device wherein the first sealing material layer is not in contact with a light emitting surface of the ultraviolet light emitting element.
  • each R 1 independently represents an alkyl group
  • each R 2 independently represents an alkoxy group or a hydroxyl group
  • p 1 , q 1 , a 1 and b 1 are p 1 + b 1 ⁇ q 1 ]:
  • [a 1 ⁇ q 1 ] 1: represents a positive number satisfying 0.25 to 9.
  • each R 1 independently represents an alkyl group
  • each R 2 independently represents an alkoxy group or a hydroxyl group
  • p 2 , q 2 , r 1 , a 2 and b 2 Represents an integer such that [a 2 ⁇ q 2 ] / [(p 2 + b 2 ⁇ q 2 ) + a 2 ⁇ q 2 + (r 1 + q 2 )] is 0.3 or more and less than 0.6.
  • the first sealing material layer includes an addition polymerization type silicone sealing material.
  • the ultraviolet light-emitting semiconductor device wherein the resin having a dialkylsiloxane structure is a resin X having a dialkylsiloxane structure represented by the following general formula (1).
  • each R 3 independently represents an alkyl group, and n represents an integer of 5 to 4000.
  • n represents an integer of 5 to 1000.
  • the second encapsulant layer is formed on the first encapsulant layer and the light emitting surface of the ultraviolet light emitting element, and the second encapsulant layer and the first encapsulant layer are formed.
  • the ultraviolet light emitting semiconductor device according to any one of [1] to [4], wherein an area in contact with the sealing material layer is smaller than an area formed by the first sealing material layer.
  • the ultraviolet light emitting semiconductor device according to any one of [1] to [5], wherein the Shore hardness of the first sealing material layer is A80 or less.
  • the first sealing material layer has adhesiveness with the second sealing material layer at the interface between the first sealing material layer and the second sealing material layer.
  • the ultraviolet light emitting semiconductor device according to any one of [6] to [6].
  • [8] The ultraviolet light-emitting semiconductor device according to any one of [1] to [7], having two or more second sealing material layers.
  • a method for producing an ultraviolet semiconductor device comprising: a base material; an ultraviolet light emitting element disposed on the base material; and a sealing material layer that seals at least a part of the ultraviolet light emitting element.
  • a first step of installing an ultraviolet light emitting element on a substrate; Potting is performed with the addition sealing type silicone sealing material or the first sealing material having the polycondensation type silicone sealing material containing a resin having a dialkylsiloxane structure so as not to cover the light emitting surface of the ultraviolet light emitting element.
  • a second sealing material having a polycondensation type silicone sealing material containing a resin having an organopolysiloxane structure represented by the general formula (2A-1) or (3A-1) is used as the ultraviolet light emitting element and the A fourth step of potting on the first encapsulant layer and curing the potted second encapsulant before curing to form the second encapsulant layer.
  • the surface of the substrate is cleaned with ozone; and
  • the second sealing material is potted on the first sealing material layer and in a range narrower than the first sealing material layer, and the second potted material is potted.
  • the supply amount of the first sealing material supplied in the second step (the first sealing material is an addition polymerization type silicone sealing material) is W1 [g], and the fourth step The ratio of W2 / W1 is in the range of 1.5 to 8, where W2 [g] is the supply amount of the second sealing material supplied in (10). Manufacturing method of ultraviolet light emitting semiconductor device.
  • the supply amount of the first sealing material supplied in the second step (the first sealing material is a polycondensation silicone sealing material) is W1 [g]
  • the fourth step The ratio of W2 / W1 is in the range of 1.5 to 13, where W2 [g] is the supply amount of the second sealing material to be supplied in (10). Manufacturing method of ultraviolet light emitting semiconductor device.
  • an ultraviolet light emitting semiconductor device that is unlikely to cause cracking or coloring (that is, an ultraviolet light emitting semiconductor device having high ultraviolet durability).
  • the manufacturing method of the said ultraviolet light-emitting semiconductor device can be provided.
  • the first sealing material layer of the ultraviolet light emitting semiconductor device of the present invention is usually a cured product of an addition polymerization type silicone sealing material or a polycondensation type silicone sealing material containing a resin having a dialkylsiloxane structure. Including things.
  • the second sealing material layer of the ultraviolet light emitting semiconductor device of the present invention is usually a polycondensation type containing a resin having an organopolysiloxane structure represented by the above general formula (2A-1) or (3A-1) Includes cured product of silicone encapsulant.
  • the first embodiment includes a flat substrate 1, an ultraviolet light emitting element 2 disposed on the substrate 1, a first sealing material layer 3, and a second sealing material layer 4.
  • the sealing material layer has a first sealing material layer 3 and a second sealing material layer 4.
  • the second sealing material layer 4 has a convex lens shape.
  • the present embodiment is characterized in that the first sealing material layer 3 is not in contact with the light emitting surface 2a of the ultraviolet light emitting element.
  • an ultraviolet light emitting element 2 that emits ultraviolet rays when electric power is supplied is disposed on the base material 1, and the light emitting surface direction of the ultraviolet light emitting element 2 (upper surface in FIG. 1). ), A sealing material layer having the second sealing material layer 4 is formed.
  • the sealing material layer By the sealing material layer, the ultraviolet light emitting element 2 is prevented from being oxidized and protected from the outside.
  • the outer surface of the second sealing material layer 4 is formed in a convex lens shape, and the convex lens effect is expressed by the second sealing material layer 4.
  • the ultraviolet light emitting element 2 is disposed at the center of the bottom surface side of the second sealing material layer 4, and is electrically connected to the outside via the wiring 5 by the electrode 6 disposed on the base material 1. Yes.
  • the first sealing material layer 3 and the second sealing material layer 4 have different physical properties after curing, and the first sealing material layer 3 after curing is the second sealing material layer 4 after curing. Higher stress relaxation.
  • the first sealing material layer 3 has low durability against ultraviolet rays having a wavelength of, for example, 300 nm or less, and when the first sealing material layer 3 is disposed on the light emission surface 2a of the ultraviolet light emitting element, the ultraviolet light is emitted. Since the light emitting element 2 and the first sealing material layer 3 are in direct contact with each other, the first sealing disposed on the light emitting surface 2a of the ultraviolet light emitting element by heat energy, light energy, or the like due to light emission of the ultraviolet light emitting element 2.
  • the first sealing material layer 3 is not disposed on the light emitting surface 2a of the ultraviolet light emitting element, the first sealing material layer 3 is hardly deteriorated, and the durability of the ultraviolet light emitting semiconductor device to ultraviolet light is reduced. Can be improved.
  • the ultraviolet light emitting semiconductor device described in Patent Document 1 International Publication No. 2015/125713 is supposed to seal a light emitting element having an emission wavelength of 350 nm or less. However, as described in Patent Document 1, when the first sealing material layer is formed on the light emitting surface of the ultraviolet light emitting element, the ultraviolet light emitting element with a short wavelength of 300 nm or less is sealed.
  • the first sealing material layer is severely deteriorated and cannot be used.
  • the first sealing material layer is not formed on the light emitting surface of the ultraviolet light emitting element, even when the ultraviolet light emitting element having a short wavelength of 300 nm or less is sealed. Further, it is possible to prevent the generation of cracks due to the deterioration of the sealing material layer and the decrease in the output from the ultraviolet light emitting element.
  • the “light emitting surface” means the upper surface of the ultraviolet light emitting element that is the surface from which the main ultraviolet light emitted from the ultraviolet light emitting element is emitted, that is, the light emitting surface 2a shown in FIG.
  • the thickness 7 of the first sealing material layer 3 is a thickness that does not cover the light emitting surface 2 a of the ultraviolet light emitting element 2 and is equal to or less than the thickness of the ultraviolet light emitting element 2.
