JP2002169286A - Photosensitive polymer composition, method for manufacturing pattern and electronic parts - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alkali developing negative heat-resistant photosensitive polymer composition which can be used under the conditions of the developer temperature (at 23 deg.C) adopted usually and the concentration of the developer usually used for the manufacture of semiconductors (e.g. with 2.38% tetramethylammonium hydroxide solution), to provide a method for manufacturing a pattern and to provide electronic parts having excellent reliability by using the above photosensitive polymer composition. SOLUTION: The photosensitive polymer composition contains (a) a polyimide precursor having the repeating unit expressed by general formula (I), (b) a compound which produces acid by light and (c) a compound which crosslinks with the component (a) in the presence of an acid. In the formula, R1 is a bivalent organic group, R2 is a bivalent organic group having a phenolic hydroxyl group, each of two R3s is independently a hydrogen atom or monovalent aliphatic group. The composition is used for manufacturing a pattern and for the electronic parts.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive polymer composition, a method for producing a pattern using the composition, and an electronic component. More specifically, the present invention relates to a surface protection film for an electronic component such as a semiconductor device by heat treatment. The present invention relates to a negative photosensitive polymer composition which is a heat-resistant polymer applicable as 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 and an interlayer insulating film of a semiconductor element because of its advantages such as excellent heat resistance and mechanical properties, easy film formation, and a flat surface. I have. When polyimide is used as a surface protective film or an interlayer insulating film, one method of forming a through hole or the like is etching using a positive photoresist. However, this method has a problem that the process involves the application 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 heat-resistant composition, a polyimide precursor composition having a photosensitive group introduced through an ester bond (Japanese Patent Publication No. 52-30207, etc.), a carbonic acid which can be dimerized or polymerized with polyamic acid by actinic radiation. A composition containing a compound containing a carbon double bond and an amino group and an aromatic bisazide (Japanese Patent Publication No. 3-36861, etc.) is known.

When using a photosensitive heat-resistant composition, it is usually applied in a solution state on a substrate, dried, irradiated with actinic rays through a mask, and unexposed portions are removed with a developer to form a pattern. I do. However, the above two compositions use an organic solvent for development. Therefore, in order to switch from the etching process using a positive photoresist to a negative photosensitive heat-resistant material, there is a problem that a change in developing equipment is required.

Therefore, a negative photosensitive heat-resistant composition which can be developed with an aqueous alkali solution has been studied, for example, an ester of a polyamic acid with an alcohol containing a phenolic hydroxyl group,
A composition containing a compound that generates an acid by light and a compound that crosslinks a polyimide with an acid (JP-A-10-30739)
No. 3), a composition containing a phenolic hydroxyl group-containing polyimide, a compound that generates an acid by light, and a compound that crosslinks the polyimide with an acid (A New Negati)
ve-Type Photosensitive Po
lymide Based on Poly (hyd
roxyimide), cross-Link
r, and a PhotoacidGenerate
or, M. Ueda, et al, Macrom
olecules 1996, 292 6427-6
431) are known. However, in these compositions, the polymer hardly dissolves in an alkali developing solution, and the developing time is longer with 2.38% tetramethylammonium hydroxide, which is usually used in semiconductor manufacturing. There are issues that must be addressed.
As described above, at present, an alkali-developable negative photosensitive polymer composition having good practicality has not been obtained.

[0006]

SUMMARY OF THE INVENTION The present invention overcomes the above-mentioned problems of the prior art. That is, the present invention provides a developer concentration (e.g.,
(2.38% tetramethylammonium hydroxide solution) to provide a method for producing an alkali-developing negative heat-resistant photosensitive polymer composition and a pattern which can be used at a commonly used developer temperature (23 ° C.). It is. Further, the present invention provides an electronic component having excellent reliability by using the above-mentioned photosensitive polymer composition.

[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 divalent organic group, R ² represents a divalent organic group having a phenolic hydroxyl group, and two R ³ each independently represent a hydrogen atom or a monovalent aliphatic group. A) a polyimide precursor having a repeating unit represented by formula (b), (b) a compound capable of generating an acid by light, and (c) the presence of an acid.
The present invention relates to a photosensitive polymer composition containing a compound that undergoes a crosslinking reaction with a component.

The present invention also relates to the above photosensitive polymer composition, wherein the component (c) is a compound having an epoxy group. The present invention also relates to the above photosensitive polymer composition, wherein the component (c) is a compound having a methylol group. The present invention also relates to the above photosensitive polymer composition, wherein the component (c) is a compound having an alkoxymethyl group.

