JP2018014493A - Uv light-emitting semiconductor device and method for manufacturing the same - Google Patents

Abstract

An ultraviolet light emitting semiconductor device with high ultraviolet durability and a method for manufacturing the ultraviolet light emitting semiconductor device that does not generate cracks or color even when an ultraviolet light emitting element is used. An ultraviolet light emitting semiconductor device including 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 material layer has a first sealing material layer 3 and a second sealing material layer 4, and the first sealing material layer is an addition polymerization type silicone sealing material or 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, and the second sealing material layer includes a polycondensation type silicone sealing material containing a resin having an organopolysiloxane structure, 1 sealing material layer is not in contact. [Selection] Figure 1

Description

  The present invention relates to an ultraviolet light emitting semiconductor device and a method for manufacturing the same.

  As 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.

  Specifically, 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. And a sealing material layer (i) using at least one sealing material (i) selected from the group consisting of a polycondensation type silicone sealing material, and then on the sealing material layer (i) A method for manufacturing a semiconductor light emitting device is described, 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.

International Publication No. 2015/125713

When the semiconductor light emitting device manufactured by the method for manufacturing a semiconductor light emitting device described in Patent Document 1 includes an ultraviolet light emitting element having an emission wavelength of 300 nm or less as the semiconductor light emitting element, the sealing material layer (i) deteriorates. As a result, there was a problem that cracks and coloring occurred in the encapsulant layer (i), thereby reducing the output from the ultraviolet light emitting element.
Therefore, 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].

［一般式（２Ａ−１）中、Ｒ^１はそれぞれ独立してアルキル基を表し、Ｒ^２はそれぞれ独立してアルコキシ基または水酸基を表し、ｐ^１、ｑ^１、ａ^１およびｂ^１は、［ｐ^１＋ｂ^１×ｑ^１］：［ａ^１×ｑ^１］＝１：０．２５〜９となる正数を表す。］

［一般式（３Ａ−１）中、Ｒ^１はそれぞれ独立してアルキル基を表し、Ｒ^２はそれぞれ独立してアルコキシ基または水酸基を表し、ｐ^２、ｑ^２、ｒ^１、ａ^２およびｂ^２は、［ａ^２×ｑ^２］／［（ｐ^２＋ｂ^２×ｑ^２）＋ａ^２×ｑ^２＋（ｒ^１＋ｑ^２）］が０．３以上０．６未満となる整数を表す。］
［２］前記第１の封止材層が、付加重合型シリコーン封止材を含む、［１］に記載の紫外線発光半導体装置。
［３］前記ジアルキルシロキサン構造を有する樹脂が、下記一般式（１）で表されるジアルキルシロキサン構造を有する樹脂Ｘである、［１］に記載の紫外線発光半導体装置。

［一般式（１）中、Ｒ^３はそれぞれ独立に、アルキル基を表し、ｎは５〜４０００の整数を表す。］
［４］前記ｎが、５〜１０００の整数である、［３］に記載の紫外線発光半導体装置。
［５］前記第２の封止材層が、前記第１の封止材層および前記紫外線発光素子の光射出面の上に形成されており、前記第２の封止材層と前記第１の封止材層とが接触する面積が、前記第１の封止材層が形成する面積よりも小さい、［１］〜［４］のいずれか１つに記載の紫外線発光半導体装置。
［６］前記第１の封止材層のショア硬度がＡ８０以下である、［１］〜［５］のいずれか１つに記載の紫外線発光半導体装置。
［７］前記第１の封止材層が、前記第１の封止材層と第２の封止材層との界面において、前記第２の封止材層と密着性を有する、［１］〜［６］のいずれか１つに記載の紫外線発光半導体装置。
［８］前記第２の封止材層を２層以上有する、［１］〜［７］のいずれか１つに記載の紫外線発光半導体装置。
［９］前記第２の封止材層の形状が、凸レンズ形状である、［１］〜［８］のいずれか１つに記載の紫外線発光半導体装置。
［１０］基材と、前記基材上に配置された紫外線発光素子と、前記紫外線発光素子の少なくとも一部を封止する封止材層とを有する紫外線半導体装置の製造方法であって、基材上に紫外線発光素子を設置する第１工程と、付加重合型シリコーン封止材、または、ジアルキルシロキサン構造を有する樹脂を含む重縮合型シリコーン封止材を有する第１の封止材を、前記紫外線発光素子の光射出面を覆わないようにポッティングする第２工程と、ポッティングされた硬化前の第１の封止材を硬化させて、第１の封止材層を形成する第３工程と、上記一般式（２Ａ−１）または（３Ａ−１）で表されるオルガノポリシロキサン構造を有する樹脂を含む重縮合型シリコーン封止材を有する第２の封止材を、前記紫外線発光素子および前記第１の封止材層の上にポッティングし、ポッティングされた硬化前の第２の封止材を硬化させて、第２の封止材層を形成する第４工程とを含む、紫外線発光半導体装置の製造方法。
［１１］基材と、前記基材上に配置された紫外線発光素子と、前記紫外線発光素子の少なくとも一部を封止する封止材層とを有する紫外線半導体装置の製造方法であって、基材上に紫外線発光素子を設置する第１工程と、前記紫外線発光素子上にマスクを設置する第１ａ工程と、付加重合型シリコーン封止材、または、ジアルキルシロキサン構造を有する樹脂を含む重縮合型シリコーン封止材を有する第１の封止材をポッティングする第２工程と、前記マスクを除去する第２ａ工程と、ポッティングされた硬化前の第１の封止材を硬化させて、第１の封止材層を形成する第３工程と、上記一般式（２Ａ−１）または（３Ａ−１）で表されるオルガノポリシロキサン構造を有する樹脂を含む重縮合型シリコーン封止材を有する第２の封止材を、前記紫外線発光素子および前記第１の封止材層の上にポッティングし、ポッティングされた硬化前の第２の封止材を硬化させて、第２の封止材層を形成する第４工程とを含む、紫外線発光半導体装置の製造方法。
［１２］前記第１工程では、前記紫外線発光素子の設置に先立って、前記基材の表面をオゾン洗浄し、かつ、前記第４工程では、前記第１の封止材層の上であり、前記第１の封止材層よりも狭い範囲に前記第２の封止材をポッティングし、ポッティングされた前記第２の封止材を硬化させて、前記第２の封止材層を形成する、［１０］または［１１］に記載の紫外線発光半導体装置の製造方法。
［１３］前記第２工程で供給する第１の封止材（当該第１の封止材は、付加重合型シリコーン封止材である）の供給量をＷ１［ｇ］とし、前記第４工程で供給する第２の封止材の供給量をＷ２［ｇ］とした場合、Ｗ２／Ｗ１の比率が１．５〜８の範囲内である、［１０］〜［１２］のいずれか１つに記載の紫外線発光半導体装置の製造方法。
［１４］前記第２工程で供給する第１の封止材（当該第１の封止材は、重縮合型シリコーン封止材である）の供給量をＷ１［ｇ］とし、前記第４工程で供給する第２の封止材の供給量をＷ２［ｇ］とした場合、Ｗ２／Ｗ１の比率が１．５〜１３の範囲内である、［１０］〜［１２］のいずれか１つに記載の紫外線発光半導体装置の製造方法。
［１５］前記第３工程での第１の封止材の硬化温度をＴａ［℃］とし、前記第４工程での第２の封止材の硬化温度をＴｂ［℃］とした場合、Ｔａ−１０＜Ｔｂ≦Ｔａ＋１００を満たす、［１０］〜［１４］のいずれか１つに記載の紫外線発光半導体装置の製造方法。 [1] 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, The material layer has a first sealing material layer and a second sealing material layer, and the first sealing material layer is made of an addition polymerization type silicone sealing material or a resin having a dialkylsiloxane structure. A polycondensation type silicone sealing material, wherein the second sealing material layer includes a resin having an organopolysiloxane structure represented by the following general formula (2A-1) or (3A-1) An ultraviolet light emitting semiconductor device comprising a type silicone sealing material, wherein the first sealing material layer is not in contact with the light emitting surface of the ultraviolet light emitting element.

