JP2001194796A - 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 to i-line, forming a fine pattern free from peeling particularly in development and excellent in heat resistance, a method for producing a pattern using the composition and electronic parts. SOLUTION: The positive type photosensitive resin composition contains (A) a polymer having an acidic group, (B) a compound which generates an acid under light and (C) an organosilicon compound of formula I (where (1) is 1-3; R is a 1-5C alkyl; and R' is H, a 1-8C alkyl or the like).

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 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 (Japanese Patent Publication No. 3-36861). When using the photosensitive polyimide precursor composition, usually applied on a substrate in a solution state and then dried,
Irradiation with actinic rays is performed through a mask, development is performed, and a pattern is formed.

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.

Also, since a and b are negative type, 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. There's a problem. Regarding the positive photosensitive polyimide precursor composition, c. a polyimide precursor having an o-nitrobenzyl group introduced through an ester bond (JP-A-60-37550), d. Composition containing polyamic acid ester containing carboxyl group and o-quinonediazide compound
168441), e. A composition containing a polyamic acid ester containing a hydroxyl group and an o-quinonediazide compound (JP-A-3-11546) is known.

Meanwhile, the degree of integration of semiconductor elements has been improving year by year, and accordingly, improvement in fine processing technology has been desired. One of the technologies that enable microfabrication is to shorten the exposure wavelength in the lithography process, and the exposure light source for pattern formation using a positive photoresist is
The conventional g-line (436 nm) to i-line (365 nm) is becoming mainstream. For this reason, the photosensitive polyimide precursor is required to be able to form a pattern using the i-line as an exposure light source from the viewpoint of common use of an exposure apparatus.

However, the positive photosensitive polyimide precursor composition described in c above has a wavelength of 300 n
m or less, there is a problem that the sensitivity is low. D and e have a problem that the adhesion between the film after development and the substrate is poor and the fine pattern is peeled off during development.

[0008]

The object of the present invention is to provide a positive photosensitive resin composition which overcomes the above-mentioned problems and has a high exposure sensitivity to i-rays, and in particular, does not peel off fine patterns during development. . The present invention also provides a positive photosensitive resin composition having excellent heat resistance, in addition to the objects of the present invention.

The present invention provides, in addition to the objects of the invention,
Particularly, the present invention provides a positive photosensitive resin composition having excellent sensitivity. The present invention also provides a method for producing a pattern which has high exposure sensitivity to i-rays, and in particular, does not peel off a fine pattern during development. Further, the present invention provides an electronic component which becomes a highly reliable semiconductor device or a multilayer wiring board having an interlayer insulating film or a surface protective film having good adhesion after high-temperature heat treatment without peeling of a pattern from a substrate. Is what you do.

[0010]

The present invention relates to (A) a polymer having an acidic group, (B) a compound capable of generating an acid by light, and (C) a compound of the general formula (I).

Embedded image (Wherein, l is an integer of 1 to 3, R is an alkyl group having 1 to 5 carbon atoms, R ′ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a hydroxyl group, a mercapto group, an alkoxy group having 1 to 5 carbon atoms. A trialkoxysilyl group, a trialkylsilyl group having an alkyl group having 1 to 5 carbon atoms, or a general formula (II)

Embedded image And a positive photosensitive resin composition containing an organosilicon compound represented by the formula:

The present invention also relates to a positive photosensitive resin composition wherein the polymer (A) having an acidic group is a polyimide precursor or a polyoxazole precursor. In the present invention, the polymer (A) having a hydroxyl group is represented by the general formula (III):

Embedded image (Wherein, R ¹ represents a tetravalent organic group, R ² represents a divalent organic group having a carboxyl group or a phenolic hydroxyl group, and each R ³ independently represents a monovalent organic group.) The present invention relates to a positive photosensitive resin composition which is a polyamic acid ester having a repeating unit represented by the formula:

The present invention also relates to a positive photosensitive resin composition wherein the compound (B) which generates an acid by light is an o-quinonediazide compound. In addition, the present invention relates to a positive photosensitive resin composition containing, in addition to the above components, a compound (D) having an acid-decomposable group whose solubility in an aqueous alkali solution is increased by an acid-catalyzed reaction.

The present invention also relates to a compound represented by the general formula (III) wherein R ¹ is a group containing one aromatic ring or two or three aromatic rings having a single bond;
Ether bond, 2,2-hexafluoropropylene bond, a sulfone bond, a tetravalent organic group having an attached chemical structure via at least one bond selected from among methylene bond and a carbonyl bond, R ² is A group containing one aromatic ring or two to three aromatic rings are bonded via at least one bond selected from a single bond, an ether bond, a 2,2-hexafluoropropylene bond, a methylene bond and a sulfone bond. The present invention relates to a positive photosensitive resin composition which is a divalent organic group having a bonded chemical structure and having at least one phenolic hydroxyl group and / or carboxyl group.

