TW201830138A - Photosensitive resin composition, resin film, cured film, production method for semiconductor device, and semiconductor device - Google Patents

Abstract

A photosensitive resin composition includes: (A) a phenol resin having a biphenol structure, (B) a photoacid generator, and a solvent.

Description

 Photosensitive resin composition, resin film, cured film, method of manufacturing semiconductor device, and semiconductor device  

The present invention relates to a photosensitive resin composition, a method of producing a semiconductor device, a resin film, a cured film, and a semiconductor device. More specifically, it relates to a resist which can be used as a resist for use in the manufacture of a semiconductor device, or a photosensitive resin composition which is used as a precursor of a heat-resistant resin of a semiconductor element surface protective film or an interlayer insulating film.

The present application claims priority to Japanese Patent Application No. 2016-220584, filed on Jan.

Conventionally, as a material for forming a surface protective film and an interlayer insulating film for a semiconductor element used in an electronic component, various resin compositions or photosensitive compositions have been proposed (for example, Patent Document 1).

Patent Document 1 discloses a photosensitive resin composition containing a phenol resin (A) having a biphenyldiyl structure in a main chain, a photoacid generator (B), and a solvent (B) from the foregoing (B) The resulting acid or heat, the compound (C) which can react with the above (A). In Patent Document 1, a phenol resin containing an unsubstituted biphenyldiyl structure is described as the phenol resin (A).

Patent Document 1: Japanese Laid-Open Patent Publication No. 2012-123378

A cured resin film for forming a surface protective film, an interlayer insulating film, or the like of a semiconductor device can be obtained by applying a photosensitive resin composition to a substrate to obtain a resin film, and performing patterning by exposing and developing the resin film Forming, the patterned resin film is then heated to harden it. In the conventional photosensitive resin composition, since the obtained resin film has a low softening point, heat resistance is low, and the pattern shape is deformed by heating, so that it may not be preferably used as a surface protective film or interlayer between semiconductor devices. Insulating film.

According to the present invention, the present invention provides a photosensitive resin composition capable of forming a resin film and a cured film having excellent heat resistance, a resin film composed of the photosensitive resin composition, and a cured film of the resin film. A semiconductor device of the cured film and a method of manufacturing a semiconductor device using the photosensitive resin composition.

The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have completed the present invention including the following aspects.

[1] A photosensitive resin composition comprising: a phenol resin (A) having a biphenol structure; a photoacid generator (B); and a solvent.

[2] The photosensitive resin composition according to the above [1], wherein the phenol resin (A) has a biphenol compound derived from an aldehyde compound, a dimethylol compound, a dimethoxymethyl compound, and A structural unit of at least one compound of the group consisting of haloalkyl compounds.

[3] The photosensitive resin composition according to the above [1] or [2], wherein the phenol resin (A) is a resin having a structural unit represented by the formula (1).

(In the formula (1), R ₁₁ and R ₁₂ are each independently selected from a hydroxyl group, a halogen atom, a carboxyl group, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, an alkyl ether group having 1 to 20 carbon atoms, and carbon. a monovalent substituent of a group of 3 to 20 saturated or unsaturated alicyclic groups or an organic group having an aromatic structure of 6 to 20, which may be through an ester bond, an ether bond, or a guanamine a bond or a carbonyl bond, p and q are each independently an integer of 0 to 3, and X ₁ and Y ₁ are each independently selected from an aliphatic group having a carbon number of 1 to 10 which may have a single bond or an unsaturated bond, a divalent substituent of a group having an alicyclic group having 3 to 20 carbon atoms and an organic group having an aromatic structure having 6 to 20 carbon atoms, wherein Y _{1 is} bonded to any one of the two benzene rings).

[4] The photosensitive resin composition according to any one of the above [1], wherein the phenol resin (A) has a repeating structural unit represented by the formula (2).

(In the formula (2), m is an integer of 2 to 10,000, and R ₁₁ and R ₁₂ are each independently a saturated or unsaturated alkyl group selected from a hydroxyl group, a halogen atom, a carboxyl group, and a carbon number of 1 to 20, and a carbon number of 1 a monovalent substituent of a group of ~20 alkyl ether groups, a saturated or unsaturated alicyclic group having 3 to 20 carbon atoms or an organic group having an aromatic structure having 6 to 20 carbon atoms, which may be used An ester bond, an ether bond, a guanamine bond or a carbonyl bond bond, p and q are each independently an integer of 0 to 3, and X ₁ and Y ₁ are each independently selected from a carbon number which may have a single bond or an unsaturated bond. a divalent substituent of an aliphatic group of 1 to 10, an alicyclic group having 3 to 20 carbon atoms, and an organic group having an aromatic structure of 6 to 20, wherein Y ₁ and 2 benzene rings Any one of the keys).

[5] The photosensitive resin composition according to any one of the above [1], wherein the photoacid generator (B) is a compound which generates an acid by irradiation of radiation having a wavelength of 200 to 500 nm. .

[6] The photosensitive resin composition according to any one of the above [1] to [5], further comprising a crosslinking agent (C) having a group reactive with the phenol resin (A).

[7] The photosensitive resin composition according to any one of the above [1], wherein the phenol resin (A) has a polystyrene-equivalent weight average molecular weight of 1,000 to 100,000.

[8] The photosensitive resin composition according to any one of [1] to [7] above which further comprises a decane coupling agent (D).

[9] The photosensitive resin composition according to any one of [1] to [8] above which further comprises a nonionic surfactant (E).

[10] The photosensitive resin composition according to any one of the above [1] to [9], further comprising a reaction accelerator (F).

[11] A method of producing a semiconductor device, comprising: a process of applying the photosensitive resin composition according to any one of the above [1] to [10] on a semiconductor substrate; and performing the photosensitive resin composition a process of heating and drying to obtain a photosensitive resin layer; a process of exposing the photosensitive resin layer by active light; a process of developing the exposed photosensitive resin layer to obtain a patterned resin layer; The resin layer which has been patterned is heated to obtain a process of hardening the resin layer.

[12] A resin film comprising the photosensitive resin composition according to any one of the above [1] to [10].

[13] A cured film of the resin film of the above [12].

[14] A semiconductor device comprising the cured film of the above [13].

According to the present invention, there is provided a photosensitive resin composition capable of forming a resin film or a cured film having excellent heat resistance, a resin film composed of the photosensitive resin composition, a cured film of the resin film, and the cured film. A semiconductor device and a method of manufacturing a semiconductor device using the above-described photosensitive resin composition.

Hereinafter, embodiments of the present invention will be described.

(Photosensitive resin composition)

The photosensitive resin composition according to the present embodiment contains a phenol resin (A) having a biphenol structure, a photoacid generator (B), and a solvent.

In the resin composition of the present embodiment, as the phenol resin (A), a resin having a biphenol structure, that is, a phenol resin having a biphenyldiyl structure having at least one hydroxyl group in the phenyl group, is used. The heat resistance of the resin film composed of the above composition is improved. Therefore, when the resin film composed of the photosensitive resin composition is exposed and developed to form a pattern, a high-resolution pattern can be formed on the resin film.

