JP2001194791A - Positive type photosensitive resin composition, method for producing pattern and electronic parts - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive type photosensitive resin composition having high exposure sensitivity even in a large film thickness, ensuring a good pattern shape and excellent in heat resistance, a method for producing a pattern and electronic parts having high reliability. SOLUTION: The positive type photosensitive resin composition contains (A) a polyimide precursor or a polyoxazole precursor, (B) a compound which generates an acid under light and (C) a compound having an acid decomposable group and having solubility to an aqueous alkali solution increased by an acid catalyzed reaction.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photosensitive resin composition, and more particularly to a polyimide-based heat-resistant resin composition which can be used as a surface protective film, an interlayer insulating film, etc. of electronic parts such as semiconductor devices by heat treatment. The present invention relates to a positive photosensitive resin composition serving as a molecule, a method for producing a pattern using the composition, and an electronic component.

[0002]

2. Description of the Related Art Polyimide has excellent heat resistance and mechanical properties.
Further, it is widely used as a surface protective film and an interlayer insulating film of a semiconductor element because of its advantages such as easy film formation and flattening of the surface. When polyimide is used as a surface protective film and an interlayer insulating film, the process of forming through holes and the like is performed mainly by an etching process using a positive photoresist. However, there is a problem that the process involves coating and peeling of a photoresist, which is complicated. Accordingly, heat-resistant materials having both photosensitivity have been studied for the purpose of streamlining work steps.

With respect to the photosensitive polyimide composition, a.
A polyimide precursor composition having a photosensitive group introduced through an ester bond (Japanese Patent Publication No. 52-30207), b. There is known a composition (JP-B-3-36861) in which a compound containing a carbon-carbon double bond and an amino group and an aromatic bisazide which can be dimerized or polymerized by actinic radiation is added to polyamic acid. When the photosensitive polyimide precursor composition is used, it is usually applied in a solution state on a substrate, dried, irradiated with an actinic ray through a mask, and developed to form a pattern.

However, a and b require the use of an organic solvent in the developing solution. Since the amount of the developer used is several times the amount of the photosensitive polyimide precursor composition used, there is a problem that a large load is imposed on the environment when processing the waste developer. Therefore, a photosensitive polyimide composition which can be developed with an aqueous developer which can easily treat a waste developer has been desired in recent years, particularly in consideration of the environment. Further, since a and b are negative types, when switching from an etching process using a positive type photoresist to a negative type photosensitive polyimide precursor, it is necessary to change a mask used in an exposure step. .

With respect to the positive photosensitive polyimide precursor composition, c. Polyimide precursor having an o-nitrobenzyl group introduced through an ester bond (Japanese Patent Application Laid-Open No. 60-37550)
Gazette), d. A composition containing a polyamic acid ester containing a carboxyl group and an o-quinonediazide compound (JP-A-4-168441); e. A composition containing a polyamic acid ester containing a hydroxyl group and an o-quinonediazide compound (JP-A-3-11546) is known. However, there is a problem that the exposure sensitivity is lowered when an attempt is made to form a high film thickness for use as a surface protective film or an interlayer insulating film.

[0006]

DISCLOSURE OF THE INVENTION The present invention overcomes the above-mentioned problems and provides a positive photosensitive resin composition having high exposure sensitivity even at a large film thickness, good pattern shape, and excellent heat resistance. Things. Another object of the present invention is to provide a method for producing a pattern having a high resolution and capable of obtaining a relief pattern having a good shape even with a large film thickness. The present invention also provides
An electronic component with high reliability is provided by having a pattern having a good shape even with a large film thickness.

[0007]

The present invention provides (A) a polyimide precursor or a polyoxazole precursor, (B) a compound capable of generating an acid by light, and (C) a solubility in an aqueous alkali solution by an acid-catalyzed reaction. The present invention relates to a positive photosensitive resin composition containing a compound having an acid-decomposable group in which is increased.

In the present invention, the component (C) may be an acid-decomposable group whose solubility in an aqueous alkali solution is increased by an acid-catalyzed reaction.

Embedded image (However, s represents an integer of 3 to 7, and each R independently represents an alkyl group having 1 to 3 carbon atoms.) The present invention relates to a positive photosensitive resin composition having a group selected from the group consisting of:

In the present invention, the component (C) may be represented by the following general formulas (1) to (9):

Embedded image (In the general formulas (1) to (9), each X is independently a hydrogen atom or an acid-decomposable group, and in each general formula, at least one X is an acid-decomposable group, and each Y is R ¹ is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
R ² is a tetravalent organic group having an aromatic ring, Z is a monovalent organic group, and l, m and n are 1 to
Is an integer of 3, p and q are 1 or 2, and r is a positive integer) with respect to the positive photosensitive resin composition.

In the present invention, the component (A) may be a compound represented by the general formula (10):

Embedded image (Wherein, R ⁴ represents a tetravalent organic group, R ⁵ represents a divalent organic group having a carboxyl group or a phenolic hydroxyl group, and each R ⁶ independently represents a monovalent organic group.) The present invention relates to a positive photosensitive resin composition which is a polyamide acid ester having a repeating unit represented by the formula:

In the present invention, the component (A) may be represented by the general formula (11):

Embedded image (Wherein, R ⁴ represents a tetravalent organic group and R ⁷ represents a divalent organic group). The present invention relates to a positive photosensitive resin composition which is a polyamic acid having a repeating unit represented by the following formula:

In the present invention, R ^{4 in the} general formula (10) or the general formula (11) may be a group containing one aromatic ring or two or three aromatic rings having a single bond, an ether bond, , 2-hexafluoropropylene bond, 2,2-propylene bond, sulfone bond, methylene bond, and a tetravalent organic group having a chemical structure bonded through at least one bond selected from carbonyl bonds; R ⁵ or R ⁷ is 1
Groups containing two or three aromatic rings are a single bond, an ether bond, a 2,2-hexafluoropropylene bond,
The present invention relates to a positive photosensitive resin composition which is a divalent organic group having a chemical structure bonded through at least one bond selected from a 2,2-propylene bond, a methylene bond and a sulfone bond.

In the present invention, the component (A) preferably comprises a compound represented by the general formula (12):

Embedded image (Wherein R ⁸ represents a divalent organic group, and R ⁹ is a tetravalent organic group containing an aromatic ring). A positive photosensitive resin which is a polybenzoxazole precursor having a repeating unit represented by the following formula: Composition.

