Photosensitive resin composition, cured product and semiconductor device

Abstract

To provide a photosensitive resin composition which can improve reliability of an obtained semiconductor device.SOLUTION: A photosensitive resin composition contains polyimide (A) having a double bond at its side chain, a crosslinking agent (B) containing a (meth)acrylate compound having an isocyanuric acid skeleton, and a polymerization initiator (C).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, a cured product, and a semiconductor device.

Background Art

[0002] Polyimide is used, for example, as a protective material, an insulating material, or a thin film for electronic materials such as color filters in liquid crystal display elements and semiconductors.

[0003] Patent Document 1 aims to provide a resin composition that is easily soluble in an alkaline developer before exposure, becomes insoluble in the alkaline developer upon exposure, and can obtain a cured pattern with a high aspect ratio and a small shrinkage of the film due to curing. A resin composition containing (A) a polyimide resin is disclosed, wherein the (A) polyimide resin has an organic group having a specific structure.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] The present invention provides a photosensitive resin composition and a cured product capable of improving the reliability of a semiconductor device obtained, and a semiconductor device with improved reliability.

Means for Solving the Problems

[0006] The inventors of the present invention have conducted intensive studies to solve the above problems. As a result, they 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 having an isocyanuric acid skeleton, and a polymerization initiator (C) can improve the reliability of a semiconductor device, and have completed the present invention.

[0007] According to the present invention, there are provided a photosensitive resin composition, a cured product, and a semiconductor device, which are shown below.

[0008] [1] A polyimide (A) having a double bond in the side chain, A crosslinking agent (B) containing a (meth)acrylate compound having an isocyanuric acid skeleton, A polymerization initiator (C), A photosensitive resin composition containing the same. [2] The photosensitive resin composition according to [1], wherein the crosslinking agent (B) contains a (meth)acrylate compound represented by the following general formula (1). [Chemical formula] (In the general formula (1), R 11 , R 12 And R 13 Each independently represents a hydrogen atom, a hydroxy group, or an organic group containing at least one functional group selected from the group consisting of a (meth)acryloyloxy group, a (meth)acryloyl group, and a hydroxy group, and an alkylene group having 1 to 10 carbon atoms or an oxyalkylene group having 1 to 10 carbon atoms, and at least one of R 11 , R 12 And R 13 Has a (meth)acryloyloxy group or a (meth)acryloyl group) [3] In the general formula (1), at least one of R 11 , R 12 And R 13 Is a group represented by the following general formula (2), and the photosensitive resin composition according to [2]. [Chemical formula] (In the general formula (2), V represents a single bond, an alkylene group having 1 to 10 carbon atoms, or an oxyalkylene group having 1 to 10 carbon atoms, and R 20represents a hydrogen atom or a methyl group, W represents a single bond or a functional group selected from the group consisting of a group represented by the general formula (2a), a group represented by the general formula (2b), and a group represented by the general formula (2c), * represents a bond, In the general formula (2a), a represents an integer of 1 to 10, and * represents a bond, In the general formula (2b), b represents an integer of 1 to 10, and * represents a bond, In the general formula (2c), c represents an integer of 1 to 10, and * represents a bond) [4] The photosensitive resin composition according to any one of [1] to [3], wherein the polyimide (A) contains a structural unit represented by the following general formula (3). [Chemical formula] (In the general formula (3), Y represents a divalent organic group) [5] The photosensitive resin composition according to [4], wherein Y in the general formula (3) is selected from the group consisting of a group represented by the following general formula (3a), a group represented by the following general formula (3b), and a group represented by the following general formula (3c). [Chemical formula] (In the general formula (3a), 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 1 's, and a plurality of R 2 's may be the same or different from each other, 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 3 's may be the same or different from each other, and * represents a bond, In the general formula (3b), 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 4A plurality of Rs 5 The Rs may be the same or different from each other, and * represents a bond, In the general formula (3c), Z represents an alkylene group having 1 to 5 carbon atoms or a divalent aromatic group, and * represents a bond.) [6] The photosensitive resin composition according to any one of [1] to [5], wherein the polyimide (A) contains a structural unit represented by the following general formula (4). [Chemical formula] (In the general formula (4), 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. A plurality of Qs may be the same or different from each other. R represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. A plurality of Rs may be the same or different from each other. X represents a single bond, -SO2-, -C(=O)-, a linear or branched alkylene group having 1 to 5 carbon atoms, or a linear or branched fluoroalkylene group having 1 to 5 carbon atoms. A plurality of Xs may be the same or different from each other.) [7] The photosensitive resin composition according to any one of [1] to [6], wherein the polyimide (A) contains a structural unit (a) represented by the following general formula (5). [Chemical formula] (In the general formula (5), m1 and m2 each independently represent an integer from 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. A plurality of 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. A plurality of Rs may be the same or different. X represents a single bond, -SO2-, -C(=O)-, a linear or branched alkylene group having 1 to 5 carbon atoms, or a linear or branched fluoroalkylene group having 1 to 5 carbon atoms. A plurality of Xs may be the same or different. Y represents a divalent organic group) [8] The structural unit (a) is represented by the general formula (5), and at least one of m1 and m2 is 1 or more, and the structural unit (a p ) and the structural unit (a) represented by the general formula (5) in which both m1 and m2 are 0 q ) and contains In the structural unit (a), when the total content of the structural unit (a p ) and the structural unit (a q ) is 100 mol%, the content of the structural unit (a p ) is 15 mol% or more. The photosensitive resin composition according to [7]. [9] When the content of the polyimide (A) 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. The photosensitive resin composition according to any one of [1] to [8].

[10] When the content of the polyimide (A) is 100 parts by mass, the content of the polymerization initiator (C) is 1 part by mass or more and 30 parts by mass or less. The photosensitive resin composition according to any one of [1] to [9].

[11] When the total amount of the solid content in the photosensitive resin composition is 100 parts by mass, the total content of the polyimide (A), the crosslinking agent (B), and the polymerization initiator (C) is 80 parts by mass or more. The photosensitive resin composition according to any one of [1] to

[10] .

[12] 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

[11] , wherein the imidization rate represented by {IM / (IM + AM)}×100 (%) is 90% or more.

[13] The photosensitive resin composition according to any one of [1] to

[12] , wherein the polymerization initiator (C) contains an oxime ester type polymerization initiator.

[14] The photosensitive resin composition according to any one of [1] to

[13] , further comprising an organic solvent.

[15] The photosensitive resin composition according to

[14] , wherein the organic solvent contains one or more selected from the group consisting of γ-butyrolactone (GBL), γ-valerolactone (GVL), 2,6-lutidine, N,N-dimethylacetamide pyruvate, 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 (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.

[16] The photosensitive resin composition according to any one of [1] to

[15] , wherein when the total amount of the solid content in the photosensitive resin composition is 100 parts by mass, the fluorine content is 10 parts by mass or less.

[17] The photosensitive resin composition according to any one of [1] to

[16] , wherein when the total amount of the solid content in the photosensitive resin composition is 100 parts by mass, the content of the polymer containing fluorine atoms is 30 parts by mass or less.

[18] When the total amount of the solid content in the photosensitive resin composition is 100 parts by mass, the photosensitive resin composition according to any one of [1] to

[17] , wherein the content of the alkali-soluble resin is 30 parts by mass or less.

[19] The oxygen transmission coefficient by the following Method 1 is 40 cm 3 ·mm / (m 2 ·day·atm) or less, and the photosensitive resin composition according to any one of [1] to

[18] . (Method 1) The photosensitive resin composition is cured at 230 °C for 3 hours to obtain a cured product having a thickness of 100 mm × 100 mm × 10 μm. For the cured product, the oxygen transmission coefficient is measured by the differential pressure method in accordance with JIS K 7126-2:2006 under the conditions of 23 °C and 60% RH.

[20] For the cured product obtained by curing the photosensitive resin composition at 230 °C for 3 hours, using a thermomechanical analysis (TMA) apparatus, the glass transition temperature (Tg) measured under the conditions of an initial temperature of 30 °C, a measurement temperature range of 30 to 400 °C, and a heating rate of 5 °C / min is 240 °C or higher, and the photosensitive resin composition according to any one of [1] to

[19] .

[21] For the cured product obtained by curing the photosensitive resin composition at 230 °C for 3 hours, in accordance with JIS K 7161:2014, using a tensile tester, the elongation at break measured under the conditions of 23 °C and an elongation rate of 5 mm / min is 6% or higher, and the photosensitive resin composition according to any one of [1] to

[20] .

[22] For the cured product obtained by curing the photosensitive resin composition at 230 °C for 3 hours, in accordance with JIS K 7161:2014, using a tensile tester, the tensile elastic modulus measured under the conditions of 23 °C and an elongation rate of 5 mm / min is 1.0 GPa or more and 4.0 GPa or less, and the photosensitive resin composition according to any one of [1] to

[21] .

[23] For the cured product obtained by curing the photosensitive resin composition at 230°C for 3 hours, the storage modulus at 220°C measured by dynamic viscoelasticity measurement (DMA) is 1.0 GPa or more and 5.0 GPa or less. The photosensitive resin composition according to any one of [1] to

[22] .

