JP2020187368A - Method of manufacturing semiconductor device - Google Patents

Abstract

To provide a method of manufacturing a semiconductor device using a photosensitive resin composition capable of forming a resin film and a cured film having excellent heat resistance.SOLUTION: The method of manufacturing a semiconductor device includes a step of applying a photosensitive resin composition for resist formation to be used for a surface protective film or an interlayer insulating film of the semiconductor device onto a semiconductor substrate, the photosensitive resin composition for resist formation containing a phenolic resin (A) having a biphenol structure, a photoacid generator (B), and a solvent. The phenolic resin (A) has a repeating structural unit represented by formula (2) derived from a biphenol compound, an aldehyde compound and the like. The weight average molecular weight in terms of polystyrene of the phenolic resin (A) is 7,000-100,000.SELECTED DRAWING: None

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 specifically, the present invention 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 device surface protective film or an interlayer insulating film.
The present 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 by reference.

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

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

Japanese Unexamined Patent Publication No. 2012-123378

The cured resin film used for forming the surface protective film and the interlayer insulating film of the semiconductor device is obtained by applying a photosensitive resin composition to a base material to obtain a resin film, and exposing and developing the resin film to form a pattern. It is subsequently obtained by heating and curing the patterned resin film. In the conventional photosensitive resin composition, the softening point of the obtained resin film is low, so that the heat resistance is low, and the pattern shape is deformed by heating. was there.

According to the present invention that solves the above problems, a resin film having excellent heat resistance and a photosensitive resin composition capable of forming a cured film, a resin film made of the photosensitive resin composition, and curing of the resin film. Provided are a film, a semiconductor device including the cured film, and a method for manufacturing a semiconductor device using the photosensitive resin composition.

（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。） As a result of diligent studies to solve the above problems, the present inventors have completed the present invention including the following forms.
[1] The following steps:
Phenolic resin (A) having a biphenol structure and
Photoacid generator (B) and
Contains solvent,
The phenol resin (A) is represented by the formula (2), which is 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. Has a repeating structural unit,
A resist-forming photosensitive resin composition used for a surface protective film or an interlayer insulating film of a semiconductor device, which has a polystyrene-equivalent weight average molecular weight of the phenol resin (A) of 7,000 to 100,000, is applied onto a semiconductor substrate. Process to do,
A step of heating and drying the resist-forming photosensitive resin composition to obtain a photosensitive resin layer.
The step of exposing the photosensitive resin layer with active rays,
A step of developing the exposed photosensitive resin layer to obtain a patterned resin layer, and a step of heating the patterned resin layer to obtain a cured resin layer.
A method for manufacturing a semiconductor device, including.

(In equation (2)
m is an integer from 2 to 10000,
R ₁₁ and R ₁₂ are independently hydroxyl groups, halogen atoms, carboxyl groups, saturated or unsaturated alkyl groups having 1 to 20 carbon atoms, alkyl ether groups having 1 to 20 carbon atoms, and 3 to 20 carbon atoms. Is a monovalent substituent selected from the group consisting of a saturated or unsaturated alicyclic group, or an organic group having an aromatic structure having 6 to 20 carbon atoms, which are an ester bond, an ether bond, an amide bond, and the like. Alternatively, it may be bonded via a carbonyl bond,
p and q are independently integers of 0 to 3, respectively.
X ₁ and Y ₁ are divalent substituents independently selected from the group consisting of a single bond or an organic group represented by the formula (3).
However, Y ₁ is bonded to one of the two benzene rings).

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

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

[3] The semiconductor device according to the above [1] or [2], wherein the resist-forming photosensitive resin composition further contains 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 the above [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 the above [1] to [4], wherein the resist-forming photosensitive resin composition further contains a nonionic surfactant (E).

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

According to the present invention, a photosensitive resin composition capable of forming a resin film or a cured film having excellent heat resistance, a resin film made of the photosensitive resin composition, a cured film of the resin film, and the curing thereof. A semiconductor device provided with a film and a method for manufacturing a semiconductor device using the photosensitive resin composition are provided.