The present invention also includes a step of applying and drying the positive photosensitive resin composition described in any of the above on a supporting substrate, a step of exposing, a step of heating, a step of developing, and a step of heating. The present invention relates to a method for producing a pattern including the same. Furthermore, the present invention relates to an electronic component having a layer of a pattern obtained by the above-mentioned manufacturing method.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A) used in the present invention is a polyimide precursor or a polyoxazole precursor, and is preferably soluble in an alkaline aqueous solution. In the exposed part, the acid generated by the change of the component (B) decomposes and changes the acid-decomposable group in the component (C) by an acid catalyzed reaction. . This change is caused by exposure and heat treatment after exposure, and a relief pattern can be formed by a difference in dissolution rate between the unexposed portion and the unexposed portion. Here, the alkaline aqueous solution is an aqueous solution exhibiting alkalinity in which tetramethylammonium hydroxide, metal hydroxide, amine and the like are dissolved in water.

The polyimide precursor or polyoxazole precursor, which is the component (A), undergoes a curing reaction after the formation of the relief pattern to form a resin film having excellent heat resistance. Examples of the type of the polyimide precursor include polyamic acid esters, polyamic acids, and polyamic acid amides, and examples of the polyoxazole precursor include polyhydroxyamides that can be polybenzoxazole. Among these, a polyimide precursor or a polyoxazole precursor having an acidic group is preferable because of its excellent exposure sensitivity at the time of pattern formation. Here, the acidic group is preferably a phenolic hydroxyl group or a carboxyl group.

Among the polyimide precursors, a polyamide acid ester having a repeating unit represented by the general formula (10) is preferable because it has high exposure sensitivity at the time of forming a relief pattern and has good developability. In general formula (10), R4 is generally a residue excluding the carboxyl group of the tetracarboxylic acid, preferably a group containing an aromatic ring, and more preferably a group having 6 to 40 carbon atoms. Examples of the group containing an aromatic ring include those containing one or more aromatic rings such as a benzene ring and a naphthalene ring. Preferably, the four binding sites for R ⁴ are present directly on the aromatic ring, in which case they may be present on the same aromatic ring or on different aromatic rings.

Examples of the group containing an aromatic ring include one aromatic ring itself or two or three aromatic rings having a single bond, an ether bond,
Heat treatment of a tetravalent organic group having a chemical structure linked via a methylene bond, an ethylene bond, a 2,2-hexafluoropropylene bond, a 2,2-propylene bond, a sulfone bond, a sulfoxide bond, a thioether bond and a carbonyl bond It is preferable from the viewpoint of the heat resistance and mechanical properties of the polyimide-based polymer later.

A phenolic hydroxyl group or a divalent organic group having a carboxyl group represented by R ⁵ in the general formula (10) refers to a phenolic hydroxyl group capable of reacting with tetracarboxylic acid or a derivative thereof to form a polyimide precursor. It is preferably a residue excluding an amino group of a diamine compound having a hydroxyl group or a carboxyl group, and is preferably a group containing an aromatic ring, and having 6 to 40 carbon atoms excluding a phenolic hydroxyl group or a carboxyl group. Are more preferred. Examples of the group containing an aromatic ring include those containing one or more aromatic rings such as a benzene ring and a naphthalene ring. Two bonding sites of R ⁵ is preferably present directly on an aromatic ring, it may be present in this case on the same aromatic ring or different and be present on the aromatic ring. The phenolic hydroxyl or carboxyl group, it is preferably present 1-8 to R ^5.

The group containing an aromatic ring represented by R ⁵ includes
One aromatic ring itself or two to three aromatic rings are a single bond, an ether bond, a methylene bond, an ethylene bond, a 2,2-hexafluoropropylene bond, a 2,2-propylene bond,
A divalent organic group having a chemical structure bonded through a sulfone bond, a sulfoxide bond, a thioether bond, and a carbonyl bond, and having at least one phenolic hydroxyl group and / or a carboxyl group is a polyimide-based polymer after heat treatment. It is preferable from the viewpoint of heat resistance and mechanical properties.

In the general formula (10), the monovalent organic group represented by R ⁶ is preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably an alkyl group, and preferably has 1 to 8 carbon atoms. Alkyl groups are more preferred. The general formula (1
In 0), there are two R ^{6 s} , which may be the same or different.

The polyamic acid ester having a repeating unit represented by the general formula (10) further has a general formula (1)
3)

Embedded image (Wherein, R ⁴ represents a tetravalent organic group, R ¹⁰ represents a divalent organic group having no carboxyl group or phenolic hydroxyl group, and each R ⁶ independently represents a monovalent organic group.) May have a repeating unit represented by

^{4 represented} by R ⁴ in the general formula (13)
The monovalent organic group and the monovalent organic group represented by R ⁶ are the same as those in the general formula (10). A phenolic hydroxyl group or a divalent organic group having no carboxyl group represented by R ¹⁰ is a residue obtained by reacting with tetracarboxylic acid or a derivative thereof to form a polyimide precursor, excluding an amino group of a diamine compound. Is preferably a group containing an aromatic ring, and more preferably a group having 6 to 40 carbon atoms. Examples of the group containing an aromatic ring include a benzene ring,
Those containing one or more aromatic rings such as a naphthalene ring are included. The two binding sites for R ¹⁰ are preferably present directly on the aromatic ring, in which case they may be present on the same aromatic ring or on different aromatic rings.

The group containing an aromatic ring represented by R ¹⁰ includes
One aromatic ring itself or two to three aromatic rings are a single bond, an ether bond, a methylene bond, an ethylene bond, a 2,2-propylene bond, a 2,2-hexafluoropropylene bond,
2 having a chemical structure linked via a sulfone bond, a sulfoxide bond, a thioether bond and a carbonyl bond
A valent organic group is preferable in terms of heat resistance and mechanical properties of the polyimide polymer after the heat treatment.

When the polyamic acid ester having a repeating unit represented by the general formula (10) has a repeating unit represented by the general formula (13), the repeating unit represented by the general formula (10) and the general formula (13) The unit ratio is preferably m / (m + n) where the former number is m and the latter number is n, and is 1.0 to 0.2. This number is 0.
If it is less than 2, the solubility of the exposed portion of the film formed by coating and drying in an aqueous alkaline solution tends to be poor. In this polyamic acid ester, the total number of the repeating units of the general formulas (10) and (13) is preferably 50 to 100% based on the total number of the polyamic acid esters,
80-100% is more preferable, and 90-100% is particularly preferable. In addition, the repeating unit referred to here is one unit composed of one acid residue and one amine residue.

The polyamic acid ester having a repeating unit represented by the general formula (10) may be, for example, a tetracarboxylic diester dihalide (chloride, bromide, etc.) and a diamine having a carboxyl group or a phenolic hydroxyl group, and Accordingly, it can be obtained by reacting with a diamine compound having no carboxyl group or phenolic hydroxyl group. In this case, the reaction is preferably performed in an organic solvent in the presence of a dehalogenating agent.

