JP7786648B2 - Photosensitive resin composition, cured product, and semiconductor device - Google Patents

Description

The present invention relates to a photosensitive resin composition, a cured product, and a semiconductor device.

Polyimides are used, for example, as protective materials in liquid crystal display elements and semiconductors, insulating materials, and thin films for electronic materials such as color filters.

Patent Document 1 discloses a resin composition containing (A) a polyimide resin, characterized in that the polyimide resin (A) has an organic group with a specific structure, with the aim of providing a resin composition that is readily soluble in an alkaline developer before exposure, becomes insoluble in the alkaline developer upon exposure, and exhibits minimal film shrinkage upon curing, allowing for the formation of a highly rectangular pattern after curing.

Japanese Patent Application Laid-Open No. 2018-070829

The present invention provides a photosensitive resin composition and cured product that can improve the reliability of the resulting semiconductor device, as well as a semiconductor device with improved reliability.

The present inventors have conducted extensive research to solve the above-mentioned problems, and as a result have found that a photosensitive resin composition containing a polyimide (A) having a double bond in a side chain, a crosslinking agent (B) containing a (meth)acrylate compound, and a polymerization initiator (C), and having an oxygen permeability coefficient of ³⁰ cm3·mm/( ^m2 ·day·atm) or less, can improve the reliability of a semiconductor device, thereby completing the present invention.

According to the present invention, the following photosensitive resin composition, cured product, and semiconductor device are provided.

[1]
a polyimide (A) having a double bond in a side chain;
a crosslinking agent (B) containing a (meth)acrylate compound;
a polymerization initiator (C),
A photosensitive resin composition having an oxygen permeability coefficient of 30 ^cm3 ·mm/( ^m2 ·day·atm) or less, measured by the following method 1:
(Method 1)
The photosensitive resin composition is cured at 230°C for 3 hours to obtain a cured product having a size of 100 mm x 100 mm x 10 μm in thickness. The oxygen permeability coefficient of the cured product is measured by a differential pressure method in accordance with JIS K 7126-2:2006 under conditions of 23°C and 60% RH.
[2]
The photosensitive resin composition according to [1], wherein the photosensitive resin composition is cured at 230°C for 3 hours to obtain a cured product, and the cured product has a glass transition temperature (Tg) of 240°C or higher, as measured using a thermomechanical analyzer (TMA) under the following conditions: an initial temperature of 30°C, a measurement temperature range of 30 to 400°C, and a heating rate of 5°C/min.
[3]
The photosensitive resin composition according to [1] or [2], wherein a cured product obtained by curing the photosensitive resin composition at 230°C for 3 hours has a breaking elongation of 10% or more, as measured using a tensile tester in accordance with JIS K 7161:2014 at 23°C and a stretching rate of 5 mm/min.
[4]
The photosensitive resin composition according to any one of [1] to [3], wherein the photosensitive resin composition is cured at 230°C for 3 hours to obtain a cured product, and the tensile modulus is measured in accordance with JIS K 7161:2014 using a tensile tester under conditions of 23°C and an elongation rate of 5 mm/min., and is from 1.0 GPa to 5.0 GPa.
[5]
The photosensitive resin composition according to any one of [1] to [4], wherein a cured product obtained by curing the photosensitive resin composition at 230°C for 3 hours has a storage modulus at 30°C of 1.0 GPa or more and 6.0 GPa or less, as measured by dynamic mechanical analysis (DMA).
[6]
[6] The photosensitive resin composition according to any one of [1] to [5], wherein the content of the crosslinking agent (B) is 1 part by mass or more and 80 parts by mass or less when the content of the polyimide (A) is 100 parts by mass.
[7]
[7] The photosensitive resin composition according to any one of [1] to [6], wherein the content of the polymerization initiator (C) is 1 part by mass or more and 30 parts by mass or less when the content of the polyimide (A) is 100 parts by mass.
[8]
The photosensitive resin composition according to any one of [1] to [7], wherein a total content of the polyimide (A), the crosslinking agent (B), and the polymerization initiator (C) is 80 parts by mass or more when a total amount of solids in the photosensitive resin composition is 100 parts by mass.
[9]
When the number of moles of imide groups contained in the polyimide (A) is IM and the number of moles of amide groups contained in the polyimide (A) is AM,
The photosensitive resin composition according to any one of [1] to [8], wherein the imidization rate, expressed as {IM/(IM+AM)}×100(%), is 90% or more.
[10]
The photosensitive resin composition according to any one of [1] to [9], wherein the polymerization initiator (C) includes an oxime ester type polymerization initiator.
[11]
The photosensitive resin composition according to any one of [1] to [10], further comprising an organic solvent.
[12]
The organic solvent is γ-butyrolactone (GBL), γ-valerolactone (GVL), 2,6-lutidine, pyruvic acid N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropionamide, dimethyl sulfoxide (DMSO), diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether (PGME), propylene glycol The photosensitive resin composition according to [11], which contains one or more compounds selected from the group consisting of 1,3-butylene glycol monomethyl ether acetate (PGMEA), methyl lactate, ethyl lactate (EL), butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and 3-methyl-2-oxazolidone.
[13]
[13] The photosensitive resin composition according to any one of [1] to [12], wherein the content of fluorine atoms is 10 parts by mass or less when the total amount of solids in the photosensitive resin composition is 100 parts by mass.
[14]
[14] The photosensitive resin composition according to any one of [1] to [13], wherein the content of the fluorine atom-containing polymer is 30 parts by mass or less when the total amount of solids in the photosensitive resin composition is 100 parts by mass.
[15]
[15] The photosensitive resin composition according to any one of [1] to [14], wherein the content of the alkali-soluble resin is 30 parts by mass or less when the total amount of solids in the photosensitive resin composition is 100 parts by mass.
[16]
The photosensitive resin composition according to any one of [1] to [15], which can be used for a semiconductor device.
[17]
A cured product of the photosensitive resin composition according to any one of [1] to [16].
[18]
A semiconductor device comprising the cured product according to [17].
[19]
an interlayer insulating film;
a resin film containing the cured product on the interlayer insulating film;
a rewiring buried in the resin film;
The semiconductor device according to [18], comprising:

The present invention provides a photosensitive resin composition and cured product that can improve the reliability of the resulting semiconductor device, as well as a semiconductor device with improved reliability.

1 is a schematic cross-sectional view showing an example of the structure of a semiconductor device.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
The drawings are for illustrative purposes only, and the shapes and dimensional ratios of the components in the drawings do not necessarily correspond to the actual products.

In this embodiment, "A to B" indicating a numerical range means A or more and B or less unless otherwise specified.

<Photosensitive resin composition>
The photosensitive resin composition of the present embodiment contains a polyimide (A) having a double bond in a side chain, a crosslinking agent (B) containing a (meth)acrylate compound, and a polymerization initiator (C), and has an oxygen permeability coefficient of 30 ^cm3 ·mm/( ^m2 ·day·atm) or less.

According to the investigations of the present inventors, it has been found that there is a correlation between the oxygen permeability coefficient of a photosensitive resin composition and the reliability of a semiconductor device containing a cured product of the photosensitive resin composition.
As a result of further investigations based on the above findings, the present inventors have found that the reliability of semiconductor devices containing cured products of photosensitive resin compositions can be improved by using the oxygen permeability coefficient measured by a differential pressure method in accordance with JIS K 7126-2:2006 under conditions of 23°C and 60% RH for a 100 mm × 100 mm × 10 μm thick cured product obtained by curing a photosensitive resin composition at 230°C for 3 hours as an index, and by setting the oxygen permeability coefficient to 30 ^cm3 ·mm/( ^m2 ·day·atm) or less, thereby completing the present invention.

From the viewpoint of further improving the reliability of the resulting semiconductor device, the oxygen permeability coefficient of the photosensitive resin composition of this embodiment is preferably 30 ^cm3 ·mm/( ^m2 ·day·atm) or less, more preferably 25 ^cm3 ·mm/( ^m2 ·day·atm) or less, even more preferably 22 ^cm3 ·mm/( ^m2 ·day·atm) or less, even more preferably 20 ^cm3 ·mm/( ^m2 ·day·atm) or less, even more preferably 15 ^cm3 ·mm/( ^m2 ·day·atm) or less, and even more preferably 9 ^cm3 ·mm/( ^m2 ·day·atm) or less. The lower limit of the oxygen permeability coefficient of the photosensitive resin composition of the present embodiment is not particularly limited, but may be 1 ^cm3 ·mm/( ^m2 ·day·atm) or more, 2 ^cm3 ·mm/( ^m2 ·day·atm) or more, or ³ cm3·mm/( ^m2 ·day·atm) or more.
From the viewpoint of further improving the reliability of the resulting semiconductor device, the oxygen permeability coefficient of the photosensitive resin composition of this embodiment is preferably from 1 ^cm3 ·mm/( ^m2 ·day·atm) to 30 ^cm3 ·mm/(m2·day·atm), more preferably from 1 cm3·mm/( ^m2 ·day·atm) to 25 ^cm3 ·mm/( ^m2 ·day·atm), even more preferably from 2 ^cm3 ·mm/( ^m2 ·day·atm) to 22 ^cm3 ·mm/( ^m2 ·day·atm), even more preferably from 2 ^cm3 ·mm/( ^m2 ·day·atm) to ^{20 cm3} ·mm/(m2·day·atm), even more preferably from 3 ^cm3 ·mm/( ^m2 ·day·atm) to 15 cm3·mm/( ^m2 ·day·atm), and even more preferably from 3 ^cm3 ·mm/( ^m2 ·day·atm) to 15 ^cm3 ·mm/( ^m2 ·day·atm). ³ ·mm/(m ² ·day·atm) or more and 9 cm ³ ·mm/(m ² ·day·atm) or less.