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.
The resin composition of the present embodiment comprises the above composition by using a resin having a biphenol structure as the phenol resin (A), that is, a phenol resin having a biphenyldiyl structure having at least one hydroxyl group in each phenyl group. The heat resistance of the resin film is improved. Therefore, when the 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 phenolic resin (A) has a structural unit derived from a biphenol compound and at least one compound selected from the group consisting of aldehyde compounds, dimethylol compounds, dimethoxymethyl compounds and dihaloalkyl compounds. In other words, the phenolic resin (A) is obtained by reacting 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 "structure derived from (substance)" refers to a structure produced by using the substance, and the case where the structure can be identified by using a usual method in the art and the case where the structure cannot be identified. Includes both.
Since such a phenol resin (A) can be produced using a commercially available raw material monomer without requiring a complicated process, the obtained photosensitive resin composition can be produced at low cost. ..

The phenolic resin (A) can be produced by any known method. Examples of the production method include 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 that can be used for producing the phenol resin (A) include 2,2'-biphenol and 4,4'-biphenol, and isomers thereof. These biphenol compounds may have a substituent, and the substituents include a hydroxyl group, a halogen, a carboxyl group, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, and an alkyl ether having 1 to 20 carbon atoms. Examples thereof include a group, a saturated or unsaturated alicyclic group having 3 to 20 carbon atoms, an organic group having an aromatic structure having 6 to 20 carbon atoms, and the like.
Such biphenol compounds are exemplified by, for example, the following compounds, but are not limited thereto.

Examples of the aldehyde compound that produces the phenolic resin (A) by the reaction with the biphenol compound include formaldehyde, acetaldehyde, propionaldehyde, pivalaldehyde, butylaldehyde, pentanal, hexanal, trioxane, glyoxal, cyclohexylaldehyde, diphenylacetaldehyde, and ethylbutylaldehyde. , Benzaldehyde, cinnamaldehyde, diphenylacetaldehyde, methyl fumaraldehyde, 3-methyl-2-butenal, glyoxylic acid, 5-norbornen-2-carboxyaldehyde, malondialdehyde, succindialdehyde, glutaaldehyde, naphthaldehyde, terephthalaldehyde And so on.

Examples of the dimethylol compound that produces the phenol resin (A) by the reaction with the biphenol compound include 2,2-bis (hydroxymethyl) butyric acid, 1,3-propanediol, 2-benzyloxy-1,3-propanediol, and 2, , 2-Dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, monoacetin, 2-methyl-2-nitro-1,3-propanediol, 5-norbornen-2,2- Dimethanol, 5-norbornen-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) adamantan, 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, Examples thereof include 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 the reaction with the biphenol compound include 2,2-bis (methoxymethyl) butyric acid, 1,3-dimethoxymethylpropane, and 2-benzyloxy-1,3-. Dimethoxymethylpropane, 2,2-dimethyl-1,3-dimethoxymethylpropane, 2,2-diethyl-1,3-dimethoxymethylpropane, 2,3-dimethoxy-1-propanolacetate, 2-methyl-2-nitro -1,3-dimethoxymethylpropane, 5-norbornene-2,2-dimethoxymethyl, 5-norbornen-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-dimethoxydodecane, 1, 4-bis (methoxymethyl) cyclohexane, 1,4-bis (methoxymethyl) cyclohexene, 1,6-bis (methoxymethyl) adamantan, 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-methoxymethylbenzoic acid-4'-methoxymethylphenyl, 4-methoxymethylbenzoic acid-4'-methoxymethylanilide, 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 can be mentioned.

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

The phenol resin (A) can be obtained by condensing the above-mentioned biphenol compound and the above-mentioned polymerization component with dehydration or dehydrohalation, but a catalyst may be used at the time of polymerization. Examples of acidic catalysts include hydrochloric acid, sulfuric acid, nitrate, phosphoric acid, phosphite, methanesulfonic acid, p-toluenesulfonic acid, dimethylsulfate, diethylsulfate, 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 can be mentioned. 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-None, Ammonia, Hexa Methylenetetramine and the like can be mentioned.

When carrying out the synthetic reaction of the phenol resin (A), an organic solvent can be used if necessary. Specific examples of the organic solvent that can be used 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, and the like. Examples thereof include, but are not limited to, toluene, xylene, γ-butyrolactone, N-methyl-2-pyrrolidone and the like.

The phenolic resin (A) may be polymerized by further using a phenolic compound other than the above-mentioned biphenolic compound 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 the formula (1).

