JP2000214586A - Photosensitive resin composition and manufacture of pattern and electronic parts by using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition easy in its manufacturing method and especially, excellent in storage stability by incorporating a specified ammonium salt and a specified polyimide precursor. SOLUTION: This photosensitive resin composition contains the ammonium salt represented by the formula (a) R4N+A- and (b) the polyimide precursor, and in the formula, each of R4 is, independently, a hydrocarbon group, and A- is an acid anion for forming an ionic bond with R4N+ and it is an acid anion of a nitric or picric or carboxylic or sulfonic acid, and the ammonium compound (a) is obtained by neutralizing an aqueous acid solution shown by H-A with R4NOH and then, removing water. The photosensitive polyimide precursor is obtained by forming an amide bond of tetracarboxylic acid anhydride or its derivative with diamine. The (a) component is used in an amount of 0.01-10 pts.wt. to 100 pts.wt. of the (b) component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive resin composition, a method for producing a pattern using the composition, and an electronic component.

[0002]

2. Description of the Related Art In recent years, in the semiconductor industry, an organic material having excellent heat resistance, such as a polyimide resin, has been used as an interlayer insulating material, which has conventionally been formed using an inorganic material, taking advantage of its characteristics. Have been.

However, formation of a circuit pattern on a semiconductor integrated circuit or a printed circuit board involves forming a resist material on the base material surface, removing unnecessary portions by exposing and etching predetermined portions, cleaning the substrate surface, and the like. Since pattern formation is performed through complicated and various processes, development of a heat-resistant photosensitive material that can use a necessary portion of the resist as an insulating material even after pattern formation by exposure and development is desired. .

As these materials, for example, heat-resistant photosensitive materials using photosensitive polyimide, cyclized polybutadiene or the like as a base polymer have been proposed. In particular, photosensitive polyimide has excellent heat resistance and elimination of impurities. Has attracted particular attention because of its ease of use.

As such a photosensitive polyimide, a system comprising a polyimide precursor and a dichromate (Japanese Patent Publication No. 49-17374) was first proposed. While having the advantages of high sensitivity and high film-forming ability, it lacks storage stability and has disadvantages such as chromium ions remaining in polyimide,
It did not reach practical use.

In order to avoid such a problem, for example, a method has been proposed in which a compound having a photosensitive group is mixed with a polyimide precursor (JP-A-54-109828). However, these photosensitive polyimides have poor storage stability, for example, have a problem in viscosity stability when left at room temperature, and accordingly, there has been a problem that development characteristics such as the shape of a pattern are changed as compared with initial values.

[0007]

DISCLOSURE OF THE INVENTION The inventions according to claims 1 and 2 provide a photosensitive resin composition which is easy to produce and has particularly excellent storage stability. A third aspect of the present invention provides a photosensitive resin composition having excellent patternability in addition to the object of the first aspect of the present invention.

The fourth aspect of the present invention provides a method for producing a pattern having a good shape by using a photosensitive resin composition having excellent storage stability. The fifth aspect of the present invention provides an electronic component having excellent reliability by having a good pattern as a surface protective film, an interlayer insulating film, and the like.

[0009]

According to the present invention, there are provided (a) a general formula (1)

Embedded image The four Rs are each independently a hydrocarbon group, A ⁻ is an anion of an acid that forms an ionic bond with R ₄ N ⁺ in the general formula (1)), and (b) The present invention relates to a photosensitive resin composition containing a polyimide precursor.

The present invention also relates to a photosensitive resin composition containing (c) a photopolymerization initiator. The present invention also provides
In the general formula (1), the group represented by A ⁻ is nitric acid,
The present invention relates to a photosensitive resin composition which is an anion of an acid selected from the group consisting of picric acid, carboxylic acid and sulfonic acid.

In the present invention, the amount of the component (a) is preferably
(B) 0.01 to 10 parts by weight based on 100 parts by weight of the component.
It relates to a photosensitive resin composition which is a part by weight. In addition, the present invention relates to a method for producing a pattern including a step of applying and drying the photosensitive resin composition on a support substrate, a step of exposing, a step of developing, and a step of heat treatment. The present invention also relates to an electronic component having a layer of a pattern obtained by the above-mentioned manufacturing method.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The (a) ammonium salt compound of the present invention is prepared by preparing an aqueous solution of an acid represented by HA
₄ It is obtained by neutralizing with an aqueous solution of NOH and then removing water. Examples of the hydrocarbon group represented by R include a methyl group,
Chain alkyl groups such as ethyl group, propyl group, butyl group and pentyl group; branched alkyl groups such as isopropyl group; alkyl groups such as cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aromatic rings such as phenyl group and toluyl group. Aromatic groups having the following are preferred. The number of carbon atoms is preferably from 1 to 15. These substituents are used alone or in combination of two or more.

