JP2007121873A - Photosensitive resin composition and method for producing semiconductor device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition capable of producing a heat resistant relief structure, excellent in in-plane uniformity after development and in in-plane uniformity after heat curing, reducing scum and excellent also in adhesion, and a method for producing a semiconductor device using the composition. <P>SOLUTION: The photosensitive resin composition contains a polyamide resin represented by formula (I) and a quinonediazidosulfonic ester of a phenol compound as a photosensitizing agent. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition. More specifically, the present invention is suitable for applications in the field of microelectronic technology, and is capable of developing with an alkaline aqueous solution and a semiconductor device using the composition. It relates to the manufacturing method.

  For the application of microelectronics, polymers that exhibit durability at high temperatures are generally well known. Precursors of such polymers such as polyimide and polybenzoxazole (PBO) can be made photoreactive with suitable additives. This precursor is converted to the desired polymer by known techniques such as exposure to high temperatures. Accordingly, polymer precursors have been used to produce protective layers, thermal insulation layers, and highly heat-resistant polymer relief structures.

  Patent Document 1 (US Pat. No. 4,371,685) discloses a positive photosensitive composition containing an alkali-soluble PBO precursor and a diazoquinone photoactive compound. The diazoquinone compound prevents the PBO precursor from dissolving in an aqueous base, and after exposure, the diazoquinone compound undergoes photolysis and is converted to indenecarboxylic acid that promotes dissolution of the PBO precursor in an alkaline developer.

  Patent Document 2 (Japanese Patent Publication No. 2002-526795) discloses a composition containing a PBO precursor partially capped with a diazoquinone compound.

A photosensitive composition containing such a PBO precursor is a system in which it is difficult to obtain a sufficient dissolution rate difference between an unexposed portion and an exposed portion, and in-plane uniformity after development and after thermosetting, scum generation, adhesion There are various problems such as sex.
U.S. Pat. No. 4,371,685 Japanese translation of PCT publication No. 2002-526795

  A photosensitive resin capable of producing a relief structure having heat resistance, excellent in-plane uniformity after development, excellent in-plane uniformity after thermosetting, reduced scum, and excellent adhesion A composition and a method for manufacturing a semiconductor device using the composition are provided.

The above problems have been achieved by the following configuration.
(1) A photosensitive resin composition containing a polyamide resin represented by the general formula (I) and a quinonediazidosulfonic acid ester photosensitizer of a phenol compound.

Ar ₁ independently represents a tetravalent organic group.
Ar ₃ independently represents a divalent organic group.
a is 60 to 100 mol%.
b is 0 to 40 mol%.
c is 2 to 500.
R ₄ and R ₅ each independently represents a divalent organic group.
R ₆ and R ₇ each independently represents a monovalent organic group.
n represents 0, 1, 2;
R ₁ independently represents an alkyl group, a cyclic alkyl group, an aryl group, an aralkyl group, an alkoxy group, a halogen atom, an acyl group, an acyloxy group or an alkoxycarbonyl group.
l independently represents 0, 1, 2, 3;
m represents 1, 2, and 3 independently.

(2) The photosensitive resin composition as described in (1) above, wherein the photosensitive agent is a quinonediazidosulfonic acid ester of a phenol compound represented by any one of the general formulas (A1) to (A4) .

In general formulas (A1) to (A3),
R ₁ independently represents an alkyl group, a cyclic alkyl group, an alkoxy group, an alkenyl group, an aryl group, an aralkyl group, a halogen atom, an acyl group, an acyloxy group, or an alkoxycarbonyl group.
R ₂ independently represents an alkyl group, a cyclic alkyl group, an alkenyl group, an aryl group, or an aralkyl group, and a plurality of R ₂ may be bonded to each other to form a ring.
a to c independently represent an integer of 1 to 3.
l, m, and n represent 0-3.
When a to c are 2 or 3, l, m and n represent 0 to 2.

In general formula (A4),
R ₃ independently represents a hydrogen atom or an alkyl group.
R ₄ and R ₅ each independently represents an alkyl group, an alkoxy group, an aryl group or a cyclic alkyl group having at least one hydroxyl group.
q and r independently represent an integer of 1 to 3.

(3) The photosensitive resin composition as described in (2) above, wherein the photosensitive agent is a quinonediazidosulfonic acid ester of the following phenol compound.

(4) The photosensitive resin composition as described in any one of (1) to (3) above, further comprising a compound having at least one methylol group.

(5) The photosensitive resin composition as described in any one of (1) to (4) above, which further contains a phenol compound represented by any one of the general formulas (B1) to (B3).

R ₁₀₀ and R ₁₀₁ independently represent a halogen atom, an alkyl group, an alkoxy group or a cycloalkyl group. m ₁ and n ₁ independently represent an integer of 0 to 4. When a plurality of R ₁₀₀ and R ₁₀₁ are present, they may be the same or different. p ₁ and q ₁ are each independently an integer of 0 to 3, provided that p ₁ + q ₁ ≧ 1.

R ₁₀₂ to R ₁₀₃ independently represent a halogen atom, an alkyl group, an alkoxy group or a cycloalkyl group. m ₂ and n ₂ independently represent an integer of 0 to 2.
p ₂ and q ₂ are each independently an integer of 0 to 3, provided that p ₂ + q ₂ ≧ 3.
R ₁₀₄ represents an alkylene group, an oxygen atom, a carbonyl group, a carbonyl ether group, a sulfur atom, a sulfonyl group or an azo group.

R ₁₀₅ represents a halogen atom, an alkyl group, an alkoxy group or a cycloalkyl group. m ₃ represents an integer of 0 to 3. R ₁₀₆ represents a hydrogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, an aryl group, or an aryl group which may have a substituent. p ₃ represents 2 or 3.

(6) The photosensitive resin composition as described in any one of (1) to (5) above, which further contains a surfactant.
(7) The photosensitive resin composition as described in any one of (1) to (6) above, which contains γ-butyrolactone and propylene glycol monomethyl ether.
(8) A semiconductor device obtained by applying the photosensitive resin composition according to any one of (1) to (7) above on a semiconductor element, prebaking, exposing, developing, and heating. Production method.

  The photosensitive resin composition of the present invention is excellent in in-plane uniformity after development, further excellent in in-plane uniformity after heat curing, scum reduction, adhesion performance, heat resistance based on polyamide resin, A relief structure excellent in mechanical properties, electrical properties, and chemical resistance can be produced, and can be suitably used for semiconductor applications, particularly as a buffer coat.

