JP2000310856A - Photosensitive resin composition, production of pattern and electronic parts - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive resin composition having high sensitivity and excellent in properties of a pattern after development by incorporating a specified tertiary amino compound, a polyimide precursor and a photopolymerization initiator. SOLUTION: The photosensitive resin composition contains (a) a tertiary amino compound of the formula, (b) a polyimide precursor and (c) a photopolymerization initiator. In the formula, R is a group containing a reactive unsaturated bond, k, k', k", n, n' and n" in the azabicyclo-ring are each 1, 2 or 3 and m, m' and m" are each 0 or 1. The group R is preferably a group containing a methacryloyl group from the viewpoint of shelf stability. The amount of the component (a) is preferably 10-200 pts.wt. based on 100 pts.wt. of the component (b) and the amount of the component (c) is 0.01-30 pts.wt. based on 100 pts.wt. of the component (b).

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, the photosensitive agent used in these photosensitive polyimides has a weak bonding force to the polyimide precursor, and there is a problem that it is difficult to provide a contrast between an exposed portion and an unexposed portion. Therefore, the efficiency of insolubilization in a solvent based on a photoreaction, that is, the sensitivity is low, and a large amount of actinic rays or actinic rays must be irradiated in practical use.

[0007]

The invention according to claims 1 and 3 has higher sensitivity and better patternability after development than a conventional photosensitive resin composition having a photosensitive group added to a polyimide precursor. The present invention provides a conductive resin composition. The invention described in claim 2 provides the effect of the invention described in claim 1 and provides a photosensitive resin composition having excellent storage stability.

The invention described in claim 4 provides a method for producing a pattern having high sensitivity and excellent patternability after development. 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 (R is a group containing a reactive unsaturated bond, and k, k ′, k ″, n, n ′ and n ″ in the azabicyclo ring are each independently 1, 2 or 3, m, m ′ and m "is independently 0
A photosensitive resin composition comprising a tertiary amino compound represented by the formula (1), (b) a polyimide precursor, and (c) a photopolymerization initiator.

The present invention also relates to a photosensitive resin composition wherein R in the general formula (1) is a group containing a methacryloyl group. Further, in the present invention, the amount of the component (a) is preferably less than the amount of the component (b).
The amount of the component (c) is 10 to 200 parts by weight based on 100 parts by weight of the component, and the amount of the component (b) is 10
The present invention relates to a photosensitive resin composition which is 0.01 to 30 parts by weight with respect to 0 parts by weight.

[0011] The present invention also relates to a method for producing a pattern comprising 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 heating. 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 (a) The tertiary amino compound represented by the general formula (1) in the present invention is a compound having a group having a reactive unsaturated bond with an azabicyclo ring having a nitrogen atom as an intersection. .

Examples of the group having a reactive unsaturated bond represented by R include a reactive unsaturated double bond functional group such as vinyl group, allyl group, acryloyl group and methacryloyl group, and a reactive unsaturated triple bond such as propargyl. Examples include a functional group, a methacryloxy group, an acryloxy group, an acryloxyalkyl group, a methacryloxyalkyl group, and a group containing an acryloyl group or a methacryloyl group at a terminal of a polyalkylene glycol chain, which include these functional groups at the terminals. Among these, a group containing a methacryloyl group is preferred in terms of storage stability. There is no limitation on the bonding position of R.