[24] The photosensitive resin composition according to any one of [1] to

[23] , which can be used for a semiconductor device.

[25] The cured product of the photosensitive resin composition according to any one of [1] to

[24] .

[26] A semiconductor device including the cured product described in

[25] .

[27] An interlayer insulating film, A resin film including the cured product described in

[25] on the interlayer insulating film, A rewiring embedded in the resin film, The semiconductor device according to

[26] , comprising: [Advantages of the Invention]

[0009] According to the present invention, it is possible to provide a photosensitive resin composition and a cured product capable of improving the reliability of a semiconductor device obtained, and a semiconductor device with improved reliability. [Brief Description of the Drawings]

[0010]

Figure 1

[0011] Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In the drawings, similar components are denoted by similar reference numerals, and the description will be omitted as appropriate. The drawings are for illustrative purposes only. The shapes, dimensional ratios, etc. of the components in the drawings do not necessarily correspond to actual articles.

[0012] In this embodiment, "A to B" indicating a numerical range represents A or more and B or less unless otherwise specified.

[0013] The photosensitive resin composition of this embodiment contains a polyimide (A) having a double bond in the side chain, a crosslinking agent (B) containing a (meth)acrylate compound having an isocyanuric acid skeleton, and a polymerization initiator (C). In this embodiment, by combining and using a polyimide (A) having a double bond in the side chain and a crosslinking agent (B) containing a (meth)acrylate compound having an isocyanuric acid skeleton, a photosensitive resin composition capable of improving the reliability of the obtained semiconductor device can be obtained. Hereinafter, each component will be described.

[0014] <Crosslinking agent (B)> The crosslinking agent (B) of this embodiment contains a (meth)acrylate compound having an isocyanuric acid skeleton.

[0015] From the viewpoint of further improving the patterning property, copper adhesion, mechanical strength, and the performance balance of the reliability of the obtained semiconductor device, the crosslinking agent (B) of this embodiment preferably contains a (meth)acrylate compound represented by the following general formula (1).

[0016]

Chemical formula

[0017] In general formula (1), R 11 , R 12 and R 13 each independently represents a hydrogen atom, a hydroxy group, or an organic group containing at least one functional group selected from the group consisting of a (meth)acryloyloxy group, a (meth)acryloyl group, and a hydroxy group and an alkylene group having 1 to 10 carbon atoms or an oxyalkylene group having 1 to 10 carbon atoms. In general formula (1), R 11 , R 12 and R 13At least one of them has a (meth)acryloyloxy group or a (meth)acryloyl group.

[0018] In general formula (1), R 11 , R 12 and R 13 From the viewpoint of further improving the performance balance of patterning property, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, preferably two of them have a (meth)acryloyloxy group or a (meth)acryloyl group, and more preferably all three have a (meth)acryloyloxy group or a (meth)acryloyl group.

[0019] In general formula (1), R 11 , R 12 and R 13 When not containing a (meth)acryloyloxy group, they are preferably a hydroxy group or an alkylene group having 1 to 10 carbon atoms containing a hydroxy group, more preferably an alkylene group having 1 to 6 carbon atoms containing a hydroxy group, and still more preferably an alkylene group having 1 to 3 carbon atoms containing a hydroxy group.

[0020] In general formula (1), R 11 , R 12 and R 13 At least one of them is preferably a group represented by the following general formula (2) from the viewpoint of further improving the performance balance of patterning property, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device.

[0021]

Chemical formula

[0022] In general formula (2), V represents a single bond, an alkylene group having 1 to 10 carbon atoms, or an oxyalkylene group having 1 to 10 carbon atoms, R 20 represents a hydrogen atom or a methyl group, W represents a single bond or a group selected from the group consisting of a group represented by general formula (2a), the group represented by the said general formula (2b), and the group represented by the said general formula (2c), and * represents a bond. In general formula (2a), a represents an integer of 1 to 10, and * represents a bond. In general formula (2b), b represents an integer of 1 to 10, and * represents a bond. In general formula (2c), c represents an integer of 1 to 10, and * represents a bond.

[0023] In general formula (1), R 11 , R 12 and R 13 are, from the viewpoint of further improving the performance balance of patterning property, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, more preferably two are groups represented by general formula (2), and even more preferably all three are groups represented by general formula (2).

[0024] In general formula (2), V is preferably an alkylene group having 1 to 4 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms, and even more preferably an alkylene group having 1 to 2 carbon atoms. In general formula (2), R 20 is preferably a hydrogen atom. In general formula (2), W is preferably a single bond.

[0025] From these, as the (meth)acrylate compound having an isocyanuric acid skeleton of the present embodiment, for example, A-9300S, A-9200YN (manufactured by Shin-Nakamura Chemical Co., Ltd.), Aronix M-215, Aronix M-313, Aronix M-315 (manufactured by Toagosei Co., Ltd.), Funcrile FA-731A (manufactured by Resonac Co., Ltd.), etc. are preferably used.

[0026] The (meth)acrylate compound having an isocyanuric acid skeleton of the present embodiment may be a urethane-type isocyanuric acid skeleton (meth)acrylate. The urethane-type isocyanuric acid skeleton (meth)acrylate is a compound having an isocyanuric acid skeleton, a urethane bond, and a (meth)acryloyl group, and examples thereof include the isocyanuric ring-containing urethane (meth)acrylate compound A described in International Publication No. 2019 / 123942.

[0027] The crosslinking agent (B) of this embodiment may contain a polyfunctional (meth)acrylate compound. The number of acryloyloxy groups contained in the polyfunctional (meth)acrylate compound of this embodiment in the molecule is preferably 2 or more and 20 or less, more preferably 3 or more and 15 or less, still more preferably 4 or more and 10 or less, still more preferably 4 or more and 8 or less, and still more preferably 5 or more and 6 or less.

[0028] The polyfunctional (meth)acrylate compound of this embodiment includes, for example, 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; tetrafunctional (meth)acrylates such as pentaerythritol tetra(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate; hexafunctional (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, and includes one or more selected from the group consisting of them.

[0029] The crosslinking agent (B) of this embodiment may contain an epoxy compound. The number of glycidyl groups contained in the epoxy compound of this embodiment in the molecule is preferably 1 or more and 6 or less, more preferably 1 or more and 3 or less, and still more preferably 1. The number of (meth)acryloyloxy groups contained in the epoxy compound of this embodiment in the molecule is preferably 0 or more and 6 or less, more preferably 0 or more and 2 or less, and still more preferably 1.

[0030] From the perspective of further improving the performance balance of patterning property, copper adhesion, mechanical strength, and the reliability of the resulting semiconductor device, when the total amount of the solid content in the photosensitive resin composition is 100 parts by mass, the content of the crosslinking agent (B) in the photosensitive resin composition of the present embodiment is preferably 1 part by mass or more, more preferably 5 parts by mass or more, still more preferably 8 parts by mass or more, still more preferably 10 parts by mass or more, still more preferably 13 parts by mass or more, still more preferably 16 parts by mass or more, and preferably 50 parts by mass or less, more preferably 45 parts by mass or less, still more preferably 40 parts by mass or less, still more preferably 35 parts by mass or less, still more preferably 30 parts by mass or less, still more preferably 28 parts by mass or less. Also, from the perspective of further improving the performance balance of patterning property, copper adhesion, mechanical strength, and the reliability of the resulting semiconductor device, when the total amount of the solid content in the photosensitive resin composition is 100 parts by mass, 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, still more preferably 8 parts by mass or more and 35 parts by mass or less, still more preferably 10 parts by mass or more and 30 parts by mass or less, still more preferably 13 parts by mass or more and 28 parts by mass or less.

[0031] <Polyimide (A)> From the perspective of further improving the performance balance of patterning property, copper adhesion, mechanical strength, and the reliability of the resulting semiconductor device, the polyimide (A) of the present embodiment preferably contains a structural unit represented by the following general formula (3).

[0032] [Chemical formula]

[0033] In the general formula (3), Y represents a divalent organic group, and from the perspective of further improving the performance balance of patterning property, copper adhesion, mechanical strength, and the reliability of the resulting semiconductor device, it is preferably a divalent group containing an alkylene group or a divalent group containing at least one aromatic ring. As the alkylene group, an alkylene group having 1 to 5 carbon atoms is preferable, and an alkylene group having 1 to 3 carbon atoms is more preferable. As the aromatic ring, a divalent benzene ring, a divalent naphthalene ring, a divalent anthracene ring or a divalent biphenyl group is preferable, and a divalent benzene ring or a divalent biphenyl group is more preferable.

[0034] In general formula (3), from the viewpoint of further improving the patterning property, copper adhesion, mechanical strength and the performance balance of the reliability of the resulting semiconductor device, Y is preferably a group represented by the following general formula (3a), a group represented by the following general formula (3b), and a group represented by the following general formula (3c). It is selected from the group consisting of, and more preferably a group represented by the following general formula (3b).

[0035]

Chemical formula

[0036] In general formula (3a), 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. A plurality of R 1 's, a plurality of R 2 's may be the same or different from each other. 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. A plurality of R 3 's may be the same or different from each other, and * represents a bond. In general formula (3b), 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. A plurality of R 4 's, a plurality of R 5 's may be the same or different from each other, and * represents a bond. In general formula (3c), Z represents an alkylene group having 1 to 5 carbon atoms or a divalent aromatic group, and * represents a bond.