[In General Formula (2A-1), each R ¹ independently represents an alkyl group, each R ² independently represents an alkoxy group or a hydroxyl group, and 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 that satisfies 0.25 to 9. ]

[In General Formula (3A-1), each R ¹ independently represents an alkyl group, each R ² independently represents an alkoxy group or a hydroxyl group, and 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. ]
[2] The ultraviolet light emitting semiconductor device according to [1], wherein the first sealing material layer includes an addition polymerization type silicone sealing material.
[3] The ultraviolet light-emitting semiconductor device according to [1], wherein the resin having a dialkylsiloxane structure is a resin X having a dialkylsiloxane structure represented by the following general formula (1).

[In General Formula (1), each R ³ independently represents an alkyl group, and n represents an integer of 5 to 4000. ]
[4] The ultraviolet light-emitting semiconductor device according to [3], wherein n is an integer of 5 to 1000.
[5] 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.
[6] The ultraviolet light emitting semiconductor device according to any one of [1] to [5], in which a Shore hardness of the first sealing material layer is A80 or less.
[7] 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], which includes two or more second sealing material layers.
[9] The ultraviolet light-emitting semiconductor device according to any one of [1] to [8], wherein the shape of the second sealing material layer is a convex lens shape.
[10] 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 the material, and 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 second step of potting so as not to cover the light emitting surface of the ultraviolet light emitting element; a third step of curing the potted first sealing material before curing to form a first sealing material layer; The 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 first sealing material The fourth and a method of manufacturing an ultraviolet light-emitting semiconductor device potting and curing the second encapsulant prior to curing that are potted to form a second sealing material layer on the.
[11] A method for manufacturing 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. 1st process which installs an ultraviolet light emitting element on a material, 1a process which installs a mask on the said ultraviolet light emitting element, a polycondensation type containing addition polymerization type silicone sealing material or resin which has a dialkylsiloxane structure A second step of potting a first encapsulant having a silicone encapsulant; a 2a step of removing the mask; and curing the potted first encapsulant before curing, A second step having a third step of forming a sealing material layer and a polycondensation type silicone sealing material containing a resin having an organopolysiloxane structure represented by the general formula (2A-1) or (3A-1); Sealing material Potting on the ultraviolet light emitting element and the first sealing material layer, and curing the potted second sealing material before curing to form a second sealing material layer; A method for manufacturing an ultraviolet light emitting semiconductor device, comprising:
[12] In the first step, prior to the installation of the ultraviolet light-emitting element, the surface of the base material is ozone-cleaned, and in the fourth step, on the first sealing material layer, The second sealing material is potted in a range narrower than the first sealing material layer, and the potted second sealing material is cured to form the second sealing material layer. [10] The method for manufacturing an ultraviolet light emitting semiconductor device according to [11].
[13] 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 When the supply amount of the second sealing material supplied in step S2 is W2 [g], the ratio of W2 / W1 is in the range of 1.5 to 8, and any one of [10] to [12] The manufacturing method of the ultraviolet-ray-emitting semiconductor device of description.
[14] 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], and the fourth step When the supply amount of the second sealing material supplied in step S2 is W2 [g], the ratio of W2 / W1 is in the range of 1.5 to 13, and any one of [10] to [12] The manufacturing method of the ultraviolet-ray-emitting semiconductor device of description.
[15] When the curing temperature of the first sealing material in the third step is Ta [° C.] and the curing temperature of the second sealing material in the fourth step is Tb [° C.], Ta The method for manufacturing an ultraviolet light emitting semiconductor device according to any one of [10] to [14], wherein −10 <Tb ≦ Ta + 100 is satisfied.

  According to the present invention, it is possible 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). Moreover, according to this invention, the manufacturing method of the said ultraviolet light-emitting semiconductor device can be provided.

It is sectional drawing which shows the outline of a structure in an example of the ultraviolet light-emitting semiconductor device of this invention. It is sectional drawing which shows the outline of a structure in an example of the ultraviolet light-emitting semiconductor device of this invention. It is sectional drawing which shows the outline of a structure in an example of the ultraviolet light-emitting semiconductor device of this invention. It is sectional drawing which shows the outline of a structure in an example of the ultraviolet light-emitting semiconductor device of this invention. It is sectional drawing which shows the outline of a structure in an example of the ultraviolet light-emitting semiconductor device of this invention. It is sectional drawing which shows the outline of the process in an example of the manufacturing method of the ultraviolet light-emitting semiconductor device of this invention. It is sectional drawing which shows the outline of the process in an example of the manufacturing method of the ultraviolet light-emitting semiconductor device of this invention. It is sectional drawing and the top view of the ultraviolet light-emitting semiconductor device manufactured in the Example.

<Ultraviolet light emitting semiconductor device>
An embodiment of the ultraviolet light emitting semiconductor device of the present invention will be described.

  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 general formula (2A-1) or (3A-1). Includes cured product of silicone encapsulant.

<< First Embodiment >>
A first embodiment of an ultraviolet light emitting semiconductor device will be described with reference to FIG. 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.

More specifically, in the present embodiment, 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.
By the sealing material layer, the ultraviolet light emitting element 2 is prevented from being oxidized and protected from the outside. Moreover, 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. Due to the convex lens effect, the diffused light is converted into parallel light, the light condensing property of the light emitted from the ultraviolet light emitting element 2 is increased, and the light extraction efficiency from the ultraviolet light emitting element 2 can be improved.
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.
However, 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. Cracks and discoloration of the material layer 3 occur, and the output from the ultraviolet light emitting element decreases.

In the present embodiment, since 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. In this case, there is a problem that the first sealing material layer is severely deteriorated and cannot be used.

According to the present embodiment, since 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.
In the present embodiment, 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.
In the present embodiment, the first sealing material layer 3 is formed so as to cover the entire upper surface of the surface of the flat substrate 1. Furthermore, 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. In the present embodiment, the second sealing material layer 4 exhibits a light condensing action at an angle θ1 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.

<< Second Embodiment >>
A second embodiment of the ultraviolet light emitting semiconductor device will be described with reference to FIG. In the present embodiment, the description of the same configuration as that of the first embodiment is omitted.
In the present embodiment, the first sealing material layer 3 is formed so as to cover the entire upper surface of the surface of the flat substrate 1. Furthermore, 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. That is, 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. When the second sealing material layer 4 is formed in this way, an angle θ2 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.