(phenol resin (A))

In one embodiment, the phenol resin (A) has at least one compound derived from a biphenol compound and a group selected from the group consisting of an aldehyde compound, a dimethylol compound, a dimethoxymethyl compound, and a dihaloalkyl compound. Structural units. In other words, the phenol resin (A) is obtained by a reaction of a biphenol compound with at least one compound selected from the group consisting of an aldehyde compound, a dimethylol compound, a dimethoxymethyl compound, and a dihaloalkyl compound.

In the present specification, the term "structure derived from (substance)" means a structure produced by using the above-mentioned substance, and includes both the case where the above structure can be confirmed by a usual method in the technical field and the case where it cannot be confirmed.

Since the phenol resin (A) does not require a complicated process and can be produced using a commercially available raw material monomer, the obtained photosensitive resin composition can be produced at low cost.

The phenol resin (A) can be produced by any publicly known method. The production method includes, for example, a condensation reaction of a biphenol compound with an aldehyde compound, a dimethylol compound, a dimethoxymethyl compound or a dihaloalkyl compound.

Examples of the biphenol compound which can be used for producing the phenol resin (A) include 2,2'-biphenol and 4,4'-biphenol, and the isomers. The biphenol compound may have a substituent, and examples of the substituent include a hydroxyl group, a halogen, a carboxyl group, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, an alkyl ether group having 1 to 20 carbon atoms, and a carbon number. A saturated or unsaturated alicyclic group of 3 to 20 or an organic group having an aromatic structure of 6 to 20 carbon atoms.

The biphenol compound is exemplified by the following compounds, for example, but is not limited thereto.

Examples of the aldehyde compound which forms the phenol resin (A) by the reaction with the above biphenol compound include formaldehyde, acetaldehyde, propionaldehyde, pivalic aldehyde, butyraldehyde, valeraldehyde, and hexanal. ,three Glyoxal, cyclohexanal, diphenylacetaldehyde, ethyl butyraldehyde, benzaldehyde, cinnamaldehyde, fumaric acid aldehyde methyl ester, 3-methyl-2-butenal, glyoxylic acid, 5-norbornene-2-carboxaldehyde, malondialdehyde, succinaldehyde, glutaraldehyde, naphthaldehyde, terephthalaldehyde, and the like.

Examples of the dimethylol compound which forms the phenol resin (A) by the reaction with the above biphenol compound include 2,2-bis(hydroxymethyl)butyric acid, 1,3-propanediol, and 2-oxime oxygen. -1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, monoacetin, 2-methyl-2-nitro -1,3-propanediol, 5-northene-2,2-dimethanol, 5-northene-2,3-dimethanol, pentaerythritol, 2-phenyl-1,3-propanediol, three Hydroxymethylethane, trimethylolpropane, 3,6-bis(hydroxymethyl)tetramethylene, 2-nitro-p-diphenylmethanol, 1,10-dihydroxydecane, 1,12-di Hydroxydodecane, 1,4-bis(hydroxymethyl)cyclohexane, 1,4-bis(hydroxymethyl)cyclohexene, 1,6-bis(hydroxymethyl)adamantane, 1,4- Benzyldiethanol, 1,3-benzenedimethanol, 2,6-bis(hydroxymethyl)-1,4-dimethoxybenzene, 2,6-bis(hydroxymethyl)-p-cresol, 2, 3-bis(hydroxymethyl)naphthalene, 2,6-bis(hydroxymethyl)naphthalene, 1,8-bis(hydroxymethyl)anthracene, 2,2'-bis(hydroxymethyl)diphenyl ether, 4 , 4'-bis(hydroxymethyl)diphenyl ether, 4,4'-bis(hydroxymethyl)diphenyl sulfide, 4,4'-bis(hydroxymethyl)benzophenone, 4-hydroxyl Methylbenzoic acid-4'-hydroxymethylphenyl, 4- Methylbenzoic acid-4'-hydroxymethylaniline, 4,4'-bis(hydroxymethyl)phenylurea, 4,4'-bis(hydroxymethyl)phenylcarbamic acid ethyl ester, 1,8 - bis(hydroxymethyl)anthracene, 4,4'-bis(hydroxymethyl)biphenyl, 2,2'-dimethyl-4,4'-bis(hydroxymethyl)biphenyl, 2,2- Bis(4-hydroxymethylphenyl)propane and the like.

The dimethoxymethyl compound which produces the phenol resin (A) by the reaction with the above-mentioned biphenol compound, for example, 2,2-bis(methoxymethyl)butyric acid, 1,3- Dimethoxymethylpropane, 2-decyloxy-1,3-dimethoxymethylpropane, 2,2-dimethyl-1,3-dimethoxymethylpropane, 2,2- Diethyl-1,3-dimethoxymethylpropane, 2,3-dimethoxy-1-propanol acetate, 2-methyl-2-nitro-1,3-dimethoxy Methylpropane, 5-northene-2,2-dimethoxymethyl ester, 5-northene-2,3-dimethoxymethyl ester, tetrakis(methoxymethyl)methane, 2 -phenyl-1,3-dimethoxymethylpropane, trimethoxyethane, trimethoxypropane, 3,6-bis(methoxymethyl)tetramethylene, 2-nitro-1, 4-bis(methoxymethyl)benzene, 1,10-dimethoxydecane, 1,12-dimethoxydodecane, 1,4-bis(methoxymethyl)cyclohexane , 1,4-bis(methoxymethyl)cyclohexene, 1,6-bis(methoxymethyl)adamantane, 1,4-bis(methoxymethyl)benzene, 1,3- Dimethoxymethylbenzene, 2,6-bis(methoxymethyl)-1,4-dimethoxybenzene, 2,6-bis(methoxymethyl)-p-cresol, 2, 3-bis(methoxymethyl)naphthalene 2,6-bis(methoxymethyl)naphthalene, 1,8-bis(methoxymethyl)anthracene, 2,2'-bis(methoxymethyl)diphenyl ether, 4,4'- Bis(methoxymethyl)diphenyl ether, 4,4'-bis(methoxymethyl)diphenyl sulfide, 4,4'-bis(methoxymethyl)benzophenone, 4 -Methoxymethylbenzoic acid-4'-methoxymethylphenyl, 4-methoxymethylbenzoic acid-4'-methoxymethylaniline, 4,4'-bis(methoxy Methyl)phenylurea, 4,4'-bis(methoxymethyl)phenylcarbamate, 1,8-bis(methoxymethyl)anthracene, 4,4'-bis (A) Oxymethyl)biphenyl, 2,2'-dimethyl-4,4'-bis(methoxymethyl)biphenyl, 2,2-bis(4-methoxymethylphenyl)propane Wait.

The dihaloalkyl compound which forms the phenol resin (A) by the reaction with the above-mentioned biphenol compound, for example, dichloroxylene, dichloromethyldimethoxybenzene, and dichloromethyl are all four. Toluene, dichloromethylbiphenyl, dichloromethyl-biphenylcarboxylic acid, dichloromethyl-biphenyldicarboxylic acid, dichloromethyl-methylbiphenyl, dichloromethyl-dimethylbiphenyl , Dichloromethyl hydrazine, ethylene glycol bis (chloroethyl) ether, diethylene glycol bis (chloroethyl) ether, triethylene glycol bis (chloroethyl) ether, tetraethylene glycol bis (chloroethane) Base) ether and the like.

These compounds may be used alone or in combination of two or more.