The tetracarboxylic diester dihalide is preferably tetracarboxylic diester dichloride. Tetracarboxylic diester dichloride can be obtained by reacting a tetracarboxylic dianhydride with an alcohol compound and reacting a tetracarboxylic diester with thionyl chloride. As the tetracarboxylic dianhydride, for example, pyromellitic dianhydride, 3,
3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylethertetracarboxylic dianhydride, 3,3 ′,
4,4′-diphenylsulfonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4 5,8-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis ( Aromatic tetracarboxylic dianhydrides such as tetracarboxylic dianhydrides such as 3,4-dicarboxyphenyl) hexafluoropropane dianhydride and 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride Anhydrides are preferred. These acid dianhydrides can be used alone or in combination of two or more.

In the polyamic acid ester, an alcohol compound is used as a raw material that becomes an ester site of the side chain. Examples of the alcohol compound include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol,
sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, isoamyl alcohol, 1-hexanol, 2-hexanol, 3-hexanol, and the like. Or two or more of them can be used in combination.

Further, a diamine is used as a raw material of the polyamic acid ester. As the diamine having a carboxyl group or a phenolic hydroxyl group, for example,
2,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 2,5-diaminoterephthalic acid, bis (4-amino-3-carboxyphenyl) methylene, 4,4′- Diamino-3,3'-dicarboxybiphenyl, 4,4'-diamino-5,5'-dicarboxy-2,2'-dimethylbiphenyl, 1,3-
Diamino-4-hydroxybenzene, 1,3-diamino-5-hydroxybenzene, 3,3′-diamino-4,
4'-dihydroxybiphenyl, 4,4'-diamino-
3,3′-dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (4-amino-3-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, 4,6-diaminoresorcinol, 4,5 -Diaminoresorcinol, bis (4-amino-3-carboxyphenyl) methane and the like. These diamine compounds having at least one phenolic hydroxyl group and / or carboxyl group can be used alone or in combination of two or more.

The diamine compound having no carboxyl group or phenolic hydroxyl group includes, for example, 4,
4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,
Examples thereof include 6-naphthalenediamine, bis (3-aminophenoxyphenyl) sulfone, 1,4-bis (4-aminophenoxy) benzene, and 4,4′-diamino-2,2′-dimethylbiphenyl. These diamine compounds can be used alone or in combination of two or more.

A method for synthesizing a polyamic acid ester having a repeating unit represented by the general formula (10) is known, and a method for synthesizing the tetracarboxylic diester compound includes, for example, It is obtained by mixing and reacting the alcohol compounds in the presence of a base. The preferred ratio (molar ratio) of the carboxylic dianhydride to the alcohol compound is 1 / (the former / the latter).
The range is 2 to 1/20, and a more preferable ratio is 1/2.
範 囲 1/5. The ratio (molar ratio) of tetracarboxylic dianhydride to base is 1/0.
001 to 1/3, more preferably 1/1/3.
The range is 0.005 to 1/1. The preferred reaction temperature is 10 to 130 ° C, and the preferred reaction time is 3 to 48 hours. A method for synthesizing tetracarboxylic diester dichloride is known, and is obtained, for example, by reacting the above tetracarboxylic diester with thionyl chloride. The preferred ratio (molar ratio) of tetracarboxylic diester to thionyl chloride is 1 / 1.1-1.2.5 for the former / the latter.
, And a more preferable ratio is from 1 / 1.5 to 1 /
2.2. The preferred reaction temperature is 0 to 100
C., and the preferred reaction time is 1 to 10 hours.

The polyamic acid ester is prepared by, for example, dissolving the diamine compound and a dehydrochlorination catalyst such as pyridine in an organic solvent, and reacting dropwise by adding tetracarboxylic diester dichloride dissolved in the organic solvent to water. It is obtained by pouring into a poor solvent, filtering off the precipitate and drying. As the organic solvent used in the reaction, for example, N-
An aprotic polar solvent such as methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphoramide, tetramethylene sulfone, γ-butyrolactone, alone or in combination of two or more Used in combination.

Desirable ratio (molar ratio) of the total amount of the diamine compound to the tetracarboxylic diester dichloride
Is in the range of 0.6 / 1 to 1 / 0.6 in the former / latter. The preferred reaction temperature is -30 to 40 ° C, and the preferred reaction time is 5 minutes to 10 hours. The preferred ratio (molar ratio) of the dehydrochlorination catalyst to the tetracarboxylic acid dichloride is in the range of 1.9 / 1.0 to 2.0 / 0.95 for the former / the latter.

Next, the case where the component (A) used is a polyamic acid having a repeating unit represented by the above general formula (11) will be described. A method for synthesizing the polyamic acid represented by the general formula (11) is known, for example,
It is obtained by reacting the tetracarboxylic dianhydride with the diamine compound having no carboxyl group or phenolic hydroxyl group in a polar solvent. Use (A)
When the component is a polyamic acid, since a carboxyl group is present in the residue of the tetracarboxylic acid, it is not necessary to use a diamine compound having a carboxyl group or a phenolic hydroxyl group as the diamine. The preferred reaction temperature is 0 to 100 ° C, and the preferred reaction time is 3 to 48 hours. Further, for the purpose of controlling the molecular weight of the polyamic acid, a monofunctional acid anhydride or amine may be added.

Next, the case where the component (A) used is a polyoxazole precursor having a repeating unit represented by the general formula (12) will be described. In the general formula (12), R8 represents a group containing one aromatic ring or two to three aromatic rings having a single bond, an ether bond, a 2,2-hexafluoropropylene bond, a 2,2-propylene bond, or a sulfone bond. , A divalent organic group having a chemical structure bonded via at least one bond selected from methylene bond and carbonyl bond, and a group containing one aromatic ring as R9 or a group containing 2 to 3 Aromatic rings are a single bond, an ether bond, a 2,2-hexafluoropropylene bond,
It is preferably a tetravalent organic group having a chemical structure bonded via at least one bond selected from a 2-propylene bond, a methylene bond and a sulfone bond.

Examples of the polyoxazole precursor include those generally obtained from dicarboxylic acid and dihydroxydiamine as raw materials. Examples of the dicarboxylic acid include isophthalic acid, terephthalic acid, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 4,4′-biphenyldicarboxylic acid, 4,4′-dicarboxydiphenyl ether, and 4,4 ′ -Dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone,
2,2-bis (p-carboxyphenyl) propane, 5
-Tert-butyl isophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid,
Examples include aliphatic dicarboxylic acids such as 4-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, oxalic acid, malonic acid, and succinic acid, and these can be used alone or in combination of two or more. . Of these, aromatic dicarboxylic acids are preferred from the viewpoint of heat resistance.