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

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The component (A) used in the present invention is a polymer having an acidic group. By having an acidic group, the polymer becomes soluble in an aqueous alkaline solution used as a developer. After exposure, the exposed portion becomes more soluble due to a change in the component (B), and has a different dissolution rate from the unexposed portion, so that a pattern having a relief structure can be formed. The alkaline aqueous solution is an aqueous solution exhibiting alkalinity in which tetramethylammonium hydroxide, metal hydroxide, amine and the like are dissolved in water. Examples of the acidic group include a carboxyl group, a phenolic hydroxyl group, and a sulfone group. The polymer used in the present invention preferably has a carboxyl group or a phenolic hydroxyl group.

Examples of the type of the polymer include polyimide precursors such as polyamic acid, polyamic acid ester, and polyamic acid amide; and polymers having excellent heat resistance such as polyhydroxyamide, polyimide, and polybenzoxazole as polyoxazole precursors. This is preferable because the film formed has excellent physical properties such as heat resistance.

Among these, a polyimide precursor and a polyoxazole precursor which can form a good pattern and which form a resin film having excellent heat resistance by a curing reaction are preferable. Among them, a polyamic acid ester having a repeating unit represented by the general formula (III) is preferable because it has high exposure sensitivity to i-line at the time of pattern formation and has excellent adhesion to a support substrate after heat treatment.

A phenolic hydroxyl group or a divalent organic group having a carboxyl group represented by R ² in the general formula (III) refers to a phenolic 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. The ^two binding sites for R ² 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. It is preferable that 1 to 8 phenolic hydroxyl groups or carboxyl groups exist in R ² .

As the group containing an aromatic ring, one aromatic ring or two or three aromatic rings may be a single bond, an ether bond, a methylene bond, an ethylene bond, a 2,2-propylene bond,
A divalent organic group having a chemical structure linked via a 2,2-hexafluoropropylene bond, a sulfone bond, a sulfoxide bond, a thioether bond and a carbonyl bond, and having at least one phenolic hydroxyl group and / or carboxyl group; No.

In formula (III), R ² represents one aromatic ring itself or two or three aromatic rings via a single bond, an ether bond, a 2,2-hexafluoropropylene bond, a sulfone bond or a carbonyl bond. Those having a bonded chemical structure and a divalent organic group having at least one phenolic hydroxyl group and / or carboxyl group are preferred from the viewpoint of heat resistance and mechanical properties of the polyimide polymer after the heat treatment.

In the formula (III), the monovalent organic group represented by R ³ 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 (I
In II), there are two R ^{3 s} , which may be the same or different.

The polyamic acid ester having a repeating unit represented by the above general formula (III) further has a general formula (I)
V)

Embedded image (Wherein, R ¹ represents a tetravalent organic group, R ⁴ represents a divalent organic group having no carboxyl group or phenolic hydroxyl group, and each R ³ independently represents a monovalent organic group. ) May be included. In the general formula (IV), a tetravalent organic group represented by R ¹ and ^{1 represented} by R ³
The valent organic group is the same as that in the general formula (III).

A phenolic hydroxyl group or a divalent organic group having no carboxyl group represented by R ⁴ is a divalent organic group other than an amino group of a diamine compound which can react with tetracarboxylic acid or a derivative thereof to form a polyimide precursor. And 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. R
^{The two} binding sites 2 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.

As the group containing an aromatic ring, 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 divalent organic group having a chemical structure linked via a 2,2-hexafluoropropylene bond, a sulfone bond, a sulfoxide bond, a thioether bond and a carbonyl bond, and having at least one phenolic hydroxyl group and / or carboxyl group; No.

In the general formula (IV), R ⁴ represents one aromatic ring itself or two or three aromatic rings via a single bond, an ether bond, a 2,2-hexafluoropropylene bond, a sulfone bond or a carbonyl bond. Those having a bonded chemical structure and a divalent organic group having at least one phenolic hydroxyl group and / or carboxyl group are preferred from the viewpoint of heat resistance and mechanical properties of the polyimide polymer after the heat treatment.

The polyamic acid ester having a repeating unit represented by the general formula (III) may be optionally substituted with a compound represented by the general formula (I)
It may have a repeating unit other than the repeating units represented by II) and (IV). For example, general formula (III) or (I
In V), a repeating unit in which a hydrogen atom is bonded instead of the monovalent hydrocarbon group represented by R ³ may be mentioned.

In a polyamic acid ester having a repeating unit represented by the general formula (III),
V) having a repeating unit represented by the general formula (II)
The ratio of the repeating unit of (I) to the general formula (IV) is represented by m / (m + n) where m is the number of the former and n is the number of the latter.
To 0.2, more preferably 1.0 to 0.4. When this value is less than 0.2, the solubility of the exposed portion of the film formed by coating and drying in an aqueous alkaline solution tends to be poor. Further, in this polyamic acid ester, the total number of the repeating units of the general formulas (II) and (III) is preferably 50 to 100%, more preferably 80 to 100%, based on the total number of the repeating units in the polyamic acid ester.
100% is more preferable, and 90 to 100% is particularly preferable. Here, the repeating unit is a unit composed of one acid residue and one amine residue.