In equation (1)
R ₁₁ and R ₁₂ are independently hydroxyl groups, halogen atoms, carboxyl groups, saturated or unsaturated alkyl groups having 1 to 20 carbon atoms, alkyl ether groups having 1 to 20 carbon atoms, and 3 to 20 carbon atoms. Is a monovalent substituent selected from the group consisting of a saturated or unsaturated alicyclic group, or an organic group having an aromatic structure having 6 to 20 carbon atoms, which are an ester bond, an ether bond, an amide bond, and the like. Alternatively, it may be bonded via a carbonyl bond,
p and q are independently integers of 0 to 3, respectively.
X ₁ and Y ₁ have an aliphatic group having 1 to 10 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, and carbon, which may independently have a single bond or an unsaturated bond, respectively. It is a divalent substituent selected from the group consisting of organic groups having an aromatic structure of several 6 to 20.
However, Y ₁ is bonded to one of the two benzene rings.

The phenolic resin (A) is contained by including the biphenol structure, that is, the biphenyldiyl structure having at least one hydroxyl group in each phenyl group in the structural unit of the formula (1) that the phenolic resin (A) can have. The heat resistance of the resin film made of the composition is improved. Therefore, when the 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.

It is preferable that R ₁₁ and R ₁₂ are independently hydroxyl groups.
It is preferable that p and q are independently integers of 0 to 2.
X ₁ and Y ₁ are organic having an aliphatic group having 1 to 10 carbon atoms and an aromatic structure having 6 to 20 carbon atoms, which may independently have a single bond or an unsaturated bond, respectively. 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" in X ₁ and Y ₁ may be a straight chain or a branched chain. The number of carbon atoms may be 1 to 7, may be 1 to 5, or may be 1 to 3. Examples of the aliphatic group include an alkylene group, an alkenylene group, an alkynylene group and the like as long as it is an aliphatic hydrocarbon group, and among these, an alkylene group is preferable, and for example, a methylene group, an ethylene group, and the like. Examples include a propylene group.

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, 6 to 12 carbon atoms, or 6 to 12 carbon atoms. It may be 6 to 9 or 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 preferable.
The "organic group having an aromatic structure having 6 to 20 carbon atoms" in X ₁ and Y ₁ is the above-mentioned "aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond" and the above-mentioned "aromatic group". It may be a divalent substituent formed by bonding "group structure" to each other.

上記式中、ｎは、０〜２０であり、０〜１０であることが好ましい。 It is more preferable that X ₁ and Y ₁ are 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 obtained by reacting the above-mentioned 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. ..

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 phenolic resin (A) substantially has a repeating unit represented by the formula (2).

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

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

In the formula (3), l and m indicate the composition ratios, l + m = 1, 0 ≦ l ≦ 1, and 0 ≦ m ≦ 1.
R _11' , R _12' , R _{11 "} and R _12" are independently hydroxyl groups, halogen atoms, carboxyl groups, saturated or unsaturated alkyl groups having 1 to 20 carbon atoms, and having 1 to 20 carbon atoms. It is 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. It may be bonded via an ester bond, an ether bond, an amide bond, or a carbonyl bond.
p and q are independently integers of 0 to 3, respectively.
X _1' , Y _1' , X _{1 "} and Y _1" are aliphatic groups having 1 to 10 carbon atoms and 3 to 10 carbon atoms, which may independently have a single bond or an unsaturated bond, respectively. It is a divalent substituent selected from the group consisting of 20 alicyclic groups and an organic group having an aromatic structure having 6 to 20 carbon atoms.
The above structure of the phenolic resin (A) can be understood by those skilled in the art from the biphenol compound used and the type of polymerizable compound.

In one embodiment, the weight average molecular weight (in terms of polystyrene) of the phenolic resin (A) is in the range of 1000 to 100,000, preferably in the range of 2000 to 50000, and more preferably in the range of 3000 to 30000. The phenol resin (A) having a weight average molecular weight in the above range has excellent solubility in a solvent and excellent mechanical properties of the obtained 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, and is not particularly limited. It may be any photosensitive resin composition of the mold. The resin composition of the present embodiment, which is photosensitive by containing 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, preferably having a wavelength of 200 to 500 nm, particularly preferably 350. It is a compound that generates an acid when irradiated with radiation having a wavelength of ~ 450 nm. Specific examples include a photosensitive diazoquinone compound, a photosensitive diazonaphthoquinone compound, a diaryliodonium salt, an onium salt such as a triarylsulfonium salt or a sulfonium-borate salt, a 2-nitrobenzyl ester compound, an N-iminosulfonate compound, and an imidesulfonate compound. , 2,6-bis (trichloromethyl) -1,3,5-triazine compound, dihydropyridine compound and the like. These may be used alone or in combination of two or more. Of these, photosensitive diazoquinone compounds and photosensitive diazonaphthoquinone compounds, which are excellent in sensitivity and solvent solubility, are preferable. Specific examples of these include 1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester, and 1,2-naphthoquinonediazide-5-sulfonic acid ester of phenol compounds. Can be 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 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. As the solvent used, 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 Examples thereof include propionate, which may be used alone 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 a solvent in the above range, a varnish in which the resin is sufficiently dissolved and has excellent handleability can be produced.

