JP2021086886A - Semiconductor device - Google Patents

Abstract

To provide a semiconductor device which can contribute to the achievement of a low profile of equipment, and superior in impact resistance.SOLUTION: A semiconductor device comprises: a semiconductor substrate; a transparent base material; a first resin layer disposed between the semiconductor substrate and the transparent base material; and a second resin layer disposed between the first resin layer and the transparent base material, or on a side of the transparent base material opposite to the semiconductor substrate. The first resin layer is formed by use of a first resin composition containing a hardening resin. The second resin layer is formed by use of a second resin composition containing a hardening resin and an infrared light-absorbing material having a maximum absorption wavelength in a wavelength region of 600-1100 nm. The first resin layer has a light transmittance of 90% or more for wavelengths of 400 nm, 700 nm and 1000 nm.SELECTED DRAWING: Figure 3

Description

The present invention relates to a semiconductor device.

In recent years, with the widespread use of digital still cameras and mobile phones with cameras, the power consumption and miniaturization of solid-state image sensors (solid-state image sensors) have been increasing, and conventional CCD (Charge Coupled Device) image sensors have been promoted. In addition, CMOS (Complementary Metal Oxide Semiconductor) image sensors have come to be 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 the structure of the CMOS image sensor, a "front-illuminated" structure and a "back-illuminated" structure are known (see, for example, Patent Documents 1 and 2 below). In the surface-illuminated CMOS image sensor of Patent Document 1, light incident from the outside passes through a glass substrate and a cavity (cavity), enters each microlens, is collected by the microlens, and then has a color filter layer and a color filter layer. It passes through the wiring layer and enters the photodiode. Then, the light incident on the photodiode is photoelectrically converted to generate a signal charge, and an electric signal is generated from this signal charge to acquire 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 the semiconductor substrate, and a color filter layer and a microlens are arranged on this one surface. A glass substrate is arranged above the microlens 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 portion without passing through the wiring layer, so that the attenuation of the light by the wiring layer is avoided and the light receiving sensitivity is enhanced.

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

Japanese Unexamined Patent Publication No. 2007-281375 Japanese Unexamined Patent Publication No. 2005-142221 Japanese Unexamined Patent Publication No. 2010-40621

By the way, semiconductor devices (solid-state image sensors) such as CCD image sensors and CMOS image sensors have high sensitivity not only to visible light but also to infrared light. Therefore, digital photography devices such as digital still cameras are provided with an infrared cut filter (IR cut filter) for cutting near infrared rays in order to bring the visibility closer to that of a person.

Since the IR cut filter has a thickness of about several hundred μm, it may hinder the reduction in height of digital photography equipment. Therefore, from the viewpoint of further reducing the height of digital photography equipment, a solid-state image sensor that does not require an IR cut filter may be required.

Further, although a transparent base material such as a glass substrate is used for the solid-state image sensor, improvement in impact resistance is required from the viewpoint of preventing the transparent base material from cracking.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a semiconductor device having excellent impact resistance, which can contribute to lowering the height of the device.

One aspect of the semiconductor device according to the present invention is a semiconductor substrate, a transparent base material, a first resin layer arranged between the semiconductor substrate and the transparent base material, the first resin layer, and the transparent material. A second resin layer is provided between the base material and the transparent base material on the side opposite to the semiconductor substrate side, and the first resin layer contains a curable resin. It is a layer formed by using the resin composition of No. 1, and the second resin layer is a second resin composition containing a curable resin and an infrared absorbing material having a maximum absorption wavelength in the wavelength region of 600 to 1100 nm. A semiconductor device that is a layer formed of a material and has a light transmittance of 90% or more at wavelengths of 400 nm, 700 nm, and 1000 nm of the first resin layer.

According to the semiconductor device, the infrared transmittance can be reduced by providing the second resin layer containing the infrared absorbing material. Therefore, for example, when the semiconductor device is used in a digital photography device, it is not necessary to provide an IR cut filter, which can contribute to lowering the height of the device. Further, the semiconductor device further includes a first resin layer. The first resin layer is a layer that satisfies a specific light transmittance condition, that is, a layer that does not contain or has a sufficiently low content of an light absorbing material such as an infrared absorbing material contained in the second resin layer. When the curable resin contains an absorbent material, the impact resistance of the resin layer tends to decrease, but it is excellent by providing the first resin layer which does not contain the absorbent material or has a sufficiently low content. Impact resistance can be obtained. By providing such a first resin layer between the semiconductor device and the transparent base material, the semiconductor device can obtain excellent impact resistance and prevent the transparent base material from cracking. it can.

The first resin composition may contain (a) (meth) acrylic polymer, (b) a compound having at least two (meth) acryloyl groups, and (c) a polymerization initiator. .. These components constitute a curable resin. Since the first resin layer is formed by using the first resin composition containing the above components, the impact resistance of the semiconductor device is further improved.

The infrared absorbing material may contain a complex compound containing copper and phosphorus. By including the complex compound containing copper and phosphorus in the infrared absorbing material, the semiconductor device can further reduce the light transmittance in the long wavelength region (for example, 800 to 1100 nm).

The infrared absorbing material may contain at least one selected from the group consisting of squalium compounds, phthalocyanine compounds and cyanine compounds. When the infrared absorbing material contains at least one selected from the group consisting of a squalium compound, a phthalocyanine compound and a cyanine compound, the semiconductor device can further reduce the light transmittance in the wavelength region of 600 to 800 nm.

The second resin layer may further contain an ultraviolet absorber. The spectral sensitivity of semiconductor devices such as CCD image sensors and CMOS image sensors is preferably close to human visibility. From this point of view, the semiconductor device has a low light transmittance in the wavelength range of 390 nm or less and a high light transmittance in the vicinity of the wavelength of 430 nm, particularly a low light transmittance in the wavelength of 350 nm and a wavelength. A high light transmittance of 430 nm may be required. Since the second resin layer contains an ultraviolet absorber, the light transmittance in the wavelength range of 390 nm or less can be reduced, and the above requirements can be realized.

According to the present invention, it is possible to provide a semiconductor device having excellent impact resistance, which can contribute to lowering the height of the device.

It is a 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. It is sectional drawing of the line AA'shown in FIG. It is sectional drawing which shows the other example of a semiconductor device. It is a drawing for comparing 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, embodiments of the present invention will be described, but the present invention is not limited to these embodiments.

As used herein, the term "(meth) acryloyl group" means at least one of an "acryloyl group" and a corresponding "methacryloyl group". The same applies to other similar expressions such as "(meth) acrylate". The numerical range indicated by using "~" indicates a range including the numerical values before and after "~" as the minimum value and the maximum value, respectively. In the numerical range described stepwise in the present specification, the upper limit value or the lower limit value of the numerical range of one step may be replaced with the upper limit value or the lower limit value of the numerical range of another step. In the numerical range described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples. The terms "layer" and "membrane" include not only a structure having a shape formed on the entire surface but also a structure having a shape partially formed when observed as a plan view. The term "process" is included in this term as long as the intended purpose of the process is achieved, not only in an independent process but also in cases where it cannot be clearly distinguished from other processes. "A or B" may include either A or B, or both. The content of each component in the composition means the total amount of the plurality of substances present in the composition when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified. Unless otherwise specified, the materials exemplified in the present specification may be used alone or in combination of two or more.

<First resin composition and first cured product>
The first resin composition according to the present embodiment contains a curable resin. The first resin composition comprises (a) (meth) acrylic polymer (hereinafter, sometimes referred to as “(a) component”) and (b) a compound having at least two (meth) acryloyl groups (hereinafter, case). Therefore, it may contain (referred to as "component (b)") and (c) a polymerization initiator (hereinafter, in some cases, referred to as "component (c)"). The first resin composition according to the present embodiment is a curable (for example, thermosetting or photocurable) resin composition. The first cured product according to the present embodiment is a cured product of the first resin composition according to the present embodiment.

According to the first resin composition according to the present embodiment, the impact resistance of the semiconductor device can be improved.

The first resin composition according to the present embodiment can be used as an adhesive composition. The first resin composition according to the present embodiment may be in the form of a liquid (varnish) or a film. The first 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 parts.