The molecular weight of the component (A) is preferably from 3,000 to 200,000 in terms of weight average molecular weight.
00 to 100,000 is more preferable. Molecular weight is measured by gel permeation chromatography,
The value can be obtained by conversion using a standard polystyrene calibration curve.

The polyamic acid ester having a repeating unit represented by the above general formula (III) may be a tetracarboxylic diester dichloride represented by the following general formula (V) and the following general formula (VI) and, if necessary, the following general formula: The formula (VI
It can be obtained by reacting with the diamine compound represented by I)

[0030]

Embedded image (Wherein R ¹ and R ³ in the formula are the same as in the general formula (III))

Embedded image (Where R ² in the formula is the same as in the general formula (III))

Embedded image (Wherein, R ⁴ in the formula is the same as general formula (IV))

The tetracarboxylic diester dichloride is obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (VIII) with an alcohol compound represented by the following general formula (IX): Can be obtained by reacting a tetracarboxylic acid diester represented by the formula with thionyl chloride.

[0032]

Embedded image (Where R ¹ in the formula is the same as in the general formula (III))

Embedded image (Where R ³ in the formula is the same as in the general formula (III))

Embedded image (Wherein R ¹ and R ³ in the formula are the same as in the general formula (III))

The compound represented by the general formula (VIII) is a tetracarboxylic dianhydride. However, from the viewpoint of heat resistance and mechanical properties of the polyimide-based polymer after the heat treatment, an aromatic group or a group of two to three is preferred. Aromatic group is a single bond, ether bond,
A carboxylic acid dianhydride having a chemical structure bonded via at least one bond selected from a 2,2-hexafluoropropylene bond, a sulfone bond, a methylene bond and a carbonyl bond is preferred.

Specific examples of these compounds include pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic acid 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 (3,
Preferred are aromatic tetracarboxylic dianhydrides such as tetracarboxylic dianhydrides such as (4-dicarboxyphenyl) hexafluoropropane dianhydride. These acid dianhydrides can be used alone or in combination of two or more.

Specific examples of the alcohol compound represented by the general formula (IX) include methanol, ethanol, n
-Propyl alcohol, isopropyl alcohol, n-
Butyl alcohol, sec-butyl alcohol, ter
t-butyl alcohol, isobutyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, isoamyl alcohol, 1-hexanol, 2-hexanol, 3-hexanol, and the like, alone or in combination of two or more. Can be used in combination.

The compound represented by the general formula (VI) is a diamine having at least one phenolic hydroxyl group and / or carboxyl group. However, from the viewpoint of heat resistance and mechanical properties of the polyimide polymer after the heat treatment. An aromatic group or two or three aromatic groups having a single bond, an ether bond,
-Diamines having a chemical structure bonded via at least one bond selected from a hexafluoropropylene bond, a sulfone bond and a methylene bond are preferred. Specific examples of these compounds include 2,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 2,5-diaminoterephthalic acid, and bis (4-amino-3-carboxy) Phenyl) 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 (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 compound represented by the above general formula (VII) is a diamine. However, from the viewpoint of heat resistance and mechanical properties of the polyimide-based polymer after the heat treatment, an aromatic group or two to three aromatic groups are simply formed. Diamines having a chemical structure bonded via at least one bond selected from a bond, an ether bond, a 2,2-hexafluoropropylene bond, a sulfone bond and a methylene bond are preferred. Specific examples of these compounds include 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-
Diaminodiphenyl sulfone, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (3-aminophenoxyphenyl) sulfone, 1,4-
Bis (4-aminophenoxy) benzene, 4,4'-diamino-2,2'-dimethylbiphenyl and the like can be mentioned. These diamine compounds can be used alone or in combination of two or more.

A method for synthesizing the tetracarboxylic diester compound represented by the general formula (X) is known.
For example, it is obtained by mixing tetracarboxylic dianhydride and an excess of the alcohol compound represented by the general formula (IX), reacting the mixture by heating, and then removing the excess alcohol compound. The preferred ratio (molar ratio) of the alcohol and the alcohol compound is in the range of 1/2 to 1/20, and the more preferred ratio is in the range of 1/2 to 1/5. The preferred reaction time is between 3 and 24 hours.

