JP2019204061A - Resin composition, cured product, semiconductor device, and manufacturing method therefor - Google Patents

Abstract

To provide a resin composition which can be used to obtain a cured product that exhibits a low light transmittance at a wavelength of 350 nm and a high light transmittance at a wavelength of 430 nm.SOLUTION: A resin composition contains (a) a (meth)acrylic polymer, (b) a compound having at least two (meth)acryloyl groups, (c) a polymerization initiator, and (d) a UV absorber, where content of the (d) component is 0.002-0.04 mass%.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition, a cured product, a semiconductor device, and a manufacturing method thereof.

  In recent years, with the spread of digital still cameras and camera-equipped mobile phones, solid-state imaging devices (solid-state imaging devices) have been reduced in power consumption and miniaturization. Conventional CCD (Charge Coupled Device) image sensors In addition, a CMOS (Complementary Metal Oxide Semiconductor, complementary metal oxide semiconductor) image sensor is used. These image sensors include a sensor unit (imaging pixel unit) in which a plurality of pixels are two-dimensionally arranged on one semiconductor chip, and a peripheral circuit unit arranged outside the sensor unit.

  As a structure of a CMOS image sensor, a “front surface irradiation type” structure and a “back surface irradiation type” structure are known (for example, see Patent Documents 1 and 2 below). In the front-illuminated CMOS image sensor of Patent Document 1, light incident from the outside passes through the glass substrate and the cavity (cavity), enters each microlens, and is collected by the microlens, and then the color filter layer and It passes through the wiring layer and enters the photodiode. Then, light incident on the photodiode is photoelectrically converted to generate a signal charge, and an electric signal is generated from the signal charge, whereby image data is acquired.

  On the other hand, in the back-illuminated CMOS image sensor of Patent Document 2, a photodiode is formed on one surface of a semiconductor substrate, and a color filter layer and a microlens are disposed on the one surface. A glass substrate is disposed above the microlens via an adhesive layer and a cavity. On the other hand, a wiring layer is disposed on the other surface of the semiconductor substrate. According to this back-illuminated structure, the light incident on the microlens is received by the light receiving unit without passing through the wiring layer, so that attenuation of light by the wiring layer is avoided and the light receiving sensitivity is increased.

  In addition, as a structure of the back-illuminated CMOS image sensor, an adhesive layer disposed on the outer peripheral side so as not to cover the microlens is surrounded by the adhesive layer on a silicon substrate including the microlens. There is known a structure in which a glass substrate is arranged through a low refractive index layer filled in a cavity (see, for example, Patent Document 3 below).

JP 2007-281375 A JP 2005-142221 A JP 2010-40621 A

  By the way, it is preferable that the spectral sensitivity of a semiconductor device such as a CCD image sensor or a CMOS image sensor is close to human visibility. From such a viewpoint, it is preferable that the light transmittance in the wavelength range of 390 nm or less is low and the light transmittance near the wavelength 430 nm is high, and in particular, the light transmittance at the wavelength 350 nm is low and the light having the wavelength 430 nm It is preferable that the transmittance is high. Therefore, it is required for a curable resin composition for obtaining a constituent member of a semiconductor device to obtain a cured product having such spectral sensitivity.

  This invention is made | formed in view of the said situation, The resin composition which can obtain the hardened | cured material which has the low light transmittance of wavelength 350nm, and the high light transmittance of wavelength 430nm, and its hardened | cured material The purpose is to provide. Furthermore, an object of this invention is to provide the semiconductor device using the said resin composition, and its manufacturing method.

  One aspect of the resin composition according to the present invention includes (a) a (meth) acrylic polymer, (b) a compound having at least two (meth) acryloyl groups, (c) a polymerization initiator, and (d) An ultraviolet absorber, and the content of the component (d) is 0.002 to 0.04 mass%.

  According to such a resin composition, a cured product having a low light transmittance at a wavelength of 350 nm and a high light transmittance at a wavelength of 430 nm can be obtained.

  One aspect of the cured product according to the present invention is a cured product of the above-described resin composition.

  One aspect of the method for producing a semiconductor device according to the present invention includes a step of curing the resin layer in a state where the resin layer containing the resin composition is disposed between the semiconductor substrate and the transparent base material.

  One aspect of the semiconductor device according to the present invention comprises a semiconductor substrate, a transparent base material, and a resin layer disposed between the semiconductor substrate and the transparent base material, wherein the resin layer is the resin composition described above. Or the hardened | cured material is included.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition which can obtain the hardened | cured material which has the low light transmittance of wavelength 350nm and the high light transmittance of wavelength 430nm, and its hardened | cured material can be provided. Furthermore, according to this invention, the semiconductor device using the said resin composition and its manufacturing method can be provided.

  The resin composition and the cured product thereof according to the present invention have a member disposed in a portion on the outer peripheral side on the substrate so as not to cover the microlens, and the resin composition in a cavity (cavity) surrounded by the member Alternatively, it can be used for either a configuration filled with a cured product thereof or a configuration in which a resin layer formed of a resin composition is formed on the entire surface of a substrate.

  ADVANTAGE OF THE INVENTION According to this invention, use of the resin composition for a semiconductor device or its manufacture can be provided. ADVANTAGE OF THE INVENTION According to this invention, use of the resin composition for an optical component or its manufacture can be provided. ADVANTAGE OF THE INVENTION According to this invention, use of the resin composition for a solid-state image sensor or its manufacture can be provided. ADVANTAGE OF THE INVENTION According to this invention, use of the hardened | cured material of the resin composition to a semiconductor device can be provided. ADVANTAGE OF THE INVENTION According to this invention, use of the hardened | cured material of the resin composition for an optical component can be provided. ADVANTAGE OF THE INVENTION According to this invention, use of the hardened | cured material of the resin composition for a solid-state image sensor can be provided.

It is process drawing which shows an example of the manufacturing method of a semiconductor device. It is process drawing which shows an example of the manufacturing method of a semiconductor device. It is a top view which shows an example of a semiconductor device. FIG. 4 is a sectional view taken along line A-A ′ shown in FIG. 3. It is sectional drawing which shows the other example of a semiconductor device. It is drawing for contrasting the manufacturing method of a semiconductor device. It is sectional drawing which shows an example of the semiconductor device which has a cavity structure.

  Hereinafter, although embodiment of this invention is described, this invention is not limited to these embodiment at all.

  In the present specification, the “(meth) acryloyl group” means at least one of “acryloyl group” and “methacryloyl group” corresponding thereto. The same applies to other similar expressions such as “(meth) acrylate”. The numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. In the numerical ranges described stepwise in the present specification, the upper limit value or lower limit value of a numerical range of a certain step may be replaced with the upper limit value or lower limit value of the numerical range of another step. In the numerical range described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples. The terms “layer” and “film” include not only a structure formed on the entire surface but also a structure formed on a part when observed as a plan view. The term “process” is not limited to an independent process, and is included in the term if the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes. “A or B” only needs to include either A or B, and may include both. The content of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. The materials exemplified in the present specification can be used singly or in combination of two or more unless otherwise specified.

<Resin composition and cured product>
The resin composition according to the present embodiment includes (a) a (meth) acrylic polymer (hereinafter referred to as “(a) component” in some cases) and (b) a compound having at least two (meth) acryloyl groups (hereinafter referred to as “a”). , Sometimes referred to as “component (b)”), (c) a polymerization initiator (hereinafter sometimes referred to as “component (c)”), and (d) an ultraviolet absorber (hereinafter referred to as “component (d)”). And the content of the component (d) is 0.002 to 0.04% by mass based on the total amount of the resin composition (total amount of solids). The resin composition according to the present embodiment is a curable (eg, thermosetting) resin composition. The cured product according to the present embodiment is a cured product of the resin composition according to the present embodiment.