[0037] In general formula (3a), R1 and R 2 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, and still more preferably a hydrogen atom or a methyl group. In the general formula (3a), R 1 and R 2 each independently is preferably such that 0 to 3 are hydrogen atoms, more preferably 0 to 2 are hydrogen atoms, and still more preferably 1 is a hydrogen atom. In the general formula (3a), R 3 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, still more preferably a hydrogen atom or a methyl group, and still more preferably a hydrogen atom.

[0038] In the general formula (3b), R 4 and R 5 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 still more preferably a hydrogen atom or a methyl group. In the general formula (3b), R 4 and R 5 each independently is preferably such that 0 to 3 are hydrogen atoms, more preferably 0 to 2 are hydrogen atoms, and still more preferably 1 is a hydrogen atom.

[0039] From the viewpoint of further improving the performance balance of the patterning property, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, the polyimide (A) of the present embodiment preferably contains a structural unit represented by the following general formula (4).

[0040]

Chemical formula

[0041] In general formula (4), m1 and m2 each independently represent an integer from 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. A plurality of 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. A plurality of Rs may be the same or different. X represents a single bond, -SO2-, -C(=O)-, a linear or branched alkylene group having 1 to 5 carbon atoms, or a linear or branched fluoroalkylene group having 1 to 5 carbon atoms. A plurality of Xs may be the same or different.

[0042] In general formula (4), from the viewpoint of further improving the performance balance of patterning property, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, m1 and m2 are preferably 0 to 2, and more preferably 0 or 1. In general formula (4), 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 containing a urethane bond, and still more preferably a divalent organic group having 2 to 4 carbon atoms containing a urethane bond. In general formula (4), 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 still more preferably a hydrogen atom. In general formula (4), X is preferably a linear or branched alkylene group having 1 to 5 carbon atoms, and more preferably a linear or branched alkylene group having 1 to 3 carbon atoms.

[0043] From these facts, the polyimide (A) of the present embodiment preferably contains a structural unit (a) represented by the following general formula (5) from the viewpoint of further improving the performance balance of patterning property, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device.

[0044] [Chemical]

[0045] In general formula (5), m1 and m2 each independently represent an integer from 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. A plurality of 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. A plurality of Rs may be the same or different. X represents a single bond, -SO2-, -C(=O)-, a linear or branched alkylene group having 1 to 5 carbon atoms, or a linear or branched fluoroalkylene group having 1 to 5 carbon atoms. A plurality of Xs may be the same or different. Y represents a divalent organic group.

[0046] From the viewpoint of further improving the performance balance of patterning property, copper adhesion, mechanical strength, and the reliability of the resulting semiconductor device, the structural unit (a) of the present embodiment is preferably represented by general formula (5), and at least one of m1 and m2 is 1 or more. p ) and the structural unit (a) represented by general formula (5) in which both m1 and m2 are 0. q ) is included.

[0047] From the viewpoint of further improving the performance balance of patterning property, copper adhesion, mechanical strength, and the reliability of the resulting semiconductor device, the content of the structural unit (a) in the polyimide (A) of the present embodiment is such that the structural unit (a) p ) and the structural unit (a) p ) and the structural unit (a) qWhen the total content is 100 mol%, it is preferably 15 mol% or more, more preferably 20 mol% or more, still more preferably 25 mol% or more, still more preferably 30 mol% or more, still more preferably 35 mol% or more, still more preferably 40 mol% or more, still more preferably 45 mol% or more, still more preferably 50 mol% or more, still more preferably 60 mol% or more, still more preferably 70 mol% or more, still more preferably 80 mol% or more, still more preferably 90 mol% or more, and preferably 100 mol% or less. Further, the content of the structural unit (a p ) in the polyimide (A) of the present embodiment is from the viewpoint of further improving the patterning property, copper adhesion, mechanical strength, and the performance balance of the reliability of the resulting semiconductor device. When the total content of the structural unit (a p ) and the structural unit (a q ) is 100 mol%, it is preferably 15 mol% or more and 100 mol% or less, more preferably 20 mol% or more and 100 mol% or less, still more preferably 25 mol% or more and 100 mol% or less, still more preferably 30 mol% or more and 100 mol% or less, still more preferably 35 mol% or more and 100 mol% or less, still more preferably 40 mol% or more and 100 mol% or less, still more preferably 45 mol% or more and 100 mol% or less, still more preferably 50 mol% or more and 100 mol% or less, still more preferably 60 mol% or more and 100 mol% or less, still more preferably 70 mol% or more and 100 mol% or less, still more preferably 80 mol% or more and 100 mol% or less, still more preferably 90 mol% or more and 100 mol% or less.

[0048] When the number of moles of imide groups contained in the polyimide (A) of the present embodiment is IM and the number of moles of amide groups contained in the polyimide (A) of the present embodiment is AM, the imidization rate represented by {IM / (IM + AM)} × 100 (%) is preferably 90% or more, more preferably 95% or more, still more preferably 98% or more, and preferably 100% or less from the viewpoint of further improving the patterning property, copper adhesion, mechanical strength, and the performance balance of the reliability of the resulting semiconductor device. In addition, from the perspective of further improving the performance balance of patterning properties, copper adhesion, mechanical strength, and 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 still more preferably 98% or more and 100% or less.

[0049] From the perspective of further improving the performance balance of patterning properties, copper adhesion, mechanical strength, and the reliability of the resulting semiconductor device, when the total amount of the solid content in the photosensitive resin composition is 100 parts by mass, the content of the polyimide (A) in the photosensitive resin composition of the present embodiment is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, still more preferably 50 parts by mass or more, still more preferably 55 parts by mass or more, and still 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, still more preferably 85 parts by mass or less, still more preferably 80 parts by mass or less, and still more preferably 75 parts by mass or less. In addition, from the perspective of further improving the performance balance of patterning properties, copper adhesion, mechanical strength, and the reliability of the resulting semiconductor device, when the total amount of the solid content in the photosensitive resin composition is 100 parts by mass, the content of the polyimide (A) in the photosensitive resin composition of the present 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, still more preferably 50 parts by mass or more and 85 parts by mass or less, still 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.

[0050] <Polymerization initiator (C)> As the polymerization initiator (C) of the present embodiment, conventionally known polymerization initiators can be used within the range capable of exerting the effects of the present invention, and examples thereof include photo radical generators and thermal radical generators. From the perspective of further improving the performance balance of patterning properties, copper adhesion, mechanical strength, and the reliability of the resulting semiconductor device, the polymerization initiator (C) of the present embodiment preferably contains a photo radical generator, and more preferably contains both a photo radical generator and a thermal radical generator.

[0051] Examples of the photo radical generator of the present embodiment include alkylphenone type polymerization initiators, oxime ester type polymerization initiators, acylphosphine oxide type polymerization initiators, etc. Specifically, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-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]-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-carbazole-3-yl]-,1-(0-acetoxyoxime), 2-(dimethylamino)-1-(4-(4-morpholino)phenyl)-2-(phenylmethyl)-1-butanone, Irgacure OXE01 (manufactured by BASF Japan), Irgacure OXE02 (manufactured by BASF Japan), Irgacure OXE03 (manufactured by BASF Japan), Irgacure OXE04 (manufactured by BASF Japan), etc. can be mentioned. The polymerization initiator (C) of the present embodiment can contain one or more of these. From the viewpoint of further improving the performance balance of patterning property, copper adhesion, mechanical strength and the reliability of the obtained semiconductor device, the polymerization initiator (C) of the present embodiment preferably contains an oxime ester type polymerization initiator, and more preferably contains Irgacure OXE01.

[0052] 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-di-butylperoxycyclohexyl)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-di-methyl-2,5-di(benzoylperoxy)hexane, t-butylperoxyacetate, 2,2-bis(t-butylperoxy)butane, t-butylperoxybenzoate, n-butyl-4,4-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, t-hexyl hydroperoxide, t-butyl hydroperoxide, and organic peroxides such as benzoyl peroxide;Examples of the azo compounds include azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2-(carbamoylazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, azodi-t-octane, azodi-t-butane, 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], etc. The polymerization initiator (C) of the present embodiment can contain one or more of these compounds. From the viewpoint of further improving the performance balance of patterning property, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, the polymerization initiator (C) of the present embodiment preferably contains an organic peroxide, and more preferably contains dicumyl peroxide.

[0053] From the viewpoint of further improving the performance balance of patterning property, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, when the total amount of the solid content in the photosensitive resin composition is 100 parts by mass, the content of the polymerization initiator (C) in the photosensitive resin composition of the present embodiment is preferably 1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, still more preferably 7 parts by mass or more, still more preferably 8 parts by mass or more, and preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 17 parts by mass or less, still more preferably 14 parts by mass or less, still more preferably 12 parts by mass or less. Also, from the viewpoint of further improving the performance balance of patterning property, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, when the total amount of the solid content in the photosensitive resin composition is 100 parts by mass, 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, still more preferably 5 parts by mass or more and 17 parts by mass or less, still more preferably 7 parts by mass or more and 14 parts by mass or less, still more preferably 8 parts by mass or more and 12 parts by mass or less.