((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), and for example, one (meth) acryloyl group. A polymer (single polymer) having a structure obtained by polymerizing one (meth) acrylic monomer in the molecule with one type, and two or more of the above (meth) acrylic monomers are copolymerized in combination. Examples thereof include a polymer (copolymer) having a structure obtained by the above, and a polymer (copolymer) having a structure obtained by copolymerizing the above (meth) acrylic monomer with another monomer. Be done. As a monomer copolymerizable with the above (meth) acrylic monomer, a compound having two or more (meth) acryloyl groups in one molecule; having one polymerizable unsaturated bond in one molecule, And, a polymerizable compound having no (meth) acryloyl group (for example, (meth) acrylonitrile, styrene, vinyl acetate and an alkene (ethylene, propylene, etc.)); two or more polymerizable unsaturated bonds in one molecule. Examples thereof include polymerizable compounds (divinylbenzene and the like) having and not having a (meth) acryloyl group. As the component (a), one type can be used alone or two or more types can be used in combination.

The component (a) is derived from a (meth) acrylic monomer having one (meth) acryloyl group in one molecule based on the total amount of the component (a) from the viewpoint of easily improving the impact resistance. It preferably has 30 to 100% by mass of structural units, 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 resistance, reflow peeling resistance, crack resistance, adhesiveness and heat resistance associated with a low elastic modulus can be easily exhibited. 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. Since the component (a) has an epoxy group, the adhesion of an inorganic material such as metal or glass to a 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, for example, by an existing method as described in WO 2015/115537. Can be done. Above all, suspension polymerization is preferable from the viewpoint of low cost and high molecular weight.

Suspension polymerization is carried out 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 unlikely to remain 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 the monomers.

In the polymerization reaction, a commonly used polymerization initiator, chain transfer agent, or the like may be used. Examples of the polymerization initiator include compounds similar to (c) the polymerization initiator described later. 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 groups are amino groups, amide groups, phosphoric acid groups, cyano groups, etc. from the viewpoint of easily avoiding problems such as gelation in a varnish state, clogging of nozzles during use, that is, generation of pinholes during spin coating. It is preferably at least one selected from the group consisting of a maleimide group and an epoxy group. Further, 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 highly preventing coloring. Further, from both of these viewpoints, the functional group is more preferably at least one selected from the group consisting of a phosphoric acid group and an epoxy group, and further 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 single amount, as exemplified in International Publication No. 2015/115537. Body; phosphate group-containing monomer; vinyl cyanide compound; N-substituted maleimides; epoxy group-containing monomer and the like can be used. As the functional group-containing monomer, one type can be used alone or two or more types can be used in combination.

Among these, it is particularly preferable to use an epoxy group-containing monomer such as glycidyl (meth) acrylate. Furthermore, the (meth) acrylic polymer obtained by using such a monomer (for example, a glycidyl group-containing (meth) acrylic polymer) is compatible with the (meth) acrylic monomer or oligomer. Is preferable. The glycidyl group-containing (meth) acrylic polymer may be synthesized by a conventional method, or a commercially available product may be obtained. Examples of commercially available products include HTR-860P-3 (Nagase Chemtex Co., Ltd., trade name) and the like. 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 a functional group is preferably in the following range based on the total amount of the component (a) from the viewpoint that the adhesive force can be easily secured and gelation can be easily prevented. 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, 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 the functional group is preferably 20% by mass or less, more preferably 10% by mass or less, further 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 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, a maleimide group and the like. Examples of the structural unit having a nitrogen atom-containing group include structural units derived from the monomer 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 the monomer other than the functional group-containing monomer that can be used in synthesizing the component (a) include (meth) acrylic acid esters as exemplified in International Publication No. 2015/115537; aromatics; aromatics. Group vinyl compounds; alicyclic monomers and the like can be mentioned. As the monomer other than the functional group-containing monomer, one type can be used alone or two or more types can be used in combination.

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, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate from the viewpoint of excellent copolymerization with a functional group-containing monomer. At least one selected from the group consisting of is more preferable.

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. Since the component (a) has an alicyclic structure, the amorphous component in the (meth) acrylic polymer increases, so that the transparency tends to increase. Further, as compared with an aliphatic structure having the same carbon number (an aliphatic structural unit or the like), the glass transition temperature (Tg) tends to be 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 the following general. Examples thereof include a compound represented by the formula (1).

［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, 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 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. is there. ]

［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, and R ¹¹ is hydrogen. It shows an atom, an alkyl group having 1 to 4 carbon atoms, or a structure represented by ^{OR 11a , and 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. [5.2.1.0 ^2,6 ] Deca-8-yl (also known as tricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate) and the like can be mentioned.

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. Therefore, 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.

The mixing ratio when the functional group-containing monomers are used in combination 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 Tg is −50 ° C. or higher, the tackiness of the first resin composition in the B stage state is appropriate and the handleability is excellent. From this 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 , 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. It is particularly preferably 1:99, and extremely preferably 20:80 to 1:99.

The component (a) is composed of a 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 X ^a 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。］

Wherein ^{(II), R 2a} represents a hydrogen atom or a methyl group, ^{Y a} is true X of substituted Hajime Tamaki which may carbons 5 to 22 (formula (I) Except for the groups that do). ]

［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。］

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) (Excluding groups corresponding to X)
Is shown. ]

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 methods include solution polymerization and suspension polymerization (pearl). The above method such as polymerization) can be used.

The weight average molecular weight of the component (a) is as follows from the viewpoint that the strength, flexibility and tackiness after film formation are appropriate, and the flowability is appropriate, so that the circuit filling property of the wiring can be easily secured. 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, still more preferably 200,000 or more, from the viewpoint of being able to maintain 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, further 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 indicates a value measured by gel permeation chromatography (GPC) as described in Examples and converted using a standard polystyrene calibration curve.

The content of the component (a) in the first resin composition is (b) from the viewpoint of showing a good storage elastic modulus, suppressing the flow during molding, and sufficiently obtaining handleability at a high temperature. The following range is preferable with respect to 100 parts by mass of the total amount of the components. 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, extremely preferably 75 parts by mass or more, and 100 parts by mass. More than a part is very preferable. The content of the component (a) is preferably 400 parts by mass or less, more preferably 350 parts by mass or less, further 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 viewpoints, the content of the component (a) is preferably 10 to 400 parts by mass.

(Component (b): Compound having at least two (meth) acryloyl groups)
In the first resin composition according to the present embodiment, the compatibility between the component (a) and the component (b) is high, and the refractive indexes of these tend to be close to each other, so that visibility can be ensured after curing. A degree of excellent transparency can be obtained. Further, 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. Further, even when phase separation occurs due to the heat of curing after radical curing, the phase separation is limited to microscopic phase separation, and variations in cured product characteristics such as visibility and adhesive strength can be suppressed. The problem of light loss can also be solved by filling the cavity with the first resin composition according to the present embodiment.

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

Examples of the monomer having at least two (meth) acryloyl groups include a polyfunctional (meth) acrylic monomer having an alicyclic structure, a polyfunctional (meth) acrylic monomer having an aliphatic structure, and a dioxane glycol structure. Examples thereof include a polyfunctional (meth) acrylic monomer having a functional group (excluding a (meth) acryloyl group) and a polyfunctional (meth) acrylic monomer having a functional group. The polyfunctional (meth) acrylic monomer having a functional group excludes a polyfunctional (meth) acrylic monomer having an alicyclic structure, an aliphatic structure or a dioxane glycol structure. The term "polyfunctional" as used herein refers to a (meth) acryloyl group, and means that the compound has at least two (meth) acryloyl groups.

As the component (b), one type can be used alone or two or more types can be used in combination.

The component (b) is composed of a polyfunctional (meth) acrylic monomer having an alicyclic structure and a polyfunctional (meth) acrylic monomer having a dioxane glycol structure from the viewpoint of easily improving impact resistance. At least one selected from the group 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.

Examples of the polyfunctional (meth) acrylic monomer include a (meth) acrylic monomer having two (meth) acryloyl groups.

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, and tricyclodecanedimethylol di (meth). Meta) acrylate (for example, Nippon Kayaku Co., Ltd., KAYARAD R-684, tricyclodecanedimethylol diacrylate), tricyclodecanedimethanol di (meth) acrylate (for example, Shin-Nakamura Chemical Industry Co., Ltd., A-DCP, Tricyclodecanedimethanol diacrylate), dioxane glycol di (meth) acrylate (for example, Nippon Kayaku Co., Ltd., KAYARAD R-604, dioxane glycol diacrylate; Shin-Nakamura Chemical Industry Co., Ltd., A-DOG, dioxane glycol diacrylate) ), Nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dicyclopentanyldi (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 di (meth) acrylate of hydroxypivalate, 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 to 15 molar modified bisphenol A type di (meth) acrylate. ) Acrylate), (poly) ethylene oxide-modified di (meth) acrylate and the like.

