JP2024095337A - Semiconductor device manufacturing method and semiconductor device - Google Patents

Abstract

The present invention provides a method for manufacturing a semiconductor device, which includes forming a laminated substrate by bonding a chip and a semiconductor substrate using a curable resin composition while suppressing the occurrence of voids at the bonding interface, and a semiconductor device including the laminated substrate.
[Solution] By using a curable resin composition containing an alkali-soluble resin (A) having an alkali-soluble structural unit (A1) having a carboxy group and/or a phenolic hydroxyl group, and an epoxy group-containing unit (A3), bonding between a chip and a semiconductor substrate is performed while controlling the reaction rate of the epoxy group in the curable resin composition.
[Selected Figure] Figure 1

Description

The present invention relates to a method for manufacturing a semiconductor device that includes forming a laminated substrate in which two exposed metal electrodes are in contact, and a semiconductor device that includes the aforementioned laminated substrate.

In recent years, in order to improve the integration density of semiconductor devices such as LSIs, three-dimensional mounting of semiconductor chips onto semiconductor wafers has been practiced. As such a three-dimensional mounting technology, a method has been proposed in which a semiconductor chip is bonded to a semiconductor wafer using a resin composition containing at least one of a polyimide precursor and a polyimide resin, and a solvent (Patent Document 1).

International Publication No. 2022/071329

When a semiconductor chip is three-dimensionally mounted on a semiconductor wafer, voids may occur at the bonding interface between the wafer and the chip. According to the description in Patent Document 1, the problem of void occurrence is improved to a certain extent, but further improvement is required for the problem of void occurrence in three-dimensional mounting of a semiconductor chip on a semiconductor wafer.
Under these circumstances, there is a demand for a method for three-dimensionally mounting semiconductor chips on a semiconductor wafer that can achieve good bonding while suppressing the occurrence of voids.

The present invention has been made in consideration of the above problems, and aims to provide a method for manufacturing a semiconductor device that includes forming a laminated substrate by bonding a chip and a semiconductor substrate using a curable resin composition while suppressing the occurrence of voids at the bonding interface, and a semiconductor device including the laminated substrate.

The present inventors have found that the above problems can be solved by using a curable resin composition containing an alkali-soluble resin (A) having an alkali-soluble structural unit (A1) having a carboxy group and/or a phenolic hydroxyl group and an epoxy group-containing unit (A3), and bonding a chip to a semiconductor substrate while controlling the reaction rate of the epoxy group in the curable resin composition, and have completed the present invention.

で表される構成単位（Ａ１）とエポキシ基含有単位（Ａ３）とを有する共重合体を含み、
前記式（ａ―１）中、Ｒは水素原子又はメチル基を表し、Ｒ^ａ０１は水酸基を有する有機基を表し、
半硬化膜において、硬化性樹脂組成物に由来するエポキシ基の反応率が２０％超８０％未満であり、
焼成された積層基板における半硬化膜が硬化した硬化膜において、硬化性樹脂組成物に由来するエポキシ基の反応率が８５％以上である、半導体装置製造方法。 A first aspect of the present invention is a method for manufacturing a semiconductor substrate, comprising the steps of: forming a first substrate including a semiconductor substrate; a semi-cured film formed by baking a resin film made of a curable resin composition and covering one main surface of the semiconductor substrate; and a first metal electrode located in the semi-cured film, one end surface of which is exposed on a surface of the semi-cured film and the other end surface of which is in contact with the semiconductor substrate;
dicing the first substrate into a plurality of chips by cutting the first substrate in a thickness direction of the first substrate;
preparing a second substrate including a substrate, an insulating film covering one main surface of the substrate, and a second metal electrode located in the insulating film, one end surface of which is exposed on the surface of the insulating film and the other end surface of which is in contact with the substrate;
a bonding step of baking the chip and the second substrate in a state in which the surface of the semi-cured film faces the surface of the insulating film and the first metal electrode is in contact with the second metal electrode, thereby bonding the chip and the second substrate to obtain a laminated substrate;
and firing the laminated substrate;
The curable resin composition contains an alkali-soluble resin (A),
The alkali-soluble resin (A) has a carboxy group and/or a phenolic hydroxyl group as the alkali-soluble group,
The alkali-soluble resin (A) is represented by the following formula (a-1):

and an epoxy group-containing unit (A3),
In the formula (a-1), R represents a hydrogen atom or a methyl group, and R represents an organic ^group having a hydroxyl group.
In the semi-cured film, the reaction rate of the epoxy group derived from the curable resin composition is more than 20% and less than 80%,
A method for manufacturing a semiconductor device, wherein in a cured film obtained by curing the semi-cured film on the baked laminated substrate, a reaction rate of epoxy groups derived from the curable resin composition is 85% or more.

で表される構成単位（Ａ１）とエポキシ基含有単位（Ａ３）とを有する共重合体を含み、
式（ａ―１）中、Ｒは水素原子又はメチル基を表し、Ｒ^ａ０１は水酸基を有する有機基を表す、半導体装置。 A second aspect of the present invention is a semiconductor device including a laminated substrate including a chip and a second substrate, the chip and the second substrate being bonded to each other,
The chip comprises a semiconductor substrate, a cured film covering one main surface of the semiconductor substrate, and a first metal electrode located in the cured film, one end surface of which is exposed on the surface of the cured film and the other end surface of which is in contact with the semiconductor substrate;
the second substrate comprises a substrate, an insulating film covering one main surface of the substrate, and a second metal electrode located in the insulating film, one end surface of which is exposed on the surface of the insulating film and the other end surface of which is in contact with the substrate;
In the laminated substrate, the cured film and the insulating film are bonded to each other, and the first metal electrode and the second metal electrode are in contact with each other.
the cured film is made of a cured product of a curable resin composition containing an alkali-soluble resin (A);
The alkali-soluble resin (A) has a carboxy group and/or a phenolic hydroxyl group as the alkali-soluble group,
The alkali-soluble resin (A) is represented by the following formula (a-1):

and an epoxy group-containing unit (A3),
In formula (a-1), R represents a hydrogen atom or a methyl group, and R ^a01 represents an organic group having a hydroxyl group.

The present invention provides a method for manufacturing a semiconductor device that uses a curable resin composition to bond a chip and a semiconductor substrate while suppressing the generation of voids at the bonding interface to form a laminated substrate, and a semiconductor device that includes the laminated substrate.

1A to 1C are diagrams illustrating a stacked state in a stacked substrate forming step in a manufacturing method of a semiconductor device.

<Curable resin composition>
Hereinafter, a curable resin composition suitable for use in the manufacturing method of a semiconductor device described later will be described. The curable resin composition exhibits excellent thermal adhesion. The use of the curable resin composition is not limited to the manufacturing method of a semiconductor device described later.

The curable resin composition contains an alkali-soluble resin (A).

The curable resin composition is preferably used for forming a semi-cured film in the manufacturing method of a semiconductor device described later. Typically, the curable resin composition is used for forming a semi-cured film that adheres to an insulating film that insulates a metal electrode in an electric/electronic device having a metal electrode. The semi-cured film is cured by baking to give an insulating film that is a cured film.
The electric/electronic device is not particularly limited, and examples thereof include communication equipment such as mobile phones, network-related electronic devices such as servers, and electronic devices such as computers, in particular the semiconductor components contained in these devices, specifically semiconductor packages known as wafer-level packages.
These electric/electronic devices have metal electrodes made of a metal such as copper or an alloy on a substrate for the electric/electronic device. Substrates for electric/electronic devices having metal electrodes include silicon substrates and substrates on which various layers and members are provided.
This metal electrode is insulated from other metal electrodes and conductive members by an insulating film formed from a curable resin composition.
In the manufacturing method of a semiconductor device described below, the above-mentioned curable resin composition is used, and bonding is performed while controlling the reaction rate of the epoxy group in the curable resin composition, thereby making it possible to suppress the generation of voids at the bonding interface during bonding in a semiconductor device manufactured by bonding.

Below, we will explain the essential and optional components contained in the curable resin composition.

<Alkali-soluble resin (A)>
The alkali-soluble resin (A) has a carboxy group and/or a phenolic hydroxyl group as the alkali-soluble group.
The alkali-soluble resin (A) has a structural unit (A1) represented by the formula (a-1) described below and an epoxy group-containing unit (A3).

[Structural unit (A1)]
The structural unit (A1) is represented by the following formula (a-1).

In formula (a-1), R is a hydrogen atom or a methyl group, and ^{R a01} is an organic group having a hydroxyl group.
Examples of the organic group represented by R ^a01 include a branched, linear, or cyclic alkyl group, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, an aralkyl group which may have a substituent, and a heteroaralkyl group which may have a substituent.
The organic group represented by R ^a01 has at least one hydroxyl group in its structure. The number of carbon atoms in the organic group is preferably 1 to 20, more preferably 6 to 12. A larger number of carbon atoms is preferable in terms of the storage stability of the curable resin composition and the low dielectric constant of the cured product of the curable resin composition. A smaller number of carbon atoms provides the curable resin composition with excellent resolution.

In terms of the alkali solubility of the alkali-soluble resin (A), it is also effective that R ^a01 in the structural unit (A1) is a hydrogen atom, that is, the structural unit (A1) is a structural unit derived from methacrylic acid, acrylic acid, etc. However, from the viewpoint of the storage stability of the curable resin composition, the structural unit (A1) is preferably an organic group having a hydroxyl group as described above.

A preferred example of the structural unit (A1) is a structural unit represented by the following formula (a-1-1):

In formula (a-1-1), R is a hydrogen atom or a methyl group. Y ^a01 is a single bond, or an alkylene group having 1 to 5 carbon atoms. R ^a001 is an alkyl group having 1 to 5 carbon atoms. a is an integer of 1 to 5. b is an integer of 0 to 4. a+b is 5 or less. When two or more R ^a001 are present, the multiple R ^a001 may be different from each other or the same.

In formula (a-1-1), R is a hydrogen atom or a methyl group, and is preferably a methyl group.
Y ^a01 is a single bond, or a linear or branched alkylene group having from 1 to 5 carbon atoms. Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, an isopropylene group, an n-butylene group, an isobutylene group, a tert-butylene group, a pentylene group, an isopentylene group, and a neopentylene group. Of these, a single bond, a methylene group, and an ethylene group are preferred.
In view of the alkali solubility of the alkali-soluble resin (A) and the heat resistance of the cured product of the curable resin composition, Y ^a01 is preferably a single bond.
a is an integer of 1 or more and 5 or less, and is preferably 1.

In the benzene ring in formula (a-1-1), when the carbon atom bonded to Y ^a01 is taken as the reference (1st position), it is preferable that a hydroxyl group is bonded to the 4th position.

R ^a001 is a linear or branched alkyl group having from 1 to 5 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group.
Of these, methyl and ethyl groups are preferred.
b is an integer of 0 to 4, and is preferably 0.

Specific examples of monomers that give the structural unit (A1) include o-hydroxyphenyl (meth)acrylate, m-hydroxyphenyl (meth)acrylate, p-hydroxyphenyl (meth)acrylate, o-hydroxybenzyl (meth)acrylate, m-hydroxybenzyl (meth)acrylate, p-hydroxybenzyl (meth)acrylate, o-hydroxyphenylethyl (meth)acrylate, m-hydroxyphenylethyl (meth)acrylate, and p-hydroxyphenylethyl (meth)acrylate. Of these, p-hydroxyphenyl (meth)acrylate and p-hydroxybenzyl (meth)acrylate are preferred, with p-hydroxyphenyl (meth)acrylate being more preferred.

The ratio of the structural unit (A1) in the alkali-soluble resin (A) is preferably 10 mol % or more and 70 mol % or less, more preferably 15 mol % or more and 60 mol % or less, and even more preferably 20 mol % or more and 50 mol % or less, based on all structural units of the alkali-soluble resin (A).
The structural unit (A1) may be present in the alkali-soluble resin (A) in the form of blocks or randomly.

[Epoxy Group-Containing Unit (A3)]
The epoxy group-containing unit (A3) is a structural unit that contains an epoxy group in its structure and is derived from a polymerizable unsaturated compound.The epoxy group is not particularly limited, and may be an alicyclic epoxy group or a linear aliphatic epoxy group.As the epoxy group-containing polymerizable unsaturated compound, an epoxy group-containing (meth)acrylic acid ester is preferred, and a linear aliphatic epoxy group-containing aliphatic (meth)acrylic acid ester or an alicyclic epoxy group-containing aliphatic (meth)acrylic acid ester is more preferred.