[0054] When the total content of polyimide (A), crosslinking agent (B), and polymerization initiator (C) in the photosensitive resin composition of the present embodiment is based on 100 parts by mass of the total solid content in the photosensitive resin composition, from the viewpoint of further improving the performance balance of patterning property, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, it is preferably 80 parts by mass or more, more preferably 85 parts by mass or more, still more preferably 90 parts by mass or more, still more preferably 93 parts by mass or more, still more preferably 95 parts by mass or more, and is preferably 100 parts by mass or less, more preferably 99 parts by mass or less. Also, when the total content of polyimide (A), crosslinking agent (B), and polymerization initiator (C) in the photosensitive resin composition of the present embodiment is based on 100 parts by mass of the total solid content in the photosensitive resin composition, from the viewpoint of further improving the performance balance of patterning property, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, it 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, still more preferably 90 parts by mass or more and 99 parts by mass or less, still more preferably 92 parts by mass or more and 99 parts by mass or less, still more preferably 95 parts by mass or more and 99 parts by mass or less.

[0055] When the content of polyimide (A) in the present embodiment is 100 parts by mass, the content of the crosslinking agent (B) in the present embodiment, from the viewpoint of further improving the performance balance of patterning property, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, is preferably 1 part by mass or more, more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, still more preferably 13 parts by mass or more, still more preferably 20 parts by mass or more, and is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, still more preferably 60 parts by mass or less, still more preferably 50 parts by mass or less, still more preferably 45 parts by mass or less. When the content of the polyimide (A) of the present embodiment is 100 parts by mass, the content of the crosslinking agent (B) of the present 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 70 parts by mass or less, still more preferably 10 parts by mass or more and 60 parts by mass or less, still more preferably 13 parts by mass or more and 50 parts by mass or less, and still more preferably 20 parts by mass or more and 45 parts by mass or less from the viewpoint of further improving the performance balance of patterning property, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device.

[0056] When the content of the polyimide (A) of the present embodiment is 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 5 parts by mass or more, still more preferably 8 parts by mass or more, still more preferably 11 parts by mass or more, and still more preferably 13 parts by mass or more, and is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, still more preferably 22 parts by mass or less, still more preferably 20 parts by mass or less, and still more preferably 17 parts by mass or less from the viewpoint of further improving the performance balance of patterning property, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device. When the content of the polyimide (A) of the present embodiment is 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 5 parts by mass or more and 25 parts by mass or less, still more preferably 8 parts by mass or more and 22 parts by mass or less, still more preferably 11 parts by mass or more and 20 parts by mass or less, and still more preferably 13 parts by mass or more and 17 parts by mass or less from the viewpoint of further improving the performance balance of patterning property, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device.

[0057] <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 promoter 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-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldiethoxysilane, N-phenyl-γ-amino-propyltrimethoxysilane; epoxy silanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidylpropyltrimethoxysilane; acrylic silanes such as γ-(methacryloxypropyl)trimethoxysilane, γ-(methacryloxypropyl)methyldimethoxysilane, γ-(methacryloxypropyl)methyldiethoxysilane; mercapto silanes such as 3-mercaptopropyltrimethoxysilane; vinyl silanes such as vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane; ureido silanes such as 3-ureidopropyltriethoxysilane; acid anhydride functional silanes such as 3-trimethoxysilylpropylsuccinic anhydride, etc. The adhesion promoter of the present embodiment can contain one or more of these. Among these, from the viewpoint of further improving the adhesion, the adhesion promoter of the present embodiment preferably contains one or more selected from the group consisting of acid anhydride functional silanes and acrylic silanes, and more preferably contains one or more selected from the group consisting of 3-trimethoxysilylpropylsuccinic anhydride and 3-(methacryloxypropyl)trimethoxysilane.

[0058] In the photosensitive resin composition of this embodiment, from the viewpoint of further improving adhesion, when the content of polyimide (A) is 100 parts by mass, the content of the adhesion promoter is preferably 0.1 part by mass or more, more preferably 1.0 part by mass or more, still more preferably 1.5 part by mass or more, and preferably 10.0 parts by mass or less, more preferably 8.0 parts by mass or less, still more preferably 7.0 parts by mass or less. Also, in the photosensitive resin composition of this embodiment, from the viewpoint of further improving adhesion, when the content of polyimide (A) is 100 parts by mass, the content of the adhesion promoter is preferably 0.1 part by mass or more and 10.0 parts by mass or less, more preferably 1.0 part by mass or more and 8.0 parts by mass or less, still more preferably 1.5 part by mass or more and 7.0 parts by mass or less.

[0059] <Surfactant> The photosensitive resin composition of this embodiment preferably further contains a surfactant. Examples of the surfactant in this embodiment include nonionic surfactants such as 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; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; fluorosurfactants commercially available under names such as F-Top EF301, F-Top EF303, F-Top EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F444, Megafac 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.); organosiloxane copolymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); (meth)acrylic acid-based copolymers Polyflow No. 57, 95 (manufactured by Kyoeisha Chemical Co., Ltd.); silicone surfactants such as polyether-modified dimethylsiloxane. The surfactant in this embodiment can include one or more of these. Among these, the surfactant in this embodiment preferably includes a silicone surfactant.

[0060] When the content of polyimide (A) is 100 parts by mass, the content of the surfactant in the photosensitive resin composition of this embodiment is preferably 0.01 part by mass or more and 0.50 part by mass or less, more preferably 0.03 part by mass or more and 0.10 part by mass or less.

[0061] <Antioxidant> From the viewpoint of suppressing the oxidation of the cured product, the photosensitive resin composition of this embodiment may contain an antioxidant. Examples of the antioxidant in this embodiment include pentaerythrityl - tetrakis〔3-(3,5 - di - t - butyl - 4 - hydroxyphenyl)propionate〕, 3,9 - bis{2 - 〔3-(3 - t - butyl - 4 - hydroxy - 5 - methylphenyl)propionyloxy〕-1,1 - dimethylethyl}2,4,8,10 - tetraoxaspiro〔5,5〕undecane, octadecyl - 3-(3,5 - di - t - butyl - 4 - hydroxyphenyl)propionate, 1,6 - hexanediol - bis〔3-(3,5 - di - t - butyl - 4 - hydroxyphenyl)propionate〕, 1,3,5 - trimethyl - 2,4,6 - tris(3,5 - di - t - butyl - 4 - hydroxybenzyl)benzene, 2,6 - di - t - butyl - 4 - methylphenol, 2,6 - di - t - butyl - 4 - ethylphenol, 2,6 - diphenyl - 4 - octadecyloxyphenol, stearyl(3,5 - di - t - butyl - 4 - hydroxyphenyl)propionate, distearyl(3,5 - di - t - butyl - 4 - hydroxybenzyl)phosphonate, thiodiethylene glycol bis〔(3,5 - di - t - butyl - 4 - hydroxyphenyl)propionate〕, 4,4'-thiobis(6 - t - butyl - m - cresol), 2 - octylthio - 4,6 - di(3,5 - di - t - butyl - 4 - hydroxyphenoxy)-s - triazine, 2,2'-methylenebis(4 - methyl - 6 - t - butylphenol), 2,-2'-methylenebis(4 - ethyl - 6 - t - butylphenol), bis〔3,3 - bis(4 - hydroxy - 3 - t - butylphenyl)butyric acid〕glycol ester, 4,4'-butylidenebis(6 - t - butyl - m - cresol), 2,2'-ethylidenebis(4,6 - di - t - butylphenol), 2,2'-ethylidenebis(4 - s - butyl - 6 - t - butylphenol), 1,1,3 - tris(2 - methyl - 4 - hydroxy - 5 - t - butylphenyl)butane, bis〔2 - t - butyl - 4 - methyl - 6-(2 - hydroxy - 3 - t - butyl - 5 - methylbenzyl)phenyl〕terephthalate, 1,3,5 - tris(2,6 - dimethyl - 3 - hydroxy - 4 - t - butylbenzyl)isocyanurate, 1,3,5 - tris(3,5 - di - t - butyl - 4 - hydroxybenzyl)-2,4,6 - trimethylbenzene, 1,3,5-Tris[(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, 2-t-butyl-4-methyl-6-(2-acryloyloxy-3-t-butyl-5-methylbenzyl)phenol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane-bis[β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate], triethylene glycol bis[β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate], 1,1'-bis(4-hydroxyphenyl)cyclohexane, 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 2,2'-methylenebis(6-(1-methylcyclohexyl)-4-methylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 3,9-bis(2-(3-t-butyl-4-hydroxy-5-methylphenylpropionyloxy)1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, 4,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'-bis(3,5-di-t-butyl-4-hydroxybenzyl)sulfide, 4,4'-thiobis(6-t-butyl-2-methylphenol), 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2,4-dimethyl-6-(1-methylcyclohexyl), styrenated phenol, 2,4-bis((octylthio)methyl)-5-methylphenol and other phenolic antioxidants; bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, tris(2,4-di-t-butylphenyl phosphite), tetrakis(2,4-di-t-butyl-5-methylphenyl)-4,4'-biphenylenediphosphonite, 3,5-di-t-butyl-4-hydroxybenzyl phosphonate-diethyl ester, bis-(2,Phosphorus-based antioxidants such as 6-dicumylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-t-butylphenyl) octyl phosphite, tris(mixed mono- and di-nonylphenyl phosphite), bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-methoxycarbonylethyl-phenyl)pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-octadecyloxycarbonylethylphenyl)pentaerythritol diphosphite; thioether-based antioxidants such as dilauryl-3,3'-thiodipropionate, bis(2-methyl-4-(3-n-dodecyl)thiopropionyloxy)-5-t-butylphenyl)sulfide, distearyl-3,3'-thiodipropionate, pentaerythritol-tetrakis(3-lauryl)thiopropionate, etc. can be mentioned, and the antioxidant of this embodiment can contain one or more of these.,