Among the above, at least one selected from the group consisting of dioxane glycol di (meth) acrylate and tricyclodecanedimethanol di (meth) acrylate is preferable from the viewpoint of easily improving impact resistance, and dioxane glycol diacrylate and At least one selected from the group consisting of tricyclodecanedimethanol diacrylate is more preferable.

Examples of the polyfunctional (meth) acrylic monomer other than the above include pentaerythritol tri (meth) acrylate and ethylene oxide-modified isocyanurate tri (meth) acrylate, which have three (meth) acryloyl groups (meth). Acrylic monomers can be mentioned.

The content of the component (b) in the first resin composition is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and more preferably 40 parts by mass with respect to 100 parts by mass of the total amount of the components (a) and (b). More than parts by mass is more preferable. 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, based on 100 parts by mass of the total amount of the components (a) and (b). 50 parts by mass or less is particularly preferable. The content of the component (b) is preferably 20 to 80 parts by mass with respect to 100 parts by mass of the total amount of the component (a) and the component (b). When the content of the component (b) is in each of the above ranges, three-dimensional crosslinking is likely to occur, so that the heat resistance tends to be further improved. Further, even when phase separation occurs after curing, the range of phase separation can be limited to the 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 semiconductors or electronic components can be easily suppressed.

(Component (c): 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 “(c2) component”). ) Can be used.

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

As the component (c1), one type can be used alone or two or more types can be used in combination.

Among the components (c1), organic peroxides are preferable from the viewpoint of easily improving impact resistance, and a good balance between handleability (shelf life, pot life, etc.) and curability of the first resin composition is preferable. From the viewpoint of maintaining the above, 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, from the viewpoint of excellent storage stability and thermosetting property, dicumyl peroxide (for example, manufactured by NOF CORPORATION, trade name: Park Mill D), And at least one selected from the group consisting of n-butyl 4,4-bis (t-butylperoxy) valerate (for example, manufactured by NOF CORPORATION, trade name: Perhexa V) is preferable.

The component (c1) can easily exhibit excellent heat resistance, peeling resistance and stress relaxation in combination with the component (a) and the component (b), and can improve the reliability of the semiconductor device (optical component, etc.). it can.

The content of the component (c1) in the first resin composition is a total amount of the components (a) and (b) 100 from the viewpoint of easily improving the impact resistance and suppressing the generation of outgas. The following range is preferable with respect to parts by mass. The content of the component (c1) is preferably 0.1 part by mass or more, more preferably 0.2 part by mass or more, further preferably 0.5 part 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, extremely preferably 3 parts by mass or less, and 2 parts by mass. Less than a part is very preferable. From these viewpoints, the content of the component (c1) is preferably 0.1 to 30 parts by mass.

As the component (c2), acylphosphine oxide, oxime esters, aromatic ketones, quinones, benzoin ether compounds, benzyl derivatives, 2,4,5-triarylimidazole dimer, acrydin derivatives, coumarin compounds, Examples thereof include N-phenylglycine and N-phenylglycine derivatives. The component (c2) may be synthesized by a conventional method, or a commercially available product may be obtained.

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

As the component (c2), one type can be used alone or two or more types can be used in combination.

Examples of the acylphosphine oxide include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (for example, 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)] (for example, IRGACURE-OXE01, BASF, trade name), 1- [9. -Ethyl-6- (2-methylbenzoyl) -9H-Carbazole-3-yl] Etanone-1- (O-acetyloxime) (for example, IRGACURE-OXE02, BASF, trade name), 1-Phenyl-1, 2-Propanedione-2- [o- (ethoxycarbonyl) oxime] (for example, Quantacure-PDO, Nippon Kayaku Co., Ltd., trade name) and the like can be mentioned.

Examples of the aromatic ketone include the compounds described in International Publication No. 2015/115537.

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

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

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 WO 2015/115537.

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

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

Examples of the N-phenylglycine derivative include N-phenylglycine butyl ester, N-p-methylphenylglycine, N-p-methylphenylglycine methyl ester, N- (2,4-dimethylphenyl) glycine, and N-methoxyphenylglycine. And so on.

The content of the component (c2) in the first resin composition is preferably 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the total amount of the components (a) and (b). Parts are more preferable, and 0.75 to 5 parts by mass is further preferable. When the content of the component (c2) is within these ranges, it is easy to highly prevent foaming, turbidity, coloring and cracking of the cured product.

(Absorbent material)
The first resin composition according to the present embodiment may contain an absorbent material such as that used for the second resin layer as long as the effects of the present invention are not impaired, but the content of the absorbent material ( The total amount) is preferably in the following range based on the total amount (total amount of solid content) of the first resin composition. The content of the absorbent material is preferably 80% by mass or less, more preferably 50% by mass or less, still more preferably 30% by mass or less, from the viewpoint of easily improving the impact resistance. The content of the light absorbing material in the first resin composition may be 0% by mass.

(Antioxidant)
The first resin composition according to the present embodiment may contain an antioxidant. Since the first resin composition according to the present invention contains an antioxidant, it is easy to suppress coloring due to deterioration of the first resin composition during heat and improve transparency during heat. Examples of the antioxidant include phenolic antioxidants, thioether-based antioxidants, thiol-based antioxidants and the like. The antioxidant may be used alone or in combination of two or more.

Examples of the phenolic antioxidant include hindered phenolic compounds and the like. Examples of the hindered phenolic compound include the compounds described in International Publication No. 2015/046422, and specific examples thereof include 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 the thioether-based antioxidant include ditridecyl 3,3-thiobispropionate (for example, "ADEKA Stub AO-503" (ADEKA Corporation)). 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, "Carens MT-PE1" (Showa Denko KK)), 1,3,5-tris (3-mercaptobutylyloxyethyl). ) -1,3,5-Triazine-2,4,6 (1H, 3H, 5H) -trion (for example, "Karensu MT-NR1" (Showa Denko KK)) and the like.

The content of the antioxidant in the first resin composition is the component (a), the component (b) and the components (b) from the viewpoint of more easily improving the impact resistance and less likely to adversely affect the radical polymerization reactivity. c) The following range is preferable with respect to 100 parts by mass of the total amount of the components. The content of the antioxidant is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, further 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, further 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 first 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-based coupling agent, an aluminum-based coupling agent, a zirconeate-based coupling agent, and a zircoaluminate-based coupling agent can be used. The coupling agent may be used alone or in combination of two or more.

The silane coupling agent may be 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) acrylic 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 the compounds exemplified in International Publication No. 2015/115537.

Examples of the titanate-based coupling agent include compounds exemplified in International Publication No. 2015/115537.

Examples of the aluminum-based coupling agent include acetalkoxyaluminum diisopropionate.

Examples of the zirconate-based coupling agent 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 the compound in which R 12} is a carboxyl group include Manshem CPG-carboxyzircoaluminate. Examples of the compound in which R ¹² is an amino group include Manshem APO-X-aminozircoaluminate solution. Each can be obtained from Rhone Poulenc.

Among these coupling agents, a silane coupling agent is preferable, a silane coupling agent having a (meth) acrylic 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. More preferred.

The content of the coupling agent in the first resin composition 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 part by mass or more, more preferably 0.5 part by mass or more, and further preferably 0.8 part by mass or more from the viewpoint that the effect of improving the adhesive strength tends to be obtained. It is preferable, and 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, and 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 viewpoints, the content of the coupling agent is preferably 0.1 to 20 parts by mass.

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

The organic solvent is not limited as long as it can uniformly stir-mix, dissolve, knead or disperse the components contained in the first 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) from the viewpoint of improving the stability of the coating film. Examples thereof include formamide, cyclohexanone, dimethylacetamide, butyl cellosolve, dimethyl sulfoxide, propylene glycol monomethyl ether acetate, N-methyl-2-pyrrolidone, γ-butyrolactone and the like). As the organic solvent, one type can be used alone or two or more types can be used in combination.

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 in the first resin composition is determined by the viscosity or the like when it is put into a varnish state. The content of the organic solvent is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, and 10 to 50% based on the total amount of the first resin composition (the total amount including the volatile components of the organic solvent and the like). Mass% is more preferred.

(Other ingredients)
The first 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), in addition to the component (b). A compound having a group and a heterocycle) may be contained. Examples of the monofunctional (meth) acrylic monomer include the (meth) acrylic monomer (such as glycidyl (meth) acrylate) exemplified in the above component (a). The monofunctional (meth) acrylic monomer may be used alone or in combination of two or more.