Specific examples of the tertiary amino compound represented by the general formula (1) include 1-azabicyclo- (2,2,
2) -Octane-3-methacrylate, 1-azabicyclo- (2,2,2) -octane-3- (diethylene glycol) methacrylate, 1-azabicyclo- (2
2,2) -Octane-3- (triethylene glycol)
Methacrylate, 1-azabicyclo- (2,2,2)-
Octane-3- (tetraethylene glycol) methacrylate, 1-azabicyclo- (2,2,2) -octane-3- (propylene glycol) methacrylate, 1-
Azabicyclo- (2,2,2) -octane-3- (ethylenediol) methacrylate, 1-azabicyclo-
(2,2,2) -octane-3- (butanediol) methacrylate, 1-azabicyclo- (2,2,2) -octane-3- (hexanediol) methacrylate, 1
-Azabicyclo- (2,2,2) -octane-3- (nonanediol) methacrylate, 1-azabicyclo-
3,5,8-trioxa- (2,2,2) -octane-
3-methacrylate, 1-azabicyclo-3,5-dioxa- (2,2,2) -octane-3-methacrylate, 1-azabicyclo-3-oxa- (2,2,2)-
Octane-3-methacrylate, 1-azabicyclo-
3,5,8-trioxa- (2,2,2) -octane-
Examples of such compounds include 3- (diethylene glycol) methacrylate and 1-azabicyclo- (2,2,2) -octane-2-methacrylate in which the methacrylate of each compound is changed to acrylate.

The amount of the component (a) used in the present invention is as follows:
The amount is preferably 10 to 200 parts by weight based on 100 parts by weight of the polyimide precursor as the component (b), and is preferably 5 to 200 parts by weight.
More preferably, the amount is from 0 to 150 parts by weight. If the amount is less than 10 parts by weight, the exposed portion is eluted during development, so that the film after development tends to remain,
If the amount exceeds 0 parts by weight, the film after the development tends to remain similarly.

As the polyimide precursor (b) in the present invention, known ones such as polyamic acid, polyamic acid ester and polyamic acid amide can be mentioned. Among them, the component (a) can be bonded by ionic bonding.
A polyimide precursor having a carboxyl group or the like is preferable, and examples thereof include polyamide acid, a partial ester or partial amide of a polyamic acid, and a polyimide using a carboxyl group-containing diamine such as 3,5-diaminobenzoic acid. Precursors and the like. These polyimide precursors may have a photosensitive group (reactive unsaturated bond or the like) which is dimerized or polymerized by light in the molecule, separately from the component (a). There is no particular limitation on the production method of various polyimide precursors, and a known method can be employed.

Examples of the polyimide precursor (b) in the present invention include those having a repeating unit represented by the following general formula (2).

Embedded image (Wherein, X represents a tetravalent organic group, Y represents a divalent organic group, Z is a monovalent organic group having a carbon-carbon unsaturated double bond, and n is 0, 1 or 2 Is)

In the general formula (2), X preferably contains an aromatic ring, and Y preferably contains an aromatic ring or a siloxane bond. As the aromatic ring, a benzene ring,
A naphthalene ring, a pyridine ring and the like are exemplified. As X and Y, one aromatic ring, 2 to 10 aromatic rings are a single bond, an ether group, an alkylene group, a fluorinated alkylene group, a sulfonyl group, a sulfoxyl group (—SO -) And those linked via a carbonyl group or the like. These may have a substituent such as a hydrocarbon group, a halogenated hydrocarbon group, or a halogen atom on the aromatic ring. Examples of the group represented by Z include a group including a vinyl group, an allyl group, an acryloyl group, and a methacryloyl group.

The above polyimide precursor is obtained by reacting a tetracarboxylic dianhydride or a derivative thereof, a diamine and, if necessary, a compound having a photosensitive group. As the tetracarboxylic dianhydride, for example, oxydiphthalic dianhydride, pyromellitic dianhydride, 3,3
4,4, -benzophenonetetracarboxylic dianhydride,
3,3,4,4, -biphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 4,4,5,8-Naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, sulfonyl diphthalate Acid anhydride, m-terphenyl-3,3,4,4-tetracarboxylic 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-
Examples thereof include 2,2, -bis {4- (2,3- or 3,4-dicarboxyphenoxy) phenyl} propane dianhydride, and these are used alone or in combination of two or more.

The diamine is not particularly restricted but includes 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-tolidine, 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} sulfone and 2,2-bis (4-aminophenyl) propane are preferred, and these may be used alone or in combination of two or more.