The phenol resin (A) can be obtained by dehydration or dehalogenation of the above biphenol compound and the above-mentioned polymerization component, and a catalyst can be used for the polymerization. Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, phosphorous acid, methanesulfonic acid, p-toluenesulfonic acid, dimethylsulfuric acid, diethylsulfonic acid, acetic acid, oxalic acid, and 1-hydroxyethylidene. Base-1,1'-diphosphonic acid, zinc acetate, boron trifluoride, boron trifluoride. Phenol complex, boron trifluoride. Ether complexes and the like. Examples of the basic catalyst include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, triethylamine, pyridine, and 4-N,N-dimethyl group. Aminopyridine, piperidine, piperidine , 1,4-dioxabicyclo[2.2.2]octane, 1,8-dioxinbicyclo[5.4.0]-7-undecene, 1,5-dioxabicyclo[4.3.0]-5- Terpene, ammonia, hexamethylenetetramine, and the like.

When the synthesis reaction of the phenol resin (A) is carried out, an organic solvent can be used as needed. Specific examples of the organic solvent that can be used include bis(2-methoxyethyl)ether, methyl cyproterone, ethyl cyproterone, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate. Diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone, toluene, xylene, γ-butyrolactone, N-methyl-2-pyrrolidone, etc., but not limited thereto These are the same.

The phenol resin (A) can be further polymerized by using a phenol compound other than the above biphenol compound within the range which does not impair the effects of the present invention.

In one embodiment, the phenol resin (A) obtained by the above compound may have a structural unit represented by the formula (1).

In the formula (1), R ₁₁ and R ₁₂ are each independently selected from a hydroxyl group, a halogen atom, a carboxyl group, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, an alkyl ether group having 1 to 20 carbon atoms, and a carbon number. a monovalent substituent of a group of 3 to 20 saturated or unsaturated alicyclic groups or an organic group having an aromatic structure of 6 to 20, which may be bonded by an ester bond, an ether bond or a guanamine bond. Or a carbonyl bond, p and q are each independently an integer of 0 to 3, and X ₁ and Y ₁ are each independently selected from an aliphatic group or a carbon having a carbon number of 1 to 10 which may have a single bond or an unsaturated bond. A divalent substituent of a group of 3 to 20 alicyclic groups and an organic group having an aromatic structure of 6 to 20 carbon atoms, wherein Y _{1 is} bonded to any one of the two benzene rings.

The phenol resin (A) may have a structural unit of the formula (1), which comprises a biphenol structure, that is, a biphenyldiyl structure having at least one hydroxyl group in the phenyl group, whereby the phenol is contained The heat resistance of the resin film composed of the composition of the resin (A) is improved. Therefore, when the resin film composed of the photosensitive resin composition is exposed and developed to form a pattern, a high-resolution pattern can be formed on the resin film.

It is preferred that R ₁₁ and R ₁₂ are each independently a hydroxyl group.

It is preferred that p and q are each independently an integer of 0 to 2.

X ₁ and Y ₁ are each independently a divalent substitution of a group selected from the group consisting of an aliphatic group having a single bond or an unsaturated bond having 1 to 10 carbon atoms and an organic group having an aromatic structure having 6 to 20 carbon atoms. The base is preferred.

The "aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond" in X ₁ and Y ₁ may be a straight chain or a branched chain. The carbon number may be 1 to 7, or may be 1 to 5, or may be 1 to 3. Examples of the aliphatic group include an alkylene group, an alkenyl group, an alkynyl group, and the like. Among them, an alkyl group is preferred. For example, a methylene group or a methyl group can be mentioned. Base, propyl and the like.

The "organic group having an aromatic structure having 6 to 20 carbon atoms" in X ₁ and Y ₁ may be a carbon number of 6 to 14, or a carbon number of 6 to 12, or a carbon number of 6 to 9. The carbon number is 6~8. The "aromatic structure" may, for example, be a phenylene group, a biphenyldiyl group or a naphthalenediyl group. Among them, a phenyl group is preferred.

The "organic group having an aromatic structure having 6 to 20 carbon atoms" in X ₁ and Y ₁ may be the "aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond" and the "aromatic structure" described above. A divalent substituent formed by bonding.

More preferably, X ₁ and Y ₁ are each independently the following organic groups.

In the above formula, n is 0 to 20, preferably 0 to 10.

The structural unit represented by the above formula (1) is composed of at least one compound selected from the group consisting of an aldehyde compound, a dimethylol compound, a dimethoxymethyl compound, and a dihaloalkyl compound. The reaction is obtained.

In the present embodiment, the phenol resin (A) has substantially the repeating unit represented by the formula (2).

In the formula (2), m is an integer of 1 to 10,000, and R ₁₁ and R ₁₂ , p and q, and X ₁ and Y ₁ are the same as defined in the formula (1).

The resin having a repeating unit structure represented by the formula (2) may be, for example, a resin having a structure represented by the formula (3).

In the formula (3), l and m represent the composition ratio, l+m=1,0 l 1,0 m _{1, R 11 ', R 12} ', R 11 " and R _12" are each independently selected from the group consisting of a hydroxyl group, a halogen atom, a carboxyl group, a saturated or unsaturated carbon atoms, an alkyl group having 1 to 20, 1 to 20 carbon atoms, a monovalent substituent of a group consisting of an alkyl ether group, a saturated or unsaturated alicyclic group having 3 to 20 carbon atoms or an organic group having an aromatic structure having 6 to 20 carbon atoms, which may be bonded by an ester bond, An ether bond, a guanamine bond, or a carbonyl bond, p and q are each independently an integer of 0 to 3, and X _{1 '} , Y _{1 '} , X _{1 ′′} , and Y _1′′ are independently selected from the group consisting of a single bond. Or a divalent substituent of an unsaturated group having an aliphatic group having 1 to 10 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, and an organic group having an aromatic structure having 6 to 20 carbon atoms.

The above structure of the phenol resin (A) can be understood by those skilled in the art from the kind of the biphenol compound and the polymerizable compound to be used.

In one embodiment, the weight average molecular weight (in terms of polystyrene) of the phenol resin (A) is in the range of 1,000 to 100,000, preferably in the range of 2,000 to 50,000, and more preferably in the range of 3,000 to 30,000. The phenol resin (A) having a weight average molecular weight in the above range is excellent in solubility in a solvent, and the obtained resin film is excellent in mechanical properties.

(Photoacid generator (B))

The photosensitive resin composition of the present embodiment is not particularly limited as long as it can induce a radiation pattern including ultraviolet rays, electron beams, and X-rays to form a resin pattern, and can be either a negative type or a positive type. Resin composition. The resin composition of the present embodiment which is photosensitive by the photoacid generator (B) can be used, for example, as a resist used in the production of a semiconductor device.

The photoacid generator (B) used in the photosensitive resin composition of the present embodiment is a compound which induces irradiation of radiation to generate an acid, and preferably has a wavelength of 200 to 500 nm, particularly preferably 350 to 450 nm. The irradiation of radiation produces a compound of acid. Specific examples thereof include a photosensitive diazonium compound, a photosensitive diazonaphthoquinone compound, a diaryliodonium salt, a triarylsulfonium salt or hydrazine. Anthracene salt such as borate, 2-nitrobenzyl ester compound, N-imidosulfonate compound, sulfhydryl sulfonate compound, 2,6-bis(trichloromethyl)-1,3,5 -three a compound, a dihydropyridine compound or the like. These may be used alone or in combination of two or more. Among them, a photosensitive diazonium compound and a photosensitive diazonaphthoquinone compound which are excellent in sensitivity and solvent solubility are preferable. Specific examples of the phenolic compound include 1,2-benzoquinonediazide-4-sulfonate, 1,2-naphthoquinonediazide-4-sulfonate, and 1,2-naphthalene. Bis-azido-5-sulfonate and the like.

