JP7173201B2 - Photosensitive resin composition, method for manufacturing semiconductor device, resin film, cured resin film, and semiconductor device - Google Patents

Description

The present invention relates to a photosensitive resin composition, a resin film, a cured resin film and a semiconductor device obtained using this photosensitive resin composition, and a method for manufacturing a semiconductor device using this photosensitive resin composition. More particularly, it relates to a photosensitive resin composition for permanent films used for forming permanent films of semiconductor devices.

Radiation-sensitive resins, whose solubility in alkaline solutions and the like changes when irradiated with radiation such as ultraviolet rays and electron beams, are used not only for ordinary photoresists used in photolithography, but also for semiconductor devices and other final products in recent years. It is also being used as a permanent film that remains patterned in electronic components.

Novolak-type phenolic resins are used as photosensitive resins when such radiation-sensitive resins are used for ordinary photoresist applications (eg, Patent Documents 1 to 4). When the radiation-sensitive resin is used for photoresist applications, the patterned resin film obtained using this radiation-sensitive resin is peeled off after the etching step. These Patent Documents 1 to 4 describe a photosensitive resin composition for a resist containing a novolac-type phenolic resin and a photoacid generator. For the purpose of improving , it has been proposed to use a novolac-type phenolic resin obtained by polymerizing a bisphenol compound having a specific structure and an aldehyde compound.

On the other hand, when the radiation-sensitive resin is used for a permanent film, the patterned resin film obtained by using the radiation-sensitive resin is not peeled off even after the etching process, and the final product is a semiconductor. It exists as a functional patterned resin in electronic parts such as elements. Such permanent films are used, for example, as protective films, insulating films, passivation films, sealing materials, spacers, etc. for semiconductor elements.

In addition to the properties of a photoresist such as heat resistance and developability, such permanent films must have excellent electrical and mechanical properties, durability in the semiconductor manufacturing process, long-term insulation reliability, and low heat resistance. Characteristics such as outgassing are required as product constituent materials.

JP 2010-39214 A JP 2013-120194 A JP-A-7-325395 JP-A-2-37348

The present invention has been made to solve the above problems, and is a photosensitive resin composition for a permanent film used for forming a permanent film provided in a semiconductor device, which has excellent developability and heat resistance. It is also an object of the present invention to provide a permanent film resin composition capable of providing a permanent film with low outgassing properties, and a permanent film and a semiconductor device obtained using such a permanent film resin composition.

The present inventors have made intensive studies to solve the above problems. As a result, by using a phenolic resin having a structural unit derived from a bisphenol compound and at least one compound selected from the group consisting of an aliphatic aldehyde compound, a dimethylol compound, a dimethoxymethyl compound and a dihaloalkyl compound, the above problem can be solved. can be solved, and the present invention has been completed.

式（３）において、
Ｘ_１は、それぞれ独立して、直鎖アルキレン基、分枝鎖アルキレン基、環状アルキレン基、芳香族基、フルオレン基、エーテル基、エステル基、チオエーテル基、スルフィド基、およびカルボニル基から選択される２価の基であり、
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、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、
Ｙ_１およびＺ_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価の基であり、
Ｚ_１は、２つのベンゼン環のうちいずれか一方に結合し、

式（４）において、
Ｒ_４１、およびＲ_４２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、
ｒ、およびｓは、それぞれ独立して、０～３の整数であり、
Ｙ_４、およびＺ_４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択され、
Ｚ_４は、２つのベンゼン環のうちいずれか一方に結合する、
永久膜用の感光性樹脂組成物が提供される。
According to the invention,
a phenolic resin (A) having a bisphenol structure;
a photoacid generator (B);
a cross-linking agent (C) having a group capable of reacting with the phenolic resin (A);
including
The phenol resin (A) has a structural unit derived from a bisphenol compound, a biphenol compound, and at least one compound selected from the group consisting of an aliphatic aldehyde compound, a dimethylol compound, a dimethoxymethyl compound and a dihaloalkyl compound. death,
The phenol resin (A) has a structural unit represented by formula (3) and a structural unit represented by formula (4),
The weight average molecular weight of the phenol resin (A) in terms of polystyrene is 1000 to 100000,
The content of the low-molecular-weight phenol compound having a molecular weight of 200 or less in the phenol resin (A) is less than 1% by mass,

In formula (3),
Each X ₁ is independently selected from a linear alkylene group, a branched alkylene group, a cyclic alkylene group, an aromatic group, a fluorene group, an ether group, an ester group, a thioether group, a sulfide group, and a carbonyl group. is a divalent group,
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, or a A saturated or unsaturated alicyclic group, or a monovalent substituent selected from the group consisting of an organic group having an aromatic structure with 6 to 20 carbon atoms, which is an ester bond, ether bond, amide bond, carbonyl may be connected via a bond,
p and q are each independently an integer from 0 to 3;
Y ₁ and Z 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 a carbon number A divalent group selected from the group consisting of organic groups having an aromatic structure of 6 to 20,
Z ₁ is attached to either one of the two benzene rings,

In formula (4),
R ₄₁ and R ₄₂ 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, optionally linked via a carbonyl bond,
r and s are each independently an integer from 0 to 3;
Y ₄ and Z ₄ 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 selected from the group consisting of organic groups having an aromatic structure of numbers 6 to 20,
Z ₄ is attached to either one of the two benzene rings,
A photosensitive resin composition for permanent films is provided.