As the anion of the acid represented by A ⁻ , an anion of an acid selected from nitric acid, picric acid, various carboxylic acids, various sulfonic acids, and the like is preferable because it can give a good pattern. As the various carboxylic acids, carboxyl groups such as benzoic acid, acetic acid, trifluoroacetic acid, phthalic acid, oxydiphthalic acid, pyromellitic acid, 3,3,4,4-benzophenonetetracarboxylic acid, etc.
Preferred are those having 4 and preferred examples of the sulfonic acid include sulfuric acid and trifluoromethanesulfonic acid.

The amount of the component (a) used in the present invention is as follows:
The amount is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the resin of the polyimide precursor of the component (b). If the amount is less than 0.01 part by weight, the viscosity at the time of storage at room temperature tends to decrease or increase, and if it exceeds 10 parts by weight, the residual film characteristics obtained after development, for example, the development pattern properties are inferior. Tend.

The polyimide precursor as the component (b) in the present invention has a photosensitive group which is dimerized or polymerized by light, and whether the exposed portion is not dissolved by a developer due to the dimerization or polymerization of the photosensitive group. It is preferably a so-called negative photosensitive polyimide precursor which is difficult to dissolve.

Examples of the photosensitive polyimide precursor include those having a repeating unit of the following general formula (2) obtained by forming an amide bond between tetracarboxylic dianhydride or a derivative thereof and a diamine. Can be

[0017]

Embedded image (Wherein X represents a tetravalent organic group, Y represents a divalent to tetravalent organic group, and A ¹ and A ² each independently represent OH, OR ¹ , N
HR ² or ^O - ^N + ^HR 3 is ^R 4 ^{R 5, R 1,}
R ² , R ³ , R ⁴ and R ⁵ are each independently a monovalent organic group, Z is a monovalent organic group having a carbon-carbon unsaturated double bond, and n is 0, 1 or 2 When n is 0, at least one of A ¹ and A ² is OR ¹ , NHR ² or O ^— N ⁺ HR ³ R ⁴ R ⁵ , wherein R ¹ , R ² and R
³ is a monovalent organic group having a carbon-carbon unsaturated double bond)

In the general formula (2), the tetravalent organic group represented by X preferably contains an aromatic ring, and the organic group represented by Y preferably contains an aromatic ring or a siloxane bond. Examples of the aromatic ring include a benzene ring, a naphthalene ring, and a pyridine ring. X and Y are 1
Composed of two aromatic rings, two to ten aromatic rings bonded via a single bond, an ether group, an alkylene group, a fluorinated alkylene group, a sulfonyl group, a sulfoxyl group (-SO-), a carbonyl group, etc. Is mentioned. These may have a substituent such as a hydrocarbon group, a halogenated hydrocarbon group, or a halogen atom on the aromatic ring.

The monovalent organic group represented by R ¹ , R ² , R ³ , R ⁴ and R ⁵ includes an alkyl group having 1 to 10 carbon atoms, a phenyl group and a carbon-carbon unsaturated double bond. In the case where R ¹ , R ² and R ³ are monovalent organic groups having a carbon-carbon unsaturated double bond, the following general formula (3)

Embedded image (However, R ⁶ , R ⁷ and R ⁸ are each independently selected from hydrogen, an alkyl group, a phenyl group, a vinyl group and a propenyl group, and R ⁹ represents a divalent organic group.) Monovalent organic groups are preferred.
As the alkyl group among R ⁶ , R ⁷ and R ⁸ , those having 1 to 4 carbon atoms can be mentioned. Also, 2 represented by R ⁹
Examples of the valent organic group include an alkylene group having 1 to 4 carbon atoms such as a methylene group, an ethylene group, and a propylene group.

