JP2000250219A - Positive photosensitive resin composition, relief pattern forming method and electronic part - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the positive photosensitive resin composition high in exposure sensitivity to 'i' line and superior in storage stability. SOLUTION: This positive photosensitive resin composition contains (A) a polyimide acid ester, having repeated units, represented by the formula and (B) a compound to be allowed to generate an acid by irradiation with light, and the relief pattern forming method comprises the following steps; coating a substrate with this composition and drying it, patternwise exposing it, developing it, and heat treating it. The relief pattern is obtained by this method as a surface protective film or an interlayer insulating film. In the formula, R1 is a tetravalent organic group; R2 is a divalent organic group, each of 3 R3 is, independently, an alkyl group or an H atom and at least 2 of them are alkyl groups; each of 3 R4 is, independently, an alkyl group or H atom and at least 2 of them are alkyl groups.

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, a method for producing a relief pattern using the composition, and an electronic component, and more particularly, to the surface protection of an electronic component such as a semiconductor element by heat treatment. The present invention relates to a positive photosensitive resin composition which is a polyimide heat-resistant polymer applicable as a film, an interlayer insulating film, and the like, a method for producing a relief pattern using the composition, and an electronic component.

[0002]

2. Description of the Related Art Polyimide is widely used as a surface protective film, an interlayer insulating film and the like of a semiconductor device because of its advantages such as excellent heat resistance and mechanical properties, easy film formation and flattening of the surface. . When polyimide is used as a surface protective film or an interlayer insulating film, a process of forming a through hole or the like is mainly performed 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. is there.

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 and an o-quinonediazide compound (JP-A-2-181149), e. Composition containing polyamic acid ester containing carboxyl group and o-quinonediazide compound
No. 168441) 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 the above c has a problem that the sensitivity is low because the wavelength of light to be exposed is mainly 300 nm or less. Further, the positive photosensitive resin compositions described in d and e have a problem that storage stability is poor.

[0007]

SUMMARY OF THE INVENTION The invention according to claim 1 overcomes the above-mentioned problems of the prior art, has a high exposure sensitivity to i-rays, and has excellent storage stability. Is provided. The invention described in claim 2 is
Another object of the present invention is to provide a positive photosensitive resin composition having excellent heat resistance in addition to the object of the invention described in claim 1. Claim 3
The invention described in (1), in addition to the object of the invention described in claim 1,
An object of the present invention is to provide a positive photosensitive resin composition having excellent sensitivity.

The invention described in claim 4 provides a method for producing a relief pattern having a good shape by using a positive photosensitive resin composition having high exposure sensitivity to i-rays and excellent storage stability. Things. The invention described in claim 5 is to provide an electronic component which is excellent in heat resistance and mechanical properties and has excellent reliability by having a polyimide pattern having a good shape.

[0009]

According to the present invention, there is provided (A) a compound represented by the following general formula (I):

Embedded image (Wherein R ¹ is a tetravalent organic group, R ² is a divalent organic group having a carboxyl group, and three R ³ are each independently an alkyl group or a hydrogen atom, at least two of which are alkyl groups. And three R ^{4 s} are each independently an alkyl group or a hydrogen atom, at least two of which are alkyl groups) and (B) an acid generated by light. The present invention relates to a positive photosensitive resin composition containing a compound.

Further, the present invention provides a compound of the general formula (I) wherein R ¹ is an aromatic group having 2 to 3 single bonds, an ether bond, 2,2-
A tetravalent organic group having a chemical structure bonded through at least one bond selected from a hexafluoropropylene bond, a sulfone bond, a methylene bond and a carbonyl bond, wherein R ² contains one aromatic ring At least one group selected from 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; And has at least one carboxyl group or sulfone group.
The present invention relates to a positive photosensitive resin composition which is a divalent organic group having two or more divalent organic groups. The present invention also relates to a positive photosensitive resin composition wherein the component (B) is an o-quinonediazide compound.

Further, the present invention provides a relief pattern comprising a step of applying the positive photosensitive resin composition according to any of the above on a support substrate, drying, exposing, developing and heating. Related to manufacturing method. Further, the present invention relates to an electronic component having a relief pattern obtained by the above-mentioned manufacturing method as a surface protective film or an interlayer insulating film.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A) used in the positive photosensitive resin composition of the present invention is a polyamic acid ester represented by the general formula (I). By having a carboxyl group in the diamine residue, the polyamic acid ester becomes soluble in an aqueous alkali solution used as a developer. After the exposure, the solubility of the exposed portion in the developer increases due to the change in the component (B), and a difference in the dissolution rate between the exposed portion and the unexposed portion develops, so that a relief pattern can be formed. The alkaline aqueous solution is an alkaline aqueous solution in which components such as tetramethylammonium hydroxide, metal hydroxide, and amine are dissolved in water.