When the epoxy group is an alicyclic epoxy group, the number of carbon atoms in the alicyclic group is not particularly limited, but is preferably 5 or more and 10 or less.

Specific examples of suitable epoxy group-containing units (A3) having an alicyclic epoxy group include structural units derived from alicyclic epoxy group-containing polymerizable unsaturated compounds represented by the following formulas (1) to (31):

In the above formula, ^R4 is a hydrogen atom or a methyl group. ^R5 is a divalent hydrocarbon group having 1 to 8 carbon atoms. ^R6 is a divalent hydrocarbon group having 1 to 20 carbon atoms. In the alicyclic epoxy group-containing polymerizable unsaturated compound represented by any of the above formulas, when a plurality of ^R4s , a plurality of ^R5s , or a plurality of ^R6s are present, the plurality of ^R4s , the plurality of ^R5s , or the plurality of ^R6s may be the same or different. w is an integer of 0 to 10.

Among these, alicyclic epoxy group-containing polymerizable unsaturated compounds represented by formulas (1) to (6), (14), (16), (18), (21), (23) to (25), and (30) are preferred, and alicyclic epoxy group-containing polymerizable unsaturated compounds represented by formulas (1) to (6) are more preferred.

When the epoxy group is a chain aliphatic epoxy group, the number of carbon atoms in the chain aliphatic epoxy group is not particularly limited, but is preferably 3 to 20, more preferably 3 to 15, and particularly preferably 3 to 10.

Examples of the epoxy group-containing unit (A3) having a linear aliphatic epoxy group include units derived from the following linear aliphatic epoxy group-containing polymerizable unsaturated compounds.

Specific examples of linear aliphatic epoxy group-containing polymerizable unsaturated compounds include epoxy alkyl (meth)acrylates such as glycidyl (meth)acrylate, 2-methyl glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 6,7-epoxyheptyl (meth)acrylate; and epoxy alkyl oxy alkyl (meth)acrylates such as 2-glycidyloxyethyl (meth)acrylate, 3-glycidyloxy-n-propyl (meth)acrylate, 4-glycidyloxy-n-butyl (meth)acrylate, 5-glycidyloxy-n-hexyl (meth)acrylate, and 6-glycidyloxy-n-hexyl (meth)acrylate.

Specific examples of epoxy group-containing polymerizable unsaturated compounds containing aromatic groups include 4-glycidyloxyphenyl (meth)acrylate, 3-glycidyloxyphenyl (meth)acrylate, 2-glycidyloxyphenyl (meth)acrylate, 4-glycidyloxyphenylmethyl (meth)acrylate, 3-glycidyloxyphenylmethyl (meth)acrylate, and 2-glycidyloxyphenylmethyl (meth)acrylate.

The ratio of the epoxy group-containing unit (A3) in the alkali-soluble resin (A) is preferably 5 mol % or more and 40 mol % or less, more preferably 10 mol % or more and 30 mol % or less, and even more preferably 15 mol % or more and 25 mol % or less, based on all the constituent units of the alkali-soluble resin (A).
When the alkali-soluble resin (A) contains the epoxy group-containing unit (A3) in the above ratio, the heat resistance and adhesion of the cured product of the curable resin composition are high, and the dielectric constant of the cured product of the curable resin composition is low.
The structural unit (A3) may be present in the alkali-soluble resin (A) in the form of blocks or randomly.

[Structural unit (A2)]
The alkali-soluble resin (A) preferably has a structural unit (A2) represented by the following formula (a-2).

In formula (a-2), R is a hydrogen atom or a methyl group, and ^Rb is a hydrocarbon group.

The hydrocarbon group represented by ^Rb preferably has 1 or more and 20 or less carbon atoms.
Examples of the hydrocarbon group represented by R ^b include a branched, linear, or cyclic alkyl group, an aryl group which may have a substituent, and an aralkyl group which may have a substituent.
The number of carbon atoms in the branched or linear alkyl group is preferably from 1 to 12, and more preferably from 1 to 6. The number of carbon atoms in the cyclic alkyl group is preferably from 6 to 20, and more preferably from 6 to 12.
The number of carbon atoms in the aryl group which may have a substituent or the aralkyl group which may have a substituent is preferably 6 to 20, and more preferably 6 to 12. When the number of carbon atoms is 20 or less, the alkaline resolution is sufficient, and when the number of carbon atoms is 1 or more, the dielectric constant of the cured product of the curable resin composition is low.

Specific examples of the structural unit (A2) include structural units derived from linear or branched alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, n-pentyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, and tert-octyl acrylate; alicyclic alkyl acrylates such as cyclohexyl acrylate, dicyclopentanyl acrylate, 2-methylcyclohexyl acrylate, and isobornyl acrylate; aralkyl acrylates such as benzyl acrylate; and aryl acrylates such as phenyl acrylate.

Structural units derived from linear or branched alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, and n-octyl methacrylate; alicyclic alkyl methacrylates such as cyclohexyl methacrylate, dicyclopentanyl methacrylate, 2-methylcyclohexyl methacrylate, and isobornyl methacrylate; aralkyl methacrylates such as benzyl methacrylate; and aryl methacrylates such as phenyl methacrylate, cresyl methacrylate, and naphthyl methacrylate are also preferred as structural unit (A2).

By including the structural unit (A2) in the alkali-soluble resin (A), the dissolution speed of the copolymer can be adjusted. As the structural unit (A2), a unit derived from a monomer having an alicyclic group is particularly preferred from the viewpoint of lowering the dielectric constant of the cured product made of the curable resin composition.

The content of the structural unit (A2) in the alkali-soluble resin (A) is preferably 5 mol % or more and 50 mol % or less based on all structural units of the alkali-soluble resin (A).
The structural unit (A2) may be present in the alkali-soluble resin (A) in the form of blocks or randomly.

[Structural unit (A4)]
The alkali-soluble resin (A) may contain a structural unit (A4) other than the structural units (A1) to (A3) as long as the desired effects are not impaired.
There are no particular limitations on the structural unit (A4), so long as it does not fall under the category of the structural units (A1) to (A3) and is a structural unit derived from a polymerizable unsaturated compound.
Examples of the structural unit (A4) include structural units derived from polymerizable unsaturated compounds selected from acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, and unsaturated nitrile compounds.

Suitable examples of acrylamides include acrylamide, N-alkylacrylamide, N-arylacrylamide, N,N-dialkylacrylamide, N,N-diarylacrylamide, N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide, and N-2-acetamidoethyl-N-acetylacrylamide.
The alkyl group in the N-alkylacrylamide and N,N-dialkylacrylamide may be substituted with a substituent such as an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a halogen atom, or a phenyl group.
The alkyl group in the N-alkylacrylamide and N,N-dialkylacrylamide preferably has 1 or more and 10 or less carbon atoms.
Specific examples of the alkyl group which may have a substituent include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a tert-butyl group, an n-heptyl group, an n-octyl group, a cyclohexyl group, a hydroxyethyl group, and a benzyl group.
Examples of the aryl group in the N-arylacrylamide and N,N-diarylacrylamide include a phenyl group and a naphthyl group.

Specific examples of methacrylamides include methacrylamide, N-alkyl methacrylamide, N-aryl methacrylamide, N,N-dialkyl methacrylamide, N,N-diaryl (methacrylamide, N-hydroxyethyl-N-methyl methacrylamide, N-methyl-N-phenyl(meth)acrylamide, and N-ethyl-N-phenyl(meth)acrylamide.
Preferred examples of the alkyl group contained in the N-alkylmethacrylamide and N,N-dialkylmethacrylamide are the same as the preferred examples of the alkyl group contained in the N-alkylacrylamide.
Preferred examples of the aryl group contained in the N-arylmethacrylamide and N,N-diarylmethacrylamide are the same as the preferred examples of the aryl group contained in the N-arylacrylamide.

Specific examples of allyl compounds include allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, and allyl lactate, as well as allyloxyethanol.

Specific examples of vinyl ethers include alkyl vinyl ethers such as hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, and tetrahydrofurfuryl vinyl ether; and vinyl aryl ethers such as vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, and vinyl anthranyl ether.

Specific examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, and vinyl naphthoate.

Specific examples of styrenes include styrene; alkyl styrenes such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, and acetoxymethylstyrene; alkoxy styrenes such as methoxystyrene, 4-methoxy-3-methylstyrene, and dimethoxystyrene; and halostyrenes such as chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4-fluoro-3-trifluoromethylstyrene.

Specific examples of unsaturated nitrile compounds include acrylonitrile and methacrylonitrile.

As the above structural unit (A4), a structural unit derived from a monomer having an alicyclic group is preferred in terms of the low dielectric constant of the cured product of the curable resin composition.

The alkali-soluble resin (A) preferably comprises the structural unit (A1), the structural unit (A2), and the structural unit (A3).
The mass average molecular weight (Mw) of the alkali-soluble resin (A) is preferably 2000 to 50000, more preferably 5,000 to 30,000. The mass average molecular weight is a value measured by gel permeation chromatography (GPC) in terms of polystyrene. When the mass average molecular weight is 2,000 or more, the film-forming property of the curable resin composition is good. When the mass average molecular weight is 50,000 or less, the alkali-soluble resin (A) has a suitable alkali solubility.

Copolymer (A) can be produced by a known radical polymerization method. Typically, copolymer (A) can be produced by dissolving monomers that provide the desired types and amounts of structural units and a radical polymerization initiator in a polymerization solvent, and then stirring the resulting solution under heating.

The alkali-soluble resin (A) may contain one or more other resins in addition to the copolymer having the structural unit (A1) and the structural unit (A3). The amount of the other resin is preferably 0 parts by mass or more and 50 parts by mass or less, and more preferably 0 parts by mass or more and 30 parts by mass or less, per 100 parts by mass of the alkali-soluble resin (A). The mass average molecular weight (Mw) of the other resin is preferably 2,000 or more and 50,000 or less, and more preferably 5,000 or more and 30,000 or less. The mass average molecular weight is a value measured by gel permeation chromatography (GPC) in terms of polystyrene.

<Acid Generator (B)>
The curable resin composition may further contain an acid generator (B). As the acid generator (B), either a photoacid generator (B1) or a thermal acid generator (B2) may be used, or both may be used in combination.

[Photoacid generator (B1)]
The photoacid generator (B1) is not particularly limited as long as it is a compound that generates an acid or an acidic group upon irradiation with actinic rays or radiation. As the photoacid generator (B1), the first to fifth acid generators described below are preferable. The first to fifth acid generators are described below.

(First Acid Generator)
The first acid generator may be a compound represented by the following formula (b1).

In the above formula (b1), X ^1b represents a sulfur atom or an iodine atom having a valence of g, and g is 1 or 2. h represents the number of repeating units of the structure in parentheses. R ^1b is an organic group bonded to X ^1b , and represents an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or an alkynyl group having 2 to 30 carbon atoms, and R ^1b may be substituted with at least one selected from the group consisting of alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, and nitro groups, and halogen. The number of R1b is g+h(g-1)+1, and ^R1b may be the same as or different from each other. Two or more R1b may be bonded to each other directly or via -O-, -S-, -SO-, -SO ₂ -, -NH-, -NR ^2b -, -CO-, -COO-, -CONH-, an alkylene group having 1 to 3 carbon atoms, or a phenylene group to form a ring structure containing X ^1b . R ^2b is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.

^X2b is a structure represented by the following formula (b2).

In the above formula (b2), X ^4b represents an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a divalent group of a heterocyclic compound having 8 to 20 carbon atoms, and X ^4b may be substituted with at least one selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, a hydroxyl group, a cyano group, a nitro group, and a halogen group. X ^5b represents -O-, -S-, -SO-, -SO ₂ -, -NH-, -NR ^2b -, -CO-, -COO-, -CONH-, an alkylene group having 1 to 3 carbon atoms, or a phenylene group. h represents the number of repeating units of the structure in parentheses. h+1 X ^4b and h X ^5b may be the same or different. R ^2b is the same as defined above.