  According to the resin composition according to the present embodiment, the resin composition contains a specific amount of the component (d) in addition to the components (a) to (c), thereby having a low light transmittance at a wavelength of 350 nm, And the hardened | cured material which has a high light transmittance with a wavelength of 430 nm can be obtained. The light transmittance at a wavelength of 350 nm is preferably less than 20%, more preferably 10% or less, still more preferably 5% or less, particularly preferably 1% or less, extremely preferably less than 1%, and very much 0.9% or less. Preferably, 0.8% or less is even more preferable. The light transmittance at a wavelength of 430 nm is preferably 70% or more, more preferably 80% or more, still more preferably 81% or more, particularly preferably 82% or more, extremely preferably 83% or more, and very preferably 84% or more, 85% or more is even more preferable.

  The resin composition according to this embodiment can be used as an adhesive composition. The resin composition according to this embodiment may be liquid (varnish-like) or film-like. The resin composition according to the present embodiment can be used as a resin composition for semiconductor devices, and can be used, for example, as a resin composition for optical components.

((A) component: (meth) acrylic polymer)
The “(meth) acrylic polymer” is a polymer having a structural unit derived from a monomer having a (meth) acryloyl group ((meth) acrylic monomer). A polymer (homopolymer) having a structure obtained by polymerizing one (meth) acrylic monomer having one in the molecule, and copolymerizing a combination of two or more (meth) acrylic monomers. And a polymer (copolymer) having a structure obtained by copolymerization, and a polymer (copolymer) having a structure obtained by copolymerizing the (meth) acrylic monomer and another monomer. It is done. As the monomer copolymerizable with the (meth) acrylic monomer, a compound having two or more (meth) acryloyl groups in one molecule; one polymerizable unsaturated bond in one molecule, And a polymerizable compound having no (meth) acryloyl group (for example, (meth) acrylonitrile, styrene, vinyl acetate and alkene (ethylene, propylene, etc.)); two or more polymerizable unsaturated bonds in one molecule And a polymerizable compound (divinylbenzene, etc.) having a (meth) acryloyl group. (A) A component can be used individually by 1 type or in combination of 2 or more types.

  The component (a) has one (meth) acryloyl group in one molecule based on the total amount of the component (a) from the viewpoint of easily obtaining a low light transmittance at a wavelength of 350 nm and a high light transmittance at a wavelength of 430 nm. It is preferable that the structural unit derived from the (meth) acrylic monomer is 30 to 100% by mass, and more preferably 50 to 100% by mass.

  The component (a) preferably has a functional group, for example, preferably has a structural unit having a functional group. In these cases, excellent stress relaxation, reflow peel resistance, crack resistance, adhesion and heat resistance associated with a low elastic modulus can be easily expressed. As the functional group, at least one selected from the group consisting of a carboxyl group, an acid anhydride group, a hydroxyl group, an amino group, an amide group, a phosphoric acid group, a cyano group, a maleimide group, and an epoxy group can be used. As the functional group, an epoxy group is preferable. When the component (a) has an epoxy group, the adhesion of an inorganic material such as metal or glass to the substrate can be improved.

  The method for introducing the functional group into the (meth) acrylic polymer is not particularly limited. Introducing a functional group into a (meth) acrylic polymer by randomly polymerizing a functional group-containing monomer having a functional group by, for example, an existing method as described in International Publication No. 2015/115537 Can do. Of these, suspension polymerization is preferable from the viewpoint of high molecular weight at low cost.

  Suspension polymerization is performed by adding a suspending agent in an aqueous solvent. As the suspending agent, it is preferable to use a nonionic water-soluble polymer from the viewpoint that ionic impurities are less likely to remain in the resulting (meth) acrylic polymer. It is preferable that the usage-amount of water-soluble polymer is 0.01-1 mass part with respect to 100 mass parts of total amounts of a monomer.

  In the polymerization reaction, generally used polymerization initiators, chain transfer agents and the like may be used. Examples of the polymerization initiator include the same compounds as those described later for (c) polymerization initiator. Examples of the chain transfer agent include thiols such as n-octyl mercaptan.

  The functional group-containing monomer is at least one selected from the group consisting of a carboxyl group, an acid anhydride group, a hydroxyl group, an amino group, an amide group, a phosphoric acid group, a cyano group, a maleimide group, and an epoxy group in one molecule. It is preferable to have at least one polymerizable carbon-carbon double bond.

  The functional group is an amino group, an amide group, a phosphate group, a cyano group, from the viewpoint of easily avoiding problems such as gelation in a varnish state, nozzles during use, that is, pinhole generation during spin coating, and the like. It is preferably at least one selected from the group consisting of a maleimide group and an epoxy group. In addition, the functional group is preferably at least one selected from the group consisting of a carboxyl group, an acid anhydride group, a hydroxyl group, a phosphoric acid group, and an epoxy group from the viewpoint of easily preventing coloring. Furthermore, from both these viewpoints, the functional group is preferably at least one selected from the group consisting of a phosphate group and an epoxy group, and more preferably an epoxy group.

  Examples of the functional group-containing monomer include a carboxyl group-containing monomer, an acid anhydride group-containing monomer, a hydroxyl group-containing monomer, and an amino group-containing monomer as exemplified in International Publication No. 2015/115537. Body; phosphoric acid group-containing monomer; vinyl cyanide compound; N-substituted maleimides; epoxy group-containing monomer and the like. A functional group containing monomer can be used individually by 1 type or in combination of 2 or more types.

  Among these, it is particularly preferable to use an epoxy group-containing monomer such as glycidyl (meth) acrylate. Furthermore, the (meth) acrylic polymer (for example, glycidyl group-containing (meth) acrylic polymer) obtained by using such a monomer is compatible with the (meth) acrylic monomer or oligomer. Is preferred. The glycidyl group-containing (meth) acrylic polymer may be synthesized by a conventional method, or a commercially available product may be obtained. As a commercial item, HTR-860P-3 (Nagase ChemteX Corporation, a brand name) etc. are mentioned. Such a (meth) acrylic polymer is preferable from the viewpoint of easily exhibiting excellent crack resistance, adhesion and heat resistance, and from the viewpoint of easily ensuring excellent storage stability.

  The content of the structural unit having the functional group is preferably in the following range based on the total amount of the component (a) from the viewpoint of easily securing adhesive force and easily preventing gelation. The content of the structural unit having a functional group is preferably 0.5% by mass or more, more preferably 0.8% by mass or more, further preferably 1.0% by mass or more, and particularly preferably 2.0% by mass or more. 3.0% by mass or more is extremely preferable. The content of the structural unit having a functional group is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 6.0% by mass or less, and particularly preferably 5.0% by mass or less. From these viewpoints, the content of the structural unit having the functional group is preferably 0.5 to 20% by mass.

  The component (a) may have a structural unit having a nitrogen atom-containing group. The content of the structural unit having a nitrogen atom-containing group in the component (a) is preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less, based on the total amount of the component (a). . It is particularly preferable that the component (a) does not include a structural unit having a nitrogen atom-containing group. Examples of the nitrogen atom-containing group include an amino group, an amide group, a cyano group, and a maleimide group. Examples of the structural unit having a nitrogen atom-containing group include structural units derived from monomers containing a nitrogen atom among the functional group-containing monomers listed above, and cyanation of (meth) acrylonitrile and the like. Examples include structural units derived from vinyl compounds.

  Examples of monomers other than the functional group-containing monomer that can be used in the synthesis of the component (a) include (meth) acrylic acid esters as exemplified in International Publication No. 2015/115537; Group vinyl compounds; alicyclic monomers and the like. Monomers other than the functional group-containing monomer can be used singly or in combination of two or more.

  Among these, (meth) acrylic acid esters are preferable from the viewpoint of easily synthesizing a (meth) acrylic polymer (for example, a (meth) acrylic polymer having a weight average molecular weight of 100,000 or more) without gelation. Among (meth) acrylic acid esters, from the viewpoint of excellent copolymerizability with a functional group-containing monomer, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate More preferred is at least one selected from the group consisting of

  The component (a) preferably has at least one selected from the group consisting of an alicyclic structure and a heterocyclic structure, and more preferably has an alicyclic structure. When the component (a) has an alicyclic structure, the amorphous component in the (meth) acrylic polymer increases, so that the transparency tends to increase. Further, compared with an aliphatic structure having the same carbon number (such as an aliphatic structural unit), the glass transition temperature (Tg) is improved and the heat resistance tends to be increased.