  • the first sealing material layer 3 is formed so as to cover the entire upper surface of the surface of the flat substrate 1.
  • the second sealing material layer 4 is formed so as to cover the upper surface of the first sealing material layer 3 and the entire light emission surface 2a of the ultraviolet light emitting element.
  • the second sealing material layer 4 exhibits a light condensing action at an angle ⁇ 1 formed by the boundary between the first sealing material layer 3 and the peripheral edge portion of the second sealing material layer 4. Therefore, the angle can be a sufficiently large angle.
  • the first sealing material layer 3 is formed so as to cover the entire upper surface of the surface of the flat substrate 1.
  • the second sealing material layer 4 is formed so as to cover a part of the upper surface of the first sealing material layer 3 and the entire light emission surface 2a of the ultraviolet light emitting element. More specifically, the second sealing material layer 4 is not formed on the peripheral edge of the first sealing material layer 3, and the second sealing material layer 4 is formed so as to surround the ultraviolet light emitting element 2. Is formed.
  • the second sealing material layer is formed on the first sealing material layer and the light emitting surface of the ultraviolet light emitting element, and the second sealing material layer, the first sealing material layer, The area which contacts is below the area which a 1st sealing material layer forms.
  • an angle ⁇ 2 equivalent to that in the first embodiment can be realized by using a smaller amount of the second sealing material than in the first embodiment, and the second sealing material can be realized.
  • the stopping material layer 4 can have an angle that is sufficiently large to exhibit a light collecting action.
  • the first sealing material layer 3 is formed so as to surround the periphery of the ultraviolet light emitting element 2 disposed on the flat substrate 1. Furthermore, the second sealing material layer 4 is formed so as to cover the upper surface and side surfaces of the first sealing material layer 3 and the entire light emission surface 2a of the ultraviolet light emitting element. More specifically, the first sealing material layer 3 is not formed on the peripheral edge portion of the flat plate base material 1, but is formed so as to surround the ultraviolet light emitting element 2. .
  • the angle ⁇ 3 formed by the boundary of the peripheral edge of the second sealing material layer 4 can be collected by using a small amount of the first sealing material. The angle can be made large enough to express
  • the first embodiment or the second embodiment is more preferable because the angle ⁇ formed by the boundary of the peripheral edge portion of the second sealing material layer 4 can be further increased.
  • a fourth embodiment of the ultraviolet light emitting semiconductor device will be described with reference to FIG.
  • the description of the same configuration as in the first to third embodiments is omitted.
  • a base material 1 having a recess 10 in which the ultraviolet light emitting element 2 is accommodated is used.
  • the ultraviolet light emitting element 2 is disposed at the center of the bottom surface 1 c of the recess 10 of the base material 1.
  • An electrode 6 is disposed on the upper surface of the ultraviolet light emitting element 2, and the electrode 6 is electrically connected to the outside through a wiring 5.
  • the first sealing material layer 3 is formed on the bottom 1 c of the recess 10 of the substrate 1.
  • the first sealing material layer 3 is not formed on the light emitting surface 2 a of the ultraviolet light emitting element 2, and the light emitting surface 2 a of the ultraviolet light emitting element 2 is in contact with the second sealing material layer 4.
  • the second sealing material layer 4 is formed so as to cover the upper surface 1 b of the substrate 1, the inner side surface 1 a of the substrate 1, the first sealing material layer 3, and the light emitting surface 2 a of the ultraviolet light emitting element 2.
  • the thickness 7 of the first sealing material layer 3 is a thickness that does not cover the light emitting surface 2 a of the ultraviolet light emitting element 2 and is equal to or less than the thickness of the ultraviolet light emitting element 2.
  • the second sealing material layer 4 exhibits a condensing function at an angle ⁇ 4 formed by the boundary between the first sealing material layer 3 and the peripheral edge portion of the second sealing material layer 4. Therefore, the angle can be a sufficiently large angle.
  • the 1st sealing material layer 3 is formed so that the bottom part 1c of the recessed part 10 of the base material 1, the inner surface 1a of the base material 1, and the upper surface 1b of the base material 1 may be covered.
  • the first sealing material layer 3 is not formed on the light emitting surface 2 a of the ultraviolet light emitting element 2, and the light emitting surface 2 a of the ultraviolet light emitting element 2 is in contact with the second sealing material layer 4.
  • the thickness 7 of the first sealing material layer 3 at the bottom is a thickness that does not cover the light emitting surface 2 a of the ultraviolet light emitting element 2 and is equal to or less than the thickness of the ultraviolet light emitting element 2.
  • the angle ⁇ 5 formed by the boundary between the first sealing material layer 3 and the peripheral edge portion of the second sealing material layer 4 is determined from the fourth embodiment. And the angle can be set to a sufficiently large angle to exhibit the light collecting action. As a result, the 2nd sealing material layer 4 can express a higher condensing effect. Furthermore, since the area of the sealing material layer 3 having a stress relaxation effect is large as compared with the fourth embodiment, the crack resistance is also excellent.
  • the ultraviolet light emitting semiconductor device of the fifth embodiment is preferable to the fourth embodiment.
  • the present embodiment is a method of manufacturing an ultraviolet light emitting semiconductor device having a base material, an ultraviolet light emitting element disposed on the base material, and a sealing material layer for sealing at least a part of the ultraviolet light emitting element.
  • a first step of installing an ultraviolet light emitting element on the substrate; Potting is performed with the addition sealing type silicone sealing material or the first sealing material having the polycondensation type silicone sealing material containing a resin having a dialkylsiloxane structure so as not to cover the light emitting surface of the ultraviolet light emitting element.
  • a second sealing material having a polycondensation type silicone sealing material containing a resin having an organopolysiloxane structure represented by the general formula (2A-1) or (3A-1) is used as the ultraviolet light emitting element and the Potting on the first encapsulant layer and curing the potted second encapsulant before curing to form a second encapsulant layer.
  • a 1st process is a process of installing the ultraviolet light emitting element 2 on a base material 1 by a conventional method.
  • the surface of the substrate 1 may be surface-modified by pretreatment as shown in FIG.
  • surface modification by ultraviolet ozone treatment is preferable.
  • Ultraviolet ozone treatment removes and cleans the surface of the substrate 1 and improves the surface of the substrate 1 to be hydrophilic, improving the wettability and improving the adhesion of the sealing material potted in the subsequent process. Can be improved.
  • the wiring 5 and the like are arranged on the substrate 1.
  • the amount of the sealing material to be supplied depends on the structure, area and volume of the base material, the ultraviolet light-emitting element, and other electrodes, What is necessary is just to adjust suitably with structures, such as wire wiring. However, an ultraviolet light emitting element, wiring, etc. are embedded, and an amount of sealing material that does not cover the light emitting surface 2a of the ultraviolet light emitting element is potted.
  • the third step is a step of curing the first sealing material 3 before curing potted in the second step.
  • the curing conditions may be set at a temperature and a time at which a normal addition polymerization reaction occurs. Specifically, under the atmospheric pressure, air Among them, the temperature is preferably 80 to 200 ° C, more preferably 100 to 150 ° C. The time is preferably 1 to 5 hours.
  • the curing temperature may be raised stepwise to be cured. .
  • curing conditions may be set at a temperature and a time at which a normal polycondensation reaction occurs. Specifically, under the atmospheric pressure, air Among them, the temperature is preferably 80 to 250 ° C, more preferably 100 to 200 ° C. The time is preferably 1 to 5 hours. In order to effectively promote the volatilization of the residual solvent in the first sealing material 3, the polycondensation reaction of the first sealing material 3, etc., the curing temperature may be raised stepwise to be cured.