[1] Polyamide resin The terminal phenol type polyamide resin contained in the photosensitive resin composition of the present invention is represented by the following general formula (I).

Ar ₁ independently represents a tetravalent organic group.
Ar ₃ independently represents a divalent organic group.
a is 60 to 100 mol%.
b is 0 to 40 mol%.
c is 2-500, preferably 2-300, more preferably 3-100.

In the group represented by Ar ₂ ,
R ₄ and R ₅ each independently represents a divalent organic group.
R ₆ and R ₇ each independently represents a monovalent organic group.
n represents 0, 1, 2;

In the end group,
R ₁ independently represents an alkyl group, a cyclic alkyl group, an aryl group, an aralkyl group, an alkoxy group, a halogen atom, an acyl group, an acyloxy group or an alkoxycarbonyl group.
m represents 1, 2, and 3 independently.
l independently represents 0, 1, 2, 3;

The alkyl group as R ₁ is preferably a linear or branched alkyl group having 1 to 15 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl. Group, pentyl group, neopentyl group, hexyl group and the like.

The cyclic alkyl group is preferably a cycloalkyl group having 3 to 30 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, and a boronyl group.
The aryl group is preferably an aryl group having 6 to 16 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and a phenanthryl group.
The aralkyl group is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.
The alkoxy group is preferably a linear or branched alkoxy group having 1 to 30 carbon atoms. For example, methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t- Examples thereof include a butoxy group and a hexyloxy group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The acyl group is preferably an acyl group having 1 to 30 carbon atoms, and examples thereof include an acetyl group, a propionyl group, a pivaloyl group, a butyryl group, and a valeryl group.
The acyloxy group is preferably an acyloxy group having 1 to 30 carbon atoms, such as an acetoxy group, methylbutinoyloxy group, methyldecinoyloxy group, propionyloxy group, butyryloxy group, valeryloxy group, palmitoyloxy group, benzoyloxy group, etc. Can be mentioned.
The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 1 to 30 carbon atoms, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, and an octyloxycarbonyl group.

  Each of the above groups may further have a substituent. Further examples of the substituent include an alkoxy group, a cycloalkyl group, an acyl group, an acyloxy group, a halogen atom, a hydroxyl group, and a carboxyl group. As for the ring structure, examples of the substituent further include an alkyl group.

The resin represented by the general formula (I) is prepared by reacting a dicarboxylic acid derivative having an Ar ₃ structure with a bisaminophenol having an Ar ₁ structure and, if necessary, a bisamino having an Ar ₂ structure to synthesize a polyamide, The terminal carboxylic acid derivative structure can be synthesized by capping with an aminophenol (for example, an aminophenol compound having an amino group at the position of the bond of the terminal group exemplified below).

  Specific examples of the terminal group that caps the terminal carboxylic acid derivative structure include the following.

In the formula, Ar ₁ is a tetravalent organic group, for example, an aromatic group, an aliphatic group, a heterocyclic group, or a combination thereof, and Ar ₃ is a divalent organic group, for example, aromatic Group, aliphatic group, heterocyclic group or a combination thereof.

  The polyamide resin (D) before the end cap generally has a degree of polymerization of 10 to 1000, and the following monomer (A), monomer (C), and, if necessary, the monomer (B) are reacted in the presence of a base. Is synthesized.

Wherein Ar ₁ , Ar ₂ , Ar ₃ are as defined above, W is Cl, OR, or OH, where R is alkyl or cycloalkyl, eg, —CH ₃ , —C ₂ H _5. N-C ₃ H ₇ , i-C ₃ H ₇ , n-C ₄ H ₉ , t-C ₄ H ₉ , cyclohexyl and the like.

  The ratio of [(A) + (B)] / (C) is generally between about 0.9 and 1.1. Monomer (A) is about 10-100 mol% of [(A) + (B)], and monomer (B) is about 0-90 mol% of [(A) + (B)].

The polyamide resin (D) may be reacted with a diazoquinone compound, and a part of hydroxyl groups may be capped with diazoquinone, that is, —OH may be —O—SO ₂ —Z (Z is a diazoquinone group).

  Examples of Z include the following groups.

Examples of the tetravalent organic group represented by Ar ₁ include the following groups.

In the formula, X ₁ represents —O—, —S—, —C (CF ₃ ) ₂ —, —CH ₂ —, —SO ₂ —, —NHCO—.
_{, -C (CH 3) 2 -} , - CO- or a group of the following.

R ¹ represents an alkyl group such as —CH ₃ , —C ₂ H ₅ , n-C ₃ H ₇ , i-C ₃ H ₇ , n-C ₄ H ₉ , t-C ₄ H ₉ , a cyclohexyl group, or the like. A cycloalkyl group;

Ar ₁ is not limited to these groups. Furthermore, monomer (A) may be a mixture of two or more monomers.

In the group represented by Ar ₂ , examples of the divalent organic group represented by R ₄ and R ₅ include an alkylene group, an arylene group, and a combination thereof, and preferably have 15 or less carbon atoms. is there.
Examples of the monovalent organic group represented by R ₆ and R ₇ include an alkyl group, an aryl group, and an aralkyl group, and preferably have 15 or less carbon atoms.
Specific examples of Ar ₂ include the following.

Examples of the divalent organic group for Ar ₃ include the following groups.

(Wherein X ₂ represents —O—, —S—, —C (CF ₃ ) ₂ —, —CH ₂ —, —SO ₂ —, —NHCO—, —C (CH ₃ ) ₂ —, —CO -)
Ar ₃ is not limited to these groups. Furthermore, monomer (C) may be a mixture of two or more monomers.

  As a diazoquinone compound made to react with a polyamide resin (D), the following are mentioned, for example, You may use multiple.

