JP7176229B2 - Resin composition, cured product, semiconductor device and manufacturing method thereof - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition, a cured product, a semiconductor device, and a method for producing the same.

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 becoming smaller and less power-consuming. In addition, CMOS (Complementary Metal Oxide Semiconductor) image sensors are being used. These image sensors include a sensor section (imaging pixel section) in which a plurality of pixels are two-dimensionally arranged on one semiconductor chip, and a peripheral circuit section arranged outside the sensor section.

As a structure of a CMOS image sensor, a "front side illumination type" structure and a "back side illumination type" structure are known (see, for example, 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, is collected by the microlens, and then passes through the color filter layer and the It passes through the wiring layer and enters the photodiode. The light incident on the photodiode is photoelectrically converted to generate a signal charge, and an electric signal is generated from the signal charge to obtain image data.

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 microlenses are arranged on this one surface. A glass substrate is placed above the microlenses via an adhesive layer and a cavity. On the other hand, a wiring layer is arranged 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 part without passing through the wiring layer, thereby avoiding attenuation of the light by the wiring layer and increasing the light-receiving sensitivity.

In addition, as the structure of the back-illuminated CMOS image sensor, on a silicon substrate provided with microlenses, an adhesive layer is arranged on the outer peripheral side so as not to cover the microlenses, and an adhesive layer is surrounded by the adhesive layer. A structure is known 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-A-2005-142221 Japanese Patent Application Laid-Open No. 2010-40621

By the way, it is preferable that the spectral sensitivity of semiconductor devices such as CCD image sensors and CMOS image sensors 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 in the vicinity of the wavelength of 430 nm is high. High transmittance is preferred. Therefore, a curable resin composition for obtaining a constituent member of a semiconductor device is required to obtain a cured product having such spectral sensitivity.

The present invention has been made in view of the above circumstances, and provides a resin composition capable of obtaining 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, and a cured product thereof. intended to provide Another object of the present invention is to provide a semiconductor device using the resin composition and a method for manufacturing the same.

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) and a UV absorber, and the content of the component (d) is 0.002 to 0.04% by 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 the cured product of the resin composition described above.

One aspect of the method for manufacturing a semiconductor device according to the present invention includes a step of curing the resin layer containing the above-described resin composition while the resin layer is disposed between the semiconductor substrate and the transparent substrate.

One aspect of the semiconductor device according to the present invention comprises a semiconductor substrate, a transparent substrate, and a resin layer disposed between the semiconductor substrate and the transparent substrate, wherein the resin layer comprises the resin composition described above. Or including its cured product.

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

The resin composition and its cured product according to the present invention have a member arranged on the outer peripheral side of the substrate so as not to cover the microlens, and the resin composition is placed in a cavity surrounded by the member. Alternatively, it can be used for both a configuration in which the cured product is filled and a configuration in which a resin layer formed from a resin composition is formed on the entire surface of the substrate.

INDUSTRIAL APPLICABILITY According to the present invention, use of a resin composition for semiconductor devices or their manufacture can be provided. INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide the use of a resin composition for optical components or their manufacture. INDUSTRIAL APPLICABILITY According to the present invention, use of a resin composition for a solid-state imaging device or its manufacture can be provided. INDUSTRIAL APPLICABILITY According to the present invention, use of a cured product of a resin composition for a semiconductor device can be provided. INDUSTRIAL APPLICABILITY According to the present invention, use of a cured product of a resin composition for optical parts can be provided. INDUSTRIAL APPLICABILITY According to the present invention, use of a cured product of a resin composition for a solid-state imaging device 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. 1 is a plan view showing an example of a semiconductor device; FIG. 4 is a cross-sectional view taken along line A-A' shown in FIG. 3; FIG. FIG. 10 is a cross-sectional view showing another example of a semiconductor device; It is drawing for comparing the manufacturing method of a semiconductor device. 1 is a cross-sectional view showing an example of a semiconductor device having a cavity structure; FIG.

Embodiments of the present invention will be described below, but the present invention is not limited to these embodiments.

As used herein, a "(meth)acryloyl group" means at least one of an "acryloyl group" and a "methacryloyl group" corresponding thereto. The same applies to other similar expressions such as "(meth)acrylate". A numerical range indicated using "-" indicates a range including the numerical values before and after "-" as the minimum and maximum values, respectively. In the numerical ranges described stepwise in this specification, the upper limit value or lower limit value of the numerical range at one step may be replaced with the upper limit value or lower limit value of the numerical range at another step. In the numerical ranges described herein, the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples. The terms "layer" and "film" include not only a shape structure formed over the entire surface but also a shape structure formed partially when viewed as a plan view. The term "process" includes not only an independent process, but also a process that is indistinguishable from other processes, provided that the intended purpose of the process is achieved. "A or B" may include either A or B, or 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 otherwise specified when there are multiple substances corresponding to each component in the composition. The materials exemplified in this 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 comprises (a) a (meth)acrylic polymer (hereinafter sometimes referred to as “(a) component”) and (b) a compound having at least two (meth)acryloyl groups (hereinafter , sometimes referred to as "(b) component"), (c) a polymerization initiator (hereinafter sometimes referred to as "(c) component"), and (d) an ultraviolet absorber (hereinafter sometimes referred to as "(d) component ”), and the content of component (d) is 0.002 to 0.04% by mass based on the total amount of the resin composition (total solid content). The resin composition according to this embodiment is a curable (for example, thermosetting) resin composition. The cured product according to this embodiment is a cured product of the resin composition according to this embodiment.

According to the resin composition according to the present embodiment, since the resin composition contains a specific amount of component (d) in addition to components (a) to (c), low light transmittance at a wavelength of 350 nm, And, a cured product having a high light transmittance at 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 preferably 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 the present embodiment may be liquid (varnish) or film. The resin composition according to the present embodiment can be used as a resin composition for semiconductor devices, and can be used as a resin composition for optical parts, for example.