Also according to the present invention,
The following steps:
a step of applying the photosensitive resin composition 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, comprising:

Moreover, according to this invention, the resin film which consists of the said photosensitive resin composition is provided.

Further, according to the present invention, there is provided a cured resin film comprising the above resin film.

Further, according to the present invention, there is provided a semiconductor device including the cured resin film as a permanent film.

According to the present invention, a permanent film resin composition capable of providing a permanent film with excellent developability and heat resistance and low outgassing, and a permanent film obtained using such a permanent film resin composition Membranes and semiconductor devices 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 of the present embodiment comprises a phenolic resin (A) having a bisphenol structure, a photoacid generator (B), and a cross-linking agent (C) having a group capable of reacting with the phenolic resin (A). include. The phenolic resin (A) has structural units derived from a bisphenol compound and at least one compound selected from the group consisting of aliphatic aldehyde compounds, dimethylol compounds, dimethoxymethyl compounds and dihaloalkyl compounds. The photosensitive resin composition of the present embodiment contains a phenol resin having a bisphenol structure as the phenol resin (A). Thereby, the resin film obtained by curing the resin composition has excellent heat resistance and low outgassing properties. Here, the low outgassing property means that the generation of outgassing from the resin film is extremely reduced during the production or use of the resin film. Such a resin film can be suitably used as a permanent film of a semiconductor device. Moreover, since such a phenol resin (A) can use a commercially available raw material monomer without requiring a complicated process, a photosensitive resin composition and a resin film can be manufactured at low cost.

(Phenolic resin (A))
In the present embodiment, the phenolic resin (A) has a structural unit derived from a bisphenol compound and at least a compound selected from the group consisting of aliphatic aldehyde compounds, dimethylol compounds, dimethoxymethyl compounds and dihaloalkyl compounds. In other words, the phenol resin (A) is obtained by reacting a bisphenol compound with at least a compound selected from the group consisting of aliphatic aldehydes, dimethylol compounds, dimethoxymethyl compounds and dihaloalkyl compounds.

Phenolic resin (A) can be produced by any known method. A production method includes a condensation reaction between a bisphenol compound and an aliphatic aldehyde, a dimethylol compound, a dimethoxymethyl compound, or a dihaloalkyl compound.

式（１）において、
Ｘ_１は、それぞれ独立して、直鎖アルキレン基、分枝鎖アルキレン基、環状アルキレン基、芳香族基、フルオレン基、エーテル基、エステル基、チオエーテル基、スルフィド基、およびカルボニル基から選択される少なくとも１つの２価の基であり、
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、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の整数である。 Bisphenol compounds that can be used to produce the phenolic resin (A) include bisphenols represented by formula (1).

In formula (1),
Each X ₁ is independently selected from a linear alkylene group, a branched alkylene group, a cyclic alkylene group, an aromatic group, a fluorene group, an ether group, an ester group, a thioether group, a sulfide group, and a carbonyl group. at least one divalent group,
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, or a A saturated or unsaturated alicyclic group, or a monovalent substituent selected from the group consisting of an organic group having an aromatic structure with 6 to 20 carbon atoms, which is an ester bond, ether bond, amide bond, carbonyl may be connected via a bond,
p and q are each independently an integer of 0-3.

Specific examples of the bisphenol compound represented by Formula (1) include, but are not limited to, the following bisphenols.

These bisphenols may be used singly or in combination. By using the above compound as the bisphenol compound, the photosensitivity of the resulting phenol resin (A) is improved.

In order to synthesize the phenol resin (A) of the present embodiment, an aldehyde compound represented by formula (2) can be used as the aliphatic aldehyde compound to be reacted with the bisphenol.
R ₂ —CHO (2)
Here, in formula (2), each R ₂ is independently hydrogen, linear alkyl having 1 to 6 carbon atoms, branched alkyl having 1 to 6 carbon atoms, and cyclic alkyl having 5 to 6 carbon atoms. is a group selected from

Specific examples of the aldehyde compound represented by formula (2) include formaldehyde, acetaldehyde, propionaldehyde, pivalaldehyde, butyraldehyde, pentanal, hexanal, trioxane, glyoxal, cyclohexylaldehyde, ethylbutyraldehyde, methyl fumaaldehyde, Examples include, but are not limited to, 3-methyl-2-butenal, glyoxylic acid, 5-norbornene-2-carboxaldehyde, malondialdehyde, succindialdehyde, glutaraldehyde, and the like. One of these aldehyde compounds may be used alone, or two or more of them may be used in combination.

In order to synthesize the phenolic resin (A) of the present embodiment, the dimethylol compound to be reacted with the above bisphenol includes 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(hydroxy methyl)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(hydroxymethyl)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-hydroxymethylbenzoic 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, etc. include, but are not limited to. One of these dimethylol compounds may be used alone, or two or more of them may be used in combination.