  • the fourth step is a resin having an organopolysiloxane structure represented by the above general formula (2A-1) or (3A-1) on the first sealing material 3 cured in the third step. Potting the second sealing material 4 having a polycondensation type silicone sealing material containing and hardening the potted second sealing material 4 before curing, thereby laminating the second sealing material 4 It is a process to do.
  • the second sealing material 4 potted in the fourth step can be supplied onto the first sealing material 3 after being cured in the third step using the dispenser 40.
  • the supply amount of the first sealing material supplied in the second step is W1 [g] and the supply amount of the second sealing material supplied in the fourth step is W2 [g]
  • the supply amount is
  • the encapsulant 1 is an addition polymerization type silicone encapsulant
  • the ratio of W2 / W1 is usually set to 0.5 to 13, preferably 1.5 to 8.
  • the sealing material is a polycondensation type silicone sealing material
  • the ratio of W2 / W1 may be set so that it is usually within a range of 0.5 to 15, preferably 1.5 to 13.
  • the resin may be dissolved in the solvent.
  • the supply amounts W1 [g] and W2 [g] indicate the amount of solvent contained in the sealing material. The amount subtracted.
  • the curing condition after supplying the second sealing material before curing in the fourth step and covering the surface of the first sealing material after curing in the third step is the third step.
  • the curing temperature in Ta is Ta [° C.] and the curing temperature in the fourth step is Tb [° C.]
  • a range of Ta ⁇ 25 ⁇ Tb ⁇ Ta + 150 is preferable, and a range of Ta ⁇ 10 ⁇ Tb ⁇ Ta + 100 is more preferable. Is more preferable.
  • the curing time at the temperature of Tb is preferably in the range of 1 to 50 hours.
  • a 4th process is a process of laminating
  • the physical property is more preferably a physical property that the first sealing material after curing obtained in the third step relaxes the stress applied to the second sealing material after curing laminated in the fourth step. preferable.
  • the ultraviolet light-emitting semiconductor device of this embodiment is preferably an ultraviolet light-emitting semiconductor device in which two or more layers of a second sealing material are laminated, from the viewpoint of barrier properties against oxygen, water, and the like. More preferably, it is an ultraviolet light emitting semiconductor device in which the second sealing material 4 is laminated.
  • the present embodiment is a method of manufacturing an ultraviolet light emitting semiconductor device having a base material, an ultraviolet light emitting element disposed on the base material, and a sealing material layer for sealing at least a part of the ultraviolet light emitting element.
  • a first step of installing an ultraviolet light emitting element on a substrate A step 1a of installing a mask on the ultraviolet light emitting element; A second step of potting an addition polymerization type silicone sealing material or a first sealing material having a polycondensation type silicone sealing material containing a resin having a dialkylsiloxane structure; A step 2a for removing the mask; A third step of curing the potted first sealing material before curing to form a first sealing material layer; A second sealing material having a polycondensation type silicone sealing material containing a resin having an organopolysiloxane structure represented by the general formula (2A-1) or (3A-1) is used as the ultraviolet light emitting element and the Potting on the first encapsulant layer and curing the potted second encapsulant before curing to form a second encapsulant layer.
  • a mask M is placed on the light emission surface of the ultraviolet light emitting element 2.
  • the material of the mask M may be any material that becomes a mask material for the ultraviolet light-emitting element 2 and can be removed in a later process.
  • a resist material can be used as the mask material.
  • the first sealing material is more efficiently compared with the sixth embodiment. Can be potted.
  • the second step is a step of potting a first sealing material including an addition polymerization type silicone sealing material or a polycondensation type silicone sealing material containing a resin having a dialkylsiloxane structure.
  • the first sealing material is potted so as to cover the substrate 1, the ultraviolet light emitting element 2, and the mask M on the ultraviolet light emitting element 2. Except for potting so as to cover the mask M, it is the same as the second step of the sixth embodiment.
  • Step 2a is a step of removing the mask M.
  • the method for removing the mask M is not particularly limited, and the mask M may be physically removed or removed using a resist stripping solution or the like.
  • the surface of the substrate is cleaned with ozone prior to the installation of the ultraviolet light emitting element, and in the fourth step, the first sealing is performed.
  • the second sealing material is potted on the stopper layer and is narrower than the first sealing material layer, and the potted second sealing material is cured to form the second sealing material. Form a material layer.
  • the first step is a step of cleaning the surface of the substrate with ozone prior to the installation of the ultraviolet light emitting element. Ozone cleaning removes and cleans the surface of the base material 1, and improves the wettability by improving the surface of the base material 1 to be hydrophilic, thereby improving the adhesion of the sealing material potted in the subsequent process. Can be made.
  • the description regarding the first to third steps is the same as the description regarding the first to third steps in the sixth embodiment.
  • the second sealing material having a polycondensation type silicone sealing material containing a resin having an organopolysiloxane structure represented by the following general formula (2A-1) or (3A-1) is irradiated with ultraviolet light. Potting on the element and the first sealing material layer in a range narrower than the first sealing material layer, curing the potted second sealing material, and the second sealing material It is a process of forming a layer. According to this embodiment, the ultraviolet light emitting semiconductor device of the second embodiment can be manufactured.
  • the base material may be any base material generally used as a substrate of a semiconductor light emitting device, for example, a base material made of a resin such as nylon, epoxy, or LCP, or a ceramic such as alumina, aluminum nitride, or LTCC.
  • a configured base material may be mentioned.
  • the shape of the substrate may be a flat plate type substrate or a cavity type substrate.
  • an electrode for electrically connecting to the ultraviolet semiconductor element to be arranged is formed on the substrate.
  • the ultraviolet light emitting element may be any ultraviolet light emitting element generally used as a semiconductor light emitting element, and examples thereof include an ultraviolet light emitting LED chip having an emission wavelength of 300 nm or less.
  • the first sealing material layer is not in contact with the light emitting surface of the ultraviolet light emitting element. Therefore, the first sealing material layer is not easily deteriorated by the short wavelength ultraviolet rays.
  • the ultraviolet light emitting LED chip include an LED chip manufactured by growing a III-V semiconductor such as InGaN or AlGaN on a substrate such as sapphire or aluminum nitride by the MOCVD method, the HVPE method, or the like.
  • One to a plurality of ultraviolet light emitting elements are installed on one base material.
  • a flip-chip method in which the MOCVD growth surface is directed to the substrate side or a face-up method in which the surface opposite to the MOCVD growth surface is directed to the substrate side is used.
  • the ultraviolet light emitting element is electrically connected to the electrode on the base material by solder.
  • the ultraviolet light-emitting element is electrically connected to the electrode on the substrate using a wire wiring such as gold. From the viewpoint of light extraction of the ultraviolet light emitting semiconductor device of the present invention, the flip chip method is preferable.
  • a second sealing material containing a polycondensation type silicone sealing material containing a resin having an organopolysiloxane structure represented by the general formula (2A-1) or (3A-1) is used in combination.
  • the sealing material used for forming the first sealing material layer is the first sealing material
  • the sealing material used for forming the second sealing material layer is the second sealing material. It is.
  • the addition polymerization type silicone sealing material is a sealing material that is polymerized by an addition reaction between a hydrosilyl group and a carbon-carbon double bond.
  • the polycondensation type silicone sealing material includes a resin having a dialkylsiloxane structure, and is obtained by subjecting a hydroxyl group bonded to a silicon atom and an alkoxy group or hydroxyl group bonded to another silicon atom to a dealcoholization reaction or a dehydration reaction. It is a sealing material that undergoes polycondensation.