(Component (a): (meth)acrylic polymer)
"(Meth)acrylic polymer" means a polymer having a structural unit derived from a monomer having a (meth)acryloyl group ((meth)acrylic monomer), for example, a (meth)acryloyl group A polymer (homopolymer) having a structure obtained by polymerizing one type of (meth)acrylic monomer in the molecule, and copolymerizing two or more types of the (meth)acrylic monomers in combination. A polymer (copolymer) having a structure obtained by and a polymer (copolymer) having a structure obtained by copolymerizing the (meth)acrylic monomer and another monomer. be done. The (meth) monomer copolymerizable with the acrylic monomer includes (meth) compounds having two or more acryloyl groups in one molecule; having one polymerizable unsaturated bond in one molecule, And polymerizable compounds having no (meth)acryloyl group (e.g., (meth)acrylonitrile, styrene, vinyl acetate and alkenes (ethylene, propylene, etc.)); two or more polymerizable unsaturated bonds in one molecule and polymerizable compounds (divinylbenzene, etc.) that do not have a (meth)acryloyl group. (a) Component can be used individually by 1 type or in combination of 2 or more types.

Component (a) has one (meth)acryloyl group in one molecule, based on the total amount of 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 preferably contains 30 to 100% by mass, more preferably 50 to 100% by mass, of structural units derived from (meth)acrylic monomers.

Component (a) preferably has a functional group, for example, preferably has a structural unit having a functional group. In these cases, excellent stress relaxation properties, reflow resistance to peeling, crack resistance, adhesiveness and heat resistance associated with a low elastic modulus can be easily exhibited. 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. As the functional group, an epoxy group is preferred. Since component (a) has an epoxy group, it is possible to improve the adhesion of inorganic materials such as metals and glass to substrates.

The method of 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, for example, by an existing method as described in WO 2015/115537 can be done. Among them, suspension polymerization is preferable from the viewpoint of enabling high molecular weight at low cost.

Suspension polymerization is carried out in an aqueous solvent with the addition of a suspending agent. As the suspending agent, it is preferable to use a nonionic water-soluble polymer from the viewpoint of low possibility of ionic impurities remaining in the obtained (meth)acrylic polymer. The amount of the water-soluble polymer used is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the total amount of monomers.

In the polymerization reaction, generally used polymerization initiators, chain transfer agents and the like may be used. Examples of the polymerization initiator include compounds similar to the polymerization initiator (c) described later. Chain transfer agents include thiols such as n-octylmercaptan.

The functional group-containing monomer has, in one molecule, 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. and at least one polymerizable carbon-carbon double bond.

From the viewpoint of easily avoiding problems such as gelation in the varnish state, clogging of nozzles during use, and pinhole generation during spin coating, the functional groups include an amino group, an amide group, a phosphoric acid group, a cyano group, It is preferably at least one selected from the group consisting of maleimide groups and epoxy groups. Moreover, 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 coloration. Furthermore, from both of these points of view, the functional group is more preferably at least one selected from the group consisting of a phosphoric acid group and an epoxy group, and more preferably an epoxy group.

Examples of functional group-containing monomers include carboxyl group-containing monomers; acid anhydride group-containing monomers; hydroxyl group-containing monomers; phosphate group-containing monomers; vinyl cyanide compounds; N-substituted maleimides; epoxy group-containing monomers and the like. The functional group-containing monomers can be used singly or in combination of two or more.

Among these, it is particularly preferable to use epoxy group-containing monomers such as glycidyl (meth)acrylate. Furthermore, the (meth)acrylic polymer (e.g., glycidyl group-containing (meth)acrylic polymer) obtained by using such a monomer is compatible with the (meth)acrylic monomer or oligomer. is preferred. A glycidyl group-containing (meth)acrylic polymer may be synthesized by a conventional method, or a commercially available product may be obtained. Commercially available products include HTR-860P-3 (trade name, Nagase ChemteX Corporation). Such a (meth)acrylic polymer is preferable from the viewpoint of easily exhibiting excellent crack resistance, adhesiveness 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 ensuring adhesive strength and easily preventing gelation. The content of the structural unit having the functional group is preferably 0.5% by mass or more, more preferably 0.8% by mass or more, still more preferably 1.0% by mass or more, and particularly preferably 2.0% by mass or more. , 3.0% by mass or more is extremely preferred. The content of the structural unit having the 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 points of view, the content of the structural unit having the functional group is preferably 0.5 to 20% by mass.

Component (a) may have a structural unit having a nitrogen atom-containing group. The content of structural units having a nitrogen atom-containing group in component (a) is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less, based on the total amount of component (a). . It is particularly preferred that component (a) does not contain 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. Further, the structural unit having a nitrogen atom-containing group includes, among the functional group-containing monomers listed above, a structural unit derived from a monomer containing a nitrogen atom, and the like. Examples include structural units derived from vinyl compounds.

Examples of monomers other than functional group-containing monomers that can be used when synthesizing the component (a) include (meth)acrylic acid esters; aromatic 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 facilitating synthesis of 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, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate are preferred from the viewpoint of excellent copolymerizability with functional group-containing monomers. At least one selected from the group consisting of is more preferable.

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. Since the component (a) has an alicyclic structure, the amount of amorphous components in the (meth)acrylic polymer increases, which tends to increase the transparency. In addition, when compared with an aliphatic structure having the same number of carbon atoms (such as an aliphatic structural unit), the glass transition temperature (Tg) tends to be improved and the heat resistance tends to be high.

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 monomers having an alicyclic structure or heterocyclic structure used in producing a (meth)acrylic polymer having a structural unit having an alicyclic structure or heterocyclic structure include the following general Compounds represented by Formula (1) are included.