The first resin composition according to the present embodiment may contain other additives. Additives include epoxy curing agents, epoxy curing accelerators, wetting improvers (fluorine-based surfactants, nonionic surfactants, higher fatty acids, etc.), defoamers (silicone oil, etc.), ion trapping agents (inorganic ions, etc.) Exchangers, etc.), refractive index adjusters, other fillers (organic fillers, inorganic fillers, etc.) and the like. These additives may be used alone or in combination of two or more.

<Second resin composition and second cured product>
The second resin composition according to the present embodiment contains a curable resin and (d) an infrared absorbing material having a maximum absorption wavelength in the wavelength region of 600 to 1100 nm (hereinafter, sometimes referred to as “component (d)”). To do. The second resin composition comprises (a) a (meth) acrylic polymer (component (a)), (b) a compound having at least two (meth) acryloyl groups (component (b)), and (c). A polymerization initiator (component (c)) and (d) an infrared absorbing material (component (d)) having a maximum absorption wavelength in the wavelength region of 600 to 1100 nm may be contained. The second resin composition according to the present embodiment is a curable (for example, thermosetting or photocurable) resin composition. The second cured product according to the present embodiment is a cured product of the second resin composition according to the present embodiment.

As the components (a) to (c), the same components as those used in the first resin composition can be used. Moreover, the preferable content thereof is also the same as in the case of the first resin composition.

In addition, the second resin composition may contain the same antioxidants, coupling agents, organic solvents, and other components as those used in the first resin composition. Moreover, the preferable content thereof is also the same as in the case of the first resin composition.

(Component (d): Infrared absorbing material having a maximum absorption wavelength in the wavelength region of 600 to 1100 nm)
The component (d) is selected from the group consisting of (d1) a complex compound containing copper and phosphorus (hereinafter, sometimes referred to as "(d1) component"), and (d2) a squalium compound, a phthalocyanine compound, and a cyanine compound. At least one kind (hereinafter, sometimes referred to as “(d2) component”) can be mentioned.

The component (d1) can absorb light in a long wavelength region (for example, 800 to 1100 nm). The component (d1) is an organic substance containing a phosphorus atom from the viewpoint of reducing the light transmittance in the long wavelength region and easily suppressing the change in the wavelength spectrum in the long wavelength region even when the light transmittance is maintained at a high temperature. It is preferred that the compound is coordinated to a copper atom. As the component (d1), one type can be used alone or two or more types can be used in combination.

The average particle size of the component (d1) is 1 nm from the viewpoint of reducing the light transmittance in the long wavelength region and easily suppressing the change in the wavelength spectrum in the long wavelength region even when kept at a high temperature. The above is preferable, 3 nm or more is more preferable, 5 nm or more is further preferable, 10 nm or more is particularly preferable, 15 nm or more is extremely preferable, 20 nm or more is very preferable, and 25 nm or more is even more preferable. The average particle size of the component (d1) is preferably 200 nm or less, more preferably 150 nm or less, further preferably 100 nm or less, particularly preferably 80 nm or less, extremely preferably 50 nm or less, and extremely preferably 40 nm from the viewpoint of excellent dispersibility and workability. The following is very preferable, and 30 nm or less is even more preferable. From these viewpoints, the average particle size of the component (d1) is preferably 1 to 200 nm.

The content of the component (d1) in the second resin composition is preferably in the following range with respect to 100 parts by mass of the component (a). The content of the component (d1) is preferably 10 parts by mass or more, more preferably 50 parts by mass or more, further preferably 100 parts by mass or more, and 200 parts by mass or more from the viewpoint of easily reducing the light transmittance in the long wavelength region. Is particularly preferable, 250 parts by mass or more is extremely preferable, 300 parts by mass or more is very preferable, and 400 parts by mass or more is even more preferable. The content of the component (d1) is preferably 500 parts by mass or less, more preferably 300 parts by mass or less, from the viewpoint of easily suppressing a change in the wavelength spectrum in the long wavelength region even when the temperature is maintained at a high temperature. , 250 parts by mass or less is further preferable, 200 parts by mass or less is particularly preferable, 150 parts by mass or less is extremely preferable, 100 parts by mass or less is very preferable, and 50 parts by mass or less is even more preferable. From these viewpoints, the content of the component (d1) is preferably 10 to 500 parts by mass.

The content of the component (d1) in the second resin composition is preferably in the following range with respect to 100 parts by mass of the total amount of the component (a) and the component (b). The content of the component (d1) is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, further preferably 40 parts by mass or more, and 80 parts by mass or more from the viewpoint of easily reducing the light transmittance in the long wavelength region. Is particularly preferable, 100 parts by mass or more is extremely preferable, 150 parts by mass or more is very preferable, and 200 parts by mass or more is even more preferable. The content of the component (d1) is preferably 300 parts by mass or less, more preferably 200 parts by mass or less, from the viewpoint of easily suppressing the change of the wavelength spectrum in the long wavelength region even when the temperature is maintained at a high temperature. , 150 parts by mass or less is further preferable, 100 parts by mass or less is particularly preferable, 80 parts by mass or less is extremely preferable, 40 parts by mass or less is very preferable, and 30 parts by mass or less is even more preferable. From these viewpoints, the content of the component (d1) is preferably 20 to 300 parts by mass.

The content of the component (d1) in the second resin composition is preferably in the following range based on the total amount (total amount of solid content) of the second resin composition. The content of the component (d1) is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 25% by mass or more, and further preferably 30% by mass or more, from the viewpoint of easily reducing the light transmittance in the long wavelength region. Is particularly preferable, 40% by mass or more is extremely preferable, 50% by mass or more is very preferable, and 60% by mass or more is even more preferable. The content of the component (d1) is preferably 70% by mass or less, more preferably 60% by mass or less, from the viewpoint of easily suppressing a change in the wavelength spectrum in the long wavelength region even when the component is kept at a high temperature. , 50% by mass or less is further preferable, 40% by mass or less is particularly preferable, 30% by mass or less is extremely preferable, 25% by mass or less is very preferable, and 20% by mass or less is even more preferable. From these viewpoints, the content of the component (d1) is preferably 10 to 70% by mass.

(Component (d2): A compound having a maximum absorption wavelength in the wavelength region of 600 to 800 nm)
The component (d2) can absorb light in the wavelength region of 600 to 800 nm. The component (d2) may contain at least one selected from the group consisting of a squalium compound (squalium pigment), a phthalocyanine compound (phthalocyanine pigment) and a cyanine compound (cyanine pigment). As the component (d2), one type can be used alone or two or more types can be used in combination.

The component (d2) is a component (d2) from the viewpoint that it is easy to suppress a change in the wavelength spectrum in the wavelength region of 600 to 800 nm even when the cured product of the second resin composition is maintained in a high humidity atmosphere. It is preferable to contain at least one selected from the group consisting of a phthalocyanine compound and a cyanine compound, and it is more preferable to contain a phthalocyanine compound.

By the way, the wavelength spectrum in the wavelength region of 600 to 800 nm in the cured product obtained by holding the cured product of the second resin composition at a high temperature greatly changes with respect to the wavelength spectrum of the second resin composition before curing. Then, since the characteristics of the second resin composition fluctuate in the curing process, it is not easy to obtain a semiconductor device having desired characteristics. Therefore, with respect to the curable second resin composition for obtaining a component of a semiconductor device, it is possible to suppress a change in the wavelength spectrum in the wavelength region of 600 to 800 nm even when the resin composition is held at a high temperature. It is preferable to do so. In this respect, the component (d2) is selected from the group consisting of a squalium compound and a phthalocyanine compound from the viewpoint that it is easy to suppress a change in the wavelength spectrum in the wavelength region of 600 to 800 nm even when the temperature is maintained at a high temperature. It preferably contains at least one type, and more preferably contains a phthalocyanine compound.

The content of the component (d2) in the second resin composition is preferably in the following range with respect to 100 parts by mass of the component (a). The content of the component (d2) is preferably 0.01 part by mass or more, more preferably 0.03 part by mass or more, and 0.05 part by mass or more from the viewpoint of easily absorbing light in the wavelength region of 600 to 800 nm. More preferably, 0.06 parts by mass or more is particularly preferable, 0.1 parts by mass or more is extremely preferable, 0.15 parts by mass or more is very preferable, and 0.2 parts by mass or more is even more preferable. The content of the component (d2) tends to suppress a change in the wavelength spectrum in the wavelength region of 600 to 800 nm even when the cured product of the second resin composition is maintained in a high humidity atmosphere. From the viewpoint, 5 parts by mass or less is preferable, 1 part by mass or less is more preferable, 0.7 parts by mass or less is further preferable, 0.5 parts by mass or less is particularly preferable, 0.4 parts by mass or less is extremely preferable, and 0. 3 parts by mass or less is very preferable, and 0.25 parts by mass or less is even more preferable. From these viewpoints, the content of the component (d2) is preferably 0.01 to 5 parts by mass.

