Photosensitive resin composition, cured product, and semiconductor device

Abstract

This photosensitive resin composition contains a polyimide (A) having a double bond in a side chain, a crosslinking agent (B) containing a (meth)acrylate compound, a polymerization initiator (C), and an antioxidant (D) having an isocyanuric acid skeleton.

Description

Photosensitive resin composition, cured product, and semiconductor device

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

[0002] Polyimides are used, for example, as protective materials in liquid crystal display devices and semiconductors, insulating materials, and thin films for electronic materials such as color filters.

[0003] Patent Document 1 discloses a resin composition containing (A) a polyimide resin, characterized in that the polyimide resin (A) has an organic group with a specific structure, for the purpose of providing a resin composition that is easily soluble in an alkaline developer before exposure, becomes insoluble in the alkaline developer upon exposure, undergoes little film shrinkage upon curing, and enables a highly rectangular pattern to be obtained after curing.

[0004] Japanese Patent Application Laid-Open No. 2018-070829

[0005] The present invention provides a photosensitive resin composition and a cured product that can improve the balance of patterning properties and the reliability of the resulting semiconductor device, as well as a semiconductor device with improved reliability.

[0006] The present inventors have conducted extensive research to solve the above-mentioned problems, and as a result have found that a photosensitive resin composition containing a polyimide (A) having a double bond in a side chain, a crosslinking agent (B) containing a (meth)acrylate compound, a polymerization initiator (C), and an antioxidant (D) having an isocyanuric acid skeleton can improve the performance balance between patterning ability and the reliability of the resulting semiconductor device, thereby completing the present invention.

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

[0008] [1] A photosensitive resin composition comprising: a polyimide (A) having a double bond in a side chain; a crosslinking agent (B) containing a (meth)acrylate compound; a polymerization initiator (C); and an antioxidant (D) having an isocyanuric acid skeleton. [2] The photosensitive resin composition according to [1], wherein the antioxidant (D) contains a compound represented by the following general formula (1): (In the general formula (1), R １１ , R １２ and R １３ each independently represents a hydrogen atom, a hydroxy group, an alkyl group or alkoxy group having 1 to 20 carbon atoms which may contain a hydroxy group, or an aryl group or aralkyl group having 6 to 30 carbon atoms which may contain at least one substituent selected from the group consisting of a hydroxy group, an alkyl group, and an alkoxy group. [3] R in the general formula (1) １１ , R １２ and R １３ [2] The photosensitive resin composition according to [1], wherein at least one of the following is a group represented by the following general formula (2): (In the general formula (2), W represents a single bond or an alkylene group having 1 to 5 carbon atoms, and R ２０ represents a hydrogen atom, a hydroxy group, or an alkyl or alkoxy group having 1 to 5 carbon atoms which may contain a hydroxy group, and when there are a plurality of R ２０ may be the same or different, and * indicates a bond. [4] R in the general formula (2) ２０ [5] The photosensitive resin composition according to any one of [1] to [4], wherein the polyimide (A) contains a structural unit represented by the following general formula (3): (In the general formula (3), Y represents a divalent organic group.) [6] The photosensitive resin composition according to [5], 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): (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 R exists in multiple places ２ may be the same or different, and 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 when there are a plurality of R ３may be the same or different, * represents a bond, and 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 R exists in multiple places ５ may be the same or different, * represents a bond, and 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. [7] The photosensitive resin composition according to any one of [1] to [6], wherein the polyimide (A) contains a structural unit represented by the following general formula (4): (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; multiple Qs may be the same or different; R represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms; multiple Rs may be the same or different; X represents a single bond, -SO ２ (a) represents a substituted or unsubstituted fluorene group; (b) represents a substituted or unsubstituted fluorene group; (c) represents a substituted or unsubstituted fluorene group; (d) represents a substituted or unsubstituted fluorene group; (e) represents a substituted or unsubstituted fluorene group; (f) represents a substituted or unsubstituted fluorene group; (g) represents a substituted or unsubstituted fluorene group; (h) represents a substituted or unsubstituted fluorene group; (i) represents a substituted or unsubstituted fluorene group; (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; multiple Qs may be the same or different; R represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms; multiple Rs may be the same or different; X represents a single bond, -SO ２-, -C(=O)-, a linear or branched alkylene group having 1 to 5 carbon atoms, a linear or branched fluoroalkylene group having 1 to 5 carbon atoms, or a substituted or unsubstituted fluorene group, and Y represents a divalent organic group. [9] The structural unit (a) is a structural unit (a) represented by the general formula (5), in which at least one of m1 and m2 is 1 or greater. ｐ ) and a structural unit (a) represented by the general formula (5) in which m1 and m2 are both 0 ｑ ) in the structural unit (a), ｐ ) and the structural unit (a ｑ When the total content of the structural units (a) is taken as 100 mol %, ｐThe photosensitive resin composition according to [8], wherein the content of the crosslinking agent (B) is 1 part by mass or more and 80 parts by mass or less when the content of the polyimide (A) is taken as 100 parts by mass.

[11] The photosensitive resin composition according to any of [1] to

[10] , wherein the content of the polymerization initiator (C) is 1 part by mass or more and 30 parts by mass or less when the content of the polyimide (A) is taken as 100 parts by mass.

[12] The photosensitive resin composition according to any of [1] to

[11] , wherein the content of the antioxidant (D) is 0.01 parts by mass or more and 20 parts by mass or less when the content of the polyimide (A) is taken as 100 parts by mass.

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

[12] , wherein the total content of the polyimide (A), the crosslinking agent (B), the polymerization initiator (C), and the antioxidant (D) is 80 parts by mass or more when the total amount of solids in the photosensitive resin composition is 100 parts by mass.

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

[13] , wherein the imidization rate, expressed as {IM / (IM+AM)}×100(%), is 90% or more when IM is the number of moles of imide groups contained in the polyimide (A) and AM is the number of moles of amide groups contained in the polyimide (A).

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

[14] , wherein the crosslinking agent (B) comprises a polyfunctional (meth)acrylate compound having 3 to 20 (meth)acryloyloxy groups or (meth)acryloyl groups in the molecule.

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

[15] , wherein the crosslinking agent (B) comprises an epoxy compound.

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

[16] , wherein the polymerization initiator (C) comprises an oxime ester-type polymerization initiator.

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

[17] , further comprising an organic solvent.

[19] The organic solvent is selected from the group consisting of γ-butyrolactone (GBL), γ-valerolactone (GVL), 2,6-lutidine, pyruvic acid N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropionamide, dimethyl sulfoxide (DMSO), diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether (PGME), and propylene glycol. The photosensitive resin composition according to

[18] , comprising one or more compounds selected from the group consisting of 1,3-butylene glycol monomethyl ether acetate (PGMEA), methyl lactate, ethyl lactate (EL), butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and 3-methyl-2-oxazolidone.

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

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

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

[20] , wherein the fluorine atom-containing polymer content is 30 parts by mass or less when the total amount of solids in the photosensitive resin composition is 100 parts by mass.

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

[21] , wherein the content of the alkali-soluble resin is 30 parts by mass or less when the total amount of solids in the photosensitive resin composition is 100 parts by mass.

[23] The oxygen permeability coefficient measured by the following method 1 is 30 cm. ３ mm / (m ２The photosensitive resin composition according to any one of [1] to

[22] , wherein the oxygen permeability coefficient is 240°C or higher, as measured using a thermomechanical analyzer (TMA) under the following conditions: an initial temperature of 30°C, a measurement temperature range of 30 to 400°C, and a heating rate of 5°C / min. (Method 1) The photosensitive resin composition is cured at 230°C for 3 hours to obtain a cured product having a size of 100 mm x 100 mm x 10 μm in thickness. The oxygen permeability coefficient of the cured product is measured using a differential pressure method in accordance with JIS K 7126-2:2006.

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

[23] , wherein the glass transition temperature (Tg) of the cured product obtained by curing the photosensitive resin composition at 230°C for 3 hours is 240°C or higher, as measured using a thermomechanical analyzer (TMA) under the following conditions: an initial temperature of 30°C, a measurement temperature range of 30 to 400°C, and a heating rate of 5°C / min.

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

[24] , wherein a cured product obtained by curing the photosensitive resin composition at 230°C for 3 hours has a breaking elongation of 10% or more, as measured using a tensile tester at 23°C and an elongation rate of 5 mm / min in accordance with JIS K 7161: 2014.

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

[25] , wherein a cured product obtained by curing the photosensitive resin composition at 230°C for 3 hours has a tensile modulus of 1.0 GPa or more and 5.0 GPa or less, as measured using a tensile tester at 23°C and an elongation rate of 5 mm / min in accordance with JIS K 7161: 2014.

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

[26] , wherein a cured product obtained by curing the photosensitive resin composition at 230°C for 3 hours has a storage modulus at 30°C of 1.0 GPa or more and 6.0 GPa or less, as measured by dynamic mechanical analysis (DMA).

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

[27] , which can be used in a semiconductor device.

[29] A cured product of the photosensitive resin composition according to any one of [1] to

[28] .

[30] A semiconductor device comprising the cured product according to

[29] .

[31] The semiconductor device according to

[30] , comprising: an interlayer insulating film; a resin film comprising the cured product on the interlayer insulating film; and rewiring embedded in the resin film.

[0009] According to the present invention, it is possible to provide a photosensitive resin composition and a cured product that can improve the performance balance between patterning properties and the reliability of the resulting semiconductor device, as well as a semiconductor device with improved reliability.

[0010] 1 is a schematic cross-sectional view showing an example of the structure of a semiconductor device.