A method for synthesizing tetracarboxylic diester dichloride is known. For example, it is obtained by reacting tetracarboxylic diester with excess thionyl chloride by heating and then removing excess thionyl chloride. The preferred ratio (molar ratio) of the tetracarboxylic diester to the excess thionyl chloride is in the range of 1 / 2.2 to 1/10, and the more preferred ratio is in the range of 1 / 2.2 to 1/5. . 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 dissolving a diamine compound represented by the general formulas (VI) and (VII) and a dehydrochlorination catalyst such as pyridine in an organic solvent, After the carboxylic acid diester dichloride is dropped and reacted, the mixture is poured into a poor solvent such as water, and the precipitate is collected by filtration and dried. Examples of the organic solvent used in the reaction include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, tetramethylene sulfone, γ-butyrolactone, and the like. Are used alone or in combination of two or more. A preferable ratio (molar ratio) of the total amount of the diamine compounds represented by the general formulas (VI) and (VII) and the tetracarboxylic diester dichloride is 0.6 / 1 to 1 / 0.6.
Range. Preferred reaction temperature is -30 to 40 ° C,
The preferred reaction time is between 5 minutes and 10 hours. The preferred ratio of the dehydrochlorination catalyst and tetracarboxylic dichloride is
The former / latter (molar ratio) is 1.9 / 1.0 to 2.0 /
The range is 0.95.

Next, the component (A) used is represented by the general formula (II)
The case other than the polyamic acid ester having the repeating unit represented by I) will be described. When the component (A) used is a polyamic acid, a dicarboxylic acid having a carboxyl group or a phenolic hydroxyl group may not be used as the diamine because a carboxyl group is present in the residue of the tetracarboxylic acid. Polyamic acid is obtained by directly reacting the tetracarboxylic dianhydride with the diamine.

When the component (A) used is a polyamide acid amide, a diamine compound having a carboxyl group or a phenolic hydroxyl group is generally used as the diamine, and the diamine compound has a carboxyl group and a phenolic hydroxyl group. The proportion of the diamine compound not used is the same as in the case of the synthesis of the polyamic acid ester.

In the synthesis of the polyamic acid ester, the polyamic acid amide may be replaced with a monoamine compound, for example, methylamine, ethylamine, n-propylamine, isopropylamine, n-amine.
-Butylamine, sec-butylamine, tert-butylamine, isobutylamine, 1-pentylamine,
2-pentylamine, 3-pentylamine, isoamylamine, 1-hexylamine, 2-hexylamine, 3
-Primary amines such as hexylamine, secondary amines such as dimethylamine, diethylamine, di-n-propylamine, diisopropylamine and di-n-butylamine, alicyclic amines such as piperazine, piperidine and morpholine, aniline, benzylamine and the like. It can be synthesized by using. The polyimide is obtained by dehydrating and ring-closing the polyamide acid amide.

As the polyoxazole precursor, there is generally mentioned a hydroxypolyamide obtained from dicarboxylic acid and dihydroxydiamine as raw materials. As the dicarboxylic acid, isophthalic acid, terephthalic acid, 2,2-
Bis (4-carboxyphenyl) hexafluoropropane, 4,4′-biphenyldicarboxylic acid, 4,4′-dicarboxydiphenyl ether, 4,4′-dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2,2-bis (p-carboxyphenyl) propane, 5-tert-butylisophthalic acid, 5
-Bromoisophthalic acid, 5-fluoroisophthalic acid, 5
-Chloroisophthalic acid, aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid,
Examples thereof include aliphatic dicarboxylic acids such as 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.

As the dihydroxyamine, 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
Aromatic diamines such as (-hydroxyphenyl) hexafluoropropane are preferred. By using an aromatic diamine, good heat resistance,
It is a polybenzoxazole precursor.

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 carried out in the presence of a dehalogenating acid catalyst. The dicarboxylic acid dichloride, which is preferably carried out in an organic solvent, can be obtained by reacting a dicarboxylic acid with thionyl chloride. Polybenzoxazole is obtained by dehydrating and ring closing the polybenzoxazole precursor.

The compound which generates an acid by light, which is the component (B) used in the present invention, is a photosensitizer and has a function of generating an acid and increasing the solubility of the irradiated portion in an aqueous alkaline solution. Things. Examples thereof include o-quinonediazide compounds, onium salts, sulfonic acid ester compounds, and the like.

The o-quinonediazide compound is, for example, an o-quinonediazide compound.
It is obtained by subjecting a quinonediazide sulfonyl chloride to a condensation reaction with a hydroxy compound, an amino compound and the like in the presence of a dehydrochlorinating catalyst. Examples of o-quinonediazidosulfonyl chlorides include 1,2-benzoquinone-2-diazido-4-sulfonyl chloride, 1,2-
Naphthoquinone-2-diazide-5-sulfonyl chloride, 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride and the like 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'-diaminodiphenylmethane, 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) hexafluoropropane and the like.

The o-quinonediazidosulfonyl chloride and the hydroxy compound or the 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.

Examples of the onium salt include an aryldiazonium salt, a diaryliodonium salt and a triarylsulfonium salt. The counter anion of the onium salt is tetrafluoroboric acid, hexafluoroantimonic acid, trifluoromethanesulfonic acid, trifluoromethanesulfonic acid or trifluoromethanesulfonic acid. Acetic acid, toluenesulfonic acid and the like are preferred.