Preferred reaction solvents are N-methyl-2-pyrrolidone (NMP), γ-butyrolactone (GBL), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), dimethyl-2-piperidone, dimethyl sulfoxide (DMSO), sulfolane, and diglyme. The most preferred solvents are N-methyl-2-pyrrolidone (NMP) and γ-butyrolactone (GBL). Any conventional reaction can be used to react a dicarboxylic acid or chloride or ester thereof with at least one aromatic and / or heterocyclic dihydroxydiamine, and optionally with at least one diamine. It's okay. Examples of suitable dicarboxylic acids are selected from the group consisting of 4,4'-diphenyl ether dicarboxylic acid, terephthalic acid, isophthalic acid and mixtures thereof. Examples of suitable dihydroxydiamine compounds are 3,3'-dihydroxy-4,4'-diaminodiphenyl ether, 3,3'-dihydroxybenzidine, hexafluoro-2,2-bis-3-amino-4-hydroxyphenylpropane And mixtures thereof. The reaction is generally carried out at about −10 to about 30 ° C. for about 6 to 48 hours. The molar ratio of (diamine + dihydroxydiamine) to (dicarboxylic acid) is about 0.9 to 1.1: 1.

For the cap of the hydroxyl group in the polyamide resin (D) with the diazoquinone compound, any suitable method for reacting with the photoactive moiety Cl—SO ₂ —Z may be used. Generally, the reaction is carried out at about 0 to about 30 ° C. for about 3 to 24 hours in the presence of a base such as pyridine, trialkylamine, methylpyridine, lutidine, n-methylmorpholine and the like. The most preferred base is triethylamine.

  The ratio of capped units is preferably 0.001 to 0.35, preferably 0.003 to 0.20, and 0.005 to 0, as a molar ratio to the total amount of phenol groups and amino groups that can be capped. .05 is most preferred.

  The addition amount of the polyamide resin is generally 50 to 99% by mass with respect to the total solid content of the photosensitive resin composition of the present invention (total amount of components constituting the finally obtained cured product excluding the solvent). , Preferably it is 60-95 mass%.

[2] Quinonediazidosulfonic acid ester of phenolic compound (photosensitive agent)
The photosensitive agent contained in the positive photosensitive resin composition of the present invention is a quinonediazide sulfonate ester of a low molecular phenol compound.
Here, the low molecular phenol compound is generally a phenol compound having a molecular weight of 150 to 1500.
In the photosensitizer, the esterification rate of the phenolic hydroxyl group by the quinonediazidosulfonic acid group is preferably 30 to 100%, and more preferably 50 to 100%.

  As the low molecular weight phenol compound for the photosensitizer, those represented by the following general formulas (A1) to (A4) are preferable, and those represented by the general formula (A4) are particularly preferable.

  First, the phenolic compounds represented by the general formulas (A1) to (A4) will be described.

In general formulas (A1) to (A3),
R ₁ independently represents an alkyl group, a cyclic alkyl group, an alkoxy group, an alkenyl group, an aryl group, an aralkyl group, a halogen atom, an acyl group, an acyloxy group, or an alkoxycarbonyl group.
R ₂ independently represents an alkyl group, a cyclic alkyl group, an alkenyl group, an aryl group, or an aralkyl group, and a plurality of R ₂ may be bonded to each other to form a ring.
a to c independently represent an integer of 1 to 3.
l, m, n, and p represent 0-3.
When a to c are 2 or 3, l, m and n represent 0 to 2.

In general formula (A4),
R ₃ independently represents a hydrogen atom or an alkyl group.
R ₄ and R ₅ each independently represents an alkyl group, an alkoxy group, an aryl group or a cyclic alkyl group having at least one hydroxyl group.
q and r independently represent an integer of 1 to 3.

  Details of each of the above substituents are as follows.

The alkyl group is preferably a linear or branched alkyl group having 1 to 15 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group. , Neopentyl group, hexyl group, heptyl group, octyl group, nonyl group and the like.
The cyclic alkyl group may be monocyclic or polycyclic. The monocyclic type is preferably a cyclic alkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. As the polycyclic type, a cyclic alkyl group having 6 to 20 carbon atoms is preferable, and examples thereof include an adamantyl group, a norbornyl group, an isobornyl group, and a camphanyl group.

The aryl group is preferably an aryl group having 6 to 16 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, a phenanthryl group, and a pyrenyl group.
The aralkyl group is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.

  The alkoxy group is preferably a linear or branched alkoxy group having 1 to 15 carbon atoms. For example, methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t- Examples include butoxy, hexyloxy, heptyloxy, octyloxy, and nonyloxy groups.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The acyl group is preferably an acyl group having 1 to 15 carbon atoms, and examples thereof include an acetyl group, a propionyl group, a pivaloyl group, a butyryl group, a valeryl group, a palmitoyl group, and a benzoyl group.
The acyloxy group is preferably an acyloxy group having 1 to 15 carbon atoms, such as an acetoxy group, a methylbutinoyloxy group, a methyldecinoyloxy group, a propionyloxy group, a butyryloxy group, a valeryloxy group, a palmitoyloxy group, a benzoyloxy group, etc. Can be mentioned.

The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 15 carbon atoms, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, an octyloxycarbonyl group, and a dodecyloxycarbonyl group.
The alkenyl group is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.

  As an alkylene group, a C2-C15 alkylene group is preferable and a C2-C8 alkylene group is more preferable.

  Each of the above groups may be further substituted with a group similar to the above (preferably a monovalent group having 10 or less carbon atoms).

R ₄ and R ₅ in the general formula (A4) are preferably groups represented by the following general formula (X).

R ₆ independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a cycloalkyl group.
s represents an integer of 1 to 3.
a represents an integer of 1 to 3.

  Specific examples of the phenol compound represented by any one of the general formulas (A1) to (A4) are shown below, but are not limited thereto.

  Moreover, the phenolic compound represented by general formula (A5) can be mentioned as a low molecular phenolic compound for photosensitive agents.

R _{a1 to} R _a3 each independently represents an alkyl group, a cyclic alkyl group, an aryl group, an aralkyl group, an alkoxy group, a halogen atom, an acyl group, an acyloxy group, an alkoxycarbonyl group, or an alkenyl group.

R _{b1 to} R _b4 each independently represents an alkyl group. R _b1 and R _b2 , or R _b3 and R _b4 may be bonded to each other to form a ring.

  l, m, and n independently represent an integer of 0 to 3.

The alkyl group as R _{a1 to} R _a3 is preferably a linear or branched alkyl group having 1 to 15 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, Examples thereof include a sec-butyl group, a pentyl group, a neopentyl group, and a hexyl group.

  The cyclic alkyl group is preferably a cycloalkyl group having 3 to 30 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, and a boronyl group.

  The aryl group is preferably an aryl group having 6 to 16 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and a phenanthryl group.

  The aralkyl group is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.