  The component (a) preferably has a structural unit having at least one selected from the group consisting of an alicyclic structure and a heterocyclic structure, and more preferably has a structural unit having an alicyclic structure. Examples of the monomer having an alicyclic structure or a heterocyclic structure used in producing a (meth) acrylic polymer having a structural unit having an alicyclic structure or a heterocyclic structure include, for example, the following general The compound represented by Formula (1) is mentioned.

[In formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alicyclic group or a heterocyclic group, X represents an alkylene group having 1 to 6 carbon atoms, and n represents 0 to 10 Indicates an integer. When n is an integer of 2 or more, a plurality of Xs may be the same or different from each other. Here, the “alicyclic group” is a group having a structure in which carbon atoms are bonded cyclically, and the “heterocyclic group” is a group having a structure in which a carbon atom and one or more heteroatoms are bonded cyclically. is there. ]

Examples of R ² include groups represented by the following formulas (2a) to (2h).

[Wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹¹ represents hydrogen. atom, an alkyl group having 1 to 4 carbon atoms, or ^represents a structure represented by ^{oR 11a, R 11a} represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]

Examples of the compound represented by the formula (1) include cyclohexyl (meth) acrylate (also known as cyclohexyl (meth) acrylate), isobornyl (meth) acrylate (also known as isobornyl (meth) acrylate), and tricyclo (meth) acrylate. And [5.2.1.0 ^2,6 ] dec-8-yl (also known as: tricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate).

  The content of these monomers other than the functional group-containing monomer is preferably adjusted so that the Tg of the component (a) is in the range of −50 to 50 ° C. For example, 2.5% by mass of glycidyl methacrylate, 43.5% by mass of methyl methacrylate, 18.5% by mass of ethyl acrylate, and 35.5% by mass of butyl acrylate are used as monomers. Thus, the component (a) which is an epoxy group-containing (meth) acrylic polymer having a Tg of 12 ° C. and a weight average molecular weight of 100,000 or more can be synthesized.

  When the functional group-containing monomer is used in combination, the mixing ratio is determined in consideration of the Tg of the (meth) acrylic polymer, and the Tg of the component (a) is preferably −50 ° C. or higher. This is because when the Tg is −50 ° C. or higher, the tackiness of the resin composition in the B-stage state is appropriate, and the handleability is excellent. From such a viewpoint, the mixing ratio of the functional group-containing monomer and the monomer other than the functional group-containing monomer (functional group-containing monomer: monomer other than the functional group-containing monomer) is 100: 0 to 0.1: 99.9, preferably 100: 0 to 1:99, more preferably 50:50 to 1:99, 30:70 to It is particularly preferably 1:99, and very preferably 20:80 to 1:99.

  The component (a) is composed of a structural unit represented by the following general formula (I), a structural unit represented by the following general formula (II), and a structural unit represented by the following general formula (III). You may have at least 1 sort chosen.

[In Formula (I), R ^1a represents a hydrogen atom or a methyl group, and X ^a represents a group containing an epoxy group. ]

[In Formula (II), R ^2a represents a hydrogen atom or a methyl group, and Y ^a represents an alicyclic group having 5 to 22 carbon atoms which may have a substituent (corresponding to X in Formula (I) The group to be excluded). ]

Wherein ^{(III), R 3a} represents a hydrogen atom or a methyl group, ^{Z a} represents a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent (Formula (I) The group corresponding to X is excluded). ]

  In the case of producing a (meth) acrylic polymer (for example, a (meth) acrylic polymer having a structural unit having a functional group) by polymerizing monomers, the polymerization methods include solution polymerization, suspension polymerization (pearl The above-described method such as polymerization) can be used.

  The weight average molecular weight of the component (a) is appropriate in terms of strength, flexibility and tackiness after film formation, and appropriate flowability. The range of is preferable. The weight average molecular weight of the component (a) is preferably 100,000 or more, more preferably 120,000 or more, and further preferably 200,000 or more, from the viewpoint of maintaining a sufficient elastic modulus (for example, an elastic modulus of 260 ° C.). 300,000 or more is particularly preferable, 400,000 or more is extremely preferable, and 450,000 or more is very preferable. The weight average molecular weight of the component (a) is preferably 3 million or less, more preferably 2 million or less, still more preferably 1 million or less, and particularly preferably 800,000 or less. From these viewpoints, the weight average molecular weight of the component (a) is preferably 100,000 to 3,000,000. The weight average molecular weight is a value measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve as described in Examples.

  The content of the component (a) shows a good storage elastic modulus, can suppress the flow at the time of molding, and from the viewpoint that the handleability at high temperature is sufficiently obtained, the total amount of the component (b) is 100 parts by mass. On the other hand, the following ranges are preferable. The content of the component (a) is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, further preferably 20 parts by mass or more, particularly preferably 50 parts by mass or more, particularly preferably 75 parts by mass or more, and 100 parts by mass. Part or more is highly preferred. 400 mass parts or less are preferable, as for content of (a) component, 350 mass parts or less are more preferable, 300 mass parts or less are further more preferable, 200 mass parts or less are especially preferable, and 150 mass parts or less are very preferable. From these viewpoints, the content of the component (a) is preferably 10 to 400 parts by mass.

((B) component: a compound having at least two (meth) acryloyl groups)
In the resin composition according to this embodiment, the compatibility between the component (a) and the component (b) is high, and these refractive indexes tend to be close, so that the visibility can be secured after curing. Transparency can be obtained. Furthermore, since the compatibility is high as described above, phase separation hardly occurs in a varnish state or a semi-cured state, and the storage stability is also excellent. Further, even when phase separation occurs due to the heat of curing after radical curing, only micro phase separation is achieved, and variations in cured properties such as visibility and adhesive strength can be suppressed. The problem of light loss can also be solved by filling the cavity with the resin composition according to this embodiment.

  Examples of the component (b) include (meth) acrylic monomers and oligomers thereof (excluding compounds corresponding to the component (a)). Component (b) may have a molecular weight (for example, a weight average molecular weight) of, for example, 20,000 or less, or 10,000 or less.

  As a monomer having at least two (meth) acryloyl groups, a polyfunctional (meth) acrylic monomer having an alicyclic structure, a polyfunctional (meth) acrylic monomer having an aliphatic structure, a dioxane glycol structure And a polyfunctional (meth) acrylic monomer having a functional group (excluding a (meth) acryloyl group). As the polyfunctional (meth) acrylic monomer having a functional group, a polyfunctional (meth) acrylic monomer having an alicyclic structure, an aliphatic structure or a dioxane glycol structure is excluded. Here, “polyfunctional” refers to a (meth) acryloyl group, and means that the compound has at least two (meth) acryloyl groups.

  (B) A component can be used individually by 1 type or in combination of 2 or more types.

  The component (b) has a polyfunctional (meth) acrylic monomer having an alicyclic structure and a dioxane glycol structure from the viewpoint of easily obtaining a low light transmittance at a wavelength of 350 nm and a high light transmittance at a wavelength of 430 nm. At least one selected from the group consisting of polyfunctional (meth) acrylic monomers is preferred. The component (b) is preferably a polyfunctional (meth) acrylic monomer having an aliphatic structure from the viewpoint of easily preventing cracks in the cured product and peeling from the substrate.

  As a polyfunctional (meth) acryl monomer, the (meth) acryl monomer which has two (meth) acryloyl groups can be mentioned, for example.