[0011] Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. The drawings are for illustrative purposes only. The shapes and dimensional ratios of the components in the drawings do not necessarily correspond to the actual products.

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

[0013] The photosensitive resin composition of this embodiment includes a polyimide (A) having a double bond in a side chain, a crosslinking agent (B) containing a (meth)acrylate compound, a polymerization initiator (C), and an antioxidant (D) having an isocyanuric acid skeleton. In this embodiment, by using a combination of the polyimide (A) having a double bond in a side chain, the crosslinking agent (B) containing a (meth)acrylate compound, the polymerization initiator (C), and the antioxidant (D) having an isocyanuric acid skeleton, it is possible to obtain a photosensitive resin composition that can improve the performance balance between patterning ability and the reliability of the resulting semiconductor device. Each component will be described below.

[0014] <Antioxidant (D)> The antioxidant (D) of this embodiment has an isocyanuric acid skeleton. The antioxidant (D) of this embodiment is not particularly limited as long as it is an antioxidant having an isocyanuric acid skeleton, and includes, for example, at least one selected from the group consisting of phenolic antioxidants, phosphite antioxidants, and thioether antioxidants, and preferably includes a phenolic antioxidant, and more preferably includes a hindered phenolic antioxidant. From the viewpoint of further improving the performance balance of patterning ability, copper adhesion, mechanical strength, and reliability of the obtained semiconductor device, the antioxidant (D) of this embodiment preferably includes a compound represented by the following general formula (1):

[0015]

[0016] In general formula (1), R １１ , R １２ and R １３ each independently represents a hydrogen atom, a hydroxy group, an alkyl group or alkoxy group having 1 to 20 carbon atoms which may contain a hydroxy group, or an aryl group or aralkyl group having 6 to 30 carbon atoms which may contain at least one substituent selected from the group consisting of a hydroxy group, an alkyl group, and an alkoxy group.

[0017] In general formula (1), R １１ , R １２ and R １３ is, from the viewpoint of further improving the performance balance among patterning property, copper adhesion, mechanical strength, and reliability of the obtained semiconductor device, preferably an aryl group or aralkyl group having 6 to 30 carbon atoms which may contain at least one substituent selected from the group consisting of a hydroxy group and an alkyl group, more preferably an aryl group or aralkyl group having 6 to 30 carbon atoms which contains at least one substituent selected from the group consisting of a hydroxy group and an alkyl group, even more preferably an aryl group or aralkyl group having 6 to 30 carbon atoms which contains a hydroxy group and an alkyl group as a substituent, even more preferably an aryl group or aralkyl group having 8 to 20 carbon atoms which contains a hydroxy group and an alkyl group as a substituent, even more preferably an aryl group or aralkyl group having 10 to 16 carbon atoms which contains a hydroxy group and an alkyl group as a substituent, even more preferably an aryl group or aralkyl group having 11 to 15 carbon atoms which contains a hydroxy group and an alkyl group as a substituent, and even more preferably an aralkyl group having 11 to 15 carbon atoms which contains a hydroxy group and an alkyl group as a substituent.

[0018] In general formula (1), R １１ , R １２ and R １３ At least one of the groups is preferably a group represented by the following general formula (2), from the viewpoint of further improving the balance of performance among patterning properties, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device.

[0019]

[0020] In the general formula (2), W represents a single bond or an alkylene group having 1 to 5 carbon atoms, and R ２０ represents a hydrogen atom, a hydroxy group, or an alkyl or alkoxy group having 1 to 5 carbon atoms which may contain a hydroxy group, and when there are a plurality of R ２０ They may be the same or different, and * indicates a bond.

[0021] In general formula (1), R １１ , R １２ and R １３ is preferably R from the viewpoint of further improving the balance of performance among patterning property, copper adhesion, mechanical strength, and reliability of the semiconductor device obtained. １１ , R １２ and R １３ are groups represented by general formula (2), and more preferably R １１ , R １２ and R １３ are all groups represented by general formula (2).

[0022] In general formula (2), W is preferably a single bond or an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms, and even more preferably a methylene group, from the viewpoint of further improving the balance of performance among patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device.

[0023] In general formula (2), R ２０ is preferably a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom, a hydroxy group, a methyl group, or a t-butyl group, from the viewpoint of further improving the balance of performance among patterning properties, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device.

[0024] In general formula (2), R ２０ Preferably, at least one of the groups is a hydroxy group, from the viewpoint of further improving the balance of performance among patterning properties, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device.

[0025] In general formula (2), R ２０In order to further improve the balance of performance among patterning property, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, preferably 0 to 3 of R are hydrogen atoms, more preferably 1 or 2 are hydrogen atoms, and even more preferably 1 is a hydrogen atom. ２０ is preferably R at the meta position of W from the viewpoint of further improving the balance of performance among patterning property, copper adhesion, mechanical strength, and reliability of the semiconductor device obtained. ２０ is a hydrogen atom.

[0026] In general formula (2), R ２０ In order to further improve the balance of performance among patterning property, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, preferably, one to three of R are hydroxy groups, more preferably, one to two are hydroxy groups, and even more preferably, one is a hydroxy group. ２０ is preferably R at the meta position of W from the viewpoint of further improving the balance of performance among patterning property, copper adhesion, mechanical strength, and reliability of the semiconductor device obtained. ２０ is a hydroxy group.

[0027] In general formula (2), R ２０ In order to further improve the balance of performance among patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, preferably 0 to 3 of R are methyl groups, more preferably 1 to 2 of R are methyl groups, and even more preferably 2 of R are methyl groups. ２０ is preferably R at the ortho position of W from the viewpoint of further improving the balance of performance among patterning property, copper adhesion, mechanical strength, and reliability of the semiconductor device obtained. ２０ is a methyl group.

[0028] In general formula (2), R ２０ In order to further improve the balance of performance among patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, preferably 0 to 3 of R are t-butyl groups, more preferably 1 to 2 are t-butyl groups, and even more preferably 1 is t-butyl group. ２０is preferably R at the para-position of W from the viewpoint of further improving the balance of performance among patterning property, copper adhesion, mechanical strength, and reliability of the semiconductor device obtained. ２０ is a t-butyl group.

[0029] In general formula (1), R １１ , R １２ and R １３ From the viewpoint of further improving the balance of performance among patterning properties, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, preferably two of the functional groups are the same, and more preferably all three of the functional groups are the same.

[0030] From the viewpoint of further improving the performance balance among patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, the content of the antioxidant (D) in the photosensitive resin composition of the present embodiment is, when the total amount of the solids in the photosensitive resin composition is taken as 100 parts by mass, preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.1 parts by mass or more, even more preferably 0.3 parts by mass or more, even more preferably 0.5 parts by mass or more, and even more preferably 0.6 parts by mass or more, and is preferably 10.0 parts by mass or less, more preferably 7.0 parts by mass or less, even more preferably 5.0 parts by mass or less, even more preferably 4.0 parts by mass or less, even more preferably 3.5 parts by mass or less, and even more preferably 3.0 parts by mass or less. From the viewpoint of further improving the performance balance of patterning ability, copper adhesion, mechanical strength, and the reliability of the resulting semiconductor device, the content of the antioxidant (D) in the photosensitive resin composition of this embodiment is preferably 0.01 to 10.0 parts by mass, more preferably 0.05 to 7.0 parts by mass, even more preferably 0.1 to 5.0 parts by mass, even more preferably 0.3 to 4.0 parts by mass, even more preferably 0.5 to 3.5 parts by mass, and even more preferably 0.6 to 3.0 parts by mass, based on 100 parts by mass of the total solid content in the photosensitive resin composition. Here, in this specification, the term "solid content in the photosensitive resin composition" refers to non-volatile components, and more specifically, to components other than the organic solvent.

[0031] <Polyimide (A)> The polyimide (A) of this embodiment has a double bond in a side chain. The double bond in the polyimide (A) preferably includes a carbon-carbon double bond, and more preferably includes a polymerizable carbon-carbon double bond. From the viewpoint of further improving the performance balance among patterning ability, copper adhesion, mechanical strength, and the reliability of the resulting semiconductor device, the polyimide (A) of this embodiment preferably includes a structural unit represented by the following general formula (3):

[0032]

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

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

[0035]

[0036] In 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 R exists in multiple places ２ may be the same or different, and 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 when there are a plurality of R ３may be the same or different, and * represents a bond. 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 R exists in multiple places ５ 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), R １ 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 even more preferably a hydrogen atom or a methyl group. １ and R ２ are each independently preferably 0 to 3 hydrogen atoms, more preferably 0 to 2 hydrogen atoms, and even more preferably 1 hydrogen atom. 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, even more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

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

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

[0040]

[0041] In 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; multiple Qs may be the same or different; R represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms; multiple Rs may be the same or different; X represents a single bond, -SO ２ It represents -, -C(=O)-, a linear or branched alkylene group having 1 to 5 carbon atoms, a linear or branched fluoroalkylene group having 1 to 5 carbon atoms, or a substituted or unsubstituted fluorene group.

[0042] In general formula (4), m1 and m2 are preferably 0 to 2, more preferably 0 or 1, from the viewpoint of further improving the performance balance of patterning ability, copper adhesion, mechanical strength, and the reliability of the resulting semiconductor device. 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, and 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 even 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 even more preferably a hydrogen atom. In general formula (4), X is preferably any one selected from the group consisting of a linear or branched alkylene group having 1 to 5 carbon atoms and a substituted or unsubstituted fluorene group, more preferably any one selected from the group consisting of a linear or branched alkylene group having 1 to 3 carbon atoms and an unsubstituted fluorene group, and even more preferably a linear or branched alkylene group having 1 to 3 carbon atoms. Here, in the substituted or unsubstituted fluorene group, the 9-position of the fluorene is the bonding site.