«Third embodiment»
A third embodiment of the ultraviolet light emitting semiconductor device will be described with reference to FIG. In the present embodiment, the description of the same configuration as the first embodiment and the second embodiment is omitted.
In the present embodiment, 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. .
When the first sealing material layer 3 is formed in this way, the angle θ3 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

  Among the first to third embodiments, the angle θ formed by the boundary of the peripheral portion of the second sealing material layer 4 can be made larger, so the first embodiment or the second embodiment is more preferable.

<< Fourth Embodiment >>
A fourth embodiment of the ultraviolet light emitting semiconductor device will be described with reference to FIG. In the present embodiment, the description of the same configuration as in the first to third embodiments is omitted.
In the present embodiment, a base material 1 having a recess 10 in which the ultraviolet light emitting element 2 is accommodated is used. In the present embodiment, 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.

In the present embodiment, 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. Yes.

In the present embodiment, 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.
In the present embodiment, the second sealing material layer 4 exhibits a condensing function at an angle θ4 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.

«Fifth embodiment»
A fifth embodiment of the ultraviolet light emitting semiconductor device will be described with reference to FIG. In the present embodiment, the description of the same configuration as in the first to fourth embodiments is omitted.
In this embodiment, 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.

In the present embodiment, 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.
When the first sealing material layer 3 is formed in this way, the angle θ5 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.

  Among the ultraviolet light emitting semiconductor devices of the present invention described above, when a base material having a concave portion (cavity type base material) is used, the ultraviolet light emitting semiconductor device of the fifth embodiment is preferable to the fourth embodiment.

<Method for manufacturing ultraviolet light emitting semiconductor device>
A preferred embodiment of the method for producing an ultraviolet light emitting semiconductor device of the present invention will be described.

<< Sixth 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, and 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 And a second step of potting so as not to cover the light emitting surface of the ultraviolet light emitting element, and a first sealing material layer that is hardened by potting is cured to form a first sealing material layer. 3 steps and 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), A light emitting element and said first Of potted on the sealing material layer, curing the second encapsulant prior to curing that is potted, including a fourth step of forming a second sealing material layer.
Hereinafter, each step will be described with reference to FIG.

[First step]
A 1st process is a process of installing the ultraviolet light emitting element 2 on a base material 1 by a conventional method. Prior to this step, the surface of the substrate 1 may be surface-modified by pretreatment as shown in FIG. As the pretreatment, 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. As a result of the first step, as shown in FIG. 6 (ii), the wiring 5 and the like are arranged on the substrate 1.

[Second step]
In the second step, as shown in FIG. 6 (iii), an addition polymerization type silicone sealing material or a first sealing material 3 containing a polycondensation type silicone sealing material containing a resin having a dialkylsiloxane structure is used. This is a step of potting so as not to cover the light emitting surface 2a of the ultraviolet light emitting element.
In this step, the first sealing material 3 is supplied onto the base material 1 by a dedicated dispenser 30. Since the ultraviolet light-emitting semiconductor device and the ultraviolet light-emitting element have various shapes depending on their intended use, 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.

[Third step]
The third step is a step of curing the first sealing material 3 before curing potted in the second step.
When the first encapsulating material 3 is an addition polymerization type silicone encapsulating material, 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 ° C. or higher and 200 ° C. or lower, and more preferably 100 ° C. or higher and 150 ° C. or lower. The time is preferably 1 hour or more and 5 hours or less. In order to effectively promote the volatilization of the solvent in the first sealing material 3 before curing, the addition polymerization reaction of the first sealing material 3, etc., the curing temperature may be raised stepwise to be cured. .

  When the first sealing material 3 is a polycondensation type silicone sealing material, 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 ° C. or higher and 250 ° C. or lower, and more preferably 100 ° C. or higher and 200 ° C. or lower. The time is preferably 1 hour or more and 5 hours or less. 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.

[Fourth step]
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. When 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 When the sealing material 1 is an addition polymerization type silicone sealing material, the ratio of W2 / W1 is preferably set to be within 0.5 to 13, and is preferably set to be within 1.5 to 8. More preferred.
In addition, when the first sealing material is a polycondensation type silicone sealing material, the ratio of W2 / W1 is preferably set to be within 0.5 to 15, and is set to be within 1.5 to 13. Is more preferable.
Depending on the type of the sealing material, the resin may be dissolved in the solvent. In this case, the supply amounts W1 [g] and W2 [g] indicate the amount of solvent contained in the sealing material. The amount subtracted.
When this ratio satisfies this range, the shape of the sealing material covering the ultraviolet light emitting element is stabilized, and as a result, the luminance as the ultraviolet light emitting semiconductor device is stabilized.

  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. Is set to Ta [° C.] and the curing temperature in the fourth step is set to Tb [° C.], a range of Ta−25 <Tb ≦ Ta + 150 is preferable, and a range of Ta−10 <Tb ≦ Ta + 100 is further preferable. Is more preferable. By curing within this range, irregular reflection or loss of light emitted from the ultraviolet light emitting element due to poor adhesion or cracks can be prevented, and the luminance as the ultraviolet light emitting semiconductor device is stabilized. The curing time at the temperature of Tb is preferably in the range of 1 to 50 hours. It is also possible to raise the temperature up to the curing temperature Tb stepwise.

  It is preferable that a 4th process is a process of laminating | stacking the 2nd sealing material after the hardening from which the physical property differs from the 1st sealing material after the hardening obtained at the 3rd process. 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.

  As an index representing such physical properties, the resin hardness after curing is effective, and the first encapsulant after curing in the third step so that the resin hardness after curing is 90-20 of the Shore hardness A And a combination of the second sealing material after curing in the fourth step so that the Shore hardness D is 90 to 20, and curing in the third step so that the Shore hardness A is 60 to 20 A combination of the first sealing material after being cured and the second sealing material after being cured in the fourth step so as to have a Shore hardness D of 90 to 60 is more preferable.

  By repeating the fourth step, it is possible to obtain an ultraviolet light emitting semiconductor device in which three or more layers of the second sealing material 4 are laminated. 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.

<< Seventh 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, a first step of installing a mask on the ultraviolet light emitting element, and an addition polymerization type silicone sealing material or a resin having a dialkylsiloxane structure. A second step of potting a first encapsulant having a polycondensation type silicone encapsulant, a 2a step of removing the mask, and curing the potted first encapsulant before curing, A polycondensation type silicone sealing material comprising a third step of forming a first sealing material layer and a resin having an organopolysiloxane structure represented by the above general formula (2A-1) or (3A-1) Have second A stopper is potted on the ultraviolet light-emitting element and the first sealing material layer, and the potted second sealing material before curing is cured to form a second sealing material layer. Including the fourth step.

  Hereinafter, each step will be described with reference to FIG. In the present embodiment, the descriptions regarding the first step, the third step, and the fourth step are the same as the descriptions regarding the first step, the third step, and the fourth step in the sixth embodiment. Hereinafter, the 1a step and the 2a step will be described.

[Step 1a]
In step 1a, as shown in FIG. 7 (iii), 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. As the mask material, for example, a resist material can be used.

  Since the light emission surface 2a of the ultraviolet light-emitting element 2 is protected by the mask M by this step, in the subsequent second step, the first sealing material is more efficiently compared with the sixth embodiment. Can be potted.