[0062] From the viewpoint of suppressing the oxidation of the cured product, when the content of polyimide (A) is 100 parts by mass, the content of the antioxidant in the photosensitive resin composition of this embodiment is preferably 0.1 part by mass or more and 10.0 parts by mass or less, more preferably 0.5 part by mass or more and 5.0 parts by mass or less.,

[0063] <Curing catalyst> From the viewpoint of further improving the performance balance of patterning property, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, the photosensitive resin composition of this embodiment may further contain a curing catalyst., 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 their derivatives; nitrogen atom-containing compounds such as quaternary ammonium salts of the above amidines or the above tertiary amines, etc. The curing catalyst of the present embodiment can contain one or more of these.

[0064] From the viewpoint of further improving the performance balance of patterning property, copper adhesion, mechanical strength, and the reliability of the resulting semiconductor device, when the content of polyimide (A) is 100 parts by mass, the content of the curing catalyst in the photosensitive resin composition of the present embodiment is preferably 0.1 part by mass or more and 5.0 parts by mass or less, more preferably 0.5 part by mass or more and 2.0 parts by mass or less.

[0065] <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, if necessary.

[0066] <Organic Solvent> From the viewpoint of further improving the performance balance of patterning property and copper adhesion, the photosensitive resin composition of the present embodiment preferably further contains an organic solvent. From the perspective of further improving the performance balance between patterning properties and copper adhesion, the organic solvent of this embodiment preferably contains one or more selected from the group consisting of γ-butyrolactone (GBL), γ-valerolactone (GVL), 2,6-lutidine, N,N-dimethylacetamide pyruvate, 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 (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, more preferably contains one or more selected from the group consisting of γ-butyrolactone (GBL) and ethyl lactate (EL), and even more preferably contains both γ-butyrolactone (GBL) and ethyl lactate (EL).

[0067] From the perspective of further improving the performance balance between patterning properties and copper adhesion, when the total amount of the solid content in the photosensitive resin composition is 100 parts by mass, the content of the organic solvent in the photosensitive resin composition of this embodiment is 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 250 parts by mass or more, and 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, and even more preferably 400 parts by mass or less. In addition, from the perspective of further improving the performance balance between patterning properties and copper adhesion, when the total amount of solids in the photosensitive resin composition is 100 parts by mass, the content of the organic solvent in the photosensitive resin composition of the present embodiment is preferably 50 parts by mass or more and 1000 parts by mass or less, more preferably 100 parts by mass or more and 800 parts by mass or less, still more preferably 150 parts by mass or more and 600 parts by mass or less, still more preferably 200 parts by mass or more and 500 parts by mass or less, still more preferably 250 parts by mass or more and 400 parts by mass or less.

[0068] From the perspective of further improving environmental compatibility, when the total amount of solids in the photosensitive resin composition is 100 parts by mass, the content of fluorine 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, still more preferably 3 parts by mass or less, still more preferably 1 part by mass or less, still more preferably 0.1 part by mass or less, still more preferably 0.05 part by mass or less, still more preferably 0.01 part by mass or less. In addition, from the perspective of further improving environmental compatibility, when the total amount of solids in the photosensitive resin composition is 100 parts by mass, the content of fluorine 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, still more preferably 0 parts by mass or more and 3 parts by mass or less, still more preferably 0 parts by mass or more and 1 part by mass or less, still more preferably 0 parts by mass or more and 0.1 part by mass or less, still more preferably 0 parts by mass or more and 0.05 part by mass or less, still more preferably 0 parts by mass or more and 0.01 part by mass or less.

[0069] From the perspective of further improving environmental compatibility, when the total amount of solids in the photosensitive resin composition is 100 parts by mass, the content of the polymer containing fluorine atoms 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, still more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, still more preferably 1 part by mass or less, still more preferably 0.1 part by mass or less, still more preferably 0.05 part by mass or less, still more preferably 0.01 part by mass or less. In addition, from the perspective of further improving environmental compatibility, when the total amount of solids in the photosensitive resin composition is 100 parts by mass, the content of the polymer containing fluorine atoms in the photosensitive resin composition of the present embodiment is preferably 0 part by mass or more and 30 parts by mass or less, more preferably 0 part by mass or more and 20 parts by mass or less, still more preferably 0 part by mass or more and 10 parts by mass or less, still more preferably 0 part by mass or more and 5 parts by mass or less, still more preferably 0 part by mass or more and 1 part by mass or less, still more preferably 0 part by mass or more and 0.1 part by mass or less, still more preferably 0 part by mass or more and 0.05 part by mass or less, still more preferably 0 part by mass or more and 0.01 part by mass or less.

[0070] From the perspective of further improving the performance balance of patterning property, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, when the total amount of solids in the photosensitive resin composition is 100 parts by mass, the content of the alkali-soluble resin in the photosensitive resin composition of the present embodiment is preferably 0 part by mass or more, and preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, still more preferably 1 part by mass or less, still more preferably 0.1 part by mass or less, still more preferably 0.05 part by mass or less, still more preferably 0.01 part by mass or less. In addition, from the perspective of further improving the performance balance of patterning property, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, when the total amount of solids in the photosensitive resin composition is 100 parts by mass, the content of the alkali-soluble resin in the photosensitive resin composition of the present embodiment is preferably 0 part by mass or more and 30 parts by mass or less, more preferably 0 part by mass or more and 20 parts by mass or less, still more preferably 0 part by mass or more and 10 parts by mass or less, still more preferably 0 part by mass or more and 5 parts by mass or less, still more preferably 0 part by mass or more and 1 part by mass or less, still more preferably 0 part by mass or more and 0.1 part by mass or less, still more preferably 0 part by mass or more and 0.05 part by mass or less, still more preferably 0 part by mass or more and 0.01 part by mass or less. In this specification, the alkali-soluble resin is a resin that dissolves in an alkali developer to a sufficient extent for patterning.

[0071] <Method for preparing photosensitive resin composition> The method for preparing the photosensitive resin composition in this embodiment is not limited, and a known method can be used according to the components contained in the photosensitive resin composition. For example, it can be prepared by mixing and dissolving each of the above-described components in a solvent.

[0072] <Oxygen transmission coefficient> The oxygen transmission coefficient of the photosensitive resin composition of this embodiment is preferably 40 cm 3 ·mm / (m 2 ·day·atm) or less, more preferably 35 cm 3 ·mm / (m 2 ·day·atm) or less, still more preferably 30 cm 3 ·mm / (m 2 ·day·atm) or less, still more preferably 25 cm 3 ·mm / (m 2 ·day·atm) or less. The lower limit value of the oxygen transmission coefficient of the photosensitive resin composition of this embodiment is not particularly limited, but it may be 1 cm 3 ·mm / (m 2 ·day·atm) or more, and may also be 3 cm 3 ·mm / (m 2 ·day·atm) or more. Also, the oxygen transmission coefficient of the photosensitive resin composition of this embodiment is preferably 1 cm 3 ·mm / (m 2 ·day·atm) or more and 40 cm 3 ·mm / (m 2 ·day·atm) or less, more preferably 1 cm 3 ·mm / (m 2 ·day·atm) or more and 35 cm 3 ·mm / (m 2 ·day·atm) or less, still more preferably 3 cm 3 ·mm / (m 2 ·day·atm) or more and 30 cm 3 ·mm / (m 2 ·day·atm) or less, still more preferably 3 cm 3 ·mm / (m2 ·day·atm) or more, 25 cm above 3 ·mm / (m 2 ·day·atm) or less.

[0073] Examples of the method for measuring the oxygen permeability coefficient of the photosensitive resin composition of the present embodiment include the following methods. First, the photosensitive resin composition is spin-coated on the surface of a silicon wafer so that the film thickness after drying becomes 10 μm, pre-baked at 110 °C for 3 minutes, and then exposed with a high-pressure mercury lamp at 600 mJ / cm 2 Then, post-baking is performed at 230 °C for 3 hours in a nitrogen atmosphere to produce a cured product with a thickness of 100 mm × 100 mm × 10 μm. Next, for the cured product, the oxygen permeability coefficient is measured by the differential pressure method in accordance with JIS K 7126-2:2006 under the conditions of 23 °C and 60% RH.