The oxygen permeability coefficient of the photosensitive resin composition of the present embodiment can be measured, for example, by the following method.
First, a photosensitive resin composition is spin-coated onto a silicon wafer surface to a dry film thickness of 10 μm, pre-baked at 110°C for 3 minutes, then exposed to 600 mJ/ ^cm2 with a high-pressure mercury lamp, and then post-baked at 230°C for 3 hours in a nitrogen atmosphere to produce a cured product measuring 100 mm x 100 mm x 10 μm in thickness. Next, the oxygen permeability coefficient of the cured product is measured by the differential pressure method in accordance with JIS K 7126-2:2006 at 23°C and 60% RH.

The oxygen permeability coefficient of a photosensitive resin composition can be adjusted to a desired value, for example, by adjusting the types and contents of components contained in the photosensitive resin composition. Specifically, the oxygen permeability coefficient of a photosensitive resin composition can be reduced by increasing the content of double bonds in the side chains of polyimide (A); reducing the content of fluorine atoms in the photosensitive resin composition; using a polyimide that does not contain fluorine atoms (or a polyimide with a low content of fluorine atoms) as polyimide (A); or including a highly polar compound such as a highly polar crosslinking agent or a highly polar antioxidant in the photosensitive resin composition.

The photosensitive resin composition of this embodiment can be obtained by adjusting the values of each physical property so as to improve the trade-off balance between elongation and hardness of the cured product.

From the viewpoint of further improving the performance balance among patterning ability, mechanical strength, and reliability of the resulting semiconductor device, the photosensitive resin composition of the present embodiment has a glass transition temperature (Tg) of preferably 240°C or higher, more preferably 250°C or higher, even more preferably 260°C or higher, even more preferably 265°C or higher, even more preferably 270°C or higher, even more preferably 275°C or higher, even more preferably 278°C or higher, and even more preferably 282°C or higher; and preferably 350°C or lower, more preferably 330°C or lower, even more preferably 320°C or lower, even more preferably 310°C or lower, even more preferably 300°C or lower, and even more preferably 295°C or lower.
Furthermore, from the viewpoint of further improving the performance balance among patterning ability, mechanical strength, and reliability of the resulting semiconductor device, the glass transition temperature (Tg) of the photosensitive resin composition of this embodiment is preferably 240°C or higher and 350°C or lower, more preferably 250°C or higher and 330°C or lower, even more preferably 260°C or higher and 320°C or lower, even more preferably 265°C or higher and 310°C or lower, even more preferably 270°C or higher and 300°C or lower, even more preferably 275°C or higher and 295°C or lower, even more preferably 278°C or higher and 295°C or lower, and even more preferably 282°C or higher and 295°C or lower.
By adjusting the glass transition temperature (Tg) of the photosensitive resin composition of this embodiment to fall within the above range, it is possible to improve the trade-off balance between elongation and hardness of the cured product.

The glass transition temperature (Tg) of the photosensitive resin composition of the present embodiment can be measured, for example, by the following method.
First, a photosensitive resin composition is spin-coated onto a silicon wafer surface to a dry film thickness of 10 μm, pre-baked at 110°C for 3 minutes, then exposed to 600 mJ/ ^cm2 with a high-pressure mercury lamp, and then post-baked at 230°C for 3 hours in a nitrogen atmosphere to produce a cured product measuring 100 mm x 100 mm x 10 μm in thickness. Next, the glass transition temperature (Tg) of the cured product is measured using a thermomechanical analyzer (TMA) under the following conditions: starting temperature 30°C, measurement temperature range 30 to 400°C, and heating rate 5°C/min.

From the viewpoint of further improving the performance balance among patterning ability, mechanical strength, and reliability of the resulting semiconductor device, the photosensitive resin composition of the present embodiment has a breaking elongation of preferably 10% or more, more preferably 20% or more, even more preferably 25% or more, even more preferably 30% or more, and even more preferably 33% or more, and preferably 70% or less, more preferably 60% or less, even more preferably 55% or less, even more preferably 50% or less, and even more preferably 45% or less.
Furthermore, from the viewpoint of further improving the performance balance among patterning ability, mechanical strength, and reliability of the resulting semiconductor device, the elongation at break of the photosensitive resin composition of the embodiment is preferably 10% or more and 70% or less, more preferably 20% or more and 60% or less, even more preferably 25% or more and 55% or less, even more preferably 30% or more and 50% or less, and even more preferably 33% or more and 45% or less.
By adjusting the elongation at break of the photosensitive resin composition of this embodiment to fall within the above range, the trade-off balance between elongation and hardness of the cured product can be improved.

The breaking elongation of the photosensitive resin composition of the present embodiment can be measured, for example, by the following method.
First, a photosensitive resin composition is spin-coated onto a silicon wafer surface to a dry film thickness of 10 μm, pre-baked at 110°C for 3 minutes, then exposed to 600 mJ/ ^cm2 with a high-pressure mercury lamp, and then post-baked at 230°C for 3 hours in a nitrogen atmosphere to produce a cured product measuring 100 mm x 100 mm x 10 μm in thickness. Next, the elongation at break of the cured product is measured using a tensile tester in accordance with JIS K 7161:2014 at 23°C and a stretching rate of 5 mm/min.

From the viewpoint of further improving the balance of mechanical strength and reliability of the resulting semiconductor device, the tensile modulus of the photosensitive resin composition of this embodiment is preferably 1.0 GPa or more, more preferably 1.5 GPa or more, even more preferably 2.0 GPa or more, and still more preferably 2.3 GPa or more. The upper limit of the tensile modulus of the photosensitive resin composition of this embodiment is not particularly limited, but may be, for example, 5.0 GPa or less or 4.0 GPa or less.
Furthermore, from the viewpoint of further improving the performance balance between the mechanical strength and the reliability of the resulting semiconductor device, the tensile modulus of the photosensitive resin composition of this embodiment is preferably 1.0 GPa or more and 5.0 GPa or less, more preferably 1.5 GPa or more and 5.0 GPa or less, even more preferably 2.0 GPa or more and 4.0 GPa or less, and even more preferably 2.3 GPa or more and 4.0 GPa or less.
By adjusting the tensile modulus of elasticity of the photosensitive resin composition of this embodiment to fall within the above range, the trade-off balance between elongation and hardness of the cured product can be improved.

The tensile modulus of elasticity of the photosensitive resin composition of the present embodiment can be measured, for example, by the following method.
First, the photosensitive resin composition is spin-coated onto the surface of a silicon wafer so that the film thickness after drying is 10 μm, and the wafer is pre-baked at 110°C for 3 minutes, then exposed to 600 mJ/ ^cm2 using a high-pressure mercury lamp, and then post-baked for 3 hours at 230°C in a nitrogen atmosphere to produce a cured product measuring 100 mm x 100 mm x 10 μm in thickness. Next, the tensile modulus of the cured product is measured using a tensile tester in accordance with JIS K 7161:2014 at 23°C and a stretching rate of 5 mm/min.

From the viewpoint of further improving the balance between mechanical strength and the reliability of the resulting semiconductor device, the storage modulus of the photosensitive resin composition of this embodiment is preferably 1.0 GPa or more, more preferably 2.0 GPa or more, even more preferably 2.5 GPa or more, and still more preferably 3.0 GPa or more. The upper limit of the storage modulus of the photosensitive resin composition of this embodiment is not particularly limited, but may be, for example, 6.0 GPa or less or 5.0 GPa or less.
Furthermore, from the viewpoint of further improving the performance balance between the mechanical strength and the reliability of the resulting semiconductor device, the storage modulus of the photosensitive resin composition of this embodiment is preferably 1.0 GPa or more and 6.0 GPa or less, more preferably 2.0 GPa or more and 6.0 GPa or less, even more preferably 2.5 GPa or more and 5.0 GPa or less, and still more preferably 3.0 GPa or more and 5.0 GPa or less.
By adjusting the storage modulus of the photosensitive resin composition of the present embodiment to fall within the above range, the trade-off balance between elongation and hardness of the cured product can be improved.

The storage modulus of the photosensitive resin composition of the present embodiment can be measured, for example, by the following method.
First, a photosensitive resin composition is spin-coated onto a silicon wafer surface to a dry film thickness of 10 μm, pre-baked at 110°C for 3 minutes, then exposed to 600 mJ/ ^cm2 with a high-pressure mercury lamp, and then post-baked at 230°C for 3 hours in a nitrogen atmosphere to produce a cured product measuring 100 mm x 100 mm x 10 μm in thickness. Next, the storage modulus of the cured product at 30°C is measured by dynamic mechanical analysis (DMA).

The following describes each component of the photosensitive resin composition of this embodiment.

<Polyimide (A)>
The polyimide (A) of this embodiment has a double bond in the side chain.
The double bond in the polyimide (A) preferably contains a carbon-carbon double bond, more preferably a polymerizable carbon-carbon double bond.
The polyimide (A) of the present embodiment preferably contains a structural unit represented by the following general formula (1), from the viewpoint of further improving the performance balance among patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device.

In general formula (1), Y represents a divalent organic group, and from the viewpoint of further improving the performance balance of patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, Y is preferably a divalent group containing an alkylene group or a divalent group containing at least one aromatic ring.
The alkylene group is preferably an alkylene group having 1 to 5 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms. The aromatic ring is preferably a divalent benzene ring, a divalent naphthalene ring, a divalent anthracene ring, or a divalent biphenyl group, more preferably a divalent benzene ring or a divalent biphenyl group.