  • Examples of the addition polymerization type silicone sealing material and the polycondensation type silicone sealing material include sealing materials containing polysiloxane described in Toray Dow Corning “Silicon catalog for electronics” published in October 2010, etc. It is done. In this specification, the dual-type silicone sealing material that polymerizes when an addition polymerization type reaction and a polycondensation type reaction occur simultaneously is classified as an addition polymerization type silicone sealing material.
  • OE-6250, OE-6336, OE-6301, and OE-6351 which are methyl silicone resin encapsulants manufactured by Toray Dow Corning
  • OE-6450, OE-6520, OE-6550, OE-6661, OE-6636, OE-6635, OE-6630, OE-6665N which are silicone-based silicone resin encapsulants
  • KE-6020, KER-6150, KER-6075, KER-2700, KER-2600, KER-2500, KER-2450, KER which are methyl silicone resin encapsulants manufactured by Shin
  • KER-2300 KER-2300; SCR-1011, SCR-1012, SCR-1016, ASP-1111, ASP-1120, ASP-, which are phenyl silicone resin encapsulants or methylphenyl silicone resin encapsulants manufactured by the same company 1031, ASP-1040, KER-6150, KER-6075, and KER-6100.
  • Specific examples of the dual type silicone sealing material include YSL-300F and YSL-350F, which are methyl silicone resin sealing materials manufactured by Yokohama Rubber, and YSH-600F and YSH, which are phenyl silicone resins manufactured by the same company. -650F.
  • a polycondensation type silicone sealing material contains resin (henceforth "resin X") which has a dialkylsiloxane structure.
  • the resin X is preferably a resin having a dialkylsiloxane structure represented by the following general formula (1).
  • R 3 is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, and further preferably a methyl group.
  • n is preferably an integer of 5 to 3000, more preferably an integer of 5 to 1500, still more preferably an integer of 5 to 1000, particularly preferably an integer of 5 to 800, and an integer of 5 to 500. Is particularly preferred. When n satisfies such a range, the gas barrier property of the first sealing material against water vapor and the like and the relaxation property against stress generated when the first sealing material is subjected to thermal shock are excellent.
  • resin X3 is more preferable.
  • Examples of the polydialkylsiloxane resin X1 having silanol groups at both ends include DMS-S12, DMS-S14, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, and DMS manufactured by Gelest. -S33, DMS-S35, DMS-S42, DMS-S45, DMS-S5; X-21-5841, KF-9701 manufactured by Shin-Etsu Chemical; FINISH WA 62M, CT 601M, CT manufactured by Asahi Kasei Wacker Silicone Examples include 5000 M and CT 6000 M.
  • R 4 each independently represents an alkyl group
  • R 5 independently represents an alkoxy group, a hydroxyl group or a halogen atom
  • m represents an integer of 1 to 4.
  • a linear alkoxy group or a branched alkoxy group is preferable, and a linear alkoxy group is more preferable.
  • the number of carbon atoms of the alkoxy group is not particularly limited, but 1 to 4 is preferable.
  • m is preferably 3 or 4, and more preferably 4.
  • the organic silicone compound monomers represented by the general formula (3) may be combined in the presence of an acid, an alkali, or a metal catalyst, in the absence of a solvent, in an organic solvent, or in a mixed solvent of an organic solvent and water. And a condensate having a molecular weight of 5000 or less obtained by a dealcoholization reaction and / or a dehydration condensation reaction.
  • the acid for example, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; organic acids such as formic acid, acetic acid, succinic acid, citric acid, propionic acid, butyric acid, lactic acid and succinic acid can be used.
  • organic acids such as formic acid, acetic acid, succinic acid, citric acid, propionic acid, butyric acid, lactic acid and succinic acid
  • alkali for example, ammonium hydroxide, tetramethylammonium hydroxide, and tetraethylammonium hydroxide can be used.
  • metal catalyst examples include metal alkoxides such as aluminum isopropoxide and zirconium isopropoxide; metal acetylacetonates such as zirconium acetylacetonate; zinc octylate, zinc benzoate, zinc p-tert-butylbenzoate, laurin Zinc acid, zinc stearate, and tin octylate can be used.
  • metal alkoxides such as aluminum isopropoxide and zirconium isopropoxide
  • metal acetylacetonates such as zirconium acetylacetonate
  • zinc octylate zinc benzoate
  • zinc p-tert-butylbenzoate zinc p-tert-butylbenzoate
  • laurin Zinc acid zinc stearate
  • tin octylate can be used.
  • the first sealing material layer after curing preferably has higher stress relaxation properties than the second sealing material layer after curing.
  • the resin hardness of the cured resin is effective, and the first sealing material layer after the curing has a Shore hardness A of 80 measured according to JIS K6253-3: 2012. The following is preferable.
  • the first sealing material layer preferably has adhesiveness with the second sealing material layer at the interface between the first sealing material layer and a second sealing material layer described later. Thereby, it can suppress remarkably that a 1st sealing material layer and the 2nd sealing material layer mentioned later peel off. By adjusting the curing temperature at the time of laminating the second sealing material layer, the adhesion between the first sealing material layer and the second sealing material layer can be improved.
  • the second sealing material includes a polycondensation type silicone sealing material containing a resin having an organopolysiloxane structure represented by the general formula (2A-1) or (3A-1). A silicone resin suitable as the second sealant will be described.
  • A1 silicon atom, A2 silicon atom, and A3 silicon atom is a structural unit represented by the following formula (A1), one oxygen atom (the oxygen atom is a silicon atom in another structural unit) In the structural unit represented by the following formula (A1 ′) or a silicon atom bonded to one R 1 and two R 2 , one bond (the bond) Is bonded to an oxygen atom bonded to a silicon atom in another structural unit) and is a silicon atom bonded to one R 1 and two R 2 .
  • the A2 silicon atom has one oxygen atom (the oxygen atom is bonded to a silicon atom in another structural unit), one bond ( The bond is a silicon atom bonded to one R 1 and one R 2 (bonded to an oxygen atom bonded to a silicon atom in another structural unit).
  • the A3 silicon atom has two oxygen atoms (the oxygen atom is bonded to a silicon atom in another structural unit), one bond ( The bond is bonded to an oxygen atom bonded to a silicon atom in another structural unit) and a silicon atom bonded to one R 1 .
  • Each R 1 independently represents an alkyl group
  • each R 2 independently represents an alkoxy group or a hydroxyl group.
  • R 1 represents carbon.
  • An alkyl group having a number of 1 to 3 is preferable, and a methyl group is more preferable.
  • R 2 is preferably an alkoxy group having 1 or 2 carbon atoms or a hydroxyl group. When R 2 is an alkoxy group, the alkoxy group is a methoxy group or an ethoxy group.
  • the structural unit represented by the formula (A1) and the structural unit represented by the formula (A1 ′) constitute the end of the organopolysiloxane chain contained in the silicone resin. Further, the structural unit represented by the formula (A3) constitutes a branched structure of an organopolysiloxane chain contained in the silicone resin. That is, the structural unit represented by the formula (A3) forms part of a network structure or a ring structure in the silicone resin.
  • the type and abundance ratio of the functional group bonded to the silicon atom can be measured by, for example, nuclear magnetic resonance spectroscopy (NMR method).
  • NMR method nuclear magnetic resonance spectroscopy
  • a strong magnetic field and a high-frequency radio wave are applied to the hydrogen nucleus or silicon nucleus in the silicone resin to resonate the nuclear magnetic moment in the nucleus.
  • the method for measuring hydrogen nuclei is called 1 H-NMR, and the method for measuring silicon nuclei is called 29 Si-NMR.
  • deuterated chloroform As a solvent used for nuclear magnetic resonance spectroscopy (NMR method), deuterated chloroform, deuterated dimethyl sulfoxide, deuterated methanol, deuterated acetone, deuterated water and the like may be selected depending on the types of various functional groups in the silicone resin.