[0043] For these reasons, 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 among patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device:

[0044]

[0045] In 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; multiple Qs may be the same or different; R represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms; multiple Rs may be the same or different; X represents a single bond, -SO ２represents -, -C(=O)-, a linear or branched alkylene group having 1 to 5 carbon atoms, a linear or branched fluoroalkylene group having 1 to 5 carbon atoms, or a substituted or unsubstituted fluorene group, and Y represents a divalent organic group.

[0046] In the general formula (5), preferred embodiments of Q, R, X, and Y are the same as the preferred embodiments of X, Q, and R in the general formula (4) and Y in the general formula (3), respectively.

[0047] From the viewpoint of further improving the balance of performance among patterning properties, copper adhesion, mechanical strength, and the reliability of the resulting semiconductor device, the structural unit (a) of this embodiment is preferably a structural unit (a) represented by general formula (5), in which at least one of m1 and m2 is 1 or more. ｐ ) and a structural unit (a) represented by general formula (5), in which m1 and m2 are both 0 ｑ ) is included.

[0048] The structural unit (a) in the polyimide (A) of this embodiment ｐ The content of the structural unit (a) is determined from the viewpoint of further improving the balance of performance among patterning property, copper adhesion, mechanical strength, and reliability of the semiconductor device obtained. ｐ ) and the structural unit (a ｑ When the total content of the structural units (a) in the polyimide (A) of this embodiment is taken as 100 mol %, the content is preferably 15 mol % or more, more preferably 20 mol % or more, even more preferably 30 mol % or more, even more preferably 35 mol % or more, even more preferably 40 mol % or more, even more preferably 45 mol % or more, even more preferably 50 mol % or more, even more preferably 60 mol % or more, even more preferably 70 mol % or more, even more preferably 80 mol % or more, even more preferably 90 mol % or more, and is preferably 100 mol % or less, more preferably 99 mol % or less, even more preferably 95 mol % or less. ｐ The content of the structural unit (a) is determined from the viewpoint of further improving the balance of performance among patterning property, copper adhesion, mechanical strength, and reliability of the semiconductor device obtained. ｐ ) and the structural unit (a ｑ) is taken as 100 mol%, the content is preferably 15 mol% or more and 100 mol% or less, more preferably 20 mol% or more and 100 mol% or less, even more preferably 30 mol% or more and 100 mol% or less, even more preferably 35 mol% or more and 100 mol% or less, even more preferably 40 mol% or more and 100 mol% or less, even more preferably 45 mol% or more and 100 mol% or less, even more preferably 50 mol% or more and 100 mol% or less, even more preferably 60 mol% or more and 100 mol% or less, even more preferably 70 mol% or more and 100 mol% or less, even more preferably 80 mol% or more and 100 mol% or less, even more preferably 80 mol% or more and 99 mol% or less, and even more preferably 90 mol% or more and 95 mol% or less.

[0049] When the number of moles of imide groups contained in the polyimide (A) of this embodiment is IM and the number of moles of amide groups contained in the polyimide (A) of this embodiment is AM, the imidization ratio, expressed as {IM / (IM+AM)}×100(%), is preferably 90% or more, more preferably 95% or more, and even more preferably 98% or more, from the viewpoint of further improving the reliability of the resulting semiconductor device. The upper limit of the imidization ratio of the polyimide (A) of this embodiment is not particularly limited, but may be, for example, 100% or less. Furthermore, from the viewpoint of further improving the reliability of the resulting semiconductor device, the imidization ratio of the polyimide (A) of this embodiment is preferably 90% or more and 100% or less, more preferably 95% or more and 100% or less, and even more preferably 98% or more and 100% or less.

[0050] From the viewpoint of further improving the performance balance among patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, the content of polyimide (A) in the photosensitive resin composition of the present embodiment is, when the total amount of the solids in the photosensitive resin composition is taken as 100 parts by mass, preferably 30 parts by mass or more, more preferably 40 parts by mass or more, even more preferably 45 parts by mass or more, even more preferably 50 parts by mass or more, and still more preferably 55 parts by mass or more, and is preferably 95 parts by mass or less, more preferably 90 parts by mass or less, even more preferably 85 parts by mass or less, even more preferably 80 parts by mass or less, and still more preferably 75 parts by mass or less. Furthermore, from the viewpoint of further improving the performance balance among patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, the content of polyimide (A) in the photosensitive resin composition of this embodiment is preferably 30 parts by mass or more and 95 parts by mass or less, more preferably 40 parts by mass or more and 90 parts by mass or less, even more preferably 45 parts by mass or more and 85 parts by mass or less, even more preferably 50 parts by mass or more and 80 parts by mass or less, and still more preferably 55 parts by mass or more and 75 parts by mass or less, when the total amount of the solid contents in the photosensitive resin composition is taken as 100 parts by mass.

[0051] <Crosslinking Agent (B)> The crosslinking agent (B) of the present embodiment includes a (meth)acrylate compound. From the viewpoint of further improving the balance of performance among patterning ability, copper adhesion, mechanical strength, and reliability of the obtained semiconductor device, the crosslinking agent (B) of the present embodiment preferably includes a polyfunctional (meth)acrylate compound.

[0052] Examples of the polyfunctional (meth)acrylate compound of the present embodiment include bifunctional (meth)acrylates such as diethylene glycol di(meth)acrylate, polyethylene glycol #200 di(meth)acrylate, and polyethylene glycol #400 di(meth)acrylate; trifunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and ethoxylated isocyanuric acid triacrylate; and pentaerythritol tetra(meth)acrylate. tetrafunctional (meth)acrylates such as dipentaerythritol hexa(meth)acrylate; octafunctional (meth)acrylates such as tripentaerythritol octa(meth)acrylate; and decafunctional (meth)acrylates such as tetrapentaerythritol deca(meth)acrylate. The polyfunctional (meth)acrylate compound of the present embodiment may contain one or more of these.

[0053] From the viewpoint of further improving the performance balance among patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, the crosslinking agent (B) of the present embodiment preferably contains a polyfunctional (meth)acrylate compound having 3 to 20 (meth)acryloyloxy groups or (meth)acryloyl groups in the molecule, more preferably contains a polyfunctional (meth)acrylate compound having 4 to 15 (meth)acryloyloxy groups or (meth)acryloyl groups in the molecule, and even more preferably contains a polyfunctional (meth)acrylate compound having 5 to 10 (meth)acryloyloxy groups or (meth)acryloyl groups in the molecule.

[0054] The crosslinking agent (B) of this embodiment may contain a (meth)acrylate compound having an isocyanuric acid skeleton. The number of (meth)acryloyloxy groups or (meth)acryloyl groups contained in the (meth)acrylate compound having an isocyanuric acid skeleton of this embodiment is preferably 1 to 6, more preferably 2 to 3, in the molecule.

[0055] The crosslinking agent (B) of this embodiment preferably contains an epoxy compound from the viewpoint of further improving the balance of performance among patterning properties, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device.

[0056] From the viewpoint of further improving the performance balance of patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, the epoxy compound of this embodiment preferably contains an epoxy compound having a (meth)acryloyloxy group or a (meth)acryloyl group. The number of glycidyl groups contained in the molecule of the epoxy compound having a (meth)acryloyloxy group or a (meth)acryloyl group of this embodiment is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1. The number of (meth)acryloyloxy groups or (meth)acryloyl groups contained in the molecule of the epoxy compound having a (meth)acryloyloxy group or a (meth)acryloyl group of this embodiment is preferably 0 to 6, more preferably 0 to 2, and even more preferably 1.

[0057] The epoxy compound of this embodiment may include an epoxy compound having a bisphenol skeleton. The number of glycidyl groups contained in the molecule of the epoxy compound having a bisphenol skeleton of this embodiment is preferably 1 to 6, more preferably 2 to 4, and even more preferably 3.

[0058] From the viewpoint of further improving the performance balance among patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, the content of the crosslinking agent (B) in the photosensitive resin composition of the present embodiment is, when the total amount of the solids in the photosensitive resin composition is taken as 100 parts by mass, preferably 1 part by mass or more, more preferably 5 parts by mass or more, even more preferably 8 parts by mass or more, even more preferably 10 parts by mass or more, even more preferably 12 parts by mass or more, even more preferably 14 parts by mass or more, and is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, even more preferably 35 parts by mass or less, even more preferably 32 parts by mass or less, even more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less. Furthermore, from the viewpoint of further improving the performance balance among patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, the content of the crosslinking agent (B) in the photosensitive resin composition of the present embodiment is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 5 parts by mass or more and 40 parts by mass or less, even more preferably 8 parts by mass or more and 35 parts by mass or less, even more preferably 10 parts by mass or more and 32 parts by mass or less, even more preferably 12 parts by mass or more and 25 parts by mass or less, and even more preferably 14 parts by mass or more and 20 parts by mass or less, when the total amount of the solids in the photosensitive resin composition is taken as 100 parts by mass.

[0059] <Polymerization initiator (C)> As the polymerization initiator (C) of this embodiment, a conventionally known polymerization initiator can be used as long as the effects of the present invention can be exhibited, and examples thereof include a photoradical generator and a thermal radical generator. From the viewpoint of further improving the performance balance of patterning ability, copper adhesion, mechanical strength, and the reliability of the obtained semiconductor device, the polymerization initiator (C) of this embodiment preferably contains a photoradical generator, and more preferably contains both a photoradical generator and a thermal radical generator.