The component (B) is used in an amount of 5 to 100 parts by weight, preferably 5 to 40 parts by weight, based on 100 parts by weight of the component (A) in view of the film thickness and sensitivity after development. When the compound that generates an acid by light as the component (B) used in the present invention is an onium salt or a sulfonic acid ester compound, the solubility in an alkaline aqueous solution increases due to the acid catalyzed reaction as the component (D). It is preferable to simultaneously include a compound having an acid-decomposable group.

As the component (D), for example, an alkali-soluble resin such as polyvinylphenol, or a hydroxyl group such as bisphenols, trisphenols, trisphenolalkanes, trinuclear phenol resins, and tetrakisphenols may be used as an acetal group. And polymers or compounds protected with an acid-decomposable group such as a ketal group.
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. (D)
Component (A) component 10 is preferred in view of film thickness and sensitivity after development.
It is preferably used in an amount of 3 to 50 parts by weight, more preferably 5 to 30 parts by weight, based on 0 parts by weight.

The component (C) used in the present invention is used for improving the adhesion between the film and the substrate after coating and drying. In the present invention, the component (C) simultaneously removes the fine pattern during development. It has been found that it is also highly effective in prevention. Specific examples of the component (C) include methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylcyphenylsilanediol, isobutylphenylsilanediol, and te.
rt-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-butyldiphenylsilanol, phenylsilanetriol, 1,4-bis (trihydroxysilyl) benzene, 1,4-bis (methyldihydroxysilyl) benzene, 1,4-bis ( Ethyldihydroxysilyl) benzene, 1,4-bis (propyldihydroxysilyl) benzene, 1,4-bis (butyldihydroxysilyl) benzene, 1,4-bis (dimethylhydroxysilyl) benzene, 1,4-bis (diethylhydroxy) (Silyl) benzene, 1,4-bis (dipropyldroxysilyl) benzene, 1,4-bis (dibutylhydroxysilyl) benzene, and the like.

The component (C) is preferably used in an amount of 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the component (A). If the amount is less than 0.1 part by weight, peeling of the fine pattern during development is likely to occur,
If the amount is more than 20 parts by weight, the solubility of the exposed portion of the film in an alkali developing solution tends to decrease. The positive photosensitive resin composition of the present invention can be obtained by dissolving a material containing the component (A), the component (B), the component (C) and, if necessary, the component (D) in a solvent.

As the solvent, for example, N-methyl-2-
Pyrrolidone, N, N-dimethylformamide, N, N-
Dimethylacetamide, dimethylsulfoxide, hexamethylphosphoramide, tetramethylene sulfone, γ-
Aprotic polar solvents such as butyrolactone, cyclohexanone, cyclopentanone, 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 other than the component (C) in order to enhance the adhesion of the cured film to the substrate. As the organic silane compound, for example,
Vinyl triethoxy silane, γ-glycidoxy propyl triethoxy silane, γ-methacryloxy propyl trimethoxy silane, urea propyl triethoxy silane and the like can be mentioned. Examples of the aluminum chelate compound include aluminum tris (acetylacetonate) and aluminum acetylacetate diisopropylate.

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 ,
SiO ₂ etc.), applied on a supporting substrate such as silicon nitride,
By drying, a film of the positive photosensitive resin composition can be obtained. Thereafter, irradiation with active light such as ultraviolet light, visible light, or radiation is performed (exposure) through a mask, and then the exposed portion is removed with a developing solution to obtain a positive relief structure pattern. The positive-type photosensitive resin composition of the present invention exhibits excellent characteristics especially for i-line exposure, so that it is preferable to perform exposure with i-line.

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, development is carried out. As a developer, it is preferable to use an alkali developer, for example, an aqueous solution of 5% by weight or less of 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. Each of these is preferably 0.01 to 100 parts by weight of the developer.
10 to 10 parts by weight, more preferably 0.1 to 5 parts by weight. Then, the resulting relief structure pattern is subjected to a heat treatment at 150 to 450 ° C. to obtain a pattern of a heat-resistant polymer having an imide ring or another cyclic group.

When the component (D) is used, it is preferable to perform a heat treatment after exposure and before development. The heat treatment is performed using an oven or a hot plate. The heating conditions are appropriately determined depending on the components of the positive photosensitive resin composition.
C. for 30 seconds to 10 minutes is preferred. 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.

This pattern is 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 manufacturing process of a semiconductor device 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 is formed on the exposed circuit element. . 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 predetermined portion of the interlayer insulating film 4 is exposed by a known photolithography technique. A window 6A is provided to perform the process (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 or carbon tetrafluoride, and a window 6B is opened. Next, the photosensitive resin layer 5 is completely removed by using an etching solution that corrodes only the photosensitive resin layer 5 without corroding the first conductor layer 3 exposed from the window 6B (step (c)).

Further, using a known photolithography technique,
The conductor layer 7 is formed, and the electrical connection with the first conductor layer 3 is made completely (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, the surface protective film is coated with the photosensitive polymer composition by a spin coating method, dried, and irradiated with light from a mask on which a pattern for forming a window 6C is drawn on a predetermined portion. A pattern is formed by developing with an aqueous solution, and heated to form a polyimide film. This polyimide film protects the conductor layer from external stress, α-rays and the like, and the resulting 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.