The photoacid generator (B) is used in an amount of from 1 to 100% by weight, preferably from 3 to 50% by weight, based on 100% by weight of the phenol resin (A).

(solvent)

The photosensitive resin composition of the present embodiment is used in the form of a varnish obtained by dissolving the above components in a solvent. Examples of the solvent to be used include N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylacetamide, dimethyl hydrazine, and diethylene glycol dimethyl ether. , diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl - 1,3-butanediol acetate, 1,3-butanediol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate and methyl 3-methoxypropionate, etc. Can be mixed.

The amount of the solvent used is 50% by weight to 1,000% by weight, preferably 100% by weight to 500% by weight based on 100% by weight of the phenol resin (A). By using a solvent in the above range, it is possible to produce a varnish which is excellent in chemical solubility and which is excellent in solubility.

(crosslinking agent (C))

The photosensitive resin composition of the present embodiment may contain a crosslinking agent (C) having a group reactive with the phenol resin (A). A resin film is produced by using the photosensitive resin composition of the present embodiment containing the crosslinking agent (C), and after exposure and development are carried out to form a pattern, followed by heat curing, the crosslinking agent (C) is obtained from a photoacid generator. (B) The action of acid or heat generated, crosslinking with the phenol resin (A). The resin film obtained from the photosensitive resin composition containing a crosslinking agent is suppressed by the phenol resin (A) having the above-described structure, and the resin film which has been patterned by heat curing is suppressed. Further, since the obtained cured film has excellent heat resistance, electrical properties, and mechanical properties, it can be used as a surface protective film and an interlayer insulating film used in a semiconductor device.

As the crosslinking agent (C) which can be used in the photosensitive resin composition of the present embodiment, a compound which can be thermally crosslinked with the phenol resin (A) is preferably used. As the crosslinking agent (C) which can be used, the following compounds are mentioned:

(1) A compound containing one or more kinds of crosslinkable groups selected from the group consisting of a methylol group and an alkoxymethyl group: for example, benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl group) Dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylbenzoic acid hydroxymethylbenzene, bis(hydroxymethyl)biphenyl, dimethyl Bis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxy Diphenyl ether, bis(methoxymethyl)benzophenone, methoxymethylbenzene methoxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(A) Oxymethyl)biphenyl; as a commercial product, CYMEL 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170 , 1174, UFR65, 300 (manufactured by Mitsui Cytec Co., Ltd.), NIKALAC MX-270, -280, -290, NIKALAC MS-11, NIKALAC MW-30, -100, -300, -390, -750 ( Manufactured by Sanwa Chemical Co., Ltd., 1,4-bis(methoxymethyl)benzene, 4,4'-biphenyldimethanol, 4,4'-bis(methoxymethyl)biphenyl, 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A (made by ASAHI YUKIZAI CORPORATION), DML-MBPC, DML-MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, DML-OC, dimethylol-Bis-C, dimethylol-BisOC-P, DML-BisOC-Z, DML-BisOCHP-Z, DML-PFP, DML-PSBP, DML-MB25, DML-MTrisPC, DML-Bis25X-34XL, DML-Bis25X-PCHP, 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6 -dimethoxymethyl-p-cresol, 2,6-diethoxymethyl-p-cresol, TriML-P, TriML-35XL, TriML-TrisCR-HAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (manufactured by HONSHU CHEMICAL INDUSTRY CO., LTD.), and the like. These compounds can be used singly or in combination.

(2) a compound having an epoxy group: for example, n-butyl glycidyl ether, 2-ethoxyhexyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, ethylene glycol diglycidyl ether, Glycidyl ether, neopentyl glycol diglycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether, glycidyl ether such as glycidyl ether of bisphenol A (or F), adipic acid condensed water Glycidyl ester, glycidyl ester such as diglycidyl phthalate, 3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexane) carboxylate, 3,4-epoxy-6- Methylcyclohexylmethyl (3,4-epoxy-6-methylcyclohexane)carboxylate, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, two Cyclopentadiene oxide, bis(2,3-epoxycyclopentyl)ether or alicyclic epoxy such as CELLOXIDE 2021, CELLOXIDE 2081, CELLOXIDE 2083, CELLOXIDE 2085, CELLOXIDE 8000, EPOLEAD GT401, manufactured by Daicel Corporation, 2,2'-(((((((((((((((()))))))) ,1-diyl)bis(4,1-phenylene))bis(oxy))bis(methylene))bis(ethylene oxide)) For example, an aliphatic polyglycidyl ether such as Techmore VG3101L (manufactured by Printec Corporation), Epolite 100MF (manufactured by KYOEISHA CHEMICAL Co., Ltd.), Epiol TMP (manufactured by NOF CORPORATION), 1, 1, 3, 3, 5, 5 - hexamethyl-1,5-bis(3-(oxiran-2-ylmethoxy)propyl) III. a decane (for example, DMS-E09 (manufactured by Gelest, Inc.));

(3) Compounds having an isocyanate group: for example, 4,4'-diphenylmethane diisocyanate, tolyl diisocyanate, 1,3-phenylene bismethylene diisocyanate, dicyclohexylmethane-4, 4 '-Diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate;

(4) Compounds having a bis-n-butylene imino group: for example, 4,4'-diphenylmethane bis-n-butylene imide, phenylmethane maleimide, and exo-benzene Bis-succinimide, bisphenol A diphenyl ether bis-s-butylene imide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenyl Methane bis-m-butylene iminoimide, 4-methyl-1,3-phenylenebissuccinimide, 1,6'-bis-s-butyleneimine-(2,2 ,4-trimethyl)hexane, 4,4'-diphenyl ether bis-n-butylene imide, 4,4'-diphenylfluorene bis-n-butylene diimide, 1,3-double (3-methylene-2-imide phenoxy)benzene, 1,3-bis(4-methyleneimine phenoxy)benzene.

The blending amount of the crosslinking agent (C) in the photosensitive resin composition is from 1 to 100% by weight, preferably from 5 to 50% by weight, based on 100% by weight of the phenol resin (A). When the blending amount is 1% by weight or more, the mechanical strength of the thermosetting film is good, and when it is 100% by weight or less, the stability of the composition in the varnish state is good, and the mechanical strength of the obtained thermosetting film is good.

(decane coupling agent (D))

The photosensitive resin composition of this embodiment may contain a decane coupling agent (D). When the photosensitive resin composition is applied onto a substrate by a decane coupling agent (D) to obtain a resin film, the adhesion to the substrate is improved.