[Second step]
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. In this step, as shown in FIG. 7 (iv), 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]
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.

<< Eighth Embodiment >>
In this embodiment, in the sixth embodiment or the seventh embodiment, in the first step, 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.

[First step]
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.

  In this embodiment, the description regarding the first to third steps is the same as the description regarding the first to third steps in the sixth embodiment.

[Fourth step]
In this step, 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.

  Hereinafter, each material used for the ultraviolet light-emitting semiconductor device of the present invention will be described.

≪Base material≫
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.
Usually, an electrode for electrically connecting to the ultraviolet semiconductor element to be arranged is formed on the substrate.

≪Ultraviolet light emitting element≫
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.
In the ultraviolet light emitting semiconductor device of the present invention, 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.
Examples of the ultraviolet light emitting LED chip include an LED chip manufactured by growing a group 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. For the installation of the ultraviolet light emitting element, 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. In the case of the flip chip method, the ultraviolet light emitting element is electrically connected to the electrode on the base material by solder. In the case of the face-up method, 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.

≪Sealing material≫
In the ultraviolet light emitting semiconductor device of the present invention, as the sealing material, an addition polymerization type silicone sealing material or a first sealing material including a polycondensation type silicone sealing material containing a resin having a dialkylsiloxane structure; A second sealing material including a polycondensation type silicone sealing material including a resin having an organopolysiloxane structure represented by the general formula (2A-1) or (3A-1) is used in combination. Specifically, the sealing material used for forming the first sealing material layer is the first sealing material, and 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.

(First sealing material)
Addition polymerization type silicone sealing material Among the first sealing materials, examples of the addition polymerization type silicone sealing material include a methyl silicone resin sealing material, a phenyl silicone resin sealing material, and a methylphenyl silicone resin. Examples thereof include a sealing material, and a methyl silicone resin sealing material is preferable because the resin hardness after curing is relatively soft.

  As these addition polymerization type silicone sealing materials, commercially available sealing materials can be used. Specifically, 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-6663, OE-6636, OE-6635, OE-6630, OE-6665N, which are silicone-based silicone resin encapsulants; methyl silicone resin manufactured by Shin-Etsu Chemical Co., Ltd. IVS4321, XE14-C2042, IVS4542, IVS4546, IVS4622, IVS4632, IVS4742, IVS4752, IVSG3445, IVSG5778, IVSG0810; Phenyl silicone resin encapsulant or methylphenyl silicone resin encapsulant manufactured by the same company XE14-C2860, XE14-C3450; KE-6020, KER-6150, KER-6075, KER-2700, KER-2600, KER-2500, KER-2450, KER, which are methyl silicone resin encapsulants manufactured by Shin-Etsu Chemical Co., Ltd. -2400, 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.

  Specifically, as the dual type silicone sealing material, YSL-300F and YSL-350F which are methyl silicone resin sealing materials manufactured by Yokohama Rubber Co., Ltd. YSH-600F and YSH which are phenyl silicone resins manufactured by the same company -650F.

-Polycondensation type silicone sealing material Among 1st sealing materials, 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).

In 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.
In general formula (1), 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.

As the resin X, for example, a polydialkylsiloxane resin X1 having silanol groups at both ends; a resin X1 and an organosilicone compound monomer represented by the following general formula (3) are subjected to dealcoholization reaction and / or hydrolysis condensation. Resin composition X2 which is a mixture with the oligomer (hereinafter, also referred to as “oligomer A”) obtained by the above-described process: dealcoholization reaction and / or hydrolysis condensation of resin X1, oligomer A, resin X1 and oligomer A The resin composition X3 which is a mixture with the oligomer (henceforth "oligomer B") obtained by this is mentioned.
Among these, 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 Co., Ltd. FINISH WA 62 M, CT 601 M, CT manufactured by Asahi Kasei Wacker Silicone 5000 M, CT 6000 M.

［一般式（３）中、Ｒ^４はそれぞれ独立してアルキル基を表し、Ｒ^５はそれぞれ独立してアルコキシ基、水酸基またはハロゲン原子を表し、ｍは１〜４の整数を表す。］

[In General Formula (3), each R ⁴ independently represents an alkyl group, each R ⁵ independently represents an alkoxy group, a hydroxyl group or a halogen atom, and m represents an integer of 1 to 4. ]

In general formula (3), the alkyl group represented by R ⁴ may be a linear alkyl group, a branched alkyl group, or an alkyl group having a cyclic structure. However, a linear alkyl group or a branched alkyl group is preferable, and a linear alkyl group is more preferable. Although carbon number of the said alkyl group is not specifically limited, 1-10 are preferable, 1-6 are more preferable, and 1-3 are more preferable.

In general formula (3), the alkoxy group represented by R ⁵ may be a linear alkoxy group, a branched alkoxy group, or an alkoxy group having a cyclic structure. However, a linear alkoxy group or a branched alkoxy group is preferable, and a linear alkoxy group is more preferable. Although carbon number of the said alkoxy group is not specifically limited, 1-4 are preferable.
In general formula (3), m is preferably 3 or 4, and more preferably 4.

  Specific examples of the organic silicone compound monomer represented by the general formula (3) include trimethylmethoxysilane, trimethylethoxysilane, trimethylisopropoxysilane, trimethylsilanol, trimethylchlorosilane, triethylmethoxysilane, and triethyl which are m = 1 compounds. Ethoxysilane, triethylisopropoxysilane, triethylsilanol, triethylchlorosilane; m = 2 compounds dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldichlorosilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyl Diisopropoxysilane, diethyldichlorosilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, diisopropyldi Propoxysilane, diisopropyldichlorosilane; m = 3 compounds methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, Examples include ethyltrichlorosilane; tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, and tetrachlorosilane, which are compounds of m = 4.

As the oligomer A, for example, 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.
As the oligomer B, for example, the resin X1 and the oligomer A are subjected to a dealcoholization reaction and / or dehydration 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. The condensate obtained by carrying out a condensation reaction is mentioned.

  Here, as 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. As the alkali, for example, ammonium hydroxide, tetramethylammonium hydroxide, and tetraethylammonium hydroxide can be used. Examples of the metal catalyst 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.

  The first sealing material layer after curing preferably has higher stress relaxation properties than the second sealing material layer after curing. As an index representing the stress relaxation property, 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.

(Second sealing material)
The second sealing material includes a polycondensation type silicone sealing material including 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 A1 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 .

In the structural unit represented by the following formula (A2), 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).

In the structural unit represented by the following formula (A3), 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, and each R ² independently represents an alkoxy group or a hydroxyl group.

In the structural unit represented by the formula (A1), the structural unit represented by the formula (A1 ′), the structural unit represented by the formula (A2), and the structural unit represented by the formula (A3), R ¹ represents carbon. A C 1-3 alkyl group is preferred, and a methyl group is more preferred. 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 an 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.

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). Nuclear magnetic resonance spectroscopy (NMR method) is described in detail in various literatures, and dedicated measuring devices are also widely available on the market. Specifically, after dissolving the silicone resin to be measured in a specific solvent, 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. By this, the kind and abundance ratio of each functional group in the silicone resin can be measured. A method for measuring hydrogen nuclei is called ¹ H-NMR, and a method for measuring silicon nuclei is called ²⁹ Si-NMR. 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 area of signals attributed as A1 silicon atoms, the area of signals 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.