The following general formula (3)

Embedded image (Wherein, m and n are each independently an integer of 1 to 10,
s is an integer of 1 to 10), or an aliphatic diamine such as diaminopolysiloxane.

As the organic solvent used in the above reaction, a polar solvent which completely dissolves the polyimide precursor to be formed is generally preferable. For example, N-methyl-2-pyrrolidone,
N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, tetramethylurea,
Hexamethylphosphoric triamide, 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. The above organic solvent is also used as a solvent for the photosensitive resin composition.

In the present invention, the above-mentioned component (a) is an essential component. In addition, it has a carbon-carbon unsaturated double bond and an amino group or a quaternary salt group which are already known. Compounds can be used in combination, and examples 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, N-diethylaminobutyl acrylate, N, N-diethylamino Butyl methacrylate and the like.

The photosensitive resin composition of the present invention includes:
(C) A photopolymerization initiator is included. Examples of the photopolymerization initiator include Michler's ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 2-t-butylanthraquinone, 2-ethylanthraquinone, 4,4, -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)
Oximino-1,3-diphenylpropanedione, 1
-Phenyl-2- (o-ethoxycarbonyl) oxyiminopropan-1-one, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone,
7-diethylamino-3-thenonylcoumarin, 3,3 ′
-Carbonylbis (7-diethylaminocoumarin), bis (cyclopentadienyl) -bis- [2,6-difluoro-3- (pyr-1-yl) phenyl] titanium, bisazides and the like. These are used alone or in combination of two or more.

Among these, preferred examples are 7-diethylamino-3-thenonylcoumarin, 3,3'-carbonylbis (7-diethylaminocoumarin), bis (cyclopentadienyl) -bis- [2, 6-difluoro-3
-(Pyr-1-yl) phenyl] titanium, bisazides and the like. The amount of the photopolymerization initiator (c) used is usually 0.1 to 100 parts by weight of the polyimide precursor (b).
The amount is from 0.01 to 30 parts by weight.

Further, the photosensitive resin composition contains an addition polymerizable compound, 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
Polyvalent (meth) such as butanediol dimethacrylate, 1,6-hexanediol methacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, and pentaerythritol tetramethacrylate;
Acrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,3-acryloyloxy-2-hydroxypropane, 1,3- Examples include 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 to be used is usually the polyimide precursor (b) 10
It is 1 to 200 parts by weight with respect to 0 parts by weight.

Further, the photosensitive resin composition of the present invention may contain a radical polymerization inhibitor or a radical polymerization inhibitor in order to enhance the stability during storage. As the radical polymerization inhibitor or the radical polymerization inhibitor, for example,
p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, N-phenyl-1-naphthylamine, N-phenyl-2- Examples include naphthylamine, cuperon, phenothiazine, 2,5-toluquinone, tannic acid, parabenzylaminophenol, nitrosamines and the like. These are used alone or in combination of two or more. When a radical polymerization inhibitor or a radical polymerization inhibitor is used, its amount is usually 0.01 to 30 parts by weight based on 100 parts by weight of the polyimide precursor (b).

Further, the photosensitive resin composition of the present invention may contain other additives known to be used in the photosensitive resin composition, for example, additives such as a plasticizer and an adhesion promoter. . The photosensitive resin composition of the present invention is applied to a substrate such as a silicon wafer, a metal substrate, or a ceramic substrate by a dipping method, a spray method, a screen printing method, a spin coating method, or the like, and the solvent is appropriately heated and dried. With this, a coating film having no tackiness can be obtained. The coating film is irradiated with actinic rays or actinic rays through a mask on which a desired pattern is drawn. As an actinic ray or actinic ray to be irradiated, 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, an X-ray, or an electron beam is used. be able to. After irradiation, a desired relief structure can be obtained by dissolving and removing an unirradiated portion with a developer.