Examples of the decane coupling agent (D) include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, and 3-glycidoxypropyltriethyl. Oxydecane, p-styryltrimethoxydecane, 3-methylpropenyloxypropylmethyldimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-methyl Propylene methoxypropyl methyl diethoxy decane, 3-methyl propylene methoxy propyl triethoxy decane, 3- propylene methoxy propyl trimethoxy decane, N-2- (amine B 3-aminopropylmethyldimethoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane, N-2-(aminoethyl)-3-amine-propyl Triethoxy decane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, 3-mercaptomethylmethyl Dimethoxydecane, 3-mercaptopropyltrimethoxydecane, bis(triethoxypropyl)tetrasulfide, 3-isocyanatepropyltriethoxydecane and by reacting an anthracene compound with an amine group a dianhydride compound or the like obtained by reacting an acid dianhydride or an acid anhydride, but is not limited thereto Wait. The decane coupling agents can be used singly or in combination.

The blending amount of the decane coupling agent (D) in the photosensitive resin composition is 0.1 to 30% by weight, preferably 1 to 20% by weight based on 100% by weight of the phenol resin (A). By using the decane coupling agent (D) within the above range, the adhesion to the substrate and the storage stability of the photosensitive resin composition can be achieved.

(nonionic surfactant (E))

The photosensitive resin composition of this embodiment may contain a nonionic surfactant (E). When the photosensitive resin composition is applied onto a substrate by the non-ionic surfactant (E), the coating property at the time of obtaining a resin film is improved, and a coating film having a uniform thickness can be obtained. Moreover, it is possible to prevent the residue or the pattern from floating when the coating film is developed.

The nonionic surfactant (E) used in the photosensitive resin composition is, for example, a compound containing a fluorine group (for example, a fluorinated alkyl group) or a decyl group or a compound having a siloxane chain as a main skeleton. In the present embodiment, it is more preferable to use a fluorine-based surfactant or a polyfluorene-based surfactant as the nonionic surfactant (E), and it is particularly preferable to use a fluorine-based surfactant. Examples of the fluorine-based surfactant include Magafac F-171, F-173, F-444, F-470, F-471, F-475, F-482, F-477, and F manufactured by DIC CORPORATION. -554, F-556 and F-557, Novec FC4430 and FC4432 manufactured by Sumitomo 3M Limited, etc., but are not limited thereto.

The blending amount of the surfactant when the surfactant is used is preferably 0.01 to 10% by weight based on 100 parts by mass of the alkali-soluble phenol resin.

(Reaction accelerator (F))

The photosensitive resin composition of this embodiment may contain a reaction accelerator (F). By including the reaction accelerator (F), thermal crosslinking of the phenol resin (A) and the crosslinking agent contained in the photosensitive resin composition can be promoted.

As the reaction accelerator (F), for example, a heterocyclic five-membered ring compound containing nitrogen or a compound which generates an acid by heat can be used. These may be used singly or in combination of plural kinds. Examples of the heterocyclic five-membered ring compound containing nitrogen used as the reaction accelerator (F) include pyrrole, pyrazole, imidazole, 1,2,3-triazole, and 1,2,4-triazole. Further, examples of the compound which generates an acid by heat as the reaction accelerator (F) include a phosphonium salt, an iodide salt, a sulfonate, a phosphate, a borate, and a salicylate. From the viewpoint of more effectively improving the hardenability at a low temperature, one or both of the sulfonate and the borate are more preferably contained in the compound which generates an acid by heat, and in consideration of heat resistance of the properties of the cured film, Particularly preferred is a borate.

(other additives)

In the photosensitive resin composition of the present embodiment, a dissolution promoter, an antioxidant, a filler, a photopolymerization initiator, a terminal blocking agent, and a sensitizer can be further used as needed within the range which does not impair the effects of the present invention. Additives.

(Manufacturing method of cured film)

According to another aspect of the present invention, there is provided a method of manufacturing a semiconductor device comprising the steps of: applying a process for applying the photosensitive resin composition of the present invention to a semiconductor substrate; and heating and drying the photosensitive resin composition. a process for obtaining a photosensitive resin layer; a process of exposing the photosensitive resin layer by active light; a process of developing the exposed photosensitive resin layer to obtain a patterned resin layer; and The formed resin layer is heated to obtain a process of hardening the resin layer.

Hereinafter, an example of this embodiment will be described.

(Method of forming a coating film)

First, the photosensitive resin composition of the present embodiment is applied to a support or a substrate, for example, a tantalum wafer, a ceramic substrate, an aluminum substrate, a SiC wafer, a GaN wafer, or the like. Among them, the substrate includes, for example, a substrate on which a semiconductor element or a display element is formed, in addition to the unprocessed substrate. In this case, in order to ensure the water-resistant adhesion between the formed pattern and the support, a bonding aid such as a decane coupling agent may be applied to the support or the substrate in advance. The application of the photosensitive resin composition can be carried out by spin coating by spin, spray coating by a spray coater, dipping, printing, roll coating, or the like.

Next, pre-baking is performed at 80 to 140 ° C for about 30 to 600 seconds to remove the solvent, thereby forming a coating film of the photosensitive resin composition. The thickness of the coating film after removing the solvent is preferably from 1 to 500 μm.

(exposure process)

Next, the coating film obtained as described above was exposed. As the active light for exposure, for example, X-rays, electron beams, ultraviolet rays, visible rays, or the like can be used, but it is preferably a wavelength of 200 to 500 nm. From the viewpoint of the resolution of the pattern and the handleability, it is preferable that the source wavelength is a region of g-ray, h-ray or i-ray of the mercury lamp, and it may be used alone or in combination of two or more kinds of light. As the exposure device, a contact aligner, a mirror projection alignment machine or a stepper is particularly preferred. After the exposure, the coating film may be heated again at a temperature of 80 to 140 ° C for about 10 to 300 seconds.

(developing process)

Next, the exposed coating film is developed to form a relief pattern. In the developing process, an appropriate developing solution can be used, for example, development by a dipping method, a paddle method, a spin coating method, or the like. By developing, the exposed portion (for a positive type) or the unexposed portion (for a negative type) is eluted from the coating film, and a relief pattern can be obtained.

As the developer, for example, inorganic bases such as sodium hydroxide, sodium carbonate, sodium citrate, and ammonia; organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine; tetramethylammonium hydroxide; An aqueous solution such as a tetra-ammonium salt such as tetrabutylammonium hydroxide; an organic solvent such as cyclopentanone, propylene glycol monomethyl ether or propylene glycol monomethyl ether acetate; and, for example, a water-soluble organic compound such as methanol or ethanol may be added. Solvent or surfactant.

Among these, an aqueous solution of tetramethylammonium hydroxide is preferred. The concentration of tetramethylammonium hydroxide in the aqueous solution is preferably from 0.5 to 10% by mass, and more preferably from 1 to 5% by mass.

After the development, the developer is removed by washing with a rinse liquid, whereby a relief pattern can be obtained. For example, distilled water, methanol, ethanol, isopropyl alcohol, propylene glycol monomethyl ether, or the like can be used alone or in combination of two or more.

(heating process)

Finally, by heating the relief pattern obtained as described above, a hardened relief pattern (cured film) can be obtained. The heating temperature is preferably from 150 ° C to 500 ° C, more preferably from 150 ° C to 400 ° C. The heating time can be set to 15 to 300 minutes. This heat treatment can be performed by a heating plate, an oven, a temperature-increasing oven capable of setting a temperature program, or the like. As the ambient gas during the heat treatment, air can be used, and an inert gas such as nitrogen or argon can also be used. Further, when it is necessary to perform heat treatment at a lower temperature, it is possible to perform heating under reduced pressure by means of a vacuum pump or the like.