The tetravalent organic group represented by R ¹ in the general formula (I) is a residue capable of forming a polyimide precursor by reacting with a diamine, excluding the carboxyl group of tetracarboxylic acid. Those having 6 to 40 carbon atoms are preferred, and groups containing an aromatic ring (benzene ring, naphthalene ring, etc.) are preferred. The amide bond and the ester bond bonded to the tetravalent organic group represented by R ¹ in the general formula (I) are preferably bonded to the ortho or peri position on the aromatic ring.

The divalent organic group having a carboxyl group represented by R ² in the general formula (I) is a group capable of forming a polyimide precursor by reacting with tetracarboxylic acid or a derivative thereof. More preferably, the diamine compound has 6 to 40 carbon atoms excluding the carboxyl group. 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. Further, it is preferable that 1 to 8 carboxyl groups are present in R2. .

In the general formula (I), R ¹ represents a small number of two or three aromatic rings selected from a single bond, an ether bond, a 2,2-hexafluoropropylene bond, a sulfone bond, a methylene bond and a carbonyl bond. Both are preferably tetravalent organic groups having a chemical structure bonded through a kind of bond, from the viewpoint of stability and mechanical properties and heat resistance of the polyimide polymer after heat treatment.

In the general formula (I), R ² represents one aromatic ring or two or three aromatic rings having a single bond, an ether bond,
Heating is a tetravalent organic group having a chemical structure bonded via at least one bond selected from a hexafluoropropylene bond, a 2,2-propylene bond, a sulfone bond, a methylene bond and a carbonyl bond; It is more preferable from the viewpoint of the mechanical properties and heat resistance of the polyimide polymer after the treatment.

In the general formula (I), of the groups represented by R ³ and R ⁴ , the alkyl group has 1 to 20 carbon atoms.
Is preferred, and an alkyl group having 1 to 8 carbon atoms is more preferred. In the general formula (I), there are three R ³ and R ⁴ , which may be the same or different.

The polyamic acid ester having a repeating unit represented by the above general formula (I) further comprises a compound represented by the following general formula (II)

Embedded image (Wherein R ¹ , R ³ and R ⁴ have the same meanings as in formula (I), and R ⁵ is a divalent organic group having no carboxyl group). You may.

The divalent organic group having no carboxyl group represented by R ⁵ is a residue excluding the amino group of the diamine compound which can react with tetracarboxylic acid or a derivative thereof to form a polyimide precursor. Yes, with 6 carbon atoms
~ 40 are 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.

In the general formula (II), R ⁵ represents one aromatic ring or two or three aromatic rings having a single bond, an ether bond,
A tetravalent organic group having a chemical structure bonded through at least one bond selected from a hexafluoropropylene bond, a sulfone bond, a methylene bond, and a carbonyl bond; It is further preferable in terms of the mechanical properties and heat resistance of the molecule.

The polyamic acid ester having a repeating unit represented by the general formula (I) may optionally have a repeating unit other than the repeating units represented by the general formulas (I) and (II). For example, an ester group (—COO—C (R ₃ ) ₃ and —COO) bonded to R ¹ in the general formula (I) or (II)
And a repeating unit to which a carboxyl group (—COOH) is bonded instead of both or any of —C (R ₄ ) ₃ ).

When the polyamic acid ester having a repeating unit represented by the general formula (I) has a repeating unit represented by the general formula (II), the general formula (I) and the general formula (II)
Is preferably m / (m + n), where m is the number of the former and n is the number of the latter, and is preferably 1.0 to 0.2, and 1.0 to 0.4. More preferably, there is.
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.

In the polyamic acid ester, the total number of the repeating units of the general formulas (I) and (II) is preferably 50 to 100% with respect to the total number of the repeating units of the polyamic acid ester. 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 molecular weight of component (A) is preferably from 3,000 to 200,000 in terms of weight average molecular weight,
00 to 100,000 is more preferable. The weight average molecular weight can be measured by gel permeation chromatography and converted to a value using a standard polystyrene calibration curve to obtain a value.

The polyamic acid ester having a repeating unit represented by the general formula (I) includes a tetracarboxylic diester dichloride represented by the following general formula (III), a diamine compound represented by the following general formula (IV), And a reaction with a diamine compound represented by the following general formula (V).