^X3b- is a counter ion of the onium, and examples thereof include a fluorinated alkylfluorophosphate anion represented by the following formula (b9), (b13), (b14), or (b17), or a borate anion represented by the following formula (b18). From the viewpoint of the film properties of the etching mask, the anion represented by the following formula (b9) is preferred.

In the above formula (b9), R ^20b is a group represented by the following formulas (b10), (b11), and (b12).

In the above formula (b10), x represents an integer of 1 or more and 4 or less. In addition, in the above formula (b11), R ^21b represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having from 1 to 6 carbon atoms, or a linear or branched alkoxy group having from 1 to 6 carbon atoms, and y represents an integer of from 1 to 3. Among these, trifluoromethanesulfonate and perfluorobutanesulfonate are preferred from the viewpoint of safety.

In the above formulas (b13) and (b14), ^Xb represents a linear or branched alkylene group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkylene group has 2 to 6 carbon atoms, preferably 3 to 5 carbon atoms, and most preferably 3 carbon atoms. Furthermore, ^Yb and ^Zb each independently represent a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkyl group has 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, and more preferably 1 to 3 carbon atoms.

The smaller the number of carbon atoms in the alkylene group of ^Xb or the number of carbon atoms in the alkyl groups of ^Yb and ^Zb , the better the solubility in organic solvents, which is preferable.

In the alkylene group of ^Xb or the alkyl groups of ^Yb and ^Zb , the greater the number of hydrogen atoms substituted with fluorine atoms, the stronger the acid strength, which is preferable. The proportion of fluorine atoms in the alkylene group or alkyl group, i.e., the fluorination rate, is preferably 70% or more and 100% or less, more preferably 90% or more and 100% or less, and most preferably a perfluoroalkylene group or perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms.

In the formula (b17), R ^3b represents an alkyl group in which 80% or more of the hydrogen atoms are substituted with fluorine atoms. j represents the number of R 3b and is an integer of 1 to 5. The j R ^3b may be the same or different.

In the above formula (b18), R ^4b to R ^7b each independently represent a fluorine atom or a phenyl group, and some or all of the hydrogen atoms of the phenyl group may be substituted with at least one selected from the group consisting of fluorine atoms and trifluoromethyl groups.

The onium ions in the compound represented by the above formula (b1) include triphenylsulfonium, tri-p-tolylsulfonium, 4-(phenylthio)phenyldiphenylsulfonium, bis[4-(diphenylsulfonio)phenyl]sulfide, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonio}phenyl]sulfide, bis{4-[bis(4-fluorophenyl)sulfonio]phenyl}sulfide, 4-(4-benzoyl-2-chlorophenylthio)phenylbis( 4-fluorophenyl)sulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldiphenylsulfonium, 2-[(diphenyl)sulfonio]thioxanthone, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldi-p-tolylsulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium sulfonium, diphenylphenacylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, phenyl[4-(4-biphenylthio)phenyl]4-biphenylsulfonium, phenyl[4-(4-biphenylthio)phenyl]3-biphenylsulfonium, [4-(4-acetophenylthio)phenyl]diphenylsulfonium, octadecylmethylphenacylsulfonium, diphenyliodonium, di-p-tolyliodonium, bis(4-dodecylphenyl)iodonium, bis(4-methoxyphenyl)iodonium, (4-octyloxyphenyl)phenyliodonium, bis(4-decyloxy)phenyliodonium, 4-(2-hydroxytetradecyloxy)phenylphenyliodonium, 4-isopropylphenyl(p-tolyl)iodonium, or 4-isobutylphenyl(p-tolyl)iodonium, etc.

In the fluorinated alkyl fluorophosphate anion represented by the above formula (b17), R ^3b represents an alkyl group substituted with a fluorine atom, and preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. Specific examples of the alkyl group include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, and tert-butyl; and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The ratio of hydrogen atoms in the alkyl group substituted with fluorine atoms is usually 80% or more, preferably 90% or more, and more preferably 100%. When the substitution rate of fluorine atoms is less than 80%, the acid strength of the onium fluorinated alkyl fluorophosphate represented by the above formula (b1) decreases.

Particularly preferred R ^3b is a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms and a fluorine atom substitution rate of 100%, specific examples of which include CF ₃ , CF ₃ CF ₂ , (CF ₃ ) ₂ CF, CF ₃ CF ₂ CF ₂ , CF ₃ CF ₂ CF ₂ CF ₂ , (CF ₃ ) ₂ CFCF ₂ , CF ₃ CF ₂ (CF ₃ ) CF, and (CF ₃ ) ₃ C. The number j of ^{R 3b} is an integer of 1 to 5, preferably 2 to 4, and particularly preferably 2 or 3.

Specific examples of preferred fluorinated alkyl fluorophosphate anions include, [(CF ₃ CF ₂ ) ₂ PF ₄ ] ⁻ , [(CF ₃ CF ₂ ) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ⁻ , [((CF ₃ ) ₂ CF) ₃ PF ₃ ] ⁻ , [(CF ₃ CF ₂ CF ₂ ) ₂ PF ₄ ] ⁻ , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ⁻ , [((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ⁻ , [( _CF CF ₂ CF ₂ CF ₂ ) ₂ PF ₄ ] ^- , or [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , of which, [(CF ₃ CF ₂ ) ₃ PF ₃ ] ^- , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ CF) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ^- , [((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ^- , or [((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ^- are particularly preferred.

Preferred specific examples of the borate anion represented by the above formula (b18) include tetrakis(pentafluorophenyl)borate ([B(C ₆ F ₅ ) ₄ ] ⁻ ), tetrakis[(trifluoromethyl)phenyl]borate ([B(C ₆ H ₄ CF ₃ ) ₄ ] ⁻ ), difluorobis(pentafluorophenyl)borate ([(C ₆ F ₅ ) ₂ BF ₂ ] ⁻ ), trifluoro(pentafluorophenyl)borate ([(C ₆ F ₅ )BF ₃ ] ⁻ ), tetrakis(difluorophenyl)borate ([B(C ₆ H ₃ F ₂ ) ₄ ] ⁻ ), and the like. Of these, tetrakis(pentafluorophenyl)borate ([B(C ₆ F ₅ ) ₄ ] ⁻ ) is particularly preferred.

(Second Acid Generator)
Examples of the second acid generator include 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(2-furyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methyl-2-furyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-ethyl-2-furyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-propyl-2-furyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-dimethoxyphenyl)ethenyl]-s-triazine, and 2,4-bis(trichloromethyl)-6-[2-(3,5-dimethoxyphenyl)ethenyl]-s-triazine. 2,4-bis(trichloromethyl)-6-[2-(3,5-dipropoxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3-methoxy-5-ethoxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3-methoxy-5-propoxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-methylenedioxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-methylenedioxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-(3,4-methylenedioxyphenyl)-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl styryl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(2-furyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(5-methyl-2-furyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, tris(1,3-dibromopropyl)-1,3,5-triazine, tris(2,3-dibromopropyl)-1,3,5-triazine, and halogen-containing triazine compounds represented by the following formula (b3), such as tris(2,3-dibromopropyl)isocyanurate, are also included.

In the above formula (b3), R ^9b , R ^10b and R ^11b each independently represent a halogenated alkyl group.

(Third Acid Generator)
Examples of the third acid generator include α-(p-toluenesulfonyloxyimino)-phenylacetonitrile, α-(benzenesulfonyloxyimino)-2,4-dichlorophenylacetonitrile, α-(benzenesulfonyloxyimino)-2,6-dichlorophenylacetonitrile, α-(2-chlorobenzenesulfonyloxyimino)-4-methoxyphenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclopentenylacetonitrile, and a compound containing an oxime sulfonate group and represented by the following formula (b4):

In the above formula (b4), R ^12b represents a monovalent, divalent, or trivalent organic group, R ^13b represents a substituted or unsubstituted saturated hydrocarbon group, unsaturated hydrocarbon group, or aromatic group, and n represents the number of repeating units of the structure in parentheses.

In the above formula (b4), examples of the aromatic group include aryl groups such as phenyl and naphthyl groups, and heteroaryl groups such as furyl and thienyl groups. These may have one or more suitable substituents on the ring, such as halogen atoms, alkyl groups, alkoxy groups, and nitro groups. R13b is particularly preferably an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, and a butyl group. In particular, a compound in which ^R12b is an aromatic group and ^R13b is an alkyl group having 1 to 4 carbon atoms is preferred.

Examples of the acid generator represented by the above formula (b4) when n=1 include compounds in which R ^12b is any one of a phenyl group, a methylphenyl group, and a methoxyphenyl group, and R ^13b is a methyl group, specifically α-(methylsulfonyloxyimino)-1-phenylacetonitrile, α-(methylsulfonyloxyimino)-1-(p-methylphenyl)acetonitrile, α-(methylsulfonyloxyimino)-1-(p-methoxyphenyl)acetonitrile, [2-(propylsulfonyloxyimino)-2,3-dihydroxythiophen-3-ylidene](o-tolyl)acetonitrile, etc. When n=2, examples of the acid generator represented by the above formula (b4) include acid generators represented by the following formula:

(Fourth Acid Generator)
Examples of the fourth acid generator include bissulfonyldiazomethanes such as bis(p-toluenesulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, and bis(2,4-dimethylphenylsulfonyl)diazomethane; nitrobenzyl derivatives such as 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, nitrobenzyl tosylate, dinitrobenzyl tosylate, nitrobenzyl sulfonate, nitrobenzyl carbonate, and dinitrobenzyl carbonate; sulfonic acid esters such as pyrogallol trimesylate, pyrogallol tritosylate, benzyl tosylate, benzyl sulfonate, N-methylsulfonyloxysuccinimide, N-trichloromethylsulfonyloxysuccinimide, N-phenylsulfonyloxymaleimide, and N-methylsulfonyloxyphthalimide; and N-(trifluoromethylsulfonyloxy)phthalimide. )phthalimide, N-(trifluoromethylsulfonyloxy)-1,8-naphthalimide, N-(trifluoromethylsulfonyloxy)-4-butyl-1,8-naphthalimide and other trifluoromethanesulfonic acid esters; onium salts such as diphenyliodonium hexafluorophosphate, (4-methoxyphenyl)phenyliodonium trifluoromethanesulfonate, bis(p-tert-butylphenyl)iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, (4-methoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, (p-tert-butylphenyl)diphenylsulfonium trifluoromethanesulfonate; benzoin tosylate, benzoin tosylates such as α-methylbenzoin tosylate; other diphenyliodonium salts, triphenylsulfonium salts, phenyldiazonium salts, benzyl carbonate, and the like.

(Fifth Acid Generator)
The fifth acid generator includes a compound containing a quinonediazide group.
The quinone diazide group-containing compound is preferably a complete ester or partial ester of a compound having one or more phenolic hydroxyl groups with a naphthoquinone diazide group-containing sulfonic acid.