[0060] Examples of the photoradical generator of this embodiment include alkylphenone-type polymerization initiators, oxime ester-type polymerization initiators, and acylphosphine oxide-type polymerization initiators. Specific examples include 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]- [N-yl]-2-hydroxy-2-methyl-1-propan-1-one, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), 2-(dimethylamino)-1-(4-(4-morpholino)phenyl)-2-(phenylmethyl)-1-butanone, Irgacure OXE01 (manufactured by BASF Japan Ltd.), Irgacure OXE02 (manufactured by BASF Japan Ltd.), Irgacure OXE03 (manufactured by BASF Japan Ltd.), Irgacure OXE04 (manufactured by BASF Japan Ltd.), and the like. The polymerization initiator (C) of the present embodiment may contain one or more of these. From the viewpoint of further improving the performance balance among patterning ability, copper adhesion, mechanical strength, and reliability of the obtained semiconductor device, the polymerization initiator (C) of the present embodiment preferably contains an oxime ester polymerization initiator, and more preferably contains Irgacure OXE01.

[0061] 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, and 2,2-bis(4,4-dibutylperoxycyclohexyl)propane. , 1,1-bis(t-butylperoxy)cyclododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di(m-toluoylperoxy)hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate , 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butyl peroxyacetate, 2,2-bis(t-butylperoxy)butane, t-butyl peroxybenzoate, 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-butyl peroxy organic peroxides such as methyl 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 benzoyl peroxide;Examples of suitable 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, and 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide]; and the polymerization initiator (C) of this embodiment can contain one or more of these. From the viewpoint of further improving the performance balance of patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, the polymerization initiator (C) of this embodiment preferably contains an organic peroxide, and more preferably contains dicumyl peroxide.

[0062] From the viewpoint of further improving the performance balance among patterning ability, copper adhesion, mechanical strength, and the reliability of the resulting semiconductor device, the content of the polymerization initiator (C) in the photosensitive resin composition of this embodiment is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 4 parts by mass or more, and even more preferably 5 parts by mass or more, and is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, even more preferably 15 parts by mass or less, and even more preferably 12 parts by mass or less, when the total amount of the solids in the photosensitive resin composition is taken as 100 parts by mass. From the viewpoint of further improving the performance balance among patterning ability, copper adhesion, mechanical strength, and the reliability of the resulting semiconductor device, the content of the polymerization initiator (C) in the photosensitive resin composition of this embodiment is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 3 parts by mass or more and 20 parts by mass or less, even more preferably 4 parts by mass or more and 15 parts by mass or less, and even more preferably 5 parts by mass or more and 12 parts by mass or less, when the total amount of the solids in the photosensitive resin composition is taken as 100 parts by mass.

[0063] From the viewpoint of further improving the performance balance among patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, the total content of the polyimide (A), crosslinking agent (B), polymerization initiator (C), and antioxidant (D) in the photosensitive resin composition of this embodiment is, when the total amount of the solids in the photosensitive resin composition is taken as 100 parts by mass, preferably 80 parts by mass or more, more preferably 85 parts by mass or more, even more preferably 90 parts by mass or more, even more preferably 92 parts by mass or more, and still more preferably 94 parts by mass or more, and is preferably 100 parts by mass or less, more preferably 99 parts by mass or less, even more preferably 98 parts by mass or less, even more preferably 97 parts by mass or less, and still more preferably 96 parts by mass or less. Furthermore, from the viewpoint of further improving the performance balance among patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, the total content of the polyimide (A), crosslinking agent (B), polymerization initiator (C), and antioxidant (D) in the photosensitive resin composition of this embodiment is preferably 80 parts by mass or more and 100 parts by mass or less, more preferably 85 parts by mass or more and 99 parts by mass or less, even more preferably 90 parts by mass or more and 98 parts by mass or less, even more preferably 92 parts by mass or more and 97 parts by mass or less, and still more preferably 94 parts by mass or more and 96 parts by mass or less, when the total amount of the solids in the photosensitive resin composition is taken as 100 parts by mass.

[0064] When the content of the polyimide (A) of the present embodiment is taken as 100 parts by mass, the content of the crosslinking agent (B) of the present embodiment is preferably 1 part by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, and even more preferably 20 parts by mass or more, from the viewpoint of further improving the performance balance of patterning ability, copper adhesion, mechanical strength, and reliability of the obtained semiconductor device, and is preferably 80 parts by mass or less, more preferably 60 parts by mass or less, even more preferably 50 parts by mass or less, even more preferably 40 parts by mass or less, and even more preferably 35 parts by mass or less. Furthermore, when the content of the polyimide (A) of this embodiment is taken as 100 parts by mass, the content of the crosslinking agent (B) of this embodiment is preferably 1 part by mass or more and 80 parts by mass or less, more preferably 5 parts by mass or more and 60 parts by mass or less, even more preferably 10 parts by mass or more and 50 parts by mass or less, even more preferably 15 parts by mass or more and 40 parts by mass or less, and even more preferably 20 parts by mass or more and 35 parts by mass or less, from the viewpoint of further improving the performance balance of patterning ability, copper adhesion, mechanical strength, and reliability of the obtained semiconductor device.

[0065] From the viewpoint of further improving the performance balance among patterning ability, copper adhesion, mechanical strength, and the reliability of the resulting semiconductor device, the content of the polymerization initiator (C) of the present embodiment is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, even more preferably 7 parts by mass or more, and even more preferably 9 parts by mass or more, and is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, even more preferably 22 parts by mass or less, even more preferably 20 parts by mass or less, and even more preferably 17 parts by mass or less, from the viewpoint of further improving the performance balance among patterning ability, copper adhesion, mechanical strength, and the reliability of the resulting semiconductor device, when the content of the polyimide (A) of the present embodiment is taken as 100 parts by mass, the content of the polymerization initiator (C) of the present embodiment is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 3 parts by mass or more and 25 parts by mass or less, even more preferably 5 parts by mass or more and 22 parts by mass or less, even more preferably 7 parts by mass or more and 20 parts by mass or less, and even more preferably 9 parts by mass or more.

[0066] When the content of the polyimide (A) of the present embodiment is taken as 100 parts by mass, the content of the antioxidant (D) of the present embodiment is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, even more preferably 0.3 parts by mass or more, even more preferably 0.5 parts by mass or more, and still more preferably 0.7 parts by mass or more, from the viewpoint of further improving the performance balance among patterning ability, copper adhesion, mechanical strength, and reliability of the obtained semiconductor device, and is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 7 parts by mass or less, and still more preferably 5 parts by mass or less. Furthermore, when the content of the polyimide (A) of the present embodiment is taken as 100 parts by mass, the content of the antioxidant (D) of the present embodiment is preferably 0.01 parts by mass or more and 20 parts by mass or less, more preferably 0.1 parts by mass or more and 15 parts by mass or less, even more preferably 0.3 parts by mass or more and 10 parts by mass or less, even more preferably 0.5 parts by mass or more and 7 parts by mass or less, and still more preferably 0.7 parts by mass or more and 5 parts by mass or less, from the viewpoint of further improving the performance balance among patterning ability, copper adhesion, mechanical strength, and reliability of the obtained semiconductor device.

[0067] <Adhesion Aid> From the viewpoint of further improving adhesion, the photosensitive resin composition of this embodiment preferably further contains an adhesion aid. Examples of the adhesion aid of this embodiment include aminosilanes such as bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldiethoxysilane, and N-phenyl-γ-aminopropyltrimethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β-(3, Examples of suitable silanes include epoxy silanes such as 4-epoxycyclohexyl)ethyltrimethoxysilane and γ-glycidylpropyltrimethoxysilane; acrylic silanes such as γ-(methacryloxypropyl)trimethoxysilane, γ-(methacryloxypropyl)methyldimethoxysilane, and γ-(methacryloxypropyl)methyldiethoxysilane; mercaptosilanes such as 3-mercaptopropyltrimethoxysilane; vinyl silanes such as vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, and vinyltrimethoxysilane; ureidosilanes such as 3-ureidopropyltriethoxysilane; and acid anhydride functional silanes such as 3-trimethoxysilylpropylsuccinic anhydride. The adhesion aid of the present embodiment may contain one or more of these. Among these, from the viewpoint of further improving adhesion, the adhesion aid of the present embodiment preferably contains one or more selected from the group consisting of epoxy silanes and acid anhydride functional silanes, and more preferably contains both 3-glycidoxypropyltrimethoxysilane and 3-trimethoxysilylpropylsuccinic anhydride.

[0068] From the viewpoint of further improving adhesion, the content of the adhesion aid in the photosensitive resin composition of this embodiment is preferably 0.1 parts by mass or more, more preferably 1.0 parts by mass or more, even more preferably 1.5 parts by mass or more, and preferably 10.0 parts by mass or less, more preferably 8.0 parts by mass or less, and even more preferably 7.0 parts by mass or less, relative to 100 parts by mass of the polyimide (A). From the viewpoint of further improving adhesion, the content of the adhesion aid in the photosensitive resin composition of this embodiment is preferably 0.1 parts by mass or more and 10.0 parts by mass or less, more preferably 1.0 parts by mass or more and 8.0 parts by mass or less, and even more preferably 1.5 parts by mass or more and 7.0 parts by mass or less, relative to 100 parts by mass of the polyimide (A).