(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 a cross-linking agent (C), patterned by exposure and development, and then heat-cured, the cross-linking agent (C) generates photoacids. Crosslinks with the phenol resin (A) by the action of acid or heat generated from the agent (B). Since the resin film obtained from the photosensitive resin composition containing the cross-linking agent contains the phenol resin (A) having the above-mentioned structure, the deformation of the patterned resin film at the time of 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 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). Examples of the cross-linking agent (C) that can be used include the following compounds:
(1) A compound containing one or more crosslinkable groups selected from the group consisting of a methylol group and an alkoxymethyl group: for example, benzenedimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, Bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) benzophenone, hydroxymethylbenzoate hydroxymethylphenyl, bis (hydroxymethyl) biphenyl, dimethylbis (hydroxymethyl) biphenyl, bis (methoxymethyl) benzene, bis (methoxymethyl) cresol , Bis (methoxymethyl) dimethoxybenzene, bis (methoxymethyl) diphenyl ether, bis (methoxymethyl) benzophenone, methoxymethylbenzoate methoxymethylphenyl, bis (methoxymethyl) biphenyl, dimethylbis (methoxymethyl) biphenyl; as commercial products Is Mel 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.) , Nicarac MX-270, 280, -290, Nicarac MS-11, Nicarac 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) Organic Materials Industry 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-diacetoximel-p-cresol, TriML-P, TriML-35XL, TriML-TrisCR-HAP , HML-TPPHBA, Examples thereof include HML-TPHAP, HMOM-TPPHBA, and HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.). These compounds can be used alone or in admixture.
(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. , Glyxyl polyglycidyl ether, sorbitol polyglycidyl ether, glycidyl ether such as bisphenol A (or F) glycidyl ether, glycidyl ester such as adipate diglycidyl ester, o-phthalic acid diglycidyl ester, 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 epoxys such as Celoxide 2021, Celoxide 2081, Celoxide 2083, Celoxide 2085, Celoxide 8000, and Epolide GT401 manufactured by Daicel Co., Ltd. , 2,2'-(((((1- (4- (2- (4- (oxylan-2-ylmethoxy) phenyl) propan-2-yl) phenyl) ether-1,1-diyl) bis (4) , 1-phenylene)) bis (oxy)) bis (methylene)) bis (oxylan)) (for example, Techmore VG3101L (manufactured by Printec Co., Ltd.)), Epolite 100MF (manufactured by Kyoeisha Chemical Industry Co., Ltd.), Epiol TMP Aliper polyglycidyl ether (manufactured by Nichiyu Co., Ltd.), 1,1,3,3,5,5-hexamethyl-1,5-bis (3- (oxylan-2-ylmethoxy) propyl) tri-siloxane (For example, DMS-E09 (manufactured by Gerest));
(3) Compounds having an isocyanate group: For example, 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, 1,3-phenylene bismethylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate;
(4) Compounds having a bismaleimide group: For example, 4,4'-diphenylmethane bismaleimide, phenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl. -4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane, 4,4'-diphenyl ether bismaleimide, 4,4'-Diphenylsulphonbismaleimide, 1,3-bis (3-maleimidephenoxy) benzene, 1,3-bis (4-maleimidephenoxy) benzene.

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

(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 adhesion to the substrate is improved when the photosensitive resin composition is applied onto the substrate to obtain a resin film.

Examples of the silane coupling agent (D) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, and 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, isocyanatepropyltriethoxysilane and a silicon compound obtained by reacting a silicon compound having an amino group with an acid dianhydride or an acid anhydride. The silane coupling agent can be used alone or in combination.

The blending 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 phenol resin (A). .. By using the silane coupling agent (D) within the above range, it is possible to achieve both adhesion to the substrate and storage stability of the photosensitive resin composition.