In order to synthesize the phenolic resin (A) of the present embodiment, the dimethoxymethyl compound to be reacted with the bisphenol includes o-dimethoxymethylbenzene, m-dimethoxymethylbenzene, p-dimethoxymethylbenzene, 1,2-dimethoxy Methylnaphthalene, 1,3-dimethoxymethylnaphthalene, 1,4-dimethoxymethylnaphthalene, 1,5-dimethoxymethylnaphthalene, 1,6-dimethoxymethylnaphthalene, 1,7-dimethoxymethylnaphthalene, 1,8-dimethoxymethylnaphthalene , 2,3-dimethoxymethylnaphthalene, 2,4-dimethoxymethylnaphthalene, 2,5-dimethoxymethylnaphthalene, 2,6-dimethoxymethylnaphthalene, 2,7-dimethoxymethylnaphthalene, 2,8-dimethoxymethylnaphthalene, 2 , 2′-dimethoxymethyldiphenyl, 2,4′-dimethoxymethyldiphenyl, 3,3′-dimethoxymethyldiphenyl, 4,4′-dimethoxymethyldiphenyl and the like, but are not limited thereto. These dimethoxymethyl compounds may be used singly or in combination.

In order to synthesize the phenol resin (A) of the present embodiment, examples of the dihaloalkyl compound to be reacted with the bisphenol include xylene dichloride, bischloromethyldimethoxybenzene, bischloromethyldurene, bischloromethylbiphenyl, bischloromethyl- Biphenylcarboxylic acid, bischloromethyl-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, but are not limited thereto. One of these dihaloalkyl compounds may be used alone, or two or more of them may be used in combination.

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 toluene, xylene, γ-butyrolactone, N-methyl-2-pyrrolidone and the like, but are not limited to these.

In the present embodiment, the phenolic resin (A) obtained from the above compound is a high molecular weight compound selected from an aliphatic aldehyde compound, a dimethylol compound, a dimethoxymethyl compound and a dihaloalkyl compound introduced into the phenolic resin skeleton and extended. It becomes resin of molecular weight. Therefore, it is excellent in heat resistance. Moreover, the introduction of the above compound into the resin skeleton promotes the increase in the molecular weight, resulting in a phenolic resin (A) in which little or no low-molecular-weight substances are present. As a result, when a resin composition containing this is cured, outgassing due to the low molecular weight substance is reduced. In addition, since the low-molecular-weight substances are reduced, when a cured film is produced from a resin composition containing this, the tensile elongation of the cured film is improved. Here, a low molecular weight substance refers to a component having a molecular weight (Mw) of 200 or less.

式（３）において、
Ｘ_１は、それぞれ独立して、直鎖アルキレン基、分枝鎖アルキレン基、環状アルキレン基、芳香族基、フルオレン基、エーテル基、エステル基、チオエーテル基、スルフィド基、およびカルボニル基から選択される少なくとも１つの２価の基であり、
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、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、
Ｙ_１およびＺ_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価の基であり、
Ｚ_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 (3).

In formula (3),
Each X ₁ is independently selected from a linear alkylene group, a branched alkylene group, a cyclic alkylene group, an aromatic group, a fluorene group, an ether group, an ester group, a thioether group, a sulfide group, and a carbonyl group. at least one divalent group,
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, or a A saturated or unsaturated alicyclic group, or a monovalent substituent selected from the group consisting of an organic group having an aromatic structure with 6 to 20 carbon atoms, which is an ester bond, ether bond, amide bond, carbonyl may be connected via a bond,
p and q are each independently an integer from 0 to 3;
Y ₁ and Z 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 a carbon number A divalent group selected from the group consisting of organic groups having an aromatic structure of 6 to 20,
Z ₁ binds to either one of the two benzene rings.

式（４）において、
Ｒ_４１、およびＲ_４２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、
ｒ、およびｓは、それぞれ独立して、０～３の整数であり、
Ｙ_４、およびＺ_４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択され、
Ｚ_４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) may further have a structural unit represented by formula (4). In other words, the phenolic resin (A) may be a copolymer consisting of the structural unit represented by formula (3) and the structural unit represented by formula (4).

In formula (4),
R ₄₁ and R ₄₂ 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, optionally linked via a carbonyl bond,
r and s are each independently an integer from 0 to 3;
Y ₄ and Z ₄ 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 selected from the group consisting of organic groups having an aromatic structure of numbers 6 to 20,
_Z4 binds to either one of the two benzene rings.

When the phenol resin (A) is a copolymer comprising a structural unit represented by formula (3) and a structural unit represented by formula (4), the formula (4 ) is preferably 10 mol % or more and 90 mol % or less.

When the phenol resin (A) has the structural unit represented by formula (4), the heat resistance of the resin film obtained from the photosensitive resin composition containing this phenol resin (A) is improved. Moreover, the resolution of the cured film obtained by curing this resin film is improved.

The structural unit or repeating unit of the phenolic resin (A) can be understood by those skilled in the art from the type of the bisphenol compound used and the type of polymerizable compound exemplified by aliphatic aldehydes and the like.

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 80,000, and more preferably in the range of 3,000 to 50,000. 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.

Further, the molecular weight distribution of the phenol resin (A) is preferably monodispersed or narrowly dispersed, for example, 1.2 to 20, more preferably 1.2 to 18, still more preferably 1 .2 to 15. When the molecular weight distribution of the phenolic resin (A) is within the above range, the pattern formability and resolution of the resin composition containing this are improved.

式（５）において、
Ｒ_４１、およびＲ_４２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、
ｒ、およびｓは、それぞれ独立して、０～３の整数であり、
Ｙ_４、およびＺ_４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択され、
Ｚ_４は、２つのベンゼン環のうちいずれか一方に結合し、
ｍは、２～１００００の整数である。 In one embodiment, in addition to the phenolic resin (A), another phenolic resin may be used in combination. As another phenol resin, a phenol resin (E) having a repeating unit represented by formula (5) can be used.