  Generally the value measured by the gel permeation chromatography (GPC) method can be used for the weight average molecular weight (Mw) of a silicone resin. 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.

  In the measurement of the weight average molecular weight by the GPC method, the solvent used for dissolving the silicone resin is preferably the same solvent as the mobile phase solvent used for the GPC measurement. Specific examples of 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 as a starting material, corresponding to each of the above-described structural units constituting the silicone resin. Here, examples of the “functional group capable of generating a siloxane bond” include a halogen atom, a hydroxyl group, and an alkoxy group. Examples of 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. 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 used 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.
Further preferably used in the silicone resin 2A-1 is that 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.

  Here, “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 80 of 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.

  In silicone resin 2A-1, 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).

In general formula (2A-1), R ¹ is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. In General Formula (2A-1), 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 abundance ratio of each structural unit in the organopolysiloxane structure represented by the general formula (2A-1) is the number of A2 silicon atoms: x ¹ (= p ¹ + b ¹ × q ¹ ) and the number of A3 silicon atoms. : The number of A3 silicon atoms with respect to the total content of y ¹ (= a ¹ × q ¹ ): y ¹ content ratio (= y ¹ / (x ¹ + y ¹ )) is in the range of 0.6 to 0.9 (That is, the ratio of the content of A3 silicon atom to 60 mol% or more and 90 mol% or less with respect to the total content of A1 silicon atom, A2 silicon atom, and A3 silicon atom) of 0.7 to 0.85 It is preferably within the range (that is, the ratio of the content of A3 silicon atoms to 70 mol% or more and 85 mol% or less with respect to the total content of A1 silicon atoms, A2 silicon atoms, and A3 silicon atoms). 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.

  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 containing the silicone resin 2A-1. Is obtained. When 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. In the present embodiment, 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.

  It is preferable that the weight average molecular weight (Mw) of silicone resin 2A-1 is 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 generating a siloxane bond as a starting material, corresponding to each structural unit described above that constitutes silicone resin 2A-1. Here, 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, with a hydrolysis condensation method at a ratio corresponding to the abundance ratio of each structural unit. 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 further be included.

  Silicone resin 2A-2 has few unreacted functional groups and is thermally stable. Therefore, silicone resin 2A-2 functions as a filler in the cured product of silicone resin 2A, and contributes to the improvement of the mechanical strength of the cured product of 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.

  As the silicone resin 2A-2, specifically, a silicone resin having a fine particle structure called silicone rubber powder or silicone resin powder can be used.

Among the silicone resins having a fine particle structure, 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. In (RSiO _3/2 ), R is preferably a methyl group.

  When the silicone resin 2A-2 is a spherical silicone resin powder, the average particle size of the silicone resin powder is preferably 0.1 μm or more and 50 μm or less, more preferably 1 μm or more and 30 μm or less, and more preferably 2 μm or more. More preferably, it is 20 μm or less.

  If the average particle size of the silicone resin powder is within the above range (0.1 μm or more and 50 μm 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 size of the silicone resin powder can be measured by, for example, a particle size distribution measuring apparatus using the “laser diffraction / scattering method” as a measurement principle. 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. Specifically, KMP-710, KMP-590, X-52-854, X-52-1621 manufactured by Shin-Etsu Chemical Co., Ltd .; Tospearl 120, Tospearl 130, Tospearl 145, Tospearl 2000B manufactured by Momentive Performance, Tospearl 1110, Tospearl; MSP-N050, MSP-N080, MSP-S110 manufactured by Nikko Rica 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 relative to the total content of silicone resin 2A-1 and silicone resin 2A-2 (in terms of resin content) is usually 20% by mass to 90% by mass, and 40% by mass to 80%. It is preferable that it is below mass%. When content of silicone resin 2A-2 is the said range, it exists in the tendency which can obtain the hardened | cured material of silicone resin 2A which was excellent in a crack resistance and UV tolerance with sufficient balance.

  Here, “crack resistance” means difficulty in entering cracks in the cured product of the 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. 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 an A1 silicon atom and an A2 silicon atom and an A3 silicon atom, and includes an A1 silicon atom and an A2 silicon atom. A ratio of the content of A3 silicon atoms to the total content of A3 silicon atoms is 30 mol% or more and less than 60 mol%, and the weight average molecular weight is 1500 or more.

  Here, “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 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.

  In silicone resin 3A-1, 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).

In general formula (3A-1), R ¹ is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. In General Formula (3A-1), 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.

In the organopolysiloxane structure represented by the general formula (3A-1), the content ratio of A3 silicon atoms to the total content of A1 silicon atoms, A2 silicon atoms, and A3 silicon atoms (= [a ² × q ² ] / [(P ² + b ² × q ² ) + a ² × q ² + (r ¹ + q ² )] is within the range of 0.3 or more and less than 0.6, and within the range of 0.35 to 0.55 It is preferable that it is 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. In the present embodiment, 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. When the weight average molecular weight of the silicone resin 3A-1 is in the above range, the thermal shock resistance of the cured product of the silicone resin 3A including the silicone resin 3A-1 tends to be improved. 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 still more 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 generating a siloxane bond as a starting material, corresponding to each structural unit described above that constitutes silicone resin 3A-1. Here, 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. 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 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. Silicone resin 3A-2 in which the ratio of the content of A3 silicon atoms to the total content of 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 May further be included.

  In silicone resin 3A-2, 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.

  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. When 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 in the above range, the UV resistance of the cured product of the silicone resin 3A including the silicone resin 3A-2 is more excellent. The weight average molecular weight of the silicone resin 3A-2 is more preferably 2000 or more and 5000 or less.

  Silicone resin 3A-2 can be synthesized using an organosilicon compound having a functional group capable of generating a siloxane bond as a starting material, corresponding to each structural unit described above that constitutes silicone resin 3A-2. Here, 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 synthesized in this way is commercially available as a silicone resin or the like.

  Here, “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 among silicon atoms contained in silicone resin 3A-2 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.

  A cured product of the silicone resin 3A including the silicone resin 3A-1 and the silicone resin 3A-2 not only has excellent UV resistance but also excellent thermal shock resistance and adhesion.

  The content (resin content) of silicone resin 3A-2 with respect to the total content of silicone resin 3A-1 and silicone resin 3A-2 is usually 5% by mass or more and 95% by mass or less, and 30% by mass or more. It is preferable that it is 90 mass% or less. When the content of the silicone resin 3A-2 is in the above range, a cured product of the silicone resin 3A having excellent balance between thermal shock resistance and UV resistance tends to be obtained. In this specification, when the silicone resin is dissolved in a solvent, 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.

(Silicone resin 4A-1)
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.

(Silicone resin 4A-2)
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 crack resistance of the cured product of the silicone resin 4A is improved. 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.

  In the silicone resin 4A, the mixing ratio of the silicone resin 4A-1 and the silicone resin 4A-2 is preferably silicone resin 4A-1: silicone resin 4A-2 = 100: 0.1 to 20 (mass ratio). . Since the silicone resin 4A-1 is a main component, it is possible to improve the resistance of the silicone resin 4A to heat generation, and it is possible to suppress deterioration against ultraviolet light.

