JP2002037886A - Polyimide, precursor thereof, photosensitive resin composition, method of forming pattern and electronic parts - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition having i-beam transmit tance and low thermal expansion after imidization, and enabling to form a pattern with excellent thermal resistance, and to provide a method of forming such a pattern, and further to provide electronic parts with high reliability. SOLUTION: The polyimide precursor comprises a structural unit expressed by formula (1) and a structural unit expressed by formula (2) (Where in formula (1), R1 and R2 each independently represents H or univalent organic group; R3 to R6 each independently represents H or a hydrocarbon group provided that at least one is a hydrocarbon group; and two bonds indicated by arrows may be inversely bonding to each other, and in formula (2), R1 and R2 each independently represents H or univalent organic group; R7 to R10 each independently represents a group containing H or F provided that at least one contains F; and two bonds indicated by arrows may be inversely bonding to each other.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimide which exhibits very excellent i-line transmittance and gives a low stress, a precursor thereof, a photosensitive resin composition using the same, 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 is complicated and diversified, such as forming a resist material on the base material surface, removing unnecessary portions by exposing and etching predetermined portions, and cleaning the substrate surface. Therefore, development of a heat-resistant photosensitive material that can use a necessary portion of a resist as an insulating material as it is 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. Particularly, 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, but this material has practical photosensitivity. In addition, it has advantages such as high film-forming ability, but has disadvantages such as lack of storage stability and chromium ions remaining in polyimide, and thus has not been put to practical use.

[0004] In order to avoid such a problem, for example, a method of mixing a compound having a photosensitive group with a polyimide precursor (Japanese Patent Application Laid-Open No. 54-109828) discloses a method in which a functional group and a photosensitive group in the polyimide precursor are mixed. A method of reacting with a functional group of a compound having a compound to give a photosensitive group (JP-A-56-2
No. 4343, Japanese Unexamined Patent Publication No. 60-100143)
And so on. However, these photosensitive polyimide precursors use a basic skeleton for an aromatic monomer having excellent heat resistance and mechanical properties.Because of the absorption of the polyimide precursor itself, the light transmittance in the ultraviolet region is low and the exposure is low. However, the photochemical reaction in the portion cannot be performed sufficiently effectively, resulting in a problem that the sensitivity is low and the shape of the pattern is deteriorated. In recent years, with the increasing integration of semiconductors, processing rules have become increasingly smaller, and higher resolutions have been required.

For this reason, a conventional contact / proximity exposure apparatus using parallel rays has been replaced by a 1: 1 projection exposure apparatus called a mirror projection and a reduction projection exposure apparatus called a stepper. The stepper utilizes a monochromatic light such as an excimer laser and a high-power oscillation line of an ultra-high pressure mercury lamp. Until now, g-line steppers using visible light (wavelength: 435 nm) called g-line of an ultra-high pressure mercury lamp have been the mainstream stepper. However, in order to respond to the demand for finer processing rules, a stepper to be used is used. Needs to be shortened. Therefore, the exposure equipment used is from a g-line stepper (wavelength: 435 nm) to an i-line stepper (wavelength: 3).
65 nm).

However, conventional photosensitive polyimide base polymers designed for contact / proximity exposure machines, mirror projection projection exposure machines, and g-line steppers have low transparency due to the above-mentioned reasons, especially i-line. (Wavelength: 365 nm) because there is almost no transmittance.
A decent pattern cannot be obtained with an i-line stepper. In addition, a polyimide film for surface protection is required to be a thicker film corresponding to LOC (lead-on-chip), which is a high-density mounting method of a semiconductor element. The problem gets worse. Therefore, there is a strong demand for a photosensitive polyimide having a high i-line transmittance and a polyimide pattern having a good pattern shape by an i-line stepper.

The diameter of a silicon wafer serving as a substrate is
It has been increasing year by year, and there has been a problem that the warpage of the silicon wafer on which the polyimide as the surface protective film is formed becomes larger than before due to the difference in thermal expansion coefficient between the polyimide and the silicon wafer. Therefore, there is a strong demand for a photosensitive polyimide having a lower thermal expansion property than conventional polyimides. In general, low thermal expansion can be achieved by making the molecular structure rigid. However, in the case of the rigid structure, almost no i-line is transmitted, so that the photosensitive characteristics deteriorate.