[0069] <Surfactant> The photosensitive resin composition of this embodiment preferably further contains a surfactant. Examples of the surfactant of this embodiment include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; polyoxyethylene dilaurate, polyoxyethylene distearate, and other polyoxyethylene dialkyl esters; nonionic surfactants such as EFTOP EF301, EFTOP EF303, and EFTOP EF352 (manufactured by Shin-Akita Chemical Industry Co., Ltd.), Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F444, and Megafac F445. Fluorine-based surfactants commercially available under the names of Gafac F470, Megafac F471, Megafac F475, Megafac F482, Megafac F477 (manufactured by DIC Corporation), Fluorad FC-430, Fluorad FC-431, Novec FC4430, Novec FC4432 (manufactured by 3M Japan Ltd.), Surflon S-381, Surflon S-382, Surflon S-383, Surflon S-393, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106 (manufactured by AGC Seimi Chemical Co., Ltd.), etc.; organosiloxane copolymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); (meth)acrylic acid copolymer Polyflow No. 57, 95 (manufactured by Kyoeisha Chemical Co., Ltd.); and silicone-based surfactants such as polyether-modified dimethylsiloxane, and the surfactant of the present embodiment may contain one or more of these. Among these, the surfactant of the present embodiment preferably contains a silicone-based surfactant.

[0070] The content of the surfactant in the photosensitive resin composition of the present embodiment is preferably 0.001 parts by mass or more and 0.5 parts by mass or less, and more preferably 0.01 parts by mass or more and 0.1 parts by mass or less, relative to 100 parts by mass of the polyimide (A).

[0071] <Curing Catalyst> The photosensitive resin composition of this embodiment preferably further contains a curing catalyst from the viewpoint of further improving the performance balance of patterning ability, copper adhesion, mechanical strength, and the reliability of the resulting semiconductor device. Examples of curing catalysts of this embodiment include phosphorus atom-containing compounds such as organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds; amidines such as dicyandiamide, 2-phenyl-4,5-dihydroxymethylimidazole, 1,8-diazabicyclo[5.4.0]undecene-7, and benzyldimethylamine, tertiary amines and derivatives thereof; and nitrogen atom-containing compounds such as quaternary ammonium salts of the above amidines or tertiary amines. The curing catalyst of this embodiment can contain one or more of these compounds. From the viewpoint of further improving the performance balance of patterning ability, copper adhesion, mechanical strength, and the reliability of the resulting semiconductor device, the curing catalyst of this embodiment preferably contains a phosphorus atom-containing compound, and more preferably contains a tetra-substituted phosphonium compound.

[0072] From the viewpoint of further improving the performance balance among patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, the content of the curing catalyst in the photosensitive resin composition of the present embodiment is preferably 0.1 parts by mass or more and 5.0 parts by mass or less, more preferably 0.5 parts by mass or more and 2.0 parts by mass or less, relative to 100 parts by mass of the polyimide (A).

[0073] <Other Additives> The photosensitive resin composition of the present embodiment may further contain other additives such as a leveling agent, a flame retardant, and a plasticizer, as needed.

[0074] <Organic Solvent> From the viewpoint of further improving the performance balance between patterning ability and copper adhesion, the photosensitive resin composition of this embodiment preferably further contains an organic solvent. From the viewpoint of further improving the performance balance between patterning ability and copper adhesion, the organic solvent of this embodiment is preferably γ-butyrolactone (GBL), γ-valerolactone (GVL), 2,6-lutidine, pyruvic acid N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropionamide, dimethyl sulfoxide (DMSO), diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGME A), methyl lactate, ethyl lactate (EL), butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and 3-methyl-2-oxazolidone, more preferably, it contains one or two or more selected from the group consisting of γ-butyrolactone (GBL) and ethyl lactate (EL), and even more preferably, it contains both γ-butyrolactone (GBL) and ethyl lactate (EL).

[0075] From the viewpoint of further improving the performance balance between patterning ability and copper adhesion, the content of the organic solvent in the photosensitive resin composition of the present embodiment is, when the total amount of the solids in the photosensitive resin composition is taken as 100 parts by mass, preferably 50 parts by mass or more, more preferably 100 parts by mass or more, even more preferably 150 parts by mass or more, even more preferably 200 parts by mass or more, even more preferably 230 parts by mass or more, and even more preferably 250 parts by mass or more, and is preferably 1000 parts by mass or less, more preferably 800 parts by mass or less, even more preferably 600 parts by mass or less, even more preferably 500 parts by mass or less, even more preferably 400 parts by mass or less, and even more preferably 350 parts by mass or less. Furthermore, from the viewpoint of further improving the performance balance between patterning ability and copper adhesion, the content of the organic solvent in the photosensitive resin composition of the present embodiment is preferably 50 parts by mass or more and 1,000 parts by mass or less, more preferably 100 parts by mass or more and 800 parts by mass or less, even more preferably 150 parts by mass or more and 600 parts by mass or less, even more preferably 200 parts by mass or more and 500 parts by mass or less, even more preferably 230 parts by mass or more and 400 parts by mass or less, and even more preferably 250 parts by mass or more and 350 parts by mass or less, when the total amount of the solids in the photosensitive resin composition is taken as 100 parts by mass.

[0076] From the viewpoint of further improving environmental compatibility, the content of fluorine atoms in the photosensitive resin composition of this embodiment is preferably 0 parts by mass or more and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less, even more preferably 1 part by mass or less, even more preferably 0.1 parts by mass or less, even more preferably 0.05 parts by mass or less, and even more preferably 0.01 parts by mass or less, when the total amount of solids in the photosensitive resin composition is 100 parts by mass. Furthermore, from the viewpoint of further improving environmental compatibility, the content of fluorine atoms in the photosensitive resin composition of this embodiment is preferably 0 parts by mass or more and 10 parts by mass or less, more preferably 0 parts by mass or more and 5 parts by mass or less, even more preferably 0 parts by mass or more and 3 parts by mass or less, even more preferably 0 parts by mass or more and 1 part by mass or less, even more preferably 0 parts by mass or more and 0.1 parts by mass or less, even more preferably 0 parts by mass or more and 0.05 parts by mass or less, and even more preferably 0 parts by mass or more and 0.01 parts by mass or less, when the total amount of solids in the photosensitive resin composition is 100 parts by mass.

[0077] From the viewpoint of further improving environmental compatibility, the content of the fluorine atom-containing polymer in the photosensitive resin composition of the present embodiment is preferably 0 parts by mass or more and preferably 30 parts by mass or less, more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, even more preferably 1 part by mass or less, even more preferably 0.1 parts by mass or less, even more preferably 0.05 parts by mass or less, and even more preferably 0.01 parts by mass or less, when the total amount of solids in the photosensitive resin composition is 100 parts by mass. Furthermore, from the viewpoint of further improving environmental compatibility, the content of the fluorine atom-containing polymer in the photosensitive resin composition of the present embodiment is preferably 0 parts by mass or more and 30 parts by mass or less, more preferably 0 parts by mass or more and 20 parts by mass or less, even more preferably 0 parts by mass or more and 10 parts by mass or less, even more preferably 0 parts by mass or more and 5 parts by mass or less, even more preferably 0 parts by mass or more and 1 part by mass or less, even more preferably 0 parts by mass or more and 0.1 parts by mass or less, even more preferably 0 parts by mass or more and 0.05 parts by mass or less, and even more preferably 0 parts by mass or more and 0.01 parts by mass or less, when the total amount of the solids in the photosensitive resin composition is 100 parts by mass.

[0078] From the viewpoint of further improving the performance balance among patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, the content of the alkali-soluble resin in the photosensitive resin composition of the present embodiment is preferably 0 parts by mass or more and preferably 30 parts by mass or less, more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, even more preferably 1 part by mass or less, even more preferably 0.1 parts by mass or less, even more preferably 0.05 parts by mass or less, and even more preferably 0.01 parts by mass or less, when the total amount of solids in the photosensitive resin composition is taken as 100 parts by mass. From the viewpoint of further improving the performance balance among patterning ability, copper adhesion, mechanical strength, and reliability of the resulting semiconductor device, the content of the alkali-soluble resin in the photosensitive resin composition of this embodiment is preferably 0 to 30 parts by mass, more preferably 0 to 20 parts by mass, even more preferably 0 to 10 parts by mass, even more preferably 0 to 5 parts by mass, even more preferably 0 to 1 part by mass, even more preferably 0 to 0.1 parts by mass, even more preferably 0 to 0.05 parts by mass, and even more preferably 0 to 0.01 parts by mass, based on 100 parts by mass of the total solid content in the photosensitive resin composition. In this specification, the alkali-soluble resin is a resin that dissolves in an alkaline developer to a degree sufficient for patterning.

[0079] <Method for preparing photosensitive resin composition> The method for preparing the photosensitive resin composition of the present embodiment is not limited, and a known method can be used depending on the components contained in the photosensitive resin composition. For example, the photosensitive resin composition can be prepared by mixing and dissolving the above-mentioned components in a solvent.

[0080] <Oxygen Permeability Coefficient> The oxygen permeability coefficient of the photosensitive resin composition of this embodiment is preferably 30 cm ３ mm / (m ２ · day · atm) or less, more preferably 25 cm ３ mm / (m ２ ·day·atm) or less, more preferably 20 cm ３ mm / (m ２The lower limit of the oxygen permeability coefficient of the photosensitive resin composition of the present embodiment is not particularly limited, but is preferably 1 cm ３ mm / (m ２ In addition, the oxygen permeability coefficient of the photosensitive resin composition of the present embodiment may be preferably 1 cm or more, from the viewpoint of further improving the reliability of the semiconductor device obtained. ３ mm / (m ２ ・day・atm) or more 30cm ３ mm / (m ２ · day · atm) or less, more preferably 1 cm ３ mm / (m ２ ・day・atm) or more 25cm ３ mm / (m ２ ·day·atm) or less, more preferably 1 cm ３ mm / (m ２ ・day・atm) or more 20cm ３ mm / (m ２ ・day・atm) or less.

