JPH1184653A - Heat resistant photosensitive polymer composition and production of pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a heat resistant photosensitive polymer compsn. having high sensitivity, capable of shortening development time and ensuring various satisfactory characteristics of a formed film, in particular adhesiveness to a substrate by incorporating a polyimide having specified repeating units, a polyamic acid having specified repeating units and a photo-acid generator. SOLUTION: The heat resistant photosensitive polymer compsn. contains a polyimide having repeating units represented by formula I, a polyamic acid having repeating units represented by formula II and a photo-acid generator. The top of a substrate is coated with the photosensitive polymer compsn. and this compsn. is dried, exposed, developed and heated to produce the objective relief pattern. In the formula I, R<1> is a tetravalent org. group and R<2> is a divalent org. group having a phenolic hydroxyl group. In the formula II, R<3> is a tetravalent org. group, R<4> is a divalent org. group, R<5> is a monovalent org. group and (q) is an integer of >=1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant photosensitive polymer composition and a method for producing a pattern using the composition, and more particularly, to a surface protective film for electronic parts such as semiconductor devices by heat treatment. The present invention relates to a positive heat-resistant photosensitive polymer composition which is a polyimide heat-resistant polymer applicable as an interlayer insulating film and the like, and a method for producing a pattern using the composition.

[0002]

2. Description of the Related Art Polyimide is widely used as a surface protective film and an interlayer insulating film 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,
1. A polyimide precursor composition having a photosensitive group introduced through an ester bond (Japanese Patent Publication No. 52-30207, etc.); Carbonizable or dimerizable or polymerizable polyamic acid by actinic radiation
There is known a composition to which a compound containing a carbon double bond and an amino group and an aromatic bisazide is added (Japanese Patent Publication No. 3-36861).

In using the photosensitive polyimide composition, usually, it is applied on a substrate in a solution state, dried, irradiated with an actinic ray through a mask, and the exposed portion is removed with a developing solution to form a pattern. However, the above compositions 1 and 2 are negative type and use an organic solvent for development. Therefore, in order to switch from an etching process using a positive photoresist to a negative photosensitive polyimide,
There is a problem that it is necessary to change the mask and the developing equipment of the exposure apparatus.

On the other hand, as for the positive type photosensitive polyimide, 3. 3. A polyimide precursor having an o-nitrobenzyl group introduced through an ester bond (JP-A-60-37550); Composition containing a polyimide containing a hydroxy group and an o-quinonediazide compound (JP-A-64-60630)
And Japanese Patent Laid-Open Publication No. 3-209478). However, there is a problem that the sensitivity of the above-mentioned 3 is low because the photosensitive wavelength is mainly 300 nm or less. In the above item 4, there is a problem that the substrate must be pre-treated because the adhesion between the film to be formed and the substrate is poor. As described above, at present, a positive photosensitive polyimide having sufficient characteristics has not been obtained.

[0006]

SUMMARY OF THE INVENTION The present invention overcomes the above-mentioned problems of the prior art. That is, the invention according to claim 1 relates to a positive heat-resistant photosensitive polymer composition having high sensitivity, a short development time, and various characteristics of a formed film, particularly, good adhesion to a substrate. The second aspect of the present invention is to provide a method for producing a pattern having a high sensitivity, a short developing time, and various characteristics of a formed film, particularly, good adhesion to a substrate.

[0007]

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

Embedded image (Wherein, R ¹ represents a tetravalent organic group, and R ² represents a divalent organic group having a phenolic hydroxyl group). A polyimide having a repeating unit represented by (b) a general formula (II)

Embedded image (Wherein, R ³ represents a tetravalent organic group, R ⁴ represents a divalent organic group, R ⁵ represents a monovalent organic group, and q represents an integer of 1 or more). The present invention relates to a heat-resistant photosensitive polymer composition containing a polyamic acid having a repeating unit and (c) a photoacid generator.