The embossed pattern obtained from the photosensitive resin composition of the present embodiment has almost no deformation at all in the heating process, and the shape of the embossed pattern before heating is maintained, and a high-resolution hardened embossed pattern can be obtained.

(semiconductor device)

The hardened relief pattern is used as a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, and a protective film of a device having a bump structure, and is manufactured by a known semiconductor device. The process combination in the method enables the fabrication of a semiconductor device. As described above, since the cured relief pattern of the present embodiment can be produced with high resolution, the semiconductor device using the cured relief pattern is excellent in electrical reliability.

Although the embodiments of the present invention have been described above, these embodiments of the present invention can also adopt various configurations other than those described above. Further, the present invention is not limited to the above-described embodiments, and modifications, improvements, etc. within a scope that can achieve the object of the present invention are included in the present invention.

 [Examples]  

Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples, but the present invention is not limited thereto.

(Synthesis Example 1)

<Synthesis of phenol resin (A-1)>

186.2 g (1.00 mol) of 4,4'-biphenol and 134.6 g (0.8 mol) of 2 were placed in a glass round bottom flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen introduction tube. 6-bis(hydroxymethyl)-p-cresol, 6.3 g (0.05 mol) of oxalic acid. After the dihydrate and 327 g of γ-butyrolactone, the polycondensation reaction was carried out at 100 ° C for 6 hours while the reaction liquid was refluxed in an oil bath while flowing nitrogen. Next, after the obtained reaction liquid was cooled to room temperature, 436 g of acetone was added and stirred and mixed until it became uniform. Thereafter, the reaction liquid droplets in the round bottom flask were mixed and mixed in 10 L of water, whereby the resin was analyzed. Then, the precipitated resin component was filtered off and recovered, and then vacuum-dried at 60 ° C to obtain a phenol resin represented by the following formula (A-1). The obtained phenol resin (A-1) had a weight average molecular weight of 9,800.

(In the formula (A-1), the bonding bond bonded to the biphenol structure is bonded to any one of the two benzene rings).

(Synthesis Example 2)

<Synthesis of phenol resin (A-2)>

186.2 g (1.00 mol) of 4,4'-biphenol and 133.0 g (0.8 mol) of 1 were added to a glass round bottom flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen introduction tube. 4-bis(methoxymethyl)benzene, 7.7 g (0.05 mol) of diethyl sulfate and 327 g of γ-butyrolactone, and then flowing the nitrogen in a round bottom flask while allowing the reaction liquid to be in an oil bath The polycondensation reaction was carried out at 100 ° C for 6 hours while refluxing. Next, after the obtained reaction liquid was cooled to room temperature, 436 g of acetone was added and stirred and mixed until it became uniform. Thereafter, the reaction liquid droplets in the round bottom flask were mixed and mixed in 10 L of water, whereby the resin was analyzed. Then, the precipitated resin component was filtered off and recovered, and then vacuum dried at 60 ° C to obtain a phenol resin represented by the following formula (A-2). The obtained phenol resin (A-2) had a weight average molecular weight of 12,300.

(In the formula (A-2), the bonding bond bonded to the biphenol structure is bonded to any one of the two benzene rings).

(Synthesis Example 3)

<Synthesis of phenol resin (A-3)>

186.2 g (1.00 mol) of 4,4'-biphenol and 193.9 g (0.8 mol) of 4 were added to a glass round bottom flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen introduction tube. 4'-bis(methoxymethyl)biphenyl, 7.7 g (0.05 mol) of diethyl sulfate and 582 g of γ-butyrolactone, and the reaction liquid was placed in a round bottom flask while flowing nitrogen. The polycondensation reaction was carried out at 100 ° C for 6 hours while refluxing in the bath. Next, after cooling the obtained reaction liquid to room temperature, 323 g of acetone was added and stirred and mixed until it became uniform. Thereafter, the reaction liquid droplets in the round bottom flask were mixed and mixed in 10 L of water, whereby the resin was analyzed. Then, the precipitated resin component was filtered off and recovered, and then vacuum dried at 60 ° C to obtain a phenol resin represented by the following formula (A-3). The obtained phenol resin (A-3) had a weight average molecular weight of 7,000.

(In the formula (A-3), the bonding bond bonded to the biphenol structure is bonded to any one of the two benzene rings).

(Synthesis Example 4)

<Synthesis of phenol resin (A-4)>

186.2 g (1.00 mol) of 2,2'-biphenol and 134.6 g (0.8 mol) of 2 were added to a glass round bottom flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen introduction tube. 6-bis(hydroxymethyl)-p-cresol, 6.3 g (0.05 mol) of oxalic acid. After the dihydrate and 327 g of γ-butyrolactone, the polycondensation reaction was carried out at 100 ° C for 6 hours while flowing the nitrogen in a round bottom flask while refluxing the reaction liquid in an oil bath. Next, after the obtained reaction liquid was cooled to room temperature, 436 g of acetone was added and stirred and mixed until it became uniform. Thereafter, the reaction liquid droplets in the round bottom flask were mixed and mixed in 10 L of water, whereby the resin was analyzed. Then, the precipitated resin component was filtered off and recovered, and then vacuum dried at 60 ° C to obtain a phenol resin represented by the following formula (A-4). The obtained phenol resin (A-4) had a weight average molecular weight of 7,700.

(In the formula (A-4), the bonding bond bonded to the biphenol structure is bonded to any one of the two benzene rings).

(Synthesis Example 5)

<Synthesis of phenol resin (A-5)>

234.2 g (1.00 mol) of pentagonal biphenyl (phloroglucide) and 133.0 g (0.8 mol) of 1, were added to a glass round bottom flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen introduction tube. After 4-bis(methoxymethyl)benzene, 7.7 g (0.05 mol) of diethyl sulfate and 375 g of γ-butyrolactone, the round bottom flask was subjected to an oil bath while flowing nitrogen to reflux the reaction liquid. At the same time, a polycondensation reaction was carried out at 100 ° C for 6 hours. Next, after the obtained reaction liquid was cooled to room temperature, 500 g of acetone was added and stirred and mixed until it became uniform. Thereafter, the reaction liquid droplets in the round bottom flask were mixed and mixed in 10 L of water, whereby the resin was analyzed. Then, the precipitated resin component was filtered off and recovered, and then vacuum dried at 60 ° C to obtain a phenol resin represented by the following formula (A-5). The obtained phenol resin (A-5) had a weight average molecular weight of 22,000.

(In the formula (A-5), the bonding bond bonded to the biphenol structure is bonded to any one of the two benzene rings).

(Synthesis Example 6)

<Synthesis of phenol resin (A-6)>

186.2 g (1.00 mol) of 4,4'-biphenol and 86.5 g (0.8 mol) of a pair of glass were placed in a round bottom flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen inlet tube. Phenol, 24.0 g (0.8 mol) of formaldehyde, 11.3 g (0.09 mol) of oxalic acid. After the dihydrate and 308 g of γ-butyrolactone, the polycondensation reaction was carried out at 100 ° C for 6 hours while flowing the nitrogen in a round bottom flask while refluxing the reaction liquid in an oil bath. Next, after the obtained reaction liquid was cooled to room temperature, 411 g of acetone was added and stirred and mixed until it became uniform. Thereafter, the reaction liquid droplets in the round bottom flask were mixed and mixed in 10 L of water, whereby the resin was analyzed. Then, the precipitated resin component was filtered off and recovered, and then vacuum dried at 60 ° C to obtain a phenol resin represented by the following formula (A-6). The obtained phenol resin (A-6) had a weight average molecular weight of 11,000.