[0026]

Embedded image (Wherein R ¹ , R ³ and R ⁴ in the formula are the same as in the general formula (I))

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

Embedded image H ₂ N—R ⁵ —NH ₂ (V) (wherein R ⁵ is the same as in the general formula (II))

The tetracarboxylic diester dichloride is represented by the general formula (VIII) obtained by reacting a tetracarboxylic dianhydride represented by the general formula (VI) with an alcohol compound represented by the general formula (VII). It can be obtained by reacting a tetracarboxylic diester with thionyl chloride.

[0028]

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

Embedded image (Where three Xs in the formula are each independently an alkyl group or a hydrogen atom, and at least two are alkyl groups;
Which gives R ³ and R ⁴ of the general formula (I))

Embedded image (Wherein R ¹ , R ³ and R ⁴ in the formula are the same as in the general formula (I))

The compound represented by the general formula (VI) is a tetracarboxylic dianhydride. However, the storage stability of the positive photosensitive resin composition and the heat resistance and mechanical properties of the polyimide polymer after the heat treatment are reduced. From the point, two or three aromatic groups are a single bond,
A carboxylic acid dianhydride having a chemical structure bonded via at least one bond selected from an ether bond, a 2,2-hexafluoropropylene bond, a sulfone bond, a methylene bond and a carbonyl bond is preferred.

Specific examples of these compounds include 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, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, etc. Tetracarboxylic dianhydride can be mentioned. In the present invention, the above acid dianhydrides can be used alone or in combination of two or more.

Specific examples of the alcohol compound represented by the general formula (VII) include 2-propanol and 2-propanol.
Butanol, tert-butyl alcohol, 2-pentanol, 2-methyl-2-butanol, 3-methyl-2-butanol, 2-hexanol, 2-methyl-2-pentanol, 2,3-dimethyl-2-pen Tanol, 2,4
-Dimethyl-2-pentanol, 3-methyl-3-pentanol, 2,3-dimethyl-2-butanol, 3,3
-Dimethyl-2-butanol and the like,
They can be used alone or in combination of two or more.

The compound represented by the general formula (IV) is a diamine having at least one carboxyl group or a sulfone group. However, in view of the heat resistance and mechanical properties of the polyimide polymer after the heat treatment, the aromatic group is an aromatic group. Or a diamine having a chemical structure in which two or three aromatic groups are bonded via at least one bond selected from a single bond, an ether bond, a 2,2-hexafluoropropylene bond, a sulfone bond, and a methylene bond Is preferred. Specific examples of these compounds include 2,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 2,5-diaminoterephthalic acid, bis (4-amino-3-carboxy) Phenyl) methylene, 4,4'-diamino-3,3 '
-Dicarboxybiphenyl, 4,4'-diamino-5
5'-dicarboxy-2,2'-dimethylbiphenyl,
Bis (4-amino-3-carboxyphenyl) methane and the like can be mentioned. These diamine compounds having at least one carboxyl group can be used alone or in combination of two or more.

The compound represented by the above general formula (V) is a diamine. From the viewpoint of heat resistance and mechanical properties of the polyimide polymer after the heat treatment, one aromatic group or two to three aromatic groups is used. Diamine having a chemical structure in which a group is bonded through at least one bond selected from a single bond, an ether bond, a 2,2-hexafluoropropylene bond, a 2,2-propylene bond, a sulfone bond and a methylene bond preferable. Specific examples of these compounds include 4,4'-
Diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-
Examples include naphthalenediamine, bis (3-aminophenoxyphenyl) sulfone, 1,4-bis (4-aminophenoxy) benzene, 4,4'-diamino-2,2'-dimethylbiphenyl, and the like. 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 (VIII) is known. For example, tetracarboxylic dianhydride and an excess of the general formula (VI)
It is obtained by mixing the alcohol compounds shown in I), reacting them by heating, and then removing excess alcohol compounds. Preferred ratio (molar ratio) between carboxylic dianhydride and alcohol compound represented by general formula (VII)
Is in the range of 1/2 to 1/20, and a more preferable ratio is in the range of 1 / 2.5 to 1/10. The preferred reaction temperature is 30 to 130 ° C, and the preferred reaction time is 3 to 24 hours. If necessary, a base catalyst can be used.