  The alkoxy group is preferably a linear or branched alkoxy group having 1 to 30 carbon atoms. For example, methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t- Examples thereof include a butoxy group and a hexyloxy group.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  The acyl group is preferably an acyl group having 1 to 30 carbon atoms, and examples thereof include an acetyl group, a propionyl group, a pivaloyl group, a butyryl group, and a valeryl group.

The acyloxy group is preferably an acyloxy group having 1 to 30 carbon atoms, such as an acetoxy group, methylbutinoyloxy group, methyldecinoyloxy group, propionyloxy group, butyryloxy group, valeryloxy group, palmitoyloxy group, benzoyloxy group, etc. Can be mentioned.

  The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 1 to 30 carbon atoms, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, and an octyloxycarbonyl group.

  The alkenyl group is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.

_Examples of the alkyl group as R _{b1 to} R _b4 include the same alkyl groups as R _{a1 to} R _a3 , preferably having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.

R _b1 and R _b2, R _b3 and R _{b4 may} combine with each other to form a ring. Specific examples of the ring include a 3- to 6-membered ring such as a cyclohexane ring.

  Each of the above groups may further have a substituent. Further examples of the substituent include an alkoxy group, a cycloalkyl group, an acyl group, an acyloxy group, a halogen atom, a hydroxyl group, and a carboxyl group. As for the ring structure, examples of the substituent further include an alkyl group.

  Specific examples of the phenol compound represented by the general formula (A5) are given below, but the invention is not limited thereto.

  Furthermore, the phenolic compound represented by general formula (A6) can be mentioned.

R _{a1 to} R _a3 each independently represents an alkyl group, a cyclic alkyl group, an aryl group, an aralkyl group, an alkoxy group, a halogen atom, an acyl group, an acyloxy group, an alkoxycarbonyl group, or an alkenyl group.

R _{b1 to} R _b4 each independently represents an alkyl group. R _b1 and R _b2 , or R _b3 and R _b4 may be bonded to each other to form a ring.

  l, m, and n independently represent an integer of 0 to 3.

  p represents 0 or 1; However, n + p = 0-3.

The alkyl group, cyclic alkyl group, aryl group, aralkyl group, alkoxy group, halogen atom, acyl group, acyloxy group, alkoxycarbonyl group and alkenyl group as R _{a1 to} R _a3 in the general formula (A6) are represented by the general formula (A5 ) As R _{a1 to} R _a3 .

_Examples of the alkyl group as R _{b1 to} R _b4 include the same alkyl groups as R _{a1 to} R _a3 , preferably having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.

R _b1 and R _b2, R _b3 and R _{b4 may} combine with each other to form a ring. Specific examples of the ring include a 3- to 6-membered ring such as a cyclohexane ring.

  Each of the above groups may further have a substituent. Further examples of the substituent include an alkoxy group, a cycloalkyl group, an acyl group, an acyloxy group, a halogen atom, a hydroxyl group, and a carboxyl group. As for the ring structure, examples of the substituent further include an alkyl group.

  p = 1 is preferable, and the substitution of the group having a benzene ring at both ends to the central benzene ring in formula (A6) is preferably a meta-substitution relationship.

  Specific examples of the phenol compound represented by the general formula (A6) are shown below, but the invention is not limited thereto.

  A commercially available phenol compound may be used as the phenol compound represented by the general formula (A6), or it may be synthesized by a known method.

  Esterification using the phenolic compounds represented by the general formulas (A1) to (A6) as quinonediazidosulfonic acid esters can also be performed by a known method.

  For example, esterification of a phenol compound represented by the general formulas (A1) to (A6) and 1,2-naphthoquinonediazide-5- (and / or -4-) sulfonyl chloride in the presence of a basic catalyst Obtained by carrying out the reaction.

  That is, a predetermined amount of the phenol compound represented by the general formulas (A1) to (A6) and 1,2-naphthoquinonediazide-5- (and / or-4-) sulfonyl chloride, dioxane, acetone, tetrahydrofuran, methyl ethyl ketone, N -A solvent such as methylpyrrolidone, chloroform, trichloroethane, trichloroethylene, dichloroethane or γ-butyllactone is charged into a flask, and a basic catalyst such as sodium hydroxide, sodium carbonate, sodium bicarbonate, triethylamine, 4-dimethylaminopyridine is prepared. 4-methylmorpholine, N-methylpiperazine, N-methylpiperidine and the like are condensed dropwise. The reaction temperature is usually -20 to 60 ° C, preferably 0 to 40 ° C.

  The obtained product is crystallized in water, washed with water, and further purified and dried.

  The addition amount of the photosensitive agent is generally 1 to 50% by mass with respect to the total solid content of the photosensitive resin composition of the present invention (total amount of components constituting the finally obtained cured product excluding the solvent). The amount is preferably 5 to 40% by mass.

[3] Concomitant photosensitizer As the photosensitizer, together with the quinonediazidosulfonic acid ester of the phenol compound represented by the general formulas (A1) to (A6), other photosensitizers such as other diazoquinone compounds (H) and dihydropyridine compounds (I) may be used in combination.
In addition, you may use a diazoquinone compound (H), without using together with the quinone diazide sulfonic acid ester of the phenol compound represented by the said general formula (A1)-(A6).

  The amount of the photosensitizer that may be used in combination is generally 99% by mass or less, preferably 99% by mass or less, preferably with respect to the quinonediazidosulfonic acid ester of the phenol compound represented by the general formulas (A1) to (A6). 80% by mass.

  The diazoquinone compound that may be used in combination is, for example, one having the following structure.

Wherein D is independently H or any of the following groups.

  However, at least one D in each compound is a diazide group.

  Examples of dihydropyridine (I) include compounds having the following structures.

In which the R ³ groups are identical or different and have the following structure: H, OH, COO— (
_{CH 2) n -CH 3, (} CH 2) n -CH 3, O- (CH 2) n -CH 3, CO- (CH 2) n -CH 3, (CF 2) n -CF 3, C 6 _{H 5, COOH, (CH 2} ) n -O- (CH 2) m -CH 3, (CH 2) n -OH,
CH ₂ ═CH— (CH ₂ ) _p —CO—CH ₂ , F, Cl, Br or I, m = 0 to 10
N = 0-10 and p = 0-4.

R ⁴ is H, a C ₁ -C ₇ alkyl group, a cycloalkyl group, or a phenyl group and a monosubstituted phenyl group.