  Examples of the (meth) acrylic monomer having two (meth) acryloyl groups include cyclohexane-1,4-dimethanol di (meth) acrylate, cyclohexane-1,3-dimethanol di (meth) acrylate, tricyclodecane dimethylol di ( (Meth) acrylate (for example, Nippon Kayaku Co., Ltd., KAYARAD R-684, tricyclodecane dimethylol diacrylate), tricyclodecane dimethanol di (meth) acrylate (for example, Shin-Nakamura Chemical Co., Ltd., A-DCP, Tricyclodecane dimethanol diacrylate), dioxane glycol di (meth) acrylate (for example, Nippon Kayaku Co., Ltd., KAYARAD R-604, dioxane glycol diacrylate; Shin-Nakamura Chemical Co., Ltd., A-DOG, dioxane glyco) Diacrylate), nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene oxide modified 1,6- Hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, (poly) ethylene oxide modified neopentyl glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) Acrylate, polypropylene glycol di (meth) acrylate, ethylene oxide modified bisphenol A type di (meth) acrylate (preferably polyethylene oxide modified bisphenol A type di Meth) acrylate, more preferably ethylene oxide 5-15 mol-modified bisphenol A Kataji (meth) acrylate), and (poly) ethylene oxide-modified phosphoric acid di (meth) acrylate.

  Among these, at least selected from the group consisting of dioxane glycol di (meth) acrylate and tricyclodecane dimethanol di (meth) acrylate from the viewpoint of easily obtaining a low light transmittance at a wavelength of 350 nm and a high light transmittance at a wavelength of 430 nm. One is preferable, and at least one selected from the group consisting of dioxane glycol diacrylate and tricyclodecane dimethanol diacrylate is more preferable.

  Examples of other polyfunctional (meth) acrylic monomers include three (meth) acryloyl groups such as pentaerythritol tri (meth) acrylate and ethylene oxide-modified isocyanuric acid tri (meth) acrylate (meth). An acrylic monomer can be mentioned.

  The content of the component (b) is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and still more preferably 40 parts by mass or more with respect to 100 parts by mass of the total amount of the components (a) and (b). The content of the component (b) is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, still more preferably 60 parts by mass or less, with respect to 100 parts by mass of the total amount of the components (a) and (b). 50 parts by mass or less is particularly preferable. As for content of (b) component, 20-80 mass parts is preferable with respect to 100 mass parts of total amounts of (a) component and (b) component. When the content of the component (b) is in the above ranges, the heat resistance tends to be further improved because three-dimensional crosslinking is easily performed. Even if phase separation occurs after curing, the phase separation range can be kept on a microscale. Therefore, variations in cured product characteristics such as visibility and adhesive strength can be easily suppressed, and warpage or cracks in the manufacturing process of a semiconductor or electronic component can be easily suppressed.

((C) component: polymerization initiator)
Examples of the component (c) include (c1) a thermal polymerization initiator (hereinafter, sometimes referred to as “(c1) component”) and / or (c2) a photopolymerization initiator (hereinafter, sometimes referred to as “(c2) component”). Can be used.

  Examples of the component (c1) include organic peroxides; azo compounds as exemplified in International Publication No. 2015/115537.

  (C1) A component can be used individually by 1 type or in combination of 2 or more types.

  Among the components (c1), an organic peroxide is preferable from the viewpoint of easily obtaining a low light transmittance at a wavelength of 350 nm and a high light transmittance at a wavelength of 430 nm, and the handleability of the resin composition (shelf life, pot life, etc.) From the viewpoint of maintaining a good balance with curability, an organic peroxide having a 10-hour half-life temperature of 90 to 150 ° C. is more preferable. The half-life temperature of the organic peroxide can be measured by the method described in International Publication No. 2015/115537.

  Among the components (c1) mentioned above, as the organic peroxide, dicumyl peroxide (for example, trade name: Park Mill D, manufactured by NOF Corporation), from the viewpoint of excellent storage stability and thermosetting, And at least 1 sort (s) chosen from the group which consists of n-butyl 4, 4-bis (t-butyl peroxy) valerate (For example, NOF Corporation make, brand name: perhexa V) is preferable.

  The component (c1) tends to exhibit excellent heat resistance, peel resistance, and stress relaxation in combination with the component (a) and the component (b), and improves the reliability of the semiconductor device (optical component or the like). it can.

  The content of the component (c1) is such that the low light transmittance at a wavelength of 350 nm and the high light transmittance at a wavelength of 430 nm are easily obtained, and from the viewpoint of easily suppressing outgassing, the components (a) and (b) The following ranges are preferable with respect to the total amount of 100 parts by mass. The content of the component (c1) is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, further preferably 0.5 parts by mass or more, and particularly preferably 1 part by mass or more. The content of the component (c1) is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, further preferably 10 parts by mass or less, particularly preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less. Part or less is highly preferred. From these viewpoints, the content of the component (c1) is preferably 0.1 to 30 parts by mass.

  As component (c2), acylphosphine oxide, oxime esters, aromatic ketones, quinones, benzoin ether compounds, benzyl derivatives, 2,4,5-triarylimidazole dimers, acridine derivatives, coumarin compounds, N-phenylglycine, N-phenylglycine derivatives and the like can be mentioned. (C2) A component may be synthesize | combined by a conventional method and a commercially available thing may be obtained.

  Among these, it is selected from the group consisting of acylphosphine oxides and oxime esters from the viewpoint of improving photocurability, from the viewpoint of increasing sensitivity, and from the viewpoint of easy transparency of cured products (cured films, etc.). At least one is preferred.

  (C2) A component can be used individually by 1 type or in combination of 2 or more types.

  Examples of the acylphosphine oxide include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (for example, IRGACURE-819, trade name of BASF), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide. (For example, LUCIRIN TPO, BASF Corporation, trade name) and the like.

  Examples of oxime esters include 1,2-octanedione-1- [4- (phenylthio) phenyl-2- (O-benzoyloxime)] (for example, IRGACURE-OXE01, BASF Corporation, trade name), 1- [9 -Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone-1- (O-acetyloxime) (eg IRGACURE-OXE02, BASF, trade name), 1-phenyl-1, 2-propanedione-2- [o- (ethoxycarbonyl) oxime] (for example, Quanture-PDO, Nippon Kayaku Co., Ltd., trade name) and the like.

  As an aromatic ketone, the compound described in the international publication 2015/115537 is mentioned, for example.

  As quinones, the compound described in international publication 2015/115537 is mentioned, for example.

  Examples of the benzoin ether compound include benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether.

  Examples of the benzyl derivative include benzoin compounds such as benzoin, methylbenzoin, and ethylbenzoin; benzyldimethyl ketal and the like.

  Examples of the 2,4,5-triarylimidazole dimer include the compounds described in International Publication No. 2015/115537.

  Examples of the acridine derivative include 9-phenylacridine, 1,7-bis (9,9'-acridinyl) heptane and the like.

  Examples of the coumarin compound include compounds described in International Publication No. 2015/115537.

  Examples of N-phenylglycine derivatives include N-phenylglycine butyl ester, Np-methylphenylglycine, Np-methylphenylglycine methyl ester, N- (2,4-dimethylphenyl) glycine, and N-methoxyphenylglycine. Etc.

  The content of the component (c2) is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (a) and (b). 75-5 mass parts is still more preferable. When the content of the component (c2) is within these ranges, foaming, turbidity, coloring, and cracks of the cured product are highly easily prevented.

((D) component: UV absorber)
The component (d) can absorb ultraviolet rays (mainly light having a wavelength of 300 to 400 nm). The component (d) may slightly absorb light in the vicinity of a wavelength of 430 nm. (D) A component can be used individually by 1 type or in combination of 2 or more types.

  The content of the component (d) is 0.002% by mass or more based on the total amount of resin composition (total amount of solid content) from the viewpoint of obtaining a low light transmittance at a wavelength of 350 nm. The content of component (d) is 0.003% by mass based on the total amount of resin composition (total amount of solids) from the viewpoint of easily obtaining a low light transmittance at a wavelength of 350 nm and a high light transmittance at a wavelength of 430 nm. The above is preferable, 0.005% by mass or more is more preferable, 0.007% by mass or more is further preferable, 0.01% by mass or more is particularly preferable, 0.015% by mass or more is extremely preferable, and 0.02% by mass or more Is very preferable, and 0.025% by mass or more is even more preferable.