(Nonionic Surfactant (E))
The photosensitive resin composition of the present embodiment may contain a nonionic surfactant (E). By containing the nonionic surfactant (E), the coatability when the photosensitive resin composition is applied onto a substrate to obtain a resin film is improved, and a coating film having a uniform thickness can be obtained. it can. In addition, it is possible to prevent residues and pattern floating when developing the coating film.

The nonionic surfactant (E) used in the photosensitive resin composition is, for example, a compound containing a fluorine group (for example, an alkyl fluorinated group) or a silanol group, or a compound having a siloxane bond as a main skeleton. In the present embodiment, it is more preferable to use a nonionic surfactant (E) containing a fluorine-based surfactant or a silicone-based surfactant, and it is particularly preferable to use a fluorine-based surfactant. Examples of the fluorine-based surfactant include Megafuck 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 Ltd., and the like, but are not limited thereto.

When a surfactant is used, the blending amount of the surfactant is preferably 0.01 to 10% by weight with respect to 100 parts by mass of the alkali-soluble phenol 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 cross-linking between the phenol resin (A) contained in the photosensitive resin composition and the cross-linking agent can be promoted.

As the reaction accelerator (F), for example, a complex five-membered ring compound containing nitrogen or a compound that generates an acid by heat can be used. These may be used alone or in combination of two or more. Examples of the nitrogen-containing complex five-membered ring compound used as the reaction accelerator (F) include pyrrole, pyrazole, imidazole, 1,2,3-triazole, and 1,2,4-triazole. Examples of the heat-generated acid compound 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 temperature, it is more preferable to contain one or both of the sulfonate and the borate among the compounds that generate acid by heat, and the heat resistance of the cured film characteristics is improved. When considered, it is particularly preferred to include borate.

(Other additives)
In the photosensitive resin composition of the present embodiment, if necessary, additives such as a dissolution accelerator, an antioxidant, a filler, a photopolymerization initiator, an end sealant and a sensitizer are added to the effect of the present invention. It may be further used as long as it does not impair.

(Manufacturing method of cured film)
Another aspect of this embodiment is as follows:
The step of applying the above-mentioned photosensitive resin composition of the present invention on a semiconductor substrate,
A step of heating and drying the photosensitive resin composition to obtain a photosensitive resin layer,
The step of exposing the photosensitive resin layer with active rays,
A step of developing the exposed photosensitive resin layer to obtain a patterned resin layer, and a step of heating the patterned resin layer to obtain a cured resin layer.
To provide a method for manufacturing a semiconductor device including. An example of this embodiment will be described below.

(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 silicon wafer, a ceramic substrate, an aluminum substrate, a SiC wafer, a GaN wafer, or the like. Here, the substrate includes, for example, a substrate on which a semiconductor element or a display element is formed on the surface, in addition to the raw substrate. At this time, in order to ensure the water resistance and adhesiveness 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 the substrate in advance. The photosensitive resin composition can be applied by rotary coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating and the like.

Next, a coating film of the photosensitive resin composition is formed by prebaking at 80 to 140 ° C. for about 30 to 600 seconds to remove the solvent. 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. As the active light beam for exposure, for example, X-ray, electron beam, ultraviolet ray, visible light and the like can be used, but those having a wavelength of 200 to 500 nm are preferable. From the viewpoint of pattern resolution and handleability, the light source wavelength is preferably in the g-line, h-line or i-line region of the mercury lamp, and may be used alone or in combination of two or more rays. As the exposure apparatus, a contact aligner, a mirror projection or a stepper is particularly preferable. After the exposure, the coating film may be reheated at 80 to 140 ° C. for about 10 to 300 seconds, if necessary.

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

As the developer, for example, inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia;
Organic amines such as ethylamine, diethylamine, triethylamine, triethanolamine;
Aqueous solutions such as 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, even if a water-soluble organic solvent such as methanol or ethanol or a surfactant is added to them. Good.
Of these, an aqueous solution of tetramethylammonium hydroxide is preferable. The concentration of tetramethylammonium hydroxide in the aqueous solution is preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass.

After the development, the relief pattern can be obtained by washing with a rinsing solution and removing the developing solution. As the rinsing solution, 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 by a hot plate, an oven, a temperature-increasing oven in which a temperature program can be set, or the like. Air may be used as the atmospheric gas for the heat treatment, or an inert gas such as nitrogen or argon may be used. When it is necessary to perform heat treatment 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 has almost or no deformation in the heating step, the shape of the relief pattern before heating is maintained, and a high-resolution cured relief pattern can be obtained.