R ⁵ is any one of the following groups.

In which R ⁶ is defined in the same way as R ³ and the NO ₂ group is in the ortho position relative to the dihydropyridine ring.

  For example, the following can be mentioned as dihydropyridine.

Wherein Y is —OR ² where R ² is a substituted or unsubstituted monovalent aromatic or aliphatic group, CN, Cl, Br or I.

[4] Methylol compound From the viewpoint of in-plane uniformity after thermosetting, it is preferable to contain a compound having at least one methylol group (methylol compound). The methylol compound preferably has no phenolic hydroxyl group.
The molecular weight of the methylol compound is preferably 150 to 1000.
As for the number of methylol groups which a methylol compound has, 2-10 are preferable.
The methylol compound preferably has an aromatic ring, and the —CH ₂ OH group is directly an aromatic ring. Examples of the aromatic ring include aromatic hydrocarbons such as benzene, naphthalene and anthracene, and heteroaromatic rings such as pyrrole and pyridine.
The methylol compound may have a skeleton in which aromatics are bonded, such as biphenyl and terphenyl, or a skeleton in which an aromatic ring is bonded to a divalent or higher valent organic group, such as diphenylmethane. Also good.

Although the specific example of a methylol compound is given below, it is not limited to these.
In the following formulas, R independently represents a hydrogen atom, an alkyl group, an alkoxy group, a carboxy group or an ester group.

  The compounding amount of the methylol compound is 1 to 100 parts by mass, more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the polyamide resin.

[5] Phenol Compound In the composition of the present invention, it is preferable to add a phenol compound represented by the general formulas (B1) to (B3) in order to prevent scum.

R ₁₀₀ and R ₁₀₁ independently represent a halogen atom, an alkyl group, an alkoxy group or a cycloalkyl group. m ₁ and n ₁ independently represent an integer of 0 to 4. When a plurality of R ₁₀₀ and R ₁₀₁ are present, they may be the same or different. p ₁ and q ₁ are each independently an integer of 0 to 3, provided that p ₁ + q ₁ ≧ 1.

  Examples of the phenol compound represented by the general formula (B1) include, but are not limited to, the following compounds.

R ₁₀₂ to R ₁₀₃ independently represent a halogen atom, an alkyl group, an alkoxy group or a cycloalkyl group. m ₂ and n ₂ independently represent an integer of 0 to 2.
p ₂ and q ₂ are each independently an integer of 0 to 3, provided that p ₂ + q ₂ ≧ 3.
R ₁₀₄ represents an alkylene group such as a methylene group, an oxygen atom, a carbonyl group, a carbonyl ether group, a sulfur atom, a sulfonyl group, or an azo group.
P ₂ + q ₂ represented by the general formula (B2) is p ₂ + q ₂ ≧ 3, but preferably p ₂ + q ₂ is 4-6.

  Although the following can be mentioned as a phenolic compound shown by general formula (B2), It is not limited to these.

R ₁₀₅ represents a halogen atom, an alkyl group, an alkoxy group or a cycloalkyl group. m ₃ represents an integer of 0 to 3. R ₁₀₆ represents a hydrogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, an aryl group, or an aryl group which may have a substituent. p ₃ represents 2 or 3.

  Examples of the phenol compound represented by the general formula (B3) include, but are not limited to, the following compounds.

  The addition amount of the phenol compound represented by any one of the general formulas (B1) to (B3) is generally 0.5 to 30 parts by mass, preferably 1 as a total amount with respect to 100 parts by mass of the polyamide resin. ˜20 parts by mass.

[6] Surfactant It is preferable in terms of adhesion to add a surfactant. Examples of the surfactant include organopolysiloxane surfactants, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol Nonionic surfactants such as distearate, and surfactants composed of acrylic or methacrylic polymers are exemplified.

Preferred surfactants include silicon surfactants and fluorine surfactants.
Examples of silicon surfactants include silicon surfactants having a siloxane structure, such as organopolysiloxane surfactants and silicon surfactants having a dimethylpolysiloxane-polyoxyalkylene copolymer structure. it can.

  The fluorosurfactant is preferably a perfluoroethylene oxide surfactant or a perfluoroalkyl group-containing oligomer surfactant copolymerized with a fluorine atom-containing ethylenically unsaturated monomer as a main component. The perfluoroethylene oxide surfactant preferably contains a component represented by the following formula, and the perfluoroethylene oxide surfactant contains 60% by mass or more of the component represented by the following formula in the perfluoroethylene oxide surfactant. More preferred.

_{C 8 F 17 -SO 2 -N (} C 2 H 5) -CH 2 -CH 2 - (- O-CH 2 -CH 2 -) n-OH
n = 1-100.

  Furthermore, among the perfluoroalkyl group-containing oligomer surfactants copolymerized with a fluorine atom-containing ethylenically unsaturated monomer as a main component, a bridged bond with a fluorine atom-containing ethylenically unsaturated monomer is particularly preferable. Perfluoroalkyl group containing copolymerized cross-linkable ethylenically unsaturated monomer and polyorganosiloxyl group-containing ethylenically unsaturated monomer as required It is an oligomeric surfactant.

  The compounding amount of the surfactant is generally 0.001 to 10 parts by mass with respect to 100 parts by mass of the polyamide resin.

[7] Adhesion promoter The photosensitive resin composition of the present invention may contain an adhesion promoter. Suitable adhesion promoters include, for example, dianhydride / DAPI / bis (3-aminopropyl) tetramethylsiloxane (BATS) polyamic acid copolymer, aminosilane, and mixtures thereof. Addition of dianhydride / DAPI / BATS polyamic acid copolymer increases adhesion properties.
The addition amount of such an adhesion promoter is generally 0.5 to 30% by mass, preferably 1.0 to 20.0% by mass, based on the total solid content of the photosensitive resin composition of the present invention. .

  The dianhydride / DAPI / BATS polyamic acid copolymer can be synthesized in a reaction solvent by reaction of tetracarboxylic dianhydride (J), BATS diamine and DAPI diamine according to the following reaction.

(In the formula, R ′ is a tetravalent group.)
Tetracarboxylic dianhydride (J) is pyromellitic dianhydride (PMDA), 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetra Carboxylic dianhydride, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride,
4,4'-perfluoroisopropyridine diphthalic dianhydride, 4,4'-oxydiphthalic anhydride, bis (3,4-dicarboxyl) tetramethyldisiloxane dianhydride, bis (
3,4-dicarboxylphenyl) dimethylsilane dianhydride, butanetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, and mixtures thereof. It is not limited.