  The content of the component (d) is 0.04% by mass or less based on the total amount of resin composition (total amount of solid content) from the viewpoint of obtaining a high light transmittance at a wavelength of 430 nm. (D) Content of a component is 0.035 mass% or less based on the total amount (total amount of solid content) of a resin composition, 0.03 mass% or less is more preferable, 0.025 mass% or less is preferable. More preferably, 0.02% by mass or less is particularly preferable, and 0.015% by mass or less is very preferable.

  The content of the component (d) is preferably in the following range with respect to 100 parts by mass of the component (a). The content of the component (d) is preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, from the viewpoint of easily obtaining a low light transmittance at a wavelength of 350 nm and a high light transmittance at a wavelength of 430 nm. 0.02 parts by mass or more is more preferable, 0.03 parts by mass or more is particularly preferable, 0.04 parts by mass or more is extremely preferable, 0.05 parts by mass or more is very preferable, and 0.06 parts by mass or more is even more preferable. . The content of the component (d) is preferably 0.1 parts by mass or less, more preferably 0.07 parts by mass or less, still more preferably 0.06 parts by mass or less, particularly preferably 0.05 parts by mass or less. 04 parts by mass or less is extremely preferable, 0.03 parts by mass or less is very preferable, and 0.025 parts by mass or less is even more preferable. From these viewpoints, the content of the component (d) is preferably 0.005 to 0.1 parts by mass.

  The content of the component (d) is preferably in the following range with respect to 100 parts by mass of the total amount of the components (a) and (b). The content of the component (d) is preferably 0.002 parts by mass or more, more preferably 0.005 parts by mass or more, from the viewpoint of easily obtaining a low light transmittance at a wavelength of 350 nm and a high light transmittance at a wavelength of 430 nm. .01 parts by mass or more is more preferable, 0.015 parts by mass or more is particularly preferable, 0.02 parts by mass or more is very preferable, 0.025 parts by mass or more is very preferable, and 0.03 parts by mass or more is even more preferable. . The content of component (d) is preferably 0.05 parts by mass or less, more preferably 0.04 parts by mass or less, still more preferably 0.035 parts by mass or less, particularly preferably 0.03 parts by mass or less. 025 parts by mass or less is extremely preferable, 0.02 parts by mass or less is very preferable, and 0.015 parts by mass or less is even more preferable. From these viewpoints, the content of the component (d) is preferably 0.002 to 0.05 parts by mass.

(Antioxidant)
The resin composition according to the present embodiment can contain an antioxidant. When the resin composition according to the present invention contains an antioxidant, it is easy to suppress coloring due to deterioration of the resin composition during heating and to improve transparency during heating. Examples of the antioxidant include phenolic antioxidants, thioether antioxidants, and thiol antioxidants. Antioxidant can be used individually by 1 type or in combination of 2 or more types.

  Examples of phenolic antioxidants include hindered phenolic compounds. Examples of the hindered phenol-based compound include compounds described in International Publication No. 2015/046422. Specifically, bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) is exemplified. ) Propionic acid] (2,4,8,10-tetraoxaspiro [5.5] undecane-3,9-diyl) bis (2,2-dimethyl-2,1-ethanediyl).

  Examples of the thioether-based antioxidant include ditridecyl 3,3-thiobispropionate (for example, “ADEKA STAB AO-503” (ADEKA)). Examples of the thiol-based antioxidant include compounds having a thiol group. Examples of the compound having a thiol group include pentaerythritol tetrakis (3-mercaptobutyrate) (for example, “Karenz MT-PE1” (Showa Denko KK)), 1,3,5-tris (3-mercaptobutyryloxyethyl). ) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (for example, “Karenz MT-NR1” (Showa Denko KK)) and the like.

  The content of the antioxidant is (a) component, (b) from the viewpoint of easily obtaining a low light transmittance at a wavelength of 350 nm and a high light transmittance at a wavelength of 430 nm, and hardly adversely affecting radical polymerization reactivity. The following ranges are preferable with respect to 100 parts by mass of the total amount of the component and component (c). The content of the antioxidant is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, still more preferably 1 part by mass or more, and particularly preferably 1.5 parts by mass or more. The content of the antioxidant is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less, and particularly preferably 2 parts by mass or less. From these viewpoints, the content of the antioxidant is preferably 0.01 to 10 parts by mass.

(Coupling agent)
The resin composition according to the present embodiment can contain a coupling agent. As the coupling agent, various coupling agents such as a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a zirconate coupling agent, and a zircoaluminate coupling agent can be used. A coupling agent can be used individually by 1 type or in combination of 2 or more types.

  The silane coupling agent may be an alkoxysilane. The silane coupling agent is, for example, at least one selected from the group consisting of a vinyl group, an epoxy group, a styryl group, a (meth) acryl group, an amino group, an isocyanurate group, a ureido group, a mercapto group, and an isocyanate group. It may be an alkoxysilane having a functional group. Specific examples of the silane coupling agent include compounds exemplified in International Publication No. 2015/115537.

  Examples of titanate coupling agents include compounds exemplified in International Publication No. 2015/115537.

  Examples of the aluminum coupling agent include acetoalkoxy aluminum diisopropionate.

  Examples of the zirconate coupling agent include tetrapropyl zirconate, tetrabutyl zirconate, tetra (triethanolamine) zirconate, tetraisopropyl zirconate, zirconium acetylacetonate, acetylacetone zirconium butyrate, and zirconium stearate butyrate. .

Examples of the zircoaluminate coupling agent include compounds represented by the following general formula (3).

[In the formula (3), R ¹² represents a carboxyl group or an amino group. ]

Examples of the compound in which R ¹² is a carboxyl group include Manschem CPG-carboxyzircoaluminate. Examples of the compound in which R ¹² is an amino group include Mansheim APO-X-amino zircoaluminate solution. Each is available from Rhône Poulenc.

  Among these coupling agents, a silane coupling agent is preferable, a silane coupling agent having a (meth) acryl group is more preferable, and γ- At least one selected from the group consisting of methacryloxypropyltrimethoxysilane (also known as 3- (trimethoxysilyl) propyl methacrylate), γ-methacryloxypropylmethyldimethoxysilane, and γ-acryloxypropyltrimethoxysilane; Further preferred.

  The content of the coupling agent is preferably in the following range with respect to 100 parts by mass of the total amount of the component (a), the component (b) and the component (c). The content of the coupling agent is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 0.8 parts by mass or more from the viewpoint that the effect of improving the adhesive strength tends to be obtained. It is preferably 1 part by mass or more. The content of the coupling agent is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and more preferably 10 parts by mass from the viewpoint that the volatile content is small and generation of voids in the cured product tends to be easily suppressed. The following is more preferable, 5 parts by mass or less is particularly preferable, 3 parts by mass or less is extremely preferable, and 2 parts by mass or less is very preferable. From these viewpoints, the content of the coupling agent is preferably 0.1 to 20 parts by mass.

(Organic solvent)
The resin composition according to the present embodiment can contain an organic solvent. A varnish-like resin composition can be obtained by dissolving or dispersing the containing component in an organic solvent. By using a varnish-like resin composition, the coating property to a base material improves and workability | operativity is favorable.