In formula (5),
R ₄₁ and R ₄₂ 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, optionally linked via a carbonyl bond,
r and s are each independently an integer from 0 to 3;
Y ₄ and Z ₄ 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 selected from the group consisting of organic groups having an aromatic structure of numbers 6 to 20,
Z ₄ is attached to either one of the two benzene rings,
m is an integer from 2 to 10,000.

The combined use of the phenolic resin (A) and the phenolic resin (E) improves the pattern formability and resolution of the resin film obtained from the photosensitive resin composition containing the phenolic resin (A). When the phenolic resin (E) is used, its amount is preferably 10% by weight to 90% by weight with respect to 100% by weight of the phenolic resin (A).

(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 as a permanent film of a semiconductor element because it can be patterned.

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 0.1 to 100% by weight, preferably 1 to 50% by weight, based on 100% by weight of the phenolic resin (A).

(Crosslinking agent (C))
The photosensitive resin composition of the present embodiment contains 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 permanent film for use in 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 resulting cured resin 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 nonionic surfactant is used, the amount of the nonionic surfactant to be blended is preferably 0.01 to 10% by weight with respect to 100% by weight of the phenolic resin (A).

(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

(solvent)
In one embodiment, the photosensitive resin composition is preferably provided 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.

<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 solvent removal 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 160° 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 weight, more preferably 1-5% by weight.

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)
Manufacturing a semiconductor device by using the cured relief pattern described above as a protective film, an insulating film, a passivation film, a sealing material, or a spacer for a semiconductor element, and further combining the steps of a known method for manufacturing a semiconductor device. can be done. 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. In addition, since the cured relief pattern of the present embodiment has low outgassing properties, a semiconductor device using the cured relief pattern has excellent electrical reliability.

式（１）において、
Ｘ _１ は、それぞれ独立して、直鎖アルキレン基、分枝鎖アルキレン基、環状アルキレン基、芳香族基、フルオレン基、エーテル基、エステル基、チオエーテル基、スルフィド基、およびカルボニル基から選択される少なくとも１つの２価の基であり、
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、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の整数である。
３． 前記脂肪族アルデヒド化合物が、式（２）で表されるアルデヒド化合物である、１．または２．に記載の感光性樹脂組成物：
Ｒ _２ －ＣＨＯ （２）
式（２）において、Ｒ _２ は、それぞれ独立して、水素、炭素数１～６の直鎖アルキル、炭素数１～６の分枝鎖アルキル、および炭素数５～６の環状アルキルから選択される基である。
４． 前記フェノール樹脂（Ａ）が、式（３）で表される構造単位を有する樹脂である、１．～３．のいずれかに記載の感光性樹脂組成物：

式（３）において、
Ｘ _１ は、それぞれ独立して、直鎖アルキレン基、分枝鎖アルキレン基、環状アルキレン基、芳香族基、フルオレン基、エーテル基、エステル基、チオエーテル基、スルフィド基、およびカルボニル基から選択される少なくとも１つの２価の基であり、
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、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、
Ｙ _１ およびＺ _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価の基であり、
Ｚ _１ は、２つのベンゼン環のうちいずれか一方に結合する。
５． 前記フェノール樹脂（Ａ）が、式（４）で表される構造単位をさらに有する、１．～４．のいずれかに記載の感光性樹脂組成物：

式（４）において、
Ｒ _４１ 、およびＲ _４２ 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、
ｒ、およびｓは、それぞれ独立して、０～３の整数であり、
Ｙ _４ 、およびＺ _４ 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択され、
Ｚ _４ は、２つのベンゼン環のうちいずれか一方に結合する。
６． 式（５）で表される繰り返し単位を有するフェノール樹脂（Ｅ）をさらに含む、１．～５．のいずれかに記載の感光性樹脂組成物：

式（５）において、
Ｒ _４１ 、およびＲ _４２ 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、
ｒ、およびｓは、それぞれ独立して、０～３の整数であり、
Ｙ _４ 、およびＺ _４ 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択され、
Ｚ _４ は、２つのベンゼン環のうちいずれか一方に結合し、
ｍは、２～１００００の整数である。
７． 前記フェノール樹脂（Ａ）のポリスチレン換算での重量平均分子量が１０００～１０００００である、１．～６．のいずれかに記載の感光性樹脂組成物。
８． シランカップリング剤をさらに含む、１．～７．のいずれかに記載の感光性樹脂組成物。
９． 非イオン性界面活性剤をさらに含む、１．～８．のいずれかに記載の感光性樹脂組成物。
１０． 反応促進剤をさらに含む、１．～９．のいずれかに記載の感光性樹脂組成物。
１１． 以下の工程：
半導体基板上に、１．～１０．のいずれかに記載の感光性樹脂組成物を塗布する工程、
前記感光性樹脂組成物を加熱乾燥して、感光性樹脂層を得る工程、
前記感光性樹脂層を活性光線で露光する工程、
前記露光された感光性樹脂層を現像して、パターニングされた樹脂層を得る工程、および、
前記パターニングされた樹脂層を加熱して、硬化樹脂層を得る工程、
を含む、半導体装置の製造方法。
１２． １．～１０．のいずれかに記載の感光性樹脂組成物からなる樹脂膜。
１３． １２．に記載の樹脂膜からなる硬化樹脂膜。
１４． １３．に記載の硬化樹脂膜を、永久膜として備える半導体装置。
１５． 前記永久膜が、半導体素子の保護膜、絶縁膜、パッシベーション膜、封止材、またはスペーサである、１４．に記載の半導体装置。 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 of embodiments will be added below.
1. a phenolic resin (A) having a bisphenol structure;
a photoacid generator (B);
a cross-linking agent (C) having a group capable of reacting with the phenolic resin (A);
including
The phenolic resin (A) has a structural unit derived from a bisphenol compound and at least one compound selected from the group consisting of an aliphatic aldehyde compound, a dimethylol compound, a dimethoxymethyl compound and a dihaloalkyl compound, for a permanent film. The photosensitive resin composition of.
2. 1. The bisphenol compound is at least one compound selected from compounds represented by formula (1); The photosensitive resin composition according to:

In formula (1),
Each X ₁ is independently selected from a linear alkylene group, a branched alkylene group, a cyclic alkylene group, an aromatic group, a fluorene group, an ether group, an ester group, a thioether group, a sulfide group, and a carbonyl group. at least one divalent group,
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, or a A saturated or unsaturated alicyclic group, or a monovalent substituent selected from the group consisting of an organic group having an aromatic structure with 6 to 20 carbon atoms, which is an ester bond, ether bond, amide bond, carbonyl may be connected via a bond,
p and q are each independently an integer of 0-3.
3. 1. The aliphatic aldehyde compound is an aldehyde compound represented by formula (2). or 2. The photosensitive resin composition according to:
R ₂ —CHO (2)
In formula (2), each R ₂ is independently selected from hydrogen, linear alkyl having 1 to 6 carbon atoms, branched alkyl having 1 to 6 carbon atoms, and cyclic alkyl having 5 to 6 carbon atoms. is a group.
4. 1. The phenolic resin (A) is a resin having a structural unit represented by formula (3). ~3. The photosensitive resin composition according to any one of:

In formula (3),
Each X ₁ is independently selected from a linear alkylene group, a branched alkylene group, a cyclic alkylene group, an aromatic group, a fluorene group, an ether group, an ester group, a thioether group, a sulfide group, and a carbonyl group. at least one divalent group,
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, or a A saturated or unsaturated alicyclic group, or a monovalent substituent selected from the group consisting of an organic group having an aromatic structure with 6 to 20 carbon atoms, which is an ester bond, ether bond, amide bond, carbonyl may be connected via a bond,
p and q are each independently an integer from 0 to 3;
Y ₁ and Z 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 a carbon number A divalent group selected from the group consisting of organic groups having an aromatic structure of 6 to 20,
Z ₁ binds to either one of the two benzene rings.
5. 1. The phenolic resin (A) further has a structural unit represented by formula (4). ~ 4. The photosensitive resin composition according to any one of:

In formula (4),
R ₄₁ and R ₄₂ 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 an ester bond, an ether bond, an amide bond, optionally linked via a carbonyl bond,
r and s are each independently an integer from 0 to 3;
Y ₄ and Z ₄ 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 selected from the group consisting of organic groups having an aromatic structure of numbers 6 to 20,
Z4 binds to either one of _the two benzene rings.
6. 1. Further containing a phenolic resin (E) having a repeating unit represented by formula (5). ~ 5. The photosensitive resin composition according to any one of:

In formula (5),
R ₄₁ and R ₄₂ each independently represents 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 an ester bond, an ether bond, an amide bond, optionally linked via a carbonyl bond,
r and s are each independently an integer from 0 to 3;
Y ₄ and Z ₄ 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 selected from the group consisting of organic groups having an aromatic structure of numbers 6 to 20,
Z ₄ is attached to either one of the two benzene rings,
m is an integer from 2 to 10,000.
7. 1. The phenol resin (A) has a weight average molecular weight of 1,000 to 100,000 in terms of polystyrene. ~6. The photosensitive resin composition according to any one of .
8. 1. further comprising a silane coupling agent; ~7. The photosensitive resin composition according to any one of .
9. 1. further comprising a nonionic surfactant; ~8. The photosensitive resin composition according to any one of .
10. 1. further comprising a reaction accelerator; ~ 9. The photosensitive resin composition according to any one of .
11. The following steps:
On a semiconductor substrate, 1. ~ 10. A step of applying the photosensitive resin composition according to any one of
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, comprising:
12. 1. ~ 10. A resin film made of the photosensitive resin composition according to any one of .
13. 12. A cured resin film comprising the resin film according to 1.
14. 13. A semiconductor device comprising the cured resin film according to 1 as a permanent film.
15. 14. The permanent film is a protective film, an insulating film, a passivation film, a sealing material, or a spacer for a semiconductor element. The semiconductor device according to .

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

（式（Ａ－１）において、ビス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)>
200.23 g (1.00 mol) of bisphenol F and 64.93 g (0.00 mol) of bisphenol F and 64.93 g (0.00 mol) of a 37% formalin aqueous solution 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. 80 mol), 6.3 g (0.05 mol) of oxalic acid dihydrate, and 224 g of γ-butyrolactone were charged, and the reaction solution was refluxed in an oil bath while flowing nitrogen. A polycondensation reaction was carried out at 100° C. for 6 hours while heating. Next, after the resulting reaction solution was cooled to room temperature, 299 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-1). The weight average molecular weight of the obtained phenol resin (A-1) was 24,800.