Methods for synthesizing tetracarboxylic diester dichloride are known, and are obtained, for example, by reacting tetracarboxylic diester with thionyl chloride. The preferred ratio (molar ratio) of the tetracarboxylic diester to thionyl chloride is in the range of 1 / 0.5 to 1/10,
A more desirable ratio is in the range of 1 / 0.7 to 1/5. The preferred reaction temperature is 0 to 100 ° C, and the preferred reaction time is 1 to 10 hours. When excess thionyl chloride is used in excess of tetracarboxylic diester dichloride, excess thionyl chloride can be removed after the completion of the reaction.

The polyamide ester is prepared by, for example, dissolving a diamine compound represented by the above general formula (IV) or (V) in an organic solvent, and dropwise adding a tetracarboxylic diester dichloride dissolved in the organic solvent. After letting
It is obtained by pouring into a poor solvent such as water, filtering and drying the precipitate. In addition, general formula (IV) and general formula (V)
When dissolving the diamine compound represented by the formula (1) in an organic solvent, a dehydrochlorinating agent such as pyridine may be added. As the organic solvent used for the reaction, for example, N-methyl-2-
Pyrrolidone, N, N-dimethylformamide, N, N-
Dimethylacetamide, dimethylsulfoxide, hexamethylphosphoramide, tetramethylene sulfone, γ-
An aprotic polar solvent such as butyrolactone is used alone or in combination of two or more.

The preferable ratio (molar ratio) of the total amount of the diamine compounds represented by the general formulas (IV) and (V) to the tetracarboxylic diester dichloride is 0.6 / 1 to 1 / l in the former / the latter. 0.6. The preferred reaction temperature is -30 to 40 ° C, and the preferred reaction time is 5 minutes to
10 hours.

The compound which generates an acid by light, which is the component (B) used in the present invention, is a photosensitive agent and has a function of generating an acid and increasing the solubility of the irradiated portion in an aqueous alkaline solution. Things. Examples of the type include an o-quinonediazide compound, an allyldiazonium salt, a diallyliodonium salt, and a triallylsulfonium salt. There is no particular limitation, but an o-quinonediazide compound is preferred because of its high sensitivity.

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, for example, benzoquinone-1,
2-diazide-4-sulfonyl chloride, naphthoquinone-1,2-diazide-5-sulfonyl chloride, naphthoquinone-1,2-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. The preferred ratio of the dehydrochlorination catalyst to o-quinonediazide sulfonyl chloride is 0.95 /
The range is from 1 to 1 / 0.95. The preferred reaction temperature is 0 to 40 ° C, and the preferred reaction time is 1 to 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. The component (B) is preferably used in an amount of 3 to 100 parts by weight, more preferably 10 to 40 parts by weight, based on 100 parts by weight of the component (A) from the viewpoint of the film thickness and sensitivity after development.

The positive photosensitive resin composition of the present invention is obtained by dissolving the components (A) and (B) 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 propylene glycol methyl ether acetate are used alone or in combination of two or more. Although the amount of the solvent is not particularly limited, it is usually used in an amount of 10 to 90% by weight based on the total amount of the resin composition.

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. Examples of the organic silane compound include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, and the like. Can be 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 is formed. Thereafter, irradiation with actinic rays such as ultraviolet rays, visible rays, and radiations is performed through a mask, and then the exposed portions are removed with a developing solution to obtain a positive relief pattern. Since the positive photosensitive resin composition of the present invention is suitable for i-line exposure, i.
Preferably, line exposure is performed.

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 solvent will not evaporate sufficiently,
It tends to contaminate the exposure apparatus and the like. When the drying temperature is high, the o-quinonediazide compound in the film of the positive photosensitive resin composition tends to decompose during drying.

Then, development is performed. As a developing solution, it is preferable to use an alkaline aqueous 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 100
The amount is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on parts by weight. Then, the resulting relief pattern is subjected to a heat treatment at 150 to 450 ° C. to obtain a relief pattern of a heat-resistant polymer having an imide ring or another cyclic group.

The positive photosensitive resin composition of the present invention can be used for electronic parts such as semiconductor devices and multilayer wiring boards. Specifically, surface protective films, interlayer insulating films, multilayer wirings and the like of semiconductor devices. It can be used for forming an interlayer insulating film or the like of a plate. The semiconductor device 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.

An example of the manufacturing process of the semiconductor device of the present invention 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 or a phenol novolak type 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. Window 6A is provided as described above (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 moisture, foreign matter, and the like. However, in the present invention, since a pattern having a good shape can be formed, the obtained semiconductor device has excellent reliability. In the above example, the interlayer insulating film can be formed using the photosensitive polymer composition of the present invention.