Examples of the developer include N-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, for example, methanol, ethanol, isopropyl alcohol, 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 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 obtained relief structure, a stable pattern of highly heat-resistant polyimide from which the photosensitive agent and the solvent have been completely removed can be obtained. The heating temperature at this time is preferably 150 to 500 ° C.
The temperature is more preferably set to 400 ° C. If the heating temperature is lower than 150 ° C., the mechanical and thermal characteristics of the polyimide pattern tend to decrease, and if it exceeds 500 ° C., the mechanical and thermal characteristics of the polyimide pattern 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 pattern tend to decrease. If the time exceeds 10 hours, the mechanical and thermal properties of the polyimide pattern 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. In addition, since the surface protective film using the photosensitive resin composition of the present invention has excellent adhesiveness with SiN, a sealing agent, and the like, the surface protective film obtained from the photosensitive resin composition of the present invention was used. The semiconductor element has extremely high reliability.

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, by using a well-known photographic etching 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.

Hereinafter, the present invention will be described in detail with reference to examples. [Synthesis example of tertiary amino compound having azabicyclo ring and reactive unsaturated functional group] After adding 50 ml of toluene to a flask equipped with a reflux tube equipped with a stirrer, 10.2 g of 3-quinuclidinol and 0.05 g of phenothiazine were added. 16 g of methacrylic acid was added with stirring under ice cooling, and then 10 g of methanesulfonic acid was slowly added. After stirring at 120 ° C. for 2 hours, the resulting reaction solution was neutralized with an aqueous potassium hydroxide solution and filtered, and then the reaction solvent was removed with an evaporator. The residue was distilled under reduced pressure to give 1-azabicyclo- (2,2,2) -octane-3-methacrylate 1.
2.2 g were obtained.

[Synthesis Example of Polyamic Acid Solution] In a three-necked flask equipped with a stirrer, a thermometer and a nitrogen inlet tube, 2,2′-
10 g of dimethyl-4,4'-diaminobiphenyl and N
70 g of -methyl-2-pyrrolidone was 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 1.5 g of 1-azabicyclo- (2,2,2) -octane-3-methacrylate obtained in the above synthesis example and 10 g of a polyamic acid resin solution were stirred and mixed, and further, 7-diethylamino was added. 0.02 g of -3-thenonyl coumarin and 0.02 g of 2,6-bis (4'-azidobenzal) -4-carboxycyclohexanone were added and dissolved by stirring, followed by filtration with a filter to obtain a solution of the photosensitive resin composition. Obtained. 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 10 μm, a pattern mask was used, and 50 mJ / cm ² was used using PLA.
Exposure was performed at an exposure amount of This is further increased to 110 ° C. and 60
After heating for 2 seconds, paddle developing using a mixed solution of N-methyl-2-pyrrolidone / methanol (weight ratio 75/25) and rinsing with ethanol, the resolution was 10
μm (minimum via hole diameter), and a very good relief pattern was obtained.

Example 2 1.5 g of 1-azabicyclo- (2,2,2) -octane-3-methacrylate obtained in the above synthesis example and 10 g of a polyamic acid resin solution were stirred and mixed. , -Carbonylbis (7-diethylaminocoumarin) 0.03 g, 2,6-bis (4'-
Azidobenzal) -4-carboxycyclohexanone
After adding and dissolving 0.02 g of a photosensitizer under stirring and filtering, a photosensitive resin composition solution was obtained by filtration with a filter. 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 10 μm, a pattern mask was used, and PLA was applied.
Exposure was performed at an exposure amount of mJ / cm ² . This is one more
After heating at 10 ° C. for 60 seconds, paddle development using a mixed solution of N-methyl-2-pyrrolidone / methanol (weight ratio 75/25) and rinsing with ethanol, the resolution reached 20 μm (minimum via hole diameter). And a relief pattern having a very good shape was obtained.