The present invention also relates to a method for producing a relief pattern including a step of applying and drying the heat-resistant photosensitive polymer composition on a support substrate, a step of exposing, a step of developing, and a step of heating.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The component (a) in the present invention is a polyimide having a repeating unit represented by the above general formula (I). In the general formula (I), the tetravalent organic group represented by R ¹ is a residue of tetracarboxylic acid, a dianhydride or a derivative thereof, which is a raw material of polyimide or polyimide isoindoloquinazolinedione; Tetravalent aromatic or aliphatic groups are preferred and have 4 to 40 carbon atoms.
Are more preferable, and a tetravalent aromatic group having 4 to 40 carbon atoms is further preferable. As the tetravalent aromatic group,
It is preferable that all of the four bonding sites include an aromatic ring (benzene ring, naphthalene ring, etc.), and all of the four bonding sites are formed from an aromatic ring. These binding sites are divided into two sets of two binding sites, and the two binding sites are preferably located at the ortho or peri position of the aromatic ring. The two sets may be from the same aromatic ring, or may be from separate aromatic rings linked through various bonds.

In the general formula (I), the divalent organic group having a phenolic hydroxyl group represented by R ² is a residue excluding an amino group of a diamine compound having a phenolic hydroxyl group, and is an aromatic group or a divalent organic group. Aliphatic groups are preferred, those having 2 to 40 carbon atoms are more preferred, and those having 2 carbon atoms are preferred.
More preferred are aromatic groups of from 40 to 40. Here, the aromatic group includes an aromatic ring (benzene ring, naphthalene ring, etc.), and it is preferable that the two binding sites are directly from the aromatic ring. May also come from different aromatic rings. Further, it is preferable that the phenolic hydroxyl group has 1 to 8, and those which are directly bonded to the aromatic ring are also preferable.

The component (a) may have a structural unit other than the repeating unit represented by the general formula (I). For example, the following general formula (III)

Embedded image (Wherein, R ⁶ represents a tetravalent organic group, and R ⁷ represents a divalent organic group having no phenolic hydroxyl group).

In the general formula (III), 4 represented by R ⁶
The description of the valent organic group is the same as that of R ¹ . Further, in formula (III), the description of the divalent organic group having no phenolic hydroxyl group represented by R ^7, except that it does not have a phenolic hydroxyl group in the description of the R ^2, the R ² Description Is the same as

In the component (a), the ratio of the repeating units of the general formulas (I) and (III) is m / (m + n), where m is the number of the former and n is the number of the latter. 0.2 to 1, more preferably 0.4 to 1. If this value is less than 0.2, the solubility in an aqueous alkaline solution tends to be poor.

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. Molecular weight is measured by gel permeation chromatography,
The value can be obtained by conversion using a standard polystyrene calibration curve. In the general formulas (I) and (III), the groups represented by R ¹ , R ² , R ⁶ and R ⁷ may be the same or different.

In the present invention, the component (a) is, for example,
Tetracarboxylic dianhydride, a diamine compound having a phenolic hydroxyl group, and optionally a diamine compound having no phenolic hydroxyl group to form a polyamic acid, and then obtained by an imidization reaction by heating. it can. In this case, the reaction is preferably performed in an organic solvent.

The tetracarboxylic dianhydride includes:
For example, pyromellitic dianhydride, 3,3 ', 4,4'-
Biphenyltetracarboxylic dianhydride, 2,3,3 ',
4'-biphenyltetracarboxylic dianhydride, 2,
2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyl ether tetracarboxylic dianhydride Anhydride, 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,2,2
3,4-cyclopentanetetracarboxylic 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, 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 3 Aromatic tetracarboxylic diacids such as 3,3 ', 4,4'-tetraphenylsilanetetracarboxylic dianhydride and 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride Are preferred, and these can be used alone or in combination of two or more.

Examples of the diamine having a phenolic hydroxyl group include 1,3-diamino-4-hydroxybenzene, 1,3-diamino-5-hydroxybenzene and 3,3'-diamino-4,4'-diamine. 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) ether, bis (4-amino-3-hydroxyphenyl) ether, bis (3- Amino-4-hydroxyphenyl) hexafluoropropane, bis (4-
Aromatic diamine compounds such as (amino-3-hydroxyphenyl) hexafluoropropane are preferable, and these are used alone or in combination of two or more.

Examples of the diamine having no phenolic hydroxyl group include, for example, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diamine
Diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, benzine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy)
Phenyl] ether, aromatic diamine compounds such as 1,4-bis (4-aminophenoxy) benzene,
These can be used alone or in combination of two or more.