The dihydroxyamine includes 3,
3'-diamino-4,4'-dihydroxybiphenyl,
4,4'-diamino-3,3'-dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxy Phenyl)
Sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (4-amino-3
-Hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane,
Preferred are aromatic diamines such as 4,6-diaminoresorcinol, 4,5-diaminoresorcinol, and bis (4-amino-3-carboxyphenyl) methane. By using an aromatic diamine, a polybenzoxazole precursor having good heat resistance can be obtained.

In the present invention, the polybenzoxazole precursor can be obtained, for example, by reacting dicarboxylic acid dihalide (chloride, bromide) with dihydroxydiamine. In this case, the reaction is preferably performed in the presence of a dehalogenation catalyst in an organic solvent. Dicarboxylic acid dichloride can be obtained by reacting dicarboxylic acid with thionyl chloride.

In the present invention, the molecular weight of the component (A) is preferably from 3,000 to 200,000, more preferably from 5,000 to 100,000 in terms of weight average molecular weight. The molecular weight can be measured by gel permeation chromatography and converted using a standard polystyrene calibration curve to obtain a value.

The compound which generates an acid by light, which is the component (B) used in the present invention, generates an acid upon exposure to light,
By inducing a decomposition reaction of the component (C), it has a function of increasing the solubility of the irradiated portion in an aqueous alkaline solution. As the component (B), for example,

Embedded image Oxadiazole derivatives substituted with a trihalomethyl group such as

[0041]

Embedded image S-triazine derivatives substituted with a trihalomethyl group such as

[0042]

Embedded image Iodonium salts such as

Embedded image Sulfonium salts such as

[0043]

Embedded image Disulfone derivatives such as

[0044]

Embedded image And the like, and o-quinonediazide derivatives.

The o-quinonediazide compound is, for example, o
-It is obtained by subjecting a quinonediazidosulfonyl chloride to a condensation reaction with a hydroxy compound, an amino compound and the like in the presence of a dehydrochlorination catalyst. Examples of o-quinonediazidosulfonyl chlorides include 1,2-naphthoquinone-2.
-Diazido-4-sulfonyl chloride can be used.

As the hydroxy compound, for example,
Hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane,
2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxy Benzophenone, 2,3,4,2 ', 3'-pentahydroxybenzophenone, 2,3,4,3', 4 ', 5'-hexahydroxybenzophenone, bis (2,3,4-trihydroxyphenyl) methane , Bis (2,3,4-trihydroxyphenyl) propane, 4b, 5,9b, 10-tetrahydro-1,3,6,8-tetrahydroxy-5,
Examples include 10-dimethylindeno [2,1-a] indene, tris (4-hydroxyphenyl) methane, and tris (4-hydroxyphenyl) ethane.

As the amino compound, for example, p-
Phenylenediamine, m-phenylenediamine, 4,
4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, o-aminophenol, m-aminophenol, p-aminophenol, 3,3'-diamino-
4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) propane, bis (4-
Amino-3-hydroxyphenyl) propane, bis (3
-Amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (4-amino-3-hydroxyphenyl) hexa Fluoropropane and the like.

The o-quinonediazidosulfonyl chloride and the hydroxy compound or amino compound are blended so that the total of the hydroxy group and the amino group is 0.5 to 1 equivalent per 1 mol of the o-quinonediazidosulfonyl chloride. Is preferred. A preferable ratio of the dehydrochlorination catalyst to o-quinonediazide sulfonyl chloride is 0.95 / 1.
１ ／ 1 / 0.95. The preferred reaction temperature is 0
４０40 ° C., and the preferred reaction time is 1-10 hours.

As the reaction solvent, for example, a solvent such as dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether, N-methylpyrrolidone and the like are used. Examples of the catalyst for dehydrochlorination include sodium carbonate, sodium hydroxide, sodium hydrogencarbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, pyridine and the like.

Among these components (B),

Embedded image Or 1,2-naphthoquinone-2-diazide-
A condensate of 4-sulfonyl chloride and a compound having a phenolic hydroxyl group is sensitive to i-line (365 nm), which is a mainstream light source for exposure, and is therefore an i-line stepper or the like.
An exposure apparatus using linear monochromatic light can be used, which is particularly preferable. The component (B) is (A) in view of the film thickness and sensitivity after development.
0.5 to 100 parts by weight of the component is preferably used.
Parts by weight, more preferably 1 to 20 parts by weight.

The compound having an acid-decomposable group whose solubility in an aqueous alkali solution is increased by the acid-catalyzed reaction, which is the component (C) used in the present invention, is defined by using the acid generated from the component (B) upon exposure as a catalyst. It is a compound that has a function of causing a decomposition reaction and increasing the solubility of a light irradiation part in an aqueous alkaline solution. As the component (C), for example, an alkali-soluble resin such as polyvinyl phenol,
Alternatively, a polymer or compound in which a hydroxyl group such as a bisphenol, a trisphenol, a trisphenol alkane, a trinuclear phenol resin, or a tetrakisphenol is protected by an acid-decomposable group such as an acetal group or a ketal group may be used. Further, a compound in which a part or all of the carboxyl group of a carboxyl group-containing acrylic or styrene-acrylic polymer such as polyacrylic acid or a copolymer of styrene and acrylic acid is protected with an acid-decomposable group may be used. As the component (C), as an acid-decomposable group whose solubility in an aqueous alkali solution is increased by an acid-catalyzed reaction,

Embedded image (Where s represents an integer of 3 to 7, and each R independently represents an alkyl group having 1 to 3 carbon atoms), wherein the hydroxyl group of the compound having a phenolic hydroxyl group is protected with an acid-decomposable group. Compounds are preferred.

Among them, compounds having the structures represented by formulas (1) to (9) are preferable as the component (C). The structure enclosed by r indicates a repeating unit of a polymer compound. Among these

Embedded image (In the above formula, each X is independently a hydrogen atom or

Embedded image Wherein at least one X in each formula is an acid-decomposable group, R ¹ is a tetravalent organic group, and R ² is a tetravalent organic group having an aromatic ring. And
Z is a monovalent organic group, p and q are 1 or 2,
r is a positive integer).

Component (C) is preferably 2 to 100 parts by weight of component (A) in view of the film thickness and sensitivity after development.
100 parts by weight, more preferably 5 to 50 parts by weight. The positive photosensitive resin composition of the present invention comprises a component (A),
It can be obtained by dissolving the components (B), (C) and, if necessary, other components in a solvent. Examples of the solvent include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, tetramethylene sulfone, γ-butyrolactone, cyclohexanone, and cyclopentanone And aprotic polar solvents such as ethyl lactate, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are used alone or in combination of two or more.