(Semiconductor device)
The above-mentioned cured 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 for a device having a bump structure, and further, a step in a known method for manufacturing a semiconductor device. By combining with, a semiconductor device can be manufactured. 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 are examples of the present invention, and various configurations other than the above can be adopted. Further, the present invention is not limited to the above-described embodiment, and modifications and improvements within the range in which the object of the present invention can be achieved are included in the present invention.

Hereinafter, the present invention will be specifically described 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 in a four-port glass round-bottom flask equipped with a thermometer, agitator, raw material inlet and dry nitrogen gas inlet. 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, it is applied while flowing nitrogen. The round-bottom flask was subjected to a polycondensation reaction at 100 ° C. for 6 hours while refluxing the reaction solution in an oil bath. Next, the obtained reaction solution was cooled to room temperature, 436 g of acetone was added, and the mixture was stirred and mixed until uniform. Then, the reaction solution in the round-bottom flask was added dropwise to 10 L of water to precipitate the resin component. Next, the precipitated resin component was collected by filtration and then vacuum dried at 60 ° C. to obtain a phenolic 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 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'-benzene and 1,4-bis in a four-necked glass round-bottom flask equipped with a thermometer, agitator, raw material inlet and dry nitrogen gas inlet. 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, a round-bottom flask is placed in an oil bath while flowing nitrogen. A polycondensation reaction was carried out at 100 ° C. for 6 hours while refluxing the reaction solution. Next, the obtained reaction solution was cooled to room temperature, 436 g of acetone was added, and the mixture was stirred and mixed until uniform. Then, the reaction solution in the round-bottom flask was added dropwise to 10 L of water to precipitate the resin component. Next, the precipitated resin component was separated by filtration and recovered, 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)>
4,4'-biphenol 186.2 g (1.00 mol) and 4,4'-in a four-port glass round-bottom flask equipped with a thermometer, agitator, raw material inlet and dry nitrogen gas inlet tube. 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-bottom flask is heated while flowing nitrogen. The polycondensation reaction was carried out at 100 ° C. for 6 hours while refluxing the reaction solution in the bath. Next, the obtained reaction solution was cooled to room temperature, 323 g of acetone was added, and the mixture was stirred and mixed until uniform. Then, the reaction solution in the round-bottom flask was added dropwise to 10 L of water to precipitate the resin component. Next, the precipitated resin component was collected by filtration and then vacuum dried at 60 ° C. to obtain a phenolic 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 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)>
18,2'-biphenol 186.2 g (1.00 mol) and 2,6-bis in a four-port glass round-bottom flask equipped with a thermometer, agitator, raw material inlet and dry nitrogen gas inlet. 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, it is applied while flowing nitrogen. The round-bottom flask was subjected to a polycondensation reaction at 100 ° C. for 6 hours while refluxing the reaction solution in an oil bath. Next, the obtained reaction solution was cooled to room temperature, 436 g of acetone was added, and the mixture was stirred and mixed until uniform. Then, the reaction solution in the round-bottom flask was added dropwise to 10 L of water to precipitate the resin component. Next, the precipitated resin component was collected by filtration and then vacuum dried at 60 ° C. to obtain a phenolic 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 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 fluoroglucolside and 1,4-bis (methoxymethyl) benzene in a four-port glass round-bottom flask equipped with a thermometer, agitator, raw material inlet and dry nitrogen gas inlet. After charging 133.0 g (0.8 mol), 7.7 g (0.05 mol) of diethyl sulfate, and 375 g of γ-butyrolactone, the round-bottom flask is oil-bathed while flowing nitrogen to reflux the reaction solution. The polycondensation reaction was carried out at 100 ° C. for 6 hours. Next, the obtained reaction solution was cooled to room temperature, 500 g of acetone was added, and the mixture was stirred and mixed until uniform. Then, the reaction solution in the round-bottom flask was added dropwise to 10 L of water to precipitate the resin component. Next, the precipitated resin component was collected by filtration and then vacuum dried at 60 ° C. to obtain a phenolic 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 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)>
In a four-port glass round-bottom flask equipped with a thermometer, stirrer, raw material inlet and dry nitrogen gas inlet, 186.2 g (1.00 mol) of 4,4'-biphenol and p-cresol 86. 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, it is applied while flowing nitrogen. The round-bottom flask was subjected to a polycondensation reaction at 100 ° C. for 6 hours while refluxing the reaction solution in an oil bath. Next, the obtained reaction solution was cooled to room temperature, 411 g of acetone was added, and the mixture was stirred and mixed until uniform. Then, the reaction solution in the round-bottom flask was added dropwise to 10 L of water to precipitate the resin component. Next, the precipitated resin component was collected by filtration and then vacuum dried at 60 ° C. to obtain a phenolic 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 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)>
In a four-necked glass round-bottom flask equipped with a thermometer, agitator, raw material inlet and dry nitrogen gas inlet, 186.2 g (1.00 mol) of 4,4'-biphenol and p-xylene chloride 140 After charging 0.0 g (0.8 mol), 7.7 g (0.05 mol) of diethyl sulfate, and 327 g of γ-butyrolactone, the reaction solution was refluxed in an oil bath in a round-bottom flask while flowing nitrogen. The polycondensation reaction was carried out at 100 ° C. for 6 hours. Next, the obtained reaction solution was cooled to room temperature, 436 g of acetone was added, and the mixture was stirred and mixed until uniform. Then, the reaction solution in the round-bottom flask was added dropwise to 10 L of water to precipitate the resin component. Next, the precipitated resin component was separated by filtration and recovered, 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 to 11 and Comparative Examples 1 and 2, photosensitive resin compositions were prepared as follows. First, each component blended according to Table 1 is dissolved in γ-butyrolactone (GBL) so that the viscosity after blending becomes about 500 mPa · s, stirred under a nitrogen atmosphere, and then polyethylene having a pore size of 0.2 μm. A varnish-like photosensitive resin composition was obtained by filtering with a manufacturing filter. Details of each component in Table 1 are as follows. The unit in Table 1 is a mass part.