  • the ratio of the content of A3 silicon atoms is the signal area attributed as A1 silicon atoms, the signal area attributed as A2 silicon atoms, and the signal attributed as A3 silicon atoms, as determined in 29 Si-NMR measurement.
  • the area of the signal attributed as the A3 silicon atom can be obtained by dividing the total area with the area of the A3.
  • the weight average molecular weight (Mw) of the silicone resin a value measured by a gel permeation chromatography (GPC) method can be generally used. Specifically, after dissolving the silicone resin in a soluble solvent, the resulting solution is passed along with the mobile phase solvent through a column using a filler having a large number of pores, and the molecular weight in the column. The content of the separated molecular weight component is detected using a differential refractometer, UV meter, viscometer, light scattering detector or the like as a detector. GPC-dedicated devices are widely commercially available, and the weight average molecular weight (Mw) is generally measured by standard polystyrene conversion. The weight average molecular weight (Mw) in this specification is measured by this standard polystyrene conversion.
  • GPC gel permeation chromatography
  • the solvent used for dissolving the silicone resin is preferably the same solvent as the mobile phase solvent used for the GPC measurement.
  • the solvent include tetrahydrofuran, chloroform, toluene, xylene, dichloromethane, dichloroethane, methanol, ethanol, isopropyl alcohol, and the like.
  • the column used for GPC measurement is commercially available, and an appropriate column may be used according to the assumed weight average molecular weight.
  • the silicone resin can be synthesized using an organosilicon compound having a functional group capable of forming a siloxane bond, corresponding to each of the above-described structural units constituting the silicone resin.
  • the “functional group capable of generating a siloxane bond” include a halogen atom, a hydroxyl group, and an alkoxy group.
  • the organosilicon compound corresponding to the structural unit represented by the formula (A3) include organotrihalosilane and organotrialkoxysilane.
  • the silicone resin can be synthesized by reacting an organic silicon compound as a starting material at a ratio corresponding to the abundance ratio of each structural unit by a hydrolysis condensation method. The abundance ratio of A3 silicon atoms contained in the silicone resin can be adjusted by appropriately selecting an organic silicon compound that is a starting material.
  • the silicone resin synthesized in this way is commercially available as a silicone resin or the like.
  • Silicone resin 2A A silicone resin 2A suitable as the second sealant will be described.
  • the silicone resin 2A includes the following silicone resin 2A-1.
  • Silicone resin 2A-1 The silicon atom contained in the silicone resin 2A-1 is substantially composed of at least one silicon atom selected from the group consisting of A1 silicon atom, A2 silicon atom and A3 silicon atom.
  • the silicon atom suitably contained in the silicone resin 2A-1 is substantially composed of at least one silicon atom selected from the group consisting of an A1 silicon atom and an A2 silicon atom, and an A3 silicon atom.
  • the ratio of the content of A3 silicon atoms to the total content of A2 silicon atoms and A3 silicon atoms is 60 mol% or more and 90 mol% or less.
  • the silicon atom contained substantially consists of at least one silicon atom selected from the group consisting of an A1 silicon atom and an A2 silicon atom, and an A3 silicon atom.
  • the ratio of the content of A3 silicon atoms to the total content of silicon atoms, A2 silicon atoms, and A3 silicon atoms is 60 mol% or more and 90 mol% or less, and the weight average molecular weight is 1500 or more and 8000 or less.
  • “consisting essentially of at least one silicon atom selected from the group consisting of A1 silicon atom, A2 silicon atom and A3 silicon atom” means that 80 of 80 silicon atoms contained in silicone resin 2A-1 It means that mol% or more is A1 silicon atom, A2 silicon atom or A3 silicon atom, 90 mol% or more is preferably A1 silicon atom, A2 silicon atom or A3 silicon atom, and 95 mol% or more is A1. More preferably, they are a silicon atom, an A2 silicon atom, or an A3 silicon atom.
  • the ratio of the content of A3 silicon atoms to the total content of A1 silicon atoms, A2 silicon atoms, and A3 silicon atoms is preferably 70 mol% or more and 85 mol% or less.
  • Silicone resin 2A-1 has an organopolysiloxane structure represented by the following general formula (2A-1).
  • R 1 is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.
  • R 2 is preferably an alkoxy group having 1 or 2 carbon atoms or a hydroxyl group. When R 2 is an alkoxy group, R 2 is a methoxy group or an ethoxy group.
  • the numerical values of p 1 , q 1 , a 1 and b 1 can be adjusted as appropriate so as to be in such a range.
  • the silicone resin 2A-1 Since the silicone resin 2A-1 has a high abundance ratio of A3 silicon atoms, a cured product of the silicone resin 2A in which the organopolysiloxane chain is formed in a network by curing the silicone resin 2A including the silicone resin 2A-1. Is obtained.
  • the abundance ratio of A3 silicon atoms is higher than the above range (0.6 to 0.9), cracks may easily occur in the cured product of the silicone resin 2A, and the above range (0.6 to 0). .9) If it is lower than that, the UV resistance of the cured product of the silicone resin 2A may be lowered.
  • the number of A2 silicon atoms and A3 silicon atoms per molecule of silicone resin 2A-1 is adjusted by controlling the molecular weight of the resin having an organopolysiloxane structure represented by the general formula (2A-1) Can do.
  • the sum of the number of A2 silicon atoms and the number of A3 silicon atoms per molecule of the silicone resin 2A-1 is preferably 5 or more.
  • the weight average molecular weight (Mw) of the silicone resin 2A-1 is preferably 1500 or more and 8000 or less. When the weight average molecular weight of the silicone resin 2A-1 is too small, the UV resistance of the cured product of the silicone resin 2A-1 tends to be low. When the weight average molecular weight of the silicone resin 2A-1 is within the above range, the UV resistance of the cured product of the silicone resin 2A-1 is more excellent.
  • the weight average molecular weight of the silicone resin 2A-1 is more preferably 2000 or more and 5000 or less.
  • Silicone resin 2A-1 can be synthesized using an organosilicon compound having a functional group capable of forming a siloxane bond, corresponding to each of the structural units described above that constitute silicone resin 2A-1.
  • the “functional group capable of generating a siloxane bond” has the same meaning as described above.
  • Examples of the organosilicon compound corresponding to the structural unit represented by the formula (A3) include organotrihalosilanes and organotrialkoxylanes.
  • Silicone resin 2A-1 can be synthesized by reacting such an organic silicon compound, which is a starting material, by a hydrolytic condensation method at a ratio corresponding to the abundance ratio of each structural unit. The silicone resin 2A-1 thus synthesized is commercially available as a silicone resin or the like.
  • Silicone resin 2A-2 The silicone resin 2A is a silicone resin 2A- having a mass reduction rate of less than 5% when heated from room temperature to 200 ° C. at a rate of temperature increase of 5 ° C./min and held in air at 200 ° C. for 5 hours. 2 may be further included.
  • Silicone resin 2A-2 has few unreacted functional groups and is thermally stable. Therefore, the silicone resin 2A-2 functions as a filler in the cured product of the silicone resin 2A, and contributes to the improvement of the mechanical strength of the cured product of the silicone resin 2A.
  • Silicone resin 2A-2 has few unreacted functional groups and is thermally stable. Therefore, even when UV light is irradiated, it is difficult to be altered. Therefore, the UV resistance of the silicone resin 2A can be further improved by blending the silicone resin 2A-2.
  • silicone resin 2A-2 specifically, a silicone resin having a fine particle structure called silicone rubber powder or silicone resin powder can be used.
  • a spherical silicone resin powder made of a polysilsesquioxane resin having a three-dimensional network structure in which a siloxane bond is represented by (RSiO 3/2 ) is preferable.