[0054]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

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,
48.08 g of propanol, 0.41 of triethylamine
g was stirred and reacted at 80 ° C. for 5 hours. Surplus 2
-Propanol is distilled off under reduced pressure to give 3,3 ', 4
4′-Diphenyl ether tetracarboxylic acid diisopropyl ester was obtained. Next, 95.17 g of thionyl chloride and 70.00 g of toluene were charged into the flask,
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 (α) of 3,3 ′, 4,4′-diphenylethertetracarboxylic acid di-n-butyl ester dichloride.

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, After adding 5.13 g of '-diaminodiphenyl ether and stirring and dissolving, 12.66 g of pyridine was added, and while maintaining the temperature at 0 to 5 ° C,
A solution (α) of 3,3 ′, 4,4′-diphenylethertetracarboxylic acid diisopropyl ester dichloride 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 isopropyl polyamidate (hereinafter referred to as polymer I). The weight average molecular weight of this polymer I was 28200 (a value measured by a gel permeation chromatography method and converted using a standard polystyrene calibration curve).

30.00 g of polymer I and 2, 3, 4,
4'-tetrahydroxybenzophenone and naphthoquinone-1,2-diazido-5-sulfonyl chloride are reduced to 1/3
7.50 g of the compound reacted at a molar ratio of NMP54.
The mixture was dissolved in 00 g 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-type photosensitive resin composition is 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 system (LD-501 manufactured by Hitachi, Ltd.)
Using 0i), exposure was performed at 800 mJ / cm ² through a mask. Next, paddle development was performed for 40 seconds using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide as a developing solution.
After washing with pure water, a relief pattern was obtained. The film thickness after development was 5.5 μm. Next, this pattern was heat-treated at 350 ° C. for 1 hour in a nitrogen atmosphere to obtain a polyimide film pattern having a thickness of 3.6 μm. The above positive photosensitive resin composition was stored at 23 ° C. for 7 days and exposed and developed in the same manner as above to obtain a relief pattern. The film thickness after drying is 6.8μ
m, the film thickness after development was 5.5 μm, and the ratio of undeveloped film remained unchanged.

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 was prepared.
48.08 g of propanol, 0.41 of triethylamine
g was stirred and reacted at 80 ° C. for 5 hours. Surplus 2
-Propanol is distilled off under reduced pressure to give 3,3 ', 4
4′-Diphenylsulfonetetracarboxylic acid diisopropyl ester was obtained. Next, 95.17 g of thionyl chloride and 70.00 g of toluene were charged into the flask,
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 (β) of 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid diisopropyl ester 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 8.64 g of 3,5-diaminobenzoic acid and 4,4'-diamino After adding 4.65 g of diphenyl ether and stirring and dissolving, pyridine 12.
66 g was added, and while maintaining the temperature at 0 to 5 ° C, 3,
A solution (β) of 3 ′, 4,4′-diphenylsulfonetetracarboxylic acid diisopropyl 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 and washed, and then dried under reduced pressure to obtain a polyamic acid isopropyl ester (hereinafter, referred to as “polyamic acid isopropyl ester”).
Polymer II). The weight average molecular weight of Polymer II is 30
700.

9.00 g of a compound obtained by reacting 30.00 g of Polymer II with 4,4'-diaminodiphenyl sulfone and naphthoquinone-1,2-diazido-5-sulfonyl chloride in a molar ratio of 1/2 was converted into 54.00 g of NMP. It was dissolved by 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 is 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 system (LD-501 manufactured by Hitachi, Ltd.)
Exposure was performed at 700 mJ / cm ² through a mask using 0i). Next, paddle development was performed for 40 seconds using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide as a developing solution.
After washing with pure water, a relief pattern was obtained. The film thickness after development was 5.2 μm. Next, this pattern was subjected to a heat treatment at 350 ° C. for 1 hour in a nitrogen atmosphere to obtain a 3.2 μm-thick polyimide film pattern. The above positive photosensitive resin composition was stored at 23 ° C. for 7 days and exposed and developed in the same manner as above to obtain a relief pattern. The film thickness after drying is 5.2μ.
m, the film thickness after development was 3.2 μm, and the undeveloped film ratio did not change.