[0081] The oxygen permeability coefficient of the photosensitive resin composition of this embodiment can be measured by, for example, the following method: First, the photosensitive resin composition is spin-coated onto the surface of a silicon wafer so that the film thickness after drying is 10 μm, and the wafer is pre-baked at 110° C. for 3 minutes. Then, the wafer is exposed to a high-pressure mercury lamp for 600 mJ / cm . ２ After that, the photoresist is post-baked in a nitrogen atmosphere at 230°C for 3 hours to prepare a cured product having a size of 100 mm x 100 mm x 10 μm in thickness. The oxygen permeability coefficient of the cured product is then measured by a differential pressure method in accordance with JIS K 7126-2:2006 under conditions of 23°C and 60% RH.

[0082] From the viewpoint of further improving the performance balance between mechanical strength and the reliability of the resulting semiconductor device, the glass transition temperature (Tg) of the photosensitive resin composition of this embodiment is preferably 240° C. or higher, more preferably 250° C. or higher, even more preferably 260° C. or higher, even more preferably 270° C. or higher, even more preferably 275° C. or higher, and even more preferably 278° C. or higher, and is preferably 350° C. or lower, more preferably 330° C. or lower, even more preferably 320° C. or lower, even more preferably 310° C. or lower, even more preferably 300° C. or lower, and even more preferably 295° C. or lower. From the viewpoint of further improving the performance balance between mechanical strength and the reliability of the resulting semiconductor device, the glass transition temperature (Tg) of the photosensitive resin composition of this embodiment is preferably 240° C. or higher and 350° C. or lower, more preferably 250° C. or higher and 330° C. or lower, even more preferably 260° C. or higher and 320° C. or lower, even more preferably 270° C. or higher and 310° C. or lower, even more preferably 275° C. or higher and 300° C. or lower, and even more preferably 278° C. or higher and 295° C.

[0083] The glass transition temperature (Tg) of the photosensitive resin composition of this embodiment can be measured by, for example, the following method: First, the photosensitive resin composition is spin-coated onto the surface of a silicon wafer so that the film thickness after drying is 10 μm, and the wafer is pre-baked at 110° C. for 3 minutes. Then, the wafer is exposed to a high-pressure mercury lamp at 600 mJ / cm ２ This is followed by post-baking for 3 hours at 230°C in a nitrogen atmosphere to produce a cured product measuring 100 mm x 100 mm x 10 μm in thickness. The glass transition temperature (Tg) of the cured product is then measured using a thermomechanical analyzer (TMA) under the following conditions: starting temperature 30°C, measurement temperature range 30 to 400°C, and temperature rise rate 5°C / min.

[0084] From the viewpoint of further improving the performance balance between the mechanical strength and the reliability of the resulting semiconductor device, the photosensitive resin composition of this embodiment has a breaking elongation of preferably 10% or more, more preferably 20% or more, even more preferably 25% or more, even more preferably 30% or more, and even more preferably 33% or more, and preferably 70% or less, more preferably 60% or less, even more preferably 50% or less, even more preferably 45% or less, and even more preferably 40% or less. From the viewpoint of further improving the performance balance between the mechanical strength and the reliability of the resulting semiconductor device, the photosensitive resin composition of this embodiment has a breaking elongation of preferably 10% or more and 70% or less, more preferably 20% or more and 60% or less, even more preferably 25% or more and 50% or less, even more preferably 30% or more and 45% or less, and even more preferably 33% or more and 40% or less.

[0085] The breaking elongation of the photosensitive resin composition of this embodiment can be measured by, for example, the following method: First, the photosensitive resin composition is spin-coated onto the surface of a silicon wafer so that the film thickness after drying is 10 μm, and the wafer is pre-baked at 110° C. for 3 minutes. Then, the wafer is exposed to a high-pressure mercury lamp at 600 mJ / cm ２ The resulting film is then post-baked at 230°C for 3 hours in a nitrogen atmosphere to produce a cured product measuring 100 mm x 100 mm x 10 µm in thickness. The cured product is then measured for elongation at break using a tensile tester in accordance with JIS K 7161:2014 at 23°C and a stretching rate of 5 mm / min.

[0086] The tensile modulus of the photosensitive resin composition of this embodiment is preferably 1.0 GPa or more, more preferably 1.5 GPa or more, even more preferably 2.0 GPa or more, and 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. The upper limit of the tensile modulus of the photosensitive resin composition of this embodiment is not particularly limited, but may be, for example, 5.0 GPa or less or 4.0 GPa or less. Furthermore, the tensile modulus of the photosensitive resin composition of this embodiment is preferably 1.0 GPa or more and 5.0 GPa or less, more preferably 1.5 GPa or more and 5.0 GPa or less, even more preferably 2.0 GPa or more and 4.0 GPa or less, from the viewpoint of further improving the performance balance between mechanical strength and the reliability of the resulting semiconductor device.

[0087] The tensile modulus of the photosensitive resin composition of this embodiment can be measured by, for example, the following method: First, the photosensitive resin composition is spin-coated onto the surface of a silicon wafer so that the film thickness after drying is 10 μm, and the wafer is pre-baked at 110° C. for 3 minutes. Then, the wafer is exposed to a high-pressure mercury lamp at 600 mJ / cm ２ The resulting film is then post-baked at 230°C for 3 hours in a nitrogen atmosphere to produce a cured product measuring 100 mm x 100 mm x 10 µm in thickness. The tensile modulus of the cured product is then measured at 23°C and a stretching rate of 5 mm / min using a tensile tester in accordance with JIS K 7161:2014.

[0088] The storage modulus of the photosensitive resin composition of this embodiment is preferably 1.0 GPa or more, more preferably 2.0 GPa or more, even more preferably 2.5 GPa or more, and 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. The upper limit of the storage modulus of the photosensitive resin composition of this embodiment is not particularly limited, but may be, for example, 6.0 GPa or less or 5.0 GPa or less. Furthermore, the storage modulus of the photosensitive resin composition of this embodiment is preferably 1.0 GPa or more and 6.0 GPa or less, more preferably 2.0 GPa or more and 6.0 GPa or less, even more preferably 2.5 GPa or more and 5.0 GPa or less, and even more preferably 3.0 GPa or more and 5.0 GPa or less, from the viewpoint of further improving the performance balance between mechanical strength and the reliability of the resulting semiconductor device.

[0089] The storage modulus of the photosensitive resin composition of this embodiment can be measured by, for example, the following method: First, the photosensitive resin composition is spin-coated onto the surface of a silicon wafer so that the film thickness after drying is 10 μm, and the wafer is pre-baked at 110° C. for 3 minutes. Then, the wafer is exposed to a high-pressure mercury lamp at 600 mJ / cm ２ After that, the film is post-baked at 230°C for 3 hours in a nitrogen atmosphere to prepare a cured product having a size of 100 mm x 100 mm x 10 µm in thickness. The storage modulus of the cured product at 30°C is then measured by dynamic mechanical analysis (DMA).

[0090] <Uses> The photosensitive resin composition of this embodiment has an improved balance of patterning properties and the reliability of the resulting semiconductor device, and can therefore be suitably used in semiconductor devices.

[0091] The photosensitive resin composition of this embodiment is suitable for use in forming resin films for semiconductor devices, such as permanent films and resists. Among these, the photosensitive resin composition of this embodiment is preferably used in applications using permanent films, due to its improved performance balance between patterning ability and the reliability of the resulting semiconductor device. The permanent film is composed of a resin film obtained by pre-baking, exposing, and developing the photosensitive resin composition, patterning it into a desired shape, and then curing it by heat treatment. The permanent film can be used as a protective film, interlayer film, dam material, etc. for semiconductor devices. The resist is composed of a resin film obtained by applying the photosensitive resin composition to an object to be masked by the resist by a method such as spin coating, roll coating, flow coating, dip coating, spray coating, or doctor coating, and then removing the solvent from the photosensitive resin composition.

[0092] <Cured Product> The cured product of this embodiment is a 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 it to form a resin film, then exposing and developing it to pattern the resin film into a desired shape, and then heat-treating the resin film to cure it. When producing a cured product, the pre-baking conditions can be, for example, 90°C or higher and 130°C or lower, and a heat treatment for 30 seconds to 1 hour or less. The heat treatment conditions can be, for example, 150°C or higher and 250°C or lower, and a heat treatment for 30 minutes to 10 hours or less.

[0093] The semiconductor device of this embodiment includes the cured product of this embodiment. The photosensitive resin composition of this embodiment has an improved balance of patterning properties and the reliability of the resulting semiconductor device, and therefore the reliability of the semiconductor device of this embodiment is improved.

[0094] From the viewpoint of further improving 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.

[0095] FIG. 1 is a schematic cross-sectional view showing an example of the structure of the semiconductor device of this embodiment. The semiconductor device 100 of this embodiment can be a semiconductor device including the above-mentioned resin film. Specifically, in the semiconductor device 100, one or more of the group consisting of the passivation film 32, the insulating layer 42, and the insulating layer 44 can be a resin film including the cured product of this embodiment. Here, the resin film is preferably a permanent film as described above.

[0096] The semiconductor device 100 is, for example, a semiconductor chip. In this case, the semiconductor device 100 is mounted on a wiring board via the bumps 52 to obtain a semiconductor package.