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

（式（Ａ－２）において、ビス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)>
Bisphenol Z268.36 (1.00 mol) and 64.93 g (0.00 mol) of bisphenol Z 268.36 (0.00 mol) and 64.93 g (0.00 mol) of a 37% formalin aqueous solution 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. 80 mol), 6.3 g (0.05 mol) of oxalic acid dihydrate, and 292 g of γ-butyrolactone were charged, and the reaction solution was refluxed in an oil bath while flowing nitrogen. A polycondensation reaction was carried out at 100° C. for 6 hours while heating. Next, after the resulting reaction solution was cooled to room temperature, 390 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 18,000.

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

（式（Ａ－３）において、ビスフェノール構造に結合する結合手は、２つのフェノール性水酸基を有する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)>
346.47 g (1.00 mol) of bisphenol M and 64.93 g (0.00 mol) of 37% formalin aqueous solution 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. 80 mol), 6.3 g (0.05 mol) of oxalic acid dihydrate, and 370 g of γ-butyrolactone were charged, and the reaction solution was refluxed in an oil bath while flowing nitrogen. A polycondensation reaction was carried out at 100° C. for 6 hours while heating. Next, after the resulting reaction solution was cooled to room temperature, 494 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 16,000.

(In Formula (A-3), the bond that binds to the bisphenol structure is bound to either one of the two phenolic hydroxyl-containing benzene rings).

（式（Ａ－４）において、ビス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)>
250.27 g (1.00 mol) of bisphenol S and 64.93 g (0.00 mol) of bisphenol S and 64.93 g (0.00 mol) of 37% formalin aqueous solution 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. 80 mol), 6.3 g (0.05 mol) of oxalic acid dihydrate, and 274 g of γ-butyrolactone were charged, and the round-bottomed flask was placed in an oil bath while flowing nitrogen to reflux the reaction solution. A polycondensation reaction was carried out at 100° C. for 6 hours. Next, after cooling the resulting reaction solution to room temperature, 366 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 19,000.

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

（式（Ａ－５）において、ビス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)>
200.23 g (1.00 mol) of bisphenol F and 2,6-bis(hydroxymethyl)- After charging 134.55 g (0.80 mol) of p-cresol, 6.3 g (0.05 mol) of oxalic acid dihydrate, and 335 g of γ-butyrolactone, the round-bottomed flask was filled with nitrogen, A polycondensation reaction was carried out at 100° C. for 6 hours while refluxing the reaction solution in an oil bath. Next, after cooling the resulting reaction solution to room temperature, 446 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 16,000.

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

（式（Ａ－６）において、ビス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)>
200.23 g (1.00 mol) of bisphenol F and 4,4′-bis(methoxymethyl) 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 193.9 g (0.8 mol) of biphenyl, 7.7 g (0.05 mol) of diethyl sulfate, and 394 g of γ-butyrolactone, the round-bottomed flask was placed in an oil bath with a nitrogen stream. A polycondensation reaction was carried out at 100° C. for 6 hours while refluxing. Next, after the resulting reaction solution was cooled to room temperature, 525 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 14,000.

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

（式（Ａ－７）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おり、ビス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-7)>
93.11 g (0.50 mol) of 4,4′-biphenol and 100.12 g of bisphenol F ( 0.50 mol), 64.93 g (0.80 mol) of a 37% formalin aqueous solution, 6.3 g (0.05 mol) of oxalic acid dihydrate, and 217 g of γ-butyrolactone, and nitrogen was introduced. A polycondensation reaction was carried out at 100° C. for 6 hours while refluxing the reaction solution in an oil bath while flowing. Next, after cooling the resulting reaction solution to room temperature, 290 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-7). The weight average molecular weight of the obtained phenol resin (A-7) was 23,000.

(In formula (A-7), the bond that binds to the biphenol structure is bonded to either one of the two benzene rings, and the bond that bonds to the bisphenol structure is either one of the two benzene rings. attached to one side).

（式（Ａ－８）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 8)
<Synthesis of phenolic resin (A-8)>
186.2 g (1.00 mol) of 4,4'-biphenol and 64% of 37% formalin aqueous solution 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 .93 g (0.80 mol), 6.3 g (0.05 mol) of oxalic acid dihydrate, and 210 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 refluxing the reaction solution. Next, after cooling the resulting reaction solution to room temperature, 280 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, and then vacuum-dried at 60° C. to obtain a phenol resin represented by the following formula (A-8). The weight average molecular weight of the obtained phenol resin (A-8) was 21,000.

(In formula (A-8), the bond that binds to the biphenol structure is bound to either one of the two benzene rings).

(Synthesis Example 9)
<Synthesis of phenolic resin (A-9)>
Phenol 94.11 (1.00 mol) and 37% formalin aqueous solution 64.93 g (0.00 mol) were placed in a four-neck glass round-bottomed flask equipped with a thermometer, a stirrer, a raw material inlet and a dry nitrogen gas inlet tube. 80 mol), 6.3 g (0.05 mol) of oxalic acid dihydrate, and 118 g of γ-butyrolactone were charged, and the reaction solution was refluxed in an oil bath while flowing nitrogen. A polycondensation reaction was carried out at 100° C. for 6 hours while heating. Next, after cooling the resulting reaction solution to room temperature, 158 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-9). The weight average molecular weight of the obtained phenol resin (A-9) was 12,000.