In addition, 4,4'-
Diaminodiphenyl ether-3-sulfonamide,
3,4'-diaminodiphenyl ether-4-sulfonamide, 3,4'-diaminodiphenyl ether-3 '
-Sulfonamide, 3,3'-diaminodiphenylether-4-sulfonamide, 4,4'-diaminodiphenylether-3-carboxamide, 3,4'-diaminodiphenylether-4-carboxamide, 3,4 '
Diamine compounds having a sulfonamide group or a carboxamide group, such as -diaminodiphenyl ether-3'-carboxamide, 3,3'-diaminodiphenyl ether-4-carboxamide, can be used alone or in combination of two or more. Is preferably used in an amount of 15 mol% or less based on the total amount of the diamine compound.
More preferably, it is used in a range of 0 mol% or less.

A method for synthesizing the polyamic acid is known, and is obtained, for example, by reacting the tetracarboxylic dianhydride with the diamine compound in a solution. The ratio (molar ratio) of the tetracarboxylic dianhydride to the diamine compound is preferably in the range of 1 / 0.7 to 0.7 / 1 for the former / the latter, and is preferably 1 / 0.8 to 0.8 /. More preferably, it is in the range of 1. Reaction temperature is 20-100 ° C
Is preferable, and the reaction time is preferably 1 to 24 hours.

As the solvent used in the reaction, for example, N
Preferred are aprotic polar solvents such as -methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and dimethylsulfoxide, and these are used alone or in combination of two or more.

A method of converting a polyamic acid into a polyimide by heating is known. For example, a polyamic acid synthesized in an organic solvent is heated in the presence of xylene or the like, and water generated by the imidization reaction is boiled with xylene. After removal, it is poured into a poor solvent such as water, and the precipitate is obtained by filtration and drying. The reaction temperature is preferably from 150 to 200C, and the reaction time is preferably from 1 to 10 hours.

When a diamine compound having no phenolic hydroxyl group is used in combination, the ratio of the diamine compound having a phenolic hydroxyl group to the diamine compound having no phenolic hydroxyl group is 20 to 100 mol%, and the latter is 80 to 80 mol%.
It is preferably used such that the total amount is 100 mol% at 0 mol%, the former is 40 to 100 mol%, and the latter is 60 to 100 mol%.
More preferably, it is used so that the total amount is 0 mol% to 100 mol%. The former diamine compound is used for imparting solubility of the polyimide to an aqueous alkali solution. If the content is less than 20 mol%, sensitivity tends to decrease and development time tends to be long.

The component (b) in the present invention is a polyamic acid having a siloxane structure having a repeating unit represented by the general formula (II). In the general formula (II), the tetravalent organic group represented by R ³ is a residue of tetracarboxylic dianhydride which is a raw material of polyimide or polyimide isoindoloquinazolinedione, and is a tetravalent aromatic group. A group or an aliphatic group is preferable, one having 4 to 40 carbon atoms is more preferable, and a tetravalent aromatic group having 4 to 40 carbon atoms is further preferable. The tetravalent aromatic group preferably includes an aromatic ring (a benzene ring, a naphthalene ring, etc.), and all four binding sites are formed from an aromatic ring. Preferably, these binding sites are divided into two sets of two binding sites, and the two binding sites are located on adjacent carbons of the aromatic ring (ie, those located at the ortho position). The two sets may be from the same aromatic ring, or may be from separate aromatic rings linked through various bonds.

In the general formula (II), the portion sandwiched between two R ⁴ is a residue excluding the amino group of the silicone diamine compound, and this portion preferably has 6 to 40 carbon atoms as a whole. . The divalent organic group represented by R ⁵ is preferably a group having 1 to 10 carbon atoms,
The alkylene group and the phenylene group having the number of carbon atoms are preferred, and two R ^{5 's} may be the same or different. As the monovalent organic group represented by R ⁶ ,
An organic group having 1 to 5 carbon atoms is preferable, and an alkyl group or a phenyl group having the above carbon number is preferable.

The component (b) may have a structural unit other than the repeating unit represented by the general formula (II). For example, the following general formula (IV)

Embedded image (Wherein, R ⁸ represents a tetravalent organic group, and R ⁹ represents a divalent organic group).

In the general formula (IV), 4 represented by R ⁸
The description of the valent organic group is the same as the description of R ¹ in the general formula (I). Further, the divalent organic group represented by R ⁹ is a residue of a diamine compound serving as a raw material of polyimide or polyimide isoindoloquinazolinedione. In the description of R ² in the general formula (I), a carboxyl group or a phenol The same is true except that it may not have a hydroxyl group.

In the component (b), the ratio of the repeating units of the general formulas (II) and (IV) is 0 / (o + p) when the former number is o and the latter number is p, and is 0. 0.3 to 1, more preferably 0.4 to 1. If this value is less than 0.3, the adhesiveness to the substrate tends to decrease.