Examples of the compound having one or more phenolic hydroxyl groups include polyhydroxybenzophenones such as 2,3,4-trihydroxybenzophenone and 2,3,4,4'-tetrahydroxybenzophenone; tris(4-hydroxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,3,5-trimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2,4-dihydroxyphenylmethane, bis(4-hydroxyphenyl)-3-methoxy-4-hydroxy trisphenol type compounds such as phenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenylmethane, and bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3,4-dihydroxyphenylmethane; 2,4-bis(3,5-dimethyl-4-hydroxybenzyl)-5-hydroxyphenol, 2,6-bis(2,5-dimethyl-4-hydroxybenzyl)-4-methylphenol, etc. Linear trinuclear phenolic compounds: 1,1-bis[3-(2-hydroxy-5-methylbenzyl)-4-hydroxy-5-cyclohexylphenyl]isopropane, bis[2,5-dimethyl-3-(4-hydroxy-5-methylbenzyl)-4-hydroxyphenyl]methane, bis[2,5-dimethyl-3-(4-hydroxybenzyl)-4-hydroxyphenyl]methane, bis[3-(3,5-dimethyl-4-hydroxybenzyl)-4-hydroxy-5-methylphenyl]methane, bis[3-(3,5-dimethyl-4-hydroxybenzyl)-4-hydroxy-5-ethylphenyl]methane, bis[3-(3,5-diethyl-4-hydroxybenzyl)-4 -hydroxy-5-methylphenyl]methane, bis[3-(3,5-diethyl-4-hydroxybenzyl)-4-hydroxy-5-ethylphenyl]methane, bis[2-hydroxy-3-(3,5-dimethyl-4-hydroxybenzyl)-5-methylphenyl]methane, bis[2-hydroxy-3-(2-hydroxy-5-methylbenzyl)-5-methylphenyl]methane, bis[4-hydroxy-3-(2-hydroxy-5-methylbenzyl)-5-methylphenyl]methane, bis[2,5-dimethyl-3-(2-hydroxy-5-methylbenzyl)-4-hydroxyphenyl]methane, and other linear tetranuclear phenol compounds; linear penta-nuclear phenol compounds such as 2,4-bis[4-hydroxy-3-(4-hydroxybenzyl)-5-methylbenzyl]-6-cyclohexylphenol, 2,6-bis[2,5-dimethyl-3-(2-hydroxy-5-methylbenzyl)-4-hydroxybenzyl]-4-methylphenol; bis(2,3,4-trihydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)methane, 2,3,4-trihydroxyphenyl-4'-hydroxyphenylmethane, 2-(2,3,4-trihydroxyphenyl)-2-(2',3',4'-trihydroxyphenyl)methane, 2-(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2-(3-fluoro-4-hydroxyphenyl)-2-(3'-fluoro-4'-hydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2-(2,3,4-trihydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2-(2,3,4-trihydroxyphenyl)-2-(4'-hydroxy-3',5'-dimethylphenyl)propane, 4,4'-[1-[4-[1 bisphenol type compounds such as 1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene, 1-[1-(3-methyl-4-hydroxyphenyl)isopropyl]-4-[1,1-bis(3-methyl-4-hydroxyphenyl)ethyl]benzene, and 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol; and condensed phenol compounds such as 1,1-bis(4-hydroxyphenyl)cyclohexane.
These compounds may be used alone or in combination of two or more kinds.

Examples of the above naphthoquinone diazide group-containing sulfonic acids include naphthoquinone-1,2-diazide-5-sulfonic acid, naphthoquinone-1,2-diazide-4-sulfonic acid, and orthoanthraquinone diazide sulfonic acid.

Other quinone diazide group-containing compounds include, for example, orthobenzoquinone diazide, orthonaphthoquinone diazide, orthoanthraquinone diazide, and orthonaphthoquinone diazide sulfonic acid esters, and nuclear-substituted derivatives thereof.
Furthermore, a reaction product of orthoquinone diazide sulfonyl chloride with a compound having a hydroxyl group or an amino group can also be used. These may be used alone or in combination of two or more kinds.
Examples of the compound having a hydroxyl group or an amino group include phenol, p-methoxyphenol, dimethylphenol, hydroquinone, bisphenol A, naphthol, pyrocatechol, pyrogallol, pyrogallol monomethyl ether, pyrogallol-1,3-dimethyl ether, gallic acid, gallic acid esterified or etherified with some hydroxyl groups remaining, aniline, and p-aminodiphenylamine.

These quinone diazide group-containing compounds can be produced, for example, by condensing a trisphenol type compound with naphthoquinone-1,2-diazide-5-sulfonyl chloride or naphthoquinone-1,2-diazide-4-sulfonyl chloride in a suitable solvent such as dioxane in the presence of an alkali such as triethanolamine, an alkali carbonate, or an alkali hydrogen carbonate, to effect complete or partial esterification.

As the fifth acid generator, it is preferable to use a non-benzophenone quinone diazide group-containing compound, and it is more preferable to use a polynuclear branched compound.

As such a fifth acid generator, naphthoquinone diazide sulfonic acid esters are particularly preferred. Among them, naphthoquinone diazide sulfonic acid esters such as 4,4'-[(3,4-dihydroxyphenyl)methylene]bis(2-cyclohexyl-5-methylphenol) and 1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene can be preferably used.

The photoacid generator (B1) may be used alone or in combination of two or more kinds.
The content of the photoacid generator (B1) in the curable resin composition is preferably 0.1 parts by mass or more and 40 parts by mass or less, and more preferably 0.1 parts by mass or more and 25 parts by mass or less, based on 100 parts by mass of the alkali-soluble resin (A).

[Thermal acid generator (B2)]
The curable resin composition preferably further contains a thermal acid generator (B2). When the curable resin composition contains the thermal acid generator (B2), it is considered that the polymerization reaction in the curable resin film (particularly the polymerization at the epoxy group in the alkali-soluble resin) is further promoted by the action of the acid generated by heat when the curable resin composition is heated, and the film density is improved.

The thermal acid generator (B2) may be appropriately selected from known ones, and may be a cationic or protonic acid catalyst such as trifluoromethanesulfonate, boron trifluoride ether complex, hexafluorophosphate, perfluorobutanesulfonic acid, boron trifluoride, etc. Among them, hexafluorophosphate, trifluoromethanesulfonic acid, and perfluorobutanesulfonic acid are preferred, and trifluoromethanesulfonic acid is more preferred.
Specific examples of the thermal acid generator (B2) include diethylammonium trifluoromethanesulfonate, triethylammonium trifluoromethanesulfonate, diisopropylammonium trifluoromethanesulfonate, and ethyldiisopropylammonium trifluoromethanesulfonate.
Among aromatic onium salts that can also be used as photoacid generators, there are those that generate cationic species by heat. Photoacid generators that generate cationic species by heat can also be used as the thermal acid generator (B2).
Examples of such thermal acid generators (B2) include San-Aid SI-45, San-Aid SI-47, San-Aid SI-60, San-Aid SI-60L, San-Aid SI-80, San-Aid SI-80L, San-Aid SI-100, San-Aid SI-100L, San-Aid SI-110L, San-Aid SI-145, San-Aid SI-150, San-Aid SI-160, San-Aid SI-180L, San-Aid SI-B3, and San-Aid SI-B3A, etc. (manufactured by Sanshin Chemical Industry Co., Ltd.); CI-2921, CI-2920, CI-2946, CI-3128, CI-2624, CI-2639, and CI-2064 (manufactured by Nippon Soda Co., Ltd.); CP-66 and CP-77 (manufactured by ADEKA Corporation); FC-520 (manufactured by 3M); K-PURE TAG-2396, K-PURE TAG-2713S, K-PURE TAG-2713, K-PURE TAG-2172, K-PURE TAG-2179, K-PURE TAG-2168E, K-PURE TAG-2722, K-PURE TAG-2507, K-PURE TAG-2678, K-PURE TAG-2681, K-PURE TAG-2679, K-PURE TAG-2690, K-PURE TAG-2700, K-PURE TAG-2710, K-PURE TAG-2100, K-PURE CDX-3027, K-PURE CXC-1615, K-PURE CXC-1616, K-PURE CXC-1750, K-PURE CXC-1738, K-PURE CXC-1614, K-PURE CXC-1742, K-PURE CXC-1743, K-PURE CXC-1613, K-PURE CXC-1739, K-PURE CXC-1751, K-PURE CXC-1766, K-PURE CXC-1763, K-PURE CXC-1736, K-PURE CXC-1756, K-PURE CXC-1821, K-PURE CXC-1802-60 (manufactured by KING INDUSTRY), and the like.
Among the above, trifluoromethanesulfonate and hexafluorophosphate are preferred as the thermal acid generator (B2), and trifluoromethanesulfonate is more preferred.

Specifically, the acid generation temperature of the thermal acid generator (B2) is preferably 110°C or higher, and more preferably 130°C or higher.

The thermal acid generator (B2) may be used alone or in combination of two or more kinds.
The content of the thermal acid generator (B2) in the curable resin composition is preferably 0.1 part by mass or more and 1.0 part by mass or less, more preferably 0.1 part by mass or more and 0.5 part by mass or less, and even more preferably 0.1 part by mass or more and 0.2 part by mass or less, relative to 100 parts by mass of the alkali-soluble resin (A).
The content of the thermal acid generator (B2) in the curable resin composition is preferably 0.1 mass % or more and 1.5 mass % or less, more preferably 0.1 mass % or more and 0.8 mass % or less, and even more preferably 0.1 mass % or more and 0.4 mass % or less, based on the mass of the total solid components of the curable resin composition.

<Silane Coupling Agent (C)>
The curable resin composition may further contain a silane coupling agent (C). When the curable resin composition contains the silane coupling agent (C), a cured product having good adhesion to a substrate can be formed from the curable resin composition.

Suitable examples of the silane coupling agent (C) include monoalkyltrialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, and n-butyltriethoxysilane; dialkyldialkoxysilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane; monophenyltrialkoxysilanes such as phenyltrimethoxysilane and phenyltriethoxysilane; diphenyldimethoxysilane and diphenyldiethoxysilane; monovinyltrialkoxysilanes such as vinyltrimethoxysilane and vinyltriethoxysilane; Coxysilane; (meth)acryloxyalkyl monoalkyl dialkoxysilanes such as 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane, and 3-methacryloxypropyl methyl diethoxysilane; (meth)acryloxyalkyl trialkoxysilanes such as 3-acryloxypropyl trimethoxysilane; amino group-containing trialkoxysilanes such as 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, and N-phenyl-3-aminopropyl trimethoxysilane; 3-glycidoxypropyl trimethoxysilane non-alicyclic epoxy group-containing alkyltrialkoxysilanes such as 3-glycidoxypropyltriethoxysilane; non-alicyclic epoxy group-containing alkylmonoalkyldialkoxysilanes such as 3-glycidoxypropylmethyldiethoxysilane; alicyclic epoxy group-containing alkyltrialkoxysilanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane; alicyclic epoxy group-containing alkylmonoalkyldialkoxysilanes such as 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane; [(3-ethyl-3-oxetanyl)methoxy]propyltrimethoxysilane, [(3-ethyl-3-oxetanyl)methoxy]propyl Examples of suitable silane coupling agents include oxetanyl group-containing alkyltrialkoxysilanes such as triethoxysilane; mercaptoalkyltrialkoxysilanes such as 3-mercaptopropyltrimethoxysilane; mercaptoalkylmonoalkyldialkoxysilanes such as 3-mercaptopropylmethyldimethoxysilane; ureidoalkyltrialkoxysilanes such as 3-ureidopropyltriethoxysilane; isocyanatoalkyltrialkoxysilanes such as 3-isocyanatopropyltriethoxysilane; acid anhydride group-containing alkyltrialkoxysilanes such as 3-trimethoxysilylpropylsuccinic anhydride; imide group-containing alkyltrialkoxysilanes such as N-t-butyl-3-(3-trimethoxysilylpropyl)succinimide; and the like. These silane coupling agents may be used alone or in combination of two or more.

The content of the silane coupling agent (C) in the curable resin composition is not particularly limited. The content of the silane coupling agent (C) is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.1 parts by mass or more and 5 parts by mass or less, and even more preferably 0.1 parts by mass or more and 1 part by mass or less, relative to 100 parts by mass of the resin (A).

<Crosslinking Agent (D)>
The curable resin composition may further contain a crosslinking agent (D). The crosslinking agent (D) is preferably at least one selected from the group consisting of an oxetane-containing compound, an epoxy group-containing compound, and a blocked isocyanate compound.

[Oxetane-containing compounds, epoxy group-containing compounds]
Examples of compounds having an oxetane group or an epoxy group include styrene oxide, phenyl glycidyl ether, o-phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, glycidyl cinnamate, methyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, glycidol, N-glycidyl phthalimide, 1,3-dibromophenyl glycidyl ether, Celloxide 2000 (manufactured by Daicel Chemical Industries, Ltd.), and oxetane alcohol.
Specific examples of the oxetane-containing compound include Aron Oxetane OXT-121, OXT-221, OX-SQ, and PNOX (all manufactured by Toagosei Co., Ltd.).
Specific examples of the epoxy group-containing compound that can be used include epoxy resin EXA4850-150 and epoxy resin EXA4850-1000 (both manufactured by DIC Corporation).

[Blocked isocyanate compound]
The blocked isocyanate compound is a compound that is inactive at room temperature, but when heated, a blocking agent such as an oxime, diketone, phenol, or caprolactam dissociates to regenerate an isocyanate group.
The blocked isocyanate compound can be produced by reacting an isocyanate compound with a blocking agent.