In general formula (1), Y is preferably selected from the group consisting of a group represented by the following general formula (1a), a group represented by the following general formula (1b), and a group represented by the following general formula (1c), from the viewpoint of further improving the performance balance of patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, and is more preferably a group represented by the following general formula (1b):

In general formula (1a), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and multiple R ^1s and multiple R ^2s may be the same or different, R ³ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and multiple R ^3s may be the same or different, and * represents a bond.
In general formula (1b), R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and multiple R ^4s and multiple R ^5s may be the same or different, and * represents a bond.
In the general formula (1c), Z represents an alkylene group having 1 to 5 carbon atoms or a divalent aromatic group, and * represents a bond.

In general formula (1a), ^R1 and ^R2 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and even more preferably a hydrogen atom or a methyl group.
In general formula (1a), preferably 0 to 3 R ¹ and R ² are each independently a hydrogen atom, more preferably 0 to 2 R 1 and R 2 are each independently a hydrogen atom, and even more preferably 1 R 1 and R 2 are each independently a hydrogen atom.
In general formula (1a), ^R3 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, even more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

In general formula (1b), ^R4 and ^R5 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and even more preferably a hydrogen atom or a methyl group.
In general formula (1b), preferably 0 to 3 R ⁴ and R ⁵ are each independently a hydrogen atom, more preferably 0 to 2 R 4 and R 5 are each independently a hydrogen atom, and even more preferably 1 R 4 and R 5 are each independently a hydrogen atom.

The polyimide (A) of this embodiment preferably contains a structural unit represented by the following general formula (2) in order to further improve the performance balance of patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device.

In general formula (2), m1 and m2 each independently represent an integer of 0 to 3; when m1 or m2 is 0, Q represents a hydrogen atom, a hydroxy group, or a monovalent organic group having 1 to 10 carbon atoms; when m1 or m2 is 1 to 3, Q represents a single bond or a divalent to tetravalent organic group having 1 to 10 carbon atoms; multiple Qs may be the same or different; R represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms; multiple Rs may be the same or different; X represents a single bond, —SO ₂ —, —C(═O)—, a linear or branched alkylene group having 1 to 5 carbon atoms, a linear or branched fluoroalkylene group having 1 to 5 carbon atoms, or a substituted or unsubstituted fluorene group.

In general formula (2), m1 and m2 are preferably 0 to 2, more preferably 0 or 1, from the viewpoint of further improving the performance balance of patterning properties, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device.
In general formula (2), when m1 or m2 is 0, Q is preferably a hydroxy group or an alkyl group having 1 to 2 carbon atoms; when m1 or m2 is 1 to 3, Q is preferably a divalent organic group having 1 to 5 carbon atoms, more preferably a divalent organic group having 1 to 5 carbon atoms and containing a urethane bond, and even more preferably a divalent organic group having 2 to 4 carbon atoms and containing a urethane bond.
In general formula (2), R is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.
In general formula (2), X is preferably any one selected from the group consisting of a linear or branched alkylene group having 1 to 5 carbon atoms and a substituted or unsubstituted fluorene group, more preferably any one selected from the group consisting of a linear or branched alkylene group having 1 to 3 carbon atoms and an unsubstituted fluorene group, and even more preferably a linear or branched alkylene group having 1 to 3 carbon atoms.
Here, in the substituted or unsubstituted fluorene group, the 9-position of the fluorene serves as the binding site.

For these reasons, the polyimide (A) of this embodiment preferably contains a structural unit (a) represented by the following general formula (3), from the viewpoint of further improving the performance balance of patterning properties, copper adhesion, mechanical strength, and the reliability of the resulting semiconductor device.

In general formula (3), m1 and m2 each independently represent an integer of 0 to 3; when m1 or m2 is 0, Q represents a hydrogen atom, a hydroxy group, or a monovalent organic group having 1 to 10 carbon atoms; when m1 or m2 is 1 to 3, Q represents a single bond or a divalent to tetravalent organic group having 1 to 10 carbon atoms; multiple Qs may be the same or different; R represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms; multiple Rs may be the same or different; X represents a single bond, —SO ₂ —, —C(═O)—, a linear or branched alkylene group having 1 to 5 carbon atoms, a linear or branched fluoroalkylene group having 1 to 5 carbon atoms, or a substituted or unsubstituted fluorene group; and Y represents a divalent organic group.

In general formula (3), the preferred embodiments of Q, R, X, and Y are the same as the preferred embodiments of X, Q, and R in general formula (2) and Y in general formula (1), respectively.

From the viewpoint of further improving the performance balance of patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, the structural unit (a) of this embodiment preferably contains a structural unit (a _p ) represented by general formula (3) in which at least one of m1 and m2 is 1 or greater, and a structural unit (a _q ) represented by general formula (3) in which both m1 and m2 are 0.

From the viewpoint of further improving the performance balance among patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, the content of the structural unit (a _p ) in the polyimide (A) of the present embodiment, when the total content of the structural unit (a _p ) and the structural unit (a _q ) is taken as 100 mol %, is preferably 30 mol % or more, more preferably 35 mol % or more, even more preferably 40 mol % or more, even more preferably 45 mol % or more, even more preferably 50 mol % or more, even more preferably 60 mol % or more, even more preferably 70 mol % or more, even more preferably 80 mol % or more, and even more preferably 90 mol % or more, and is preferably 100 mol % or less, more preferably 99 mol % or less, and even more preferably 95 mol % or less.
Furthermore, from the viewpoint of further improving the performance balance among patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, the content of the structural unit (a _p ) in the polyimide (A) of this embodiment, when the total content of the structural unit (a _p ) and the structural unit (a _q ) is taken as 100 mol %, is preferably 30 mol % or more and 100 mol % or less, more preferably 35 mol % or more and 100 mol % or less, even more preferably 40 mol % or more and 100 mol % or less, even more preferably 45 mol % or more and 100 mol % or less, even more preferably 50 mol % or more and 100 mol % or less, even more preferably 60 mol % or more and 100 mol % or less, even more preferably 70 mol % or more and 100 mol % or less, even more preferably 80 mol % or more and 100 mol % or less, even more preferably 80 mol % or more and 99 mol % or less, and even more preferably 90 mol % or more and 95 mol % or less.

When the number of moles of imide groups contained in the polyimide (A) of this embodiment is IM and the number of moles of amide groups contained in the polyimide (A) of this embodiment is AM, the imidization rate, expressed as {IM/(IM+AM)}×100(%), is preferably 90% or more, more preferably 95% or more, and even more preferably 98% or more, from the viewpoint of further improving the reliability of the resulting semiconductor device. The upper limit of the imidization rate of the polyimide (A) of this embodiment is not particularly limited, but may be, for example, 100% or less.
Moreover, from the viewpoint of further improving the reliability of the resulting semiconductor device, the imidization rate of the polyimide (A) of the present embodiment is preferably 90% or more and 100% or less, more preferably 95% or more and 100% or less, and even more preferably 98% or more and 100% or less.

From the viewpoint of further improving the performance balance among patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, the content of polyimide (A) in the photosensitive resin composition of the present embodiment is, when the total amount of the solids in the photosensitive resin composition is taken as 100 parts by mass, preferably 30 parts by mass or more, more preferably 40 parts by mass or more, even more preferably 50 parts by mass or more, even more preferably 55 parts by mass or more, and even more preferably 60 parts by mass or more, and is preferably 95 parts by mass or less, more preferably 90 parts by mass or less, even more preferably 85 parts by mass or less, even more preferably 80 parts by mass or less, and even more preferably 75 parts by mass or less.
Furthermore, from the viewpoint of further improving the performance balance among patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, the content of polyimide (A) in the photosensitive resin composition of this embodiment is preferably 30 parts by mass or more and 95 parts by mass or less, more preferably 40 parts by mass or more and 90 parts by mass or less, even more preferably 50 parts by mass or more and 85 parts by mass or less, even more preferably 55 parts by mass or more and 80 parts by mass or less, and still more preferably 60 parts by mass or more and 75 parts by mass or less, when the total amount of the solid contents in the photosensitive resin composition is taken as 100 parts by mass.
In this specification, the term "solid content in the photosensitive resin composition" refers to non-volatile components, and more specifically, components other than the organic solvent.

<Crosslinking agent (B)>
The crosslinking agent (B) of the present embodiment includes a (meth)acrylate compound.
The crosslinking agent (B) of this embodiment preferably contains a polyfunctional (meth)acrylate compound from the viewpoint of further improving the balance of performance among patterning properties, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device.

Examples of the polyfunctional (meth)acrylate compound of this embodiment include bifunctional (meth)acrylates such as diethylene glycol di(meth)acrylate, polyethylene glycol #200 di(meth)acrylate, and polyethylene glycol #400 di(meth)acrylate; trifunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and ethoxylated isocyanuric acid triacrylate; and pentaerythritol tetra(meth)acrylate. tetrafunctional (meth)acrylates such as dipentaerythritol hexa(meth)acrylate; octafunctional (meth)acrylates such as tripentaerythritol octa(meth)acrylate; and decafunctional (meth)acrylates such as tetrapentaerythritol deca(meth)acrylate. The polyfunctional (meth)acrylate compound of the present embodiment may contain one or more of these.

From the viewpoint of further improving the performance balance of patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, the crosslinking agent (B) of this embodiment preferably contains a polyfunctional (meth)acrylate compound having 3 to 20 (meth)acryloyloxy groups or (meth)acryloyl groups in the molecule, more preferably contains a polyfunctional (meth)acrylate compound having 4 to 15 (meth)acryloyloxy groups or (meth)acryloyl groups in the molecule, and even more preferably contains a polyfunctional (meth)acrylate compound having 5 to 10 (meth)acryloyloxy groups or (meth)acryloyl groups in the molecule.