  • R is preferably a methyl group.
  • the average particle size of the silicone resin powder is preferably 0.1 ⁇ m or more and 50 ⁇ m or less, more preferably 1 ⁇ m or more and 30 ⁇ m or less, and more preferably 2 ⁇ m or more. More preferably, it is 20 ⁇ m or less.
  • the average particle size of the silicone resin powder is within the above range (0.1 ⁇ m or more and 50 ⁇ m or less), peeling occurs at the interface between the cured product of the silicone resin 2A and the substrate, the white turbidity of the cured product of the silicone resin 2A, the silicone resin It tends to suppress a decrease in light transmittance of the cured product of 2A.
  • the average particle diameter of the silicone resin powder can be measured by, for example, a particle size distribution measuring apparatus based on the measurement principle of “laser diffraction / scattering method”.
  • This method measures the particle size distribution of particles by utilizing the fact that when a particle is irradiated with a laser beam (monochromatic light), diffracted light and scattered light are emitted in various directions according to the size of the particle. It is a technique, and the average particle diameter can be obtained from the distribution state of diffracted light and scattered light.
  • Devices using the “laser diffraction / scattering method” as a measurement principle are commercially available from many manufacturers.
  • a commercially available product can be used as the silicone resin 2A-2.
  • Tospearl 120, Tospearl 130, Tospearl 145, Tospearl 2000B manufactured by Momentive Performance, Tospearl 1110, Tospearl; MSP-N050, MSP-N080 and MSP-S110 manufactured by Nikko Jamaica Co., Ltd. may be mentioned.
  • the total content of the silicone resin 2A-1, the silicone resin 2A-2 and the solvent contained in the silicone resin 2A composition liquid containing the silicone resin 2A and a solvent for dissolving or dispersing the silicone resin 2A is 80% by mass or more. It is preferable that it is 90 mass% or more.
  • the content of silicone resin 2A-2 (in terms of resin content) with respect to the total content of silicone resin 2A-1 and silicone resin 2A-2 is usually 20% by mass to 90% by mass, and 40% by mass to 80% by mass. It is preferable that it is below mass%.
  • the content of the silicone resin 2A-2 is in the above range, a cured product of the silicone resin 2A having excellent balance of crack resistance and UV resistance tends to be obtained.
  • crack resistance means the difficulty of cracks in the cured silicone resin. Moreover, the property that a crack is hard to enter into the cured product of the silicone resin may be expressed as “high crack resistance”.
  • Silicone resin 3A A silicone resin 3A suitable as the second sealant will be described.
  • the silicone resin 3A includes the following silicone resin 3A-1.
  • Silicone resin 3A-1 The silicon atom contained in the silicone resin 3A-1 is substantially composed of at least one silicon atom selected from the group consisting of A1 silicon atom and A2 silicon atom, and A3 silicon atom, Silicone in which the ratio of the content of A3 silicon atom to the total content of A1 silicon atom, A2 silicon atom and A3 silicon atom is 30 mol% or more and less than 60 mol%, and the weight average molecular weight is 1500 or more Resin.
  • substantially consisting of at least one silicon atom selected from the group consisting of A1 silicon atom and A2 silicon atom and A3 silicon atom means among silicon atoms contained in silicone resin 3A-1 80 mol% or more means A1 silicon atom or A2 silicon atom and A3 silicon atom, and 90 mol% or more is preferably A1 silicon atom or A2 silicon atom and A3 silicon atom, It is more preferable that 95 mol% or more are A1 silicon atom or A2 silicon atom and A3 silicon atom.
  • the ratio of the content of A3 silicon atoms to the total content of A1 silicon atoms, A2 silicon atoms, and A3 silicon atoms is preferably 35 mol% or more and 55 mol% or less. More preferably, it is 40 mol% or more and 50 mol% or less.
  • Silicone resin 3A-1 has an organopolysiloxane structure represented by the following general formula (3A-1).
  • R 1 is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.
  • R 2 is preferably an alkoxy group having 1 or 2 carbon atoms or a hydroxyl group. When R 2 is an alkoxy group, R 2 is a methoxy group or an ethoxy group.
  • the content ratio of A3 silicon atoms to the total content of A1 silicon atoms, A2 silicon atoms, and A3 silicon atoms is within the range of 0.3 or more and less than 0.6. It is preferably in the range of 35 to 0.55, and more preferably in the range of 0.4 to 0.5.
  • the number of A1 silicon atoms, A2 silicon atoms and A3 silicon atoms in one molecule of silicone resin 3A-1 is such that the resin having an organopolysiloxane structure represented by the general formula (3A-1) has a desired molecular weight. Is adjusted as appropriate.
  • the sum of the number of A1 silicon atoms, the number of A2 silicon atoms and the number of A3 silicon atoms in one molecule of the silicone resin 3A-1 is preferably 5 or more.
  • the weight average molecular weight (Mw) of the silicone resin 3A-1 is 1500 or more.
  • the weight average molecular weight of the silicone resin 3A-1 is preferably 1500 or more and 8000 or less, more preferably 1500 or more and 7000 or less, and further preferably 1500 or more and 6000 or less.
  • Silicone resin 3A-1 can be synthesized using an organosilicon compound having a functional group capable of forming a siloxane bond as a starting material, corresponding to the above-described structural units constituting silicone resin 3A-1.
  • the “functional group capable of generating a siloxane bond” has the same meaning as described above.
  • Examples of the organosilicon compound corresponding to the structural unit represented by the formula (A3) include organotrihalosilanes and organotrialkoxylanes.
  • Silicone resin 3A-1 can be synthesized by reacting such an organic silicon compound, which is a starting material, with a hydrolysis condensation method at a ratio corresponding to the abundance ratio of each structural unit. The silicone resin 3A-1 thus synthesized is commercially available as a silicone resin or the like.
  • Silicone resin 3A-2 The silicone resin 3A is The contained silicon atom is substantially composed of at least one silicon atom selected from the group consisting of A1 silicon atom and A2 silicon atom, and A3 silicon atom, The ratio of the content of A3 silicon atoms to the total content of A1 silicon atoms, A2 silicon atoms, and A3 silicon atoms is 60 mol% or more and 90 mol% or less, and the weight average molecular weight is 1500 or more and 8000 or less. Further, silicone resin 3A-2 may be further contained.
  • the ratio of the content of A3 silicon atoms to the total content of A1 silicon atoms, A2 silicon atoms, and A3 silicon atoms is preferably 70 mol% or more and 85 mol% or less.
  • the silicone resin 3A-2 Since the silicone resin 3A-2 has a high abundance ratio of A3 silicon atoms, a cured product of the silicone resin 3A in which the organopolysiloxane chain is formed in a network by curing the silicone resin 3A including the silicone resin 3A-2. Is obtained.
  • the abundance ratio of A3 silicon atoms is higher than the above range (0.6 to 0.9)
  • the thermal shock resistance of the cured product of the silicone resin 3A may be lowered, and the above range (0.6 to 0). .9) If lower, the UV resistance of the silicone resin 3A may be lowered.
  • the weight average molecular weight (Mw) of the silicone resin 3A-2 is 1500 or more and 8000 or less. When the weight average molecular weight of the silicone resin 3A-2 is within the above range, the UV resistance of the cured product of the silicone resin 3A including the silicone resin 3A-2 is further improved.
  • the weight average molecular weight of the silicone resin 3A-2 is more preferably 2000 or more and 5000 or less.
  • the silicone resin 3A-2 can be synthesized using an organosilicon compound having a functional group capable of forming a siloxane bond corresponding to each of the structural units described above constituting the silicone resin 3A-2.