The positive photosensitive resin composition of the present invention may contain an organic silane compound, an aluminum chelate compound and the like in order to enhance the adhesion of the cured film to the substrate. As the organic silane compound, for example, vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane,
Ureapropyltriethoxysilane, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylcyphenylsilanediol,
Isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol,
Ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n
-Butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenyl Silanol, phenylsilanetriol, 1,4-bis (trihydroxysilyl) benzene, 1,4-bis (methyldihydroxysilyl) benzene, 1,4-bis (ethyldihydroxysilyl) benzene, 1,4-bis (propyldihydroxy) Silyl) benzene, 1,4-bis (butyldihydroxysilyl) benzene, 1,4-bis (dimethylhydroxysilyl) benzene, 1, - bis (diethyl hydroxy silyl) benzene, 1,4-bis (dipropyl mud silyl) benzene, 1,4-bis (dibutyl hydroxy silyl) benzene. Aluminum chelate compounds include, for example, tris (acetylacetonate)
Aluminum and acetyl acetate aluminum diisopropylate are exemplified.

The positive photosensitive resin composition of the present invention can be used for a glass substrate, a semiconductor, a metal oxide insulator (for example, TiO 2,
SiO2, etc.), coated on a supporting substrate such as silicon nitride,
A film can be obtained by drying. Thereafter, irradiation (exposure) of actinic rays such as ultraviolet rays, visible rays, and radiations is performed through a mask, and then heat treatment is performed as necessary, and then the exposed portions are removed with a developing solution to form a positive relief pattern. can get.

Drying is usually performed using an oven or a hot plate. Drying conditions are appropriately determined depending on the components of the positive photosensitive resin composition. When a hot plate is used, drying is preferably performed at 60 to 140 ° C. for 30 seconds to 10 minutes. If the drying temperature is low, the fine pattern tends to peel off during development. On the other hand, when the drying temperature is high, the dissolution rate of the exposed portion in the developer tends to decrease, and the sensitivity tends to decrease.

Then, if necessary, a heat treatment is carried out in order to accelerate the decomposition reaction of the component (C) in the light irradiation part. The heating conditions are appropriately determined depending on the components of the positive photosensitive resin composition.
It is preferable to carry out at a temperature of 140 ° C. for 30 seconds to 10 minutes. When the heating temperature is low, the compound having an acid-decomposable group, whose solubility in an aqueous alkali solution is increased by an acid-catalyzed reaction, does not efficiently decompose and the sensitivity tends to decrease. When the heating temperature is high, the dissolution rate of the exposed portion in the developer decreases, and the development time tends to be long.

Next, development is carried out. As a developing solution, it is preferable to use an aqueous alkaline solution, for example, an aqueous solution of 5% by weight or less such as sodium hydroxide, potassium hydroxide, sodium silicate, tetramethylammonium hydroxide, or the like. Preferably, a 1.5 to 3.0% by weight aqueous solution or the like is used, and a more preferred developer is a 1.5 to 3.0% by weight aqueous solution of tetramethylammonium hydroxide.
Further, an alcohol or a surfactant may be added to the above-mentioned developer for use. These are respectively developer 1
The amount is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, per 100 parts by weight.

Next, 15 was added to the obtained relief pattern.
Heat treatment at 0 to 450 ° C. results in a pattern of a heat-resistant polymer having an imide ring and other cyclic groups. The positive photosensitive resin composition of the present invention is particularly suitable as a resin composition for forming a heat-resistant polymer having a thickness of 8 μm or more. This pattern can be used as an interlayer insulating film or a surface protection film of an electronic component such as a semiconductor device or a multilayer wiring board. The electronic component of the present invention is not particularly limited except that it has a surface protective film and an interlayer insulating film formed using the composition, and can have various structures.

As an example of the electronic component of the present invention, an example of a semiconductor device manufacturing process will be described below. FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure. In the figure, a semiconductor substrate such as a Si substrate having a circuit element is covered with a protective film 2 such as a silicon oxide film except for a predetermined portion of the circuit element, and a first conductor layer on the exposed circuit element is formed. . A film 4 of a polyimide resin or the like as an interlayer insulating film is formed on the semiconductor substrate by a spin coating method or the like (step (a)). Next, a photosensitive resin layer 5 of a chlorinated rubber type, a phenol novolak type or the like is formed on the interlayer insulating film 4 by spin coating, and a window is formed by a known photolithography technique so that a predetermined portion of the interlayer insulating film is exposed. 6A is provided (step (b)).

The interlayer insulating film 4 in the window 6A is selectively etched by a dry etching means using a gas such as oxygen and tetrafluoride gas to open a window 6B.
Next, the photosensitive resin 5 is completely removed using an etching solution that does not corrode the first conductor layer 3 exposed from the window 6B, but corrodes only the photosensitive resin layer 5 (step (c)). Further, the second conductor layer 7 is formed by using a known photolithography technique, and the electrical connection with the first conductor layer 3 is completely performed (step (d)). When a multilayer wiring structure of three or more layers is formed, the above steps are repeated to form each layer.

Next, a surface protection film 8 is formed. In the example of this figure, this surface protective film is coated with the photosensitive resin composition by the spin coating method, dried, and irradiated with light from a reticle on which a pattern for forming a window 6C is drawn on a predetermined portion. In accordance with the above, a pattern is formed by developing with an aqueous alkali solution, and heated to form a heat-resistant resin film. This heat-resistant resin film forms a conductive layer with external stress,
The semiconductor device is protected from α rays and the like, and the obtained semiconductor device has excellent reliability. In the above example, the interlayer insulating film can be formed using the photosensitive resin composition of the present invention.

[0063]

The present invention will be described below in more detail with reference to examples. Example 1 In a 0.5-liter flask equipped with a stirrer and a thermometer, 24.82 g of 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride, 9.62 g of n-propyl alcohol, and 0 of triethylamine were added. .40 g and 103.30 g of N-methylpyrrolidone were stirred and reacted at room temperature for 24 hours to obtain 3,3 ′, 4,4′-diphenylethertetracarboxylic acid di-n-propyl ester. Next, after cooling the flask to 5 ° C., 18.08 g of thionyl chloride was added dropwise, and the mixture was reacted for 1 hour.
A solution (α) of 3 ′, 4,4′-diphenylethertetracarboxylic acid di-n-propyl ester dichloride was obtained.