The molecular weight of the component (b) is preferably 1,000 to 100,000 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. In addition, in a plurality of repeating units of the general formulas (II) and (IV), R ⁴ , R ⁵ , R ⁶ , R ⁸ and R ⁹
May be the same or different.

In the present invention, the component (b) is tetracarboxylic dianhydride, represented by the following general formula (V):

Embedded image (Wherein R ⁴ , R ⁵ and q are the same as those in the general formula (II))
Can be obtained by reacting a diamine compound represented by the formula (1) and other diamine compounds as required in a solution.
As the tetracarboxylic dianhydride, those described above and the like are used alone or in combination of two or more.

As the diamine compound represented by the general formula (V), for example,

Embedded image And the like.

As a commercially available product, in the general formula (V), when R ⁴ is both a trimethylene group and R ⁵ is a methyl group, q is 1; About 20, about 30 on average, and about 50 on average, LP-7100 and X-
22-161AS, X-22-161A, X-22-1
61B, X-22-161C and X-22-161E
(All manufactured by Shin-Etsu Chemical Co., Ltd., trade names) are preferred. Examples of other diamine compounds include the diamine compounds described in the description of the component (a), and these may be used alone or in combination of two or more.

As the solvent used in the reaction, for example, N
Aprotic polar solvents such as -methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphoramide, tetramethylenesulfone, γ-butyrolactone, and the like; Or in combination of two or more.

In the production of the component (b), preferably, the diamine compound is first dissolved in the above-mentioned aprotic solvent, and then tetracarboxylic dianhydride is added.
Stir while maintaining the temperature at 0 ° C. or lower, more preferably around room temperature or lower. The preferred mixing ratio (molar ratio) of the diamine compound represented by the general formula (V) to the other diamine compound is in the range of 7/3 to 1/0 in the former / the latter. The preferred compounding ratio (molar ratio) of all diamine compounds to tetracarboxylic dianhydride is in the range of 0.8 / 1 to 1 / 0.8, more preferably 0.9 / 1 to 1 / 0.9. Range. The reaction time is preferably 3 to 24 hours.

In the heat-resistant photosensitive polymer composition of the present invention, the amount of the component (b) is determined based on the adhesion between the formed film and the substrate and the allowable width of the residual film ratio. The amount is preferably 1 to 50 parts by weight, more preferably 2 to 20 parts by weight with respect to parts by weight.

The photoacid generator as the component (c) used in the present invention is a photosensitizer, and generates an acid upon irradiation with light.
An o-quinonediazide compound which has a function of increasing the alkali solubility of the irradiated portion, and is not particularly limited, is preferably an o-quinonediazide compound which changes to a 3-indenecarboxylic acid type by light irradiation, because of its high effect. o-
The quinonediazide compound can be obtained, for example, 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 the o-quinonediazide sulfonyl chloride 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,
10-dimethylindeno [2,1-a] indene, tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane and the like can be used.

Examples of the amino compound include 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 can be used.

The o-quinonediazidosulfonyl chloride and the hydroxy compound and / 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. Preferably. The preferred ratio between the dehydrochlorination catalyst and o-quinonediazide sulfonyl chloride is 0.95.
/ 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, 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 hydrogen carbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, pyridine and the like.

In the heat-resistant photosensitive polymer composition of the present invention, the amount of the component (c) is determined based on the difference in dissolution rate between the exposed and unexposed portions and the allowable range of sensitivity. The amount is preferably 5 to 100 parts by weight, more preferably 10 to 40 parts by weight with respect to parts by weight.

The heat-resistant photosensitive polymer composition of the present invention can be obtained by dissolving the components (a), (b) and (c) in a solvent. Examples of the solvent include N-methyl-2-pyrrolidone, N, N-dimethylformamide,
Aprotic polar solvents such as N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphoramide, tetramethylene sulfone, and γ-butyrolactone are preferred, and these may be used alone or in combination of two or more.

The heat-resistant photopolymer composition of the present invention comprises
Further, if necessary, an organic silane compound or an aluminum chelate compound can be contained as an adhesion aid. Examples of the organic silane compound include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, and the like. Can be

As the aluminum chelate compound, for example,
Tris (acetylacetonate) aluminum, acetyl acetate aluminum diisopropylate and the like can be mentioned. When using an adhesion aid, component (a) 100
0.1 to 20 parts by weight, preferably 1 to 20 parts by weight,
10 parts by weight is more preferred.