  • the “functional group capable of generating a siloxane bond” has the same meaning as described above.
  • Examples of the organosilicon compound corresponding to the structural unit represented by the formula (A3) include organotrihalosilanes and organotrialkoxylanes.
  • Silicone resin 3A-2 can be synthesized by reacting such an organic silicon compound, which is a starting material, with a hydrolysis condensation method at a ratio corresponding to the abundance ratio of each structural unit. Silicone resin 3A-2 thus synthesized is commercially available as a silicone resin or the like.
  • substantially consisting of at least one silicon atom selected from the group consisting of A1 silicon atom and A2 silicon atom and A3 silicon atom means that the silicon resin 3A-2 contains silicon atoms 80 mol% or more means A1 silicon atom or A2 silicon atom and A3 silicon atom, and 90 mol% or more is preferably A1 silicon atom or A2 silicon atom and A3 silicon atom, It is more preferable that 95 mol% or more are A1 silicon atom or A2 silicon atom and A3 silicon atom.
  • the cured product of the silicone resin 3A including the silicone resin 3A-1 and the silicone resin 3A-2 has not only excellent UV resistance but also excellent thermal shock resistance and adhesion.
  • the content (resin content) of the silicone resin 3A-2 with respect to the total content of the silicone resin 3A-1 and the silicone resin 3A-2 is usually 5% by mass to 95% by mass, and 30% by mass or more. It is preferable that it is 90 mass% or less.
  • the content of the silicone resin 3A-2 is in the above range, a cured product of the silicone resin 3A having a well-balanced thermal shock resistance and UV resistance tends to be obtained.
  • the resin content is calculated based on the mass of the silicone resin, excluding the mass of the solvent.
  • the total content (resin content) of the silicone resin 3A-1 and the silicone resin 3A-2 contained in the silicone resin 3A is preferably 15% by mass or more, and more preferably 50% by mass or more.
  • Silicone resin 4A A silicone resin 4A suitable as the second sealant will be described.
  • Silicone resin 4A includes silicone resin 4A-1 having an organopolysiloxane structure represented by the general formula (2A-1) and a silicone resin having an organopolysiloxane structure represented by the general formula (3A-1). 4A-2.
  • the weight average molecular weight (Mw) of the silicone resin 4A-1 is usually 1500 or more and 8000 or less.
  • the weight average molecular weight of the silicone resin 4A-1 is preferably 1500 or more and 7000 or less, and more preferably 2000 or more and 5000 or less.
  • the weight average molecular weight of the silicone resin 4A-2 is usually less than 1500. When the weight average molecular weight of the silicone resin 4A-2 is in the above range, the cured product of the silicone resin 4A has good crack resistance.
  • the weight average molecular weight of the silicone resin 4A-2 is preferably 200 or more and less than 1500, and more preferably 250 or more and 1000 or less.
  • the 2nd sealing material further contains the curing catalyst.
  • the second sealant contains a curing catalyst
  • a solution containing the silicone resins 2A to 4A and a solution containing the curing catalyst are prepared separately, and before using the second sealing material. It is preferable to mix these solutions.
  • the curing catalyst examples include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; organic acids such as formic acid, acetic acid, succinic acid, citric acid, propionic acid, butyric acid, lactic acid and succinic acid.
  • the curing catalyst may be an alkaline compound. Examples of the alkaline compound include ammonium hydroxide, tetramethylammonium hydroxide, and tetraethylammonium hydroxide. Examples of other curing catalysts include metal alkoxides such as aluminum isopropoxide and zirconium isopropoxide; and metal acetylacetonates such as zirconium acetylacetonate.
  • a solution obtained by dissolving the first sealing material before curing in a solvent may be used.
  • a solution obtained by dissolving the second sealing material before curing in a solvent may be used.
  • the solvent examples include ketone solvents such as acetone and methyl ethyl ketone; alcohol solvents such as methanol, ethanol, isopropyl alcohol, and normal propyl alcohol; hydrocarbon solvents such as hexane, cyclohexane, heptane, and benzene; acetic acid such as methyl acetate and ethyl acetate.
  • ketone solvents such as acetone and methyl ethyl ketone
  • alcohol solvents such as methanol, ethanol, isopropyl alcohol, and normal propyl alcohol
  • hydrocarbon solvents such as hexane, cyclohexane, heptane, and benzene
  • acetic acid such as methyl acetate and ethyl acetate.
  • the solvent contained in the second sealing material has an ester bond and / or an ether bond, has no hydroxy group, and has a boiling point of 100 ° C. or more and 200 ° C. under 1 atm.
  • the following solvent is preferable, and a solvent having a boiling point under 1 atm of 120 ° C. or higher and 200 ° C. or lower is more preferable. If the boiling point at 1 atm is 100 ° C. or higher, preferably 120 ° C. or higher, the solvent is difficult to volatilize during operations such as weighing, mixing, and potting, so that the operability tends to be improved. If the boiling point under 1 atm is 200 ° C.
  • Suitable solvents contained in the second sealing material include, for example, ester solvents such as butyl acetate and butyl butyrate; ether solvents such as dioxane; glycol ether solvents such as ethylene glycol diethyl ether and diethylene glycol diethyl ether; And glycol ester solvents such as ethoxyethyl and 2-butoxyethyl acetate.
  • solvents from the viewpoint of crack resistance of the cured product of the second sealing material, it has a hydroxy group and has a boiling point of 100 ° C. or higher at 1 atm and a melting point of 25 ° C. or lower.
  • a solvent is preferred.
  • suitable solvents contained in the second sealing material include alcohol solvents such as butanol, hexanol and octanol; glycol solvents such as diethylene glycol monoethyl ether.
  • the silicone resin used for the second sealing material is preferably the silicone resin 2A or the silicone resin 3A, and more preferably the silicone resin 2A.
  • FIG. 8A shows a cross-sectional view of the ultraviolet light emitting semiconductor device manufactured in Example 1.
  • FIG. 2B is a plan view of the ultraviolet light emitting semiconductor device manufactured in Example 1.
  • FIG. 8A is a cross-sectional view taken along the line AA in FIG.
  • the obtained sealing material liquid was used for light emission of the ultraviolet light emitting element 2 on an AlN cavity type UV-LED substrate (3.5 mm ⁇ 3.5 mm, light output 30 mW) on which the ultraviolet light emitting element 2 (emission wavelength: 285 nm) was installed. 1.3 mg was dropped on a portion other than the surface 2a with a dispenser. Then, the sealing material was hardened by hold
  • the first sealing material layer 3 was not formed on the light emitting surface 2 a of the ultraviolet light emitting element 2.
  • the gray portion is a region where the first sealing material layer 3 is formed.
  • 13.8 mg of the second sealing material prepared in Production Example 1 was dropped with a dispenser so as to cover the first sealing material layer 3 and the light emission surface 2a of the ultraviolet light emitting element 2.
  • the polycondensation type silicone sealing material was hardened by hold
  • the thickness L of the second sealing material layer 4 was 1.19 mm.
  • an ultraviolet light emitting semiconductor device having a first sealing material layer and a second sealing material layer was manufactured.
  • first sealing material layer made of a cured product of an addition condensation type silicone sealing material.
  • a first sealing material layer was formed on the light emitting surface of the ultraviolet light emitting element.
  • 13.0 mg of the second sealing material prepared in Production Example 1 was dropped with a dispenser so as to cover the surface of the first sealing material layer.
  • the polycondensation type silicone sealing material was hardened by hold
  • the thickness of the second sealing material layer was 1.13 mm.
  • an ultraviolet light emitting semiconductor device having a first sealing material layer and a second sealing material layer was manufactured.