[0070]

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, thermometer, and Dimroth condenser, 24.82 g of 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride, n-
59.30 g of butyl alcohol was charged and reacted by stirring at 95 ° C. for 5 hours. Excess n-butyl alcohol was distilled off under reduced pressure to obtain 3,3 ′, 4,4′-diphenylethertetracarboxylic acid di-n-butyl ester. Next, 95.17 g of thionyl chloride and 70.00 g of toluene were charged into the flask and reacted at 40 ° C. for 3 hours. Excessive thionyl chloride is azeotroped with toluene under reduced pressure,
Removed. 186 g of N-methylpyrrolidone are added,
A solution (α) of 3,3 ′, 4,4′-diphenylethertetracarboxylic acid di-n-butyl ester dichloride was obtained. Next, 95 g of N-methylpyrrolidone (NMP) was charged into a 0.5-liter flask equipped with a stirrer, a thermometer and a Dimroth condenser, and 8.28 g of 3,5-diaminobenzoic acid and 4,4′-diamino 5.13 g of diphenyl ether was added and dissolved by stirring.
66 g was added, and while maintaining the temperature at 0 to 5 ° C, 3,
The solution (α) of 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, the precipitate was collected, washed, and dried under reduced pressure to obtain a polyamic acid n-butyl ester having a weight average molecular weight of 27,800 (hereinafter referred to as polymer I).

30.00 g of Polymer I was added to 54.0 NMP.
0 g, dissolve with stirring and diphenylsilanediol 0.90
g, and the mixture was stirred. Then, 7.50 g of a compound obtained by reacting 2,3,4,4′-tetrahydroxybenzophenone and naphthoquinone-1,2-diazido-5-sulfonyl chloride at a molar ratio of 1/3 was dissolved. I let it. 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 125 ° C. for 3 minutes on a hot plate to give 6.8 μm.
m was obtained as a positive photosensitive resin composition film. This coating has i
Line reduction projection exposure equipment (LD-50 manufactured by Hitachi, Ltd.)
Using 10i), exposure was performed at 800 mJ / cm ² through a mask having a 100 to 3 μm uniform width line / interval pattern. Subsequently, paddle development was performed for 70 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. There were no peeled patterns. The film thickness after development was 5.5 μm. Next, this pattern was heated at 350 ° C.
Heat treatment was performed for a time to obtain a 3.6 μm-thick polyimide film pattern.

Example 2 In a 0.5 liter flask equipped with a stirrer, thermometer and Dimroth condenser, 28.66 g of 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride, n-
59.30 g of butyl alcohol was charged and reacted by stirring at 95 ° C. for 5 hours. Excess n-butyl alcohol was distilled off under reduced pressure to obtain 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid di-n-butyl ester. Next, 95.17 g of thionyl chloride and 70.00 g of toluene were charged into the flask and reacted at 40 ° C. for 3 hours. Excessive thionyl chloride is azeotroped with toluene under reduced pressure,
Removed. 186 g of N-methylpyrrolidone are added,
A solution (β) of 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid di-n-butyl dichloride was obtained. Next, 95 g of N-methylpyrrolidone was charged into a 0.5-liter flask equipped with a stirrer, a thermometer, and a Dimroth condenser, and 8.64 of 3,5-diaminobenzoic acid was added.
g, 4.65 g of 4,4′-diaminodiphenyl ether
Was added and stirred and dissolved. Then, 12.66 g of pyridine was added, and while keeping the temperature at 0 to 5 ° C, 3,3 ′, 4,
The solution (β) of 4′-diphenylsulfonetetracarboxylic 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 polyamic acid n-butyl ester having a weight average molecular weight of 29,500 (hereinafter referred to as polymer II).

30.00 g of Polymer II was dissolved in 54.00 g of γ-butyrolactone with stirring, 0.90 g of 1,4-bis (dihydroxymethyl) benzene was added and stirred, and then 4,4′-diaminodiphenylsulfone and naphthoquinone were added. -1,2-diazido-5-sulfonyl chloride with 1
9.00 g of the compound reacted at a molar ratio of / 2 was dissolved. 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 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 to obtain 6.4 μm.
m was obtained as a positive photosensitive resin composition film. This coating has i
Line reduction projection exposure equipment (LD-50 manufactured by Hitachi, Ltd.)
Using 10i), exposure was performed at 700 mJ / cm ² through a mask having a 100 to 3 μm equal-width line / interval pattern. Next, paddle development was performed for 180 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. There were no peeled patterns. The film thickness after development was 5.2 μm. Next, this pattern was heated at 350 ° C.
Heat treatment was performed for a time to obtain a polyimide film pattern having a thickness of 3.5 μm.