The content of the component (d2) in the second resin composition is preferably in the following range with respect to 100 parts by mass of the total amount of the component (a) and the component (b). The content of the component (d2) is preferably 0.01 part by mass or more, more preferably 0.02 part by mass or more, and 0.03 part by mass or more from the viewpoint of easily absorbing light in the wavelength region of 600 to 800 nm. More preferably, 0.04 parts by mass or more is particularly preferable, 0.05 parts by mass or more is extremely preferable, 0.07 parts by mass or more is very preferable, and 0.1 parts by mass or more is even more preferable. The content of the component (d2) tends to suppress a change in the wavelength spectrum in the wavelength region of 600 to 800 nm even when the cured product of the second resin composition is maintained in a high humidity atmosphere. From the viewpoint, 1 part by mass or less is preferable, 0.5 part by mass or less is more preferable, 0.4 part by mass or less is further preferable, 0.3 part by mass or less is particularly preferable, and 0.2 part by mass or less is extremely preferable. 0.15 parts by mass or less is very preferable, and 0.12 parts by mass or less is even more preferable. From these viewpoints, the content of the component (d2) is preferably 0.01 to 1 part by mass.

The content of the component (d2) in the second resin composition is preferably in the following range based on the total amount (total amount of solid content) of the second resin composition. The content of the component (d2) is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and preferably 0.01% by mass or more from the viewpoint of easily absorbing light in the wavelength region of 600 to 800 nm. More preferably, 0.03% by mass or more is particularly preferable, 0.05% by mass or more is extremely preferable, 0.07% by mass or more is very preferable, and 0.09% by mass or more is even more preferable. The content of the component (d2) tends to suppress a change in the wavelength spectrum in the wavelength region of 600 to 800 nm even when the cured product of the second resin composition is maintained in a high humidity atmosphere. From the viewpoint, 1% by mass or less is preferable, 0.5% by mass or less is more preferable, 0.3% by mass or less is further preferable, 0.25% by mass or less is particularly preferable, and 0.2% by mass or less is extremely preferable. 0.15% by mass or less is very preferable, and 0.1% by mass or less is even more preferable. From these viewpoints, the content of the component (d2) is preferably 0.001 to 1% by mass.

(Other absorbent materials)
The second resin composition according to the present embodiment may contain an absorbent material other than the component (d1) and the component (d2). Examples of other light absorbing materials include (e) an ultraviolet absorber (hereinafter, in some cases, referred to as “component (e)”). The ultraviolet absorber can absorb ultraviolet rays (mainly light having a wavelength of 300 to 400 nm). Other light-absorbing materials may be used alone or in combination of two or more.

When the second resin composition according to the present embodiment contains two or more of the component (d1), the component (d2), and other light-absorbing materials other than the components (d1) and (d2). , The total amount of the light absorbing material is preferably in the following range.

The content (total amount) of the absorbent material is preferably in the following range with respect to 100 parts by mass of the component (a). The content of the absorbing material is preferably 0.01 part by mass or more, more preferably 0.03 part by mass or more, further preferably 0.05 part by mass or more, and 0, from the viewpoint of easily absorbing light in a desired wavelength region. .06 parts by mass or more is particularly preferable, 0.1 parts by mass or more is extremely preferable, 0.15 parts by mass or more is very preferable, and 0.2 parts by mass or more is even more preferable. The content of the absorbing material is from the viewpoint that it is easy to suppress the change of the wavelength spectrum in the desired wavelength region even when the cured product of the second resin composition is held in an atmosphere of high temperature or high humidity. 5, 5 parts by mass or less is preferable, 1 part by mass or less is more preferable, 0.7 parts by mass or less is further preferable, 0.5 parts by mass or less is particularly preferable, 0.4 parts by mass or less is extremely preferable, and 0.3 parts by mass is extremely preferable. It is very preferably parts or less, and even more preferably 0.25 parts by mass or less. From these viewpoints, the content of the light absorbing material is preferably 0.01 to 5 parts by mass.

The content of the absorbent material is preferably in the following range with respect to 100 parts by mass of the total amount of the component (a) and the component (b). The content of the absorbing material is preferably 0.01 part by mass or more, more preferably 0.02 part by mass or more, further preferably 0.03 part by mass or more, and 0, from the viewpoint of easily absorbing light in a desired wavelength region. .04 parts by mass or more is particularly preferable, 0.05 parts by mass or more is extremely preferable, 0.07 parts by mass or more is very preferable, and 0.1 parts by mass or more is even more preferable. The content of the absorbing material is from the viewpoint that it is easy to suppress the change of the wavelength spectrum in the desired wavelength region even when the cured product of the second resin composition is held in an atmosphere of high temperature or high humidity. 1, 1 part by mass or less is preferable, 0.5 part by mass or less is more preferable, 0.4 part by mass or less is further preferable, 0.3 part by mass or less is particularly preferable, 0.2 part by mass or less is extremely preferable, and 0. 15 parts by mass or less is very preferable, and 0.12 parts by mass or less is even more preferable. From these viewpoints, the content of the light absorbing material is preferably 0.01 to 1 part by mass.

The content of the absorbent material is preferably in the following range based on the total amount (total amount of solid content) of the second resin composition. The content of the absorbing material is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, further preferably 0.01% by mass or more, and 0, from the viewpoint of easily absorbing light in a desired wavelength region. 3.03% by mass or more is particularly preferable, 0.05% by mass or more is extremely preferable, 0.07% by mass or more is very preferable, and 0.09% by mass or more is even more preferable. The content of the absorbing material is from the viewpoint that it is easy to suppress the change of the wavelength spectrum in the desired wavelength region even when the cured product of the second resin composition is held in an atmosphere of high temperature or high humidity. 1, 1% by mass or less is preferable, 0.5% by mass or less is more preferable, 0.3% by mass or less is further preferable, 0.25% by mass or less is particularly preferable, 0.2% by mass or less is extremely preferable, and 0. 15% by mass or less is very preferable, and 0.1% by mass or less is even more preferable. From these viewpoints, the content of the light absorbing material is preferably 0.001 to 1% by mass.

When the second resin composition according to the present embodiment contains the component (e), the content of the component (e) is preferably in the following range.

The content of the component (e) in the second resin composition is preferably in the following range with respect to 100 parts by mass of the component (a). The content of the component (e) is preferably 0.001 part by mass or more, more preferably 0.003 part by mass or more, further preferably 0.005 part by mass or more, and 0.01 mass by mass from the viewpoint of easily absorbing ultraviolet rays. More than parts is particularly preferable, 0.015 parts by mass or more is extremely preferable, and 0.02 parts by mass or more is very preferable. The content of the component (e) tends to suppress a change in the wavelength spectrum of a desired wavelength region even when the cured product of the second resin composition is held in an atmosphere of high temperature or high humidity. From the viewpoint, 1 part by mass or less is preferable, 0.5 part by mass or less is more preferable, 0.3 part by mass or less is further preferable, 0.1 part by mass or less is particularly preferable, and 0.05 part by mass or less is extremely preferable. 0.04 parts by mass or less is very preferable, and 0.03 parts by mass or less is even more preferable. From these viewpoints, the content of the component (e) is preferably 0.001 to 1 part by mass.

The content of the component (e) in the second resin composition 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 (e) is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, further preferably 0.03 parts by mass or more, and 0.04 parts by mass from the viewpoint of easily absorbing ultraviolet rays. More than parts are particularly preferable, 0.06 parts by mass or more is extremely preferable, 0.08 parts by mass or more is very preferable, and 0.1 parts by mass or more is even more preferable. The content of the component (e) tends to suppress a change in the wavelength spectrum of a desired wavelength region even when the cured product of the second resin composition is held in an atmosphere of high temperature or high humidity. From the viewpoint, 1 part by mass or less is preferable, 0.5 part by mass or less is more preferable, 0.4 part by mass or less is further preferable, 0.3 part by mass or less is particularly preferable, and 0.2 part by mass or less is extremely preferable. 0.15 parts by mass or less is very preferable, and 0.12 parts by mass or less is even more preferable. From these viewpoints, the content of the component (e) is preferably 0.01 to 1 part by mass.