（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 by Synthesis Example 1 (A-2) Phenolic resin obtained by Synthesis Example 2 or Synthesis Example 7 (A-3) Phenolic resin obtained by Synthesis Example 3 (A-1) A-4) Phenolic resin obtained by Synthetic Example 4 (A-5) Phenolic resin obtained by Synthetic Example 5 (A-6) Phenolic resin obtained by Synthetic Example 6 (A-7) Phenol Novolac resin (PR-50731 manufactured by Sumitomo Bakelite Co., Ltd., polystyrene-equivalent weight average molecular weight (Mw) = 11,000)

(A-8) Phenolic 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 the following formula (B-1) (B-2) Naphthoquinone compound having the structure of the following formula (B-2) (B-3) CPI-210S (manufactured by Sun Appro Co., Ltd.)

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

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

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

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

<(G) Phenol compound>
(G-1) Fluorogluside (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 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 curing, the softening point should be high.

<Evaluation of phenolic resin-2 (Evaluation of alkali solubility)>
The phenolic resins (A-1) to (A-8) were dissolved in gamma-butyrolactone to obtain a resin solution. 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 film thickness of about 3 μm. The obtained 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. The results are shown in Table 1.

<Patterning Evaluation-1 (Examples 1 to 8, 10 to 11 and Comparative Examples 1 to 2)>
The photosensitive resin compositions obtained above are each applied on 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 film thickness of about 9.0 μm. Got An i-line stepper (NSR-4425i manufactured by Nikon Corporation) is used through this coating film through a mask manufactured by Toppan Printing Co., Ltd. (test chart No. 1: a remaining pattern and a punching pattern having a width of 0.88 to 50 μm are drawn). Then, the exposure amount was changed and the irradiation was performed.
Next, a 2.38% tetramethylammonium hydroxide aqueous solution was used as a developing solution, 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 paddle was performed twice. The exposed portion was dissolved and removed by development, and then rinsed with pure water for 10 seconds. The resolution of the line pattern was evaluated with a pattern exposed with an energy of the minimum exposure amount + 100 mJ / cm ² in which a 100 μm square via hole pattern is formed. The results are shown in Table 2 as the pattern resolution (μm). The resolution should be small for creating fine wiring.