It is preferable that the groups represented by -COA ¹ and -COA ² and the two amide groups bonded to X are all directly bonded to an aromatic ring. In this case, the groups represented by -COA ¹ and -COA ² Is preferably located at the ortho or peri position with respect to either one of the amide groups.

Examples of the group represented by Z include a group containing a vinyl group, an allyl group, an acryloyl group, and a methacryloyl group. The polyimide precursor is obtained using tetracarboxylic dianhydride or derivative, diamine and other compounds as necessary.

As the above tetracarboxylic dianhydride,
For example, oxydiphthalic dianhydride, pyromellitic dianhydride, 3,3,4,4, -benzophenonetetracarboxylic dianhydride, 3,3,4,4, -biphenyltetracarboxylic dianhydride, 1 2,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3 5,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, sulfonyldiphthalic anhydride, m-terphenyl-3,3,4,4-tetracarboxylic acid Acid dianhydride, p-terphenyl-3,3
4,4, -tetracarboxylic dianhydride, 1,1,1,
3,3,3, -Hexafluoro-2,2, -bis (2,
3- or 3,4, -dicarboxyphenyl) propanhydride, 2,2, -bis (2,3- or 3,4-dicarboxyphenyl) propane dianhydride, 2,2, -bis {4
-(2,3- or 3,4-dicarboxyphenoxy) phenyl} propane dianhydride, 1,1,1,3,3,3
-Hexafluoro-2,2, -bis {4- (2,3- or 3,4-dicarboxyphenoxy) phenyl} propane dianhydride; and the like, alone or in combination of two or more. Used.

The diamine is not particularly limited, but is 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2 '. , 6,6'-tetramethyl-4,4 '
-Diaminobiphenyl, 3,3 ', 5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4,-(or 3,4,-, 3,3,-, 2,4,-, 2,2,-)
Diaminodiphenyl ether, 4,4,-(or 3,
4,-, 3,3,-, 2,4,-, 2,2,-) diaminodiphenylmethane, 4,4,-(or 3,4,-,
3,3,-, 2,4,-, 2,2,-) diaminodiphenylsulfone, 4,4,-(or 3,4,-, 3,3,
-, 2,4,-, 2,2,-) sulfide, 3,3,-
Diaminodiphenyl sulfone and paraphenylenediamine, metaphenylenediamine, p-xylylenediamine, m-xylylenediamine, o-trizine, o-tolidine sulfone, 4,4, -methylene-bis- (2,6
-Diethylaniline), 4,4, -methylene-bis-
(2,6-diisopropylaniline), 2,4-diaminomesitylene, 1,5, -diaminonaphthalene, 4,
4, -benzophenonediamine, bis- {4- (4,-
Aminophenoxy) phenyl} sulfone, 1,1,1,
3,3,3-hexafluoro-2-, 2-bis (4-aminophenyl) propane, 2,2-bis {4- (4,-
Aminophenoxy) phenyl} propane, 3,3, -dimethyl-4,4, -diaminodiphenylmethane, 3,
3,5,5-tetramethyl-4,4, -diaminodiphenylmethane, bis {4- (3, -aminophenoxy)
Phenyl disulfone and 2,2-bis (4-aminophenyl) propane are preferred, and these are used alone or in combination of two or more.

The following general formula (4)

Embedded image (M and n are each independently an integer of 1 to 10, and S is 1 to
An aliphatic diamine such as diaminopolysiloxane represented by the following formula:

As the organic solvent used for the synthesis reaction of the polyimide precursor, a polar solvent which completely dissolves the produced polyimide precursor is generally preferred.
2-pyrrolidone, N, N-dimethylacetamide, N,
N-dimethylformamide, dimethylsulfoxide, tetramethylurea, hexamethylphosphoric triamide and γ
-Butyrolactone and the like.

Other than the polar solvent, ketones,
Esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons such as acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate , Diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4
-Dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene and the like can also be used. These organic solvents are used alone or in combination of two or more.

As a polyimide precursor having a photosensitive group, a compound having a carbon-carbon unsaturated double bond and an amino group or a quaternized salt thereof is a compound having a carboxyl group and an amino group of a polyamic acid or a quaternized salt thereof. Polyimide precursor in the form of a ionic bond at the salt group, polyamide acid ester having a carbon-carbon unsaturated double bond in the side chain via an ester bond, carbon-carbon unsaturated double bond in the side chain via an amide bond Examples include a polyimide precursor in which a carbon-carbon unsaturated double bond is introduced into a side chain via a covalent bond such as a polyamide acid amide having a heavy bond.