The crosslinking agent (B) of the present embodiment may contain a (meth)acrylate compound having an isocyanuric acid skeleton. By containing a (meth)acrylate compound having an isocyanuric acid skeleton, it becomes easier to adjust the oxygen permeability coefficient of the photosensitive resin composition to a more appropriate range.
The number of (meth)acryloyloxy groups or (meth)acryloyl groups contained in the molecule of the (meth)acrylate compound having an isocyanuric acid skeleton of this embodiment is preferably 1 or more and 6 or less, more preferably 2 or more and 3 or less.

The crosslinking agent (B) of this embodiment preferably contains an epoxy compound from the viewpoint of further improving the performance balance of patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device.

The epoxy compound of the present embodiment preferably contains an epoxy compound having a (meth)acryloyloxy group or a (meth)acryloyl group, from the viewpoint of further improving the balance of performance among patterning properties, copper adhesion, mechanical strength, and reliability of the obtained semiconductor device.
The number of glycidyl groups contained in the molecule of the epoxy compound having a (meth)acryloyloxy group or a (meth)acryloyl group of the present embodiment is preferably 1 or more and 6 or less, more preferably 1 or more and 3 or less, and even more preferably 1.
The number of (meth)acryloyloxy groups or (meth)acryloyl groups contained in the molecule of the epoxy compound having a (meth)acryloyloxy group or a (meth)acryloyl group of the present embodiment is preferably 0 or more and 6 or less, more preferably 0 or more and 2 or less, and even more preferably 1.

The epoxy compound of the present embodiment may include an epoxy compound having a bisphenol skeleton.
The number of glycidyl groups contained in the molecule of the epoxy compound having a bisphenol skeleton of this embodiment is preferably 1 or more and 6 or less, more preferably 2 or more and 4 or less, and even more preferably 3.

From the viewpoint of further improving the performance balance among patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, the content of the crosslinking agent (B) in the photosensitive resin composition of the present embodiment is, when the total amount of the solids in the photosensitive resin composition is taken as 100 parts by mass, preferably 1 part by mass or more, more preferably 5 parts by mass or more, even more preferably 8 parts by mass or more, even more preferably 10 parts by mass or more, even more preferably 12 parts by mass or more, even more preferably 14 parts by mass or more, and is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, even more preferably 35 parts by mass or less, even more preferably 30 parts by mass or less, even more preferably 26 parts by mass or less, and even more preferably 23 parts by mass or less.
Furthermore, from the viewpoint of further improving the performance balance among patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, the content of the crosslinking agent (B) in the photosensitive resin composition of the present embodiment is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 5 parts by mass or more and 40 parts by mass or less, even more preferably 8 parts by mass or more and 35 parts by mass or less, even more preferably 10 parts by mass or more and 30 parts by mass or less, even more preferably 12 parts by mass or more and 26 parts by mass or less, and even more preferably 14 parts by mass or more and 23 parts by mass or less, when the total amount of the solid contents in the photosensitive resin composition is taken as 100 parts by mass.

<Polymerization initiator (C)>
As the polymerization initiator (C) of this embodiment, a conventionally known polymerization initiator can be used as long as the effects of the present invention can be exhibited, and examples thereof include a photoradical generator and a thermal radical generator. From the viewpoint of further improving the performance balance of patterning ability, copper adhesion, mechanical strength, and the reliability of the resulting semiconductor device, the polymerization initiator (C) of this embodiment preferably contains a photoradical generator, and more preferably contains both a photoradical generator and a thermal radical generator.

Examples of the photoradical generator of this embodiment include alkylphenone-type polymerization initiators, oxime ester-type polymerization initiators, and acylphosphine oxide-type polymerization initiators. Specific examples include 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]- [N-yl]-2-hydroxy-2-methyl-1-propan-1-one, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), 2-(dimethylamino)-1-(4-(4-morpholino)phenyl)-2-(phenylmethyl)-1-butanone, Irgacure OXE01 (manufactured by BASF Japan Ltd.), Irgacure OXE02 (manufactured by BASF Japan Ltd.), Irgacure OXE03 (manufactured by BASF Japan Ltd.), Irgacure OXE04 (manufactured by BASF Japan Ltd.), and the like. The polymerization initiator (C) of the present embodiment can contain one or more of these.
The polymerization initiator (C) of the present embodiment preferably contains an oxime ester-type polymerization initiator, and more preferably contains Irgacure OXE01, from the viewpoint of further improving the performance balance among patterning ability, copper adhesion, mechanical strength, and reliability of the obtained semiconductor device.

Examples of the thermal radical generator of the present embodiment include 1,1-bis(t-butylperoxy)2-methylcyclohexane, 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(4,4-dibutylperoxycyclohexyl)propane, 1,1-bis(t-butylperoxy)cyclododecane, t-hexylperoxyisopropyl monocarbonate, t -butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di(m-toluoylperoxy)hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butylperoxyacetate, 2,2-bis(t-butylperoxy)butane, t-butylperoxybenzoate, n-butyl-4,4-bis(t-butylperoxy) bis(t-butylperoxy)valerate, di-t-butylperoxyisophthalate, α,α'-bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide organic peroxides such as benzoyl hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, and the like; and azo compounds such as azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2-(carbamoylazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, azodi-t-octane, azodi-t-butane, and 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide]; and the like, and the polymerization initiator (C) of the present embodiment can contain one or more of these.
The polymerization initiator (C) of the present embodiment preferably contains an organic peroxide, and more preferably contains dicumyl peroxide, from the viewpoint of further improving the performance balance among patterning ability, copper adhesion, mechanical strength, and reliability of the obtained semiconductor device.

From the viewpoint of further improving the performance balance among patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, the content of the polymerization initiator (C) in the photosensitive resin composition of the present embodiment is, when the total amount of the solids in the photosensitive resin composition is taken as 100 parts by mass, preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, and still more preferably 6 parts by mass or more, and is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, even more preferably 15 parts by mass or less, and still more preferably 12 parts by mass or less.
Furthermore, from the viewpoint of further improving the performance balance among patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, the content of the polymerization initiator (C) in the photosensitive resin composition of the present embodiment is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 3 parts by mass or more and 20 parts by mass or less, even more preferably 5 parts by mass or more and 15 parts by mass or less, and still more preferably 6 parts by mass or more and 12 parts by mass or less, when the total amount of the solid contents in the photosensitive resin composition is taken as 100 parts by mass.

From the viewpoint of further improving the performance balance among patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, the total content of the polyimide (A), crosslinking agent (B), and polymerization initiator (C) in the photosensitive resin composition of this embodiment is, when the total amount of the solids in the photosensitive resin composition is taken as 100 parts by mass, preferably 80 parts by mass or more, more preferably 85 parts by mass or more, even more preferably 90 parts by mass or more, even more preferably 92 parts by mass or more, and still more preferably 94 parts by mass or more, and is preferably 100 parts by mass or less, more preferably 99 parts by mass or less, even more preferably 98 parts by mass or less, even more preferably 97 parts by mass or less, and still more preferably 96 parts by mass or less.
Furthermore, from the viewpoint of further improving the performance balance among patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, the total content of the polyimide (A), crosslinking agent (B), and polymerization initiator (C) in the photosensitive resin composition of this embodiment is preferably 80 parts by mass or more and 100 parts by mass or less, more preferably 85 parts by mass or more and 99 parts by mass or less, even more preferably 90 parts by mass or more and 98 parts by mass or less, even more preferably 92 parts by mass or more and 97 parts by mass or less, and still more preferably 94 parts by mass or more and 96 parts by mass or less, when the total amount of the solids in the photosensitive resin composition is taken as 100 parts by mass.

When the content of the polyimide (A) of the present embodiment is taken as 100 parts by mass, the content of the crosslinking agent (B) of the present embodiment is preferably 1 part by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, and even more preferably 20 parts by mass or more, from the viewpoint of further improving the performance balance of patterning ability, copper adhesion, mechanical strength, and reliability of the obtained semiconductor device, and is preferably 80 parts by mass or less, more preferably 60 parts by mass or less, even more preferably 50 parts by mass or less, even more preferably 40 parts by mass or less, and even more preferably 35 parts by mass or less.
Furthermore, when the content of the polyimide (A) of this embodiment is taken as 100 parts by mass, the content of the crosslinking agent (B) of this embodiment is preferably 1 part by mass or more and 80 parts by mass or less, more preferably 5 parts by mass or more and 60 parts by mass or less, even more preferably 10 parts by mass or more and 50 parts by mass or less, even more preferably 15 parts by mass or more and 40 parts by mass or less, and even more preferably 20 parts by mass or more and 35 parts by mass or less, from the viewpoint of further improving the performance balance of patterning ability, copper adhesion, mechanical strength, and reliability of the obtained semiconductor device.

When the content of the polyimide (A) of the present embodiment is taken as 100 parts by mass, the content of the polymerization initiator (C) of the present embodiment is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, even more preferably 7 parts by mass or more, and even more preferably 9 parts by mass or more, from the viewpoint of further improving the performance balance of patterning ability, copper adhesion, mechanical strength, and reliability of the obtained semiconductor device, and is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, even more preferably 22 parts by mass or less, even more preferably 20 parts by mass or less, and even more preferably 17 parts by mass or less.
Furthermore, when the content of the polyimide (A) of the present embodiment is taken as 100 parts by mass, the content of the polymerization initiator (C) of the present embodiment is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 3 parts by mass or more and 25 parts by mass or less, even more preferably 5 parts by mass or more and 22 parts by mass or less, even more preferably 7 parts by mass or more and 20 parts by mass or less, and still more preferably 9 parts by mass or more and 17 parts by mass or less, from the viewpoint of further improving the performance balance of patterning ability, copper adhesion, mechanical strength, and reliability of the obtained semiconductor device.