[Comparative Example 1] 1 used in Example 1
When the same amount of dimethylaminoethyl methacrylate was added in place of -azabicyclo- (2,2,2) -octane-3-methacrylate, and otherwise the composition was exactly the same as in the example, and the same treatment was carried out. In the exposed area, the solubility in the developing solution was reduced, and the exposed area was eluted due to insufficient exposure, and no good pattern was formed.

[Comparative Example 2] 1 used in Example 2
When the same amount of dimethylaminoethyl methacrylate was added in place of -azabicyclo- (2,2,2) -octane-3-methacrylate, and otherwise the composition was exactly the same as in the example, and the same treatment was carried out. In the exposed area, the solubility in the developing solution was lowered, and due to insufficient exposure, elution and peeling of the exposed area occurred, and no good pattern was formed.

[0046]

The photosensitive resin composition of the present invention has higher sensitivity and better patternability after development than a conventional photosensitive resin composition obtained by adding a photosensitive group to a polyimide precursor. Further, the photosensitive resin composition of the present invention is further excellent in storage stability.

According to the pattern manufacturing method of the present invention,
A pattern having high sensitivity and excellent patternability after development can be formed. Further, the electronic component of the present invention has a good pattern as a surface protective film, an interlayer insulating film, and the like,
It is excellent in 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: 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) C08F 290/14 C08F 290/144 4J043 C08K 5/3412 C08K 5/3412 4J100 C08L 79/08 C08L 79/08 G03F 7/004 501 G03F 7/004 501 // C08G 73/10 C08G 73/10 H01L 23/12 H01L 23/12 NF term (reference) 2H025 AA00 AA01 AA03 AA10 AB16 AB17 AC01 AD01 BC14 BC34 BC81 BC87 CA01 CA20 CA26 CA27 CA28 CA39 CB25 FA03 FA14 FA29 4J002 CM041 CP171 EE036 EE056 EN027 EN066 EN076 EQ036 ER006 EU017 EU236 EV046 EV316 EZ006 FD146 GP03 GQ00 4J011 QA03 RA10 SA02 SA22 SA25 SA26 SA29 SA31 SA36 SA42 SA63 SA64 SA78 SA01 SA26 SA83 SA01 SA01 SA01 BA06 BA07 BA28 BA29 BA30 BA32 BA40 BA50 BB01 BB02 DB06 DB09 DB11 DB29 DB36 G A07 4J027 AC03 AC06 AC09 AD04 AD06 AJ08 BA13 CB10 CC05 CD06 CD10 4J043 PA02 PA19 RA35 SA06 SB01 TA14 TA22 TB01 UA121 UA131 UA132 UA142 UA151 UA152 UA252 UA261 UA262 UA362 UB011 UB02122 UB UB UB 012 UB 012 UB 012 ZB22 4J100 AL08P BA02P BC65P CA01 CA04 JA37 JA38

Claims (5)

[Claims] (1) (a) General formula (1) (R is a group containing a reactive unsaturated bond, and k, k ′, k ″, n, n ′ and n ″ in the azabicyclo ring are each independently 1, 2 or 3, m, m ′ and m "is independently 0
A photosensitive resin composition comprising a tertiary amino compound represented by formula (1), (b) a polyimide precursor, and (c) a photopolymerization initiator. 2. The photosensitive resin composition according to claim 1, wherein R in the general formula (1) is a group containing a methacryloyl group. 3. The amount of the component (a) is 100% by the amount of the component (b).
The amount of the component (c) is 0.1 to 200 parts by weight based on 100 parts by weight of the component (b).
3. The photosensitive resin composition according to claim 1, wherein the amount is from 0.01 to 30 parts by weight. 4. A method for producing a pattern, comprising a step of applying and drying the photosensitive resin composition according to claim 1, 2 or 3 on a supporting substrate, a step of exposing, a step of developing and a step of heating. 5. An electronic component having a pattern layer obtained by the method according to claim 4.