［式（１）中、Ｒ^１は水素原子又はメチル基を示し、Ｒ^２は脂環基又は複素環基を示し、Ｘは炭素数１～６のアルキレン基を示し、ｎは０～１０の整数を示す。ｎが２以上の整数であるとき、複数存在するＸは互いに同一であっても異なっていてもよい。ここで「脂環基」とは、炭素原子が環状に結合した構造を有する基であり、「複素環基」とは、炭素原子及び１以上のヘテロ原子が環状に結合した構造を有する基である。］

[In the 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, multiple X's may be the same or different. Here, the “alicyclic group” is a group having a structure in which carbon atoms are cyclically bonded, and the “heterocyclic group” is a group having a structure in which a carbon atom and one or more heteroatoms are cyclically bonded. be. ]

［式中、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０はそれぞれ独立に、水素原子又は炭素数１～４のアルキル基を示し、Ｒ^１１は水素原子、炭素数１～４のアルキル基、又は、ＯＲ^１１ａで示される構造を示し、Ｒ^１１ａは水素原子又は炭素数１～８のアルキル基を示す。］ Examples of R ² include groups represented by the following formulas (2a) to (2h).

[In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or an alkyl group having ¹ to 4 carbon atoms; an atom, an alkyl group having 1 to 4 carbon atoms, or a structure represented by OR ^11a , where R ^11a represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]

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

The content of these monomers other than the functional group-containing monomer is preferably adjusted so that the Tg of component (a) is in the range of -50 to 50°C. For example, as monomers, 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 can be used. The (a) component, 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 monomers are used in combination, the mixing ratio is determined in consideration of the Tg of the (meth)acrylic polymer, and the Tg of 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 point of view, 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 , preferably 100:0 to 0.1:99.9, more preferably 100:0 to 1:99, even more preferably 50:50 to 1:99, 30:70 to 1:99 is particularly preferred, and 20:80 to 1:99 is very particularly preferred.

Component (a) is selected from the group consisting 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). It may have at least one selected.

［式（Ｉ）中、Ｒ^１ａは、水素原子又はメチル基を示し、Ｘ^ａは、エポキシ基を含む基を示す。］

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

［式（ＩＩ）中、Ｒ^２ａは、水素原子又はメチル基を示し、Ｙ^ａは、置換基を有していてもよい炭素数５～２２の脂環基（式（Ｉ）のＸに該当する基を除く）を示す。］

[In formula (II), R ^2a represents a hydrogen atom or a methyl group, Y ^a represents an optionally substituted alicyclic group having 5 to 22 carbon atoms (corresponding to X in formula (I) excluding the group that does). ]

［式（ＩＩＩ）中、Ｒ^３ａは、水素原子又はメチル基を示し、Ｚ^ａは、置換基を有していてもよい炭素数１～１０の直鎖又は分岐アルキル基（式（Ｉ）のＸに該当する基を除く）を示す。］

[In formula (III), R ^3a represents a hydrogen atom or a methyl group, and Z ^a represents an optionally substituted linear or branched alkyl group having 1 to 10 carbon atoms (of formula (I) excluding groups corresponding to X). ]

When a (meth)acrylic polymer (for example, a (meth)acrylic polymer having a structural unit having a functional group) is produced by polymerizing a monomer, the polymerization method may be solution polymerization or suspension polymerization (Pearl polymerization) can be used.

The weight-average molecular weight of the component (a) is such that the strength, flexibility, and tackiness after film formation are suitable, and the flowability is suitable, so that the circuit filling property of the wiring can be easily ensured. is preferred. The weight-average molecular weight of the component (a) is preferably 100,000 or more, more preferably 120,000 or more, and even more preferably 200,000 or more, from the viewpoint of being able to maintain a sufficient elastic modulus (e.g., elastic modulus at 260°C). , 300,000 or more are particularly preferred, 400,000 or more are extremely preferred, and 450,000 or more are very preferred. The weight average molecular weight of 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 points of view, the weight average molecular weight of component (a) is preferably 100,000 to 3,000,000. The weight-average molecular weight is measured by gel permeation chromatography (GPC) as described in Examples and converted using a standard polystyrene calibration curve.

The total content of component (a) is 100 parts by mass from the viewpoint of exhibiting a good storage elastic modulus, suppressing flow during molding, and obtaining sufficient handleability at high temperatures. In contrast, the following range is preferable. The content of component (a) is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, still more preferably 20 parts by mass or more, particularly preferably 50 parts by mass or more, extremely preferably 75 parts by mass or more, and 100 parts by mass. Part or more is highly preferred. The content of component (a) is preferably 400 parts by mass or less, more preferably 350 parts by mass or less, even more preferably 300 parts by mass or less, particularly preferably 200 parts by mass or less, and extremely preferably 150 parts by mass or less. From these points of view, the content of component (a) is preferably 10 to 400 parts by mass.

(Component (b): a compound having at least two (meth)acryloyl groups)
In the resin composition according to the present embodiment, the compatibility between the component (a) and the component (b) is high, and the refractive indices of these components tend to be close to each other. transparency can be obtained. Furthermore, since the compatibility is high as described above, phase separation is unlikely to occur in the varnish state or the semi-cured state, and the storage stability is also excellent. In addition, even if phase separation occurs due to the heat of curing after radical curing, the phase separation remains microscopic, and variations in cured product properties such as visibility and adhesive strength can be suppressed. The problem of optical loss can also be solved by filling the cavity with the resin composition according to the present embodiment.

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

Monomers having at least two (meth)acryloyl groups include polyfunctional (meth)acrylic monomers having an alicyclic structure, polyfunctional (meth)acrylic monomers having an aliphatic structure, and dioxane glycol structures. and polyfunctional (meth)acrylic monomers having functional groups (excluding (meth)acryloyl groups). Polyfunctional (meth)acrylic monomers having functional groups exclude polyfunctional (meth)acrylic monomers having an alicyclic structure, an aliphatic structure or a dioxane glycol structure. The term "polyfunctional" as used herein refers to (meth)acryloyl groups, and means having at least two (meth)acryloyl groups in the compound.