<Antioxidants>
From the viewpoint of further improving the balance of performance among patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, the photosensitive resin composition of this embodiment preferably further contains an antioxidant, more preferably an antioxidant having an isocyanuric acid skeleton. By including the antioxidant having an isocyanuric acid skeleton, it becomes easier to adjust the oxygen permeability coefficient of the photosensitive resin composition to a more appropriate range.
The antioxidant of the present embodiment includes, for example, at least one selected from the group consisting of a phenol-based antioxidant, a phosphite-based antioxidant, and a thioether-based antioxidant, and preferably includes a phenol-based antioxidant, and more preferably includes a hindered phenol-based antioxidant.

The antioxidant of this embodiment preferably contains a compound represented by the following general formula (4) from the viewpoint of further improving the performance balance of patterning properties, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device.

In general formula (4), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, a hydroxy group, an alkyl group or alkoxy group having 1 to 20 carbon atoms which may contain a hydroxy group, or an aryl group or aralkyl group having 6 to 30 carbon atoms which may contain at least one substituent selected from the group consisting of a hydroxy group, an alkyl group and an alkoxy group.

In general formula (4), from the viewpoint of further improving the performance balance of patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, R ¹¹ , R ¹² , and R ¹³ are preferably an aryl group or aralkyl group having 6 to 30 carbon atoms which may contain at least one substituent selected from the group consisting of a hydroxy group and an alkyl group, more preferably an aryl group or aralkyl group having 6 to 30 carbon atoms which contains at least one substituent selected from the group consisting of a hydroxy group and an alkyl group, even more preferably an aryl group or aralkyl group having 6 to 30 carbon atoms which contains a hydroxy group and an alkyl group as a substituent, even more preferably an aryl group or aralkyl group having 8 to 20 carbon atoms which contains a hydroxy group and an alkyl group as a substituent, even more preferably an aryl group or aralkyl group having 10 to 16 carbon atoms which contains a hydroxy group and an alkyl group as a substituent, even more preferably an aryl group or aralkyl group having 11 to 15 carbon atoms which contains a hydroxy group and an alkyl group as a substituent, and even more preferably an aralkyl group having 11 to 15 carbon atoms which contains a hydroxy group and an alkyl group as a substituent.

In general formula (4), at least one of R ¹¹ , R ¹² and R ¹³ is preferably a group represented by the following general formula (5), from the viewpoint of further improving the performance balance of patterning properties, copper adhesion, mechanical strength and reliability of the resulting semiconductor device.

In general formula (5), W represents a single bond or an alkylene group having 1 to 5 carbon atoms, R ²⁰ represents a hydrogen atom, a hydroxy group, or an alkyl or alkoxy group having 1 to 5 carbon atoms which may contain a hydroxy group, and multiple R ^20s may be the same or different, and * represents a bond.

In general formula (4), from the viewpoint of further improving the balance of performance ^among patterning property, copper adhesion, mechanical strength ^, and reliability of the obtained semiconductor device, preferably, two or more of R ¹¹ , R ¹² , and R ¹³ are groups represented by general formula (5), and more preferably, all of R ¹¹ , R ^{12 ,} and R ¹³ are groups represented by general formula (5).

In general formula (5), W is preferably a single bond or an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 to 2 carbon atoms, and even more preferably a methylene group, from the viewpoint of further improving the performance balance of patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device.

In general formula (5), R ²⁰ is preferably a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom, a hydroxy group, a methyl group, or a t-butyl group, from the viewpoint of further improving the balance of performance among patterning properties, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device.

In general formula (5), at least one of R ²⁰ is preferably a hydroxy group, from the viewpoint of further improving the balance of performance among patterning properties, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device.

In general formula (5), from the viewpoint of further improving the performance balance of patterning property, copper adhesion, mechanical strength, and reliability of the obtained semiconductor device, preferably 0 to 3 R ²⁰ are hydrogen atoms, more preferably 1 or 2 are hydrogen atoms, and even more preferably 1 is a hydrogen atom.
In general formula (5), R ²⁰ at the meta position of W is preferably a hydrogen ^atom , from the viewpoint of further improving the balance of performance among patterning properties, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device.

In general formula (5), from the viewpoint of further improving the balance of performance among patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, preferably 1 to 3 R ²⁰ are hydroxy groups, more preferably 1 to 2 R 20 are hydroxy groups, and even more preferably 1 R 20 is a hydroxy group.
In general formula (5), R ²⁰ at the meta position of W is preferably a hydroxy ^group , from the viewpoint of further improving the balance of performance among patterning properties, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device.

In general formula (5), from the viewpoint of further improving the performance balance of patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, preferably 0 to 3 R ^20s are methyl groups, more preferably 1 to 2 R 20s are methyl groups, and even more preferably 2 R 20s are methyl groups.
In general formula (5), R ²⁰ at the ortho position of W is preferably a methyl ^group , from the viewpoint of further improving the balance of performance among patterning properties, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device.

In general formula (5), from the viewpoint of further improving the balance of performance among patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, preferably 0 to 3 R ^20s are t-butyl groups, more preferably 1 or 2 R 20s are t-butyl groups, and even more preferably 1 R 20 is a t-butyl group.
In general formula (5), R ²⁰ at the para-position of W is preferably a t- ^{butyl group} , from the viewpoint of further improving the balance of performance among patterning properties, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device.

In general formula (4), from the viewpoint of further improving the balance of performance among patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, preferably two of R ¹¹ , R ¹² , and R ¹³ are the same functional group, and more preferably all three are the same functional group.

From the viewpoint of further improving the performance balance among patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, the content of the antioxidant in the photosensitive resin composition of the present embodiment is, when the total amount of the solids in the photosensitive resin composition is taken as 100 parts by mass, preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.1 parts by mass or more, even more preferably 0.3 parts by mass or more, even more preferably 0.5 parts by mass or more, and even more preferably 0.6 parts by mass or more, and is preferably 10.0 parts by mass or less, more preferably 7.0 parts by mass or less, even more preferably 5.0 parts by mass or less, even more preferably 4.0 parts by mass or less, even more preferably 3.5 parts by mass or less, and even more preferably 3.0 parts by mass or less.
Furthermore, from the viewpoint of further improving the performance balance among patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, the content of the antioxidant in the photosensitive resin composition of this embodiment is preferably 0.01 parts by mass or more and 10.0 parts by mass or less, more preferably 0.05 parts by mass or more and 7.0 parts by mass or less, even more preferably 0.1 parts by mass or more and 5.0 parts by mass or less, even more preferably 0.3 parts by mass or more and 4.0 parts by mass or less, even more preferably 0.5 parts by mass or more and 3.5 parts by mass or less, and even more preferably 0.6 parts by mass or more and 3.0 parts by mass or less, when the total amount of the solids in the photosensitive resin composition is taken as 100 parts by mass.

<Adhesion aid>
The photosensitive resin composition of the present embodiment preferably further contains an adhesion aid from the viewpoint of further improving adhesion.
Examples of the adhesion aid of the present embodiment include aminosilanes such as bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldiethoxysilane, and N-phenyl-γ-aminopropyltrimethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, or β-(3, Examples of suitable silanes include epoxy silanes such as 4-epoxycyclohexyl)ethyltrimethoxysilane and γ-glycidylpropyltrimethoxysilane; acrylic silanes such as γ-(methacryloxypropyl)trimethoxysilane, γ-(methacryloxypropyl)methyldimethoxysilane, and γ-(methacryloxypropyl)methyldiethoxysilane; mercaptosilanes such as 3-mercaptopropyltrimethoxysilane; vinyl silanes such as vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, and vinyltrimethoxysilane; ureidosilanes such as 3-ureidopropyltriethoxysilane; and acid anhydride functional silanes such as 3-trimethoxysilylpropylsuccinic anhydride. The adhesion aid of the present embodiment may contain one or more of these.
Among these, from the viewpoint of further improving adhesion, the adhesion aid of the present embodiment preferably contains one or more selected from the group consisting of epoxy silanes and acid anhydride functional silanes, and more preferably contains both 3-glycidoxypropyltrimethoxysilane and 3-trimethoxysilylpropylsuccinic anhydride.

From the viewpoint of further improving adhesion, the content of the adhesion aid in the photosensitive resin composition of the present embodiment is preferably 0.1 parts by mass or more, more preferably 1.0 parts by mass or more, even more preferably 1.5 parts by mass or more, and is preferably 10.0 parts by mass or less, more preferably 8.0 parts by mass or less, even more preferably 7.0 parts by mass or less, relative to 100 parts by mass of the polyimide (A).
From the viewpoint of further improving adhesion, the content of the adhesion aid in the photosensitive resin composition of the present embodiment is preferably 0.1 parts by mass or more and 10.0 parts by mass or less, more preferably 1.0 parts by mass or more and 8.0 parts by mass or less, and even more preferably 1.5 parts by mass or more and 7.0 parts by mass or less, relative to 100 parts by mass of the polyimide (A).

<Surfactant>
The photosensitive resin composition of this embodiment preferably further contains a surfactant.
Examples of surfactants of the present embodiment include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; Eftop EF301, Eftop EF303, and Eftop EF352 (manufactured by Shin-Akita Chemical Industry Co., Ltd.), Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F444, and Megafac F544. Fluorine-based surfactants commercially available under the names of Gafac F470, Megafac F471, Megafac F475, Megafac F482, Megafac F477 (manufactured by DIC Corporation), Fluorad FC-430, Fluorad FC-431, Novec FC4430, Novec FC4432 (manufactured by 3M Japan Ltd.), Surflon S-381, Surflon S-382, Surflon S-383, Surflon S-393, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106 (manufactured by AGC Seimi Chemical Co., Ltd.), etc.; organosiloxane copolymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); (meth)acrylic acid copolymer Polyflow No. 57, 95 (manufactured by Kyoeisha Chemical Co., Ltd.); silicone surfactants such as polyether-modified dimethylsiloxane, and the surfactant of the present embodiment may contain one or more of these.
Among these, the surfactant of the present embodiment preferably includes a silicone surfactant.