As the isocyanate compound, known compounds can be used. Examples of the isocyanate compound include aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate; alicyclic diisocyanates such as dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated tolylene diisocyanate; aromatic diisocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, and naphthylene diisocyanate; and dicyclohexylmethane-4,4'-diisocyanate, biuret forms, isocyanurate forms, and adducts of trimethylolpropane thereof. Among these, preferred are aliphatic diisocyanates such as hexamethylene diisocyanate and lysine diisocyanate; alicyclic diisocyanates such as dicyclohexyl diisocyanate and isophorone diisocyanate; aromatic diisocyanates such as tolylene diisocyanate, tolidine diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate and naphthylene diisocyanate; and biuret forms, isocyanurate forms, and adducts with trimethylolpropane of these.
Among these, the adduct is preferably an adduct of an aliphatic diisocyanate and trimethylolpropane, the biuret is preferably a reaction product of hexamethylene diisocyanate with water or a tertiary alcohol, and the isocyanurate is preferably a trimer of hexamethylene diisocyanate.

A blocking agent is a compound that is added to a polyisocyanate group and is stable at room temperature but is liberated when heated to a dissociation temperature or higher to generate an isocyanate group.
Specific examples of blocking agents include lactam compounds such as γ-butyrolactam, ε-caprolactam, γ-valerolactam, and propiolactam; oxime compounds such as methyl ethyl ketoxime, methyl isoamyl ketoxime, methyl isobutyl ketoxime, formamide oxime, acetamide oxime, acetoxime, diacetyl monooxime, benzophenone oxime, and cyclohexanone oxime; monocyclic phenol compounds such as phenol, cresol, catechol, and nitrophenol; polycyclic phenol compounds such as 1-naphthol; alcohol compounds such as methyl alcohol, ethyl alcohol, isopropyl alcohol, tert-butyl alcohol, trimethylolpropane, and 2-ethylhexyl alcohol; ether compounds such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether; and active methylene compounds such as malonic acid alkyl esters, malonic acid dialkyl esters, acetoacetate alkyl esters, and acetylacetone.
The blocking agent can be used alone or in combination of two or more kinds.

The reaction between the isocyanate compound and the blocking agent is carried out, for example, in a solvent having no active hydrogen, under heating at 50° C. to 100° C., and in the presence of a blocking catalyst as necessary. Examples of the solvent having no active hydrogen include 1,4-dioxane and cellosolve acetate.
The ratio of the isocyanate compound to the blocking agent is not particularly limited, but is preferably 0.95:1.0 to 1.1:1.0, more preferably 1:1.05 to 1.15, in terms of the equivalent ratio of the isocyanate group in the isocyanate compound to the blocking agent.
As the blocking catalyst, known substances can be used, and examples thereof include metal alcoholates such as sodium methylate, sodium ethylate, sodium phenolate, and potassium methylate; tetraalkylammonium hydroxides such as tetramethylammonium, tetraethylammonium, and tetrabutylammonium; organic weak acid salts thereof such as acetates, octylates, myristates, and benzoates; and alkali metal salts of alkylcarboxylic acids such as acetate, caproic acid, octylate, and myristic acid.
The blocked catalysts may be used alone or in combination of two or more.

Commercially available blocked isocyanate compounds can also be used. Specific examples of commercially available products include TPA-B80E (product name, manufactured by Asahi Kasei Corporation, isocyanate type), 17B-60P (product name, manufactured by Asahi Kasei Corporation, biuret type), and E402-B80B (product name, manufactured by Asahi Kasei Corporation, adduct type).

The blocked isocyanate compounds can be used alone or in combination of two or more kinds.
The content of the blocked isocyanate compound in the curable resin composition is preferably 1 mass % or more and 60 mass % or less, more preferably 5 mass % or more and 50 mass % or less, and even more preferably 10 mass % or more and 40 mass % or less, based on the mass of the total solid components of the curable resin composition.

As the crosslinking agent (D), a blocked isocyanate compound is preferred from the viewpoint of improving the mechanical properties of a cured product made of the curable resin composition.
Among the blocked isocyanate compounds, adduct-type blocked isocyanate compounds are preferred.
In the case of using an adduct type blocked isocyanate compound, the content of the adduct type blocked isocyanate compound in the curable resin composition is preferably 10 mass % or more and 40 mass % or less, and more preferably 15 mass % or more and 25 mass % or less, based on the mass of the total solid components of the curable resin composition.

<Organic Solvent (S)>
The curable resin composition usually contains an organic solvent (S). The type of the organic solvent (S) is not particularly limited as long as it does not impair the object of the present invention, and may be appropriately selected from organic solvents that have been conventionally used in photosensitive compositions.

Specific examples of organic solvents (S) include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; polyhydric alcohols and derivatives thereof such as ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether acetate, dipropylene glycol, monomethyl ether of dipropylene glycol monoacetate, monoethyl ether, monopropyl ether, monobutyl ether, and monophenyl ether; Examples of the esters include cyclic ethers such as oxane, ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, and 3-methyl-3-methoxybutyl acetate, and aromatic hydrocarbons such as toluene and xylene. These may be used alone or in a mixture of two or more.

The content of the organic solvent (S) is not particularly limited as long as it does not impair the object of the present invention. It is preferable to use the organic solvent (S) in a range in which the solid content concentration of the curable resin composition is 30% by mass or more and 70% by mass or less.

<Additive (E)>
The curable resin composition may contain the following additives as the additive (E).
The curable resin composition may further contain a surfactant in order to improve coating properties, defoaming properties, leveling properties, and the like.
As the surfactant, for example, a fluorine-based surfactant or a silicone-based surfactant is preferably used.
Specific examples of the fluorine-based surfactant include commercially available fluorine-based surfactants such as BM-1000, BM-1100 (all manufactured by BM Chemie), Megafac F142D, Megafac F172, Megafac F173, Megafac F183 (all manufactured by Dainippon Ink and Chemicals, Inc.), Fluorad FC-135, Fluorad FC-170C, Fluorad FC-430, Fluorad FC-431 (all manufactured by Sumitomo 3M Limited), Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145 (all manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, and SF-8428 (all manufactured by Toray Silicones Co., Ltd.), but are not limited thereto.
As the silicone surfactant, an unmodified silicone surfactant, a polyether-modified silicone surfactant, a polyester-modified silicone surfactant, an alkyl-modified silicone surfactant, an aralkyl-modified silicone surfactant, a reactive silicone surfactant, and the like can be preferably used.
As the silicone surfactant, commercially available silicone surfactants can be used. Specific examples of commercially available silicone surfactants include Paintad M (manufactured by Dow Corning Toray Co., Ltd.), Topika K1000, Topika K2000, Topika K5000 (all manufactured by Takachiho Sangyo Co., Ltd.), XL-121 (polyether-modified silicone surfactant, manufactured by Clariant), and BYK-310 (polyester-modified silicone surfactant, manufactured by BYK-Chemie).

The curable resin composition may contain a sensitizer. There are no particular limitations on the sensitizer, and various compounds that are used as sensitizers in conventionally known positive resists can be used. Examples of sensitizers include compounds having a phenolic hydroxyl group with a molecular weight of 1000 or less.

The curable resin composition may contain an antifoaming agent. The antifoaming agent is not particularly limited and may be any conventionally known agent, such as a silicone-based compound or a fluorine-based compound.

The curable resin composition may contain an antioxidant. The antioxidant is not particularly limited, and any conventionally known antioxidant may be used, such as hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.

The curable resin composition may contain a polymerization inhibitor. The polymerization inhibitor is not particularly limited, and any conventionally known polymerization inhibitor may be used, such as methoquinone, hydroquinone, methylhydroquinone, p-methoxyphenol, pyrogallol, tert-butylcatechol, and phenothiazine.

The curable resin composition may contain an adhesion improver to improve adhesion between a metal electrode or an insulating film formed on a substrate for an electric/electronic device having a metal electrode and a semi-cured film formed using the curable resin composition. The adhesion improver is not particularly limited, and a conventionally known adhesion improver can be used, such as benzotriazole.

<Method for preparing curable resin composition>
The curable resin composition is prepared by mixing and stirring the above-mentioned components in a conventional manner. Examples of devices that can be used when mixing and stirring the above-mentioned components include a dissolver, a homogenizer, and a three-roll mill. After the above-mentioned components are mixed uniformly, the resulting mixture may be further filtered using a mesh, a membrane filter, or the like.

<Method for manufacturing semiconductor device>
The method for producing a semiconductor device includes the steps of processing a semiconductor substrate using the above-mentioned curable resin composition to produce a semiconductor chip, and bonding the semiconductor chip to the substrate.
More specifically, the method for manufacturing a semiconductor device includes the steps of:
forming a first substrate including a semiconductor substrate, a semi-cured film formed by baking a resin film made of a curable resin composition and covering one main surface of the semiconductor substrate, and a first metal electrode located in the semi-cured film, one end surface of which is exposed on a surface of the semi-cured film and the other end surface of which is in contact with the semiconductor substrate;
dicing the first substrate into a plurality of chips by cutting the first substrate in a thickness direction of the first substrate;
preparing a second substrate including a substrate, an insulating film covering one main surface of the substrate, and a second metal electrode located in the insulating film, one end surface of which is exposed on the surface of the insulating film and the other end surface of which is in contact with the substrate;
a bonding step of baking the chip and the second substrate in a state in which the surface of the semi-cured film faces the surface of the insulating film and the first metal electrode is in contact with the second metal electrode, thereby bonding the chip and the second substrate to obtain a laminated substrate;
and firing the laminated substrate.
The baking temperature in bonding is preferably 100° C. or higher and 200° C. or lower.
Hereinafter, forming the first substrate will also be referred to as the "first substrate formation process," dicing to divide the first substrate into multiple chips will also be referred to as the "chip formation process," preparing the second substrate will also be referred to as the "second substrate preparation process," and bonding to obtain a laminated substrate in which the chip and second substrate are joined and firing the laminated substrate will also be referred to as the "laminated substrate formation process."

<First Substrate Forming Process>
The first substrate is formed by a non-photosensitive or photosensitive process as described below.

[Non-photosensitive process]
A suitable example of the non-photosensitive process includes the following methods 1) to 3).
1) forming a resin film made of a curable resin composition on a main surface of a semiconductor substrate in contact with a first metal electrode;
2) baking the resin film to form a semi-cured film in which the reaction rate of the epoxy groups derived from the curable resin composition is more than 20% and less than 80%; and 3) polishing the semi-cured film so that the first metal electrode is exposed from the surface of the semi-cured film.

In the above method, when forming the resin film, a curable resin composition is applied to at least the portion of the semiconductor substrate having the first metal electrode where the semi-cured film is to be formed, to form a coating film.
The metal constituting the first metal electrode is preferably copper, gold, or aluminum, and more preferably copper. The size and shape of the first metal electrode are not particularly limited. The size and shape of the first metal electrode are appropriately selected depending on the type of semiconductor device and the performance required for the semiconductor device. The shape of the first metal electrode is not particularly limited. Typical examples of the shape of the first metal electrode include a cylindrical shape, a rectangular column, a hexagonal column, or the like.
Typically, the diameter of the first metal electrode is preferably 1 μm or more and 500 μm or less, more preferably 4 μm or more and 400 μm or less, and even more preferably 4 μm or more and 200 μm or less.
The diameter of the first metal electrode is the diameter of the first metal electrode exposed from the surface of the semi-cured film. When the cross-sectional shape of the first metal electrode is not circular, the diameter of the first metal electrode is the equivalent circle diameter of the cross-section of the first metal electrode.
The surface of the first metal electrode may be subjected to a plating treatment, preferably a plating treatment using tin and silver.

Methods that can be used to apply the curable resin composition include spin coating, slit coating, roll coating, screen printing, inkjet, and applicator methods. When using printing methods such as screen printing and inkjet, it is possible to apply the curable resin composition only to the areas where a resin film is to be formed.

The thickness of the coating film is not particularly limited, but is preferably 0.5 μm or more, more preferably 0.5 μm to 300 μm, particularly preferably 1 μm to 150 μm, and most preferably 1 μm to 50 μm.

Next, the coating film is dried or baked as necessary. Baking is performed so that the reaction rate of the epoxy groups derived from the curable resin composition in the semi-cured film obtained by baking is more than 20% and less than 80%. The reaction rate of the epoxy groups derived from the curable resin composition in the semi-cured film obtained by baking is preferably more than 20% and less than 80%, more preferably 40% or more and 70% or less.
The baking temperature is not particularly limited as long as the reaction rate of the epoxy group is within a predetermined range. The baking temperature is preferably 100° C. or more and 200° C. or less. The baking time varies depending on the types and blending ratios of each component in the curable resin composition, the coating film thickness, etc., but is usually about 2 minutes or more and 120 minutes or less.