The heat-resistant photosensitive polymer composition of the present invention can be formed into a polyimide relief pattern through the steps of coating and drying on a supporting substrate, exposing, developing, and heating. . In the step of coating on a supporting substrate and drying, the heat-resistant photosensitive polymer composition is coated on a supporting substrate such as a glass substrate, a semiconductor, a metal oxide insulator (eg, TiO ₂ , SiO ₂ ), or silicon nitride. After spin coating using a spinner or the like, drying is performed using a hot plate, an oven, or the like.

Next, in the exposure step, the photosensitive polymer composition coated on the supporting substrate is irradiated with actinic rays such as ultraviolet rays, visible rays and radiation through a mask. In the developing step, a relief pattern is obtained by removing the exposed portion with a developing solution. Preferred examples of the developer include aqueous alkali solutions such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine and tetramethylammonium hydroxide. The base concentration of these aqueous solutions is 0.
The content is preferably 1 to 10% by weight. Further, an alcohol or a surfactant may be added to the above-mentioned developer for use. Each of these may be added in an amount of preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the developer.

Then, in the heat treatment step, the obtained relief pattern is preferably subjected to a heat treatment at 150 to 450 ° C. to obtain a heat-resistant polyimide relief pattern having an imide ring or another cyclic group.

[0048]

The present invention will be described below with reference to examples. Example 1 N-methyl-2-pyrrolidone 1 was placed in a 0.5 liter flask equipped with a stirrer, thermometer and Dimroth condenser.
96 g and xylene 48 g were charged, and bis (3-amino-4
-Hydroxyphenyl) hexafluoropropane 21.
After 98 g (0.06 mol) and 9.94 g (0.03 mol) of 4,4'-diaminodiphenylsulfone were added and dissolved by stirring, 3,3 ', 4,4'-biphenylsulfonetetracarboxylic acid dicarboxylic acid was added. 35.82 g (0.10 mol) of anhydride was added, and stirring was continued for 3 hours to obtain a polyamic acid solution.

Next, a moisture meter was attached to the flask, and
After heating at 60 ° C. for 2 hours, water generated by the imidization reaction is removed by azeotropic distillation with xylene. After cooling, the solution is poured into 3 liters of water, and the precipitate is collected, washed, and dried under reduced pressure. A polyimide was obtained.

In a 0.5-liter flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a Dimroth condenser, N-
142 g of methyl-2-pyrrolidone was charged, 24.85 g (0.1 mol) of a silicone diamine compound (LP7100, manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and the mixture was stirred. Next, 35.83 g of 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride (0.13 g) was added to the solution.
Mol), and the mixture was stirred and reacted at 25 ° C. for 8 hours. The solution was poured into 1.5 liters of water, the precipitate was collected, washed, and dried under reduced pressure to obtain a polyamic acid.

Orthoquinone diazide compound 2 obtained by reacting 15.00 g of polyimide, 0.75 g of polyamic acid, and reacting tris (4-hydroxyphenyl) methane with naphthoquinone-1,2-diazido-5-sulfonyl chloride in a molar ratio of 1/3. 0.25 g of γ-butyrolactone 45.0
The mixture was stirred and dissolved in 0 g. This solution was filtered under pressure using a Teflon filter having a pore size of 3 μm to obtain a photosensitive polymer composition.

The obtained photosensitive polymer composition was spin-coated on a silicon wafer using a spinner, and dried by heating at 110 ° C. for 3 minutes on a hot plate to obtain a coating film of 5 μm. Using a PLA (manufactured by Canon Inc.) as an exposure machine, 100 to 500 mJ / cm ²
Was exposed. Next, paddle development was performed for 40 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. By pattern observation, the proper exposure is 250 mJ / cm ²
It was determined. The obtained relief pattern was heated at 350 ° C. for 1 hour under a nitrogen atmosphere to obtain a polyimide film pattern. The evaluation of the adhesiveness between the polyimide film and the substrate was performed by the crosscut tape method (JIS K5400).
00/100 (0/100 is all peeled, 100/100
Represents no peeling).