The present invention also relates to a photosensitive polymer composition wherein the component (c) is a compound further having a phenolic hydroxyl group. The present invention also relates to a method for producing a pattern, comprising a step of applying and drying the photosensitive polymer composition according to any of the above on a support substrate, a step of exposing, a step of developing, and a step of heating. Furthermore, the present invention relates to an electronic component having a pattern obtained by the above-mentioned manufacturing method as a surface protective film or an interlayer insulating film.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The polyimide precursor as the component (a) of the present invention has a phenolic hydroxyl group and is soluble in an aqueous alkali solution used as a developer. In the present invention, the acid generated from the component (b) upon exposure causes the component (c) to undergo a crosslinking reaction with the component (a), thereby lowering the dissolution rate of the exposed part and causing a difference in dissolution rate from the unexposed part. A pattern can be formed. Further, by heating as required, the crosslinking reaction between the component (a) and the component (c) can be accelerated. The alkaline aqueous solution is an aqueous solution exhibiting alkalinity in which tetramethylammonium hydroxide, metal hydroxide, amine and the like are dissolved in water. The component (a) becomes a heat-resistant surface protective film or interlayer insulating film by heat treatment after forming a relief-shaped pattern.

In the general formula (I) showing the structure of the repeating unit of the polyimide precursor (a), the tetravalent organic group represented by R ¹ reacts with a diamine to form a polyimide precursor. Is a residue of a tetracarboxylic acid, a dianhydride or a derivative thereof, which is preferably a tetravalent aromatic group or an aliphatic group, and has 4 to 40 carbon atoms.
Are more preferable, and a tetravalent aromatic group having 4 to 40 carbon atoms is further preferable. An aromatic group refers to a group containing an aromatic ring (benzene ring, naphthalene ring, etc.). As the tetravalent aromatic group, one in which all four binding sites are present on an aromatic ring is preferable. 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 present on the same aromatic ring or may be present on 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 phenol capable of reacting with a carboxylic acid compound or a derivative thereof to form a polyimide precursor structure. It is a residue excluding the amino group of the diamine having a hydroxyl group, and is preferably an aromatic group, and more preferably an aromatic group having 2 to 40 carbon atoms. Here, as the aromatic group, those in which two bonding sites of an amino group are directly present on an aromatic ring are preferable. In this case, even though the two bonding sites are present on the same aromatic ring, different aromatic rings are used. May be present. The phenolic hydroxyl group is 1 to 8
It is preferable that these are also directly bonded to the aromatic ring.

In the general formula (I), R ³ is a hydrogen atom or a monovalent aliphatic group, preferably an aliphatic group having 1 to 20 carbon atoms.

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

In the present invention, the component (a) is, for example,
It can be obtained by reacting a tetracarboxylic diester dihalide (chloride, bromide or the like), a diamine having a phenolic hydroxyl group, and, if necessary, a diamine having no phenolic hydroxyl group. in this case,
The reaction is preferably performed in an organic solvent in the presence of a dehalogenating agent. The tetracarboxylic diester dihalide is preferably tetracarboxylic diester dichloride. The tetracarboxylic diester dichloride can be obtained by reacting a tetracarboxylic diester obtained by reacting a tetracarboxylic dianhydride with an alcohol compound and thionyl chloride.

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.

The alcohol used as a raw material of the tetracarboxylic diester includes, for example, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, isobutyl alcohol, 1-pentanol, 2-pentanol, Alcohols such as pentanol, 3-pentanol, isoamyl alcohol, 1-hexanol, 2-hexanol, and 3-hexanol are preferred, and these can be used alone or in combination of two or more.

Further, as the diamine having a phenolic hydroxyl group, for example, 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) 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)
Aromatic diamines such as -hydroxyphenyl) hexafluoropropane and bis (4-amino-3-hydroxyphenyl) hexafluoropropane are preferred, and these are used alone or in combination of two or more.

Further, the diamine having no phenolic hydroxyl group includes, for example, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane,
4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, benzine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-
Aminophenoxyphenyl) propane, bis (3-aminophenoxyphenyl) propane, 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.