The semi-cured film formed on the semiconductor substrate is polished until one end face of the first metal electrode is exposed from the semi-cured film, thereby forming a first substrate.
The polishing method is not particularly limited, but cutting polishing and chemical mechanical polishing are preferable. Polishing may be performed by only cutting polishing or chemical mechanical polishing, or may be performed by a combination of cutting polishing and chemical mechanical polishing.

[Photosensitive process]
A suitable example of the photoexposure process includes the following steps 1) to 4).
1) forming a patterned semi-cured film serving as a mold for forming a first electrode on a semiconductor substrate by a photolithography method using a curable resin composition; and
When forming a patterned semi-cured film, a resin film made of a curable resin composition is baked to set the reaction rate of epoxy groups derived from the curable resin composition to more than 20% and less than 80%;
2) sputtering a metal onto the patterned semi-cured film to form a metal film on the surface of the semiconductor substrate exposed at the bottom of the recess in the semi-cured film where the metal electrode is to be formed;
3) after forming the metal film, filling the recesses in the patterned semi-cured film with metal by plating to form a first metal electrode; and 4) polishing the patterned semi-cured film after plating until the semi-cured film and an end face of the first metal electrode are exposed.

The patterned semi-cured film as a mold for forming the first electrode is formed by applying a curable resin composition onto a semiconductor substrate, selectively exposing the coating film made of the curable resin composition to light, developing the exposed coating film, and baking the developed resin film. The resin film is baked so that the reaction rate of the epoxy groups derived from the curable resin composition in the resin film after baking is more than 20% and less than 80%. The reaction rate of the epoxy groups derived from the curable resin composition in the resin film after baking is preferably more than 20% and less than 80%, and more preferably 40% or more and 70% or less.

Methods that can be used to apply the curable resin composition include spin coating, slit coating, roll coating, screen printing, inkjet printing, and applicator methods.

The thickness of the coating film is not particularly limited, but is preferably 0.5 μm or more, more preferably 0.5 μm to 300 μm, particularly preferably 1 μm to 150 μm, and most preferably 1 μm to 50 μm.

The formed coating film is subjected to selective positional exposure (pattern exposure) by a method such as exposing it to actinic rays or radiation through a mask with a predetermined pattern. The film is irradiated (exposed) with actinic rays or radiation, for example, ultraviolet rays or visible light with a wavelength of 300 nm or more and 500 nm or less.

Examples of radiation sources that can be used include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, argon gas lasers, etc. Radiation includes microwaves, infrared rays, visible light, ultraviolet rays, X-rays, gamma rays, electron beams, proton beams, neutron beams, ion beams, etc. The radiation dose varies depending on the composition of the curable resin composition and the thickness of the coating film, but is, for example, 100 mJ/ ^cm2 or more and 10,000 mJ/cm2 or ^less when an ultra-high pressure mercury lamp is used.

In the case of position-selective exposure, the exposed semi-cured film is developed according to a conventional method, and unnecessary portions are dissolved and removed to form an insulating film of a desired shape. In this case, the above organic solvent (S) or an alkaline aqueous solution can be used as the developer. The alkali-soluble resin (A) has a carboxyl group and/or a phenolic hydroxyl group. Therefore, the exposed semi-cured film can be developed with an alkaline aqueous solution.

Examples of alkaline aqueous solutions used as developing solutions include aqueous solutions of alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide (tetramethylammonium hydroxide), tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5,4,0]-7-undecene, and 1,5-diazabicyclo[4,3,0]-5-nonane. In addition, aqueous solutions of the above-mentioned alkaline solutions to which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant has been added can also be used as developing solutions.

The development time varies depending on the composition of the curable resin composition and the thickness of the coating film, but is usually between 1 minute and 30 minutes. The development method may be any of the following: puddle method, dipping method, paddle method, spray development method, etc.

After development, the film is washed with running water for 30 to 90 seconds, and then dried using an air gun or oven.

The baking conditions for the developed resin film are the same as those for the resin film described for the non-photosensitive process.

In this way, a patterned semi-cured film is formed as a mold for forming the first electrode.

Next, a metal is sputtered onto the patterned semi-cured film to form a metal film on the surface of the semiconductor substrate exposed at the bottom of the recess in the semi-cured film where the metal electrode is to be formed. This metal film serves as a seed layer for plating.

After forming a metal film on the bottom of a recess in the patterned semi-cured film where a metal electrode is to be formed, the recess in the patterned semi-cured film is filled with metal by plating to form a first metal electrode.
The metal constituting the first metal electrode is preferably copper, gold or aluminum, and more preferably copper.

The patterned semi-cured film after plating is polished until the semi-cured film and an end face of the first metal electrode are exposed, thereby forming a first substrate in which one end face of the first metal electrode is exposed from the semi-cured film.
The polishing method is not particularly limited, but it is preferable to employ chemical mechanical polishing.

<Chip Formation Process>
The first substrate is divided into chips of a predetermined size by dicing, which can be performed by a dicer method, a laser method, a scribe method, or the like.

<Second Substrate Preparation Step>
The second substrate is not particularly limited as long as it is a substrate having an insulating film on a substrate and a second metal electrode having one end surface exposed from the surface of the insulating film and the other end surface in contact with the substrate.
The method for forming the second substrate is the same as the method for forming the first substrate having a first metal electrode, one end surface of which is exposed on the surface of the semi-cured film and the other end surface of which is in contact with the semiconductor substrate, described in the first substrate forming step above. The insulating film of the second substrate may be formed using a material other than the curable resin composition described above.

The insulating film may be an organic or inorganic material, and is not particularly limited, as long as it has the desired insulating performance. Specifically, when the insulating film is made of an organic material, an insulating film made of a resin composition containing an insulating resin such as a polyimide resin can be used. When the insulating film is made of an inorganic material, an insulating film made of _SiO2 or the like can be used.

<Laminated substrate forming process>
The laminated substrate forming process will be described with reference to the drawings. In Fig. 1, the main surface of the chip 100 having the semi-cured film 12 and the main surface of the second substrate 200 having the insulating film 22 are opposed to each other, and the chip 100 and the second substrate 200 are laminated so that the first metal electrode 11 and the second metal electrode 21 are in contact with each other.

The stacked chips 100 and the second substrate 200 are bonded together by baking to form a stacked substrate. The baking temperature is not particularly limited, but is preferably 100° C. or higher and 200° C. or lower.
The baking conditions in the laminated substrate formation process vary depending on the types, mixing ratios, and film thicknesses of the components in the semi-cured film 12 and the insulating film 22, but are usually from 2 minutes to 120 minutes.

By firing the laminated substrate, the chip 100 and the second substrate 200 are bonded in the laminated substrate. The firing temperature is not particularly limited as long as the chip 100 and the second substrate 200 are firmly bonded in the laminated substrate. Preferably, the laminated substrate is fired at 180°C or higher and 230°C or lower to more firmly bond the chip 100 and the second substrate 200. The laminated substrate thus obtained can be used as a semiconductor device as is, or can be suitably incorporated into various semiconductor devices.

で表される構成単位（Ａ１）とエポキシ基含有単位（Ａ３）とを有する共重合体を含み、
式（ａ―１）中、Ｒは水素原子又はメチル基を表し、Ｒ^ａ０１は水酸基を有する有機基を表し、
半硬化膜において、硬化性樹脂組成物に由来するエポキシ基の反応率が２０％超８０％未満であり、
焼成された積層基板における半硬化膜が硬化した硬化膜において、硬化性樹脂組成物に由来するエポキシ基の反応率が８５％以上である、半導体装置製造方法。
（２）ボンディングにおけるベーク温度が、１００℃以上２００℃以下である、（１）に記載の半導体製造装置。
（３）第１基板が以下の工程１）～３）：
１）半導体基板の、第１金属電極が接している主面上に硬化性樹脂組成物からなる樹脂膜を形成すること、
２）樹脂膜をベークして、硬化性樹脂組成物に由来するエポキシ基の反応率が２０％超８０％未満である半硬化膜を形成すること、及び
３）第１金属電極が、半硬化膜表面から露出するように半硬化膜を研磨すること、
によって形成される、（１）又は（２）に記載の半導体装置製造方法。
（４）第１基板が以下の工程１）～４）：
１）半導体基板上に、硬化性樹脂組成物を用いて、フォトリソグラフィー法により第１金属電極形成用の鋳型となるパターニングされた半硬化膜を形成し、且つ、
パターニングされた半硬化膜を形成する際に、硬化性樹脂組成物からなる樹脂膜をベークして、硬化性樹脂組成物に由来するエポキシ基の反応率を２０％超８０％未満とすることと、
２）パターニングされた半硬化膜に対して金属をスパッタし、半硬化膜中の電極が形成される凹部の底部において露出している半導体基板の表面に、金属膜を形成することと、
３）金属膜を形成した後に、パターン化された半硬化膜の凹部中にめっきにより金属を充填し、第１金属電極を形成すること、及び
４）めっきが施された後のパターン化された半硬化膜を、半硬化膜と、第１金属電極の端面とが露出するまで研磨すること、
によって形成される、（１）又は（２）に記載の半導体装置製造方法。
（５）硬化性樹脂組成物が酸発生剤（Ｂ）を含む、（１）～（４）のいずれか１つに記載の半導体装置製造方法。
（６）硬化性樹脂組成物がシランカップリング剤（Ｃ）を含む、（１）～（５）のいずれか１つに記載の半導体装置製造方法。
（７）硬化性樹脂組成物が架橋剤（Ｄ）を含み、
架橋剤（Ｄ）は、ブロックイソシアネート化合物を含む、（１）～（６）のいずれか１つに記載の半導体装置製造方法。
（８）共重合体は、さらに、下記式（ａ－２）：

で表される構成単位（Ａ２）を有し、
式（ａ―２）中、Ｒは水素原子又はメチル基を表し、Ｒ^ｂは炭化水素基を表す、
（１）～（７）のいずれか１つに記載の半導体装置製造方法。
（９）絶縁膜が、硬化性樹脂組成物からなる樹脂膜をベークして形成され、且つ硬化性樹脂組成物に由来するエポキシ基の反応率が２０％超８０％未満である半硬化膜である、（１）～（８）のいずれか１つに記載の半導体装置製造方法。
（１０）チップと、第２基板とからなり、チップと第２基板とが互いに接合された積層基板を含む半導体装置であって、
チップが、半導体基板と、半導体基板の一方の主面を被覆する硬化膜と、硬化膜中に位置し、一方の端面が硬化膜の表面に露出し、且つ他方の端面が半導体基板に接触している第１金属電極と、を備え、
第２基板が、基板と、基板の一方の主面を被覆する絶縁膜と、絶縁膜中に位置し、一方の端面が絶縁膜の表面に露出し、且つ他方の端面が基板に接触している第２金属電極と、を備え、
積層基板において、硬化膜と、絶縁膜とが接合されており、第１金属電極と第２金属電極とが接しており、
硬化膜が、アルカリ可溶性樹脂（Ａ）を含む硬化性樹脂組成物の硬化物からなり、
アルカリ可溶性樹脂（Ａ）は、アルカリ可溶性基として、カルボキシ基、及び／又はフェノール性水酸基を有し、
アルカリ可溶性樹脂（Ａ）は、下記式（ａ－１）：