(In the formula (A-6), the bonding bond bonded to the biphenol structure is bonded to any one of the two benzene rings).

(Synthesis Example 7)

<Synthesis of phenol resin (A-2)>

186.2 g (1.00 mol) of 4,4'-biphenol and 140.0 g (0.8 mol) of dichloride were added to a glass round bottom flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen introduction tube. After p-xylene, 7.7 g (0.05 mol) of diethyl sulfate and 327 g of γ-butyrolactone, the reaction liquid was refluxed in an oil bath while flowing nitrogen at 100 ° C while flowing nitrogen. 6 hours of polycondensation reaction. Next, after the obtained reaction liquid was cooled to room temperature, 436 g of acetone was added and stirred and mixed until it became uniform. Thereafter, the reaction liquid droplets in the round bottom flask were mixed and mixed in 10 L of water, whereby the resin was analyzed. Then, the precipitated resin component was filtered off and recovered, and then vacuum dried at 60 ° C to obtain a phenol resin represented by the following formula (A-2). The obtained phenol resin (A-2) had a weight average molecular weight of 13,500.

(In the formula (A-2), the bonding bond bonded to the biphenol structure is bonded to any one of the two benzene rings).

(Preparation of photosensitive resin composition)

For each of Examples 1 to 11 and Comparative Examples 1 and 2, a photosensitive resin composition was prepared as follows. First, the viscosity after blending becomes about 500 mPa. In the manner of s, the components blended according to Table 1 were dissolved in γ-butyrolactone (GBL) and stirred under a nitrogen atmosphere, and then filtered through a polyethylene filter having a pore size of 0.2 μm to obtain a varnish. A photosensitive resin composition. The details of each component in Table 1 are as follows. Further, the units in Table 1 are parts by mass.

<(A) Phenolic Resin>

(A-1) Phenolic resin obtained by the above Synthesis Example 1

(A-2) Phenolic resin obtained by the above Synthesis Example 2 or Synthesis Example 7

(A-3) Phenolic resin obtained by the above Synthesis Example 3

(A-4) Phenolic resin obtained by the above Synthesis Example 4

(A-5) Phenolic resin obtained by the above Synthesis Example 5

(A-6) Phenolic resin obtained by the above Synthesis Example 6

(A-7) Novolak resin (PR-50731, manufactured by Sumitomo Bakelite Co., Ltd., polystyrene-equivalent weight average molecular weight (Mw) = 11,000)

(A-8) phenol biphenyl aralkyl resin (MEIWA PLASTIC INDUSTRIES, LTD., MEH-7851, polystyrene-equivalent weight average molecular weight (Mw) = 2,000)

<(B) Photoacid generator>

(B-1) a naphthoquinone compound having the structure of the following formula (B-1)

(B-2) a naphthoquinone compound having the structure of the following formula (B-2)

(B-3) CPI-210S (manufactured by San-Apro Ltd.)

<(C) Crosslinker>

(C-1) NIKALAC MX-270 (manufactured by SANWA CHEMICAL CO., LTD.)

(C-2) TML-BPA (manufactured by HONSHU CHEMICAL INDUSTRY CO., LTD.)

(C-3) CELLOXIDE 2021P (manufactured by Daicel Corporation)

<(D) decane coupling agent>

(D-1) KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)

(D-2) KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd.)

(D-3) KBM-846 (manufactured by Shin-Etsu Chemical Co., Ltd.)

<(E) surfactant]

(E-1) F444 (made by DIC CORPORATION)

<(F) Thermal acid generator, hot base generator>

(F-1) Sunaid SI-150 (made by SANSHIN CHEMICAL INDUSTRY CO., LTD.)

(F-2) UCAT SA506 (manufactured by San-Apro Ltd.)

<(G)phenol compound>

(G-1) pentahydroxybiphenyl

(G-2) biphenol

<(H) Solvent>

(H-1) γ-butyrolactone

<Evaluation of phenol resin-1 (measurement of softening point)>

The softening point of the phenol resin of (A-1) to (A-8) was measured in accordance with JIS K 2207. The device used was an ASP-M2SP manufactured by MEITEC CORPORATION. The results are shown in Table 1. From the viewpoint of pattern maintenance performance at the time of final hardening, it is preferred that the softening point is high.

<Evaluation of phenol resin-2 (alkali solubility evaluation)>

The phenol resin of (A-1) to (A-8) was dissolved in γ-butyrolactone to obtain a resin solution. The obtained solution was applied onto a 4 Å wafer by a spin coater, and then prebaked at 120 ° C for 3 minutes by a hot plate to obtain a coating film having a film thickness of about 3 μm. The coating film obtained was immersed in a 2.38% tetramethylammonium hydroxide aqueous solution at 23 ° C for 3 minutes to confirm the solubility of the coating film. The results are shown in Table 1.

<Pattern formation evaluation-1 (Examples 1 to 8, Examples 10 to 11 and Comparative Examples 1 to 2)>

The photosensitive resin composition obtained above was applied onto a 8 Å wafer by a spin coater, and then prebaked at 120 ° C for 3 minutes by a hot plate to obtain a film thickness of about 9.0 μm. Coating film. The coating film was made of a mask made by TOPPAN PRINTING CO., LTD. (test drawing No. 1: a residual pattern having a width of 0.88 to 50 μm and a hollow pattern), and an i-ray stepping machine (NSR-manufactured by Nikon Corporation) was used. 4425i), the amount of exposure was changed to illuminate.

Then, as a developing solution, a 2.38% tetramethylammonium hydroxide aqueous solution was used, and the development time was adjusted so that the difference between the film thickness after prebaking and the film thickness after development was 1.0 μm, and the immersion development was performed twice. After the exposure portion was dissolved and removed, it was rinsed with pure water for 10 seconds. The resolution of the line pattern was evaluated by patterning the exposure with a minimum exposure amount of +100 mJ/cm ² of a square via pattern of 100 μm. In Table 2, the results are shown as pattern resolution (μm). From the viewpoint of fabricating fine wiring, the resolution is preferably small.

<Pattern formation evaluation-2 (Example 9)>

The photosensitive resin composition obtained above was applied onto a 8 Å wafer by a spin coater, and then prebaked at 120 ° C for 3 minutes by a hot plate to obtain a film thickness of about 9.0 μm. Coating film. The coating film was made of a mask made by TOPPAN PRINTING CO., LTD. (test drawing No. 1: a residual pattern having a width of 0.88 to 50 μm and a hollow pattern), and an i-ray stepping machine (NSR-manufactured by Nikon Corporation) was used. 4425i), the amount of exposure was changed to illuminate.