Further, 2,5-diaminobenzoic acid, 3,4
-Diaminobenzoic acid, 3,5-diaminobenzoic acid, 2,
5-diaminoterephthalic acid, bis (4-amino-3-carboxyphenyl) methylene, bis (4-amino-3-
Carboxyphenyl) ether, 4,4'-diamino-
Diamines having a carboxyl group such as 3,3'-dicarboxybiphenyl and 4,4'-diamino-5,5'-dicarboxy-2,2'-dimethylbiphenyl can be used alone or in combination of two or more. When used in combination, these are preferably used in an amount of 15 mol% or less, more preferably 10 mol% or less, based on the total amount of the diamine compound.

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 '
Diamines having a sulfonamide group or a carboxamide group such as -diaminodiphenyl ether-3'-carboxamide and 3,3'-diaminodiphenyl ether-4-carboxamide can be used alone or in combination of two or more. It is preferably used in an amount of 15 mol% or less, more preferably 10 mol% or less, based on the total amount of the diamine compound.

The method for synthesizing the tetracarboxylic diester compound is, for example, obtained by mixing the tetracarboxylic dianhydride and the alcohol compound in an organic solvent in the presence of a base. The ratio (molar ratio) of the tetracarboxylic dianhydride to the alcohol compound is preferably in the range of 1/2 to 1 / 2.5 for the former / latter, and most preferably 1/2. Further, the ratio (molar ratio) of the tetracarboxylic dianhydride and the base is preferably in the range of 1 / 0.001 to 1/3 in the former / latter, and is preferably 1 / 0.005 to 1/2. Is more preferable. The reaction temperature is preferably from 10 to 60C, and the reaction time is preferably from 3 to 24 hours.

A method for synthesizing tetracarboxylic diester dichloride is known, and is obtained, for example, by reacting dicarboxylic acid or tetracarboxylic diester dissolved in an organic solvent dropwise with thionyl chloride. The ratio (molar ratio) of dicarboxylic acid or tetracarboxylic acid diester to thionyl chloride is preferably in the range of 1 / 1.1 to 1 / 2.5 for the former / latter and 1 / 1.4 to 1/2. .2 is more preferable. Reaction temperature is -20 to 40 ° C
Is preferable, and the reaction time is preferably 1 to 10 hours.

The copolymer of the polyimide precursor is, for example,
The diamine having a phenolic hydroxyl group and a dehalogenating agent such as pyridine are dissolved in an organic solvent, and a mixture of tetracarboxylic diester dihalide dissolved in the organic solvent is dropped and reacted, and then into a poor solvent such as water. It is obtained by charging, filtering off the precipitate and drying. The ratio (molar ratio) of the total amount of the diamine to the total amount of the tetracarboxylic acid diester dihalide is 0.6 / 1 to 1/0.
6 is preferable, and the range of 0.7 / 1 to 1 / 0.7 is more preferable. The reaction temperature is preferably -20 to 40C,
The reaction time is preferably 1 to 10 hours. As for the ratio of the total amount of the dehalogenating agent and the tetracarboxylic diester dihalide, the former / the latter (molar ratio) is 1.8 / 1 to 2.2 / 1.
Is more preferable, and the range of 1.9 / 1 to 2.1 / 1 is more preferable.

For the polyimide precursor, for example, the above-mentioned diamine having a phenolic hydroxyl group and a dehalogenating agent such as pyridine are dissolved in an organic solvent, and a tetracarboxylic diester dihalide dissolved in the organic solvent is dropped and reacted. Thereafter, it is obtained by pouring into a poor solvent such as water, filtering and drying the precipitate.

The compound which generates an acid by light, which is the component (b) used in the present invention, has a function of generating an acid and crosslinking the component (c). Examples of the type include triarylsulfonium salts, diaryliodonium salts, nitrobenzyl sulfonic acid esters, o-quinonediazide compounds, and the like.

The triarylsulfonium salts include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium bromide, triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium-p Examples of diaryliodonium salts such as toluenesulfonate include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroarsenate, diphenyliodonium-p-toluenesulfonate, diphenyliodonium-9, 10- Methoxy anthracene-2-sulfonate, bis (4-t- butylphenyl) and the like iodonium trifluoromethane sulfonates.

Examples of the sulfonic acid nitrobenzyl ester include p-nitrobenzyl-9,10-dimethoxyanthracene-2-sulfonate, p-nitrobenzyl-9,
And 10-diethoxyanthracene-2-sulfonate.