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

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. Component (b) is preferably a polyfunctional (meth)acrylic monomer having an aliphatic structure from the viewpoint of facilitating prevention of cracks in the cured product and separation from the substrate.

Examples of polyfunctional (meth)acrylic monomers include (meth)acrylic monomers having two (meth)acryloyl groups.

Examples of (meth)acrylic monomers having two (meth)acryloyl groups include cyclohexane-1,4-dimethanol di(meth)acrylate, cyclohexane-1,3-dimethanol di(meth)acrylate, tricyclodecanedimethylol di( meth) acrylate (e.g., Nippon Kayaku Co., Ltd., KAYARAD R-684, tricyclodecanedimethanol diacrylate), tricyclodecanedimethanol di(meth)acrylate (e.g., 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 glycol 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, neopentyl glycol hydroxypivalate 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 5 to 15 mol of ethylene oxide modified bisphenol A-type di(meth)acrylate); ) acrylate), (poly)ethylene oxide-modified phosphate di(meth)acrylate, and the like.

Among the above, at least selected from the group consisting of dioxane glycol di(meth)acrylate and tricyclodecanedimethanol 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 preferred, and at least one selected from the group consisting of dioxane glycol diacrylate and tricyclodecanedimethanol diacrylate is more preferred.

Examples of polyfunctional (meth)acrylic monomers other than the above include (meth)acryloyl groups having three (meth)acryloyl groups, such as pentaerythritol tri(meth)acrylate and ethylene oxide-modified isocyanuric acid tri(meth)acrylate. Acrylic monomers may be mentioned.

The content of component (b) is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and even more preferably 40 parts by mass or more with respect to 100 parts by mass as the total of components (a) and (b). The content of component (b) is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, and even more preferably 60 parts by mass or less with respect to 100 parts by mass as the total amount of components (a) and (b). 50 parts by mass or less is particularly preferred. The content of component (b) is preferably 20 to 80 parts by mass with respect to 100 parts by mass as the total of components (a) and (b). When the content of the component (b) is in each of the ranges described above, three-dimensional cross-linking is likely to occur, and the heat resistance tends to be further improved. Moreover, even if phase separation occurs after curing, the range of phase separation can be limited to a microscale. Therefore, variations in cured product properties such as visibility and adhesive strength can be easily suppressed, and warping or cracking in the manufacturing process of semiconductors or electronic parts can be easily suppressed.

((c) component: polymerization initiator)
As the component (c), for example, (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.

Component (c1) includes organic peroxides and azo compounds, as exemplified in International Publication No. 2015/115537.

(c1) component can be used individually by 1 type or in combination of 2 or more types.

Among the components (c1), organic peroxides are 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. Organic peroxides having a 10-hour half-life temperature of 90 to 150° C. are more preferable from the viewpoint of maintaining a good balance with curability. In addition, the half-life temperature of the organic peroxide can be measured by the method described in International Publication No. 2015/115537.

Among the above-mentioned component (c1), from the viewpoint of excellent storage stability and thermosetting properties, dicumyl peroxide (for example, manufactured by NOF Corporation, trade name: Permil D), and at least one selected from the group consisting of n-butyl 4,4-bis(t-butylperoxy)valerate (eg NOF Corporation, trade name: Perhexa V).

Component (c1), in combination with components (a) and (b), tends to exhibit excellent heat resistance, peeling resistance and stress relaxation, and can improve the reliability of semiconductor devices (optical components, etc.). can.

The content of the component (c1) is determined 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 from the viewpoint of easily suppressing the generation of outgassing. The following range is preferable with respect to 100 parts by mass of the total amount of The content of component (c1) is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, still more preferably 0.5 parts by mass or more, and particularly preferably 1 part by mass or more. The content of component (c1) is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, particularly preferably 5 parts by mass or less, extremely preferably 3 parts by mass or less, and 2 parts by mass. Part or less is highly preferred. From these points of view, the content of component (c1) is preferably 0.1 to 30 parts by mass.

(c2) components include acylphosphine oxides, oxime esters, aromatic ketones, quinones, benzoin ether compounds, benzyl derivatives, 2,4,5-triarylimidazole dimers, acridine derivatives, coumarin compounds, Examples include N-phenylglycine and N-phenylglycine derivatives. Component (c2) may be synthesized by a conventional method, or may be commercially available.

Among these, it is selected from the group consisting of acylphosphine oxides and oxime esters from the viewpoint of improving the photocurability, the viewpoint of increasing sensitivity, and the viewpoint that the cured product (cured film, etc.) tends to have excellent transparency. At least one is preferred.

(c2) component can be used individually by 1 type or in combination of 2 or more types.

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

Examples of oxime esters include 1,2-octanedione-1-[4-(phenylthio)phenyl-2-(O-benzoyloxime)] (eg, IRGACURE-OXE01, BASF, 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] (eg, Quantacure-PDO, trade name of Nippon Kayaku Co., Ltd.), and the like.

Aromatic ketones include, for example, compounds described in WO2015/115537.

Examples of quinones include compounds described in International Publication No. 2015/115537.

Benzoin ether compounds include benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether and the like.

Benzyl derivatives include benzoin compounds such as benzoin, methylbenzoin and ethylbenzoin; benzyl dimethyl ketal and the like.

Examples of 2,4,5-triarylimidazole dimers include compounds described in WO 2015/115537.

Acridine derivatives include 9-phenylacridine, 1,7-bis(9,9'-acridinyl)heptane and the like.

Coumarin compounds include, for example, compounds described in International Publication No. 2015/115537.

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 component (c2) is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, more preferably 0.5 to 10 parts by mass, based on 100 parts by mass as the total of components (a) and (b). 75 to 5 parts by mass is more preferable. When the content of component (c2) is within these ranges, foaming, turbidity, coloration and cracking of the cured product can be highly prevented.