[0097] The semiconductor device 100 includes a semiconductor substrate on which semiconductor elements such as transistors are provided, and a multilayer wiring layer (not shown) provided on the semiconductor substrate. The uppermost layer of the multilayer wiring layer includes an interlayer insulating film 30 and a top-layer wiring 34 provided on the interlayer insulating film 30. The top-layer wiring 34 is made of, for example, aluminum (Al). A passivation film 32 is provided on the interlayer insulating film 30 and the top-layer wiring 34. An opening is provided in a portion of the passivation film 32, through which the top-layer wiring 34 is exposed.

[0098] A redistribution layer 40 is provided on the passivation film 32. The redistribution layer 40 has an insulating layer 42 provided on the passivation film 32, redistribution lines 46 provided on the insulating layer 42, and an insulating layer 44 provided on the insulating layer 42 and the redistribution lines 46. An opening connected to the top-layer wiring 34 is formed in the insulating layer 42. The redistribution lines 46 are formed on the insulating layer 42 and in the openings provided in the insulating layer 42, and are connected to the top-layer wiring 34. An opening connected to the redistribution lines 46 is formed in the insulating layer 44.

[0099] Bumps 52 are formed in the openings provided in the insulating layer 44 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.

[0100] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than those described above can be adopted as long as they do not impair the effects of the present invention.

[0101] The embodiments of the present invention will be described in detail based on examples and comparative examples, but the present invention is not limited to the examples.

[0102] <Compounds used in polymer synthesis> The following compounds were used in polymer synthesis.

[0103] 2,2-bis(3-amino-4-hydroxyphenyl)propane (hereinafter also referred to as BAPA) represented by the following formula.

[0104]

[0105] 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.

[0106]

[0107] 4,4-diamino-3,3-diethyl-5,5-dimethyldiphenylmethane (hereinafter also referred to as MED-J) represented by the following formula.

[0108]

[0109] 9,9-bis(3-amino-4-hydroxyphenyl)fluorene (hereinafter also referred to as BAHF) represented by the following formula.

[0110]

[0111] <Synthesis of Polymer 1> First, 27.5 g (106.6 mmol) of BAPA, 146.5 g (236.8 mmol) of TMPBP-TME, and 30.1 g (106.6 mmol) of MED-J were placed in an appropriately sized reaction vessel equipped with a stirrer and a condenser. Then, 767.6 g of γ-butyrolactone (GBL) was added to the reaction vessel. After bubbling nitrogen for 10 minutes, the temperature was raised to 60°C with stirring, and the reaction was carried out for 1.5 hours. The reaction was then carried out at 180°C for an additional 3 hours to polymerize BAPA, TMPBP-TME, and MED-J, producing a polymerized solution. Next, 60.2 g (426.3 mmol) of 2-isocyanatoethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.6 g (10.0 mmol) of 2-hydroxy-1,4-naphthoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.), and 83.3 g of GBL were added to the entire amount of the obtained polyimide solution (213.2 mmol in terms of hydroxyl groups). The temperature was then raised to 120°C with stirring, and the reaction was carried out for 6 hours. The obtained reaction solution was diluted with tetrahydrofuran to prepare a diluted solution, and then the diluted solution was added dropwise to methanol to precipitate a white solid. The obtained white solid was collected and vacuum-dried at a temperature of 40°C, yielding 218.1 g of Polymer 1. １ H-NMR measurement confirmed a peak in the aromatic region (6.8 ppm to 8.9 ppm) with an area ratio corresponding to the number of protons. Furthermore, based on 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 crosslinking groups was 93%. The resulting polymer 1 contained a repeating unit represented by the following formula:

[0112] (In the above formula, x:y=50:50)

[0113] <Synthesis of Polymer 2> Polymer 2 was obtained in the same manner as in the synthesis of Polymer 1, except that the amounts of BAPA, TMPBP-TME, and MED-J added were changed so that the ratio of x to y in the repeating units contained in the polymer was x:y=87:13.

[0114] <Synthesis of Polymer 3> Polymer 3 was obtained in the same manner as in the synthesis of Polymer 1, except that the amounts of BAPA, TMPBP-TME, and MED-J added were changed so that the ratio of x to y in the repeating units contained in the polymer was x:y=93:7.

[0115] <Synthesis of Polymer 4> Polymer 4 was obtained in the same manner as in the synthesis of Polymer 1, except that the amounts of BAPA and TMPBP-TME added were changed so that the ratio of x to y in the repeating units contained in the polymer was x:y=100:0, and MED-J was not added.

[0116] <Synthesis of Polymer 5> Polymer 5 was obtained in the same manner as in the synthesis of Polymer 1, except that the amounts of BAPA, TMPBP-TME, and MED-J added were changed so that the ratio of x to y in the repeating units contained in the polymer was x:y=25:75.

[0117] <Synthesis of Polymer 6> Polymer 6 was obtained in the same manner as in the synthesis of Polymer 1, except that the amounts of BAPA and TMPBP-TME added were changed so that the ratio of x' (repeating units in which 2-isocyanatoethyl acrylate is not introduced in x) to y in the repeating units contained in the polymer was x':y=100:0, MED-J was not added, and 2-isocyanatoethyl acrylate was not added to the polyimide solution, so that the introduction rate of the crosslinking group was 0%.

[0118] <Synthesis of Polymer 7> First, 40.6 g (106.6 mmol) of BAHF, 146.5 g (236.8 mmol) of TMPBP-TME, and 30.1 g (106.6 mmol) of MED-J were placed in an appropriately sized reaction vessel equipped with a stirrer and a condenser. Then, 816.5 g of γ-butyrolactone (GBL) was added to the reaction vessel. After bubbling nitrogen for 10 minutes, the temperature was raised to 60°C with stirring, and the reaction was carried out for 1.5 hours. The reaction was then carried out at 180°C for an additional 3 hours, polymerizing the BAHF, TMPBP-TME, and MED-J to produce a polymerized solution. Next, 60.2 g (426.3 mmol) of 2-isocyanatoethyl acrylate (Tokyo Chemical Industry Co., Ltd.), 1.8 g (10.0 mmol) of 2-hydroxy-1,4-naphthoquinone (Tokyo Chemical Industry Co., Ltd.), and 90.6 g of GBL were added to the entire amount of the obtained polyimide solution (213.2 mmol in terms of hydroxyl groups). The temperature was then raised to 120°C with stirring, and the reaction was carried out for 6 hours. The obtained reaction solution was diluted with tetrahydrofuran to prepare a diluted solution, and then the diluted solution was added dropwise to methanol to precipitate a white solid. The obtained white solid was collected and vacuum-dried at 40°C, yielding 220.2 g of Polymer 7. １ H-NMR analysis confirmed a peak in the aromatic region (6.8 ppm to 8.9 ppm) with an area ratio corresponding to the number of protons. Furthermore, based on 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 crosslinking groups was 85%. The resulting polymer 7 contained a repeating unit represented by the following formula:

[0119] (In the above formula, x:y=50:50)

[0120] <Components Used in Preparation of Photosensitive Resin Compositions> The following components were used in preparing the photosensitive resin compositions of the Examples and Comparative Examples.

[0121] Acrylate compound 1: a polyfunctional acrylate compound represented by the following formula (Viscoat #802, manufactured by Osaka Organic Chemical Industry Ltd.)

[0122] Acrylate compound 2: a polyfunctional acrylate compound represented by the following formula (A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.) Acrylate compound 3: a polyfunctional acrylate compound represented by the following formula (A-9300S-NT, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0123] Acrylate compound 4: a bifunctional acrylate compound represented by the following formula (Viscoat #230, manufactured by Osaka Organic Chemical Industry Ltd.)

[0124] Epoxy compound 1: 4-hydroxybutyl acrylate glycidyl ether represented by the following formula (4HBAGE, manufactured by Shinryo Corporation)

[0125] Epoxy compound 2: a trifunctional epoxy compound represented by the following formula (VG3101L, manufactured by Printec Co., Ltd.)

[0126] Polymerization initiator 1: a compound represented by the following formula (Irgacure OXE01, manufactured by BASF)

[0127] Polymerization initiator 2: Dicumyl peroxide represented by the following formula (Perkadox BC, manufactured by Nouryon)

[0128] Antioxidant 1: Compound represented by the following formula (KEMINOX 179, manufactured by Chemipro Chemicals Co., Ltd.)

[0129] Adhesion aid 1: 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) represented by the following formula

[0130] Adhesion aid 2: 3-trimethoxysilylpropylsuccinic anhydride represented by the following formula (X-12-967C, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0131] Adhesion aid 3: 3-methacryloxypropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) represented by the following formula

[0132] Curing catalyst 1: a tetra-substituted phosphonium compound represented by the following formula (tetraphenylphosphonium 4,4'-sulfonyldiphenolate, manufactured by Sumitomo Bakelite Co., Ltd.)

[0133] Surfactant 1: Silicone surfactant (BYK Corporation, BYK-349)

[0134] Solvent 1: Ethyl lactate (EL) Solvent 2: γ-butyrolactone (GBL)

[0135] (Examples 1 to 8, Comparative Examples 1 and 2) <Preparation of Photosensitive Resin Composition> The polymer and each component were mixed in a solvent in the blending ratios shown in Table 1 to prepare the photosensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 and 2.