-Curing catalyst It is preferable that the 2nd sealing material further contains the curing catalyst. When the second sealant contains a curing catalyst, a solution containing the above silicone resins 2A to 4A and a solution containing the curing catalyst are prepared separately, and before the second sealing material is used. It is preferable to mix these solutions.

  Examples of the curing catalyst 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.

-Solvent In the step of potting the first sealing material before curing, a solution obtained by dissolving the first sealing material before curing in a solvent may be used. In the step of potting the second sealing material before curing, a solution obtained by dissolving the second sealing material before curing in a solvent may be used.

  Examples of the solvent 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. Ester solvent; ether solvent such as tetrahydrofuran; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monoethyl hexyl ether, ethylene glycol monophenyl ether, ethylene Glycol monobenzyl ether, diethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monoethyl hexyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monoisopropyl Ether, propylene glycol monobutyl ether, propylene glycol monohexyl ether, propylene glycol monoethyl hexyl ether, propylene glycol monophenyl ether, propylene glycol monobenzyl ether, dipropylene glycol mono Til ether, dipropylene glycol monoethyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monohexyl ether, dipropylene glycol monoethyl hexyl ether, dipropylene glycol monophenyl ether, dipropylene glycol monobenzyl ether, etc. Glycol ether solvent: ethylene glycol monoethyl ether acetate, ethylene glycol monoisopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monohexyl ether acetate, ethylene glycol monoethyl hexyl ether acetate, ethylene glycol monophenyl ether acetate, ethyl A glycol ester solvent in which an acetic acid group is added to a glycol ether solvent, such as glycol glycol monobenzyl ether acetate.

  Among the above-mentioned solvents, 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. or lower, the solvent is unlikely to remain in the cured product of the second sealing material, so that light in a short wavelength region of 300 nm or less tends to be transmitted.

  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.

Of the above-mentioned 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.
Examples of 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.

  In the ultraviolet light emitting semiconductor device of the present invention, 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.

  EXAMPLES Hereinafter, the present invention will be specifically described by showing examples and comparative examples, but the present invention is not limited to the following examples.

[Production Example 1]
<Preparation of second sealing material>
Resin A having an organopolysiloxane structure represented by the general formula (2A-1) (Mw = 3500, R ¹ = methyl group, R ² = methoxy group or hydroxyl group, and the abundance ratio of each structural unit is shown in Table 1. 42 g, resin B (trade name “KMP-701”, manufactured by Shin-Etsu Chemical Co., Ltd.) 18 g and 2-ethoxyethyl acetate 20 g are added to a plastic container, sealed, and then stirred with a stirrer for 12 hours. Thus, a second sealing material was obtained.

[Example 1]
The ultraviolet semiconductor device according to the fifth embodiment, which is an embodiment of the ultraviolet semiconductor device of the present invention, is manufactured by the same method as the sixth embodiment, which is an embodiment of the method for manufacturing the ultraviolet semiconductor device of the present invention. did. FIG. 8A shows a cross-sectional view of the ultraviolet light emitting semiconductor device manufactured in Example 1. FIG. 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.

  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. 1.3 mg was dropped on a portion other than the surface 2a with a dispenser. Then, the sealing material was hardened by hold | maintaining at 100 degreeC for 1 hour and 150 degreeC for 5 hours, and the 1st sealing material layer 3 which consists of a hardened | cured material of an addition polymerization type silicone sealing material was formed. The first sealing material layer 3 was not formed on the light emitting surface 2 a of the ultraviolet light emitting element 2. In the plan view of the ultraviolet light emitting semiconductor device shown in FIG. 8B, the gray portion is a region where the first sealing material layer 3 is formed.

Next, 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. Then, the polycondensation type silicone sealing material was hardened by hold | maintaining at 160 degreeC for 50 hours, and the 2nd sealing material layer 4 which consists of a hardened | cured material of a polycondensation type silicone sealing material was formed. The thickness L of the second sealing material layer 4 was 1.19 mm.
The ratio W2 / W1 of the supply amount W1 (= 1.3 mg) of the addition polymerization type silicone sealing material and the supply amount W2 (= 10.4 mg) of the polycondensation type silicone sealing material was 8.0. .
Through the above steps, an ultraviolet light emitting semiconductor device having a first sealing material layer and a second sealing material layer was manufactured.

[Comparative Example 1]
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 is so covered as to cover the ultraviolet light emitting element in the AlN cavity type UV-LED substrate (3.5 mm × 3.5 mm, light output 30 mW) provided with the ultraviolet light emitting element (emission wavelength: 285 nm). 1.7 mg was dropped with a dispenser. Then, the sealing material was hardened by holding at 100 ° C. for 1 hour and 150 ° C. for 5 hours to obtain a 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.

Next, 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. Then, the polycondensation type silicone sealing material was hardened by hold | maintaining at 160 degreeC for 50 hours, and the 2nd sealing material layer which consists of a hardened | cured material of a polycondensation type silicone sealing material was formed. The thickness of the second sealing material layer was 1.13 mm.
Ratio of supply amount W1 (= 1.7 mg) of addition polymerization type silicone sealing material and supply amount W2 (= 9.8) of polycondensation type silicone sealing material: W2 / W1 was 5.8. .
Through the above steps, 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. Then, the sealing material was hardened by hold | maintaining at 100 degreeC for 1 hour and 150 degreeC for 5 hours, and the 1st sealing material layer 3 which consists of a hardened | cured material of an addition polymerization type silicone sealing material was formed. The first sealing material layer 3 was not formed on the light emitting surface 2 a of the ultraviolet light emitting element 2. In the plan view of the ultraviolet light emitting semiconductor device shown in FIG. 8B, the gray portion is a region where the first sealing material layer 3 is formed.

Next, 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. Then, the polycondensation type silicone sealing material was hardened by hold | maintaining at 160 degreeC for 50 hours, and the 2nd sealing material layer 4 which consists of a hardened | cured material of a polycondensation type silicone sealing material was formed. The thickness L of the second sealing material layer 4 was 1.11 mm.
Ratio of supply amount W1 (= 1.2 mg) of addition polymerization type silicone sealing material and supply amount W2 (= 10.4 mg) of polycondensation type silicone sealing material: W2 / W1 was 8.7. .
Through the above steps, an ultraviolet light emitting semiconductor device having a first sealing material layer and a second sealing material layer was manufactured.

[Comparative 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 is used for the light emitting surface other than the ultraviolet light emitting element on the AlN cavity type UV-LED substrate (3.5 mm × 3.5 mm, light output 30 mW) provided with the ultraviolet light emitting element (emission wavelength: 285 nm). 1.1 mg was added dropwise to the portion with a dispenser. Then, the sealing material was hardened by hold | maintaining at 100 degreeC for 1 hour and 150 degreeC for 5 hours, and the 1st sealing material layer which consists of a hardened | cured material of an addition polymerization type silicone sealing material was formed. The first sealing material layer was not formed on the light emission surface of the ultraviolet light emitting element.

Next, 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. 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 0.99 mm.
Ratio of supply amount W1 (= 1.1 mg) of addition polymerization type silicone sealing material and supply amount W2 (= 8.0) of addition polymerization type silicone sealing material: W2 / W1 was 7.3. .
Through the above steps, an ultraviolet light emitting semiconductor device having a first sealing material layer and a second sealing material layer was manufactured.