The content of the surfactant in the photosensitive resin composition of this embodiment is preferably 0.001 parts by mass or more and 0.5 parts by mass or less, and more preferably 0.01 parts by mass or more and 0.1 parts by mass or less, when the content of polyimide (A) is 100 parts by mass.

<Curing catalyst>
The photosensitive resin composition of this embodiment preferably further contains a curing catalyst from the viewpoint of further improving the balance of performance among patterning properties, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device.
Examples of the curing catalyst of the present embodiment include phosphorus atom-containing compounds such as organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds; amidines such as dicyandiamide, 2-phenyl-4,5-dihydroxymethylimidazole, 1,8-diazabicyclo[5.4.0]undecene-7, and benzyldimethylamine, tertiary amines and derivatives thereof; and nitrogen atom-containing compounds such as quaternary ammonium salts of the above amidines or the above tertiary amines. The curing catalyst of the present embodiment can contain one or more of these compounds.
The curing catalyst of the present embodiment preferably contains a phosphorus atom-containing compound, and more preferably contains a tetra-substituted phosphonium compound, from the viewpoint of further improving the performance balance among patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device.

In order to further improve the performance balance of patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, the content of the curing catalyst in the photosensitive resin composition of this embodiment is preferably 0.1 parts by mass or more and 5.0 parts by mass or less, more preferably 0.5 parts by mass or more and 2.0 parts by mass or less, relative to 100 parts by mass of the polyimide (A).

<Other additives>
The photosensitive resin composition of the present embodiment may further contain other additives such as a leveling agent, a flame retardant, and a plasticizer, as needed.

<Organic solvent>
The photosensitive resin composition of the present embodiment preferably further contains an organic solvent from the viewpoint of further improving the balance of patterning properties and copper adhesion properties.
From the viewpoint of further improving the balance of patterning properties and copper adhesion, the organic solvent of the present embodiment is preferably γ-butyrolactone (GBL), γ-valerolactone (GVL), 2,6-lutidine, pyruvic acid N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropionamide, dimethyl sulfoxide (DMSO), diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGME A), methyl lactate, ethyl lactate (EL), butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and 3-methyl-2-oxazolidone, more preferably, it contains one or two or more selected from the group consisting of γ-butyrolactone (GBL) and ethyl lactate (EL), and even more preferably, it contains both γ-butyrolactone (GBL) and ethyl lactate (EL).

From the viewpoint of further improving the performance balance between patterning ability and copper adhesion, the content of the organic solvent in the photosensitive resin composition of the present embodiment is, when the total amount of the solids in the photosensitive resin composition is taken as 100 parts by mass, preferably 50 parts by mass or more, more preferably 100 parts by mass or more, even more preferably 150 parts by mass or more, even more preferably 200 parts by mass or more, even more preferably 230 parts by mass or more, and even more preferably 260 parts by mass or more, and is preferably 1000 parts by mass or less, more preferably 800 parts by mass or less, even more preferably 600 parts by mass or less, even more preferably 500 parts by mass or less, even more preferably 400 parts by mass or less, and even more preferably 350 parts by mass or less.
Furthermore, from the viewpoint of further improving the performance balance between patterning ability and copper adhesion, the content of the organic solvent in the photosensitive resin composition of the present embodiment is preferably 50 parts by mass or more and 1,000 parts by mass or less, more preferably 100 parts by mass or more and 800 parts by mass or less, even more preferably 150 parts by mass or more and 600 parts by mass or less, even more preferably 200 parts by mass or more and 500 parts by mass or less, even more preferably 230 parts by mass or more and 400 parts by mass or less, and even more preferably 260 parts by mass or more and 350 parts by mass or less, when the total amount of the solids in the photosensitive resin composition is taken as 100 parts by mass.

From the viewpoint of further improving environmental compatibility, the content of fluorine atoms in the photosensitive resin composition of the present embodiment is preferably 0 parts by mass or more and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less, even more preferably 1 part by mass or less, even more preferably 0.1 parts by mass or less, even more preferably 0.05 parts by mass or less, and even more preferably 0.01 parts by mass or less, when the total amount of solids in the photosensitive resin composition is 100 parts by mass.
Furthermore, from the viewpoint of further improving environmental compatibility, the content of fluorine atoms in the photosensitive resin composition of the present embodiment is preferably 0 parts by mass or more and 10 parts by mass or less, more preferably 0 parts by mass or more and 5 parts by mass or less, even more preferably 0 parts by mass or more and 3 parts by mass or less, even more preferably 0 parts by mass or more and 1 part by mass or less, even more preferably 0 parts by mass or more and 0.1 parts by mass or less, even more preferably 0 parts by mass or more and 0.05 parts by mass or less, and even more preferably 0 parts by mass or more and 0.01 parts by mass or less, when the total amount of the solid content in the photosensitive resin composition is 100 parts by mass.
By setting the content of fluorine atoms in the photosensitive resin composition of this embodiment within the above numerical range, it becomes easier to adjust the oxygen permeability coefficient of the photosensitive resin composition to a more appropriate range.

From the viewpoint of further improving environmental compatibility, the content of the fluorine atom-containing polymer in the photosensitive resin composition of the present embodiment is preferably 0 parts by mass or more and preferably 30 parts by mass or less, more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, even more preferably 1 part by mass or less, even more preferably 0.1 parts by mass or less, even more preferably 0.05 parts by mass or less, and even more preferably 0.01 parts by mass or less, when the total amount of solids in the photosensitive resin composition is 100 parts by mass.
Furthermore, from the viewpoint of further improving environmental compatibility, the content of the fluorine atom-containing polymer in the photosensitive resin composition of the present embodiment is preferably 0 parts by mass or more and 30 parts by mass or less, more preferably 0 parts by mass or more and 20 parts by mass or less, even more preferably 0 parts by mass or more and 10 parts by mass or less, even more preferably 0 parts by mass or more and 5 parts by mass or less, even more preferably 0 parts by mass or more and 1 part by mass or less, even more preferably 0 parts by mass or more and 0.1 parts by mass or less, even more preferably 0 parts by mass or more and 0.05 parts by mass or less, and even more preferably 0 parts by mass or more and 0.01 parts by mass or less, when the total amount of the solids in the photosensitive resin composition is 100 parts by mass.
By setting the content of the fluorine atom-containing polymer in the photosensitive resin composition of this embodiment within the above numerical range, it becomes easier to adjust the oxygen permeability coefficient of the photosensitive resin composition to a more appropriate range.

From the viewpoint of further improving the performance balance among patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, the content of the alkali-soluble resin in the photosensitive resin composition of the present embodiment is preferably 0 parts by mass or more and preferably 30 parts by mass or less, more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, even more preferably 1 part by mass or less, even more preferably 0.1 parts by mass or less, even more preferably 0.05 parts by mass or less, and even more preferably 0.01 parts by mass or less, when the total amount of solids in the photosensitive resin composition is taken as 100 parts by mass.
Furthermore, from the viewpoint of further improving the performance balance among patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, the content of the alkali-soluble resin in the photosensitive resin composition of this embodiment is preferably 0 parts by mass or more and 30 parts by mass or less, more preferably 0 parts by mass or more and 20 parts by mass or less, even more preferably 0 parts by mass or more and 10 parts by mass or less, even more preferably 0 parts by mass or more and 5 parts by mass or less, even more preferably 0 parts by mass or more and 1 part by mass or less, even more preferably 0 parts by mass or more and 0.1 parts by mass or less, even more preferably 0 parts by mass or more and 0.05 parts by mass or less, and even more preferably 0 parts by mass or more and 0.01 parts by mass or less, when the total amount of the solids in the photosensitive resin composition is taken as 100 parts by mass.
In this specification, the alkali-soluble resin is a resin that dissolves in an alkali developer to an extent sufficient for patterning.

<Method for preparing photosensitive resin composition>
The method for preparing the photosensitive resin composition in this embodiment is not limited, and any known method can be used depending on the components contained in the photosensitive resin composition.
For example, the above-mentioned components can be mixed and dissolved in a solvent to prepare the composition.

<Application>
The photosensitive resin composition of this embodiment can be suitably used in semiconductor devices because the reliability of the resulting semiconductor devices is improved.

The photosensitive resin composition of the present embodiment is suitably used for forming a resin film for a semiconductor device, such as a permanent film, a resist, etc. Among these, the photosensitive resin composition of the present embodiment is preferably used for applications using a permanent film, since the reliability of the semiconductor device obtained from the composition is improved.
The permanent film is a resin film obtained by pre-baking, exposing, and developing a photosensitive resin composition, patterning it into a desired shape, and then curing it by heat treatment. The permanent film can be used as a protective film, an interlayer film, a dam material, etc. in semiconductor devices.
The resist is composed of a resin film obtained by applying a photosensitive resin composition to an object to be masked by the resist by a method such as spin coating, roll coating, flow coating, dip coating, spray coating, or doctor coating, and then removing the solvent from the photosensitive resin composition.