Next, 105.48 g of N-methylpyrrolidone was charged into a 0.5-liter flask equipped with a stirrer, a thermometer and a Dimroth condenser, and bis (3-amino-4-hydroxyphenyl) hexafluoropropane 2
After adding 6.37 g and dissolving with stirring, pyridine 24.
65 g, and keeping the temperature at 0-5 ° C,
A solution (α) of 3 ′, 4,4′-diphenylethertetracarboxylic acid di-n-propyl ester dichloride was added dropwise over 1 hour, and then stirring was continued for 1 hour. The solution was poured into 4 liters of water, the precipitate was collected, washed, and dried under reduced pressure to obtain a polyamic acid ester having a weight average molecular weight of 27,300 (hereinafter referred to as polymer I).

Polymer 10.00 g, N- (trifluoromethanesulfonyloxy) naphthalimide 0.5
g, a polyhydroxy compound having a tetrahydropyranyl group of the following formula as an acid-decomposable group (4-hydroxybenzyl group to α, α, α'-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene) Hexadduct (4
2.00 g of -hydroxybenzyl group added to 4-hydroxyphenyl group at 2- and 6-positions (tetrahydropyranyl group substitution rate 0.78)

Embedded image Was dissolved in 14.39 g of N-methylpyrrolidone with stirring.
This solution was filtered under pressure using a 3 μm-pore Teflon (registered trademark) filter to obtain a positive photosensitive resin composition.

The obtained positive-type photosensitive resin composition was spin-coated on a silicon wafer using a spinner, and heated and dried at 110 ° C. for 2 minutes on a hot plate to obtain 15.7.
A μm coating was obtained. This coating film was exposed at 100 to 1100 mJ / cm ² through a reticle using an i-line reduction projection exposure apparatus (PFA3000iw manufactured by Canon Inc.). Next, heating was performed on a hot plate at 120 ° C. for 2 minutes, and then paddle development was performed for 100 seconds using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide as a developing solution, followed by washing with pure water to obtain a relief pattern. From the pattern observation, the proper exposure was determined to be 500 mJ / cm ² . The film thickness after development was 11.0 μm. Then
When this pattern was heated at 350 ° C. for 1 hour in a nitrogen atmosphere, a good polyimide film pattern was obtained.

Example 2 In a 0.5-liter flask equipped with a stirrer and a thermometer, 24.82 g of 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride and 11.86 g of n-butyl alcohol were used. , 0.40 g of triethylamine and 110.03 g of N-methylpyrrolidone were stirred and reacted at room temperature for 24 hours to obtain 3,3 ′, 4,4′-diphenylethertetracarboxylic acid di-n-butyl ester.
Then, after the flask was cooled to 5 ° C., thionyl chloride 1
7.61 g was added dropwise, and reacted for 1 hour.
4,4'-diphenylethertetracarboxylic acid di-n-
A solution (β) of butyl ester dichloride was obtained.

Next, 74.40 g of N-methylpyrrolidone was charged into a 0.5-liter flask equipped with a stirrer, a thermometer and a Dimroth condenser, and bis (3-amino-
After adding and dissolving 18.60 g of 4-hydroxyphenyl) propane with stirring, 23.41 g of pyridine was added,
While maintaining the temperature at 0 to 5 ° C., a solution (β) of 3,3 ′, 4,4′-diphenylethertetracarboxylic acid di-n-butyl ester dichloride was added dropwise over 1 hour, and then stirring was continued for 1 hour. The solution was poured into 4 liters of water, and the precipitate was collected, washed, and dried under reduced pressure to obtain a weight average molecular weight of 2
4,800 polyamic acid esters were obtained (hereinafter referred to as polymer II).

10.00 g of polymer II, tris (4-
Hydroxyphenyl) methane and naphthoquinone-1,2-
0.50 g of a compound obtained by reacting diazido-4-sulfonyl chloride in a molar ratio of 1 / 2.9, a polyhydroxy compound having a tetrahydropyranyl group as an acid-decomposable group (α,
Hexadduct of 4-hydroxybenzyl group to α, α'-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene (4-hydroxybenzyl group
Positions to be added to the -hydroxyphenyl group are 2 and 6
Position) (substitution rate of tetrahydropyranyl group 0.78) 2.
00g, 0.30 g of 1,4-bis (hydroxydimethylsilyl) benzene and 14.39 g of N-methylpyrrolidone
To dissolve. This solution was filtered under pressure using a Teflon filter having a pore size of 3 μm to obtain a positive photosensitive resin composition.

The obtained positive photosensitive resin composition was spin-coated on a silicon wafer using a spinner, and heated and dried at 110 ° C. for 2 minutes on a hot plate to obtain 15.3.
A μm coating was obtained. This coating film was exposed at 100 to 1100 mJ / cm ² through a reticle using an i-line reduction projection exposure apparatus (PFA3000iw manufactured by Canon Inc.). Next, heating was performed at 110 ° C. for 2 minutes on a hot plate, and then paddle development was performed for 160 seconds using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide as a developing solution, followed by washing with pure water to obtain a relief pattern. From the pattern observation, the proper exposure was determined to be 400 mJ / cm ² . The film thickness after development was 9.46 μm. Next, when this pattern was subjected to heat treatment at 350 ° C. for 1 hour in a nitrogen atmosphere, a good polyimide film pattern was obtained.

Example 3 In a 0.5-liter flask equipped with a stirrer and a thermometer, 24.82 g of 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride and 11.86 g of s-butyl alcohol were added. , Triethylamine (0.40 g) and N-methylpyrrolidone (110.03 g) were stirred and reacted at 60 ° C. for 24 hours to obtain 3,3 ′, 4,4′-diphenylethertetracarboxylic acid dis-butyl ester. Next, after cooling the flask to 5 ° C., 18.08 g of thionyl chloride was added dropwise, and the mixture was reacted for 1 hour.
A solution (γ) of 3 ′, 4,4′-diphenylethertetracarboxylic acid di-s-butyl ester dichloride was obtained.

Next, 47.97 g of N-methylpyrrolidone was charged into a 0.5-liter flask equipped with a stirrer, a thermometer, and a Dimroth condenser, and 4.33 g of 4,4′-diaminodiphenyl ether was added. 7.67 g of diaminobenzoic acid was added and dissolved by stirring.
4.05 g was added and the temperature was maintained at 0-5 ° C.
The solution (γ) of 3,3 ′, 4,4′-diphenylethertetracarboxylic acid di-s-butyl ester dichloride was added to 1
After dropwise addition over time, stirring was continued for 1 hour. The solution was poured into 4 liters of water, the precipitate was collected, washed, and dried under reduced pressure to obtain a polyamic acid ester having a weight average molecular weight of 25,100 (hereinafter referred to as polymer III).