  The organic solvent is not particularly limited as long as it can uniformly stir, mix, dissolve, knead or disperse the components contained in the resin composition, and a conventionally known solvent can be used. Examples of the organic solvent include alcohol solvents, ether solvents, ketone solvents, amide solvents, aromatic hydrocarbon solvents, ester solvents, nitrile solvents, and the like. Specific examples of the organic solvent include solvents having a low boiling point (diethyl ether, acetone, methanol, tetrahydrofuran, hexane, ethyl acetate, ethanol, methyl ethyl ketone, 2-propanol, etc.) from the viewpoint of easily suppressing volatilization at low temperatures. High boiling point solvents (toluene, methyl isobutyl ketone, 1-butanol, 2-methoxyethanol, 2-ethoxyethanol, xylene, N, N-dimethylacetamide, N, N-dimethyl from the viewpoint of improving the stability of the coating film, etc. Formamide, cyclohexanone, dimethylacetamide, butyl cellosolve, dimethyl sulfoxide, propylene glycol monomethyl ether acetate, N-methyl-2-pyrrolidone, γ-butyrolactone, etc.). An organic solvent can be used individually by 1 type or in combination of 2 or more types.

  Among these, at least one selected from the group consisting of methyl ethyl ketone, cyclohexanone, and propylene glycol monomethyl ether acetate is preferable from the viewpoint of excellent solubility and fast drying speed.

  The content of the organic solvent is determined by the viscosity when the varnish is used. The content of the organic solvent is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, and 10 to 50% by mass based on the total amount of the resin composition (total amount including volatile components such as the organic solvent). Further preferred.

(Other ingredients)
In addition to the component (b), the resin composition according to the present embodiment is a monofunctional (meth) acrylic monomer (a compound having one (meth) acryloyl group. For example, one (meth) acryloyl group and a complex A compound having a ring). Examples of the monofunctional (meth) acrylic monomer include the (meth) acrylic monomer exemplified by the component (a) (such as glycidyl (meth) acrylate). A monofunctional (meth) acryl monomer can be used individually by 1 type or in combination of 2 or more types.

  The resin composition according to the present embodiment may contain other additives. Additives include epoxy curing agents, epoxy curing accelerators, wetting improvers (fluorine surfactants, nonionic surfactants, higher fatty acids, etc.), antifoaming agents (silicone oil, etc.), ion trap agents (inorganic ions) Exchangers, etc.), refractive index adjusting agents, other fillers (organic fillers, inorganic fillers, etc.) and the like. These additives can be used individually by 1 type or in combination of 2 or more types.

<Method for Manufacturing Semiconductor Device>
The manufacturing method of the semiconductor device according to the present embodiment cures the resin layer in a state where the resin layer (adhesive layer) including the resin composition according to the present embodiment is disposed between the semiconductor substrate and the transparent substrate. The process (cured material formation process) to perform is provided. For example, the method for manufacturing a semiconductor device according to the present embodiment includes a step of forming a resin layer containing the resin composition according to the present embodiment on a semiconductor substrate (resin layer forming step), and the resin layer is formed on the semiconductor substrate. And a step (cured product forming step) of curing the resin layer in a state of being disposed between the transparent substrate. A resin layer consists of a resin composition concerning this embodiment, for example. A transparent substrate (glass substrate etc.) is a transparent substrate (glass substrate etc.), for example. The cured product forming step includes a step of pressing the semiconductor substrate and the transparent base material between the semiconductor substrate and the transparent base material (crimping step), and a step of curing the resin layer (curing step). You may do it. The crimping process and the curing process are not necessarily independent processes, and curing may be performed simultaneously while performing the crimping.

  FIG. 1 and FIG. 2 are process diagrams illustrating an example of a method for manufacturing a semiconductor device according to this embodiment, and are process diagrams illustrating a manufacturing method using a dispensing method. First, as shown to Fig.1 (a), the laminated body provided with the support base material 10 and the semiconductor substrate 20 mounted on the support base material 10 is prepared. The terminals (not shown) of the support base 10 and the semiconductor substrate 20 are electrically connected by a wire 15. In the case where the semiconductor device is a solid-state image sensor, for example, a light receiving unit is disposed on the semiconductor substrate 20. Next, as shown in FIG. 1B, after the resin composition is supplied onto the semiconductor substrate 20 by a dispensing method, the resin layer 30 is formed by heating and drying as shown in FIG. Form on top. For example, the resin layer 30 is formed so as to cover the light receiving portion of the semiconductor substrate 20. Next, as shown in FIG. 2B, the transparent substrate 40 is pressure-bonded onto the resin layer 30. Then, as shown in FIG. 2C, the resin layer 30 is cured to form a resin layer (cured product) 30a, whereby the semiconductor device 100 is obtained.

  Hereinafter, each step will be further described.

(Resin layer forming process)
As a resin layer formation process, the method of apply | coating the resin composition which concerns on this embodiment on a semiconductor substrate, or the method of affixing a film-form resin composition on a semiconductor substrate, for example is employable. The semiconductor substrate may be, for example, any of a semiconductor wafer and a semiconductor element (semiconductor chip).

  Examples of the method for applying the resin composition include methods such as a dispensing method (syringe dispensing method, etc.), a spin coating method, a die coating method, and a knife coating method. When the method of sticking the film-like resin composition is adopted, it is preferable to laminate in the range of 0 to 90 ° C. in order to ensure sufficient wetting and spreading. Moreover, in order to affix uniformly, it is preferable to perform roll lamination.

  The manufacturing method of a film-form resin composition is demonstrated below. For example, the resin composition according to the present embodiment is uniformly applied on a support film and heated under conditions where the solvent used is sufficiently volatilized (for example, at a temperature of 60 to 200 ° C. for 0.1 to 30 minutes). Thus, a film-like resin composition is formed. At this time, the solvent amount of the resin composition, the viscosity, and the initial coating thickness (when using a coater such as a die coater or a comma coater, the coater and support so that the film-like resin composition has a desired thickness. Adjust the gap with the film), adjust the drying temperature, air volume, etc.

  The support film preferably has flatness. For example, since a support film such as a PET film has high adhesion due to static electricity, a smoothing agent may be used in order to improve workability. Depending on the type and temperature of the smoothing agent, fine unevenness may be transferred to the adhesive and the flatness may be lowered. Therefore, it is preferable to use a support film that does not use a smoothing agent, or a support film that contains few smoothing agents. In addition, a support film such as a polyethylene film is preferable from the viewpoint of excellent flexibility, but it is preferable to appropriately select the thickness and density of the support film so that roll marks and the like are not transferred to the resin layer surface during lamination.

(Crimping process)
Subsequently, the resin layer formed on the semiconductor substrate is heat-dried as necessary. There is no particular limitation on the drying temperature, but when the varnish-like resin composition is used by dissolving or dispersing the components in a solvent, the drying temperature is a viewpoint that tends to suppress the generation of bubbles due to foaming of the solvent during drying. Therefore, it is preferably 10 to 50 ° C. lower than the boiling point of the solvent used. From the same viewpoint, the drying temperature is more preferably 15 to 45 ° C. lower than the boiling point of the solvent used, and further preferably 20 to 40 ° C. lower than the boiling point of the solvent used.

  In addition, when a varnish-like resin composition is used by dissolving or dispersing the components in a solvent, the residual amount of the solvent can be reduced as much as possible from the viewpoint of easily suppressing the generation of bubbles due to foaming of the solvent after curing. preferable.

  There are no particular limitations on the conditions for performing the above-mentioned heat drying, as long as the solvent used is sufficiently volatilized, and the component (c) does not substantially generate radicals, but usually at 40 to 100 ° C., Heat for 0.1 to 90 minutes. Note that “substantially no radicals” means that radicals are not generated at all, or very little if any, and thus the polymerization reaction does not proceed or proceeds temporarily. In other words, the conditions are such that the physical properties of the resin layer are not affected. Moreover, it is preferable to dry under reduced pressure conditions from the viewpoint of reducing the residual amount of the solvent while suppressing the generation of radicals from the component (c) due to heating.

  Volatile components (residual solvent, low molecular weight impurities, reaction products, decomposition) present inside or on the surface of the resin layer from the viewpoint of easily preventing the resin layer from peeling during solder reflow due to foaming during heat curing of the resin layer It is preferable to sufficiently reduce the product, moisture derived from the material, surface adsorbed water, and the like.