As the o-quinonediazide compound, a compound obtained by subjecting naphthoquinone-1,2-diazide-4-sulfonyl chloride and a hydroxy compound to a condensation reaction in the presence of a dehydrochlorinating agent can be used. Examples of the hydroxy compound include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, and 2,3,4-trihydroxybenzophenone , 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 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 dehydrochlorinating agent include sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, pyridine and the like.

In the photosensitive polymer composition of the present invention,
The amount of the component (b) is preferably from 0.1 to 50 parts by weight, more preferably from 0.5 to 30 parts by weight, per 100 parts by weight of the component (a), in view of the sensitivity and the allowable width of the developing time. .

As the component (c) of the present invention, a compound having an epoxy group, a compound having a methylol group, and a compound having an alkoxymethyl group are preferable. Among these, a compound having a phenolic hydroxyl group as an alkali-soluble group is further preferable. Is preferred.

Specific examples of the compound having an epoxy group include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, cresol novolak type epoxy resin, phenol novolak type epoxy resin, cricidylamine type epoxy resin. Epoxy resins such as epoxy resins and polysulfide type epoxy resins are exemplified. Examples of the compound having a methylol group include dimethylol urea, trimethylol melamine,
Hexamethylolmelamine, dimethylolethyleneurea, dimethylolpropyleneurea and the like can be mentioned. Examples of the compound having an alkoxymethyl group include 1,4-
Bis (methoxyphenoxy) benzene, trimethoxymethylmelamine, hexamethoxymethylmelamine and the like can be mentioned.

Further, compounds having a phenolic hydroxyl group include 3,3'-methylenebis (2-hydroxy-5-methylbenzenemethanol), 4,4'-
(1-methylethylidene) bis [2-methyl-6-hydroxymethylphenol], 3,3 ', 5,5',-tetrakis (hydroxymethyl) [(1,1'-biphenyl) -4,4'- Diol], 4,4 ′-(1-methylethylidene) bis [2,6-bis (hydroxymethyl) phenol], 2,2′-methylenebis (4,6-bishydroxymethylphenol), 2,6-bis [(2-hydroxy-3-hydroxymethyl-5-methylphenyl) methyl] -4-methylphenol, bis (2-hydroxy-3-methoxy-5-methylphenyl) methane and the like can be used.

In the photosensitive polymer composition of the present invention,
Component (c) is added in an amount of 0.1 to 100 parts by weight of component (a) in view of sensitivity and the allowable width of residues generated during development.
5 to 30 parts by weight are preferable, and 1 to 20 parts by weight is more preferable.

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

In order to improve the coating property, a solvent such as diethyl ketone, diisobutyl ketone, methyl amyl ketone, ethyl lactate, propylene glycol monomethyl ether acerate, etc. can be used in combination. The heat-resistant photosensitive polymer composition of the present invention may further contain an organic silane compound or an aluminum chelate compound as an adhesion assistant, if necessary.

As the organic silane compound, for example, γ-
Aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, γ
-Glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, ureapropyltriethoxysilane and the like. Examples of the aluminum chelate compound include aluminum tris (acetylacetonate) and aluminum acetylacetate diisopropylate. When an adhesion aid is used, 0.1 to 2 parts by weight per 100 parts by weight of the component (a) is used.
0 parts by weight is preferable, and 0.5 to 10 parts by weight is more preferable.

The photosensitive polymer composition of the present invention can be formed into a polyimide pattern through a step of coating and drying on a supporting substrate, a step of exposing, a step of developing and a step of heating. In the step of coating and drying on a supporting substrate, a glass substrate, a semiconductor, a metal oxide insulator (for example, T
iO ₂ , SiO _2, etc.), silicon nitride, etc.
The photosensitive polymer composition is spin-coated using a spinner or the like, and then dried 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. After the exposure, heating is performed using a hot plate, an oven, or the like as necessary.

In the developing step, a relief pattern is obtained by removing the exposed portion with a developing solution. Examples of the developer include an aqueous alkali solution such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide. The base concentration of these aqueous solutions is 0.1
Preferably, the content is 10 to 10% by weight.

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. Next, in the heat treatment step,
Preferably 150 to 4 in the obtained relief pattern
Heat treatment at 50 ° C. results in a heat-resistant polyimide pattern having an imide ring and other cyclic groups.

The photosensitive polymer composition of the present invention can be used for electronic parts such as semiconductor devices and multilayer wiring boards, and specifically, surface protective films, interlayer insulating films, and multilayer wiring boards of semiconductor devices. Can be used to form an interlayer insulating film and the like.
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 a process for manufacturing 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, Si having a circuit element
A semiconductor substrate such as a substrate 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 formed on a predetermined portion. And develop with an aqueous alkali solution to form a pattern, and then heat 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 polymer composition of the present invention.