[0008]

SUMMARY OF THE INVENTION The present invention is to provide a polyimide and a precursor thereof which have both good i-line transmittance and low thermal expansion after imidization. The present invention also provides
Having both good i-line permeability and low thermal expansion after imidization,
An object of the present invention is to provide a photosensitive resin composition capable of forming a pattern having excellent heat resistance. Another object of the present invention is to provide a method for producing a pattern capable of forming a pattern having excellent heat resistance while achieving both good i-line transmittance and low thermal expansion after imidization. Further, the present invention provides an electronic component having excellent reliability because the residual stress after the formation of the polyimide film is extremely small and the film pattern has both good heat resistance and low stress.

[0009]

Means for Solving the Problems The present invention provides the following (1)-
Regarding (7). (1) General formula (1)

Embedded image (Wherein R ¹ and R ² are each independently a hydrogen atom or a monovalent organic group, and R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or a hydrocarbon group; Is a hydrocarbon group, and the two bonds indicated by the arrows may be mutually oppositely bonded), and a general formula (2)

Embedded image (Wherein R ¹ and R ² are each independently a hydrogen atom or a monovalent organic group, and R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a group containing a hydrogen atom or a fluorine atom. , At least one of which is a group containing a fluorine atom, and the two bonds indicated by arrows may be mutually oppositely bonded).

(2) General formula (3)

Embedded image (Wherein R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or a hydrocarbon group, and at least one is a hydrocarbon group); and a general formula (4)

Embedded image (Wherein R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a group containing a hydrogen atom or a fluorine atom, and at least one is a group containing a fluorine atom). A polyimide having a unit.

(3) A photosensitive resin composition containing the polyimide precursor according to (1). (4) A method for producing a pattern comprising a step of applying and drying the photosensitive resin composition according to (3) above on a support substrate, a step of exposing, a step of developing, and a step of heat treatment. (5) The method for producing a pattern according to (4), wherein the step of exposing is performed using i-rays as an exposure light source.

(6) An electronic component having a pattern layer obtained by the manufacturing method according to (4) or (5). (7) An electronic component comprising the polyimide layer according to (2).

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The polyimide precursor of the present invention contains structural units represented by the general formulas (1) and (2). In the general formulas (1) and (2), R ¹
And the monovalent organic group represented by R ² has 1 to 2 carbon atoms.
0 hydrocarbon group (alkyl group, cycloalkyl group, aryl group, allyl group, aralkyl group, etc.), group having a carbon-carbon unsaturated double bond (for example, acryloxyalkyl group (alkyl group having 1 to 1 carbon atoms) 10) and a photopolymerizable group such as a methacryloxyalkyl group (1 to 10 carbon atoms of the alkyl group).

When the polyimide precursor of the present invention is used in a photosensitive resin composition, when most or all of R ¹ and R ² have a photopolymerizable group, a photosensitive resin composition of a solvent development type is used. When a part of R ¹ or R ² is a hydrogen atom, either a solvent developing type or an alkali developing type photosensitive resin composition can be used. In the general formula (1), R ^{3 to} R ⁶ include, in addition to a hydrogen atom, a phenyl group, an alkyl group, a benzyl group, and the like. From the viewpoint of i-line permeability and low residual stress, an alkyl group is preferable. Carbon number 1
An alkyl group of 5 is more preferable, and a methyl group is most preferable for low residual stress. R ^{3 to} R ⁶ are at least 1
One is a hydrocarbon group, but preferably two or more are hydrocarbon groups, and more preferably all four are hydrocarbon groups.

In the general formula (2), R ^{7 to} R ¹⁰ are groups having at least one of them containing a fluorine atom from the viewpoint of i-ray permeability and solubility. It is preferably a group containing an atom. Preferred examples of the group containing a fluorine atom include a fluorine atom itself and a fluoroalkyl group such as a trifluoromethyl group. The group preferably has 1 to 5 carbon atoms. Among them, a trifluoromethyl group is particularly preferred.

The polyimide precursor of the present invention is synthesized by reacting a tetracarboxylic acid or a derivative thereof giving the structures of the general formulas (1) and (2) with a diamine in an organic solvent used as required. can do.
Examples of the tetracarboxylic acid include derivatives such as pyromellitic acid or its acid dianhydride.