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

The content of component (d) is 0.002% by mass or more based on the total amount of the resin composition (total solid content) from the viewpoint of obtaining 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 the 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. 0.005% by mass or more is more preferable, 0.007% by mass or more is still more 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 preferable. is very preferred, and 0.025% by mass or more is even more preferred.

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

The content of component (d) is preferably within the following ranges per 100 parts by mass of component (a). The content of 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 weight or more are more preferred, 0.03 parts by weight or more are particularly preferred, 0.04 parts by weight or more are extremely preferred, 0.05 parts by weight or more are very preferred, and 0.06 parts by weight or more are even more preferred. . 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, and 0.1 part by mass or less. 04 parts by weight or less is extremely preferred, 0.03 parts by weight or less is very preferred, and 0.025 parts by weight or less is even more preferred. From these points of view, the content of component (d) is preferably 0.005 to 0.1 part by mass.

The content of component (d) is preferably in the following range with respect to 100 parts by mass of the total amount of components (a) and (b). The content of 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. 0.01 parts by weight or more are more preferred, 0.015 parts by weight or more are particularly preferred, 0.02 parts by weight or more are extremely preferred, 0.025 parts by weight or more are very preferred, and 0.03 parts by weight or more are even more preferred. . 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 weight or less is extremely preferred, 0.02 parts by weight or less is very preferred, and 0.015 parts by weight or less is even more preferred. From these points of view, the content of component (d) is preferably 0.002 to 0.05 parts by mass.

(Antioxidant)
The resin composition according to this embodiment can contain an antioxidant. When the resin composition according to the present invention contains an antioxidant, coloration due to degradation of the resin composition during heat is suppressed, and transparency during heat is easily improved. Antioxidants include phenol antioxidants, thioether antioxidants, thiol antioxidants, and the like. An antioxidant can be used individually by 1 type or in combination of 2 or more types.

Phenolic antioxidants include hindered phenolic compounds and the like. Examples of the hindered phenol compound include compounds described in WO 2015/046422, specifically 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) and the like.

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

The content of the antioxidant is selected from the viewpoints that it is easy to obtain a low light transmittance at a wavelength of 350 nm and a high light transmittance at a wavelength of 430 nm, and from the viewpoint that the radical polymerization reactivity is less likely to be adversely affected. The following range is preferable with respect to 100 parts by mass of the total amount of 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 points of view, the content of the antioxidant is preferably 0.01 to 10 parts by mass.

(coupling agent)
The resin composition according to this embodiment can contain a coupling agent. As the coupling agent, various coupling agents such as silane coupling agents, titanate coupling agents, aluminum coupling agents, zirconate coupling agents, and zircoaluminate coupling agents 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. Silane coupling agents include, for example, vinyl groups, epoxy groups, styryl groups, (meth)acryl groups, amino groups, isocyanurate groups, ureido groups, mercapto groups, and at least one selected from the group consisting of isocyanate groups. 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-based coupling agents include compounds exemplified in International Publication No. 2015/115537.

Examples of aluminum-based coupling agents include acetoalkoxyaluminum diisopropionate.

Zirconate-based coupling agents include tetrapropyl zirconate, tetrabutyl zirconate, tetra(triethanolamine) zirconate, tetraisopropyl zirconate, zirconium acetylacetonate, acetylacetone zirconium butyrate, zirconium stearate butyrate, and the like. .

［式（３）中、Ｒ^１２はカルボキシル基又はアミノ基を示す。］ Examples of the zircoaluminate-based coupling agent include compounds represented by the following general formula (3).

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

Examples of compounds in which R ¹² is a carboxyl group include Manschem CPG-carboxyzylcoaluminate. Compounds in which R ¹² is an amino group include Manshem APO-X-aminozircoaluminate solution and the like. Each available from Rhone-Poulenc.

Among these coupling agents, a silane coupling agent is preferable, and a silane coupling agent having a (meth)acrylic group is more preferable, from the viewpoint of improving the bonding or wettability of the interface between materials. At least one selected from the group consisting of methacryloxypropyltrimethoxysilane (alias: 3-(trimethoxysilyl)propyl methacrylate), γ-methacryloxypropylmethyldimethoxysilane, and γ-acryloxypropyltrimethoxysilane More preferred.

The content of the coupling agent is preferably within the following ranges per 100 parts by mass of the total amount of components (a), (b) and (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 further preferably 0.8 parts by mass or more, from the viewpoint that the effect of improving the adhesive strength tends to be obtained. Preferably, 1 part by mass or more is particularly preferable. The content of the coupling agent is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, more preferably 10 parts by mass, from the viewpoint that the volatile content is small and the 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 points of view, the content of the coupling agent is preferably 0.1 to 20 parts by mass.

(organic solvent)
The resin composition according to this embodiment can contain an organic solvent. A varnish-like resin composition can be obtained by dissolving or dispersing the components in an organic solvent. By using the varnish-like resin composition, the coatability to the substrate is improved and the workability is good.

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 conventionally known solvents can be used. Examples of the organic solvent include alcohol-based, ether-based, ketone-based, amide-based, aromatic hydrocarbon-based, ester-based, and nitrile-based solvents. Specific examples of the organic solvent include low boiling point solvents (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 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 high drying rate.

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

(other ingredients)
In addition to the component (b), the resin composition according to the present embodiment contains a monofunctional (meth)acrylic monomer (a compound having one (meth)acryloyl group. For example, one (meth)acryloyl group and a complex compound having a ring). The monofunctional (meth)acrylic monomer includes, for example, the (meth)acrylic monomers exemplified for the component (a) (glycidyl (meth)acrylate, etc.). A monofunctional (meth)acrylic monomer can be used individually by 1 type or in combination of 2 or more types.