[0047]

The present invention will be described below with reference to examples. Example 1 In a 0.3-liter flask equipped with a stirrer and a thermometer, 21.72 g (0.07 mol) of 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride and isopropyl alcohol were added. 41 g (0.14 mol), 0.21 g (0.0021 mol) of triethylamine and 56.0 g of N-methylpyrrolidone (NMP) were charged, and 1 g at room temperature.
The mixture was stirred and reacted for 20 hours to obtain an NMP solution (α) of 3,3 ′, 4,4′-diphenylethertetracarboxylic acid diisopropyl ester.

Then, the flask was cooled to 0 ° C., 14.99 g (0.126 mol) of thionyl chloride was added dropwise, and the mixture was reacted for 30 minutes to give 3,3 ′, 4,4′-diphenylethertetracarboxylic acid diisopropyl ester dichloride. To obtain a solution (β).

Next, 102.6 g of NMP was charged into a 0.5-liter flask equipped with a stirrer and a thermometer.
After adding 25.64 g (0.07 mol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane and dissolving with stirring, 19.77 g of pyridine (0.25 mol) was added.
Mol), and keeping the temperature at 0-5 ° C,
Solution (β) of 3 ′, 4,4′-diphenylethertetracarboxylic acid diisopropyl ester dichloride
After dropping 1.28 g in 20 minutes, stirring was continued for 1 hour. The solution was poured into 3 liters of water, and the precipitate was collected, washed, and dried under reduced pressure to obtain a polyimide precursor (γ).

15.00 g of polyimide precursor (γ), 0.80 g of triphenylsulfonium trifluoromethanesulfonate, bisphenol A type epoxy resin (YL
-980 (product name Yuka Shell Epoxy Co., Ltd.))
0.15g, 50% of ureapropyltriethoxysilane
0.90 g of the methanol solution was dissolved in 31.88 g of NMP with stirring. This solution was filtered under pressure using a Teflon (registered trademark) 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 by using a spinner, and dried by heating on a hot plate at 100 ° C. for 2 minutes to obtain a coating film of 5 μm. Using an i-line stepper (manufactured by Canon Inc.) as an exposure machine on this coating film, 100 to 80 through a reticle.
After exposure at 0 mJ / cm ² , heating was performed at 120 ° C. for 3 minutes. Next, paddle development was performed at 23 ° C. for 90 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. According to the pattern observation, the proper exposure amount was 480 mJ /
cm ² was determined. When the obtained relief pattern was subjected to heat treatment at 350 ° C. for 1 hour in a nitrogen atmosphere, a good polyimide film pattern was obtained.

Example 2 15.00 of the polyimide precursor (γ) obtained in Example 1
g, triphenylsulfonium trifluoromethanesulfonate 0.80 g, trimethylolmelamine 0.15
g, 0.90 g of a 50% methanol solution of ureapropyltriethoxysilane was dissolved in 31.88 g of NMP 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 was spin-coated on a silicon wafer using a spinner, and dried by heating on a hot plate at 100 ° C. for 2 minutes to obtain a coating film of 5 μm. Using an i-line stepper (manufactured by Canon Inc.) as an exposure machine on this coating film, 100 to 80 through a reticle.
After exposure at 0 mJ / cm ² , heating was performed at 120 ° C. for 3 minutes. Next, paddle development was performed at 23 ° C. 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. By pattern observation, proper exposure amount is 390mJ / c
it is determined that m ^2. When the obtained relief pattern was subjected to heat treatment at 350 ° C. for 1 hour in a nitrogen atmosphere, a good polyimide film pattern was obtained.

Example 3 The polyimide precursor (γ) obtained in Example 1 was 15.00.
g, triphenylsulfonium trifluoromethanesulfonate 0.80 g, 3,3′-methylenebis (2-hydroxy-5-methylbenzenemethanol) 0.15
g, 0.90 g of a 50% methanol solution of ureapropyltriethoxysilane was dissolved in 31.88 g of NMP 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 was spin-coated on a silicon wafer using a spinner, and dried by heating at 100 ° C. for 2 minutes on a hot plate to obtain a coating film of 5 μm. Using an i-line stepper (manufactured by Canon Inc.) as an exposure machine for this coating film, 100 to 800 mJ via a reticle.
/ Cm ² , and then heated at 120 ° C. for 3 minutes. Then, 2.3 of tetramethylammonium hydroxide
Paddle development was performed at 23 ° C. for 45 seconds using an 8% by weight aqueous solution as a developing solution, followed by washing with pure water to obtain a relief pattern. By pattern observation, the appropriate exposure was determined to be 560 mJ / cm ² . When the obtained relief pattern was subjected to heat treatment at 350 ° C. for 1 hour in a nitrogen atmosphere, a good polyimide film pattern was obtained.