  The DAPI / BATS molar ratio is about 0.1 / 99.9 to 99.9 / 0.1. A preferred molar ratio is about 10/90 to 40/60, and a most preferred molar ratio is about 15/85 to 30/70.

  Preferred reaction solvents are N-methyl-2-pyrrolidinone (NMP), γ-butyrolactone (GBL), N, N-dimethylformamide (DMP), N, N-dimethylacetamide (DMAC), dimethyl sulfoxide (DMSO), sulfolane. And diglyme. The most preferred reaction solvents are N-methyl-2-pyrrolidinone (NMP) and γ-butyrolactone (GBL).

  Any suitable reaction may be used to react the dianhydride with the above two diamines. Generally, the reaction is carried out at about 10 to about 50 ° C. for about 6 to 48 hours. The molar ratio of dianhydride to diamine should be about 0.9 to 1.1: 1.

  The photosensitive resin composition of the present invention can further contain other additives such as a leveling agent.

[8] Solvent In the photosensitive resin composition of the present invention, it is preferable to use at least a photosensitizer and an amide resin as a solution dissolved in a solvent.
In this case, the total solid content concentration of the photosensitive resin composition of the present invention is preferably 25 to 45% by mass.

Suitable solvents include N-methylpyrrolidone (NMP), γ-butyrolactone (GBL), N, N-dimethylacetamide (DMAc), dimethyl-2-piperidone, N, N-dimethylformamide (DMF), and these There are organic solvents such as, but not limited to, mixtures. Preferred solvents are γ-butyrolactone and N-methylpyrrolidone. Most preferred is γ-butyrolactone.

From the viewpoint of adhesion, a mixed solvent containing γ-butyrolactone and propylene glycol monoalkyl ether is preferable, and a mixed solvent in which the total amount of γ-butyrolactone and propylene glycol monoalkyl ether is 70% by mass or more of the total amount of the solvent is more preferable.
The mixing ratio of γ-butyrolactone / propylene glycol monoalkyl ether is preferably in the range of 95/5 to 50/50 as a mass ratio.

  Examples of the propylene glycol monoalkyl ether include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether, and propylene glycol monomethyl ether is preferable.

Furthermore, a mixed solvent composed of γ-butyrolactone and propylene glycol monoalkyl ether and a solvent having a dipole moment of 3.5 debye or more is preferable.
Solvents with a dipole moment of 3.5 debye or more include N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, N, N-dimethylformamide, N, N-dimethylacetamide, ε-caprolactam, acetonitrile, acrylonitrile, benzonitrile , Butanenitrile, crotonaldehyde, ethylene carbonate, formamide, isobutylnitrile, methacrylonitrile, N-methylacetamide, 4-methylbutanenitrile, N-methylformamide, pentanenitrile, pentaneacetonitrile, propanenitrile, propiononitrile, 2-pyrrolidinone 1,3-dimethyl-2-imidazole. Among these, N-methyl-2-pyrrolidone, dimethyl sulfoxide, and sulfolane are preferable. Note that one kind or two or more kinds of solvents having a dipole moment of 3.5 debye or more may be used.

[9] Pattern Forming Method As a method for forming a relief pattern using the photosensitive resin composition of the present invention, (a) a photosensitive resin composition containing a polyamide resin, a photosensitive agent, and a solvent is used as a suitable substrate. Coated on, (b) baked this coated substrate, (c) exposed with actinic light or radiation, (d) developed with aqueous developer, and (e) cured to cure. A relief pattern can be formed.

  The coated and exposed substrate can also be baked at elevated temperatures prior to development. Further, the developed substrate may be rinsed before curing.

  Thus, with the photosensitive resin composition of this invention, it apply | coats on a semiconductor element so that the thickness after heat curing may become predetermined thickness (for example, 0.1-30 micrometers), prebaking, exposure, image development, and heat curing. Thus, a semiconductor device can be manufactured.

  Hereinafter, a method for forming a relief pattern will be described in more detail.

  The photosensitive resin composition of the present invention is coated on a suitable substrate. The substrate is for example a semiconductor material such as a silicon wafer or a ceramic substrate, glass, metal or plastic. Coating methods include, but are not limited to, spray coating, spin coating, offset printing, roller coating, screen printing, extrusion coating, meniscus coating, curtain coating, and dip coating.

  The coating film is pre-baked for several minutes to half an hour at an elevated temperature of about 70-120 ° C., depending on the method, to evaporate the remaining solvent. Subsequently, the resulting dry film is exposed to actinic rays or radiation in a preferred pattern through a mask. As actinic rays or radiation, X-rays, electron beams, ultraviolet rays, visible rays and the like can be used. The most preferred radiation is one having wavelengths of 436 nm (g-line) and 365 nm (i-line).

  Advantageously, the coated and exposed substrate is heated to a temperature of about 70-120 ° C. following exposure to actinic light or radiation. The coated and exposed substrate is heated in this temperature range for a short time, typically a few seconds to a few minutes. This stage of the method is commonly referred to in the art as post-exposure baking.

  The coating film is then developed with an aqueous developer and a relief pattern is formed. Examples of the aqueous developer include inorganic alkali (eg, potassium hydroxide, sodium hydroxide, aqueous ammonia), primary amine (eg, ethylamine, n-propylamine), secondary amine (eg, diethylamine, di-n-propyl). Amines), tertiary amines (eg, triethylamine), alcohol amines (eg, triethanolamine), quaternary ammonium salts (eg, tetramethylammonium hydroxide, tetraethylammonium hydroxide), and alkaline solutions such as mixtures thereof There is. The most preferred developer is one containing tetramethylammonium hydroxide. In addition, an appropriate amount of surfactant may be added to the developer. Development can be carried out by dipping, spraying, paddling, or other similar development methods.

In some cases, the relief pattern is then rinsed using deionized water. Next, in order to obtain a final pattern of a polymer having high heat resistance, an oxazole ring is formed by curing the relief pattern. Curing is carried out by so as to obtain an oxazole ring forming a highly heat resisting final pattern, baking the substrate at a glass transition temperature T _g of the polymer. Generally, temperatures above about 200 ° C. are used. It is preferred to use a temperature of about 250-400 ° C.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these.