[0074] From the viewpoint of further improving the performance balance of the mechanical strength and the reliability of the resulting semiconductor device, the glass transition temperature (Tg) of the photosensitive resin composition of the present embodiment is preferably 240 °C or higher, more preferably 245 °C or higher, still more preferably 250 °C or higher, and preferably 300 °C or lower, more preferably 290 °C or lower, still more preferably 280 °C or lower. Also, from the viewpoint of further improving the performance balance of the mechanical strength and the reliability of the resulting semiconductor device, the glass transition temperature (Tg) of the photosensitive resin composition of the present embodiment is preferably 240 °C or higher and 300 °C or lower, more preferably 245 °C or higher and 290 °C or lower, still more preferably 250 °C or higher and 280 °C or lower.

[0075] Examples of the method for measuring the glass transition temperature (Tg) of the photosensitive resin composition of the present embodiment include the following methods. First, the photosensitive resin composition is spin-coated on the surface of a silicon wafer so that the film thickness after drying becomes 10 μm, pre-baked at 110 °C for 3 minutes, and then exposed with a high-pressure mercury lamp at 600 mJ / cm 2Perform exposure, and then perform post-baking at 230°C for 3 hours in a nitrogen atmosphere to produce a cured product with a thickness of 100 mm × 100 mm × 10 μm. Next, for the cured product, measure the glass transition temperature (Tg) using a thermomechanical analysis (TMA) apparatus under the conditions of an initial temperature of 30°C, a measurement temperature range of 30 to 400°C, and a heating rate of 5°C / min.

[0076] From the viewpoint of further improving the balance of mechanical strength and the reliability performance of the resulting semiconductor device, the elongation at break of the photosensitive resin composition of this embodiment is preferably 6% or more, more preferably 8% or more, still more preferably 9% or more, and preferably 55% or less, more preferably 50% or less, still more preferably 47% or less. Also, from the viewpoint of further improving the balance of mechanical strength and the reliability performance of the resulting semiconductor device, the elongation at break of the photosensitive resin composition of the embodiment is preferably 6% or more and 55% or less, more preferably 8% or more and 50% or less, still more preferably 9% or more and 47% or less.

[0077] Examples of the method for measuring the elongation at break of the photosensitive resin composition of this embodiment include the following method. First, spin-coat the photosensitive resin composition on the surface of a silicon wafer so that the film thickness after drying becomes 10 μm, perform pre-baking at 110°C for 3 minutes, and then perform exposure with a high-pressure mercury lamp at 600 mJ / cm 2 Perform exposure, and then perform post-baking at 230°C for 3 hours in a nitrogen atmosphere to produce a cured product with a thickness of 100 mm × 100 mm × 10 μm. Next, for the cured product, measure the elongation at break using a tensile tester under the conditions of 23°C and an elongation rate of 5 mm / min in accordance with JIS K 7161:2014.

[0078] The tensile elastic modulus of the photosensitive resin composition of the present embodiment is preferably 1.0 GPa or more, more preferably 1.5 GPa or more, still more preferably 2.0 GPa or more, and even more preferably 2.3 GPa or more from the viewpoint of further improving the performance balance between mechanical strength and the reliability of the resulting semiconductor device, and is preferably 4.0 GPa or less, more preferably 3.7 GPa or less, still more preferably 3.5 GPa or less, and even more preferably 3.2 GPa or less. Also, the tensile elastic modulus of the photosensitive resin composition of the present embodiment is preferably 1.0 GPa or more and 4.0 GPa or less, more preferably 1.5 GPa or more and 3.7 GPa or less, still more preferably 2.0 GPa or more and 3.5 GPa or less, and even more preferably 2.3 GPa or more and 3.2 GPa or less from the viewpoint of further improving the performance balance between mechanical strength and the reliability of the resulting semiconductor device.

[0079] Examples of the method for measuring the tensile elastic modulus of the photosensitive resin composition of the present embodiment include the following method. First, the photosensitive resin composition is spin-coated on the surface of a silicon wafer so that the film thickness after drying becomes 10 μm, pre-baked at 110 °C for 3 minutes, and then exposed with a high-pressure mercury lamp at 600 mJ / cm 2 Then, a post-bake is performed at 230 °C for 3 hours in a nitrogen atmosphere to produce a cured product having a thickness of 100 mm × 100 mm × 10 μm. Next, for the cured product, in accordance with JIS K 7161:2014, the tensile elastic modulus is measured using a tensile testing machine under the conditions of 23 °C and a tensile speed of 5 mm / min.

[0080] The storage elastic modulus of the photosensitive resin composition of the present embodiment is preferably 1.0 GPa or more, more preferably 2.0 GPa or more, still more preferably 2.5 GPa or more, and even more preferably 3.0 GPa or more from the viewpoint of further improving the performance balance between mechanical strength and the reliability of the resulting semiconductor device, and is preferably 5.0 GPa or less, more preferably 4.6 GPa or less, still more preferably 4.3 GPa or less, and even more preferably 4.0 GPa or less. Also, from the viewpoint of further improving the performance balance between the mechanical strength and the reliability of the resulting semiconductor device, the storage elastic modulus of the photosensitive resin composition of the present embodiment is preferably 1.0 GPa or more and 5.0 GPa or less, more preferably 2.0 GPa or more and 4.6 GPa or less, still more preferably 2.5 GPa or more and 4.3 GPa or less, and even more preferably 3.0 GPa or more and 4.0 GPa or less.

[0081] Examples of the method for measuring the storage elastic modulus of the photosensitive resin composition of the present embodiment include the following method. First, the photosensitive resin composition is spin-coated on the surface of a silicon wafer so that the film thickness after drying becomes 10 μm, pre-baked at 110° C. for 3 minutes, and then exposed with a high-pressure mercury lamp at 600 mJ / cm 2 Then, post-baking is performed at 230° C. for 3 hours in a nitrogen atmosphere to produce a cured product having a thickness of 100 mm × 100 mm × 10 μm. Next, the storage elastic modulus at 220° C. measured by dynamic viscoelasticity measurement (DMA) is measured for the cured product.

[0082] <Use> Since the reliability of the resulting semiconductor device is improved, the photosensitive resin composition of the present embodiment can be suitably used for semiconductor devices.

[0083] The photosensitive resin composition of the present embodiment is suitably used for forming resin films for semiconductor devices such as permanent films and resists. Among these, since the reliability of the resulting semiconductor device is improved, the photosensitive resin composition of the present embodiment is preferably used for applications using permanent films. The permanent film is composed of a resin film obtained by performing pre-baking, exposure, and development on the photosensitive resin composition, patterning it into a desired shape, and then curing it by heat treatment. The permanent film can be used for protective films, interlayer films, dam materials, etc. of semiconductor devices. The resist is composed of a resin film obtained by applying a photosensitive resin composition to an object to be masked for the resist by a method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, etc., and removing the solvent from the photosensitive resin composition.

[0084] <Cured product> The cured product of this embodiment is the cured product of the photosensitive resin composition of this embodiment. The cured product of this embodiment can be produced, for example, by applying the photosensitive resin composition of this embodiment to a substrate, pre-baking to dry and form a resin film, then patterning the resin film into a desired shape by exposure and development, and then curing the resin film by heat treatment. When producing the cured product, the pre-baking conditions can be, for example, heat treatment at 90°C or higher and 130°C or lower for 30 seconds or more and 1 hour or less. Also, the heat treatment conditions can be, for example, heat treatment at 150°C or higher and 250°C or lower for 30 minutes or more and 10 hours or less.

[0085] The semiconductor device of this embodiment includes the cured product of this embodiment. Since the reliability of the semiconductor device obtained by using the photosensitive resin composition of this embodiment is improved, the semiconductor device of this embodiment has improved reliability.

[0086] From the viewpoint of further improving the reliability, the semiconductor device of this embodiment preferably includes 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.

[0087] FIG. 1 shows a schematic cross-sectional view schematically 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 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 a resin film containing the cured product of this embodiment. Here, the resin film is preferably the permanent film described above.

[0088] The semiconductor device 100 is, for example, a semiconductor chip. In this case, for example, a semiconductor package can be obtained by mounting the semiconductor device 100 on a wiring board via bumps 52.

[0089] The semiconductor device 100 includes a semiconductor substrate provided with semiconductor elements such as transistors, and a multilayer wiring layer (not shown) provided on the semiconductor substrate. On the uppermost layer of the multilayer wiring layer, an interlayer insulating film 30 and an uppermost layer wiring 34 provided on the interlayer insulating film 30 are provided. The uppermost layer wiring 34 is made of, for example, aluminum Al. Further, a passivation film 32 is provided on the interlayer insulating film 30 and on the uppermost layer wiring 34. An opening is provided in a part of the passivation film 32 through which the uppermost layer wiring 34 is exposed.

[0090] A rewiring layer 40 is provided on the passivation film 32. The rewiring layer 40 includes an insulating layer 42 provided on the passivation film 32, a rewiring 46 provided on the insulating layer 42, and an insulating layer 44 provided on the insulating layer 42 and on the rewiring 46. An opening for connecting to the uppermost layer wiring 34 is formed in the insulating layer 42. The rewiring 46 is formed on the insulating layer 42 and in the opening provided in the insulating layer 42, and is connected to the uppermost layer wiring 34. An opening for connecting to the rewiring 46 is provided in the insulating layer 44.