[Comparative Example 3]
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 is used for the light emitting surface other than the ultraviolet light emitting element on the AlN cavity type UV-LED substrate (3.5 mm × 3.5 mm, light output 30 mW) provided with the ultraviolet light emitting element (emission wavelength: 285 nm). 1.1 mg was added dropwise to the portion with a dispenser. Then, the sealing material was hardened by hold | maintaining at 100 degreeC for 1 hour and 150 degreeC for 5 hours, and the 1st sealing material layer which consists of a hardened | cured material of an addition polymerization type silicone sealing material was formed. The first sealing material layer was not formed on the light emission surface of the ultraviolet light emitting element.

  Next, 5.0 g of 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. is 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. Thereafter, 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.

Ratio of supply amount W1 (= 1.1 mg) of addition polymerization type silicone sealing material and supply amount W2 (= 8.0) of addition polymerization type silicone sealing material: W2 / W1 was 7.3. .
Through the above steps, an ultraviolet light emitting semiconductor device having a first sealing material layer and a second sealing material layer was manufactured.

[Comparative Example 4]
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 is used for the light emitting surface other than the ultraviolet light emitting element on the AlN cavity type UV-LED substrate (3.5 mm × 3.5 mm, light output 30 mW) provided with the ultraviolet light emitting element (emission wavelength: 285 nm). 1.2 mg was added dropwise to the portion with a dispenser. Then, the sealing material was hardened by hold | maintaining at 100 degreeC for 1 hour and 150 degreeC for 5 hours, and the 1st sealing material layer which consists of a hardened | cured material of an addition polymerization type silicone sealing material was formed. The first sealing material layer was not formed on the light emission surface of the ultraviolet light emitting element.

Next, 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. Thereafter, 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.
Ratio of supply amount W1 (= 1.2 mg) of addition polymerization type silicone sealing material and supply amount W2 (= 9.3) of addition polymerization type silicone sealing material: W2 / W1 was 7.8. .
Through the above steps, an ultraviolet light emitting semiconductor device having a first sealing material layer and a second sealing material layer was manufactured.

[Comparative Example 5]
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 is used for the light emitting surface other than the ultraviolet light emitting element on the AlN cavity type UV-LED substrate (3.5 mm × 3.5 mm, light output 30 mW) provided with the ultraviolet light emitting element (emission wavelength: 285 nm). 1.2 mg was added dropwise to the portion with a dispenser. Then, the sealing material was hardened by hold | maintaining at 100 degreeC for 1 hour and 150 degreeC for 5 hours, and the 1st sealing material layer which consists of a hardened | cured material of an addition polymerization type silicone sealing material was formed. The first sealing material layer was not formed on the light emission surface of the ultraviolet light emitting element.

Next, after adding 5.0 g each of the liquid A and liquid B (both solvent-free liquid) of addition polymerization type silicone sealing material OE-6351 manufactured by Toray Dow Corning Co., Ltd. to the same plastic container, 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. Then, the addition polymerization type silicone sealing material was hardened by hold | maintaining at 150 degreeC for 1 hour, and the 2nd sealing material layer which consists of a hardened | cured material of an addition polymerization type silicone sealing material was formed. The thickness of the second sealing material layer was 0.95 mm.
The ratio of the supply amount W1 (= 1.2 mg) of the addition polymerization type silicone sealing material to the supply amount W2 (= 7.5) of the addition polymerization type silicone sealing material: W2 / W1 was 6.3. .
Through the above steps, an ultraviolet light emitting semiconductor device having a first sealing material layer and a second sealing material layer was manufactured.

[Comparative Example 6]
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 is used for the light emitting surface other than the ultraviolet light emitting element on the AlN cavity type UV-LED substrate (3.5 mm × 3.5 mm, light output 30 mW) provided with the ultraviolet light emitting element (emission wavelength: 285 nm). 1.2 mg was added dropwise to the portion with a dispenser. Then, the sealing material was hardened by hold | maintaining at 100 degreeC for 1 hour and 150 degreeC for 5 hours, and the 1st sealing material layer which consists of a hardened | cured material of an addition polymerization type silicone sealing material was formed. The first sealing material layer was not formed on the light emission surface of the ultraviolet light emitting element.

  Next, 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. 8.3 mg of the obtained sealing material liquid was dropped with a dispenser so as to cover the first sealing material layer and the light emitting surface of the ultraviolet light emitting element. Thereafter, 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. Here, “Composeran 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). It is a polycondensation type silicone having no organopolysiloxane structure.

Ratio of supply amount W1 (= 1.2 mg) of addition polymerization type silicone sealing material and supply amount W2 (= 8.3) of addition polymerization type silicone sealing material: W2 / W1 was 6.9. .
Through the above steps, an ultraviolet light emitting semiconductor device having a first sealing material layer and a second sealing material layer was manufactured.

[Comparative Example 7]
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 is used for the light emitting surface other than the ultraviolet light emitting element on the AlN cavity type UV-LED substrate (3.5 mm × 3.5 mm, light output 30 mW) provided with the ultraviolet light emitting element (emission wavelength: 285 nm). 1.2 mg was added dropwise to the portion with a dispenser. Then, the sealing material was hardened by hold | maintaining at 100 degreeC for 1 hour and 150 degreeC for 5 hours, and the 1st sealing material layer which consists of a hardened | cured material of an addition polymerization type silicone sealing material was formed. The first sealing material layer was not formed on the light emission surface of the ultraviolet light emitting element.

Next, A solution 3g and B solution 6g (both solvent-free solution) of addition polymerization type silicone sealing material OE-6663 manufactured by Toray Dow Corning Co., Ltd. are 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. Then, the addition polymerization type silicone sealing material was hardened by hold | maintaining at 150 degreeC for 1 hour, and the 2nd sealing material layer which consists of a hardened | cured material of an addition polymerization type silicone sealing material was formed. The thickness of the second sealing material layer was 1.12 mm.
Ratio of supply amount W1 (= 1.2 mg) of addition polymerization type silicone sealing material and supply amount W2 (= 9.0) of addition polymerization type silicone sealing material: W2 / W1 was 7.5. .
Through the above steps, an ultraviolet light emitting semiconductor device having a first sealing material layer and a second sealing material layer was manufactured.

-Evaluation of hardness of first sealing material layer In Examples 1-2 and Comparative Examples 1-7, Shore hardness A measured according to JIS K6253-3: 2012 of the first sealing material layer is both , 32.

Evaluation of adhesion between the first sealing material layer and the second sealing material layer About the ultraviolet light emitting semiconductor devices manufactured in Examples 1 and 2 and Comparative Examples 1 to 7, before and after the following heat shock test The interface between the first sealing material layer and the second sealing material layer was observed with a microscope (magnification: 100 times).
As a result, in both the ultraviolet light emitting semiconductor devices manufactured in Examples 1 and 2 and Comparative Examples 1 to 7, the first sealing material layer and the second sealing material layer were peeled before and after the heat shock test. However, the first sealing material layer and the second sealing material layer had adhesiveness.