<Cured product>
The cured product of this embodiment is a cured product of the photosensitive resin composition of this embodiment.
The cured product of the present embodiment can be produced, for example, by applying the photosensitive resin composition of the present embodiment to a substrate, pre-baking to dry it and form a resin film, then exposing and developing it to pattern the resin film into a desired shape, and then heat-treating the resin film to cure it.
When producing a cured product, the pre-baking conditions can be, for example, a heat treatment at 90° C. to 130° C. for 30 seconds to 1 hour, or a heat treatment condition can be, for example, a heat treatment at 150° C. to 250° C. for 30 minutes to 10 hours.

The semiconductor device of this embodiment includes the cured product of this embodiment.
The photosensitive resin composition of this embodiment improves the reliability of the semiconductor device obtained, and therefore the semiconductor device of this embodiment has improved reliability.

From the viewpoint of further improving reliability, the semiconductor device of this embodiment preferably comprises an interlayer insulating film, a resin film containing the cured product of this embodiment on the interlayer insulating film, and rewiring embedded in the resin film.

FIG. 1 is a schematic cross-sectional view showing an example of the structure of the semiconductor device of this embodiment.
The semiconductor device 100 of this embodiment can be a semiconductor device including the above-mentioned resin film. Specifically, in the semiconductor device 100, one or more of the group consisting of the passivation film 32, the insulating layer 42, and the insulating layer 44 can be made of a resin film including the cured product of this embodiment. Here, the resin film is preferably the above-mentioned permanent film.

The semiconductor device 100 is, for example, a semiconductor chip. In this case, a semiconductor package is obtained by mounting the semiconductor device 100 on a wiring substrate via bumps 52.

The semiconductor device 100 includes a semiconductor substrate on which semiconductor elements such as transistors are provided, and a multilayer wiring layer (not shown) provided on the semiconductor substrate. The uppermost layer of the multilayer wiring layer includes an interlayer insulating film 30 and a top-layer wiring 34 provided on the interlayer insulating film 30. The top-layer wiring 34 is made of, for example, aluminum (Al). A passivation film 32 is provided on the interlayer insulating film 30 and the top-layer wiring 34. An opening is provided in part of the passivation film 32, exposing the top-layer wiring 34.

A redistribution layer 40 is provided on the passivation film 32. The redistribution layer 40 has an insulating layer 42 provided on the passivation film 32, redistribution 46 provided on the insulating layer 42, and an insulating layer 44 provided on the insulating layer 42 and the redistribution 46. An opening is formed in the insulating layer 42 to connect to the top-layer wiring 34. The redistribution 46 is formed on the insulating layer 42 and in the opening provided in the insulating layer 42, and is connected to the top-layer wiring 34. An opening is formed in the insulating layer 44 to connect to the redistribution 46.

Bumps 52 are formed in the openings in the insulating layer 44, for example, via an under-bump metallurgy (UBM) layer 50. The semiconductor device 100 is connected to a wiring board or the like, for example, via the bumps 52.

The above describes embodiments of the present invention, but these are merely examples of the present invention, and various configurations other than those described above can be adopted as long as they do not impair the effects of the present invention.

Embodiments of the present invention will be described in detail based on examples and comparative examples. Note that the present invention is not limited to the examples.

<Compounds used in polymer synthesis>
The following compounds were used in the synthesis of the polymer:

2,2-bis(3-amino-4-hydroxyphenyl)propane (hereinafter also referred to as BAPA), represented by the formula below.

4-[4-(1,3-dioxoisobenzofuran-5-ylcarbonyloxy)-2,3,5-trimethylphenyl]-2,3,6-trimethylphenyl-1,3-dioxoisobenzofuran-5-carboxylate (hereinafter also referred to as TMPBP-TME), represented by the formula below.

4,4-diamino-3,3-diethyl-5,5-dimethyldiphenylmethane (hereinafter also referred to as MED-J), represented by the formula below.

<Synthesis of Polymer 1>
First, 27.5 g (106.6 mmol) of BAPA, 146.5 g (236.8 mmol) of TMPBP-TME, and 30.1 g (106.6 mmol) of MED-J were placed in an appropriately sized reaction vessel equipped with a stirrer and a condenser, followed by the addition of 767.6 g of γ-butyrolactone (GBL).
After bubbling nitrogen for 10 minutes, the temperature was raised to 60°C while stirring, and the reaction was carried out for 1.5 hours. Thereafter, the reaction was further carried out for 3 hours at 180°C, whereby BAPA, TMPBP-TME, and MED-J were polymerized to prepare a polymerized solution.
Next, 60.2 g (426.3 mmol) of 2-isocyanatoethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.6 g (10.0 mmol) of 2-hydroxy-1,4-naphthoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.), and 83.3 g of GBL were added to the entire amount of the obtained polyimide solution (213.2 mmol in terms of hydroxyl groups). Thereafter, the temperature was raised to 120°C with stirring, and the mixture was allowed to react for 6 hours.
The resulting reaction solution was diluted with tetrahydrofuran to prepare a diluted solution, which was then added dropwise to methanol to precipitate a white solid. The resulting white solid was collected and vacuum-dried at 40° C. to obtain 218.1 g of Polymer 1.
When ¹ H-NMR measurement was carried out, a peak was confirmed in the aromatic region (6.8 ppm to 8.9 ppm) with an area ratio corresponding to the number of protons.
Furthermore, from the area ratio of the aromatic region (6.8 ppm to 8.9 ppm) to the alkene region (5.8 ppm to 6.5 ppm), the introduction rate of the crosslinking group was 93%.
The obtained polymer 1 contained a repeating unit represented by the following formula in part.

(In the above formula, x:y=50:50)

<Synthesis of Polymer 2>
Polymer 2 was obtained in the same manner as in the synthesis of Polymer 1, except that the amounts of BAPA, TMPBP-TME, and MED-J added were changed so that the ratio of x to y in the repeating units contained in the polymer was x:y=87:13.

<Synthesis of Polymer 3>
Polymer 3 was obtained in the same manner as in the synthesis of Polymer 1, except that the amounts of BAPA, TMPBP-TME, and MED-J added were changed so that the ratio of x to y in the repeating units contained in the polymer was x:y=93:7.

<Synthesis of Polymer 4>
Polymer 4 was obtained in the same manner as in the synthesis of Polymer 1, except that the amounts of BAPA and TMPBP-TME added were changed so that the ratio of x to y in the repeating units contained in the polymer was x:y=100:0, and MED-J was not added.

<Synthesis of Polymer 5>
Polymer 5 was obtained in the same manner as in the synthesis of Polymer 1, except that the amounts of BAPA, TMPBP-TME, and MED-J added were changed so that the ratio of x to y in the repeating units contained in the polymer was x:y=25:75.

<Synthesis of Polymer 6>
Polymer 6 was obtained in the same manner as in the synthesis of Polymer 1, except that the amounts of BAPA, TMPBP-TME, and MED-J added were changed so that the ratio of x to y in the repeating units contained in the polymer was x:y=23:77.

<Components used in preparing photosensitive resin composition>
The following components were used to prepare the photosensitive resin compositions of the Examples and Comparative Examples.

Acrylate compound 1: a polyfunctional acrylate compound represented by the following formula (Viscoat #802, manufactured by Osaka Organic Chemical Industry Ltd.)

Acrylate compound 2: a polyfunctional acrylate compound represented by the following formula (A-DPHSVF, manufactured by Shin-Nakamura Chemical Co., Ltd.)
Acrylate compound 3: a polyfunctional acrylate compound represented by the following formula (A-9300S-NT, manufactured by Shin-Nakamura Chemical Co., Ltd.)

Acrylate compound 4: a bifunctional acrylate compound represented by the following formula (Viscoat #230, manufactured by Osaka Organic Chemical Industry Ltd.)

Epoxy compound 1: 4-hydroxybutyl acrylate glycidyl ether represented by the following formula (4HBAGE, manufactured by Shinryo Corporation)

Epoxy compound 2: a trifunctional epoxy compound represented by the following formula (VG3101L, manufactured by Printec Co., Ltd.)

Polymerization initiator 1: a compound represented by the following formula (Irgacure OXE01, manufactured by BASF)

Polymerization initiator 2: Dicumyl peroxide represented by the following formula (Perkadox BC, manufactured by Nouryon)

Antioxidant 1: Compound represented by the following formula (KEMINOX 179, manufactured by Chemipro Chemicals Co., Ltd.)

Adhesion aid 1: 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) represented by the following formula

Adhesion aid 2: 3-trimethoxysilylpropylsuccinic anhydride represented by the following formula (X-12-967C, manufactured by Shin-Etsu Chemical Co., Ltd.)

Adhesion aid 3: 3-methacryloxypropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) represented by the following formula

Curing catalyst 1: a tetra-substituted phosphonium compound represented by the following formula (tetraphenylphosphonium 4,4'-sulfonyldiphenolate, manufactured by Sumitomo Bakelite Co., Ltd.)

Surfactant 1: Silicone surfactant (BYK, BYK-349)

Solvent 1: Ethyl lactate (EL)
Solvent 2: γ-butyl lactone (GBL)

(Examples 1 to 9, Comparative Example 1)
<Preparation of Photosensitive Resin Composition>
The polymer and each component were mixed in a solvent in the blending ratios shown in Table 1 to prepare the photosensitive resin compositions of Examples 1 to 9 and Comparative Example 1.

<Patterning ability>
The photosensitive resin composition of each example and comparative example was applied to an 8-inch silicon wafer using a spin coater. After application, the wafer was prebaked on a hot plate at 110°C for 3 minutes in the atmosphere to obtain a coating film with a thickness of approximately 5 μm. This coating film was irradiated with i-rays through a mask on which via patterns of multiple widths (4 μm and 5 μm) were drawn. An i-ray stepper (Nikon Corporation, NSR-4425i) was used for the irradiation. After exposure, the wafer was spray-developed for 60 seconds using cyclopentanone as the developer, and then spray-developed for 10 seconds using PGMEA as the developer to dissolve and remove the unexposed areas, thereby obtaining a via pattern. The cross section of the obtained via pattern was observed using a benchtop SEM. The width at the midpoint between the bottom and opening of the via pattern was defined as the via width, and the patterning ability was evaluated according to the following criteria. The results are shown in Table 1.
A: 4 μm and 5 μm via patterns are opened. B: 5 μm via pattern is opened, 4 μm via pattern is not opened. C: 4 μm and 5 μm via patterns are not opened.