The resin composition according to this embodiment may contain other additives. Additives include epoxy curing agents, epoxy curing accelerators, wetting agents (fluorosurfactants, nonionic surfactants, higher fatty acids, etc.), antifoaming agents (silicone oil, etc.), ion trapping agents (inorganic ion exchangers, etc.), refractive index modifiers, and other fillers (organic fillers, inorganic fillers, etc.). These additives can be used singly or in combination of two or more.

<Method for manufacturing a semiconductor device>
In the method for manufacturing a semiconductor device according to the present embodiment, the resin layer (adhesive layer) containing the resin composition according to the present embodiment is placed between a semiconductor substrate and a transparent substrate, and the resin layer is cured. (cured product forming step). 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 a step of curing the resin layer in a state of being arranged between the transparent base material (cured material forming step). A resin layer consists of the resin composition which concerns on this embodiment, for example. A transparent substrate (such as a glass substrate) is, for example, a transparent substrate (such as a glass substrate). The step of forming a cured product includes a step of sandwiching a resin layer between a semiconductor substrate and a transparent substrate, pressing the semiconductor substrate and the transparent substrate together (pressing step), and curing the resin layer (curing step). You may have The crimping step and the curing step do not necessarily have to be independent steps, and curing may be performed at the same time as crimping.

1 and 2 are process diagrams showing an example of the manufacturing method of the semiconductor device according to the present embodiment, and are process diagrams illustrating the manufacturing method using the dispensing method. First, as shown in FIG. 1A, a laminate including a supporting base 10 and a semiconductor substrate 20 mounted on the supporting base 10 is prepared. Terminals (not shown) of the support base 10 and the semiconductor substrate 20 are electrically connected by wires 15 . If the semiconductor device is a solid-state imaging device, for example, a light receiving section is arranged above the semiconductor substrate 20 . Next, as shown in FIG. 1(b), a resin composition is supplied onto the semiconductor substrate 20 by a dispensing method, and then the resin layer 30 is removed from the semiconductor substrate 20 by heating and drying as shown in FIG. 2(a). 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 semiconductor device 100 is obtained by curing the resin layer 30 to form a resin layer (cured product) 30a.

Each step will be further described below.

(Resin layer forming step)
As the resin layer forming step, for example, a method of applying the resin composition according to the present embodiment onto a semiconductor substrate or a method of attaching a film-like resin composition to the semiconductor substrate can be employed. The semiconductor substrate may be, for example, either a semiconductor wafer or a semiconductor element (semiconductor chip).

Methods for applying the resin composition include a dispensing method (such as a syringe dispensing method), a spin coating method, a die coating method, a knife coating method, and the like. When a method of attaching a film-shaped resin composition is employed, lamination is preferably performed at a temperature in the range of 0 to 90° C. in order to ensure sufficient wetting and spreading. Moreover, it is preferable to perform roll lamination in order to stick uniformly.

A method for producing a film-like resin composition will be described below. For example, the resin composition according to the present embodiment is uniformly applied on the support film, and the solvent used is sufficiently volatilized (for example, at a temperature of 60 to 200 ° C. for 0.1 to 30 minutes). to form a film-like resin composition. At this time, the amount of solvent, viscosity, and initial thickness of the resin composition (when using a coater such as a die coater or a comma coater, the coater and the support are adjusted so that the film-shaped resin composition has a desired thickness. Adjust the gap with the film), 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 is sometimes used to improve workability. Depending on the type and temperature of the smoothing agent, fine unevenness may be transferred to the adhesive, resulting in a decrease in flatness. Therefore, it is preferable to use a support film containing no smoothing agent or a support film containing a small amount of smoothing agent. From the viewpoint of excellent flexibility, a support film such as a polyethylene film is preferable, but the thickness and density of the support film are preferably selected appropriately so that roll marks and the like are not transferred to the surface of the resin layer during lamination.

(Crimping process)
Subsequently, the resin layer formed on the semiconductor substrate is dried by heating if necessary. The drying temperature is not particularly limited, but when a varnish-like resin composition is used by dissolving or dispersing the ingredients in a solvent, the drying temperature is from the viewpoint of easily suppressing 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 point of view, the drying temperature is more preferably 15 to 45°C lower than the boiling point of the solvent used, and still more preferably 20 to 40°C lower than the boiling point of the solvent used.

Further, when a varnish-like resin composition is used by dissolving or dispersing the components in a solvent, the residual amount of the solvent should be minimized from the viewpoint of easily suppressing the generation of air bubbles due to foaming of the solvent after curing. preferable.

The conditions for the heat drying are not particularly limited as long as the solvent used is sufficiently volatilized and the component (c) does not substantially generate radicals. It is carried out by heating for 0.1 to 90 minutes. The term "substantially does not generate radicals" means that radicals are not generated at all, or even if they are generated, the amount is very small. However, it is a condition that does not affect the physical properties of the resin layer. Moreover, from the viewpoint of reducing the residual amount of the solvent while suppressing radical generation from the component (c) due to heating, it is preferable to dry under reduced pressure conditions.

From the viewpoint of easily suppressing peeling of the resin layer during solder reflow due to foaming during heat curing of the resin layer, volatile components present inside or on the surface of the resin layer (residual solvent, low molecular weight impurities, reaction products, decomposition It is preferable to sufficiently reduce water content derived from products, materials, surface adsorbed water, etc.).

After drying by heating, a transparent substrate is press-bonded onto the resin layer. The heat drying can be omitted when a method of attaching a film-shaped resin composition is employed in the resin layer forming step.

(Curing process)
After the semiconductor substrate and the transparent substrate are pressure-bonded with the resin layer interposed therebetween, the resin layer is cured to form a cured product. Examples of the curing method include a method of curing by heat and/or light, and curing by heat is particularly preferred.

In the curing step of forming a cured product of the resin layer, it is preferable to select a temperature and perform heat curing (cure) for 1 to 2 hours while gradually increasing the temperature. Thermal curing is preferably carried out at 100-200°C.