  After heat drying, a transparent substrate is pressure-bonded onto the resin layer. In addition, the said heat drying can be abbreviate | omitted when the method of affixing a film-form resin composition in a resin layer formation process is employ | adopted.

(Curing process)
After the semiconductor substrate and the transparent substrate are pressure-bonded via the resin layer, the cured product is formed by curing the resin layer. Examples of the curing method include a method of curing with heat and / or light, and it is particularly preferable to cure with heat.

  In the curing step for forming a cured product of the resin layer, it is preferable that the thermal curing (curing) is performed for 1 to 2 hours while selecting the temperature and gradually increasing the temperature. It is preferable to perform thermosetting at 100-200 degreeC.

<Semiconductor device>
The semiconductor device according to the present embodiment includes a semiconductor substrate, a transparent base material, and a resin layer (adhesive layer) disposed between the semiconductor substrate and the transparent base material. For example, the semiconductor device according to the present embodiment includes a semiconductor substrate, a resin layer (adhesive layer) disposed on the semiconductor substrate, a transparent base material bonded to the semiconductor substrate via the resin layer, Is provided. The resin layer includes the resin composition according to the present embodiment or a cured product thereof. The transparent base material is disposed on the semiconductor substrate via a resin layer, for example.

  Examples of the semiconductor device include an optical component. Examples of the optical component include an optical device such as a solid-state image sensor. Examples of the solid-state imaging device include a CCD image sensor and a CMOS image sensor (for example, a backside illumination type CMOS image sensor). A CMOS image sensor which is an example of a semiconductor device according to the present embodiment is built in, for example, a mobile phone. In this case, the CMOS image sensor is mounted on the mother board of the mobile phone via a solder ball, and an optical lens is disposed above the sensor (that is, on the side of a transparent substrate such as a glass substrate).

  In the semiconductor device (for example, a solid-state image sensor) according to the present embodiment, a light receiving portion disposed on a main surface (for example, an upper surface) of a semiconductor substrate may be covered with a resin layer. The semiconductor device (for example, a solid-state image sensor) according to the present embodiment includes, for example, a semiconductor substrate having a light receiving portion disposed on an upper surface, a resin layer disposed on the semiconductor substrate so as to cover the light receiving portion, and the resin A transparent base material bonded to the semiconductor substrate through a layer. The semiconductor device according to the present embodiment is a member (for example, a frame-shaped member) disposed on a region (for example, the outer peripheral portion of the main surface) located on the outer peripheral side of the main surface with respect to the main surface of the semiconductor substrate. May be provided. The member may have an opening (cavity) that exposes the light receiving portion, and a resin layer may be disposed (filled) in the opening. In the semiconductor device according to the present embodiment, the space between the semiconductor substrate and the transparent base material may be sealed only by the resin layer. In the semiconductor device according to this embodiment, a part or the whole of the semiconductor substrate may be sealed with a resin layer. The resin layer may be disposed around the semiconductor substrate and / or the transparent substrate, in addition to between the semiconductor substrate and the transparent substrate.

  The semiconductor device according to this embodiment has, for example, a non-cavity structure using the resin composition according to this embodiment. Hereinafter, as an example of the semiconductor device according to the present embodiment, a CMOS image sensor that is a back-illuminated solid-state imaging element will be described with reference to the drawings as the case may be.

  FIG. 3 is a plan view showing an example of the semiconductor device (first embodiment, CMOS image sensor). 4 is a cross-sectional view taken along line A-A ′ shown in FIG. 3. The CMOS image sensor 1a includes a sensor unit (light receiving unit) 3a in which a plurality of microlenses 2 are arranged in a central region. A peripheral circuit portion 3b in which a circuit is formed exists around the sensor portion 3a. The glass substrate 4 is arrange | positioned so that the sensor part 3a may be covered at least.

  As shown in FIG. 4, a plurality of photodiodes 2 a are arranged on one surface of the silicon substrate 5. A color filter 2b is disposed on the upper surface of the photodiode 2a so as to cover at least the photodiode 2a, and a microlens 2 is disposed on the upper surface of the color filter 2b. The color filter 2b is disposed for each photodiode 2a, and each microlens 2 is disposed at a position corresponding to each color filter 2b. The resin layer 6a containing the resin composition according to this embodiment or a cured product thereof is formed on the entire surface of the region where the microlenses 2 are disposed on one surface side of the silicon substrate 5, and on the resin layer 6a. A glass substrate 4 is disposed on the surface. Thereby, the CMOS image sensor 1a has a structure without a cavity (non-cavity structure). On the other hand, a wiring layer 7 is disposed on the other surface side of the silicon substrate 5, and solder balls 8 are disposed on the lower surface of the wiring layer 7.

  FIG. 5 is a cross-sectional view showing another example of the semiconductor device (second embodiment, CMOS image sensor). In the CMOS image sensor 1 b shown in FIG. 5, a frame-like member 9 is arranged on the outer peripheral side portion of the microlens 2 so as not to cover the microlens 2 arranged on the silicon substrate 5, and a transparent glass substrate 4. Is arranged on the upper surface of the frame-shaped member 9. A portion surrounded by the glass substrate 4, the silicon substrate 5, and the frame-shaped member 9 is filled with the resin layer 6 b containing the resin composition according to the present embodiment or a cured product thereof, and a non-cavity structure is formed. Yes. In the semiconductor device of FIG. 5, the resin layer 6b serves as an adhesive for adhering the glass substrate 4 and the silicon substrate 5, fills the cavity, and seals the microlens 2, photodiode 2a, and color filter 2b. Also plays a role as a sealing material to stop.

  In a non-cavity structure using an adhesive rib (frame-shaped resin layer), an adhesive rib (hereinafter simply referred to as “rib”) is formed so as to surround the light receiving portion, and then the light receiving portion is formed. The sealing material which has transparency is filled so that it may seal, and the board | substrate (for example, glass substrate) which has transparency is adhere | attached. For example, in the non-cavity structure of FIG. 5, after forming the frame-like member 9, the resin layer 6b is formed by filling the cavity with a resin composition. The non-cavity structure produced in this way can sufficiently provide adhesion even at portions other than the ribs, and a more reliable non-cavity structure can be obtained. On the other hand, in the non-cavity structure of FIG. 4, the glass substrate 4 and the silicon substrate 5 are bonded via the resin layer 6a including the resin composition according to the present embodiment or a cured product thereof without providing ribs. Yes. This is because the resin composition and its cured product according to this embodiment can function as an adhesive and a sealing material. In this case, compared with the non-cavity structure (second embodiment) shown in FIG. 5, the non-cavity structure (first embodiment) shown in FIG. Can do. In addition, facilities such as a printing machine, an exposure machine, and a developing machine necessary for forming the rib are not necessary.

  FIG. 6 is a drawing for comparing semiconductor device manufacturing methods. FIG. 6A shows a semiconductor device manufacturing method (rib forming process) according to the second embodiment. FIG. 6B shows the semiconductor device manufacturing method (entire sealing process) according to the first embodiment. In the method of manufacturing a semiconductor device according to the second embodiment, (a) resin formation (lamination, spin coating, etc.), (b) exposure, (c) development, (d) glass sealing, (e) resin curing, and (F) Each process of dicing is required. On the other hand, in the manufacturing method of the semiconductor device according to the first embodiment, since the formation of the rib (frame-shaped adhesive) is unnecessary by using the resin composition according to the present embodiment, (b) exposure and (C) No development process is required. Thereby, after forming a resin layer on a semiconductor substrate, it can seal with a transparent base material (glass base material etc.) immediately. Then, it can be separated into pieces by dicing or the like.

  FIG. 7 is a cross-sectional view illustrating an example of a semiconductor device (backside illumination type solid-state imaging device) having a cavity structure. In FIG. 7, a cavity 9 a surrounded by the glass substrate 4 and the frame-like member 9 exists on the silicon substrate 5. In the cavity structure, an adhesive is formed into a frame shape using photolithography, a printing method, a dispensing method or the like, and then the glass substrate 4 and the silicon substrate 5 are bonded via the obtained frame-shaped member 9. Therefore, the cavity structure does not require a sealing material as in the present embodiment, but requires a frame-like adhesive.