(1) Synthesis of Resin A-1 In a three-necked flask (500 ml), 36.63 g (0.1 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane, m-aminophenol 1 .64 g (15 mmol), 18.19 g (0.23 mol) pyridine and 150 g N-methyl-2-pyrrolidone (NMP) were added. The solution was stirred at room temperature until all solids dissolved, then cooled at -20 to -25 ° C in a dry ice / acetone bath. To this solution, 32.46 g (0.11 mol) of 1,4-oxydibenzoyl chloride dissolved in 100 g of NMP was added dropwise. After the addition was complete, the resulting mixture was stirred at room temperature for 18 hours. The viscous solution was charged with 5 l of deionized water with vigorous stirring, the precipitated white powder was collected by filtration and washed with deionized water and a water / methanol (50/50) mixture. The polymer was dried under vacuum at 40 ° C. for 24 hours to obtain the target resin A-1. The yield was almost quantitative, and the intrinsic viscosity of Resin A-1 was 0.26 dL / g measured in NMP at a concentration of 0.5 g / dL at 25 ° C.

(2) Synthesis of Resin A-2 Resin A-2 was prepared in the same manner except that the amount of 1,4-oxydibenzoyl chloride used in the synthesis example of Resin A-1 was changed to 30.99 g (0.105 mol). Was synthesized. The yield was almost quantitative and the intrinsic viscosity of Resin A-2 was 0.20 dL / g measured in NMP at a concentration of 0.5 g / dL at 25 ° C.

(3) Synthesis of Resin A-3 Resin A-3 was synthesized in the same manner as in the synthesis example of Resin A-1, except that 1/4 equivalent of 1,4-oxydibenzoyl chloride was changed to isophthalic acid chloride. The yield was almost quantitative and the intrinsic viscosity of Resin A-3 was 0.27 dL / g measured in NMP at a concentration of 0.5 g / dL at 25 ° C.
(4) Synthesis of Resin A-4 (Comparative Resin) Resin A-1 having norbornene as a terminal group in JP-A No. 2000-275833 was synthesized by the method described in the publication.

6). Photosensitizer Synthesis Example (1) Synthesis of Photosensitizer (B1) (Synthesis Example (1))
In a three-necked flask, 21.6 g of phenol compound (BP-1) and 200 mL of 1,4-dioxane were added and dissolved until uniform. Next, 27 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride was added and dissolved. The reaction vessel was cooled to 10 ° C. with ice water, and then 11.1 g of triethylamine was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred for 4 hours. After completion of the reaction, distilled water was added to dissolve the deposited salt, stirred for 30 minutes, neutralized with dilute hydrochloric acid, and crystallized in 1 L of distilled water. The precipitated dark yellow powder was collected by filtration. The residue was dissolved again in 200 mL of dioxane and crystallized in 1 L of distilled water. The precipitated filtrate was filtered, and the filtrate was washed with 1 L of distilled water and filtered to recover 40 g of the target product (B1) as a dark yellow powder. As a result of analyzing the obtained (B1) by high performance liquid chromatography (S1525 manufactured by Waters), the purity of the esterified product of the phenol compound (BP-1) was 99% (detection wavelength: 254 nm).

（ＢＰ−１）

(BP-1)

(2) Synthesis of photosensitizer (B2) (Synthesis Example (2))
In a three-necked flask, 21.6 g of phenol compound (BP-1) and 200 mL of 1,4-dioxane were added and dissolved until uniform. Next, 27 g of 1,2-naphthoquinonediazide-4-sulfonyl chloride was added and dissolved. The reaction vessel was cooled to 10 ° C. with ice water, and then 11.1 g of triethylamine was added dropwise over 1 hour. It stirred for 24 hours after completion | finish of dripping. After completion of the reaction, distilled water was added to dissolve the deposited salt, stirred for 30 minutes, neutralized with dilute hydrochloric acid, and crystallized in 1 L of distilled water. The precipitated dark yellow powder was collected by filtration. The residue was dissolved again in 200 mL of dioxane and crystallized in 1 L of distilled water. The precipitated filtrate was filtered, and the filtrate was washed with 1 L of distilled water and filtered to recover 39 g of the target product (B2) as a dark yellow powder. As a result of analyzing the obtained (B2) by high performance liquid chromatography (S1525 manufactured by Waters), the purity of the esterified product of the phenol compound (BP-1) was 98% (detection wavelength: 254 nm).

(3) Synthesis of Photosensitizer (B3) Photosensitizer (B3) was synthesized in the same manner as in Synthesis Example (1) except that the phenol compound used was changed to (BP-2). As a result of analyzing the obtained (B3) by high performance liquid chromatography (S1525 manufactured by Waters), the purity of the esterified product of the phenol compound (BP-2) was 99% (detection wavelength: 254 nm).

(4) Synthesis of photosensitizer (B4) Synthesis example except that the phenol compound used was changed to (BP-3) and the amount of 1,2-naphthoquinonediazide-5-sulfonyl chloride used was increased 1.5 times. Photosensitive agent (B4) was synthesized by the same method as (1). As a result of analyzing the obtained (B4) by high performance liquid chromatography (S1525 manufactured by Waters), the purity of the esterified product of the phenol compound (BP-3) was 99% (detection wavelength: 254 nm).

(5) Synthesis of photosensitizer (B5) Synthesis example except that the phenol compound used was changed to (BP-4) and the amount of 1,2-naphthoquinonediazide-5-sulfonyl chloride used was 2.5 times. Photosensitive agent (B5) was synthesized by the same method as (1). As a result of analyzing the obtained (B5) by high performance liquid chromatography (S1525, manufactured by Waters), the purity of the esterified product of the phenol compound (BP-4) was 99% (detection wavelength: 254 nm).

(6) Synthesis of Photosensitizer (B6) Synthesis Example (1) except that the phenol compound used was changed to (BP-5) and the amount of 1,2-naphthoquinonediazide-5-sulfonyl chloride used was doubled. ) To prepare a photosensitizer (B6). As a result of analyzing the obtained (B6) by high performance liquid chromatography (S1525, manufactured by Waters), the purity of the esterified product of the phenol compound (BP-5) was 99% (detection wavelength: 254 nm).