[0136] <Patterning Ability> The photosensitive resin composition of each Example and Comparative Example was applied to an 8-inch silicon wafer using a spin coater. After application, the wafer was pre-baked on a hot plate in the atmosphere at 110°C for 3 minutes to obtain a coating film with a thickness of approximately 5 μm. This coating film was irradiated with i-rays through a mask on which via patterns of multiple widths (4 μm and 5 μm) were drawn. An i-ray stepper (Nikon Corporation, NSR-4425i) was used for the irradiation. After exposure, the wafer was spray-developed for 60 seconds using cyclopentanone as the developer, and then spray-developed for 10 seconds using PGMEA as the developer to dissolve and remove the unexposed areas, thereby obtaining a via pattern. The cross section of the obtained via pattern was observed using a benchtop SEM. The width at the midpoint between the bottom and opening of the via pattern was defined as the via width, and the patterning ability was evaluated according to the following criteria. The results are shown in Table 1. A: 4 μm and 5 μm via patterns are opened. B: 5 μm via pattern is opened, 4 μm via pattern is not opened. C: 4 μm and 5 μm via patterns are not opened.

[0137] <Reliability> Copper wiring with a line width of 5 μm and a thickness of 2 μm was formed on an 8-inch silicon wafer. Next, the photosensitive resin composition of each Example and Comparative Example was applied to the surface of the silicon wafer on which the copper wiring had been formed so that the film thickness after drying would be 10 μm, and the wafer was prebaked at 110° C. for 3 minutes. After that, the wafer was exposed to a high-pressure mercury lamp at 600 mJ / cm ２After that, the photosensitive resin composition was cured by post-baking at 230°C for 3 hours in a nitrogen atmosphere to obtain a test piece. The obtained test piece was then heat-treated in air at 230°C for 30 minutes. The test piece was then cut perpendicular to the silicon wafer surface, 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: No cracks or migration at the interface between the copper wiring and the cured product B: Cracks or migration at the interface between the copper wiring and the cured product

[0138] <Preparation of Cured Product> The photosensitive resin composition of each Example and Comparative Example was spin-coated onto the surface of a silicon wafer so that the film thickness after drying would be 10 μm, and the coating was pre-baked at 110° C. for 3 minutes. After that, the coating was heated with a high-pressure mercury lamp at 600 mJ / cm ２ After that, the resist was post-baked at 230° C. for 3 hours in a nitrogen atmosphere to prepare a cured product measuring 100 mm×100 mm×10 μm in thickness.

[0139] <Oxygen Permeability Coefficient> The oxygen permeability coefficient of the cured products of each Example and Comparative Example was measured at 23°C and 60% RH by a differential pressure method in accordance with JIS K 7126-2: 2006. The results are shown in Table 1.

[0140] <Glass Transition Temperature (Tg)> The glass transition temperature (Tg) of the cured products of each Example and Comparative Example was measured using a thermomechanical analyzer (TMA) (TMA-7100, manufactured by Hitachi High-Technologies Corporation) under the following conditions: starting temperature 30°C, measurement temperature range 30 to 400°C, and heating rate 5°C / min. The results are shown in Table 1.

[0141] <Elongation at break and tensile modulus> For the cured products of each Example and Comparative Example, the elongation at break and tensile modulus were measured at 23°C and a stretching rate of 5 mm / min using a tensile tester (STB-1225S, manufactured by AMD) in accordance with JIS K 7161: 2014. The results are shown in Table 1.

[0142] <Storage Modulus> The storage modulus of each of the cured products of each Example and Comparative Example was measured at 30° C. by dynamic mechanical analysis (DMA) using a DMA device (DMA-Q800, manufactured by TA Instruments). The results are shown in Table 1.

[0143]

[0144] This application claims priority based on Japanese Patent Application No. 2023-219150, filed December 26, 2023, the disclosure of which is incorporated herein by reference in its entirety.

[0145] 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 photosensitive resin composition comprising a polyimide (A) having a double bond in a side chain, a crosslinking agent (B) containing a (meth)acrylate compound, a polymerization initiator (C), and an antioxidant (D) having an isocyanuric acid skeleton.

2. The photosensitive resin composition according to claim 1, wherein the antioxidant (D) contains a compound represented by the following general formula (1). (In the general formula (1), R １１ , R １２ and R １３ each independently represents a hydrogen atom, a hydroxy group, an alkyl group or an alkoxy group having 1 to 20 carbon atoms which may contain a hydroxy group, or an aryl group or an aralkyl group having 6 to 30 carbon atoms which may contain at least one substituent selected from the group consisting of a hydroxy group, an alkyl group and an alkoxy group) 3. R in the general formula (1) １１ , R １２ and R １３ Among them, at least one is a group represented by the following general formula (2). The photosensitive resin composition according to claim 2. (In the general formula (2), W represents a single bond or an alkylene group having 1 to 5 carbon atoms, and R ２０ represents a hydrogen atom, a hydroxy group, or an alkyl group or an alkoxy group having 1 to 5 carbon atoms which may contain a hydroxy group. A plurality of R ２０ 's may be the same or different from each other, and * represents a bond) 4. R in the general formula (2) ２０ The photosensitive resin composition according to claim 3, wherein at least one of them is a hydroxy group.

5. The photosensitive resin composition according to any one of claims 1 to 4, wherein the polyimide (A) contains a structural unit represented by the following general formula (3). (In the general formula (3), Y represents a divalent organic group) 6. The photosensitive resin composition according to claim 5, 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). (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. 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. A plurality of R ３ 's may be the same or different from each other. * 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. A plurality of R ４ 's and a plurality of R ５ 's may be the same or different from each other. * 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.) 7. The photosensitive resin composition according to any one of claims 1 to 6, wherein the polyimide (A) contains a structural unit represented by the following general formula (4). (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. 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, a linear or branched fluoroalkylene group having 1 to 5 carbon atoms, or a substituted or unsubstituted fluorene group).

8. The photosensitive resin composition according to any one of claims 1 to 7, wherein the polyimide (A) contains a structural unit (a) represented by the following general formula (5). (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, a linear or branched fluoroalkylene group having 1 to 5 carbon atoms, or a substituted or unsubstituted fluorene group. Y represents a divalent organic group) 9. 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 8.

10. The photosensitive resin composition according to any one of claims 1 to 9, wherein 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.

11. The photosensitive resin composition according to any one of claims 1 to 10, wherein 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.

12. The photosensitive resin composition according to any one of claims 1 to 11, wherein when the content of the polyimide (A) is 100 parts by mass, the content of the antioxidant (D) is 0.01 part by mass or more and 20 parts by mass or less.

13. The photosensitive resin composition according to any one of claims 1 to 12, wherein 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), the polymerization initiator (C), and the antioxidant (D) is 80 parts by mass or more.

14. 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 imidization rate represented by {IM / (IM + AM)} × 100 (%) is 90% or more. The photosensitive resin composition according to any one of claims 1 to 13.

15. The photosensitive resin composition according to any one of claims 1 to 14, wherein the crosslinking agent (B) contains a polyfunctional (meth)acrylate compound having 3 or more and 20 or less (meth)acryloyloxy groups or (meth)acryloyl groups in the molecule.

16. The photosensitive resin composition according to any one of claims 1 to 15, wherein the crosslinking agent (B) contains an epoxy compound.

17. The photosensitive resin composition according to any one of claims 1 to 16, wherein the polymerization initiator (C) contains an oxime ester type polymerization initiator.

18. The photosensitive resin composition according to any one of claims 1 to 17, further comprising an organic solvent.

19. The photosensitive resin composition according to claim 18, 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.

20. The photosensitive resin composition according to any one of claims 1 to 19, wherein when the total amount of the solid content in the photosensitive resin composition is 100 parts by mass, the content of fluorine atoms is 10 parts by mass or less.

21. The photosensitive resin composition according to any one of claims 1 to 20, 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.

22. The photosensitive resin composition according to any one of claims 1 to 21, 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.

23. The oxygen permeability coefficient according to the following Method 1 is 30 cm ３ ·mm / (m ２ ·day·atm) or less, and the photosensitive resin composition according to any one of claims 1 to 22. (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 permeability coefficient is measured by a differential pressure method in accordance with JIS K 7126-2:2006 under the conditions of 23 °C and 60% RH.

24. The photosensitive resin composition according to any one of claims 1 to 23, wherein for the cured product obtained by curing the photosensitive resin composition at 230 °C for 3 hours, the glass transition temperature (Tg) measured under the conditions of a starting temperature of 30 °C, a measurement temperature range of 30 to 400 °C, and a heating rate of 5 °C / min using a thermomechanical analysis (TMA) apparatus is 240 °C or higher.

25. 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 testing machine, the elongation at break measured under the conditions of 23°C and a stretching rate of 5 mm / min is 10% or more. The photosensitive resin composition according to any one of claims 1 to 24.

26. 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 testing machine, the tensile modulus measured under the conditions of 23°C and a stretching rate of 5 mm / min is 1.0 GPa or more and 5.0 GPa or less. The photosensitive resin composition according to any one of claims 1 to 25.

27. For the cured product obtained by curing the photosensitive resin composition at 230°C for 3 hours, the storage modulus at 30°C measured by dynamic viscoelasticity measurement (DMA) is 1.0 GPa or more and 6.0 GPa or less. The photosensitive resin composition according to any one of claims 1 to 26.

28. The photosensitive resin composition according to any one of claims 1 to 27, which can be used in a semiconductor device.

29. A cured product of the photosensitive resin composition according to any one of claims 1 to 28.

30. A semiconductor device including the cured product according to claim 29.

31. The semiconductor device according to claim 30, comprising an interlayer insulating film, a resin film containing the cured product on the interlayer insulating film, and a rewiring embedded in the resin film.

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