Example 3 In a 0.5 liter flask equipped with a stirrer, thermometer and Dimroth condenser, pyromellitic dianhydride 17.4 was placed.
5 g and n-butyl alcohol 59.30 g were charged, and 95
The mixture was stirred and reacted at 5 ° C. for 5 hours. Excess n-butyl alcohol was distilled off under reduced pressure to obtain pyronellitic acid di-n-butyl ester. Next, 95.17 g of thionyl chloride and 70.00 g of toluene were charged into the flask and reacted at 40 ° C. for 3 hours. Excess thionyl chloride was azeotroped with toluene under reduced pressure and removed. 186 g of N-methylpyrrolidone was added to obtain a solution (γ) of di-n-butyl pyromellitic acid dichloride. Next, 95 g of N-methylpyrrolidone was charged into a 0.5-liter flask equipped with a stirrer, a thermometer and a Dimroth condenser, and 19.63 g of bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added. After adding 6.56 g of 4'-diaminodiphenylsulfone and stirring and dissolving, 12.66 g of pyridine is added and the solution of di-n-butyl pyromellitic acid dichloride (γ) is added while maintaining the temperature at 0 to 5 ° C. Was added dropwise over 1 hour, and 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 n-butyl ester having a weight average molecular weight of 17,200 (hereinafter, referred to as polymer III).

30.3 g of Polymer III was added to NMP5
The mixture was dissolved by stirring in 4.00 g, and triphenylsilanol was added in an amount of 0.1 g.
After adding 12 g and further stirring, 6.00 g of a compound obtained by reacting tris (4-hydroxyphenyl) methane and naphthoquinone-1,2-diazido-5-sulfonyl chloride in a molar ratio of 1 / 2.5 was dissolved. Was. This solution is
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-type photosensitive resin composition is spin-coated on a silicon wafer using a spinner, and dried by heating at 90 ° C. for 3 minutes on a hot plate to obtain a 6.4 μm-thick film of the positive-type photosensitive resin composition. I got
An i-line reduction projection exposure apparatus (LD-5010i, manufactured by Hitachi, Ltd.) was applied to this coating film through a mask having a uniform width / interval pattern of 100 to 3 μm to obtain a film of 600 mJ / c.
It was the exposure of m ^2. Next, paddle development was performed for 80 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. There were no peeled patterns. The film thickness after development is 5.
It was 6 μm. Next, this pattern was heat-treated at 350 ° C. for 1 hour in a nitrogen atmosphere to obtain a 3.4 μm-thick polyimide film pattern.

Comparative Example 1 In a 0.5-liter flask equipped with a stirrer, a thermometer and a Dimroth condenser, 24.82 g of 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride, n-
59.30 g of butyl alcohol was charged and reacted by stirring at 95 ° C. for 5 hours. Excess n-butyl alcohol was distilled off under reduced pressure to obtain 3,3 ′, 4,4′-diphenylethertetracarboxylic acid di-n-butyl ester. Next, 95.17 g of thionyl chloride and 70.00 g of toluene were charged into the flask and reacted at 40 ° C. for 3 hours. Excessive thionyl chloride is azeotroped with toluene under reduced pressure,
Removed. 186 g of N-methylpyrrolidone are added,
A solution (δ) of 3,3 ′, 4,4′-diphenylethertetracarboxylic acid di-n-butyl dichloride was obtained. Next, 95 g of N-methylpyrrolidone was charged into a 0.5-liter flask equipped with a stirrer, a thermometer and a Dimroth condenser, and 7.30 of 3,5-diaminobenzoic acid was added.
g, 4,4'-diaminodiphenyl ether, 6.41 g
Was added and stirred and dissolved. Then, 12.66 g of pyridine was added, and while keeping the temperature at 0 to 5 ° C, 3,3 ′, 4,
A solution (δ) of 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, the precipitate was collected, washed, and dried under reduced pressure to obtain a polyamic acid n-butyl ester (hereinafter, referred to as polymer IV).

30.00 g of Polymer IV was added to NMP54.
The compound was stirred and dissolved in 00 g, and 7.50 g of a compound obtained by reacting 2,3,4,4′-tetrahydroxybenzophenone and naphthoquinone-1,2-diazido-5-sulfonyl chloride at a molar ratio of 1/3 was dissolved. . 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 125 ° C. for 3 minutes on a hot plate to give 6.8 μm.
m was obtained as a positive photosensitive resin composition film. This coating has i
Line reduction projection exposure equipment (LD-50 manufactured by Hitachi, Ltd.)
Using 10i), exposure was performed at 1000 mJ / cm ² through a mask having a 100 to 3 μm uniform width line / interval pattern. Subsequently, paddle development was performed for 70 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. 10 μm
The following patterns were peeled. The film thickness after development is 5.0
μm. Next, this pattern was formed under a nitrogen atmosphere for 3 hours.
Heat treatment was performed at 50 ° C. for 1 hour to obtain a 3.2 μm-thick polyimide film pattern.