[0091] In the opening provided in the insulating layer 44, bumps 52 are formed via, for example, an Under Bump Metallurgy (UBM) layer 50. The semiconductor device 100 is connected to a wiring board or the like via the bumps 52, for example.

[0092] Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than those described above can be adopted as long as the effects of the present invention are not impaired.

Example

[0093] Embodiments of the present invention will be described in detail based on examples and comparative examples. Note that the present invention is not limited only to the examples.

[0094] <Compound used for the synthesis of the polymer> In the synthesis of the polymer, the following compounds were used.

[0095] 2,2-Bis(3-amino-4-hydroxyphenyl)propane (hereinafter also referred to as BAPA) represented by the following formula.

[0096]

Chemical formula

[0097] 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 following formula.

[0098]

Chemical formula

[0099] 4,4-Diamino-3,3-diethyl-5,5-dimethyldiphenylmethane (hereinafter also referred to as MED-J) represented by the following formula.

[0100]

Chemical formula

[0101] <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 a reaction vessel of an appropriate size equipped with a stirrer and a cooling tube. Then, 767.6 g of γ-butyrolactone (GBL) was further added to the reaction vessel. After purging with nitrogen for 10 minutes, the temperature was raised to 60 °C with stirring and reacted for 1.5 hours. Then, by further reacting at 180 °C for 3 hours, BAPA, TMPBP-TME, and MED-J were polymerized to prepare a polymerization solution. Next, to the entire amount of the obtained polyimide solution (213.2 mmol in terms of hydroxyl groups), 60.2 g (426.3 mmol) of 2-isocyanatoethyl acrylate (hereinafter also referred to as AOI, manufactured by Showa Denko K.K.) and 83.3 g of GBL were added. Then, the temperature was raised to 120 °C with stirring and reacted for 6 hours. The obtained reaction solution was diluted with tetrahydrofuran to prepare a diluted solution, and then the diluted solution was dropped into methanol to precipitate a white solid. The obtained white solid was recovered and vacuum dried at 40 °C to obtain 218.1 g of Polymer 1. 1 When 1H-NMR measurement was performed, peaks were confirmed in the aromatic region (6.8 ppm to 8.9 ppm) at an area ratio corresponding to the number of protons. Also, from the area ratio between the aromatic region (6.8 ppm to 8.9 ppm) and 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 a part thereof.

[0102]

Chemical formula

[0103] <Synthesis of Polymer 2> Polymer 2 was obtained in the same manner as the synthesis of Polymer 1, except that the addition amounts of BAPA, TMPBP-TME, and MED-J were changed so that the ratio of x to y in the repeating unit contained in the polymer was x:y = 25:75.

[0104] <Synthesis of Polymer 3> Polymer 3 was obtained in the same manner as the synthesis of Polymer 1, except that the addition amounts of BAPA, TMPBP-TME, and MED-J were changed so that the ratio of x to y in the repeating unit contained in the polymer was x:y = 75:25.

[0105] <Synthesis of Polymer 4> Polymer 4 was obtained in the same manner as the synthesis of Polymer 1, except that the addition amounts of BAPA and TMPBP-TME were changed so that the ratio of x to y in the repeating unit contained in the polymer was x:y = 100:0, and MED-J was not added.

[0106] <Synthesis of Polymer 5> Polymer 5 was obtained in the same manner as the synthesis of Polymer 1, except that AOI was not added to the polyimide solution and the introduction rate of the crosslinking group was set to 0%.

[0107] <Components Used in the Preparation of the Photosensitive Resin Composition> The following components were used in the preparation of the photosensitive resin compositions of the examples and comparative examples.

[0108] · Acrylate Compound 1: A polyfunctional acrylate compound represented by the following formula (manufactured by Shin-Nakamura Chemical Co., Ltd., A-9300S-NT)

Chemical formula

[0109] · Acrylate Compound 2: A bifunctional acrylate compound represented by the following formula (manufactured by Toagosei Co., Ltd., M-215)

Chemical formula

[0110] · Acrylate Compound 3: A polyfunctional acrylate compound represented by the following formula (manufactured by Shin-Nakamura Chemical Co., Ltd., A-DPH)

Chemical formula

[0111] · Epoxy compound 1: 4-hydroxybutyl acrylate glycidyl ether represented by the following formula (manufactured by Shinryo Corporation, 4HBAGE)

Chemical formula

[0112] · Polymerization initiator 1: Compound represented by the following formula (manufactured by BASF, Irgacure OXE01)

Chemical formula

[0113] · Polymerization initiator 2: Dicumyl peroxide represented by the following formula (manufactured by NOURYON, Perkadox BC)

Chemical formula

[0114] · Adhesion promoter 1: 3-trimethoxysilylpropyl succinic anhydride represented by the following formula (manufactured by Shin-Etsu Chemical Co., Ltd., X-12-967C)

Chemical formula

[0115] · Adhesion promoter 2: 3-(methacryloxypropyl)trimethoxysilane represented by the following formula (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503)

Chemical formula

[0116] · Surfactant 1: Silicone-based surfactant (manufactured by BYK, BYK-349)

[0117] · Solvent 1: Ethyl lactate (EL) · Solvent 2: γ-Butyrolactone (GBL)

[0118] (Examples 1 to 10, Comparative Examples 1 to 2) <Preparation of photosensitive resin composition> The polymer and each component were mixed in a solvent at the formulation ratios shown in Table 1, and photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 2 were prepared.

[0119] <Patterning property> The photosensitive resin compositions of each example and each comparative example were applied onto an 8-inch silicon wafer using a spin coater. After application, pre-baking was performed on a hot plate at 110 °C for 3 minutes in the atmosphere to obtain a coating film with a thickness of about 5 μm. This coating film was irradiated with i-line through a mask on which via patterns of a plurality of widths (4 μm and 5 μm) were drawn. For the irradiation, an i-line stepper (manufactured by Nikon Corporation, NSR-4425i) was used. After exposure, cyclopentanone was used as a developer, and spray development was performed for 30 seconds. Further, PGMEA was used as a developer, and spray development was performed for 10 seconds to dissolve and remove the unexposed portions, thereby obtaining a via pattern. The cross-section of the obtained via pattern was observed using a desktop SEM. The width at the height between the bottom surface and the opening of the via pattern was defined as the via width, and the patterning property was evaluated according to the following criteria. The results are shown in Table 1. A: The 4-μm and 5-μm via patterns are open B: The 5-μm via pattern is open and the 4-μm via pattern is not open C: The 4-μm and 5-μm via patterns are not open

[0120] <Adhesion to copper> The photosensitive resin compositions of each example and each comparative example were applied onto a silicon wafer with a copper plating formed on its surface using a spin coater, and then pre-baked on a hot plate at 120 °C for 3 minutes to obtain a coating film with a thickness of about 10 μm. The obtained coating film was heated in an oven at 230 °C for 180 minutes while maintaining the oxygen concentration at 1000 ppm or less to obtain a cured film of the photosensitive resin composition. Next, 100 patterns of 1 mm × 1 mm were created using a cutter. Then, a cellophane tape (registered trademark) with a peel strength of 3.0 mN / 10 mm was well attached to the surface of such a pattern, and then the cellophane tape (registered trademark) was peeled off vertically. Next, the number of peeled patterns was counted, and the adhesion to copper was evaluated according to the following criteria. The results are shown in Table 1. A: The number of peeled patterns is less than 10 B: The number of peeled patterns is 10 or more

[0121] <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 compositions of each example and each comparative example were applied to the surface of the silicon wafer on which the copper wiring was formed so that the film thickness after drying would be 10 μm. After pre-baking at 110°C for 3 minutes, exposure was performed with a high-pressure mercury lamp at 600 mJ / cm 2 Then, post-baking was performed at 230°C for 3 hours in a nitrogen atmosphere to cure the photosensitive resin composition, obtaining test pieces. Next, the obtained test pieces were heat-treated under the conditions of 230°C for 30 minutes in the atmosphere. Then, the test pieces were cut in a direction perpendicular to the surface of the silicon wafer, and the cross-section was observed with a scanning electron microscope (S-4700, manufactured by Hitachi High-Technologies Corporation), and the reliability was evaluated according to the following criteria. The results are shown in Table 1. A: There are no cracks or migrations at the interface between the copper wiring and the cured product B: There are almost no cracks or migrations at the interface between the copper wiring and the cured product C: There are cracks or migrations at the interface between the copper wiring and the cured product

[0122] <Preparation of cured product> Regarding the photosensitive resin compositions of each example and each comparative example, spin coating was performed on the surface of the silicon wafer so that the film thickness after drying would be 10 μm. After pre-baking at 110°C for 3 minutes, exposure was performed with a high-pressure mercury lamp at 600 mJ / cm 2 Then, post-baking was performed at 230°C for 3 hours in a nitrogen atmosphere to prepare a cured product with a thickness of 100 mm × 100 mm × 10 μm.

[0123] <Oxygen permeability coefficient> Regarding the cured products of each example and each comparative example, the oxygen permeability coefficient was measured by the differential pressure method in accordance with JIS K 7126-2:2006 under the conditions of 23°C and 60% RH. The results are shown in Table 1.