で表される構成単位（Ａ１）とエポキシ基含有単位（Ａ３）とを有する共重合体を含み、
式（ａ―１）中、Ｒは水素原子又はメチル基を表し、Ｒ^ａ０１は水酸基を有する有機基を表す、半導体装置。 As described above, the present inventors provide the following (1) to (10).
(1) forming a first substrate including a semiconductor substrate, a semi-cured film formed by baking a resin film made of a curable resin composition and covering one main surface of the semiconductor substrate, and a first metal electrode located in the semi-cured film, one end surface of which is exposed on a surface of the semi-cured film and the other end surface of which is in contact with the semiconductor substrate;
dicing the first substrate into a plurality of chips by cutting the first substrate in a thickness direction of the first substrate;
preparing a second substrate including a substrate, an insulating film covering one main surface of the substrate, and a second metal electrode located in the insulating film, one end surface of which is exposed on the surface of the insulating film and the other end surface of which is in contact with the substrate;
a bonding step of baking the chip and the second substrate in a state in which the surface of the semi-cured film faces the surface of the insulating film and the first metal electrode is in contact with the second metal electrode, thereby bonding the chip and the second substrate to obtain a laminated substrate;
and firing the laminated substrate;
The curable resin composition contains an alkali-soluble resin (A),
The alkali-soluble resin (A) has a carboxy group and/or a phenolic hydroxyl group as the alkali-soluble group,
The alkali-soluble resin (A) is represented by the following formula (a-1):

and an epoxy group-containing unit (A3),
In formula (a-1), R represents a hydrogen atom or a methyl group, and R ^a01 represents an organic group having a hydroxyl group.
In the semi-cured film, the reaction rate of the epoxy group derived from the curable resin composition is more than 20% and less than 80%,
A method for manufacturing a semiconductor device, wherein in a cured film obtained by curing the semi-cured film on the baked laminated substrate, a reaction rate of epoxy groups derived from the curable resin composition is 85% or more.
(2) The semiconductor manufacturing apparatus according to (1), wherein the baking temperature in bonding is 100° C. or higher and 200° C. or lower.
(3) The first substrate is subjected to the following steps 1) to 3):
1) forming a resin film made of a curable resin composition on a main surface of a semiconductor substrate in contact with a first metal electrode;
2) baking the resin film to form a semi-cured film in which the reaction rate of the epoxy group derived from the curable resin composition is more than 20% and less than 80%; and 3) polishing the semi-cured film so that the first metal electrode is exposed from the surface of the semi-cured film.
The method for manufacturing a semiconductor device according to (1) or (2),
(4) The first substrate is subjected to the following steps 1) to 4):
1) forming a patterned semi-cured film serving as a mold for forming a first metal electrode on a semiconductor substrate by a photolithography method using a curable resin composition; and
When forming a patterned semi-cured film, a resin film made of a curable resin composition is baked to set a reaction rate of epoxy groups derived from the curable resin composition to more than 20% and less than 80%;
2) sputtering a metal onto the patterned semi-cured film to form a metal film on the surface of the semiconductor substrate exposed at the bottom of a recess in the semi-cured film where an electrode is to be formed;
3) after forming the metal film, filling the recesses of the patterned semi-cured film with metal by plating to form a first metal electrode; and 4) polishing the patterned semi-cured film after plating until the semi-cured film and an end face of the first metal electrode are exposed.
The method for manufacturing a semiconductor device according to (1) or (2),
(5) The method for producing a semiconductor device according to any one of (1) to (4), wherein the curable resin composition contains an acid generator (B).
(6) The method for producing a semiconductor device according to any one of (1) to (5), wherein the curable resin composition contains a silane coupling agent (C).
(7) The curable resin composition contains a crosslinking agent (D),
The method for producing a semiconductor device according to any one of (1) to (6), wherein the crosslinking agent (D) contains a blocked isocyanate compound.
(8) The copolymer further comprises a copolymer represented by the following formula (a-2):

The structural unit (A2) is represented by the following formula:
In formula (a-2), R represents a hydrogen atom or a methyl group, and ^Rb represents a hydrocarbon group.
The method for manufacturing a semiconductor device according to any one of (1) to (7).
(9) The method for manufacturing a semiconductor device according to any one of (1) to (8), wherein the insulating film is a semi-cured film formed by baking a resin film made of a curable resin composition, and the reaction rate of the epoxy groups derived from the curable resin composition is more than 20% and less than 80%.
(10) A semiconductor device including a laminated substrate including a chip and a second substrate, the chip and the second substrate being bonded to each other,
The chip comprises a semiconductor substrate, a cured film covering one main surface of the semiconductor substrate, and a first metal electrode located in the cured film, one end surface of which is exposed on the surface of the cured film and the other end surface of which is in contact with the semiconductor substrate;
the second substrate comprises a substrate, an insulating film covering one main surface of the substrate, and a second metal electrode located in the insulating film, one end surface of which is exposed on the surface of the insulating film and the other end surface of which is in contact with the substrate;
In the laminated substrate, the cured film and the insulating film are bonded to each other, and the first metal electrode and the second metal electrode are in contact with each other.
the cured film is made of a cured product of a curable resin composition containing an alkali-soluble resin (A);
The alkali-soluble resin (A) has a carboxy group and/or a phenolic hydroxyl group as the alkali-soluble group,
The alkali-soluble resin (A) is represented by the following formula (a-1):

and an epoxy group-containing unit (A3),
In formula (a-1), R represents a hydrogen atom or a methyl group, and R ^a01 represents an organic group having a hydroxyl group.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

また、アルカリ可溶性樹脂（Ａ）として、上記の構成単位Ｉ４０モル％、上記の構成単位ＩＩ４０モル％、及び上記の構成単位ＩＩＩ２０モル％からなる樹脂（Ａ２）（質量平均分子量：１７，０００）と、上記の構成単位Ｉ４０モル％、上記の構成単位ＩＩ４０モル％、及び上記の構成単位ＩＩＩ２０モル％からなる樹脂（Ａ３）（質量平均分子量：６
，８００）とを用いた。
酸発生剤（Ｂ）として、光酸発生剤（Ｂ１）であるナフトキノンジアジド基含有化合物（下記化合物（Ｂ’）－１に対し、ナフトキノンジアジド－５－スルホン酸エステルを２モル反応させたもの））と、熱酸発生剤（Ｂ２）であるＫＩＮＧ ＩＮＤＵＳＴＲＹ社製 Ｋ－Ｐｕｒｅ（登録商標） ＴＡＧ－２６９０（製品名）とを用いた。

シランカップリング剤（Ｃ）として、ダウ・東レ株式会社ＯＦＳ－６０４０Ｓｉｌａｎｅ（製品名）、を用いた。
架橋剤（Ｄ）として、ブロックイソシアネート（旭化成ケミカルズ社製 Ｅ４０２－Ｂ８０Ｂ（製品名））を用いた。 <Preparation of Curable Resin Composition>
As the alkali-soluble resin (A), a resin (A1) (mass average molecular weight: 17,000) consisting of the following structural units I to III was used. In the following formula, the numerical values on the right side of the parentheses indicate the molar ratio of each structural unit in the resin.

As the alkali-soluble resin (A), there was used a resin (A2) (mass average molecular weight: 17,000) consisting of 40 mol % of the structural unit I, 40 mol % of the structural unit II, and 20 mol % of the structural unit III, and a resin (A3) (mass average molecular weight: 6
, 800) were used.
As the acid generator (B), a naphthoquinone diazide group-containing compound (a compound (B')-1 shown below was reacted with 2 moles of naphthoquinone diazide-5-sulfonic acid ester) as a photoacid generator (B1) and KING INDUSTRY's K-Pure (registered trademark) TAG-2690 (product name) as a thermal acid generator (B2) were used.

As the silane coupling agent (C), OFS-6040 Silane (product name) manufactured by Dow Toray Co., Ltd. was used.
As the crosslinking agent (D), a blocked isocyanate (product name E402-B80B manufactured by Asahi Kasei Chemicals Corporation) was used.

Preparation Example 1
100 parts by mass of an alkali-soluble resin (A), 20 parts by mass of a photoacid generator (B1), 1 part by mass of a silane coupling agent (C), 0.2 parts by mass of a thermal acid generator (B2), and 20 parts by mass of a crosslinking agent (D) were dispersed and dissolved in a solvent so that the solid content concentration of the curable resin composition was 33% by mass, to prepare a curable resin composition (P1). A mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) was used as the solvent. The mixing ratio (weight ratio) of the solvents was PGMEA:PGME=3:2.

Preparation Example 2
60 parts by mass of resin (A2), 15 parts by mass of resin (A3), 25 parts by mass of photoacid generator (B1), 1 part by mass of silane coupling agent (C), and 0.1 parts by mass of surfactant (BYK-310 (manufactured by BYK-Chemie)) were dispersed and dissolved in a solvent so that the solid content concentration of the curable resin composition was 33% by mass, to prepare a curable resin composition (P2). A mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) was used as the solvent. The mixing ratio (weight ratio) of the solvents was PGMEA:PGME=3:2.

<Preparation of polyimide resin film-forming composition>
The resin was polymerized according to the description of Production Example 1 of Japanese Patent No. 7136894 to obtain a polyimide precursor. The obtained polyimide precursor was dissolved in γ-butyrolactone to a concentration of 30% by mass. To the obtained solution, 5% by mass of an oxime ester initiator (Irgacure OXE02 (manufactured by BASF Japan)) relative to the mass of the polyimide precursor, 0.05% by mass of a polymerization inhibitor (Irganox 1010 (manufactured by BASF Japan)) relative to the mass of the polyimide precursor, 0.02% by mass of a surfactant (Polyflow NO. 77 (manufactured by Kyoeisha Chemical Co., Ltd.)) relative to the mass of the polyimide precursor, and 3% by mass of N-[3-(triethoxysilyl)propyl]phthalic acid amide relative to the mass of the polyimide precursor were added to obtain a polyimide resin film-forming composition.

<Preparation of First Substrate>
A first substrate was prepared by the following method: As the curable resin composition, the above-mentioned curable resin composition (P1), curable resin composition (P2), or polyimide resin film-forming composition was used.

[First substrate A1]
(Non-photosensitive process)
A silicon wafer having a cylindrical first metal electrode formed on one main surface of copper with a diameter of 20 μm and a height of 5 μm and a tin-silver plating with a thickness of 2 μm on the tip of the copper was used as a substrate. A curable resin composition (P1) was applied to a film thickness of 10 μm on the main surface of the substrate having the first metal electrode. The substrate coated with the curable resin composition (P1) was heated at 100° C. for 300 seconds, and then baked under the conditions shown in Table 1 to form a semi-cured film. After baking, chemical mechanical polishing was performed until the tin-silver plating was exposed from the semi-cured film, and a first substrate was prepared. The first substrate was designated as a first substrate A1.

[First substrate A2]
(Non-photosensitive process)
A silicon wafer having a cylindrical first metal electrode formed on one main surface of copper with a diameter of 20 μm and a height of 5 μm and a tin-silver plating with a thickness of 2 μm on the tip of the copper was used as a substrate. A curable resin composition (P2) was applied to a film thickness of 10 μm on the main surface of the substrate having the first metal electrode. The substrate coated with the curable resin composition (P2) was heated at 100° C. for 300 seconds, and then baked under the conditions shown in Table 1 to form a semi-cured film. After baking, chemical mechanical polishing was performed until the tin-silver plating was exposed from the semi-cured film, and a first substrate was prepared. The first substrate was designated as a first substrate A2.

[First substrate B1]
(Photosensitive process)

A curable resin composition (P1) was applied to a silicon wafer to a film thickness of 7 μm. The substrate coated with the curable resin composition (P1) was heated at 100° C. for 300 seconds. The resin film was then exposed to light through a positive mask that formed via holes with a diameter of 20 μm. The exposed resin film was developed using 2.38% tetramethylammonium hydroxide. The developed resin film was baked under the conditions shown in Table 2 to form a patterned semi-cured film. After development, the patterned semi-cured film was subjected to copper sputtering to form a copper film on the bottom of the recesses in the patterned semi-cured film. Next, copper was plated by sputtering into the recesses in the patterned semi-cured film so that the height from the silicon wafer surface was 10 μm. After plating, chemical mechanical polishing was performed until the semi-cured film was exposed, and a first substrate was produced. This first substrate is referred to as the first substrate B1.

[First substrate B2]
(Photosensitive process)

A curable resin composition (P2) was applied to a silicon wafer to a film thickness of 7 μm. The substrate coated with the curable resin composition (P2) was heated at 100° C. for 300 seconds. The resin film was then exposed to light through a positive mask that formed via holes with a diameter of 20 μm. The exposed resin film was developed using 2.38% tetramethylammonium hydroxide. The developed resin film was baked under the conditions shown in Table 2 to form a patterned semi-cured film. After development, the patterned semi-cured film was subjected to copper sputtering to form a copper film on the bottom of the recesses in the patterned semi-cured film. Next, copper was plated by sputtering into the recesses in the patterned semi-cured film so that the height from the silicon wafer surface was 10 μm. After plating, chemical mechanical polishing was performed until the semi-cured film was exposed, and a first substrate was produced. This first substrate is referred to as the first substrate B2.