(Synthesis Example 10)
<Synthesis of phenolic resin (A-10)>
64.88 m-cresol (0.60 mol) and 43.26 p-cresol (0 .40 mol), 64.93 g (0.80 mol) of a 37% formalin aqueous solution, 6.3 g (0.05 mol) of oxalic acid dihydrate, and 132 g of γ-butyrolactone, and then nitrogen is flowed. 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, 176 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-10). The weight average molecular weight of the obtained phenol resin (A-10) was 13,000.

(Preparation of photosensitive resin composition)
For each of Examples 6, 7 and 10, Reference Examples 1-5, 8, 9 and 11 and Comparative Examples 1 and 2, photosensitive resin compositions were prepared as follows. First, each component blended according to Table 2 was stirred under a nitrogen atmosphere, and then filtered through a polyethylene filter having a pore size of 0.2 μm to obtain a varnish-like photosensitive resin composition. Details of each component in Table 2 are as follows. Moreover, the unit in Table 2 is parts by weight.

<(A) Phenolic resin>
(A-1) Phenolic resin obtained in Synthesis Example 1 above (A-2) Phenolic resin obtained in Synthesis Example 2 above (A-3) Phenolic resin obtained in Synthesis Example 3 above (A-4) Phenolic resin (A-5) obtained in Synthesis Example 4 above Phenolic resin (A-6) obtained in Synthesis example 5 Phenolic resin (A-7) obtained in Synthesis example 6 above Synthesis example 7 Obtained Phenolic Resin (A-8) Phenolic Resin Obtained in Synthesis Example 8 (A-9) Phenolic Resin Obtained in Synthesis Example 9 (A-10) Phenolic Resin Obtained in Synthesis Example 10

<(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.)

<(D) Silane coupling agent>
(D-1) KBM-403 (manufactured by Shin-Etsu Silicone Co., Ltd.)
(D-2) KBM-585 (manufactured by Shin-Etsu Silicone Co., Ltd.)
(D-3) KBM-9659 (manufactured by Shin-Etsu Silicone Co., Ltd.)

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

<(F) Thermal acid generator>
(F-1) San-Aid SI-150 (manufactured by Sanshin Chemical Co., Ltd.)
(F-2) Irgacure PAG121 (manufactured by BASF Japan)

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

<(H) Solvent>
(H-1) γ-butyrolactone

<Evaluation of phenolic resin-1 (measurement of low-molecular-weight phenolic compound)>
For the phenolic resins (A-1) to (A-10), the content of low-molecular-weight phenolic compounds having a molecular weight of 200 or less was quantified by gel permeation chromatography. The apparatus used was HLC-8320GPC (manufactured by Tosoh Corporation). Table 1 shows the results. From the viewpoint of reducing the outgassing of the cured film, the content of the low-molecular-weight phenol compound should be as small as possible.

<Evaluation of outgas amount of cured film>
Each of the photosensitive resin compositions obtained above was coated 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 thickness of about 1.2 μm. got (For Reference Examples 9 and 11 and Example 10 , after pre-baking, the coating film was irradiated with ultraviolet rays of 1000 mJ/cm ² , and then subjected to post-exposure baking at 120° C. for 3 minutes.) The resulting coated wafer was heated. It was placed in an oven, heated from room temperature to 200° C. at a rate of 5° C./min while flowing nitrogen, heat-treated at 200° C. for 60 minutes, and cooled to room temperature to obtain a silicon wafer with a cured film. Thereafter, the film was peeled off by immersing it in a 2% aqueous hydrogen fluoride solution, and dried at 80° C. for 10 hours to obtain a cured film of the photosensitive resin composition. The resulting cured film was heated to 200° C. at a heating rate of 10° C./min using GC-MS (gas chromatography-mass spectrometry), and organic volatile components generated were quantified. When the total amount of all organic volatile components was 100 ppm or less, it was evaluated as "O", and when it exceeded 100 ppm, it was evaluated as "x".

<Evaluation of tensile elongation of cured film>
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 obtain a coating film having a thickness of about 12 μm. rice field. (For Reference Examples 9 and 11 and Example 10 , after pre-baking, the coating film was irradiated with ultraviolet rays of 1000 mJ/cm ² , and then subjected to post-exposure baking at 120° C. for 3 minutes.) The resulting coated wafer was heated. It was placed in an oven, heated from room temperature to 200° C. at a rate of 5° C./min while flowing nitrogen, heat-treated at 200° C. for 60 minutes, and cooled to room temperature to obtain a silicon wafer with a cured film. Next, the cured film-attached wafer was cut into 4.5 mm wide and 8 cm long wafers with a dicing machine. C. for 10 hours to obtain a test piece. The obtained test piece was set in a tensile tester (Tensilon RTC-1210A, manufactured by Orientec Co., Ltd.) so that the distance between chucks was 20 mm, and then a tensile test was performed under the conditions of 5 mm/min in an atmosphere of 23 ° C. Then, the tensile elongation of the test piece was calculated from the following formula.
Tensile elongation rate (%) = (distance between chucks at break/distance between initial chucks - 1) x 100
A higher tensile elongation is desirable from the viewpoint of preventing cracks in the film in the semiconductor device.