Next, baking treatment was performed at 100 ° C for 2 minutes by a hot plate. Next, as a developing solution, a 2.38% tetramethylammonium hydroxide aqueous solution was used for 30 seconds × 2 times of immersion development, whereby the exposed portion was dissolved and removed, and then rinsed with pure water for 10 seconds. The resolution of the line pattern was evaluated by patterning the exposure with an energy of a minimum exposure amount of +5 mJ/cm ² which forms a line of 5 μm. In Table 2, the results are shown as pattern resolution (μm). From the viewpoint of fabricating fine wiring, the resolution is small.

<Evaluation of resolution after hardening (Examples 1 to 11 and Comparative Examples 1 and 2)>

The wafer having the pattern obtained by the pattern formation evaluation-1 and the pattern formation evaluation-2 was placed in a heating oven, and the temperature was raised from room temperature to 200° C. at 5° C./min while flowing nitrogen, and in this state, Heat treatment was carried out at 200 ° C for 60 minutes, and cooled to room temperature. The heated patterned pattern of the wafer was subjected to microscopic observation, and the resolution of the line was evaluated. In Table 2, the results are shown as the resolution (μm) after hardening. From the viewpoint of forming a fine pattern, the resolution is preferably small.

<Production of Semiconductor Device>

The photosensitive resin compositions of Examples 1 to 11 and Comparative Examples 1 and 2 were applied to the dummy device wafer having an aluminum circuit on the surface, and finally patterned to be 5 μm, and then patterned and cured. After that, it is divided into individual wafer sizes, and is mounted on a lead frame for a 16Pin DIP (Dual Inline Package) using a conductive paste, followed by an epoxy resin for semiconductor sealing (Sumitomo Bakelite CO). , manufactured by E. Co., Ltd., EME-6300H), and a semiconductor device was produced by sealing molding.

<Reliability Evaluation-1 (Electrical Connectivity) of Semiconductor Device>

The electrical connection inspection of each of the ten semiconductor devices obtained by the above method was performed, and those having no electrical connection failure among all the ten semiconductor devices were evaluated as A, and those having electrical connection failure among one or more of the ten semiconductor devices were evaluated. For B.

<Reliability Evaluation of Semiconductor Device-2 (Moisture Resistance)>

Each of the ten semiconductor devices obtained by the above method was treated at 85 ° C / 85% humidity for 168 hours, and then immersed in a solder bath at 260 ° C for 10 seconds, followed by high-temperature, high-humidity pressure cooker treatment (125). °C, 2.3atm, 100% relative humidity), the electrical connection was checked.

Those who did not have electrical connection failure among all the ten semiconductor devices were evaluated as A, and those who observed electrical connection failure in one or more of the ten semiconductor devices were evaluated as B.

Table 2 showing the examples and comparative examples will be described below.

The coating film formed from the phenol resins (A-1) to (A-6) of the examples showed good alkali solubility. Further, the softening point of the coating film was 180 ° C or more. Thereby, these phenol resins are useful, for example, as a resist used in the production of a semiconductor device.

Further, the coating film formed of the photosensitive resin composition containing the phenol resins (A-1) to (A-6) of the examples has good pattern formability. Further, in the semiconductor device including the cured film, there is no defect in electrical connectivity, and after storage under high temperature and high humidity, no defects caused by corrosion of the aluminum circuit occur. Therefore, it is expected that the cured film is useful as an interlayer insulating film of a semiconductor device.

 [Industrial Availability]  

A photosensitive resin composition capable of forming a resin film and a cured film having excellent heat resistance, a resin film composed of the photosensitive resin composition, a cured film of the resin film, and a semiconductor device including the cured film, and A method of manufacturing a semiconductor device using the above-described photosensitive resin composition.

Claims (14)

 A photosensitive resin composition comprising: a phenol resin (A) having a biphenol structure; a photoacid generator (B); and a solvent.    The photosensitive resin composition of claim 1, wherein the phenol resin (A) has a biphenol compound derived from an aldehyde compound, a dimethylol compound, a dimethoxymethyl compound, and a dihalogen. A structural unit of at least one compound of the group consisting of alkyl compounds.   The photosensitive resin composition of the first or second aspect of the invention, wherein the phenol resin (A) is a resin having a structural unit represented by the formula (1), In the formula (1), R ₁₁ and R ₁₂ are each independently selected from a hydroxyl group, a halogen atom, a carboxyl group, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, an alkyl ether group having 1 to 20 carbon atoms, and a carbon number. a monovalent substituent of a group of 3 to 20 saturated or unsaturated alicyclic groups or an organic group having an aromatic structure of 6 to 20, which may be bonded by an ester bond, an ether bond or a guanamine bond. Or a carbonyl bond, p and q are each independently an integer of 0 to 3, and X ₁ and Y ₁ are each independently selected from an aliphatic group or a carbon having a carbon number of 1 to 10 which may have a single bond or an unsaturated bond. A divalent substituent of a group of 3 to 20 alicyclic groups and an organic group having an aromatic structure of 6 to 20 carbon atoms, wherein Y _{1 is} bonded to any one of the two benzene rings. The photosensitive resin composition of claim 1 or 2, wherein the phenol resin (A) has a repeating structural unit represented by the formula (2), In the formula (2), m is an integer of 2 to 10,000, and R ₁₁ and R ₁₂ are each independently selected from a hydroxyl group, a halogen atom, a carboxyl group, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, and a carbon number of 1 to 2. a monovalent substituent of a group consisting of an alkyl ether group of 20, a saturated or unsaturated alicyclic group having 3 to 20 carbon atoms or an organic group having an aromatic structure having 6 to 20 carbon atoms, which may be ester-substituted a bond, an ether bond, a guanamine bond or a carbonyl bond bond, p and q are each independently an integer of 0 to 3, and X ₁ and Y ₁ are each independently selected from a carbon number which may have a single bond or an unsaturated bond. a divalent substituent of a group consisting of an aliphatic group of 10, an alicyclic group having 3 to 20 carbon atoms, and an organic group having an aromatic structure of 6 to 20, wherein Y ₁ and 2 benzene rings are Any one of the keys.  The photosensitive resin composition of the first or second aspect of the invention, wherein the photoacid generator (B) is a compound which generates an acid by irradiation with radiation having a wavelength of 200 to 500 nm.    The photosensitive resin composition of claim 1 or 2, which further comprises a crosslinking agent (C) having a group reactive with the phenol resin (A).    The photosensitive resin composition of the first or second aspect of the invention, wherein the phenol resin (A) has a polystyrene-equivalent weight average molecular weight of 1,000 to 100,000.    The photosensitive resin composition of claim 1 or 2 further comprising a decane coupling agent (D).    The photosensitive resin composition of claim 1 or 2, which further comprises a nonionic surfactant (E).    The photosensitive resin composition of claim 1 or 2 further comprising a reaction accelerator (F).    A method of manufacturing a semiconductor device comprising the steps of: coating a photosensitive resin composition of claim 1 or 2 on a semiconductor substrate; and heating and drying the photosensitive resin composition to obtain a photosensitive resin a process of exposing the photosensitive resin layer by active light; developing the exposed photosensitive resin layer to obtain a patterned resin layer; and forming the patterned resin layer Heating is performed to obtain a process of hardening the resin layer.    A resin film comprising the photosensitive resin composition of claim 1 or 2.    A cured film which is a cured film of a resin film of claim 12 of the patent application.    A semiconductor device comprising the cured film of claim 13 of the patent application.