Example 2 N-methyl-2-pyrrolidone 1 was placed in a 0.5 liter flask equipped with a stirrer, thermometer and Dimroth condenser.
64 g and xylene 40 g were charged and bis (3-amino-4
-Hydroxyphenyl) sulfone 14.02 g (0.0
5 mol), 4,4'-diaminodiphenylsulfone 1
After adding 2.42 g (0.05 mol) and stirring and dissolving, 27.92 g (0.09 mol) of 3,3 ′, 4,4′-biphenylethertetracarboxylic dianhydride was added. Stirring was continued for an hour to obtain a polyamic acid solution.

Next, a moisture meter was attached to the flask, and 1
After heating at 60 ° C. for 2 hours, water generated by the imidization reaction is removed by azeotropy with xylene. After cooling, the solution is poured into 1.5 liter of water, and the precipitate is collected, washed, and dried under reduced pressure. Thus, a polyimide was obtained.

15.00 g of this polyimide, 0.75 g of the polyamic acid prepared in Example 1, tris (4-hydroxyphenyl) methane and naphthoquinone-1,2-diazide-5-sulfonyl chloride in a molar ratio of 1/3. 2.25 g of the reacted compound was added to N-methylpyrrolidone.
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 photosensitive polymer composition. The obtained photosensitive polymer composition is spin-coated on a silicon wafer using a spinner,
Heating and drying was performed at 10 ° C. for 3 minutes to obtain a coating film of 5 μm.
PLA (manufactured by Canon Inc.) as an exposure machine on this coating film
Was exposed through a mask at 100 to 500 mJ / cm ² . Subsequently, paddle development was performed for 30 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. By pattern observation, the proper exposure was determined to be 250 mJ / cm ² . The obtained relief pattern is placed in a nitrogen atmosphere at 350
Heat treatment was performed at 1 ° C. for 1 hour to obtain a polyimide film pattern. Adhesion between the polyimide film and the substrate was 100/100 by a crosscut tape method (JIS K5400).

Comparative Example 1 15.00 g of the polyimide obtained in Example 1, tris (4-hydroxyphenyl) methane and naphthoquinone-
2.25 g of a compound obtained by reacting 1,2-diazide-5-sulfonyl chloride at a molar ratio of 1/3 was dissolved under stirring in 45.00 g of γ-butyrolactone. This solution was filtered under pressure using a Teflon filter having a pore size of 3 μm to obtain a photosensitive polymer composition. The obtained photosensitive polymer composition was spin-coated on a silicon wafer using a spinner, and dried by heating at 80 ° C. for 3 minutes on a hot plate to obtain a 6 μm coating film. Using a PLA (manufactured by Canon Inc.) as an exposure machine, 100 to 500 mJ / cm ²
Was exposed. Next, paddle development was performed for 40 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. By pattern observation, proper exposure is 300 mJ / cm ²
It was determined. The obtained relief pattern was heated at 350 ° C. for 1 hour under a nitrogen atmosphere to obtain a polyimide film pattern. The adhesiveness between the polyimide film and the substrate was 0/100 by a crosscut tape method (JIS K5400).

[0057]

The heat-resistant photosensitive polymer composition according to claim 1 has high sensitivity, can shorten the developing time, and has good properties of the formed film, particularly good adhesion to the substrate. According to the method for producing a pattern according to the second aspect, the sensitivity is high, the development time can be shortened, and various characteristics of the formed film, particularly, good adhesion to a substrate are provided. A surface protective film and an interlayer insulating film of a semiconductor element or the like can be formed.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/40 501 G03F 7/40 501 H01L 21/027 H01L 21/312 B 21/312 H05K 3/28 D H05K 3/28 3 / 46 T 3/46 H01L 21/30 502R 571 (72) Inventor Shun-ichiro Uchimura 4-3-1-1, Higashicho, Hitachi City, Ibaraki Prefecture Inside the Yamazaki Plant of Hitachi Chemical Co., Ltd.

Claims (2)

[Claims] (A) General formula (I) (Wherein, R ¹ represents a tetravalent organic group, and R ² represents a divalent organic group having a phenolic hydroxyl group). (B) a polyimide having a repeating unit represented by the following general formula (II): Formula 2 (Wherein, R ³ represents a tetravalent organic group, R ⁴ represents a divalent organic group, R ⁵ represents a monovalent organic group, and q represents an integer of 1 or more). A heat-resistant photosensitive polymer composition comprising a polyamic acid having a repeating unit and (c) a photoacid generator. 2. A step of applying and drying the heat-resistant photosensitive polymer composition according to claim 1 on a support substrate,
A method for producing a pattern including a developing step and a heat treatment step.