Comparative Example 2 A photosensitive resin composition was prepared in the same manner as in Example 1 except that 0.90 g of γ-aminopropyltrimethoxysilane was added instead of diphenylsilanediol. Immediately after adding 7.50 g of a compound obtained by reacting 2,3,4,4′-tetrahydroxybenzophenone and naphthoquinone-1,2-diazide-5-sulfonyl chloride at a molar ratio of 1/3 and stirring, the composition was immediately stirred. It became black and insolubles were formed, and did not lead to pattern formation.

As can be seen from the above examples and comparative examples, in the examples of the present invention, the sensitivity to i-line was excellent, and the pattern did not peel off after development. Peeling occurred, and in Comparative Example 2, insolubles were generated during preparation of the photosensitive resin composition, and did not lead to the formation of a pattern.

[0083]

The positive photosensitive resin composition of the present invention has a high exposure sensitivity to i-rays and, in particular, does not peel off a fine pattern during development. Further, the positive photosensitive resin composition of the present invention exhibits the effects of the above invention, and can form a film having excellent heat resistance.

Further, the positive photosensitive resin composition of the present invention comprises:
The effects of the invention are achieved, and the sensitivity is particularly excellent. Further, according to the method for producing a pattern of the present invention, since a relief pattern having high exposure sensitivity to i-rays and particularly without peeling of a fine pattern at the time of development can be obtained, surface protection of a semiconductor element or the like which easily exhibits good characteristics can be obtained. A film, an interlayer insulating film, and the like can be formed.

Further, the electronic component of the present invention is a highly reliable semiconductor device or multilayer wiring board having an interlayer insulating film or a surface protective film having good adhesion after high-temperature heat treatment without peeling of a pattern from a substrate. Becomes

[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.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 101/02 C08L 101/02 G03F 7/004 501 G03F 7/004 501 503 503Z 7/022 7/022 7 / 037 7/037 501 501 7/039 501 7/039 501 601 601 7/40 501 7/40 501 H01L 21/027 H01L 21/30 502R (72) Inventor Masataka Nunomura 4-13 Higashicho, Hitachi City, Ibaraki Prefecture No. 1 Inside the Yamazaki Development Center, Hitachi Chemical Dupont Microsystems Co., Ltd. (72) Inventor Takanori Ansai 4-13-1, Higashimachi, Hitachi City, Ibaraki Prefecture F-term in the Yamazaki Development Center, Hitachi Chemical Dupont Microsystems Co., Ltd. 2H025 AA00 AA10 AA14 AB15 AB16 AC01 AD03 BE00 BE01 BG00 CB25 CB26 CB42 CC06 FA03 FA17 FA29 2H096 AA25 BA10 BA20 EA02 GA08 HA01 JA04 4J002 BC122 CC062 CM021 CM041 EB116 EQ016 EQ036 EV256 EX047 GP03

Claims (8)

[Claims] (1) a polymer having an acidic group, (B) a compound capable of generating an acid by light, and (C) a compound represented by the general formula (I): (Wherein, l is an integer of 1 to 3, R is an alkyl group having 1 to 5 carbon atoms, R ′ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a hydroxyl group, a mercapto group, an alkoxy group having 1 to 5 carbon atoms. A trialkoxysilyl group having a group, a trialkylsilyl group having an alkyl group having 1 to 5 carbon atoms or a general formula (II) A positive-type photosensitive resin composition containing an organic silicon compound represented by the following formula: 2. The positive photosensitive resin composition according to claim 1, wherein the polymer (A) having an acidic group is a polyimide precursor or a polyoxazole precursor. 3. The polymer (A) having an acidic group is represented by the general formula (III): (Wherein, R ¹ represents a tetravalent organic group, R ² represents a divalent organic group having a carboxyl group or a phenolic hydroxyl group, and each R ³ 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 following formula: 4. A compound (B) which generates an acid by light,
The positive photosensitive resin composition according to claim 1, which is a quinonediazide compound. 5. The positive photosensitive resin composition according to claim 1, further comprising (D) a compound having an acid-decomposable group whose solubility in an aqueous alkali solution is increased by an acid-catalyzed reaction. . 6. A compound of the formula (III) wherein R ¹ is a group containing one aromatic ring or two or three aromatic rings are a single bond, an ether bond,
A tetravalent organic group having a chemical structure bonded via at least one bond selected from a 2,2-hexafluoropropylene bond, a sulfone bond, a methylene bond and a carbonyl bond, wherein R ² is one Chemistry in which a group containing an aromatic ring or two to three aromatic rings are bonded via at least one bond selected from a single bond, an ether bond, a 2,2-hexafluoropropylene bond, a methylene bond and a sulfone bond The positive photosensitive resin composition according to claim 3, which is a divalent organic group having a structure and having at least one phenolic hydroxyl group and / or carboxyl group. 7. A step of applying the positive photosensitive resin composition according to any one of claims 1 to 6 on a supporting substrate and drying the composition.
A method for producing a pattern including a step of exposing, a step of developing, and a step of heat treatment. 8. An electronic component having a layer of a pattern obtained by the method according to claim 7.