<Patterning Evaluation-1 (Examples 6 and 7 , Reference Examples 1-5 and Comparative Examples 1-2)>
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 was irradiated through a test mask having a stepwise hole pattern and line pattern with a size of 1 μm to 100 μm using an i-line stepper (NSR-4425i manufactured by Nikon Corporation) 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). It should be noted that the smaller the resolution, the better for creating fine wiring.

<Patterning Evaluation-2 ( Reference Examples 9, 11 and Example 10 )>
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 was irradiated through a test mask having a stepwise hole pattern and line pattern with a size of 1 μm to 100 μm using an i-line stepper (NSR-4425i manufactured by Nikon Corporation) while changing the exposure amount.
Next, baking treatment was performed on a hot plate at 120° C. for 3 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 + the minimum exposure amount for forming a line of 5 μm. The results are shown in Table 2 as pattern resolution (μm). It should be noted that the smaller the resolution, the better for creating fine wiring.

<Resolution evaluation after curing>
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 6, 7, 10, Reference Examples 1-5, 8, 9, 11 and Comparative Examples 1 and 2 were each finalized. After coating so as to have a thickness of 5 μm, it was patterned and cured. 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.

<Evaluation of semiconductor device reliability (electrical connectivity)>
Conduct electrical connection checks on each of the 10 semiconductor devices obtained by the above method,
"○" indicates that there was no electrical connection failure in all 10 semiconductor devices,
"X" indicates that there was an electrical connection failure in one or more semiconductor devices out of 10,
evaluated as
<Evaluation of semiconductor device reliability (humidity 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.
"○" indicates that there was no electrical connection failure in all 10 semiconductor devices,
"X" indicates that electrical connection failure was observed in 1 or more semiconductor devices out of 10,
evaluated as

Table 2 showing examples , reference examples and comparative examples is shown below.

The resin films formed from the resin compositions containing the phenolic resins (A-1) to (A-7) of Examples 6, 7, 10 and Reference Examples 1-5, 8, 9, and 11 had good heat resistance. and pattern resolution, and the cured resin film exhibited good developability. In addition, all of these cured resin films produced a reduced amount of outgassing. Moreover, the tensile elongation of these cured resin films exceeded 20%. Furthermore, the semiconductor device provided with the cured resin film formed from the photosensitive resin composition containing the phenolic resins (A-1) to (A-7) of Examples and Reference Examples had no defective electrical connectivity, and After storage at high temperature and high humidity, no defects due to corrosion of the aluminum circuit occurred. Therefore, the cured film is useful as a permanent film for semiconductor devices.

Claims (10)

a phenolic resin (A) having a bisphenol structure;
a photoacid generator (B);
a cross-linking agent (C) having a group capable of reacting with the phenolic resin (A);
including
The phenol resin (A) has a structural unit derived from a bisphenol compound, a biphenol compound, and at least one compound selected from the group consisting of an aliphatic aldehyde compound, a dimethylol compound, a dimethoxymethyl compound and a dihaloalkyl compound. death,
The phenol resin (A) has a structural unit represented by formula (3) and a structural unit represented by formula (4),
The weight average molecular weight of the phenol resin (A) in terms of polystyrene is 1000 to 100000,
The content of the low-molecular-weight phenol compound having a molecular weight of 200 or less in the phenol resin (A) is less than 1% by mass,

In formula (3),
Each X ₁ is independently selected from a linear alkylene group, a branched alkylene group, a cyclic alkylene group, an aromatic group, a fluorene group, an ether group, an ester group, a thioether group, a sulfide group, and a carbonyl group. is a divalent group,
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, or a A saturated or unsaturated alicyclic group, or a monovalent substituent selected from the group consisting of an organic group having an aromatic structure with 6 to 20 carbon atoms, which is an ester bond, ether bond, amide bond, carbonyl may be connected via a bond,
p and q are each independently an integer from 0 to 3;
Y ₁ and Z 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 a carbon number A divalent group selected from the group consisting of organic groups having an aromatic structure of 6 to 20,
Z ₁ is attached to either one of the two benzene rings,

In formula (4),
R ₄₁ and R ₄₂ 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, optionally linked via a carbonyl bond,
r and s are each independently an integer from 0 to 3;
Y ₄ and Z ₄ 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 selected from the group consisting of organic groups having an aromatic structure of numbers 6 to 20,
Z ₄ is attached to either one of the two benzene rings,
A photosensitive resin composition for permanent films. The photosensitive resin composition according to claim 1, further comprising a phenol resin (E) having a repeating unit represented by formula (A-8):

In formula (A-8),
m is an integer from 2 to 10,000. 3. The photosensitive resin composition according to claim 1, further comprising a silane coupling agent. 4. The photosensitive resin composition according to any one of claims 1 to 3, further comprising a nonionic surfactant. 5. The photosensitive resin composition according to any one of claims 1 to 4, further comprising a reaction accelerator. The following steps:
A step of applying the photosensitive resin composition according to any one of claims 1 to 5 on 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, comprising: A resin film comprising the photosensitive resin composition according to any one of claims 1 to 5. A cured resin film comprising the resin film according to claim 7 . A semiconductor device comprising the cured resin film according to claim 8 as a permanent film. 10. The semiconductor device according to claim 9, wherein said permanent film is a protective film of a semiconductor element, an insulating film, a passivation film, a sealing material, or a spacer.