  • Example 2 Add 5.0 g of each of A and B liquids (both solvent-free liquids) of addition polymerization type silicone sealing material KER-2700 manufactured by Shin-Etsu Chemical Co., Ltd. to the same plastic container, and then defoaming and mixing. Liquid.
  • the obtained sealing material liquid was used for light emission of the ultraviolet light emitting element 2 on an AlN cavity type UV-LED substrate (3.5 mm ⁇ 3.5 mm, light output 30 mW) on which the ultraviolet light emitting element 2 (emission wavelength: 285 nm) was installed. 1.2 mg was dripped at parts other than the surface 2a with a dispenser.
  • the sealing material was hardened by hold
  • the first sealing material layer 3 was not formed on the light emitting surface 2 a of the ultraviolet light emitting element 2.
  • the gray portion is a region where the first sealing material layer 3 is formed.
  • 13.8 mg of the second sealing material prepared in Production Example 1 was dropped with a dispenser so as to cover the first sealing material layer 3 and the light emission surface 2a of the ultraviolet light emitting element 2.
  • the polycondensation type silicone sealing material was hardened by hold
  • the thickness L of the second sealing material layer 4 was 1.11 mm.
  • the sealing material was hardened by hold
  • the first sealing material layer was not formed on the light emission surface of the ultraviolet light emitting element.
  • 8.0 mg of the addition polymerization type silicone sealing material KER-2700 prepared as described above was dropped with a dispenser so as to cover the first sealing material layer and the light emitting surface of the ultraviolet light emitting element. Thereafter, the addition polymerization type silicone sealing material is cured by holding at 100 ° C. for 1 hour and at 150 ° C.
  • the sealing material was hardened by hold
  • the first sealing material layer was not formed on the light emission surface of the ultraviolet light emitting element.
  • 5.0 g each of liquid A and liquid B (both solvent-free) of addition polymerization type silicone sealing material KER-2500 manufactured by Shin-Etsu Chemical Co., Ltd. was added to the same plastic container, and then defoamed and mixed. And prepared. 8.0 mg of the obtained sealing material liquid was dropped with a dispenser so as to cover the first sealing material layer and the light emitting surface of the ultraviolet light emitting element.
  • the addition polymerization type silicone sealing material is cured by holding at 100 ° C. for 1 hour and at 150 ° C. for 5 hours to form a second sealing material layer made of a cured product of the addition polymerization type silicone sealing material. did.
  • the thickness of the second sealing material layer was 0.89 mm.
  • the sealing material was hardened by hold
  • the first sealing material layer was not formed on the light emission surface of the ultraviolet light emitting element.
  • 5.0 g each of liquid A and liquid B (both solvent-free) of addition polymerization type silicone sealing material IVS-4542 made by Momentive Performance Materials Japan GK is added to the same plastic container. Then, the mixture was defoamed and mixed. 9.3 mg of the obtained sealing material liquid was dropped with a dispenser so as to cover the first sealing material layer and the light emission surface of the ultraviolet light emitting element.
  • the addition polymerization type silicone sealing material is cured by holding at 80 ° C. for 1.5 hours and at 150 ° C. for 1 hour, and a second sealing material layer comprising a cured product of the addition polymerization type silicone sealing material Formed.
  • the thickness of the second sealing material layer was 0.99 mm.
  • the sealing material was hardened by hold
  • the first sealing material layer was not formed on the light emission surface of the ultraviolet light emitting element.
  • 5.0 g of each of liquid A and liquid B (both solvent-free) of addition polymerization type silicone sealing material OE-6351 manufactured by Toray Dow Corning Co., Ltd. was added to the same plastic container, followed by defoaming Mix and prepare. 7.5 mg of the obtained sealing material liquid was dropped with a dispenser so as to cover the first sealing material layer and the light emission surface of the ultraviolet light emitting element.
  • the addition polymerization type silicone sealing material was hardened by hold
  • the thickness of the second sealing material layer was 0.95 mm.
  • the sealing material was hardened by hold
  • the first sealing material layer was not formed on the light emission surface of the ultraviolet light emitting element.
  • 10 g of polycondensation type silicone “Composeran SL402” manufactured by Arakawa Chemical Industries, Ltd. and 0.05 g of dioctyltin dilaurate “Neostan U-810” manufactured by Nitto Kasei Co., Ltd. are put in the same plastic container and defoamed and mixed. Prepared.
  • the polycondensation type silicone sealing material is cured by holding at 105 ° C. for 1 hour and at 150 ° C. for 1 hour to form a second sealing material layer made of a cured product of the polycondensation type silicone sealing material. did.
  • the thickness of the second sealing material layer was 0.95 mm.
  • “COMPOCELAN SL402” manufactured by Arakawa Chemical Industries, Ltd. is a polycondensation type silicone having a structure in which a dialkylsiloxane structure is crosslinked with silica, and is represented by the general formula (2A-1) or (3A-1).
  • the sealing material was hardened by hold
  • the first sealing material layer was not formed on the light emission surface of the ultraviolet light emitting element.
  • 3 g of liquid A and 6 g of liquid B (both solvent-free) of addition polymerization type silicone sealing material OE-6663 manufactured by Toray Dow Corning Co., Ltd. were added to the same plastic container, and then defoamed and mixed. Prepared. 9.0 mg of the obtained sealing material liquid was dropped with a dispenser so as to cover the first sealing material layer and the light emitting surface of the ultraviolet light emitting element.
  • the addition polymerization type silicone sealing material was hardened by hold
  • the thickness of the second sealing material layer was 1.12 mm.
  • the ultraviolet light emitting semiconductor device manufactured in Example 1 had a high relative luminous intensity even after the energization test 1, and no cracks were confirmed.
  • the ultraviolet light emitting semiconductor device manufactured in Comparative Example 1 had a low relative luminous intensity after generation test 1, and the occurrence of cracks was also confirmed. Therefore, it was found that the ultraviolet light emitting semiconductor device manufactured in Example 1 was excellent in ultraviolet durability and crack resistance.
  • the ultraviolet light emitting device produced in Example 2 had high relative luminous intensity even after the energization test 2, and no cracks were confirmed.
  • the ultraviolet light emitting devices manufactured in Comparative Examples 2 to 6 had a low relative luminous intensity after the energization test 2.
  • the ultraviolet light emitting devices manufactured in Comparative Examples 3 to 5 were confirmed to have cracks after the energization test 2. Therefore, it was found that the ultraviolet light emitting semiconductor device manufactured in Example 2 was excellent in ultraviolet durability and crack resistance.
  • 1 base material
  • 2 ultraviolet light emitting element
  • 2a light emitting surface of ultraviolet light emitting element
  • 3 first sealing material layer
  • 4 second sealing material layer
  • 5 wiring
  • 6 electrode
  • 7 Thickness of the first sealing material layer
  • 8 thickness of the second sealing material layer
  • 30, 40 dispenser
  • M mask
  • an ultraviolet light emitting semiconductor device that is unlikely to cause cracking or coloring (that is, an ultraviolet light emitting semiconductor device having high ultraviolet durability).
  • the manufacturing method of the said ultraviolet light-emitting semiconductor device can be provided.

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JP7252820B2 (ja) 2019-04-12 2023-04-05 日機装株式会社 半導体発光装置及びその製造方法
WO2021070347A1 (ja) * 2019-10-10 2021-04-15 株式会社エンプラス 発光装置および殺菌装置
JP2021150428A (ja) * 2020-03-18 2021-09-27 日機装株式会社 半導体発光装置

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WO2015115341A1 (ja) * 2014-01-31 2015-08-06 住友化学株式会社 半導体発光装置の製造方法
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JP7250560B2 (ja) 2019-02-20 2023-04-03 旭化成株式会社 紫外線発光装置

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