(7) Synthesis of Photosensitizer (B7) Synthesis Example (2) except that the phenol compound used was changed to (BP-5) and the amount of 1,2-naphthoquinonediazide-4-sulfonyl chloride used was doubled. ) To prepare a photosensitizer (B7). As a result of analyzing the obtained (B7) by high performance liquid chromatography (S1525 manufactured by Waters), the purity of the esterified product of the phenol compound (BP-5) was 97.5% (detection wavelength: 254 nm).

(7) Preparation of photosensitive resin composition 2% by mass of the following adhesion promoter C (alkoxysilane compound) with respect to the resin, photosensitive agent and resin shown in Table 1, and further, if necessary, γ- 100 g of a solution having a solid content concentration of 30% by mass dissolved in butyrolactone was prepared, followed by filtration with a tetrafluoroethylene cassette-type filter (0.2 μm) to prepare a photosensitive resin composition.
For Example 14, the solvent was a mixed solvent of γ-butyrolactone / propylene glycol monomethyl ether (mass ratio 8/2).

(8) Evaluation of in-plane uniformity (after development) The prepared composition was spin coated on a silicon wafer and baked on a hot plate at 120 ° C. for 3 minutes to obtain a film having a thickness of 7 μm. The film is exposed using an i-line stepper using a 5 micron via-hole repeating pattern mask, then developed with 0.262N aqueous tetramethylammonium hydroxide (TMAH) solution, followed by removal. Rinse with ion water. The entire surface of a 200 mm wafer was exposed with an exposure amount for reproducing a 5 micron via hole pattern, the pattern size was increased by 30 points, and the size variation was represented by 3σ.

(9) Evaluation of in-plane uniformity (after thermosetting) The wafer obtained in (8) above was heat-cured at 150 ° C. for 30 minutes and at 300 ° C. for 1 hour under nitrogen conditions, and the pattern size of the obtained wafer was 30 points. The side length was shown, and the size variation was expressed by 3σ.
(10) Scum The wafer obtained in the above (8) was observed using 2360 manufactured by KLA-Tencor, and all the residues remaining in the space were counted as development residues, and the number of development residues was counted.

(11) Adhesion Ten wafers were prepared in the above (9), and the obtained wafers were immersed in a 1% hydrofluoric acid aqueous solution at room temperature for 1 minute to confirm the presence or absence of pattern peeling. The number of samples peeled out of 10 sheets was counted.

W-2
_{C 8 F 17 -SO 2 -N (} C 2 H 5) -CH 2 -CH 2 - (- O-CH 2 -CH 2 -) n-OH
n = 1-100.

  From the results in Table 1, it can be seen that the photosensitive resin composition of the present invention has excellent in-plane uniformity after development and after curing, reduced scum, and excellent adhesion.

Claims (8)

A photosensitive resin composition comprising a polyamide resin represented by the general formula (I) and a quinonediazidosulfonic acid ester photosensitizer of a phenol compound.

Ar ₁ independently represents a tetravalent organic group.
Ar ₃ independently represents a divalent organic group.
a is 60 to 100 mol%.
b is 0 to 40 mol%.
c is 2 to 500.
R ₄ and R ₅ each independently represents a divalent organic group.
R ₆ and R ₇ each independently represents a monovalent organic group.
n represents 0, 1, 2;
R ₁ independently represents an alkyl group, a cyclic alkyl group, an aryl group, an aralkyl group, an alkoxy group, a halogen atom, an acyl group, an acyloxy group or an alkoxycarbonyl group.
l independently represents 0, 1, 2, 3;
m represents 1, 2, and 3 independently. The photosensitive resin composition according to claim 1, wherein the photosensitive agent is a quinonediazide sulfonic acid ester of a phenol compound represented by any one of the general formulas (A1) to (A4).

In general formulas (A1) to (A3),
R ₁ independently represents an alkyl group, a cyclic alkyl group, an alkoxy group, an alkenyl group, an aryl group, an aralkyl group, a halogen atom, an acyl group, an acyloxy group, or an alkoxycarbonyl group.
R ₂ independently represents an alkyl group, a cyclic alkyl group, an alkenyl group, an aryl group, or an aralkyl group, and a plurality of R ₂ may be bonded to each other to form a ring.
a to c independently represent an integer of 1 to 3.
l, m, and n represent 0-3.
When a to c are 2 or 3, l, m and n represent 0 to 2.
In general formula (A4),
R ₃ independently represents a hydrogen atom or an alkyl group.
R ₄ and R ₅ each independently represents an alkyl group, an alkoxy group, an aryl group or a cyclic alkyl group having at least one hydroxyl group.
q and r independently represent an integer of 1 to 3. The photosensitive resin composition according to claim 2, wherein the photosensitive agent is a quinonediazidosulfonic acid ester of the following phenol compound.

  The photosensitive resin composition according to claim 1, further comprising a compound having at least one methylol group. Furthermore, the phenolic compound represented by either of general formula (B1)-(B3) is contained, The photosensitive resin composition in any one of Claims 1-4 characterized by the above-mentioned.

R ₁₀₀ and R ₁₀₁ independently represent a halogen atom, an alkyl group, an alkoxy group or a cycloalkyl group. m ₁ and n ₁ independently represent an integer of 0 to 4. When a plurality of R ₁₀₀ and R ₁₀₁ are present, they may be the same or different. p ₁ and q ₁ are each independently an integer of 0 to 3, provided that p ₁ + q ₁ ≧ 1.

R ₁₀₂ to R ₁₀₃ independently represent a halogen atom, an alkyl group, an alkoxy group or a cycloalkyl group. m ₂ and n ₂ independently represent an integer of 0 to 2.
p ₂ and q ₂ are each independently an integer of 0 to 3, provided that p ₂ + q ₂ ≧ 3.
R ₁₀₄ represents an alkylene group, an oxygen atom, a carbonyl group, a carbonyl ether group, a sulfur atom, a sulfonyl group or an azo group.

R ₁₀₅ represents a halogen atom, an alkyl group, an alkoxy group or a cycloalkyl group. m ₃ represents an integer of 0 to 3. R ₁₀₆ represents a hydrogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, an aryl group, or an aryl group which may have a substituent. p ₃ represents 2 or 3.   Furthermore, surfactant is contained, The photosensitive resin composition in any one of Claims 1-5 characterized by the above-mentioned.   The photosensitive resin composition according to claim 1, comprising γ-butyrolactone and propylene glycol monomethyl ether.   A method for producing a semiconductor device, which is obtained by applying the photosensitive resin composition according to claim 1 on a semiconductor element, prebaking, exposing, developing, and heating.