  The non-cavity structure has the following advantages compared to the cavity structure.

  In the cavity structure, foreign matter adhering to a microlens, a glass substrate, or the like also causes deterioration in image quality. This is because the cavity is exposed between the formation of the adhesive and the bonding of the glass substrate. On the other hand, in the non-cavity structure of the present embodiment, since the exposed time is small, the adhesion of foreign matters is reduced.

  In the non-cavity structure, the bonding area between the resin layer and the glass substrate is wide. Therefore, in the non-cavity structure of the present embodiment, compared with the cavity structure in which the glass substrate is bonded only by the frame-shaped resin layer, there is less variation in stress in the element due to the adhesive, and the adhesive is peeled off, deformed, etc. Is reduced.

  Although the embodiment has been described above, the present invention is not limited to the embodiment. For example, with regard to each of the above embodiments, a form in which a person skilled in the art appropriately added, deleted, or changed a design, or a form in which a process has been added, omitted, or changed in conditions does not contradict the spirit of the present invention. As long as it is within the scope of the present invention. For example, in the said embodiment, although the example which uses a glass base material as a transparent base material was shown, this invention is not limited to this, If it is a transparent base material which comprises required intensity | strength, rigidity, and light transmittance Good.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

<Preparation of components contained in resin composition>
The following ingredients were prepared.

((Meth) acrylic polymer)
A (meth) acrylic polymer (a1) was synthesized by the following procedure.

Acrylic acid tricyclo [5.2.1.0 ^2,6 ] dec-8-yl (FA-513A, Hitachi Chemical Co., Ltd., trade name) 300 g, butyl acrylate (BA) 350 g, butyl methacrylate (BMA) 300 g Then, 50 g of glycidyl methacrylate (GMA) and 50 g of 2-ethylhexyl methacrylate (2EHMA) were mixed to obtain a monomer mixture. 5 g of dilauroyl peroxide and 0.45 g of n-octyl mercaptan (chain transfer agent) were dissolved in the obtained monomer mixture to obtain a mixed solution.

Polyvinyl alcohol (suspending agent) 0.44 g and ion-exchanged water 2000 g were added to a 5 L autoclave equipped with a stirrer and a condenser. Next, the mixed solution was added while stirring, and polymerization was performed at 60 ° C. for 5 hours under a stirring rotation speed of 250 min ^{−1 in} a nitrogen atmosphere. Next, polymerization was performed at 90 ° C. for 2 hours to obtain resin particles (polymerization rate was 99% by mass method). The resin particles were washed with water, dehydrated and dried to obtain a (meth) acrylic polymer (a1). The weight average molecular weight of the obtained (meth) acrylic polymer (a1) was 480,000.

The weight average molecular weight of the (meth) acrylic polymer (a1) was converted from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). The calibration curve was approximated by a cubic equation using a standard polystyrene kit PStQuick series C (Tosoh Corporation, trade name). The GPC conditions are shown below.
Pump: L6000 Pump (Hitachi, Ltd.)
Detector: L3300 RI Monitor (Hitachi, Ltd.)
Column: Gelpack GL-S300MDT-5 (two in total) (Hitachi Chemical Co., Ltd., trade name)
Column size: Diameter 8mm x 300mm
Eluent: DMF / THF (mass ratio 1/1) + LiBr · H ₂ O 0.03 mol / L + H ₃ PO ₄ 0.06 mol / L
Sample concentration: 0.1% by mass
Flow rate: 1 mL / min
Measurement temperature: 40 ° C

(Bifunctional (meth) acrylic monomer)
R-604: Nippon Kayaku Co., Ltd., trade name “KAYARAD R-604”, dioxane glycol diacrylate

(Polymerization initiator)
Park Mill D: NOF Corporation, trade name “Park Mill D”, thermal polymerization initiator, dicumyl peroxide, 1 hour half-life temperature 135.7 ° C., 10 hour half-life temperature 116.4 ° C.

(Absorbing material)
UV absorber

(Antioxidant)
AO-80: ADEKA Corporation, trade name “ADEKA STAB AO-80”, hindered phenol antioxidant, bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] (2 , 4,8,10-tetraoxaspiro [5.5] undecane-3,9-diyl) bis (2,2-dimethyl-2,1-ethanediyl AO-503: ADEKA Corporation, trade name “ADK STAB AO-” 503 ", thioether-based antioxidant, ditridecyl 3,3-thiobispropionate MT-PE1: Showa Denko K.K., trade name" Karenz MT-PE1 ", pentaerythritol tetrakis (3-mercaptobutyrate)

(Other)
ACMO: KJ Chemicals Co., Ltd., trade name “ACMO”, acryloylmorpholine, monofunctional (meth) acrylic monomer SZ-6030: Toray Dow Corning Co., Ltd., trade name “SZ-6030”, γ-methacryloyloxypropyltri Methoxysilane, coupling agent PGMEA: Kanto Chemical Co., Inc., propylene glycol 1-monomethyl ether 2-acetate, organic solvent

<Preparation of resin composition>
200 parts by weight of (meth) acrylic polymer (a1), 160 parts by weight of R-604, 4 parts by weight of Park Mill D, 5 parts by weight of AO-80, 1 part by weight of AO-503, 1 part by mass of MT-PE1, 40 parts by mass of ACMO, 4 parts by mass of SZ-6030, and 400 parts by mass of PGMEA were mixed, and then the ultraviolet absorber was mixed, and the usage amounts shown in Table 1 The resin composition of the Example and comparative example containing the ultraviolet absorber of this was obtained.

<Evaluation>
After apply | coating the resin composition of an Example and a comparative example on a glass base material, it dried at 70 degreeC / 10 minutes and 100 degreeC / 10 minutes, and produced the film-form resin film of film thickness 150 micrometers. Next, a cured film was obtained by performing a heat treatment at 200 ° C./2 hours under vacuum to cure the resin film. Thereafter, the transmittance (spectral spectrum) of the cured film at 25 ° C. was measured. Specifically, using a spectrophotometer U4100 (trade name, Hitachi, Ltd., start 800 nm, end 300 nm, scan speed 600 nm / min, sampling interval 1.0 nm, baseline: Air), a wavelength range of 300 to 800 nm. Then, the transmittance was measured to obtain light transmittance at wavelengths of 350 nm and 430 nm. The measurement results are shown in Table 1.

  According to Table 1, in the Example, it was confirmed that the hardened | cured material which has the low light transmittance of wavelength 350nm and the high light transmittance of wavelength 430nm is obtained.

DESCRIPTION OF SYMBOLS 1a, 1b ... CMOS image sensor (semiconductor device), 2 ... Micro lens, 2a ... Photodiode, 2b ... Color filter, 3a ... Sensor part, 3b ... Peripheral circuit part, 4 ... Glass substrate (transparent base material), 5 ... Silicon substrate (semiconductor substrate), 6a, 6b, 30, 30a ... resin layer, 7 ... wiring layer, 8 ... solder ball, 9 ... frame member, 9a ... cavity, 10 ... support substrate, 15 ... wire, 20 ... Semiconductor substrate, 40 ... transparent substrate, 100 ... semiconductor device.

Claims (4)

(A) a (meth) acrylic polymer, (b) a compound having at least two (meth) acryloyl groups, (c) a polymerization initiator, and (d) an ultraviolet absorber,
The resin composition whose content of the said (d) component is 0.002-0.04 mass%.   A cured product of the resin composition according to claim 1.   A method for manufacturing a semiconductor device, comprising: a step of curing the resin layer in a state where a resin layer containing the resin composition according to claim 1 is disposed between a semiconductor substrate and a transparent base material. A semiconductor substrate, a transparent base, and a resin layer disposed between the semiconductor substrate and the transparent base,
The semiconductor device in which the said resin layer contains the resin composition of Claim 1, or its hardened | cured material.