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, 0.1% of triethylamine.
41 g was charged and stirred at 80 ° C. for 5 hours to react. Excess n-butyl alcohol is distilled off under reduced pressure to obtain 3,
3 ', 4,4'-Diphenylethertetracarboxylic acid di-n-butyl ester was obtained. 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 and 3,3 ', 4,4'-
A solution (δ) of diphenyl ether tetracarboxylic acid di-n-butyl ester 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 g of 3,5-diaminobenzoic acid, 4,4'-diamino 6.41 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,
A solution (δ) of 3 ', 4,4'-diphenylethertetracarboxylic acid di-n-butyl ester dichloride was added dropwise over 1 hour, and 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 (hereinafter, referred to as polymer III). The weight average molecular weight of Polymer III is 273
00.

30.00 g of Polymer III and 2,3,4
4'-tetrahydroxybenzophenone and naphthoquinone-1,2-diazido-5-sulfonyl chloride are reduced to 1/3
7.50 g of the compound reacted at a molar ratio of NMP 5
The mixture was dissolved in 4.00 g 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 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 system (LD-501 manufactured by Hitachi, Ltd.)
Using 0i), exposure was performed at 1000 mJ / cm ² through a mask. 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. The film thickness after development was 5.0 μm. Next, this pattern was subjected to a heat treatment at 350 ° C. for 1 hour in a nitrogen atmosphere, and a film thickness of 3.2 μm
m was obtained as a polyimide film pattern. The above positive photosensitive resin composition was stored at 23 ° C. for 7 days and exposed and developed in the same manner as above to obtain a relief pattern. The film thickness after drying is 5.
The film thickness after development was 0 μm, and the film thickness after development was 1.2 μm.

As can be seen from the above Examples and Comparative Examples, in the Examples of the present invention, the sensitivity to i-ray was excellent and the storage stability was good, but Comparative Example 1 was subjected to storage at 23 ° C. The rate has changed.

[0068]

The positive photosensitive resin composition according to the first aspect has high exposure sensitivity to i-rays and excellent storage stability. The positive photosensitive resin composition according to the second aspect has the effects of the invention according to the first aspect, and is further excellent in heat resistance. The positive photosensitive resin composition according to the third aspect has the effects of the invention according to the first aspect, and is particularly excellent in sensitivity.

According to the method for producing a relief pattern according to the fourth aspect, by using a positive photosensitive resin composition having high exposure sensitivity to i-line and excellent storage stability,
A relief pattern having a good shape can be obtained. The electronic component according to claim 5 is excellent in heat resistance and mechanical properties, and is excellent in reliability by having a polyimide pattern having a good shape.

[Brief description of the drawings]

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

[Explanation of symbols]

 REFERENCE SIGNS LIST 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

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Nagatoshi Fujieda 4-3-1-1, Higashicho, Hitachi City, Ibaraki Prefecture Hitachi Chemical DuPont Microsystems Co., Ltd. Yamazaki Development Center F-term (reference) AD03 BE00 BE01 CB25 FA03 FA17 FA29 5F058 AA10 AC02 AC07 AF04 AG01 AH02

Claims (5)

[Claims] (A) General formula (I) (Wherein R ¹ is a tetravalent organic group, R ² is a divalent organic group having a carboxyl group, and three R ³ are each independently an alkyl group or a hydrogen atom, at least two of which are alkyl groups. And three R ^{4 s} are each independently an alkyl group or a hydrogen atom, at least two of which are alkyl groups) and (B) an acid generated by light. A positive photosensitive resin composition containing a compound. 2. The aromatic group of the formula (I) wherein R ¹ is 2 to 3 is selected from a single bond, an ether bond, a 2,2-hexafluoropropylene bond, a sulfone bond, a methylene bond and a carbonyl bond. Is a tetravalent organic group having a chemical structure bonded through at least one type of bond, wherein R ² is a group containing one aromatic ring or two or three aromatic groups are a single bond, an ether bond, It has a chemical structure linked via at least one bond selected from a 2,2-hexafluoropropylene bond, a 2,2-propylene bond, a sulfone bond, a methylene bond and a carbonyl bond, and has at least one carboxyl group. The positive photosensitive resin composition according to claim 1, wherein the positive photosensitive resin composition is a divalent organic group. 3. The positive photosensitive resin composition according to claim 1, wherein the component (B) is an o-quinonediazide compound. 4. A method for producing a relief pattern, comprising the steps of applying the positive photosensitive resin composition according to claim 1, 2 or 3 onto a support substrate and drying, exposing, developing, and heating. Law. 5. An electronic component comprising a relief pattern obtained by the method according to claim 4 as a surface protective film or an interlayer insulating film.