<Reliability>
Copper wiring with a line width of 5 μm and a thickness of 2 μm was formed on an 8-inch silicon wafer. Next, the photosensitive resin composition of each example and comparative example was applied to the silicon wafer surface on which the copper wiring was formed so that the film thickness after drying was 10 μm, and after pre-baking at 110 ° C for 3 minutes, exposure to 600 mJ / cm ² was performed with a high-pressure mercury lamp, and then post-baking was performed for 3 hours at 230 ° C in a nitrogen atmosphere to cure the photosensitive resin composition, and a test piece was obtained. The obtained test piece was then heat-treated under atmospheric conditions at 230 ° C for 30 minutes. Next, the test piece was cut perpendicular to the silicon wafer surface, and the cross section was observed with a scanning electron microscope (Hitachi High-Technologies Corporation, S-4700), and reliability was evaluated according to the following criteria. The results are shown in Table 1.
A: No cracks or migration at the interface between the copper wiring and the cured product. B: Almost no cracks or migration at the interface between the copper wiring and the cured product. C: Cracks or migration at the interface between the copper wiring and the cured product.

<Preparation of cured product>
The photosensitive resin composition of each Example and Comparative Example was spin-coated onto the surface of a silicon wafer so that the film thickness after drying would be 10 μm, and the coating was pre-baked at 110° C. for 3 minutes, then exposed to 600 mJ/ ^cm2 using a high-pressure mercury lamp. Thereafter, the coating was post-baked at 230° C. for 3 hours in a nitrogen atmosphere to produce a cured product measuring 100 mm × 100 mm × 10 μm in thickness.

<Oxygen permeability coefficient>
The oxygen permeability coefficient of the cured products of each example and comparative example was measured at 23°C and 60% RH by the differential pressure method in accordance with JIS K 7126-2: 2006. The results are shown in Table 1.

<Glass transition temperature (Tg)>
The glass transition temperature (Tg) of the cured products of each Example and Comparative Example was measured using a thermomechanical analyzer (TMA) (TMA-7100, manufactured by Hitachi High-Technologies Corporation) under the following conditions: starting temperature 30°C, measurement temperature range 30 to 400°C, and heating rate 5°C/min. The results are shown in Table 1.

<Elongation at break, tensile modulus>
For the cured products of each Example and Comparative Example, the breaking elongation and tensile modulus were measured at 23°C and a stretching rate of 5 mm/min using a tensile tester (AMD, STB-1225S) in accordance with JIS K 7161: 2014. The results are shown in Table 1.

<Storage modulus>
The storage modulus of each of the cured products of the examples and comparative examples was measured at 30°C by dynamic mechanical analysis (DMA) using a DMA device (DMA-Q800, manufactured by TA Instruments). The results are shown in Table 1.

This application claims priority based on Japanese Patent Application No. 2023-219175, filed December 26, 2023, the entire disclosure of which is incorporated herein by reference.

100 Semiconductor device 30 Interlayer insulating film 32 Passivation film 34 Top layer wiring 40 Rewiring layer 42 Insulating layer 44 Insulating layer 46 Rewiring 50 UBM layer 52 Bump

Claims (16)

a polyimide (A) having a double bond in a side chain;
a crosslinking agent (B) containing a (meth)acrylate compound;
a polymerization initiator (C),
The oxygen permeability coefficient measured by the following method 1 is 30 ^cm3 ·mm/( ^m2 ·day·atm) or less,
further comprising an antioxidant;
The polyimide (A) contains a structural unit represented by the following general formula (1):
In the general formula (1), Y is selected from the group consisting of a group represented by the following general formula (1a), a group represented by the following general formula (1b), and a group represented by the following general formula (1c),
The antioxidant includes an antioxidant having an isocyanuric acid skeleton,
a content of the antioxidant in the photosensitive resin composition is 0.1 parts by mass or more and 10.0 parts by mass or less, when the total amount of solids in the photosensitive resin composition is 100 parts by mass;
the content of the crosslinking agent (B) is 1 part by mass or more and 80 parts by mass or less when the content of the polyimide (A) is 100 parts by mass,
the content of fluorine atoms is 10 parts by mass or less when the total amount of solids in the photosensitive resin composition is 100 parts by mass,
a photosensitive resin composition in which the content of the fluorine atom-containing polymer is 30 parts by mass or less when the total amount of solids in the photosensitive resin composition is 100 parts by mass ;
(Method 1)
The photosensitive resin composition is spin-coated onto a silicon wafer surface to a dry film thickness of 10 μm, pre-baked at 110°C for 3 minutes, exposed to 600 mJ/ ^cm2 using a high-pressure mercury lamp, and then post-baked for 3 hours at 230°C in a nitrogen atmosphere to obtain a cured product measuring 100 mm x 100 mm x 10 μm in thickness. The oxygen permeability coefficient of the cured product is measured by a differential pressure method in accordance with JIS K 7126-2:2006 at 23°C and 60% RH.
(In the general formula (1a), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and a plurality of R ^1s and a plurality of R ^2s may be the same or different, R ³ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and a plurality of R ^3s may be the same or different, * represents a bond,
In the general formula (1b), R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and a plurality of R ^4s and a plurality of R ^5s may be the same or different, * represents a bond,
In the general formula (1c), Z represents an alkylene group having 1 to 5 carbon atoms or a divalent aromatic group, and * represents a bond. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is spin-coated onto a silicon wafer surface to a film thickness of 10 μm after drying, pre-baked at 110°C for 3 minutes, exposed to 600 mJ/ ^cm2 using a high-pressure mercury lamp, and then post-baked at 230°C for 3 hours in a nitrogen atmosphere. The cured product obtained has a glass transition temperature (Tg) of 240°C or higher as measured using a thermomechanical analyzer (TMA) under conditions of a starting temperature of 30°C, a measurement temperature range of 30 to 400°C, and a heating rate of 5°C/min. 3. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is spin-coated onto a surface of a silicon wafer to a film thickness of 10 μm after drying, pre-baked at 110° C. for 3 minutes, exposed to 600 mJ/ ^cm2 using a high-pressure mercury lamp, and then post-baked at 230° C. for 3 hours in a nitrogen atmosphere. The cured product has a breaking elongation of 10% or more as measured at 23° C. and a stretching rate of 5 mm/min using a tensile tester in accordance with JIS K 7161:2014. 3. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is spin-coated onto a silicon wafer surface to a film thickness of 10 μm after drying, pre-baked at 110° C. for 3 minutes, exposed to 600 mJ/cm ² using a high-pressure mercury lamp, and then post-baked at 230° C. for 3 hours in a nitrogen atmosphere. The cured product has a tensile modulus of elasticity of 1.0 GPa or more and 5.0 GPa or less, as measured at 23° C. and a stretching rate of 5 mm/min using a tensile tester in accordance with JIS K 7161:2014. 3. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is spin-coated onto a silicon wafer surface to a film thickness of 10 μm after drying, pre-baked at 110° C. for 3 minutes, exposed to 600 mJ/ ^cm2 with a high-pressure mercury lamp, and then post-baked at 230° C. for 3 hours in a nitrogen atmosphere to obtain a cured product, which has a storage modulus at 30° C. measured by dynamic mechanical analysis (DMA) of 1.0 GPa or more and 6.0 GPa or less. The photosensitive resin composition according to claim 1 or 2, wherein the content of the polymerization initiator (C) is 1 part by mass or more and 30 parts by mass or less when the content of the polyimide (A) is 100 parts by mass. The photosensitive resin composition according to claim 1 or 2, wherein the total content of the polyimide (A), the crosslinking agent (B), and the polymerization initiator (C) is 80 parts by mass or more when the total amount of solids in the photosensitive resin composition is 100 parts by mass. When the number of moles of imide groups contained in the polyimide (A) is IM and the number of moles of amide groups contained in the polyimide (A) is AM,
3. The photosensitive resin composition according to claim 1, wherein the imidization rate, expressed as {IM/(IM+AM)}×100(%), is 90% or more. The photosensitive resin composition according to claim 1 or 2, wherein the polymerization initiator (C) includes an oxime ester-type polymerization initiator. The photosensitive resin composition according to claim 1 or 2, further comprising an organic solvent. The organic solvent is γ-butyrolactone (GBL), γ-valerolactone (GVL), 2,6-lutidine, pyruvic acid N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropionamide, dimethyl sulfoxide (DMSO), diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether (PGME), propylene glycol The photosensitive resin composition according to claim 10, comprising one or more selected from the group consisting of 1,3-butylene glycol monomethyl ether acetate (PGMEA), methyl lactate, ethyl lactate (EL), butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and 3-methyl- 2 -oxazolidone. The photosensitive resin composition according to claim 1 or 2, wherein the content of the alkali-soluble resin is 30 parts by mass or less, based on 100 parts by mass of the total amount of solids in the photosensitive resin composition. The photosensitive resin composition according to claim 1 or 2, which can be used in semiconductor devices. A cured product of the photosensitive resin composition according to claim 1 or 2. A semiconductor device comprising the cured product according to claim 14 . an interlayer insulating film;
a resin film containing the cured product on the interlayer insulating film;
a rewiring buried in the resin film;
The semiconductor device according to claim 15 , comprising: