JP7111129B2 - Semiconductor device manufacturing method - Google Patents

Description

The present invention relates to a photosensitive resin composition, a method for manufacturing a semiconductor device, a resin film, a cured film, and a semiconductor device. More particularly, it relates to a photosensitive resin composition that can be used as a resist used in the manufacture of semiconductor devices, or as a precursor of a heat-resistant resin used in a semiconductor element surface protective film or an interlayer insulating film.
This application claims priority based on Japanese Patent Application No. 2016-220584 filed in Japan on November 11, 2016, the contents of which are incorporated herein.

Conventionally, various resin compositions or photosensitive compositions have been proposed as materials for use in forming surface protective films, interlayer insulating films, etc. used for semiconductor elements in electronic components (e.g., Patent Documents 1).

In Patent Document 1, in a solvent, a phenol resin (A) having a biphenyldiyl structure in the main chain, a photoacid generator (B), and an acid generated from the (B) or by heat, the (A ) and a compound (C) capable of reacting therewith. Patent Document 1 describes a phenol resin containing an unsubstituted biphenyldiyl structure as the phenol resin (A).

JP 2012-123378 A

A cured resin film used for forming a surface protective film and an interlayer insulating film of a semiconductor device is obtained by applying a photosensitive resin composition to a substrate to obtain a resin film, exposing and developing the resin film to form a pattern, Subsequently, it is obtained by heating and curing the patterned resin film. With conventional photosensitive resin compositions, the resulting resin film has a low softening point and low heat resistance, and the pattern shape is deformed by heating. was there.

According to the present invention for solving the above problems, a photosensitive resin composition capable of forming a resin film and a cured film having excellent heat resistance, a resin film comprising the photosensitive resin composition, and curing of the resin film A film, a semiconductor device comprising the cured film, and a method of manufacturing a semiconductor device using the photosensitive resin composition are provided.

（式（２）において、
ｍは、２～１００００の整数であり、
Ｒ_１１、およびＲ_１２は、それぞれ独立して、水酸基、ハロゲン原子、カルボキシル基、炭素数１～２０の飽和または不飽和のアルキル基、炭素数１～２０のアルキルエーテル基、炭素数３～２０の飽和または不飽和の脂環式基、または炭素数６～２０の芳香族構造を有する有機基からなる群から選ばれる１価の置換基であり、これらはエステル結合、エーテル結合、アミド結合、またはカルボニル結合を介して結合していてもよく、
ｐ、およびｑは、それぞれ独立して、０～３の整数であり、
Ｘ_１、およびＹ_１は、それぞれ独立して、単結合、または式（３）で表される有機基からなる群から選ばれる２価の置換基であり、
ただし、Ｙ_１は、２つのベンゼン環のうちいずれか一方に結合する）。

（式（３）において、ｎは、０～２０である。） The inventors of the present invention have made intensive studies to solve the above problems, and as a result, have completed the present invention including the following aspects.
[1] the following steps:
The 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 results in a polystyrene consisting of only repeating structural units represented by the formula (2). A step of forming a phenol resin (A) having a biphenol structure and having a converted weight average molecular weight of 7,000 to 100,000;
A step of mixing the phenolic resin (A), the photoacid generator (B), and a solvent to form a photosensitive resin composition for forming a resist used for a surface protective film or an interlayer insulating film of a semiconductor device. ,
applying the resist-forming photosensitive resin composition onto a semiconductor substrate;
a step of drying the resist-forming photosensitive resin composition by heating to obtain a photosensitive resin layer;
exposing the photosensitive resin layer with actinic rays;
developing the exposed photosensitive resin layer to obtain a patterned resin layer; and heating the patterned resin layer to obtain a cured resin layer;
A method of manufacturing a semiconductor device, comprising:

(In formula (2),
m is an integer from 2 to 10000,
R ₁₁ and R ₁₂ each independently represent 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, an alkyl ether group having 1 to 20 carbon atoms, or 3 to 20 carbon atoms. A saturated or unsaturated alicyclic group, or a monovalent substituent selected from the group consisting of an organic group having an aromatic structure having 6 to 20 carbon atoms, these are ester bonds, ether bonds, amide bonds, or may be attached via a carbonyl bond,
p and q are each independently an integer of 0 to 3;
X ₁ and Y ₁ are each independently a single bond or a divalent substituent selected from the group consisting of organic groups represented by formula (3),
However, Y ₁ is bound to either one of the two benzene rings).

(In formula (3), n is 0 to 20.)

[2] The method for manufacturing a semiconductor device according to [1] above, wherein the photoacid generator (B) is a compound that generates an acid when irradiated with radiation having a wavelength of 200 to 500 nm.

[3] The semiconductor device according to [1] or [2], wherein the resist-forming photosensitive resin composition further includes a cross-linking agent (C) having a group capable of reacting with the phenol resin (A). Production method.

[4] The method for manufacturing a semiconductor device according to any one of [1] to [3], wherein the resist-forming photosensitive resin composition further contains a silane coupling agent (D).

[5] The method for manufacturing a semiconductor device according to any one of [1] to [4], wherein the resist-forming photosensitive resin composition further contains a nonionic surfactant (E).

[6] The method for manufacturing a semiconductor device according to any one of [1] to [5], wherein the resist-forming photosensitive resin composition further contains a reaction accelerator (F).

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 comprising the photosensitive resin composition, a cured film of the resin film, and the cured film. A semiconductor device comprising a film and a method of manufacturing a semiconductor device using the photosensitive resin composition are provided.

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below.

(Photosensitive resin composition)
The photosensitive resin composition according to this embodiment contains a phenolic resin (A) having a biphenol structure, a photoacid generator (B), and a solvent.
The resin composition of the present embodiment is made of the above composition by using a resin having a biphenol structure, that is, a phenol resin having a biphenyldiyl structure having at least one hydroxyl group in each phenyl group, as the phenol resin (A). The heat resistance of the resin film is improved. Therefore, when a resin film made of the photosensitive resin composition is exposed and developed to form a pattern, a high-resolution pattern can be formed on the resin film.

(Phenolic resin (A))
In one embodiment, the phenol resin (A) has structural units derived from a biphenol compound and at least one compound selected from the group consisting of an aldehyde compound, a dimethylol compound, a dimethoxymethyl compound and a dihaloalkyl compound. In other words, the phenol resin (A) is obtained by reacting a biphenol compound with at least one compound selected from the group consisting of aldehyde compounds, dimethylol compounds, dimethoxymethyl compounds and dihaloalkyl compounds.
As used herein, the term "structure derived from (substance)" refers to a structure produced using the substance, and the structure can be identified using a conventional method in the art or cannot be identified. and both.
Since such a phenol resin (A) can be produced using commercially available raw material monomers without requiring complicated steps, the resulting photosensitive resin composition can be produced at low cost. .

Phenolic resin (A) can be produced by any known method. Examples of the production method include a condensation reaction between a biphenol compound and an aldehyde compound, a dimethylol compound, a dimethoxymethyl compound, or a dihaloalkyl compound.

Biphenol compounds that can be used to produce the phenolic resin (A) include 2,2'-biphenol and 4,4'-biphenol, and isomers thereof. These biphenol compounds may have a substituent, which may be a hydroxyl group, a halogen, a carboxyl group, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, or an alkyl ether having 1 to 20 carbon atoms. groups, saturated or unsaturated alicyclic groups having 3 to 20 carbon atoms, or organic groups having an aromatic structure having 6 to 20 carbon atoms.
Such biphenol compounds are exemplified by, but not limited to, the following compounds.

Examples of the aldehyde compound that produces the phenolic resin (A) by reaction with the biphenol compound include formaldehyde, acetaldehyde, propionaldehyde, pivalaldehyde, butyraldehyde, pentanal, hexanal, trioxane, glyoxal, cyclohexylaldehyde, diphenylacetaldehyde, and ethylbutyraldehyde. , benzaldehyde, cinnamaldehyde, diphenylacetaldehyde, methyl fumaaldehyde, 3-methyl-2-butenal, glyoxylic acid, 5-norbornene-2-carboxaldehyde, malondialdehyde, succindialdehyde, glutaraldehyde, naphthaldehyde, terephthalaldehyde etc.

Examples of the dimethylol compound that produces the phenolic resin (A) by reaction with the biphenol compound include 2,2-bis(hydroxymethyl)butyric acid, 1,3-propanediol, 2-benzyloxy-1,3-propanediol, 2 ,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, monoacetin, 2-methyl-2-nitro-1,3-propanediol, 5-norbornene-2,2- dimethanol, 5-norbornene-2,3-dimethanol, pentaerythritol, 2-phenyl-1,3-propanediol, trimethylolethane, trimethylolpropane, 3,6-bis(hydroxymethyl)durene, 2-nitro -p-xylylene glycol, 1,10-dihydroxydecane, 1,12-dihydroxydodecane, 1,4-bis(hydroxymethyl)cyclohexane, 1,4-bis(hydroxymethyl)cyclohexene, 1,6-bis(hydroxy methyl)adamantane, 1,4-benzenedimethanol, 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)diphenylthioether, 4,4'-bis(hydroxymethyl)benzophenone, 4-hydroxymethylbenzoic acid-4'-hydroxymethylphenyl, 4-hydroxy methylbenzoic acid-4'-hydroxymethylanilide, 4,4'-bis(hydroxymethyl)phenylurea, 4,4'-bis(hydroxymethyl)phenylurethane, 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.

Examples of the dimethoxymethyl compound that produces the phenolic resin (A) by reaction with the biphenol compound include 2,2-bis(methoxymethyl)butyric acid, 1,3-dimethoxymethylpropane, 2-benzyloxy-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-dimethoxymethylpropane, 5-norbornene-2,2-dimethoxymethyl, 5-norbornene-2,3-dimethoxymethyl, tetrakis(methoxymethyl)methane, 2-phenyl-1,3-dimethoxymethylpropane, trimethoxyethane, trimethoxypropane, 3,6-bis(methoxymethyl)durene, 2-nitro-1,4-bis(methoxymethyl)benzene, 1,10-dimethoxydecane, 1,12-dimethoxidedecane, 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)diphenylthioether , 4,4′-bis(methoxymethyl)benzophenone, 4′-methoxymethylphenyl 4-methoxymethylbenzoate, 4′-methoxymethylanilide 4-methoxymethylbenzoate, 4,4′-bis(methoxymethyl) ) phenylurea, 4,4′-bis(methoxymethyl)phenylurethane, 1,8-bis(methoxymethyl)anthracene, 4,4′-bis(methoxymethyl)biphenyl, 2,2′-dimethyl-4,4 '-bis(methoxymethyl)biphenyl, 2,2-bis(4-methoxymethylphenyl)propane and the like.

Examples of the dihaloalkyl compound that produces the phenolic resin (A) by reaction with the biphenol compound include xylene dichloride, bischloromethyldimethoxybenzene, bischloromethyldurene, bischloromethylbiphenyl, bischloromethyl-biphenylcarboxylic acid, bis chloromethyl-biphenyldicarboxylic acid, bischloromethyl-methylbiphenyl, bischloromethyl-dimethylbiphenyl, bischloromethylanthracene, ethylene glycol bis(chloroethyl) ether, diethylene glycol bis(chloroethyl) ether, triethylene glycol bis(chloroethyl) ether, tetraethylene glycol bis(chloroethyl) ether and the like.
The above compounds may be used singly or in combination of two or more.

The phenol resin (A) can be obtained by condensing the above biphenol compound and the above polymerization component by dehydration or dehydrohalogenation, and a catalyst may be used during the polymerization. Acidic catalysts include, for example, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, phosphorous acid, methanesulfonic acid, p-toluenesulfonic acid, dimethylsulfuric acid, diethylsulfuric acid, acetic acid, oxalic acid, 1-hydroxyethylidene-1,1 '-diphosphonic acid, zinc acetate, boron trifluoride, boron trifluoride/phenol complex, boron trifluoride/ether complex and the like. Examples of alkaline catalysts include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, triethylamine, pyridine, 4-N,N-dimethylaminopyridine, piperidine, piperazine, 1 , 4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonene, ammonia, hexa methylenetetramine and the like.

An organic solvent can be used as necessary when carrying out the synthesis reaction of the phenol resin (A). Specific examples of usable organic solvents include bis(2-methoxyethyl) ether, methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone, Examples include, but are not limited to, toluene, xylene, γ-butyrolactone, N-methyl-2-pyrrolidone, and the like.

The phenolic resin (A) may be obtained by further using and polymerizing a phenolic compound other than the biphenolic compound described above within a range that does not impair the effects of the present invention.

式（１）において、
Ｒ_１１、およびＲ_１２は、それぞれ独立して、水酸基、ハロゲン原子、カルボキシル基、炭素数１～２０の飽和または不飽和のアルキル基、炭素数１～２０のアルキルエーテル基、炭素数３～２０の飽和または不飽和の脂環式基、または炭素数６～２０の芳香族構造を有する有機基からなる群から選ばれる１価の置換基であり、これらはエステル結合、エーテル結合、アミド結合、またはカルボニル結合を介して結合していてもよく、
ｐ、およびｑは、それぞれ独立して、０～３の整数であり、
Ｘ_１、およびＹ_１は、それぞれ独立して、単結合、または不飽和結合を有していてもよい炭素数１～１０の脂肪族基、炭素数３～２０の脂環式基、および炭素数６～２０の芳香族構造を有する有機基からなる群から選ばれる２価の置換基であり、
ただし、Ｙ_１は、２つのベンゼン環のうちいずれか一方に結合する。 In one embodiment, the phenolic resin (A) obtained from the above compound may have a structural unit represented by formula (1).

In formula (1),
R ₁₁ and R ₁₂ each independently represent 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, an alkyl ether group having 1 to 20 carbon atoms, or 3 to 20 carbon atoms. A saturated or unsaturated alicyclic group, or a monovalent substituent selected from the group consisting of an organic group having an aromatic structure having 6 to 20 carbon atoms, these are ester bonds, ether bonds, amide bonds, or may be attached via a carbonyl bond,
p and q are each independently an integer of 0 to 3;
X ₁ and Y ₁ are each independently a single bond or an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond, an alicyclic group having 3 to 20 carbon atoms, and carbon A divalent substituent selected from the group consisting of organic groups having an aromatic structure of numbers 6 to 20,
However, Y ₁ is bonded to either one of the two benzene rings.

In the structural unit of formula (1) that the phenolic resin (A) may have, the phenolic resin (A) is included by including a biphenol structure, that is, a biphenyldiyl structure having at least one hydroxyl group in each phenyl group. The heat resistance of the resin film made of the composition is improved. Therefore, when a resin film made of the photosensitive resin composition is exposed and developed to form a pattern, a high-resolution pattern can be formed on the resin film.

R ₁₁ and R ₁₂ are each independently preferably a hydroxyl group.
Preferably, p and q are each independently an integer of 0-2.
X ₁ and Y ₁ are each independently a single bond or an organic It is preferably a divalent substituent selected from the group consisting of groups.

The “aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond” for X ₁ and Y ₁ may be linear or branched. The number of carbon atoms may be 1-7, 1-5, or 1-3. As the aliphatic group, if it is an aliphatic hydrocarbon group, an alkylene group, an alkenylene group, an alkynylene group, etc. can be mentioned, and among these, an alkylene group is preferable. A propylene group and the like can be mentioned.

The “organic group having an aromatic structure having 6 to 20 carbon atoms” in X ₁ and Y ₁ may have 6 to 14 carbon atoms, may have 6 to 12 carbon atoms, or may have 6 to 12 carbon atoms. It may be 6 to 9, or may have 6 to 8 carbon atoms. Examples of the "aromatic structure" include a phenylene group, a biphenyldiyl group, a naphthalenediyl group, and the like, and among these, a phenylene group is preferred.
The “organic group having an aromatic structure having 6 to 20 carbon atoms” for X ₁ and Y ₁ is the same as the above “aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond” and the above “aromatic It may be a divalent substituent formed by mutually bonding "group structure".

上記式中、ｎは、０～２０であり、０～１０であることが好ましい。 X ₁ and Y ₁ are each independently more preferably the following organic groups.

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

The structural unit represented by the above formula (1) is obtained by reacting the above biphenol compound with at least one compound selected from the group consisting of aldehyde compounds, dimethylol compounds, dimethoxymethyl compounds and dihaloalkyl compounds. .

ここで、式（２）において、ｍは、１～１００００の整数であり、Ｒ_１１、およびＲ_１２、ｐ、およびｑ、ならびにＸ_１、およびＹ_１は、式（１）における定義と同様である。 In the present embodiment, the phenol resin (A) substantially has repeating units represented by formula (2).

Here, in formula (2), m is an integer of 1 to 10000, and R ₁₁ , R ₁₂ , p and q, X ₁ and Y ₁ are the same as defined in formula (1). be.

式（３）において、ｌおよびｍは構成比を示し、ｌ＋ｍ＝１であり、０≦ｌ≦１、０≦ｍ≦１であり、
Ｒ_１１'、Ｒ_１２'、Ｒ_１１"およびＲ_１２"は、それぞれ独立して、水酸基、ハロゲン原子、カルボキシル基、炭素数１～２０の飽和または不飽和のアルキル基、炭素数１～２０のアルキルエーテル基、炭素数３～２０の飽和または不飽和の脂環式基、または炭素数６～２０の芳香族構造を有する有機基からなる群から選ばれる１価の置換基であり、これらはエステル結合、エーテル結合、アミド結合、カルボニル結合を介して結合していてもよく、
ｐ、およびｑは、それぞれ独立して、０～３の整数であり、
Ｘ_１'、Ｙ_１'、Ｘ_１"およびＹ_１"は、それぞれ独立して、単結合、または不飽和結合を有していてもよい炭素数１～１０の脂肪族基、炭素数３～２０の脂環式基、および炭素数６～２０の芳香族構造を有する有機基からなる群から選ばれる２価の置換基である。
フェノール樹脂（Ａ）の上記構造は、用いるビフェノール化合物と、重合性化合物の種類から当業者に理解され得る。 A resin having a repeating unit structure represented by formula (2) may be, for example, a resin having a structure represented by formula (3).

In formula (3), l and m represent a composition ratio, l + m = 1, 0 ≤ l ≤ 1, 0 ≤ m ≤ 1,
R _11′ , R _12′ , R _11″ and R _12″ are each independently a hydroxyl group, a halogen atom, a carboxyl group, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, A monovalent substituent selected from the 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, may be bonded via an ester bond, an ether bond, an amide bond, or a carbonyl bond,
p and q are each independently an integer of 0 to 3;
X _1′ , Y _1′ , X _1″ and Y _1″ are each independently a single bond or an aliphatic group having 1 to 10 carbon atoms optionally having an unsaturated bond, 3 to It is a divalent substituent selected from the group consisting of 20 alicyclic groups and organic groups having an aromatic structure with 6 to 20 carbon atoms.
The above structure of the phenolic resin (A) can be understood by those skilled in the art from the types of biphenol compounds and polymerizable compounds used.

In one embodiment, the weight average molecular weight (polystyrene equivalent) 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 phenolic resin (A) having a weight-average molecular weight within the above range has excellent solubility in solvents and excellent mechanical properties of the resulting resin film.

(Photoacid generator (B))
The photosensitive resin composition of the present embodiment is not particularly limited as long as it is a composition capable of forming a resin pattern in response to radiation such as ultraviolet rays, electron beams, and X-rays. It may be any type of photosensitive resin composition. The resin composition of the present embodiment, which has photosensitivity due to the inclusion of the photoacid generator (B), can be used, for example, as a resist used in the manufacture of semiconductor devices.

The photoacid generator (B) used in the photosensitive resin composition of the present embodiment is a compound that generates an acid in response to irradiated radiation. It is a compound that generates an acid when irradiated with radiation having a wavelength of up to 450 nm. Specific examples include photosensitive diazoquinone compounds, photosensitive diazonaphthoquinone compounds, diaryliodonium salts, onium salts such as triarylsulfonium salts or sulfonium borate salts, 2-nitrobenzyl ester compounds, N-iminosulfonate compounds, imidosulfonate compounds. , 2,6-bis(trichloromethyl)-1,3,5-triazine compounds, dihydropyridine compounds and the like. These may be used individually by 1 type, and may use 2 or more types together. Among them, a photosensitive diazoquinone compound and a photosensitive diazonaphthoquinone compound, which are excellent in sensitivity and solvent solubility, are preferable. Specific examples of these include 1,2-benzoquinonediazide-4-sulfonate esters, 1,2-naphthoquinonediazide-4-sulfonate esters, and 1,2-naphthoquinonediazide-5-sulfonate esters of phenol compounds. mentioned.

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

(solvent)
The photosensitive resin composition of this embodiment is used in the form of a varnish obtained by dissolving the above components in a solvent. Solvents used include N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylacetamide, dimethylsulfoxide, 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-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate and methyl-3-methoxy propionate and the like, which may be used singly or in combination.

The amount of the solvent used is 50% by weight to 1000% by weight, preferably 100% by weight to 500% by weight, based on 100% by weight of the phenol resin (A). By using the solvent within the above range, it is possible to prepare a varnish in which the resin is sufficiently dissolved and which is excellent in handleability.

(Crosslinking agent (C))
The photosensitive resin composition of the present embodiment may contain a cross-linking agent (C) having a group capable of reacting with the phenol resin (A). When a resin film is prepared using the photosensitive resin composition of the present embodiment containing the cross-linking agent (C), and is patterned by exposure and development and then heat-cured, the cross-linking agent (C) is photoacid-generating. It crosslinks with the phenolic resin (A) by the action of the acid generated from the agent (B) or heat. Since the resin film obtained from the photosensitive resin composition containing a cross-linking agent contains the phenol resin (A) having the structure described above, deformation of the patterned resin film during heat curing is suppressed. In addition, 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 for semiconductor devices.

As the cross-linking agent (C) that can be used in the photosensitive resin composition of the present embodiment, it is preferable to use a compound that can be thermally cross-linked with the phenol resin (A). Cross-linking agents (C) that may be used include the following compounds:
(1) compounds containing one or more crosslinkable groups selected from the group consisting of methylol groups and alkoxymethyl groups: for example, benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, Bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol , bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methoxymethylphenyl methoxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl; as commercial products 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.) , Nicalac MX-270, -280, -290, Nicalac MS-11, Nicalac 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, commercially available 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A (Asahi Yakuzai Kogyo Co., Ltd.), 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-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymer-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) compounds having an epoxy group: for example, n-butyl glycidyl ether, 2-ethoxyhexyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether , glycidyl ethers such as glycerol polyglycidyl ether, sorbitol polyglycidyl ether, glycidyl ether of bisphenol A (or F), glycidyl esters such as diglycidyl adipate, o-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, dicyclopentanediene oxide, bis(2,3-epoxycyclopentyl) ether, and alicyclic epoxies such as Celoxide 2021, Celoxide 2081, Celoxide 2083, Celoxide 2085, Celoxide 8000, and Epolead GT401 manufactured by Daicel Co., Ltd. , 2,2′-(((((1-(4-(2-(4-(oxiran-2-ylmethoxy)phenyl)propan-2-yl)phenyl)ethane-1,1-diyl)bis(4 ,1-phenylene))bis(oxy))bis(methylene))bis(oxirane)) (for example, Techmore VG3101L (manufactured by Printec Co., Ltd.)), Epolite 100MF (manufactured by Kyoeisha Chemical Industry Co., Ltd.), Epiol TMP Aliphatic polyglycidyl ethers (manufactured by NOF Corporation), 1,1,3,3,5,5-hexamethyl-1,5-bis(3-(oxiran-2-ylmethoxy)propyl)trisiloxane (For example, DMS-E09 (manufactured by Gelest));
(3) compounds having an isocyanate group: for example, 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, 1,3-phenylenebismethylene diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate;
(4) compounds having a bismaleimide group: for example, 4,4'-diphenylmethanebismaleimide, phenylmethanemaleimide, m-phenylenebismaleimide, bisphenol A diphenylether bismaleimide, 3,3'-dimethyl-5,5'-diethyl -4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenylether bismaleimide, 4,4'-diphenylsulfonebismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene.

The amount of the cross-linking agent (C) in the photosensitive resin composition is 1-100% by weight, preferably 5-50% by weight, based on 100% by weight of the phenolic resin (A). When the amount is 1% by weight or more, the mechanical strength of the thermoset 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 thermoset film is improved. Good strength.

(Silane coupling agent (D))
The photosensitive resin composition of the present embodiment may contain a silane coupling agent (D). By containing the silane coupling agent (D), the adhesiveness to the substrate is improved when the photosensitive resin composition is applied onto the substrate to obtain a resin film.

Silane coupling agents (D) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3- methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(amino ethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltri Methoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxypropyl)tetrasulfide, 3- Examples thereof include, but are not limited to, isocyanatopropyltriethoxysilane, and a silicon compound obtained by reacting a silicon compound having an amino group with an acid dianhydride or an acid anhydride. Silane coupling agents can be used alone or in combination.

The amount of the silane 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 phenolic resin (A). . By using the silane coupling agent (D) within the above range, both adhesion to the substrate and 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). By containing the nonionic surfactant (E), the coating property when the photosensitive resin composition is coated on a substrate to obtain a resin film is improved, and a coating film having a uniform thickness can be obtained. can. In addition, it is possible to prevent residues and patterns from rising 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 (eg, a fluorinated alkyl group) or a silanol group, or a compound having a siloxane bond as a main skeleton. In this embodiment, as the nonionic surfactant (E), it is more preferable to use a fluorine-based surfactant or a silicone-based surfactant, and it is particularly preferable to use a fluorine-based surfactant. Examples of fluorosurfactants include Megafac 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, and the like, but are not limited thereto.

When a surfactant is used, the amount of the surfactant to be blended is preferably 0.01 to 10% by weight with respect to 100 parts by mass of the alkali-soluble phenolic resin.

(Reaction accelerator (F))
The photosensitive resin composition of the present embodiment may contain a reaction accelerator (F). By containing the reaction accelerator (F), thermal crosslinking between the phenolic resin (A) contained in the photosensitive resin composition and the crosslinking agent can be promoted.

As the reaction accelerator (F), for example, a nitrogen-containing five-membered heterocyclic compound or a compound that generates an acid by heat can be used. These may be used alone, or may be used in combination. Nitrogen-containing five-membered heterocyclic compounds used as the reaction accelerator (F) include, for example, pyrrole, pyrazole, imidazole, 1,2,3-triazole, and 1,2,4-triazole. Examples of compounds that generate acid by heat and used as the reaction accelerator (F) include sulfonium salts, iodonium salts, sulfonates, phosphates, borates, and salicylates. From the viewpoint of more effectively improving the curability at low temperatures, it is more preferable to contain one or both of a sulfonate and a borate among the compounds that generate acid by heat, and improve the heat resistance of the cured film properties. Of these considerations, the inclusion of borate is particularly preferred.

(other additives)
Additives such as dissolution accelerators, antioxidants, fillers, photopolymerization initiators, terminal blockers and sensitizers may be added to the photosensitive resin composition of the present embodiment as necessary to achieve the effect of the present invention. may be further used as long as it does not impair the

(Method for producing cured film)
Another aspect of this embodiment is the step of:
a step of applying the above-described photosensitive resin composition of the present invention onto a semiconductor substrate;
a step of drying the photosensitive resin composition by heating to obtain a photosensitive resin layer;
exposing the photosensitive resin layer with actinic rays;
developing the exposed photosensitive resin layer to obtain a patterned resin layer; and heating the patterned resin layer to obtain a cured resin layer;
A method of manufacturing a semiconductor device is provided. An example of this embodiment will be described below.

(Method for forming coating film)
First, the photosensitive resin composition of this embodiment is applied to a support or substrate such as a silicon wafer, ceramic substrate, aluminum substrate, SiC wafer, GaN wafer, and the like. Here, the substrate includes, in addition to an unprocessed substrate, a substrate having, for example, a semiconductor element or a display element formed thereon. At this time, in order to ensure water-resistant adhesion between the pattern to be formed and the support, an adhesion aid such as a silane coupling agent may be applied to the support or substrate in advance. Application of the photosensitive resin composition can be performed by spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, or the like.

Next, prebaking 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 1 to 500 μm.

(Exposure process)
Next, the coating film obtained as described above is exposed. Actinic rays for exposure include, for example, X-rays, electron rays, ultraviolet rays, visible rays, etc., and those with a wavelength of 200 to 500 nm are preferred. From the viewpoints of pattern resolution and handleability, the light source wavelength is preferably in the g-line, h-line or i-line region of a mercury lamp, and may be used alone or in combination of two or more rays. A contact aligner, a mirror projection or a stepper are particularly preferred as the exposure device. After exposure, if necessary, the coating film may be heated again at 80 to 140° C. for about 10 to 300 seconds.

(Development process)
Next, the exposed coating film is developed to form a relief pattern. In this development step, development can be carried out using an appropriate developer, for example, by a method such as an immersion method, a puddle method, or a rotary spray method. By development, an exposed portion (in the case of a positive type) or an unexposed portion (in the case of a negative type) is eluted and removed from the coating film, and a relief pattern can be obtained.

Examples of the developer include inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia;
organic amines such as ethylamine, diethylamine, triethylamine, triethanolamine;
aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide;
Organic solvents such as cyclopentanone, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate can be used, and these include water-soluble organic solvents such as methanol and ethanol, or even if a surfactant is added. good.
Among these, tetramethylammonium hydroxide aqueous solution is preferred. The concentration of tetramethylammonium hydroxide in the aqueous solution is preferably 0.5-10% by mass, more preferably 1-5% by mass.

A relief pattern can be obtained by washing with a rinse solution after development and removing the developer. As the rinse liquid, for example, distilled water, methanol, ethanol, isopropanol, propylene glycol monomethyl ether, and the like can be used alone or in combination of two or more.

(Heating process)
Finally, a cured relief pattern (cured film) can be obtained by heating the relief pattern obtained as described above. The heating temperature is preferably 150°C to 500°C, more preferably 150°C to 400°C. The heating time can be 15 to 300 minutes. This heat treatment can be performed using a hot plate, an oven, a heating oven in which a temperature program can be set, or the like. As the atmosphere gas for the heat treatment, air may be used, or an inert gas such as nitrogen or argon may be used. Moreover, when it is necessary to heat-treat at a lower temperature, heating may be performed under reduced pressure using a vacuum pump or the like.
The relief pattern obtained from the photosensitive resin composition of the present embodiment undergoes little or no deformation during the heating step, maintains the shape of the relief pattern before heating, and can provide a cured relief pattern with high resolution.

(semiconductor device)
The cured relief pattern described above 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 for a device having a bump structure. By combining with, a semiconductor device can be manufactured. As described above, the cured relief pattern of the present embodiment can be produced with high resolution, so that the semiconductor device using it has excellent electrical reliability.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than those described above can also be adopted. Moreover, the present invention is not limited to the above-described embodiments, and includes modifications, improvements, etc. within the scope of achieving the object of the present invention.

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

（式（Ａ－１）において、ビフェノール構造に結合する結合手は、２つのベンゼン環のうちいずれか一方に結合している）。 (Synthesis example 1)
<Synthesis of phenolic resin (A-1)>
186.2 g (1.00 mol) of 4,4'-biphenol and 2,6-bis- After charging 134.6 g (0.8 mol) of (hydroxymethyl)-p-cresol, 6.3 g (0.05 mol) of oxalic acid dihydrate, and 327 g of γ-butyrolactone, the mixture was blown with nitrogen. The polycondensation reaction was carried out at 100° C. for 6 hours while refluxing the reaction solution in the round-bottomed flask in an oil bath. Next, after cooling the resulting reaction solution to room temperature, 436 g of acetone was added and mixed with stirring until uniform. After that, the resin component was precipitated by dropping and mixing the reaction liquid in the round-bottomed flask with 10 L of water. Next, after the precipitated resin component was collected by filtration, it was vacuum-dried at 60° C. to obtain a phenol resin represented by the following formula (A-1). The weight average molecular weight of the obtained phenol resin (A-1) was 9,800.

(In formula (A-1), the bond that binds to the biphenol structure is bound to either one of the two benzene rings).

（式（Ａ－２）において、ビフェノール構造に結合する結合手は、２つのベンゼン環のうちいずれか一方に結合している）。 (Synthesis example 2)
<Synthesis of phenolic resin (A-2)>
186.2 g (1.00 mol) of 4,4'-biphenol and 1,4-bis- After charging 133.0 g (0.8 mol) of (methoxymethyl)benzene, 7.7 g (0.05 mol) of diethyl sulfate, and 327 g of γ-butyrolactone, the round bottom flask was placed in an oil bath while flushing with nitrogen. A polycondensation reaction was carried out at 100° C. for 6 hours while the reaction solution was refluxed. Next, after cooling the resulting reaction solution to room temperature, 436 g of acetone was added and mixed with stirring until uniform. After that, the resin component was precipitated by dropping and mixing the reaction liquid in the round-bottomed flask with 10 L of water. Next, the precipitated resin component was collected by filtration, and then vacuum-dried at 60° C. to obtain a phenol resin represented by the following formula (A-2). The weight average molecular weight of the obtained phenol resin (A-2) was 12,300.

(In formula (A-2), the bond that binds to the biphenol structure is bound to either one of the two benzene rings).

（式（Ａ－３）において、ビフェノール構造に結合する結合手は、２つのベンゼン環のうちいずれか一方に結合している）。 (Synthesis Example 3)
<Synthesis of phenolic resin (A-3)>
186.2 g (1.00 mol) of 4,4'-biphenol and 4,4'- After charging 193.9 g (0.8 mol) of bis(methoxymethyl)biphenyl, 7.7 g (0.05 mol) of diethyl sulfate, and 582 g of γ-butyrolactone, the round-bottomed flask was immersed in an oil stream while flowing nitrogen. A polycondensation reaction was carried out at 100° C. for 6 hours while refluxing the reaction solution in a bath. Next, after cooling the resulting reaction solution to room temperature, 323 g of acetone was added and mixed with stirring until uniform. After that, the resin component was precipitated by dropping and mixing the reaction liquid in the round-bottomed flask with 10 L of water. Next, the precipitated resin component was collected by filtration and vacuum-dried at 60° C. to obtain a phenol resin represented by the following formula (A-3). The weight average molecular weight of the obtained phenol resin (A-3) was 7,000.

(In formula (A-3), the bond that binds to the biphenol structure is bound to either one of the two benzene rings).

（式（Ａ－４）において、ビフェノール構造に結合する結合手は、２つのベンゼン環のうちいずれか一方に結合している）。 (Synthesis Example 4)
<Synthesis of phenolic resin (A-4)>
186.2 g (1.00 mol) of 2,2'-biphenol and 2,6-bis- After charging 134.6 g (0.8 mol) of (hydroxymethyl)-p-cresol, 6.3 g (0.05 mol) of oxalic acid dihydrate, and 327 g of γ-butyrolactone, the mixture was blown with nitrogen. The polycondensation reaction was carried out at 100° C. for 6 hours while refluxing the reaction solution in the round-bottomed flask in an oil bath. Next, after cooling the resulting reaction solution to room temperature, 436 g of acetone was added and mixed with stirring until uniform. After that, the resin component was precipitated by dropping and mixing the reaction liquid in the round-bottomed flask with 10 L of water. Next, the precipitated resin component was separated by filtration and collected, followed by vacuum drying at 60° C. to obtain a phenol resin represented by the following formula (A-4). The weight average molecular weight of the obtained phenol resin (A-4) was 7,700.

(In formula (A-4), the bond that binds to the biphenol structure is bound to either one of the two benzene rings).

（式（Ａ－５）において、ビフェノール構造に結合する結合手は、２つのベンゼン環のうちいずれか一方に結合している）。 (Synthesis Example 5)
<Synthesis of phenolic resin (A-5)>
234.2 g (1.00 mol) of phloroglucide and 1,4-bis(methoxymethyl)benzene were placed in a four-neck glass round-bottom flask equipped with a thermometer, a stirrer, a raw material inlet and a dry nitrogen gas inlet tube. After charging 133.0 g (0.8 mol) of diethyl sulfate, 7.7 g (0.05 mol) of diethyl sulfate, and 375 g of γ-butyrolactone, the round-bottomed flask was placed in an oil bath while flowing nitrogen, and the reaction solution was refluxed. A polycondensation reaction was carried out at 100° C. for 6 hours. Next, after cooling the resulting reaction solution to room temperature, 500 g of acetone was added and mixed with stirring until uniform. After that, the resin component was precipitated by dropping and mixing the reaction liquid in the round-bottomed flask with 10 L of water. Next, the precipitated resin component was separated by filtration and collected, followed by vacuum drying at 60° C. to obtain a phenol resin represented by the following formula (A-5). The weight average molecular weight of the obtained phenol resin (A-5) was 22,000.

(In formula (A-5), the bond that binds to the biphenol structure is bound to either one of the two benzene rings).

（式（Ａ－６）において、ビフェノール構造に結合する結合手は、２つのベンゼン環のうちいずれか一方に結合している）。 (Synthesis Example 6)
<Synthesis of phenolic resin (A-6)>
186.2 g (1.00 mol) of 4,4'-biphenol and 86.5 g (1.00 mol) of 4,4'-biphenol and 86.5 g of p-cresol were placed in a four-neck glass round-bottom flask equipped with a thermometer, a stirrer, a raw material inlet and a dry nitrogen gas inlet tube. After charging 5 g (0.8 mol), 24.0 g (0.8 mol) of formaldehyde, 11.3 g (0.09 mol) of oxalic acid dihydrate, and 308 g of γ-butyrolactone, pour it while flowing nitrogen. The polycondensation reaction was carried out at 100° C. for 6 hours while refluxing the reaction solution in the round-bottomed flask in an oil bath. Next, after the resulting reaction solution was cooled to room temperature, 411 g of acetone was added and mixed with stirring until uniform. After that, the resin component was precipitated by dropping and mixing the reaction liquid in the round-bottomed flask with 10 L of water. Next, the precipitated resin component was collected by filtration, and then vacuum-dried at 60° C. to obtain a phenol resin represented by the following formula (A-6). The weight average molecular weight of the obtained phenol resin (A-6) was 11,000.

(In formula (A-6), the bond that binds to the biphenol structure is bound to either one of the two benzene rings).

（式（Ａ－２）において、ビフェノール構造に結合する結合手は、２つのベンゼン環のうちいずれか一方に結合している）。 (Synthesis Example 7)
<Synthesis of phenolic resin (A-2)>
186.2 g (1.00 mol) of 4,4′-biphenol and 140 p-xylene dichloride were placed in a four-neck glass round bottom flask equipped with a thermometer, a stirrer, a raw material inlet and a dry nitrogen gas inlet tube. 0 g (0.8 mol), 7.7 g (0.05 mol) of diethyl sulfate, and 327 g of γ-butyrolactone were charged, and the round-bottomed flask was placed in an oil bath to reflux the reaction solution while flowing nitrogen. A polycondensation reaction was carried out at 100° C. for 6 hours. Next, after cooling the resulting reaction solution to room temperature, 436 g of acetone was added and mixed with stirring until uniform. After that, the resin component was precipitated by dropping and mixing the reaction liquid in the round-bottomed flask with 10 L of water. Next, the precipitated resin component was collected by filtration, and then vacuum-dried at 60° C. to obtain a phenol resin represented by the following formula (A-2). The weight average molecular weight of the obtained phenol resin (A-2) was 13,500.

(In formula (A-2), the bond that binds to the biphenol structure is bound to either one of the two benzene rings).

(Preparation of photosensitive resin composition)
For each of Examples 1-11 and Comparative Examples 1-2, a photosensitive resin composition was prepared as follows. First, each component blended according to Table 1 was dissolved in γ-butyrolactone (GBL) so that the viscosity after blending was about 500 mPa s, and stirred under a nitrogen atmosphere. A varnish-like photosensitive resin composition was obtained by filtering with a filter manufactured by the company. Details of each component in Table 1 are as follows. In addition, the units in Table 1 are parts by mass.

（Ａ－８）フェノールビフェニルアラルキル樹脂（明和化成（株）製、ＭＥＨ－７８５１、ポリスチレン換算重量平均分子量（Ｍｗ）＝２，０００）

<(A) Phenolic resin>
(A-1) Phenolic resin obtained in Synthesis Example 1 (A-2) Phenolic resin obtained in Synthesis Example 2 or Synthesis Example 7 (A-3) Phenolic resin obtained in Synthesis Example 3 ( A-4) Phenolic resin obtained in Synthesis Example 4 above (A-5) Phenolic resin obtained in Synthesis Example 5 above (A-6) Phenolic resin obtained in Synthesis Example 6 above (A-7) Phenol 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 (manufactured by Meiwa Kasei Co., Ltd., MEH-7851, polystyrene equivalent weight average molecular weight (Mw) = 2,000)

<(B) Photoacid generator>
(B-1) Naphthoquinone compound having the structure of formula (B-1) below (B-2) Naphthoquinone compound having the structure of formula (B-2) below (B-3) CPI-210S (manufactured by San-Apro Co., Ltd.)

<(C) Crosslinking agent>
(C-1) Nikalac MX-270 (manufactured by Sanwa Chemical Co., Ltd.)
(C-2) TML-BPA (manufactured by Honshu Chemical Co., Ltd.)
(C-3) Celoxide 2021P (manufactured by Daicel Co., Ltd.)

<(D) Silane coupling agent>
(D-1) KBM-403 (manufactured by Shin-Etsu Silicone Co., Ltd.)
(D-2) KBM-503 (manufactured by Shin-Etsu Silicone Co., Ltd.)
(D-3) KBM-846 (manufactured by Shin-Etsu Silicone Co., Ltd.)

<(E) Surfactant>
(E-1) F444 (manufactured by DIC Corporation)

<(F) Thermal acid generator, thermal base generator>
(F-1) San-Aid SI-150 (manufactured by Sanshin Chemical Co., Ltd.)
(F-2) UCAT SA506 (manufactured by San-Apro Co., Ltd.)

<(G) Phenolic compound>
(G-1) phloroglucide (G-2) biphenol

<(H) Solvent>
(H-1) γ-butyrolactone

<Evaluation of phenolic resin-1 (measurement of softening point)>
The softening points of the phenolic resins (A-1) to (A-8) were measured according to JIS K 2207. The device used was ASP-M2SP manufactured by Meitec. Table 1 shows the results. A higher softening point is preferable from the viewpoint of pattern maintenance performance at the time of final curing.

<Evaluation of phenolic resin-2 (alkali solubility evaluation)>
Phenolic resins (A-1) to (A-8) were dissolved in gamma-butyrolactone to obtain resin solutions. The obtained solution was applied onto a 4-inch silicon wafer using a spin coater, and then prebaked on a hot plate at 120° C. for 3 minutes to obtain a coating film having a thickness of about 3 μm. The resulting coating film was immersed in a 2.38% tetramethylammonium hydroxide aqueous solution at 23° C. for 3 minutes to confirm the solubility of the coating film. Table 1 shows the results.

<Patterning Evaluation-1 (Examples 1 to 8, 10 to 11, and Comparative Examples 1 and 2)>
Each of the photosensitive resin compositions obtained above was applied onto an 8-inch silicon wafer using a spin coater, and then prebaked on a hot plate at 120° C. for 3 minutes to form a coating film having a thickness of about 9.0 μm. got This coating film is passed through a mask manufactured by Toppan Printing Co., Ltd. (test chart No. 1: a pattern with a width of 0.88 to 50 μm is drawn, and an i-line stepper (NSR-4425i manufactured by Nikon Corporation) is used. Then, irradiation was performed while changing the exposure amount.
Next, using a 2.38% tetramethylammonium hydroxide aqueous solution as a developer, 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 puddle was performed twice. After dissolving and removing the exposed portion by developing, the film was rinsed with pure water for 10 seconds. The resolution of the line pattern was evaluated with the pattern exposed with the energy of 100 mJ/cm ² +100 mJ/cm 2 minimum exposure for forming a 100 μm square via hole pattern. The results are shown in Table 2 as pattern resolution (μm). A smaller resolution is better for creating fine wiring.

<Patterning Evaluation-2 (Example 9)>
Each of the photosensitive resin compositions obtained above was applied onto an 8-inch silicon wafer using a spin coater, and then prebaked on a hot plate at 120° C. for 3 minutes to form a coating film having a thickness of about 9.0 μm. got This coating film is passed through a mask manufactured by Toppan Printing Co., Ltd. (test chart No. 1: a pattern with a width of 0.88 to 50 μm is drawn, and an i-line stepper (NSR-4425i manufactured by Nikon Corporation) is used. Then, irradiation was performed while changing the exposure amount.
Next, baking treatment was performed on a hot plate at 100° C. for 2 minutes. Next, using a 2.38% tetramethylammonium hydroxide aqueous solution as a developer, puddle development was performed twice for 30 seconds to dissolve and remove the exposed areas, followed by rinsing with pure water for 10 seconds. The resolution of the line pattern was evaluated with the pattern exposed with the energy of 100 mJ/cm ² +100 mJ/cm 2 minimum exposure for forming 5 μm lines. The results are shown in Table 2 as pattern resolution (μm). A smaller resolution is better for creating fine wiring.

<Evaluation of resolution after curing (Examples 1 to 11, Comparative Examples 1 and 2)>
The patterned wafers obtained in the above patterning evaluations -1 and -2 are placed in a heating oven, heated from room temperature to 200°C at 5°C/min while flowing nitrogen, and then heated at 200°C for 60 minutes. Work up and cool to room temperature. Microscopy was performed on the heated patterned wafers to assess line resolution. The results are shown in Table 2 as post-curing resolution (μm). A smaller resolution is better for forming a fine pattern.

<Fabrication of semiconductor device>
Using a simulated element wafer having an aluminum circuit on the surface, the photosensitive resin compositions of Examples 1 to 11 and Comparative Examples 1 and 2 were each applied to a final thickness of 5 μm, and then patterned and cured. did. After that, it is divided by chip size and mounted on a lead frame for 16-pin DIP (Dual Inline Package) using conductive paste, and then sealed with epoxy resin for semiconductor sealing (EME-6300H manufactured by Sumitomo Bakelite Co., Ltd.). A semiconductor device was fabricated by molding.
<Semiconductor device reliability evaluation - 1 (electrical connectivity)>
Conduct electrical connection checks on each of the 10 semiconductor devices obtained by the above method,
A for those with no electrical connection failure in all 10 semiconductor devices,
B for one or more semiconductor devices out of 10 having electrical connection failure;
evaluated as
<Semiconductor Device Reliability Evaluation-2 (Moisture Resistance)>
Ten semiconductor devices each obtained by the above method were treated for 168 hours under conditions of 85° C./85% humidity, then immersed in a 260° C. solder bath for 10 seconds, and then placed in a high-temperature, high-humidity pressure cooker. Treatment (125° C., 2.3 atm, 100% relative humidity) was applied to check electrical connections.
A for those with no electrical connection failure in all 10 semiconductor devices,
B for which electrical connection failure was observed in one or more semiconductor devices out of 10;
evaluated as

Table 2 showing examples and comparative examples is shown below.

The coating films formed from the phenolic resins (A-1) to (A-6) of Examples exhibited good alkali solubility. Moreover, the softening points of these coating films were all 180° C. or higher. Accordingly, these phenolic resins are useful, for example, as resists used in the manufacture of semiconductor devices.
Moreover, the coating films formed from the photosensitive resin compositions containing the phenol resins (A-1) to (A-6) of Examples had good patterning formability. In addition, the semiconductor device provided with the cured film had no defective electrical connection, and after storage at high temperature and high humidity, no defects due to corrosion of the aluminum circuit occurred. Therefore, the cured film is expected to be useful as an interlayer insulating film for semiconductor devices.

Claims (6)

The following steps:
The 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 results in a polystyrene consisting of only repeating structural units represented by the formula (2). A step of forming a phenol resin (A) having a biphenol structure and having a converted weight average molecular weight of 7,000 to 100,000;
A step of mixing the phenolic resin (A), the photoacid generator (B), and a solvent to form a photosensitive resin composition for forming a resist used for a surface protective film or an interlayer insulating film of a semiconductor device. ,
applying the resist-forming photosensitive resin composition onto a semiconductor substrate;
a step of drying the resist-forming photosensitive resin composition by heating to obtain a photosensitive resin layer;
exposing the photosensitive resin layer with actinic rays;
developing the exposed photosensitive resin layer to obtain a patterned resin layer; and heating the patterned resin layer to obtain a cured resin layer;
A method of manufacturing a semiconductor device, comprising:

(In formula (2),
m is an integer from 2 to 10000,
R ₁₁ and R ₁₂ each independently represent 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, an alkyl ether group having 1 to 20 carbon atoms, or 3 to 20 carbon atoms. A saturated or unsaturated alicyclic group, or a monovalent substituent selected from the group consisting of an organic group having an aromatic structure having 6 to 20 carbon atoms, these are ester bonds, ether bonds, amide bonds, or may be attached via a carbonyl bond,
p and q are each independently an integer of 0 to 3;
X ₁ and Y ₁ are each independently a single bond or a divalent substituent selected from the group consisting of organic groups represented by formula (3),
However, Y ₁ is bound to either one of the two benzene rings).

(In formula (3), n is 0 to 20.) 2. The method of manufacturing a semiconductor device according to claim 1, wherein the photoacid generator (B) is a compound that generates an acid when irradiated with radiation having a wavelength of 200 to 500 nm. 3. The method of manufacturing a semiconductor device according to claim 1, wherein said resist-forming photosensitive resin composition further contains a cross-linking agent (C) having a group capable of reacting with said phenol resin (A). 4. The method of manufacturing a semiconductor device according to claim 1, wherein said resist-forming photosensitive resin composition further contains a silane coupling agent (D). 5. The method of manufacturing a semiconductor device according to claim 1, wherein said resist-forming photosensitive resin composition further contains a nonionic surfactant (E). 6. The method of manufacturing a semiconductor device according to claim 1, wherein said photosensitive resin composition for forming a resist further contains a reaction accelerator (F).