Among these, the present invention is particularly suitable for developing a composition containing a polyimide precursor in which a carbon-carbon unsaturated double bond is introduced by the ionic bond. When a carbon-carbon unsaturated double bond is introduced by an ionic bond, the amount of the compound having the carbon-carbon unsaturated double bond and an amino group or a group of a quaternized salt thereof is determined by photocurability, heat resistance and the like. In view of the above, the amount is preferably an equimolar ± 50 mol% with respect to the carboxyl group of the polyamic acid.

Examples of the compound having a carbon-carbon unsaturated double bond and an amino group or a group of a quaternized salt thereof include the following compounds. N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, N, N-dimethylaminoethyl methacrylate,
N, N-dimethylaminopropyl methacrylate, N,
N-dimethylaminobutyl acrylate, N, N-dimethylaminobutyl methacrylate, N, N-diethylaminoethyl acrylate, N, N-diethylaminopropyl acrylate, N, N-diethylaminoethyl methacrylate, N, N-diethylaminopropyl methacrylate, N-diethylaminobutyl acrylate,
N, N-diethylaminobutyl methacrylate.

In the present invention, it is bad that a photopolymerization initiator is further contained as the component (c). Although there is no particular limitation on the photopolymerization initiator, for example, Michler's ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 2-t-butylanthraquinone, 2-ethylanthraquinone,
4, -bis (diethylamino) benzophenone, acetophenone, benzophenone, thioxanthone, 2,2-
Dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl- [4
-(Methylthio) phenyl] -2-morpholino-1-
Propanone, benzyl, diphenyl disulfide, phenanthrenequinone, 2-isopropylthioxanthone,
Riboflavin tetrabutyrate, 2,6-bis (p-diethylaminobenzal) -4-methyl-4-azacyclohexanone, N-ethyl-N- (p-chlorophenyl)
Glycine, N-phenyldiethanolamine, 2- (o
-Ethoxycarbonyl) oxyimino-1,3-diphenylpropanedione, 1-phenyl-2- (o-ethoxycarbonyl) oxyiminopropan-1-one, 3,
3,4,4, -tetra (t-butylperoxycarbonyl) benzophenone, 3,3, -carbonylbis (7
-Diethylaminocoumarin), bis (cyclopentadienyl) -bis- [2,6-difluoro-3- (pyri-1
-Yl) phenyl] titanium and the like. They are,
They are used alone or in combination of two or more.

The amount of the photopolymerization initiator used is preferably 0.01 to 30% by weight, more preferably 0.05 to 10% by weight, based on the amount of the component (b).
If the amount is less than 0.01% by weight, the photosensitivity tends to be poor, and if it exceeds 30% by weight, the mechanical properties of the film tend to be inferior.

Further, the photosensitive resin composition of the present invention may contain an addition polymerizable compound having a carbon-carbon unsaturated double bond, if necessary. Examples of the addition polymerizable compound include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, and trimethylolpropane. Triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4
-Butanediol dimethacrylate, 1,6-hexanediol methacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N -Vinylpyrrolidone, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,
3-acryloyloxy-2-hydroxypropane,
Examples include 1,3-methacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide and the like. These are used alone or in combination of two or more.

The amount of the addition polymerizable compound used is (b)
The amount is preferably 1 to 200% by weight based on the amount of the components. If the amount is less than 1% by weight, the photosensitive properties such as solubility in a developer tend to be poor, and if it exceeds 200% by weight, the mechanical properties of the film tend to be inferior.

Further, the photosensitive resin composition of the present invention may contain a bisazide compound, if necessary. As the bisazide compound, for example,

Embedded image And the like. These may be used alone or in combination of two or more.

The amount of the bisazide compound used is preferably 0.01 to 30% by weight, more preferably 0.05 to 10% by weight, based on the amount of the component (b). If the amount is less than 0.01% by weight, the photosensitivity tends to be poor, and if it exceeds 30% by weight, the mechanical properties of the film tend to be inferior.