The content of the component (e) in the second resin composition is preferably in the following range based on the total amount (total amount of solid content) of the second resin composition. The content of the component (e) is preferably 0.001% by mass or more, more preferably 0.003% by mass or more, further preferably 0.005% by mass or more, and 0.007% by mass from the viewpoint of easily absorbing ultraviolet rays. % Or more is particularly preferable, and 0.009% by mass or more is extremely preferable. The content of the component (e) tends to suppress a change in the wavelength spectrum of a desired wavelength region even when the cured product of the second resin composition is held in an atmosphere of high temperature or high humidity. From the viewpoint, 1% by mass or less is preferable, 0.5% by mass or less is more preferable, 0.1% by mass or less is further preferable, 0.05% by mass or less is particularly preferable, and 0.03% by mass or less is extremely preferable. 0.02% by mass or less is very preferable, and 0.01% by mass or less is even more preferable. From these viewpoints, the content of the component (e) is preferably 0.001 to 1% by mass.

<Manufacturing method of semiconductor devices>
The method for manufacturing a semiconductor device according to the present embodiment includes a step of forming a first resin layer on a semiconductor substrate to obtain a first laminate (first laminate step) and a second step on a transparent substrate. A step of forming a resin layer and obtaining a second laminate (second laminate step), the first laminate and the second laminate, at least the first resin layer is the semiconductor substrate. A step of laminating so as to be arranged between the transparent base material and the transparent base material (third laminating step) is provided. Here, the order in which the first laminating step and the second laminating step are performed is not particularly limited.

The method for manufacturing a semiconductor device according to the present embodiment may include a step of curing or semi-curing the first resin layer (first curing step) before the third laminating step. The method for manufacturing a semiconductor device according to the present embodiment may include a step of curing or semi-curing the second resin layer (second curing step) before the third laminating step. The method for manufacturing a semiconductor device according to the present embodiment may include a third curing step of curing at least one of the first resin layer and the second resin layer at the same time as or after the third laminating step. .. Here, the order in which the first curing step and the second curing step are performed is not particularly limited.

The first resin layer is made of, for example, the first resin composition according to the present embodiment. The second resin layer is made of, for example, the second resin composition according to the present embodiment. The transparent substrate (glass substrate or the like) is, for example, a transparent substrate (glass substrate or the like).

In the third laminating step, at least one of the first resin layer and the second resin layer may be sandwiched between the semiconductor substrate and the transparent base material, and the semiconductor substrate and the transparent base material may be pressure-bonded. The third laminating step and the third curing step do not necessarily have to be independent steps, and curing may be performed at the same time while laminating (crimping).

FIG. 1 is a process diagram showing an example of a method for manufacturing a semiconductor device according to the present embodiment. First, as shown in FIG. 1A, the first resin composition is applied onto the semiconductor substrate 12 to form the first resin layer 14, and then heat-drying and the first curing step are performed. The resin layer 14 of No. 1 is semi-cured to obtain a first laminated body 10 (first laminating step). Further, as shown in FIG. 1B, a second resin composition is applied onto the transparent base material 22 to form a second resin layer 24, and heat drying and a second curing step are performed. The second resin layer 24 is semi-cured to obtain a second laminated body 20 (second laminating step). Next, as shown in FIG. 1C, the first laminate 10 and the second laminate 20 are formed, and the first resin layer 14 and the second resin layer 24 are the semiconductor substrate 12 and the transparent substrate. It is crimped so as to be sandwiched between the resin layer 22 and the first resin layer 14 and the second resin layer 24 are cured by performing a third curing step to cure the first resin layer (cured product) 14a and the first resin layer 24. The resin layer (cured product) 24a of 2 is formed. As a result, as shown in FIG. 1D, the semiconductor device 100 is obtained.

Hereinafter, each step will be further described.

(First laminating step)
As the first laminating step, for example, a method of applying the first resin composition according to the present embodiment on the semiconductor substrate or a method of attaching the film-shaped first resin composition to the semiconductor substrate is adopted. can do. The semiconductor substrate may be, for example, either a semiconductor wafer or a semiconductor element (semiconductor chip).

Examples of the method for applying the first resin composition include a dispensing method (syringe dispensing method and the like), a spin coating method, a die coating method, a knife coating method and the like. When the method of pasting the first resin composition in the form of a film is adopted, it is preferable to laminate in the range of 0 to 90 ° C. in order to secure sufficient wet spread. In addition, it is preferable to perform roll laminating in order to adhere evenly.

A method for producing the first film-like resin composition will be described below. For example, the first resin composition according to the present embodiment is uniformly applied onto 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). By heating, a film-like first resin composition is formed. At this time, a coater such as a die coater or a comma coater is used so that the film-shaped first resin composition has a desired thickness, so that the amount of solvent, the viscosity, and the initial thickness of the coating of the first resin composition are obtained. If so, adjust the gap between the coater and the support film), the drying temperature, the 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 to improve workability. Depending on the type and temperature of the smoothing agent, subtle irregularities may be transferred to the adhesive and the flatness may decrease. Therefore, it is preferable to use a support film that does not use a smoothing agent or a support film that does not use a smoothing agent. Further, from the viewpoint of excellent flexibility, a support film such as a polyethylene film is preferable, 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 surface of the resin layer during laminating.

Next, the first resin layer formed on the semiconductor substrate is heat-dried, if necessary. The drying temperature is not particularly limited, but when a varnish-like first resin composition in which the contained components are dissolved or dispersed in a solvent is used, the drying temperature suppresses the generation of bubbles due to foaming of the solvent during drying. From the viewpoint of easy operation, it is preferable that the temperature is 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.

Further, when the varnish-like first resin composition in which the contained components are dissolved or dispersed in the solvent is used, the residual amount of the solvent is minimized from the viewpoint that it is easy to suppress the generation of bubbles due to the foaming of the solvent after curing. It is preferable to do so.

The above-mentioned conditions for heat-drying are not particularly limited as long as the solvent used is sufficiently volatilized, but are usually carried out by heating at 40 to 100 ° C. for 0.1 to 90 minutes.

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

The heat drying can be omitted when the first resin layer is formed by the method of pasting the first resin composition in the form of a film.

(First curing step)
Next, if necessary, a first curing step of curing or semi-curing the first resin layer is performed. Examples of the curing method include a method of curing or semi-curing by heat and / or light, and in particular, curing or semi-curing by heat is preferable.

In the first curing step, it is preferable that the thermosetting (cure) is carried out for 1 to 2 hours while selecting a temperature and gradually raising the temperature. The thermosetting is preferably performed at 100 to 200 ° C. Semi-curing (precure) by heat is preferably performed at 40 to 120 ° C. for 0.05 to 2.0 hours.

(Second laminating process)
As the second laminating step, for example, a method of applying the second resin composition according to the present embodiment on a transparent base material, or a method of attaching a film-like second resin composition to a transparent base material. Can be adopted. Examples of the transparent base material include a glass base material and the like. The second laminating step can be performed in the same manner as the first laminating step.

(Second curing step)
The second curing step can be performed in the same manner as the first curing step.

(Third laminating process)
The first laminate and the second laminate obtained by the above method are pressure-bonded so that the first resin layer and the second resin layer are sandwiched between the semiconductor substrate and the transparent substrate. From the viewpoint of improving the adhesion between the first resin layer and the second resin layer, at least one of the first resin layer and the second resin layer is in an uncured state (the first or second curing step has not been performed yet). It is preferably in the state of implementation) or in the semi-cured state.

(Third curing step)
A cured product is formed by crimping the semiconductor substrate and the transparent base material via the first and second resin layers and then curing the first and second resin layers. Examples of the curing method include a method of curing by heat and / or light, and in particular, curing by heat is preferable.

In the third curing step of forming the cured product of the first and second resin layers, it is preferable that the thermosetting (cure) is carried out for 1 to 2 hours while selecting a temperature and gradually raising the temperature. The thermosetting is preferably performed at 100 to 200 ° C.

<Semiconductor device>
The semiconductor device according to the present embodiment includes a semiconductor substrate, a transparent base material, a first resin layer formed by using a first resin composition containing a curable resin, a curable resin, and 600 to 1100 nm. A second resin layer formed by using a second resin composition containing an infrared absorbing material having a maximum absorption wavelength in the wavelength region of the above is provided. Here, the first resin layer is arranged between the semiconductor substrate and the transparent substrate. The second resin layer is arranged between the first resin layer and the transparent base material, or on the side opposite to the semiconductor substrate side of the transparent base material.