<Semiconductor device>
A semiconductor device according to this 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 this embodiment includes a semiconductor substrate, a resin layer (adhesive layer) disposed on the semiconductor substrate, a transparent base material adhered to the semiconductor substrate via the resin layer, Prepare. The resin layer contains the resin composition according to the present embodiment or a cured product thereof. The transparent base material is arranged on the semiconductor substrate via a resin layer, for example.

Examples of semiconductor devices include optical components. Optical components include, for example, optical devices such as solid-state imaging devices. Solid-state imaging devices include CCD image sensors, CMOS image sensors (for example, backside illumination CMOS image sensors), and the like. A CMOS image sensor, which is an example of the semiconductor device according to this embodiment, is incorporated in, for example, a mobile phone. In this case, the CMOS image sensor is mounted on the motherboard of the mobile phone via solder balls, and an optical lens is arranged above the sensor (that is, on the side of the transparent base material such as glass base material).

In the semiconductor device (for example, a solid-state imaging device) according to this embodiment, the light-receiving section arranged on the main surface (for example, the upper surface) of the semiconductor substrate may be covered with a resin layer. A semiconductor device (for example, a solid-state imaging device) 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 and a transparent substrate adhered to the semiconductor substrate via a layer. In the semiconductor device according to the present embodiment, a member (eg, a frame-shaped member) is arranged on a region (eg, outer peripheral portion of the main surface) located on the outer peripheral side of the main surface from the light receiving portion on the main surface of the semiconductor substrate. may be provided. The member may have an opening (cavity) that exposes the light receiving section, and the opening may be filled with a resin layer. In the semiconductor device according to this embodiment, the space between the semiconductor substrate and the transparent substrate may be sealed only with the resin layer. In the semiconductor device according to this embodiment, part or the whole of the semiconductor substrate may be sealed with a resin layer. The resin layer may be arranged 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, which is a back-illuminated solid-state imaging device, will be described with reference to the drawings as the case may be.

FIG. 3 is a plan view showing an example of a semiconductor device (first embodiment, CMOS image sensor). FIG. 4 is a cross-sectional view taken along line A-A' shown in FIG. The CMOS image sensor 1a has a sensor portion (light receiving portion) 3a in which a plurality of microlenses 2 are arranged in a central area. A peripheral circuit section 3b in which a circuit is formed exists around the sensor section 3a. A glass substrate 4 is arranged so as to cover at least the sensor portion 3a.

As shown in FIG. 4, a plurality of photodiodes 2a are arranged on one surface of the silicon substrate 5 . A color filter 2b is arranged on the upper surface of the photodiode 2a so as to cover at least the photodiode 2a, and a microlens 2 is arranged on the upper surface of the color filter 2b. A color filter 2b is arranged for each photodiode 2a, and each microlens 2 is arranged at a position corresponding to each color filter 2b. The resin layer 6a containing the resin composition or its cured product according to the present embodiment is formed on the entire surface of the region where the microlenses 2 are arranged on one surface side of the silicon substrate 5, and is formed on the resin layer 6a. A glass substrate 4 is arranged in the . Thereby, the CMOS image sensor 1a has a structure without a cavity (non-cavity structure). On the other hand, the wiring layer 7 is arranged on the other side of the silicon substrate 5 , and the solder balls 8 are arranged 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 1b shown in FIG. 5, a frame-shaped member 9 is arranged on the outer peripheral side of the microlens 2 so as not to cover the microlens 2 arranged on the silicon substrate 5, and a glass substrate 4 having transparency is arranged. is arranged on the upper surface of the frame member 9 . A portion surrounded by the glass substrate 4, the silicon substrate 5, and the frame-shaped member 9 is filled with a resin layer 6b containing the resin composition according to the present embodiment or a cured product thereof, thereby forming a non-cavity structure. there is In the semiconductor device of FIG. 5, the resin layer 6b serves not only as an adhesive for bonding the glass substrate 4 and the silicon substrate 5, but also fills the cavity to seal the microlens 2, the photodiode 2a and the color filter 2b. It also plays a role as a sealing material to stop.

In the non-cavity structure using ribs having adhesiveness (frame-shaped resin layer), ribs having adhesiveness (hereinafter also simply referred to as “ribs”) are formed so as to surround the light receiving portion, and then the light receiving portion is attached. A transparent sealing material is filled so as to seal, and a transparent substrate (for example, a glass substrate) is adhered. For example, in the non-cavity structure of FIG. 5, after forming the frame member 9, the resin layer 6b is formed by filling the cavity with the resin composition. The non-cavity structure produced in this manner can provide sufficient adhesiveness even in 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 through the resin layer 6a containing the resin composition or its cured product according to the present embodiment without providing ribs. there is 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, the non-cavity structure (first embodiment) shown in FIG. 4 does not require the formation of ribs as compared with the non-cavity structure (second embodiment) shown in FIG. can be done. In addition, equipment such as a printing machine, an exposure machine, and a developing machine required for forming ribs is not required.

FIG. 6 is a drawing for comparing the manufacturing methods of the semiconductor device. FIG. 6A shows a method of manufacturing a semiconductor device (a rib forming process) according to the second embodiment. FIG. 6B shows the method of manufacturing the semiconductor device (full surface sealing process) according to the first embodiment. In the method for manufacturing a semiconductor device according to the second embodiment, (a) resin formation (laminate, spin coat, etc.), (b) exposure, (c) development, (d) glass sealing, (e) resin curing, and , (f) each step of dicing is required. On the other hand, in the method for manufacturing a semiconductor device according to the first embodiment, by using the resin composition according to the present embodiment, it is unnecessary to form ribs (frame-shaped adhesive), so (b) exposure and (c) No development step is required. As a result, immediately after the resin layer is formed on the semiconductor substrate, it can be sealed with a transparent substrate (such as a glass substrate). After that, it can be separated into individual pieces by dicing or the like.