The photosensitive resin composition of the present invention may further contain a radical polymerization inhibitor or a radical polymerization inhibitor in order to further enhance the stability during storage. Examples of the radical polymerization inhibitor or the radical polymerization inhibitor include, for example, p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, Examples include N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, cuperon, phenothiazine, 2,5-toluquinone, tannic acid, parabenzylaminophenol, nitrosamines and the like. These are used alone or in combination of two or more.

The amount of the radical polymerization inhibitor or the radical polymerization inhibitor used is based on 100 parts by weight of the component (b).
It is preferably 0.01 to 30 parts by weight, and 0.05
More preferably, the amount is from 10 to 10 parts by weight. If the amount is less than 0.01 part by weight, the stability during storage tends to be poor, and if it exceeds 30 parts by weight, the photosensitivity and the mechanical properties of the film tend to be inferior.

The photosensitive resin composition of the present invention is applied onto a supporting substrate such as a silicon wafer, a metal substrate, a ceramic substrate or the like by an immersion method, a spray method, a screen printing method, a spin coating method or the like, and the solvent is moderately applied. By heating and drying, a coating film having no tackiness can be obtained. On this coating,
Actinic rays or actinic rays are irradiated and exposed through a mask on which a desired pattern is drawn. The actinic rays or actinic rays to be irradiated include a contact / proximity exposure machine using an ultra-high pressure mercury lamp, a mirror projection exposure machine, an i-ray stepper, a g-ray stepper, other ultraviolet rays, a visible light source,
X-rays and electron beams can be used. After the irradiation, a desired negative pattern is obtained by dissolving and removing the unirradiated portion with a developing solution.

Next, development is carried out.
Methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, tetramethylurea, hexamethylphosphoric triamide, γ-butyrolactone, water or alcohols, ketones, esters, lactones , Ethers, halogenated hydrocarbons, hydrocarbons such as methanol, ethanol, isopropyl alcohol, acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, Diethyl malonate, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,
4-Dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene and the like are used alone or in combination of two or more. In addition, a basic solution such as an aqueous solution of tetramethylammonium hydroxide or an aqueous solution of triethanolamine is used. After the development, rinsing is performed with water or a poor solvent as necessary. By heating the pattern thus obtained, a stable high heat-resistant polyimide pattern from which the photosensitive agent and the solvent have been completely removed is obtained.

The heating temperature at this time is preferably from 150 to 500 ° C., more preferably from 200 to 400 ° C. When the heating temperature is lower than 150 ° C.,
The mechanical and thermal properties of the polyimide film tend to decrease, and when the temperature exceeds 500 ° C., the mechanical and thermal properties of the polyimide film tend to decrease.

The heating time at this time is 0.05 to 1
Preferably, it is 0 hours. This heating time is 0.0
If the time is less than 5 hours, the mechanical and thermal properties of the polyimide film tend to decrease, and if the time exceeds 10 hours, the mechanical and thermal properties of the polyimide film tend to decrease.

As described above, the photosensitive resin composition of the present invention comprises:
It can be used as a surface protective film for semiconductors, an interlayer insulating film of a multilayer wiring board, and the like. Since the surface protective film using the photosensitive resin composition of the present invention has excellent adhesion to SiN, a sealing agent, and the like, a semiconductor device using the surface protective film obtained from the photosensitive resin composition of the present invention. Is extremely reliable.

The electronic component of the present invention is not particularly limited except that it has a surface protective film and an interlayer insulating film formed using the composition, and can have various structures. An example of a manufacturing process of a semiconductor device will be described below as an example of the electronic component of the present invention.

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 stress, α-rays and the like, and the resulting semiconductor device has excellent reliability. In the above example, the interlayer insulating film can be formed using the photosensitive resin composition of the present invention.

[0049]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. Synthesis Example 1 (Synthesis of tetraalkylammonium salt compound) After 30 ml of water was added to a flask equipped with a stirrer, 9.7 g of tetrabutylammonium bromide was added, and trifluoromethanesulfonic acid 4.5 was added with stirring under ice cooling.
g was added slowly. After stirring at room temperature for 1 hour, the obtained reaction solution was filtered, and the obtained solid was washed with water. The solid was dried under vacuum to obtain 9.2 g of a tetraalkylammonium salt compound.