Examples of semiconductor devices include optical components. Examples of the optical component include an optical device such as a solid-state image sensor. Examples of the solid-state image sensor include a CCD image sensor, a CMOS image sensor (for example, a back-illuminated CMOS image sensor) and the like. The CMOS image sensor, which is an example of the 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 motherboard of the mobile phone via a solder ball, and the optical lens is arranged above the sensor (that is, on the transparent base material side such as a glass base material).

In the semiconductor device (for example, a solid-state image sensor) according to the present embodiment, the light receiving portion arranged on the main surface (for example, the upper surface) of the semiconductor substrate may be covered with the first 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 arranged on the upper surface and a first resin layer arranged on the semiconductor substrate so as to cover the light receiving portion. A transparent base material adhered to the semiconductor substrate via the first resin layer or the first and second resin layers. The semiconductor device according to the present embodiment is a member (for example, a frame-shaped member) arranged on a region (for example, the outer peripheral portion of the main surface) located on the main surface of the semiconductor substrate on the outer peripheral side of the main surface from the light receiving portion. May be equipped. The member may have an opening (cavity) for exposing the light receiving portion, and the first resin layer or the first and second resin layers may be arranged (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 first resin layer or the first and second resin layers. In the semiconductor device according to the present embodiment, a part or the whole of the semiconductor substrate may be sealed with the first resin layer or the first and second resin layers. The first resin layer, or the first and second resin layers, may be arranged between the semiconductor substrate and the transparent substrate and / or around the semiconductor substrate and / or the transparent substrate.

The semiconductor device according to the present embodiment has, for example, a non-cavity structure using the first and second resin compositions according to the present 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 image sensor, will be described with reference to the drawings in some cases.

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

As shown in FIG. 3, 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. The 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 first resin layer 6a containing the first resin composition or a cured product thereof according to the present embodiment is formed on one surface side of the silicon substrate 5 over the entire surface on the region where the microlens 2 is arranged. There is. On the first resin layer 6a, a second resin layer 6b containing the second resin composition according to the present embodiment or a cured product thereof is formed. A glass substrate 4 is arranged on the second resin layer 6b. As a result, 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 surface side of the silicon substrate 5, and the solder balls 8 are arranged on the lower surface of the wiring layer 7.

FIG. 4 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. 4, 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 the glass substrate 4 has transparency. Is arranged on the upper surface of the frame-shaped member 9. In the portion surrounded by the glass substrate 4, the silicon substrate 5, and the frame-shaped member 9, the first resin layer 6c (silicon substrate 5 side) containing the first resin composition according to the present embodiment or a cured product thereof, A second resin layer 6d (glass substrate 4 side) containing the second resin composition or a cured product thereof according to the present embodiment is filled, and a non-cavity structure is formed. In the semiconductor device of FIG. 4, the first resin layer 6c and the second resin layer 6d serve as an adhesive for adhering the glass substrate 4 and the silicon substrate 5, and also fill the cavity to form a microlens. 2. It also plays a role as a sealing material for sealing the photodiode 2a and the color filter 2b.

In a non-cavity structure using adhesive ribs (frame-shaped resin layer), adhesive ribs (hereinafter, also simply referred to as “ribs”) are formed so as to surround the light receiving portion, and then the light receiving portion is formed. A transparent encapsulant is filled and a transparent substrate (for example, a glass substrate) is adhered so as to be sealed. For example, in the non-cavity structure of FIG. 4, after forming the frame-shaped member 9, the cavity is filled with the first resin composition and the second resin composition to form the first resin layer 6c and the second resin. Layer 6d is formed. The non-cavity structure thus produced can sufficiently impart adhesiveness to a portion other than the rib, and a more reliable non-cavity structure can be obtained. On the other hand, in the non-cavity structure of FIG. 3, the first resin composition 6a containing the first resin composition according to the present embodiment or a cured product thereof and the second resin layer 6a according to the present embodiment without providing ribs. The glass substrate 4 and the silicon substrate 5 are adhered to each other via a second resin layer 6b containing the resin composition or a cured product thereof. This is because the first resin composition and its cured product according to this embodiment, and the second resin composition and its cured product according to this embodiment can function as an adhesive and a sealing material. Is. In this case, the non-cavity structure (first embodiment) shown in FIG. 3 does not require the formation of ribs as compared with the non-cavity structure (second embodiment) shown in FIG. 4, and a semiconductor device can be easily manufactured. Can be done. In addition, equipment such as a printing machine, an exposure machine, and a developing machine necessary for forming ribs is not required.

In the semiconductor device of the present embodiment, the light transmittances of the first resin layers 6a and 6c at wavelengths of 400 nm, 700 nm and 1000 nm are all 90% or more. As a result, the semiconductor device can obtain excellent impact resistance. Further, from the viewpoint of obtaining more excellent impact resistance, the light transmittance at each of the above wavelengths is more preferably 95% or more, further preferably 99% or more.

The thickness of the first resin layers 6a and 6c is not particularly limited, but may be, for example, 10 to 100 μm, 20 to 80 μm, or 30 to 80 μm. When the thickness is within the above range, the impact resistance tends to be improved.

The thickness of the second resin layers 6b and 6d is not particularly limited, but may be, for example, 10 to 300 μm, 20 to 200 μm, or 30 to 100 μm. If the thickness exceeds 300 μm, it tends to be difficult to obtain a uniform thickness, and if it is less than 10 μm, it tends to be difficult to obtain a uniform coating film.

_{The ratio (D 1} / D _{2 ) of the thickness D 1} (μm) of the first resin layers 6a, 6c to the thickness _{D 2} (μm) of the second resin layers 6b, 6d is 0.03 to 1. It can be 0. When the ratio (D ₁ / D ₂ ) is within the above range, it tends to be easy to achieve both improvement in impact resistance and reduction in infrared transmittance in a well-balanced manner.

FIG. 5 is a drawing for comparing manufacturing methods of semiconductor devices. FIG. 5A shows a manufacturing method (rib forming process) of the semiconductor device according to the second embodiment. FIG. 5B shows a manufacturing method (total sealing process) of the semiconductor device according to the first embodiment. In the method for 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 step of dicing is required. On the other hand, in the method for manufacturing a semiconductor device according to the first embodiment, the formation of ribs (frame-shaped adhesive) is unnecessary by using the first and second resin compositions according to the present embodiment. , (B) Exposure and (c) Development steps are not required. As a result, after forming the first resin layer on the semiconductor substrate, it can be immediately sealed with a transparent base material (glass base material or the like) having a second resin layer. After that, it can be separated into individual pieces by dicing or the like.

FIG. 6 is a cross-sectional view showing an example of a semiconductor device (back-illuminated solid-state imaging device) having a cavity structure. In FIG. 6, a cavity 9a surrounded by a glass substrate 4 and a frame-shaped member 9 exists on the silicon substrate 5. In the cavity structure, an adhesive is formed into a frame shape by using photolithography, a printing method, a dispensing method, or the like, and then the glass substrate 4 and the silicon substrate 5 are bonded to each other 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-shaped adhesive.

The non-cavity structure has the following merits as compared with the cavity structure.

In the cavity structure, foreign matter adhering to the microlens, the glass base material, or the like also causes deterioration of image quality. This is because the cavity is exposed from the time when the adhesive is formed until the glass base material is adhered. On the other hand, in the non-cavity structure of the present embodiment, since the exposed time is short, the adhesion of foreign matter is reduced.

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

Although the embodiments have been described above, the present invention is not limited to the above embodiments. For example, with respect to each of the above embodiments, a form in which a person skilled in the art appropriately adds, deletes, or changes the design, or a form in which a process is added, omitted, or a condition is changed does not contradict the gist of the present invention. As long as it is included in the scope of the present invention. For example, in the above embodiment, an example in which a glass base material is used as the transparent base material has been shown, but the present invention is not limited to this, and any transparent base material having the required strength, rigidity and light transmittance Good.

Further, in the above embodiment, an example in which the second resin layer is arranged between the first resin layer and the transparent base material is shown, but the second resin layer is a semiconductor substrate of the transparent base material. It may be formed on the surface opposite to the side.

Further, in the above embodiment, a method of manufacturing a semiconductor device by producing a first laminated body and a second laminated body and then laminating them together is shown. For example, a second laminated body is used. After producing and curing or semi-curing the second resin layer, the first resin layer is formed on the second resin layer, and then the semiconductor substrate is placed on the first resin layer and pressure-bonded. Then, the semiconductor device may be manufactured.