Polymer III (10.00 g), diphenyliodonium 8-anilinonaphthalene-1-sulfonate (0.50 g), polyhydroxy compound having a tetrahydropyranyl group as an acid-decomposable group (α, α, α'-tris (4- 4-hydroxybenzyl group hexa-adduct to (hydroxyphenyl) -1-ethyl-4-isopropylbenzene (positions of 4-hydroxybenzyl group added to 4-hydroxyphenyl group are 2- and 6-positions) (tetrahydropyranyl group 2.00 g was dissolved in 14.39 g of N-methylpyrrolidone with stirring.
The mixture was filtered under pressure using a Teflon filter having a pore size of μm to obtain a positive photosensitive resin composition.

The obtained positive photosensitive resin composition was spin-coated on a silicon wafer using a spinner, and dried by heating at 100 ° C. for 3 minutes on a hot plate.
A film of a positive photosensitive resin composition having a thickness of μm was obtained. An i-line reduction projection exposure apparatus (PFA30 manufactured by Canon Inc.)
00iw), via reticle, 100-110
Exposure was performed at 0 mJ / cm ² . Then heating on a hot plate at 100 ° C. for 2 minutes, then 2.38% by weight
Using tetramethylammonium hydroxide aqueous solution as developer
Paddle development was performed for 40 seconds, and washing with pure water was performed to obtain a relief pattern. The proper exposure is 500m from pattern observation
J / cm ² was determined. Film thickness after development is 12.3 μm
Met. Next, this pattern is formed in a nitrogen atmosphere at 350
When heat-treated at 1 ° C. for 1 hour, a good polyimide film pattern was obtained.

Example 4 10.00 g of polymer I, diphenyliodonium 8
-Anilinonaphthalene-1-sulfonate 0.50 g,
Polyhydroxy compound having 1-ethoxyethyl group as an acid-decomposable group represented by the following formula (4-hydroxybenzyl group hexa to α, α, α'-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene) 2.00 g of an adduct (positions to be added to the 4-hydroxyphenyl group of the 4-hydroxybenzyl group are at positions 2 and 6) (substitution ratio of 1-ethoxyethyl group: 0.30)

Embedded image Was dissolved in 14.39 g of γ-butyrolactone with stirring. This solution was filtered under pressure using a Teflon filter having a pore size of 3 μm to obtain a positive photosensitive resin composition.

The obtained positive photosensitive resin composition was spin-coated on a silicon wafer using a spinner, and dried by heating at 95 ° C. for 3 minutes on a hot plate to obtain 16.3 μm.
m was obtained as a positive photosensitive resin composition film. This coating has i
Line reduction projection exposure equipment (PFA300 manufactured by Canon Inc.)
0iw), via reticle, 100-1100
Exposure at mJ / cm ² was performed. Then, a 2.38% by weight aqueous solution of tetramethylammonium hydroxide was used as a developing solution,
Paddle development was performed for 2 seconds, followed by washing with pure water to obtain a relief pattern. From the pattern observation, the proper exposure is 500 mJ /
cm ² was determined. The film thickness after development was 11.5 μm. Next, when this pattern was subjected to heat treatment at 350 ° C. for 1 hour in a nitrogen atmosphere, a good polyimide film pattern was obtained.

Example 5 4,4'-Diphenyletherdicarboxylic acid was placed in a 0.5 liter flask equipped with a stirrer and a thermometer.
After 66 g and 117.06 g of N-methylpyrrolidone were charged and the flask was cooled to 5 ° C., thionyl chloride was added.
08 g was added dropwise and reacted for 1 hour to obtain a solution (ε) of 4,4′-diphenylethertetracarboxylic acid chloride. Next, 111.34 g of N-methylpyrrolidone was charged into a 0.5-liter flask equipped with a stirrer, a thermometer and a Dimroth condenser, and bis (3-amino-4-) was added.
(Hydroxyphenyl) hexafluoropropane 27.8
After adding 4 g and dissolving with stirring, 24.05 g of pyridine was added.
Was added and a solution (ε) of 4,4′-diphenyletherdicarboxylic acid chloride was added dropwise over 1 hour while maintaining the temperature at 0 to 5 ° C., and then stirring was continued for 1 hour. The solution was poured into 4 liters of water, and the precipitate was collected, washed, and dried under reduced pressure to obtain a polyhydroxyamide having a weight average molecular weight of 29,500 (hereinafter referred to as polymer IV).

Polymer 10.00 g, diphenyliodonium 8-anilinonaphthalene-1-sulfonate 0.50 g, polyhydroxy compound having a tetrahydropyranyl group as an acid-decomposable group (α, α, α′-tris (4
-Hydroxyphenyl) -1-ethyl-4-isopropylbenzene hexa-adduct (positions to be added to the 4-hydroxyphenyl group of the 4-hydroxybenzyl group are at positions 2 and 6) (tetrahydropyranyl 2.00 g of a group substitution rate (0.78) was dissolved under stirring in 14.39 g of N-methylpyrrolidone. 3 μm of this solution
The mixture was filtered under pressure using a Teflon filter having pores to obtain a positive photosensitive resin composition.

The obtained positive photosensitive resin composition was spin-coated on a silicon wafer using a spinner, and dried by heating at 110 ° C. for 2 minutes on a hot plate to obtain 15.6.
A film of a positive photosensitive resin composition having a thickness of μm was obtained. An i-line reduction projection exposure apparatus (PFA30 manufactured by Canon Inc.)
00iw), via reticle, 100-110
Exposure was performed at 0 mJ / cm ² . Next, heating was performed at 110 ° C. for 2 minutes on a hot plate, and then 2.38% by weight.
Using tetramethylammonium hydroxide aqueous solution as developer
Paddle development was performed for 20 seconds, followed by washing with pure water to obtain a relief pattern. The proper exposure is 600m from pattern observation
J / cm ² was determined. Film thickness after development is 11.3 μm
Met. Next, this pattern is formed in a nitrogen atmosphere at 350
Heat treatment at 1 ° C. for 1 hour gave a good polyoxazole film pattern.

Comparative Example 1 In a 0.5-liter flask equipped with a stirrer and a thermometer, 24.82 g of 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride and 11.86 g of n-butyl alcohol were added. , 0.40 g of triethylamine and 110.03 g of N-methylpyrrolidone were stirred and reacted at room temperature for 24 hours to obtain 3,3 ′, 4,4′-diphenylethertetracarboxylic acid di-n-butyl ester.
Then, after the flask was cooled to 5 ° C., thionyl chloride 1
7.61 g was added dropwise, and reacted for 1 hour.
4,4'-diphenylethertetracarboxylic acid di-n-
A solution (δ) of butyl ester dichloride was obtained.