Synthesis Example 2 (Synthesis of Polyamic Acid Solution) In a three-necked flask equipped with a stirrer, a thermometer and a nitrogen inlet tube, 2,2'-dimethyl-4,4'-diaminobiphenyl 1 was added.
0 g and 70 g of N-methyl-2-pyrrolidone were added, and the mixture was stirred and dissolved at room temperature. To this, 15 g of oxydiphthalic dianhydride was added and stirred for 8 hours to obtain a viscous polyamic acid resin solution.

Example 1 0.1 g of the tetraalkylammonium salt compound obtained in the above Synthesis Examples 1 and 2 and 10 g of a polyamic acid resin solution were stirred and mixed, and 0.027 g of a bisazide compound (AZ) represented by the following structural formula was further added. 0.027 g of aminobenzophenone compound (CM), oxime compound (OX)
After adding and dissolving each component of 0.054 g and 1.5 g of 3-dimethylaminopropyl methacrylate with stirring, the mixture was filtered with a filter to obtain a photosensitive resin composition solution having a viscosity of 50 poise.

[0052]

Embedded image When this solution was allowed to stand at room temperature for 30 days under light-shielding conditions, it was confirmed that the viscosity was only 0.7 poise lower than the initial value, and there was almost no change in viscosity. This solution was dropped on a silicon wafer and spin-coated. Next, after heating at 90 ° C. for 150 seconds using a hot plate to form a coating film of 12 μm, a pattern mask was applied.
Exposure was performed with a line stepper. This is further increased to 110 ° C. and 60
After heating for 2 seconds, paddle development using a mixed solution of N-methyl-2-pyrrolidone / water (weight ratio 75/25) and rinsing with ethanol, a good relief pattern similar to that before standing was obtained. .

COMPARATIVE EXAMPLE 1 Except that the tetraalkylammonium salt compound used in Example 1 was not added, and the composition was treated exactly the same as in Example 1 except that the viscosity was 10% lower than the initial value. Poise was also decreasing. When the resin left at room temperature was used, the solubility of the resin in the unexposed part in the developing solution was reduced, and no pattern was formed within the same developing time.

Example 2 1.0 g of the tetraalkylammonium salt compound used in Example 1 was added, and the mixture was treated in exactly the same manner as in Example 1 except for the amount of the photosensitive compound having a viscosity of 45 poise. A resin composition solution was obtained. When this solution was allowed to stand at room temperature for 30 days under light-shielding conditions, it was confirmed that the viscosity was only 0.5 poise lower than the initial value and there was almost no change in viscosity. Further, when a pattern treatment was performed in the same manner as in Example 10 using this solution, a good relief pattern was obtained in the same manner as before the standing.

[0055]

The photosensitive resin compositions according to claims 1 and 2 are easy to produce and are particularly excellent in storage stability. Claim 3
The photosensitive resin composition described above has the effects of the invention described in claim 1 and is further excellent in patternability.

According to the pattern manufacturing method of the fourth aspect,
By using a photosensitive resin composition having excellent storage stability, a pattern having a good shape can be obtained. The electronic component according to the fifth aspect is excellent in reliability by having a good pattern as a surface protective film, an interlayer insulating film, and the like.

[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: 1st conductor layer,
4 ... interlayer insulating film layer, 5 ... photosensitive resin layer, 6A, 6B, 6
C: window, 7: second conductor layer, 8: surface protective film layer.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/004 501 G03F 7/004 501 H01L 21/312 H01L 21/312 D

Claims (6)

[Claims] (1) (a) General formula (1) (The four Rs are each independently a hydrocarbon group, and A ⁻ is an anion of an acid that forms an ionic bond with R ₄ N ⁺ in the general formula (1)). b) A photosensitive resin composition containing a polyimide precursor. 2. The photosensitive resin composition according to claim 1, further comprising (c) a photopolymerization initiator. In 3. A general formula (1), A ^- a group represented nitric acid, picric acid, according to claim 1 or 2 is an anion of an acid selected from the group consisting of carboxylic acid and sulfonic acid
The photosensitive resin composition as described in the above. 4. The amount of component (a) is less than 100% of component (b).
4. The photosensitive resin composition according to claim 1, wherein the amount is 0.01 to 10 parts by weight based on parts by weight. 5. A method for producing a pattern, comprising a step of applying the photosensitive resin composition according to claim 1 on a support substrate, drying, exposing, developing and heating. . 6. An electronic component having a pattern layer obtained by the method according to claim 5.