It is possible to use a tetracarboxylic acid or a derivative thereof that gives a structure other than the general formula (1) to the extent that the i-line transmittance, low stress property, heat resistance and the like are not reduced. For example, oxydiphthalic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 3,6,7-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid,
3,4,9,10-perylenetetracarboxylic acid, sulfonyldiphthalic acid, m-terphenyl-3,3 ', 4,
4'-tetracarboxylic acid, p-terphenyl-3,
3 ', 4,4'-tetracarboxylic acid, 1,1,1,3,
3,3-hexafluoro-2,2-bis (2,3- or 3,4-dicarboxyphenyl) propane, 2,2-
Bis (2,3- or 3,4-dicarboxyphenyl) propane, 2,2-bis {4 '-(2,3- or 3,4-
Dicarboxyphenoxy) phenyl @ propane, 1,
1,1,3,3,3-hexafluoro-2,2-bis {4 '-(2,3- or 3,4-dicarboxyphenoxy) phenyl} propane, the following general formula (5)

Embedded image And an aromatic tetracarboxylic acid such as a tetracarboxylic acid represented by the following formula. These are used alone or in combination of two or more.

Examples of the derivative of tetracarboxylic acid include tetracarboxylic acid, tetracarboxylic dianhydride, tetracarboxylic acid chloride and the like. From the viewpoint of reactivity and the like, the reaction partner of the diamine is preferably a tetracarboxylic dianhydride when synthesizing a polyamic acid, and a tetracarboxylic acid chloride when synthesizing a polyamic acid ester.

As the diamine component giving the structure of the general formula (1) or (2), for example,

Embedded image And the like are preferred. In addition to these, diamines other than those described above can be used to the extent that the i-line transmittance, low stress property, heat resistance, and the like are not reduced.

The diamine providing a structure other than the general formulas (1) and (2) is not particularly limited.
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 '
-) Diaminodiphenyl sulfone, 4,4'- (or 3,4'-, 3,3'-, 2,4'-, 2,2'-) diaminodiphenyl sulfide, paraphenylenediamine, metaphenylenediamine, p -Xylylenediamine, m-xylylenediamine, o-tolidine, o-tolidinesulfone, 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, 2,2-bis (4-aminophenyl)
Examples thereof include aliphatic diamines such as propane and diaminopolysiloxane, which are used alone or in combination of two or more.

The organic solvent used in the above reaction is preferably a polar solvent which completely dissolves the polyimide precursor to be produced, for example, N-methyl-2-pyrrolidone, N, N
-Dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, tetramethylurea, hexamethylphosphoric triamide, γ-butyrolactone and the like.

In addition to the polar solvent, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons and the like can also be used. For example, 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 be mentioned. These organic solvents are used alone or in combination of two or more.

In the polyimide precursor of the present invention, the ratio of the structural unit represented by the general formula (1) to the structural unit represented by the general formula (2) depends on the storage stability of the varnish and the adhesiveness to the substrate. For this reason, the former / latter is preferably 70/30 to 1/99 (molar ratio), and 50/50 to 10/90.
(Molar ratio) is more preferable.

Further, structural units other than the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) are 10% of all the structural units in view of i-line transmittance and low stress.
%, Preferably 5% or less.

The molecular weight of the polyimide precursor of the present invention is not particularly limited.
It is preferable to set it to 0000 in terms of heat resistance and solubility. The molecular weight can be determined by gel permeation chromatography and converted using a standard polystyrene calibration curve.

The method for producing the polyimide precursor of the present invention is not particularly limited, and various known methods can be used.

An alcohol compound is used to form the side chain ester of the polyimide precursor. As the alcohol compound, when providing a photopolymerizable photosensitive group to produce a polyimide precursor for a negative photosensitive resin composition, hydroxymethyl acrylate, hydroxymethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl Unsaturated alcohol compounds such as methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate and hydroxybutyl methacrylate are preferred, and among them, hydroxyalkyl acrylate or hydroxyalkyl methacrylate having an alkyl chain having 1 to 10 carbon atoms is preferably used. .

As the alcohol compound, a saturated alcohol compound is mainly used for producing a polyimide precursor for a positive photosensitive resin composition, and examples thereof include methanol, ethanol, and n-propyl alcohol. , Isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-
Butyl alcohol, isobutyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, isoamyl alcohol, 1-hexanol, 2-hexanol, alkyl alcohols having 1 to 10 carbon atoms such as 3-hexanol, These can be used alone or in combination of two or more.