Comparative Example 1 N-methyl-2-pyrrolidone (80.5 g) and xylene (20.1 g) were charged into a 0.5-liter flask equipped with a stirrer, a thermometer and a Dimroth condenser.
13. diamino-4 "-hydroxytriphenylmethane
52 g (0.05 mol), 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride 1
9.99 g (0.05 mol) 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 to obtain polyimide. (Δ) was obtained.

15.00 g of the obtained polyimide (δ),
0.80 g of triphenylsulfonium trifluoromethanesulfonate, 0.15 g of 3,3′-methylenebis (2-hydroxy-5-methylbenzenemethanol) and 0.90 g of a 50% methanol solution of ureapropyltriethoxysilane were added to 31.88 g of NMP. Stir and dissolve. 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 100 ° C. for 2 minutes on a hot plate to obtain a coating film of 5 μm. Using an i-line stepper (manufactured by Canon Inc.) as an exposure machine on this coating film, 100 to 80 through a reticle.
After exposure at 0 mJ / cm ² , heating was performed at 120 ° C. for 3 minutes. Next, paddle development was performed at 23 ° C. for 3 minutes using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide as a developing solution, and the substrate was washed with pure water. However, the unexposed portions did not dissolve and no relief pattern was obtained.

[0060]

The photosensitive polymer composition of the present invention can be subjected to negative-type alkali development, and can be developed at room temperature using a 2.38% aqueous solution of tetramethylammonium hydroxide which is usually used for semiconductor production. Thus, a pattern having a good shape can be formed. The electronic component of the present invention having the above pattern has excellent reliability.

[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.

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) H01L 21/312 H01L 21/312 BD (72) Inventor Masayuki Oe 4-3-1-1, Higashicho, Hitachi City, Ibaraki Prefecture Hitachi Chemical (72) Inventor Takanori Anzai 4-3-1, Higashimachi, Hitachi, Ibaraki Pref. Hitachi Chemical Seiko Dupont Microsystems Co., Ltd. Yamazaki Development Center (72) Inventor Nagatoshi Fujieda Ibaraki 4-13-1, Higashi-cho, Hitachi, Japan Hitachi Chemical DuPont Microsystems, Inc. Yamazaki Development Center F term (reference) 2H025 AA10 AB16 AB17 AC01 AD01 BE00 BE01 BE07 CB25 CB43 CC17 CC20 FA17 4J002 CD052 CD062 CD112 CD132 CM041 EB106 EE036 EE056 EJ016 EJ017 EJ036 EJ037 EJ046 EQ036 EV246 EV296 FD146 FD152 FD157 5F058 AC01 AC02 AC07 AF04 AG01 AH02 AH03

Claims (7)

[Claims] (1) (a) General formula (I) (Wherein, R ¹ represents a divalent organic group, R ² represents a divalent organic group having a phenolic hydroxyl group, and two R ³ each independently represent a hydrogen atom or a monovalent aliphatic group. A) a polyimide precursor having a repeating unit represented by formula (b), (b) a compound capable of generating an acid by light, and (c) the presence of an acid.
A photosensitive polymer composition comprising a compound that undergoes a crosslinking reaction with a component. 2. The photosensitive polymer composition according to claim 1, wherein component (c) is a compound having an epoxy group. 3. The photosensitive polymer composition according to claim 1, wherein component (c) is a compound having a methylol group. 4. The photosensitive polymer composition according to claim 1, wherein the component (c) is a compound having an alkoxymethyl group. 5. The photosensitive polymer composition according to claim 2, wherein component (c) is a compound further having a phenolic hydroxyl group. 6. A method for producing a pattern comprising the steps of applying the photosensitive polymer composition according to claim 1 on a support substrate, drying, exposing, developing, and heating. Law. 7. An electronic component having a pattern obtained by the method according to claim 6 as a surface protective film or an interlayer insulating film.