<Patterning Evaluation-2 (Example 9)>
The photosensitive resin compositions obtained above are each applied on 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 film thickness of about 9.0 μm. Got An i-line stepper (NSR-4425i manufactured by Nikon Corporation) is used through this coating film through a mask manufactured by Toppan Printing Co., Ltd. (test chart No. 1: a remaining pattern and a punching pattern having a width of 0.88 to 50 μm are drawn). Then, the exposure amount was changed and the irradiation was performed.
Next, a hot plate was baked at 100 ° C. for 2 minutes. Next, a 2.38% aqueous solution of tetramethylammonium hydroxide was used as a developing solution, and the exposed portion was dissolved and removed by paddle development for 30 seconds × 2 times, and then rinsed with pure water for 10 seconds. The resolution of the line pattern was evaluated with a pattern exposed with an energy of the minimum exposure amount + 100 mJ / cm ² in which a line of 5 μm is formed. The results are shown in Table 2 as the pattern resolution (μm). The resolution should be small for creating fine wiring.

<Resolution evaluation after curing (Examples 1 to 11, Comparative Examples 1 to 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. It was treated and cooled to room temperature. The heated patterned wafer was observed under a microscope to evaluate the line resolution. The results are shown in Table 2 as the resolution (μm) after curing. The resolution should be small in forming a fine pattern.

<Manufacturing of semiconductor devices>
Using a simulated device wafer provided with 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 size of 5 μm, and then patterned and cured. did. After that, it is divided for each chip size, mounted on a lead frame for 16-pin DIP (Dual Inline Package) using a conductive paste, and then sealed with an epoxy resin for semiconductor encapsulation (EME-6300H, manufactured by Sumitomo Bakelite). It was molded to produce a semiconductor device.
<Semiconductor device reliability evaluation-1 (electrical connectivity)>
The electrical connection of each of the 10 semiconductor devices obtained by the above method was checked.
All 10 semiconductor devices with no electrical connection failure are A,
B, which had an electrical connection failure in one or more semiconductor devices out of ten
Evaluated as.
<Semiconductor device reliability evaluation-2 (moisture resistance)>
Each of the 10 semiconductor devices obtained by the above method was treated at 85 ° C./85% humidity for 168 hours, then immersed in a 260 ° C. solder bath for 10 seconds, and then a high-temperature, high-humidity pressure cooker. Treatment (125 ° C., 2.3 atm, 100% relative humidity) was performed to check the electrical connection.
All 10 semiconductor devices with no electrical connection failure are A,
B, for which electrical connection failure was observed in one or more semiconductor devices out of ten
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 the examples showed good alkali solubility. Moreover, the softening point of this coating film was 180 ° C. or higher. Thereby, these phenolic resins are useful, for example, as resists used in the manufacture of semiconductor devices.
In addition, the coating film formed from the photosensitive resin composition containing the phenolic resins (A-1) to (A-6) of the examples had good patterning formability. Further, the semiconductor device provided with the cured film had no defect in electrical connectivity, and no defect due to corrosion of the aluminum circuit occurred after storage under high temperature and high humidity. Therefore, the cured film is expected to be useful as an interlayer insulating film for semiconductor devices.

Claims (6)

The following steps:
Phenolic resin (A) having a biphenol structure and
Photoacid generator (B) and
Contains solvent,
The phenol resin (A) is represented by the formula (2), which is 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. Has a repeating structural unit,
A resist-forming photosensitive resin composition used for a surface protective film or an interlayer insulating film of a semiconductor device, which has a polystyrene-equivalent weight average molecular weight of the phenol resin (A) of 7,000 to 100,000, is applied onto a semiconductor substrate. Process to do,
A step of heating and drying the resist-forming photosensitive resin composition to obtain a photosensitive resin layer.
The step of exposing the photosensitive resin layer with active rays,
A step of developing the exposed photosensitive resin layer to obtain a patterned resin layer, and a step of heating the patterned resin layer to obtain a cured resin layer.
A method for manufacturing a semiconductor device, including.

(In equation (2)
m is an integer from 2 to 10000,
R ₁₁ and R ₁₂ are independently hydroxyl groups, halogen atoms, carboxyl groups, saturated or unsaturated alkyl groups having 1 to 20 carbon atoms, alkyl ether groups having 1 to 20 carbon atoms, and 3 to 20 carbon atoms. Is a monovalent substituent selected from the group consisting of a saturated or unsaturated alicyclic group, or an organic group having an aromatic structure having 6 to 20 carbon atoms, which are an ester bond, an ether bond, an amide bond, and the like. Alternatively, it may be bonded via a carbonyl bond,
p and q are independently integers of 0 to 3, respectively.
X ₁ and Y ₁ are divalent substituents independently selected from the group consisting of a single bond or an organic group represented by the formula (3).
However, Y ₁ is bonded to one of the two benzene rings).

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