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

The non-cavity structure has the following advantages over the cavity structure.

In the cavity structure, foreign substances adhering to microlenses, glass substrates, etc. also cause deterioration in image quality. This is because the cavity is exposed during the period from forming the adhesive to bonding the glass substrate. On the other hand, in the non-cavity structure of the present embodiment, the exposure time is short, so adhesion of foreign matter is reduced.

In the non-cavity structure, the bonding area between the resin layer and the glass substrate is large. Therefore, in the non-cavity structure of the present embodiment, compared with the cavity structure in which the glass base material is adhered only by the frame-shaped resin layer, the stress caused by the adhesive in the element has less variation, and peeling, deformation, etc. of the adhesive can occur. is reduced.

Although the embodiment has been described above, the present invention is not limited to the embodiment. For example, with respect to each of the above-described embodiments, those skilled in the art may appropriately add, delete, or change the design of components, or add, omit, or change the conditions of steps, without departing from the spirit of the present invention. as long as it is within the scope of the present invention. For example, in the above embodiment, an example of using a glass substrate as a transparent substrate was shown, but the present invention is not limited to this, and any transparent substrate having the necessary strength, rigidity and light transmittance can be used. good.

EXAMPLES The present invention will be described in more detail below based on examples and comparative examples, but the present invention is not limited to the following examples.

<Preparation of Components of Resin Composition>
The following ingredients were prepared.

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

Tricyclo[5.2.1.0 ^2,6 ]dec-8-yl acrylate (FA-513A, Hitachi Chemical Co., Ltd., trade name) 300 g, butyl acrylate (BA) 350 g, butyl methacrylate (BMA) 300 g , 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-octylmercaptan (chain transfer agent) were dissolved in the resulting monomer mixture to obtain a mixture.

0.44 g of polyvinyl alcohol (suspending agent) and 2000 g of deionized water were added to a 5 L autoclave equipped with a stirrer and condenser. Then, the mixed solution was added while stirring, and polymerization was carried out at 60° C. for 5 hours under a nitrogen atmosphere at a stirring speed of 250 min ⁻¹ . Then, polymerization was carried out at 90° C. for 2 hours to obtain resin particles (the 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). A calibration curve was approximated by a cubic equation using a standard polystyrene kit PStQuick Series C (trade name, manufactured by Tosoh Corporation). GPC conditions are shown below.
Pump: L6000 Pump (Hitachi, Ltd.)
Detector: L3300 RI Monitor (Hitachi, Ltd.)
Column: Gelpack GL-S300MDT-5 (2 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: 1mL/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)
Percumyl D: NOF Corporation, trade name "Percumyl D", thermal polymerization initiator, dicumyl peroxide, 1 hour half-life temperature 135.7 ° C., 10 hour half-life temperature 116.4 ° C.

(light absorbing material)
UV absorber

(Antioxidant)
AO-80: ADEKA Corporation, trade name "ADEKA STAB AO-80", hindered phenolic 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 Co., Ltd., trade name “ADEKA STAB AO- 503", thioether antioxidant, ditridecyl 3,3-thiobispropionate MT-PE1: Showa Denko Co., Ltd., trade name "Kalenz MT-PE1", pentaerythritol tetrakis (3-mercaptobutyrate)

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

<Preparation of resin composition>
200 parts by mass of the (meth)acrylic polymer (a1), 160 parts by mass of R-604, 4 parts by mass of Permir D, 5 parts by mass of AO-80, 1 part by mass of AO-503, After mixing 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, an ultraviolet absorber is mixed, and the amount shown in Table 1. were obtained as resin compositions of Examples and Comparative Examples containing the UV absorber of No.

<Evaluation>
A film-like resin film having a thickness of 150 μm was produced by applying the resin compositions of Examples and Comparative Examples onto a glass substrate and then drying at 70° C./10 minutes and 100° C./10 minutes. Next, a cured film was obtained by performing heat treatment at 200° C./2 hours under vacuum to cure the resin film. After that, the transmittance (spectral spectrum) of the cured film at 25°C was measured. Specifically, 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) with a wavelength range of 300 to 800 nm to obtain light transmittance at wavelengths of 350 nm and 430 nm. Table 1 shows the measurement results.

According to Table 1, it was confirmed that cured products having a low light transmittance at a wavelength of 350 nm and a high light transmittance at a wavelength of 430 nm were obtained in Examples.

1a, 1b... CMOS image sensor (semiconductor device), 2... microlens, 2a... photodiode, 2b... color filter, 3a... sensor section, 3b... peripheral circuit section, 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-shaped member 9a Cavity 10 Support base 15 Wire 20 Semiconductor substrate 40...Transparent base material 100...Semiconductor device.

Claims (7)

(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 weight average molecular weight of the component (a) is 100,000 or more,
The content of the component (b) is 20 parts by mass or more with respect to 100 parts by mass of the total amount of the component (a) and the component (b),
A resin composition in which the content of component (d) is 0.002 to 0.04% by mass based on the total amount (total solid content) of the resin composition. The resin composition according to claim 1, wherein the component (a) has a structural unit having an alicyclic structure. The resin composition according to claim 1 or 2, wherein the component (a) has a structural unit having an epoxy group. The resin composition according to any one of claims 1 to 3, wherein the component (c) contains a thermal polymerization initiator. A cured product of the resin composition according to any one of claims 1 to 4 . Manufacture of a semiconductor device, comprising a step of curing a resin layer containing the resin composition according to any one of claims 1 to 4 while the resin layer is disposed between a semiconductor substrate and a transparent base material. Method. comprising a semiconductor substrate, a transparent substrate, and a resin layer disposed between the semiconductor substrate and the transparent substrate;
A semiconductor device, wherein the resin layer comprises the resin composition according to any one of claims 1 to 4 or a cured product thereof.

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