Further, the semiconductor device may further include a resin layer other than the first resin layer and the second resin layer. For example, a semiconductor device contains a light absorbing material different from that of the second resin layer, and has a third resin layer having the same structure as the second resin layer except for the light absorbing material. It may be provided between the materials or on the side opposite to the semiconductor substrate side of the transparent base material. In this case, for example, the component (d1) may be contained in the second resin layer, and the component (d2) in the third resin layer may be contained. By containing the component (d1) and the component (d2) in separate layers, the light transmittance in both the wavelength region of 600 to 800 nm and the long wavelength region (for example, 800 to 1100 nm) can be further reduced. Can be done.

Further, the semiconductor device may include a third resin layer having the same structure as the first resin layer between the second resin layer and the transparent base material. In this case, the impact resistance of the semiconductor device can be further improved, and cracking of the transparent base material can be more sufficiently prevented.

In the semiconductor device of the present embodiment, when at least two of the first resin layer, the second resin layer, and the third resin layer provided as needed are adjacent to each other, the boundary between the layers is clear. It may not be necessary, and some of the components of one layer may be mixed in the other layer. When the boundary between the layers is not clear, the first resin layer, the second resin layer, and the third resin layer are formed in the first resin region, the second resin region, and the third resin region, respectively. There may be.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.

<Synthesis of (meth) acrylic polymer>
The (meth) acrylic polymer (a1) was synthesized by the following procedure.

Tricycloacrylate [5.2.1.0 ^2,6 ] Deca-8-yl (FA-513A, Hitachi Kasei 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. A mixed solution was obtained by dissolving 5 g of dilauroyl peroxide and 0.45 g of n-octyl mercaptan (chain transfer agent) in the obtained monomer mixture.

0.44 g of polyvinyl alcohol (suspension agent) and 2000 g of ion-exchanged water were added to a 5 L autoclave equipped with a stirrer and a condenser. Next, the above mixture was added with stirring, and the mixture was polymerized at 60 ° C. for 5 hours under ^{a stirring rotation speed of 250 min -1 and a nitrogen atmosphere.}
Then, it was polymerized 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 formula using a standard polystyrene kit PStQuick series C (Tosoh Corporation, trade name). The conditions for GPC are shown below.
Pump: L6000 Pump (Hitachi, Ltd.)
Detector: L3300 RI Monitor (Hitachi, Ltd.)
Column: Gelpack GL-S300MDT-5 (2 in total) (Hitachi Kasei Co., Ltd., product 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

<Preparation of ingredients contained in the resin composition>
The following ingredients were prepared.
(A) Component (meth) acrylic polymer synthesized by the above method (a1)
(B) Ingredient R-604: Nippon Kayaku Co., Ltd., trade name "KAYARAD R-604", dioxane glycol diacrylate (c) Ingredient Park Mill D: Nikko Co., Ltd., 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
(D) Component HKC-5: Complex compound containing copper and phosphorus (compound in which an organic compound containing a phosphorus atom coordinates with a copper atom), manufactured by Konica Minolta, with an average particle size of 25 nm.
HKC-7: Complex compound containing copper and phosphorus (compound in which an organic compound containing a phosphorus atom coordinates with a copper atom), manufactured by Konica Minolta, with an average particle size of 14 nm.
HK-7: Organic dye compound, manufactured by Konica Minolta Co., Ltd., absorption wavelength 700 to 780 nm
FDR-004: Phthalocyanine pigment, manufactured by Yamada Chemical Co., Ltd., absorption wavelength 700-730 nm
(E) Component UV-1: Ultraviolet absorber, absorption wavelength 300-400 nm
(Antioxidant)
AO-80: Made by 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: Made by ADEKA Corporation, trade name "ADEKA Sulfide" AO-503 ”, thioether-based antioxidant, ditridecyl 3,3-thiobispropionate MT-PE1: manufactured by Showa Denko Co., Ltd., trade name“ Karenz MT-PE1 ”, pentaerythritol tetrakis (3-mercaptobutylate)
(Other ingredients)
ACMO: KJ Chemicals Co., Ltd., trade name "ACMO", acryloyl morpholine, monofunctional (meth) acrylic monomer SZ-6030: Toray Dow Corning Co., Ltd., trade name "SZ-6030", γ-methacryloyloxy Propyltrimethoxysilane, coupling agent (organic solvent)
PGMEA: Propylene glycol 1-monomethyl ether 2-acetate manufactured by Kanto Chemical Co., Inc.

(Example 1)
<Preparation of resin composition>
The components shown in Table 1 were mixed in the blending amounts (unit: parts by mass) shown in the same table to obtain a first resin composition and a second resin composition.

<Manufacturing of laminated body>
A film having a film thickness of 120 μm is obtained by applying the second resin composition on a glass substrate having a length of 100 mm, a width of 100 mm, and a thickness of 0.5 mm and then drying the second resin composition at 70 ° C./10 minutes and 100 ° C./10 minutes. A second resin layer in the shape of a shape was formed. Next, the first resin composition is applied onto the second resin layer and then dried at 70 ° C./10 minutes and 100 ° C./10 minutes to form a film-like first resin layer having a film thickness of 50 μm. Formed. Then, the first resin layer and the second resin layer were cured by heating at 200 ° C. for 2 hours in a vacuum environment. As a result, a laminated body in which the glass base material / the second resin layer (cured product) / the first resin layer (cured product) was laminated in this order was obtained. The light transmittance of the first resin layer (cured product) at wavelengths of 400 nm, 700 nm and 1000 nm was 90% or more. The light transmittance was measured by using a first resin layer (cured product) single layer formed to the same thickness by the same method as described above, and by the same method as the measurement of the transmission spectrum described later.

[Evaluation of impact resistance]
The laminate obtained in the examples and the same glass substrate used in the examples for comparison were placed on a concrete floor. The laminate of the example was placed so that the first resin layer was in contact with the floor. Then, an iron ball drop test was conducted by the following method. That is, a 100 g iron ball was dropped by its own weight from 15 cm above the surface of the glass substrate to collide with the glass substrate, and the presence or absence of cracks in the glass substrate was confirmed. As a result, the glass base material to be compared was cracked, but the laminated body of the example did not crack. From this result, it was confirmed that the impact resistance can be improved by providing the first and second resin layers.

[Measurement of transmission spectrum]
The transmittance (spectral spectrum) of the laminate obtained in the example at 25 ° C. was measured. Specifically, a spectrophotometer U4100 (trade name, Hitachi, Ltd., start 1200 nm, end 300 nm, scan speed 600 nm / min, sampling interval 1.0 nm, baseline: Air) is used in the wavelength range of 300 to 1200 nm. The transmittance was measured with. As a result, the results shown in Table 2 were obtained.

1a, 1b ... CMOS image sensor (semiconductor device), 2 ... microlens, 2a ... photodiode, 2b ... color filter, 3a ... sensor unit, 3b ... peripheral circuit unit, 4 ... glass substrate (transparent substrate), 5 ... Silicon substrate (semiconductor substrate), 6a, 6c, 14 ... 1st resin layer, 6b, 6d, 24 ... 2nd resin layer, 7 ... wiring layer, 8 ... solder ball, 9 ... frame-shaped member, 9a ... cavity 10, ... 1st laminate, 12 ... semiconductor substrate, 20 ... second laminate, 22 ... transparent substrate, 100 ... semiconductor device.

Claims (5)

With a semiconductor substrate
With a transparent base material
A first resin layer arranged between the semiconductor substrate and the transparent substrate,
A second resin layer arranged between the first resin layer and the transparent base material, or on the side of the transparent base material opposite to the semiconductor substrate side.
With
The first resin layer is a layer formed by using the first resin composition containing a curable resin.
The second resin layer is a layer formed by using a second resin composition containing a curable resin and an infrared absorbing material having a maximum absorption wavelength in a wavelength region of 600 to 1100 nm.
A semiconductor device having a light transmittance of 90% or more at wavelengths of 400 nm, 700 nm, and 1000 nm of the first resin layer. Claim that the first resin composition contains (a) (meth) acrylic polymer, (b) a compound having at least two (meth) acryloyl groups, and (c) a polymerization initiator. The semiconductor device according to 1. The semiconductor device according to claim 1 or 2, wherein the infrared absorbing material contains a complex compound containing copper and phosphorus. The semiconductor device according to any one of claims 1 to 3, wherein the infrared absorbing material contains at least one selected from the group consisting of a squalium compound, a phthalocyanine compound and a cyanine compound. The semiconductor device according to any one of claims 1 to 4, wherein the second resin layer further contains an ultraviolet absorber.

Images