[Heat shock test (thermal shock test)]
First, it was confirmed that no crack was generated in the ultraviolet light emitting semiconductor device. Next, using a thermal shock device (trade name “TSE-11-A”, manufactured by ESPEC Corporation), the ultraviolet light emitting semiconductor device is exposed at 85 ° C. for 30 minutes, and then exposed at −30 ° C. for 30 minutes. The operation to be performed is one cycle. This test was repeated 100 cycles. Then, the presence or absence of crack generation was confirmed. The presence or absence of cracks was observed using a digital microscope (trade name “VHX-2000”, manufactured by Keyence). The results are shown in Tables 2 and 3.

-Evaluation of UV durability The following light-emitting test 1 was performed on the UV light-emitting semiconductor devices manufactured in Example 1 and Comparative Example 1. For the ultraviolet light emitting semiconductor devices manufactured in Example 2 and Comparative Examples 2 to 7, the following energization test 2 was performed.

[Electrification test 1]
First, a current of 200 mA is passed through the ultraviolet light emitting semiconductor device, and the total radiant flux before energization of the ultraviolet light emitting semiconductor device (0 hours) is measured with a total luminous flux measuring device (trade name “OP-RADIANT-UV UV LED integration integral”). Measurement was performed using a “sphere system” (manufactured by Ocean Photonics).
Next, the ultraviolet light emitting semiconductor device was held in a constant temperature bath at 17 ° C. for 140 hours while a current of 350 mA was passed through the ultraviolet light emitting semiconductor device. Thereafter, a current of 200 mA was passed through the ultraviolet light emitting semiconductor device, and the total radiant flux after the ultraviolet light emitting semiconductor device was energized (140 hours) was measured using a total luminous flux measuring machine.
Next, the luminous intensity retention (relative luminous intensity) was calculated from the following equation. The results are shown in Table 2.

[Luminance retention rate (relative luminous intensity) (%)] =
[(Total radiant flux after powering for 140 hours (mW)) / (total radiant flux before powering (mW))] × 100

  Thereafter, the presence or absence of cracks was observed using a digital microscope. The results are shown in Table 2.

[Energization test 2]
First, a current of 200 mA is passed through the ultraviolet light emitting semiconductor device, and the total radiant flux before energization of the ultraviolet light emitting semiconductor device (0 hours) is measured with a total luminous flux measuring device (trade name “OP-RADIANT-UV UV LED integration integral”). Measurement was performed using a “sphere system” (manufactured by Ocean Photonics).
Next, the ultraviolet light emitting semiconductor device was held in a thermostat at 30 ° C. for 70 hours while a current of 500 mA was passed through the ultraviolet light emitting semiconductor device. Thereafter, a current of 200 mA was passed through the ultraviolet light emitting semiconductor device, and the total radiant flux after energization of the ultraviolet light emitting semiconductor device (70 hours) was measured using a total luminous flux measuring machine.
Next, the luminous intensity retention (relative luminous intensity) was calculated from the following equation. The results are shown in Table 3.

[Luminance retention rate (relative luminous intensity) (%)] =
[(Total radiant flux after 70 hours energization (mW)) / (total radiant flux before energization (mW))] × 100

Thereafter, the presence or absence of cracks was observed using a digital microscope. The results are shown in Table 3.
Note that the ultraviolet light emitting semiconductor device manufactured in Comparative Example 7 was not subjected to the energization test because the output significantly decreased during energization when measuring the total luminous flux before the energization test.

  As shown in Table 2, 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. On the other hand, 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.

  As shown in Table 3, 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. On the other hand, the ultraviolet light emitting devices manufactured in Comparative Examples 2 to 6 had a low relative luminous intensity after the energization test 2. Further, in the ultraviolet light emitting devices manufactured in Comparative Examples 3 to 5, occurrence of cracks was confirmed 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

  According to the present invention, it is possible 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). Moreover, according to this invention, the manufacturing method of the said ultraviolet light-emitting semiconductor device can be provided.

Claims (15)

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,
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.

[In General Formula (2A-1), each R ¹ independently represents an alkyl group, each R ² independently represents an alkoxy group or a hydroxyl group, and 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 that satisfies 0.25 to 9. ]

[In General Formula (3A-1), each R ¹ independently represents an alkyl group, each R ² independently represents an alkoxy group or a hydroxyl group, and 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 ultraviolet light emitting semiconductor device according to claim 1, wherein the first sealing material layer includes an addition polymerization type silicone sealing material. The ultraviolet light-emitting semiconductor device according to claim 1, wherein the resin having a dialkylsiloxane structure is a resin X having a dialkylsiloxane structure represented by the following general formula (1).

[In General Formula (1), each R ³ independently represents an alkyl group, and n represents an integer of 5 to 4000. ]   The ultraviolet light-emitting semiconductor device according to claim 3, wherein n is an integer of 5 to 1000.   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 and the first sealing are formed. The ultraviolet light-emitting semiconductor device according to claim 1, wherein an area in contact with the material layer is smaller than an area formed by the first sealing material layer.   The ultraviolet light-emitting semiconductor device according to claim 1, wherein the first sealing material layer has a Shore hardness of 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 the above.   The ultraviolet light-emitting semiconductor device according to claim 1, comprising two or more second sealing material layers.   The ultraviolet light-emitting semiconductor device according to claim 1, wherein a shape of the second sealing material layer is a convex lens shape. 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 step;
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 following general formula (2A-1) or (3A-1), 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. Device manufacturing method.

[In General Formula (2A-1), each R ¹ independently represents an alkyl group, each R ² independently represents an alkoxy group or a hydroxyl group, and 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 that satisfies 0.25 to 9. ]

[In General Formula (3A-1), each R ¹ independently represents an alkyl group, each R ² independently represents an alkoxy group or a hydroxyl group, and 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. ] 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;
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 following general formula (2A-1) or (3A-1), 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. Device manufacturing method.

[In General Formula (2A-1), each R ¹ independently represents an alkyl group, each R ² independently represents an alkoxy group or a hydroxyl group, and 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 that satisfies 0.25 to 9. ]

[In General Formula (3A-1), each R ¹ independently represents an alkyl group, each R ² independently represents an alkoxy group or a hydroxyl group, and 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. ] In the first step, prior to the installation of the ultraviolet light emitting element, the surface of the base material is cleaned with ozone, and
In the fourth step, 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 method for manufacturing an ultraviolet light emitting semiconductor device according to claim 10, wherein the second sealing material layer is formed by curing the sealing material.   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 first sealing material is supplied in the fourth step. The ultraviolet light emission according to any one of claims 10 to 12, wherein a ratio of W2 / W1 is in a range of 1.5 to 8 when a supply amount of the second sealing material is W2 [g]. A method for manufacturing a semiconductor device.   The supply amount of the first sealing material supplied in the second step (the first sealing material is a polycondensation type silicone sealing material) is W1 [g] and is supplied in the fourth step. The ultraviolet light emission according to any one of claims 10 to 12, wherein a ratio of W2 / W1 is in a range of 1.5 to 13 when a supply amount of the second sealing material is W2 [g]. A method for manufacturing a semiconductor device.   When the curing temperature of the first sealing material in the third step is Ta [° C.] and the curing temperature of the second sealing material in the fourth step is Tb [° C.], Ta-10 < The method for manufacturing an ultraviolet light emitting semiconductor device according to claim 10, wherein Tb ≦ Ta + 100 is satisfied.

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