Then, 47.97 g of N-methylpyrrolidone was charged into a 0.5-liter flask equipped with a stirrer, a thermometer, and a Dimroth condenser, and 4.33 g of 4,4′-diaminodiphenyl ether and 3,5- 7.67 g of diaminobenzoic acid was added and dissolved by stirring.
2.78 g are added and the temperature is kept at 0-5 ° C.
The solution (δ) of 3,3 ′, 4,4′-diphenylethertetracarboxylic acid di-n-butyl ester dichloride was added to 1
After dropwise addition over time, stirring was continued for 1 hour. The solution was poured into 4 liters of water, the precipitate was collected, washed, and dried under reduced pressure to obtain a polyamic acid ester having a weight average molecular weight of 22,000 (hereinafter, referred to as polymer V). Polymer V 1
0.00g of 2.0g of a compound obtained by reacting 2,3,4,4'-tetrahydroxybenzophenone with naphthoquinone-1,2-diazido-5-sulfonyl chloride in a molar ratio of 1 / 3.0 was converted to N-methyl. It was dissolved by stirring in 14.39 g of pyrrolidone. This solution was filtered under pressure using a Teflon filter having a pore size of 3 μm to obtain a positive photosensitive resin composition.

The obtained positive photosensitive resin composition was spin-coated on a silicon wafer by using a spinner, and dried by heating at 125 ° C. for 3 minutes on a hot plate.
A film of a positive photosensitive resin composition having a thickness of μm was obtained. An i-line reduction projection exposure apparatus (Canon PFA3000i)
w) through a reticle, 100 to 1100 mJ
/ Cm ² . Next, paddle development was performed for 140 seconds using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide as a developing solution, and the substrate was washed with pure water.
The pattern was not completed even in cm ² . The film thickness of the unexposed portion after the development was 11.5 μm. As can be seen from the above Examples and Comparative Examples, the Examples of the present invention were excellent in exposure sensitivity, while the Comparative Examples were inferior in sensitivity.

[0083]

The positive photosensitive resin composition of the present invention has a high exposure sensitivity and can form a film having a good pattern shape and excellent heat resistance even with a large film thickness. In addition, according to the pattern manufacturing method of the present invention, a pattern having a good shape can be obtained even with a large film thickness because the resolution is high and the exposure sensitivity is high.
Further, the electronic component of the present invention is excellent in reliability having an interlayer insulating film or a surface protective film having a pattern of a good shape even with a large film thickness.

[Brief description of the drawings]

FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Semiconductor substrate, 2 ... Protective film, 3 ... First conductor layer, 4 ... Interlayer insulating film layer, 5 ... Photosensitive resin layer, 6A, 6B, 6C ... Window,
7: second conductor layer, 8: surface protective film layer.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 21/027 H01L 21/30 502R (72) Inventor Takanori Anzai 4-3-1, Higashicho, Hitachi City, Ibaraki Prefecture Hitachi Chemical Dupont Microsystems Co., Ltd. Yamazaki Development Center (72) Inventor Nagatoshi Fujieda 4-3-1 Higashicho, Hitachi City, Ibaraki Prefecture Hitachi Chemical Dupont Microsystems Co., Ltd. Yamazaki Development Center F-term (reference) 2H025 AA01 AA03 AA10 AB16 AB17 AC01 AD03 BE00 BE07 BE10 BG00 CB19 CB25 CB34 CB43 FA12 FA17 FA29 4J002 BC042 BC122 BG012 CD052 CL002 CM011 CM021 CM041 EB116 EJ016 EJ036 EJ056 EJ066 EL087 EV076 EV216 EV216 EU216 216 216 216 216 216 216

Claims (9)

[Claims] (A) a polyimide precursor or a polyoxazole precursor, (B) a compound generating an acid by light, and (C) an acid-decomposable group whose solubility in an aqueous alkali solution increases by an acid-catalyzed reaction. Positive photosensitive resin composition comprising a compound having The component (C) is an acid-decomposable group whose solubility in an aqueous alkali solution is increased by an acid-catalyzed reaction. The positive photosensitive resin composition according to claim 1, wherein s represents an integer of 3 to 7, and each R independently represents an alkyl group having 1 to 3 carbon atoms. . The component (C) is represented by the following general formulas (1) to (9): (In the general formulas (1) to (9), each X is independently a hydrogen atom or an acid-decomposable group, and in each general formula, at least one X is an acid-decomposable group, and each Y is R ¹ is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
R ² is a tetravalent organic group having an aromatic ring, Z is a monovalent organic group, and l, m and n are 1 to
The positive photosensitive resin composition according to claim 1, wherein the compound is a compound having a structure represented by the following formula: wherein n is an integer of 3, p and q are 1 or 2, and r is a positive integer. The component (A) is represented by the general formula (10): (Wherein, R ⁴ represents a tetravalent organic group, R ⁵ represents a divalent organic group having a carboxyl group or a phenolic hydroxyl group, and each R ⁶ independently represents a monovalent organic group.) The positive photosensitive resin composition according to claim 1, which is a polyamic acid ester having a repeating unit represented by the formula: (5) The component (A) has the general formula (11): ^4. The positive-type photosensitive material according to claim 1, which is a polyamic acid having a repeating unit represented by the formula: wherein R ⁴ represents a tetravalent organic group and R ⁷ represents a divalent organic group. Resin composition. 6. general formula (10) or the general formula (11) R ⁴
Is a group containing one aromatic ring or two or three aromatic rings having a single bond, an ether bond, a 2,2-hexafluoropropylene bond, a 2,2-propylene bond, a sulfone bond, a methylene bond, and a carbonyl bond. A tetravalent organic group having a chemical structure linked via at least one bond selected from the group consisting of R ^{5 and} R ⁷ , wherein R ⁵ or R ⁷ is a group containing one aromatic ring or 2
~ 3 aromatic rings are a single bond, an ether bond, a 2,2-hexafluoropropylene bond, a 2,2-propylene bond,
6. The positive photosensitive resin composition according to claim 4, which is a divalent organic group having a chemical structure bonded through at least one bond selected from a methylene bond and a sulfone bond. (7) The component (A) is represented by the general formula (12): Wherein R ⁸ is a divalent organic group, and R ⁹ is a tetravalent organic group containing an aromatic ring, which is a polybenzoxazole precursor having a repeating unit represented by the following formula: Or a positive photosensitive resin composition according to item 3. 8. A step of applying and drying the positive photosensitive resin composition according to claim 1 on a support substrate, exposing, heating, developing, and heating. A method for producing a pattern including: 9. An electronic component having a pattern layer obtained by the method according to claim 8.