<Chip preparation>
Using a DAD3360 manufactured by DISCO, blade dicing was carried out by a known method to produce the following chips.

[Chip A1]
The first substrate A1 was diced into chips of 5 mm square to obtain chips A1.

[Chip A2]
The first substrate A2 was diced into chips of 5 mm square to obtain the chips A2.

[Chip B1]
The first substrate B1 was diced into chips of 5 mm square to obtain chips B1.

[Chip B2]
The first substrate B2 was diced into chips of 5 mm square to obtain chips B2.

<Preparation of Second Substrate>
[Second Substrate Ai]
The second substrate Ai was prepared in the same manner as the above-mentioned first substrate A1, except that the baking temperature was 160°C.

[Second Substrate Aii]
The second substrate Aii was prepared in the same manner as the above-mentioned first substrate A2, except that the baking temperature was 160°C.

[Second Substrate Bi]
The second substrate Bi was prepared by the same method as the above-mentioned method for preparing the first substrate B1.

[Substrate 2Bii]
The second substrate Bii was prepared by the same method as the above-mentioned method for preparing the first substrate B2.

[Second Substrate C]
(Non-photosensitive process)
A silicon wafer was used as a substrate, on one of the main surfaces of which was formed a cylindrical first metal electrode having a diameter of 20 μm and a height of 5 μm of copper and a tin-silver plating of 2 μm thickness on the tip of the copper. A polyimide resin film-forming composition was applied to a film thickness of 10 μm on the main surface of the substrate that was provided with the first metal electrode. The substrate on which the polyimide resin film-forming composition was applied was heated at 150° C. for 300 seconds, and then baked at 350° C. for 30 minutes to form an insulating film. After baking, chemical mechanical polishing was performed until the tin-silver plating was exposed from the insulating film, and a second substrate was prepared. The second substrate was designated as second substrate C.

[Second Substrate D]
(Photosensitive process)
A polyimide resin film-forming composition was applied to a silicon wafer with a film thickness of 7 μm. The substrate on which the polyimide resin film-forming composition was applied was heated at 150° C. for 300 seconds. The resin film was then exposed to light through a positive mask for forming a via hole with a diameter of 20 μm. The exposed resin film was developed using cyclopentanone. The developed resin film was baked under the conditions shown in Table 2 to form a patterned semi-cured film. After development, the patterned semi-cured film was subjected to copper sputtering to form a copper film on the bottom of the recess of the patterned semi-cured film. Next, copper was plated by sputtering into the recess of the patterned semi-cured film so that the height from the silicon wafer surface was 10 μm. After plating, chemical mechanical polishing was performed until the semi-cured film was exposed, and a second substrate was produced. The second substrate was designated as second substrate D.

[Second Substrate E]
A substrate was used which had a silicon oxide film on its surface having a copper electrode with a diameter of 20 μm.

<Preparation of a laminated substrate used in a semiconductor device>
According to the method described in the laminated substrate formation process described above, the chip and second substrate prepared under the baking conditions shown in Tables 1 and 2 were attached under conditions of 160°C and 1.4 MPa-5 seconds, and a laminated substrate was produced under the post-lamination firing conditions shown in Tables 1 and 2.

<Evaluation>
The laminated substrates obtained in Examples 1 to 16 and Comparative Examples 1 to 9 were evaluated for epoxy reaction rate, appearance, bonding strength (shear test), and void generation according to the following methods. The evaluation results are shown in Tables 3 and 4.

[Epoxy reaction rate]
A semi-cured film was formed by applying the curable resin composition to a thickness of 7 μm on a silicon wafer and then heating at 100° C. for 300 seconds and baking under the conditions shown in Tables 1 and 2. The epoxy group reaction rate after baking was calculated using the semi-cured film according to the following formula.
Furthermore, the semi-cured film was baked under the conditions shown in Tables 1 and 2 to form a cured film. Using the cured film, the epoxy reaction rate after baking was calculated according to the following formula.
The curable resin composition was applied to a silicon wafer to a thickness of 7 μm and then heated at 100° C. for 300 seconds. The IR measurement results of the resin film that was not baked or sintered were used as a standard specimen with a reaction rate of 0.
Measuring equipment: FT/IR 4000 (manufactured by JASCO)
Measurement method: Permeation method Epoxy reaction rate = (1 - (Area 1 / Area 2) / (Area 3 / Area 4)) x 100
Area 1: epoxy group peak area = area value of 900-930 cm ⁻¹ Area 2: benzene peak area = area value of 1480-1530 cm ⁻¹ Area 3: standard epoxy peak area = area value of 900-930 cm ⁻¹ of standard Area 4: standard benzene peak area = area value of 1480-1530 cm ⁻¹ of standard

[exterior]
The peripheral edge of the chip on the laminated substrate was visually observed.
The case where the cured film did not protrude onto the peripheral edge of the chip was marked with "O", and the case where the cured film protruded onto the peripheral edge of the chip was marked with "X".

[Bonding strength (shear test)]
The prepared laminated substrate was fixed using a bond tester (Condor Sigma, XYZTEC) under the condition of room temperature (23° C.). A shear force was applied to the chip of the prepared laminated substrate, and the force required to peel off the chip was measured as the bonding strength.
The bonding strength was evaluated by rating it as follows: if the shear force at which the chip peeled off was 15 MPa or more, it was rated as "good"; if the shear force at which the chip peeled off was less than 15 MPa, it was rated as "bad."

[Void generation]
The produced laminated substrate was subjected to ultrasonic testing under the conditions described below using the ultrasonic measuring device described below to check for the presence or absence of voids.
Measurement device: Sonoscan Gen6
Measurement mode: C-Scan
Frequency: 100Mz
The occurrence of voids was evaluated by rating it as follows: if no voids were observed, it was rated as ◯; if voids were observed, it was rated as x.

According to Tables 3 and 4, it can be seen that the laminated substrates described in Examples 1 to 16, which were formed by using a curable resin composition that satisfies the above-mentioned specified requirements and by a method in which the reaction rate of the epoxy groups derived from the curable resin composition in the baked semi-cured film is more than 20% and less than 80%, and in the cured film obtained by baking the semi-cured film, the reaction rate of the epoxy groups derived from the curable resin composition is 85% or more, have a cured film that exhibits good appearance, has strong bonding strength, and is free of voids.
On the other hand, it can be seen that the laminate substrates of Comparative Examples 1 to 4 and Comparative Examples 6 to 8, which were formed by a method in which the reaction rate of the epoxy groups derived from the curable resin composition in the baked semi-cured film was 20% or less, or 80% or more, did not exhibit a good appearance, had weak bonding strength, and had cured films having voids.
In addition, it is found that the laminated substrates of Comparative Example 5 and Comparative Example 9, which were formed by a method in which the reaction rate of the epoxy groups derived from the curable resin composition in the baked semi-cured film was more than 20% and less than 80%, but the reaction rate of the epoxy groups derived from the curable resin composition in the cured film obtained by baking the semi-cured film was less than 85%, had weak bonding strength.

REFERENCE SIGNS LIST 100 Chip 10 Substrate 11 First metal electrode 12 Semi-cured film 200 Second substrate 20 Substrate 21 Second metal electrode 22 Insulating film

Claims (10)

forming a first substrate including a semiconductor substrate, a semi-cured film formed by baking a resin film made of a curable resin composition and covering one main surface of the semiconductor substrate, and a first metal electrode located in the semi-cured film, one end surface of which is exposed on a surface of the semi-cured film and the other end surface of which is in contact with the semiconductor substrate;
dicing the first substrate into a plurality of chips by cutting the first substrate in a thickness direction of the first substrate;
preparing a second substrate including a substrate, an insulating film covering one main surface of the substrate, and a second metal electrode located in the insulating film, one end surface of the second metal electrode being exposed on a surface of the insulating film and the other end surface of the second metal electrode being in contact with the substrate;
a bonding step of bonding the chip and the second substrate together to obtain a laminated substrate by baking the chip and the second substrate in a state in which a surface of the semi-cured film faces a surface of the insulating film and the first metal electrode is in contact with the second metal electrode;
and firing the laminated substrate;
The curable resin composition contains an alkali-soluble resin (A),
The alkali-soluble resin (A) has a carboxy group and/or a phenolic hydroxyl group as an alkali-soluble group,
The alkali-soluble resin (A) is represented by the following formula (a-1):

and an epoxy group-containing unit (A3),
In the formula (a-1), R represents a hydrogen atom or a methyl group, and R represents an organic ^group having a hydroxyl group.
In the semi-cured film, a reaction rate of epoxy groups derived from the curable resin composition is more than 20% and less than 80%,
a cured film obtained by curing the semi-cured film in the baked laminated substrate, the curable resin composition having a reaction rate of 85% or more. The semiconductor manufacturing device according to claim 1, wherein the baking temperature in the bonding is 100°C or higher and 200°C or lower. The first substrate is subjected to the following steps 1) to 3):
1) forming a resin film made of the curable resin composition on a main surface of the semiconductor substrate in contact with the first metal electrode;
2) baking the resin film to form a semi-cured film in which a reaction rate of an epoxy group derived from the curable resin composition is more than 20% and less than 80%; and 3) polishing the semi-cured film so that the first metal electrode is exposed from a surface of the semi-cured film.
2. The method of claim 1, wherein the semiconductor device is formed by The first substrate is subjected to the following steps 1) to 4):
1) forming a patterned semi-cured film, which serves as a mold for forming the first metal electrode, on the semiconductor substrate by a photolithography method using the curable resin composition; and
When forming the patterned semi-cured film, baking the resin film made of the curable resin composition to set the reaction rate of epoxy groups derived from the curable resin composition to more than 20% and less than 80%;
2) sputtering a metal onto the patterned semi-cured film to form a metal film on a surface of the semiconductor substrate exposed at a bottom of a recess in the semi-cured film in which the electrode is to be formed;
3) after forming the metal film, filling the recesses of the patterned semi-cured film with metal by plating to form the first metal electrode; and 4) polishing the patterned semi-cured film after plating until the semi-cured film and an end surface of the first metal electrode are exposed.
2. The method of claim 1, wherein the semiconductor device is formed by The method for manufacturing a semiconductor device according to any one of claims 1 to 4, wherein the curable resin composition contains an acid generator (B). The method for manufacturing a semiconductor device according to any one of claims 1 to 4, wherein the curable resin composition contains a silane coupling agent (C). The curable resin composition contains a crosslinking agent (D),
5. The method for producing a semiconductor device according to claim 1, wherein the crosslinking agent (D) includes a blocked isocyanate compound. The copolymer further comprises a copolymer represented by the following formula (a-2):

The structural unit (A2) is represented by the following formula:
In the formula (a-2), R represents a hydrogen atom or a methyl group, and ^Rb represents a hydrocarbon group.
The method for manufacturing a semiconductor device according to any one of claims 1 to 3. The semiconductor device manufacturing method according to any one of claims 1 to 4, wherein the insulating film is a semi-cured film formed by baking a resin film made of the curable resin composition, and the reaction rate of the epoxy groups derived from the curable resin composition is more than 20% and less than 80%. A semiconductor device including a laminated substrate including a chip and a second substrate, the chip and the second substrate being bonded to each other,
The chip comprises a semiconductor substrate, a cured film covering one main surface of the semiconductor substrate, and a first metal electrode located in the cured film, one end surface of which is exposed on a surface of the cured film and the other end surface of which is in contact with the semiconductor substrate;
the second substrate comprises a substrate, an insulating film covering one main surface of the substrate, and a second metal electrode located in the insulating film, one end surface of which is exposed on a surface of the insulating film and the other end surface of which is in contact with the substrate;
In the laminated substrate, the cured film and the insulating film are bonded to each other, and the first metal electrode and the second metal electrode are in contact with each other.
the cured film is made of a cured product of a curable resin composition containing an alkali-soluble resin (A),
The alkali-soluble resin (A) has a carboxy group and/or a phenolic hydroxyl group as an alkali-soluble group,
The alkali-soluble resin (A) is represented by the following formula (a-1):

and an epoxy group-containing unit (A3),
In formula (a-1), R represents a hydrogen atom or a methyl group, and R ^a01 represents an organic group having a hydroxyl group.

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