[0124] <Glass transition temperature (Tg)> For the cured products of each example and each comparative example, using a thermomechanical analysis (TMA) apparatus (manufactured by Hitachi High-Tech Corporation, TMA-7100), the glass transition temperature (Tg) was measured under the conditions of an initial temperature of 30°C, a measurement temperature range of 30 to 400°C, and a heating rate of 5°C / min. The results are shown in Table 1.

[0125] <Elongation at break, tensile modulus> For the cured products of each example and each comparative example, in accordance with JIS K 7161:2014, using a tensile testing machine (manufactured by AMD Corporation, STB-1225S), the elongation at break and the tensile modulus were measured under the conditions of 23°C and an elongation rate of 5 mm / min. The results are shown in Table 1.

[0126] <Storage modulus> For the cured products of each example and each comparative example, using a DMA apparatus (manufactured by TA Instruments, DMA-Q800), the storage modulus at 220°C was measured by dynamic viscoelastic measurement (DMA). The results are shown in Table 1.

[0127]

Table 1

Explanation of symbols

[0128] 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

1. A polyimide (A) having a double bond in the side chain, A crosslinking agent (B) containing a (meth) acrylate compound having an isocyanuric acid skeleton, A polymerization initiator (C), A photosensitive resin composition comprising.

2. The photosensitive resin composition according to claim 1, wherein the crosslinking agent (B) contains a (meth) acrylate compound represented by the following general formula (1). 【Chemical 1】 (In the general formula (1), R １１ , R １２ and R １３ each independently represents a hydrogen atom, a hydroxy group, or an organic group containing at least one functional group selected from the group consisting of a (meth)acryloyloxy group, a (meth)acryloyl group, and a hydroxy group, and an alkylene group having 1 to 10 carbon atoms or an oxyalkylene group having 1 to 10 carbon atoms, and at least one of R １１ , R １２ and R １３ has a (meth)acryloyloxy group or a (meth)acryloyl group)

3. R in the general formula (1) １１ , R １２ and R １３ At least one of is a group represented by the following general formula (2), The photosensitive resin composition according to claim 2. 【Chemical Formula 2】 (In the general formula (2), V represents a single bond, an alkylene group having 1 to 10 carbon atoms, or an oxyalkylene group having 1 to 10 carbon atoms, and R ２０ represents a hydrogen atom or a methyl group, W represents a single bond or a functional group selected from the group consisting of a group represented by the general formula (2a), a group represented by the general formula (2b), and a group represented by the general formula (2c), and * represents a bond, In the general formula (2a), a represents an integer of 1 to 10, and * represents a bond, In the general formula (2b), b represents an integer of 1 to 10, and * represents a bond, In the general formula (2c), c represents an integer of 1 to 10, and * represents a bond)

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the polyimide (A) contains a structural unit represented by the following general formula (3). [Chemical Formula 3] (In the general formula (3), Y represents a divalent organic group)

5. The photosensitive resin composition according to claim 4, wherein Y in the general formula (3) is selected from the group consisting of a group represented by the following general formula (3a), a group represented by the following general formula (3b), and a group represented by the following general formula (3c). 【Chemical 4】 (In the general formula (3a), R １ and R ２ each independently 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 １ 's, and a plurality of R ２ 's may be the same or different from each other, 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 ３ 's may be the same or different from each other, and * represents a bond, In the general formula (3b), R ４ and R ５ each independently 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 ４ 's, a plurality of R ５ 's may be the same or different from each other, and * represents a bond, In the general formula (3c), Z represents an alkylene group having 1 to 5 carbon atoms or a divalent aromatic group, and * represents a bond)

6. The photosensitive resin composition according to any one of claims 1 to 3, wherein the polyimide (A) contains a structural unit represented by the following general formula (4). 【Chemical Formula 5】 (In the general formula (4), m1 and m2 each independently represent an integer of 0 to 3, Q represents a hydrogen atom, a hydroxy group or a monovalent organic group having 1 to 10 carbon atoms when m1 or m2 is 0, and represents a single bond or a divalent to tetravalent organic group having 1 to 10 carbon atoms when m1 or m2 is 1 to 3. A plurality of 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. A plurality of 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, or a linear or branched fluoroalkylene group having 1 to 5 carbon atoms. A plurality of Xs may be the same or different.)

7. The photosensitive resin composition according to any one of claims 1 to 3, wherein the polyimide (A) contains a structural unit (a) represented by the following general formula (5). [Chemical Formula 6] (In the general formula (5), 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. A plurality of 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. A plurality of 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, or a linear or branched fluoroalkylene group having 1 to 5 carbon atoms. A plurality of Xs may be the same or different. Y represents a divalent organic group)

8. The constitutional unit (a) is a constitutional unit (a) represented by the general formula (5) in which at least one of m1 and m2 is 1 or more ｐ ), and a constitutional unit (a) represented by the general formula (5) in which both m1 and m2 are 0 ｑ ), and In the constitutional unit (a), when the total content of the constitutional unit (a ｐ ) and the constitutional unit (a ｑ ) is 100 mol%, the content of the constitutional unit (a ｐ ) is 15 mol% or more. The photosensitive resin composition according to claim 7.

9. When the content of the polyimide (A) 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, and the photosensitive resin composition according to any one of claims 1 to 3.

10. When the content of the polyimide (A) is 100 parts by mass, the content of the polymerization initiator (C) is 1 part by mass or more and 30 parts by mass or less, and the photosensitive resin composition according to any one of claims 1 to 3.

11. When the total amount of the solid content in the photosensitive resin composition is 100 parts by mass, the total content of the polyimide (A), the crosslinking agent (B), and the polymerization initiator (C) is 80 parts by mass or more, and the photosensitive resin composition according to any one of claims 1 to 3.

12. 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 claims 1 to 3, wherein the imidization rate represented by {IM / (IM + AM)} × 100 (%) is 90% or more.

13. The photosensitive resin composition according to any one of claims 1 to 3, wherein the polymerization initiator (C) contains an oxime ester type polymerization initiator.

14. The photosensitive resin composition according to any one of claims 1 to 3, further comprising an organic solvent.

15. The photosensitive resin composition according to claim 14, wherein the organic solvent contains one or more selected from the group consisting of γ-butyrolactone (GBL), γ-valerolactone (GVL), 2,6-lutidine, N,N-dimethylacetamide of pyruvic acid, 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 (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.

16. The photosensitive resin composition according to any one of claims 1 to 3, wherein when the total amount of the solid content in the photosensitive resin composition is 100 parts by mass, the fluorine content is 10 parts by mass or less.

17. The photosensitive resin composition according to any one of claims 1 to 3, wherein when the total amount of the solid content in the photosensitive resin composition is 100 parts by mass, the content of the polymer containing fluorine atoms is 30 parts by mass or less.

18. The photosensitive resin composition according to any one of claims 1 to 3, wherein when the total amount of the solid content in the photosensitive resin composition is 100 parts by mass, the content of the alkali-soluble resin is 30 parts by mass or less.

19. The oxygen permeability coefficient according to the following Method 1 is 40 cm ３ ·mm / (m ２ ·day·atm) or less, and the photosensitive resin composition according to any one of claims 1 to 3. (Method 1) The photosensitive resin composition is cured at 230 °C for 3 hours to obtain a cured product having a thickness of 100 mm × 100 mm × 10 μm. For the cured product, the oxygen transmission coefficient is measured by the differential pressure method in accordance with JIS K 7126-2:2006 under the conditions of 23 °C and 60% RH.

20. For the cured product obtained by curing the photosensitive resin composition at 230 °C for 3 hours, using a thermomechanical analysis (TMA) apparatus, the glass transition temperature (Tg) measured under the conditions of an initial temperature of 30 °C, a measurement temperature range of 30 to 400 °C, and a heating rate of 5 °C / min is 240 °C or higher. The photosensitive resin composition according to any one of claims 1 to 3.

21. For the cured product obtained by curing the photosensitive resin composition at 230 °C for 3 hours, in accordance with JIS K 7161:2014, using a tensile tester, the elongation at break measured under the conditions of 23 °C and an elongation rate of 5 mm / min is 6% or higher. The photosensitive resin composition according to any one of claims 1 to 3.

22. For the cured product obtained by curing the photosensitive resin composition at 230 °C for 3 hours, in accordance with JIS K 7161:2014, using a tensile tester, the tensile elastic modulus measured under the conditions of 23 °C and an elongation rate of 5 mm / min is 1.0 GPa or more and 4.0 GPa or less. The photosensitive resin composition according to any one of claims 1 to 3.

23. For the cured product obtained by curing the photosensitive resin composition at 230 °C for 3 hours, the storage elastic modulus at 220 °C measured by dynamic viscoelasticity measurement (DMA) is 1.0 GPa or more and 5.0 GPa or less. The photosensitive resin composition according to any one of claims 1 to 3.

24. The photosensitive resin composition according to any one of claims 1 to 3, which can be used for a semiconductor device.

25. The cured product of the photosensitive resin composition according to any one of claims 1 to 3.

26. A semiconductor device including the cured product according to claim 25.

27. An interlayer insulating film, A resin film including the cured product according to claim 25 on the interlayer insulating film, And a rewiring embedded in the resin film. The semiconductor device according to claim 26, comprising:

Images