The reaction of each component can be performed by a well-known method. That is, the thionyl chloride method, the DCC method, the isoimide method, and the like are known. As the organic solvent used in the reaction, a polar solvent that completely dissolves the produced polyimide precursor is preferable, for example, N-methyl-2-pyrrolidone,
N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, tetramethylurea,
Hexamethylphosphoric triamide, γ-butyrolactone, and the like.

In addition to the polar solvent, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons and the like can also be used. For example, 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,
Examples thereof include chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, and the like. These organic solvents are used alone or in combination of two or more.

The polyimide of the present invention can be synthesized by closing the polyimide precursor. Ring closure can usually be performed by heating. The heating conditions are not particularly limited, but the heating temperature is 80 to 450.
It is preferably set to ° C. If the heating temperature is lower than 80 ° C., the ring closure reaction tends to be slow, and if it exceeds 450 ° C., the produced polymer tends to deteriorate. Also,
The heating time is preferably set to 10 to 100 minutes.
If the heating time is less than 10 minutes, the ring closure reaction tends to be slow, and if it exceeds 100 minutes, the produced polymer tends to be deteriorated and the workability tends to be reduced.

The photosensitive resin composition of the present invention can be obtained by imparting photosensitivity to the polyimide precursor composition. Examples of the method for imparting photosensitivity include, for example, a method of introducing a group having a carbon-carbon unsaturated double bond by a covalent bond on the side of the polyimide precursor, and ionizing an acrylic compound having an amino group at a carboxyl group of the polyimide precursor. A known method such as a method of introducing by bonding, a method of mixing a monomer reactive with the polyimide precursor, and a photosensitizing agent such as a photoacid generator and a photobase generator can be used.

Examples of the acrylic compound having an amino group used for forming an ionic bond in a side chain include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, and dimethylaminopropyl. Dialkylaminoalkyl acrylates or methacrylates such as methacrylate, diethylaminopropyl acrylate, diethylaminopropyl methacrylate, dimethylaminobutyl acrylate, dimethylaminobutyl methacrylate, diethylaminobutyl acrylate, diethylaminobutyl methacrylate, and the like are preferable. -10, alkyl chain having 1-10 carbon atoms Dialkylaminoalkyl acrylates or methacrylates are used as preferred.

In the photosensitive resin composition of the present invention, a photopolymerization initiator is generally contained in order to obtain a negative photosensitive resin composition. Examples of the photopolymerization initiator include Michler's ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether,
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, diphenyldisulfide, 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) oxyiminopropane-
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, 1,3-diphenyl-1,2,3-propanetrione-2- (o-ethoxycarbonyl) oxime, and the like. These are used alone or in combination of two or more.

The use amount of the photopolymerization initiator is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the total amount of the polyimide precursor. . If the amount is less than 0.01 part by weight, the photosensitivity tends to be inferior, and if it exceeds 30 parts by weight, the mechanical properties of the film tend to be inferior.

The negative photosensitive resin composition can contain 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-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, 1,3-methacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, and the like. Can be These are used alone or in combination of two or more.

The addition polymerizable compound is preferably used in an amount of 1 to 200 parts by weight based on 100 parts by weight of the total amount of the polyimide precursor. When the amount is less than 1 part by weight, the photosensitive characteristics including solubility in a developer tend to be inferior, and when it exceeds 200 parts by weight, the mechanical characteristics of the film tend to be inferior.

The negative photosensitive resin composition 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.

The amount of the radical polymerization inhibitor or the radical polymerization inhibitor is preferably 0.01 to 30 parts by weight based on 100 parts by weight of the total amount of the polyimide precursor.
More preferably, it is 0.05 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.

On the other hand, when producing a positive photosensitive resin composition, it is preferable to use a compound which generates an acid by light together with the polyimide precursor. The compound that generates an acid by light has a function of generating an acid and increasing the solubility of the irradiated portion in a developing solution (aqueous alkaline solution). Examples thereof include o-quinonediazide compounds, aryldiazonium salts, diaryliodonium salts, and triarylsulfonium salts. The compound which generates an acid by light is preferably 5 to 100 parts by weight, more preferably 10 to 100 parts by weight, based on the total amount of the polyimide precursor, from the viewpoint of the film thickness and sensitivity after development.
４０40 parts by weight are used.

The photosensitive resin composition of the present invention can be obtained in a solution state by dissolving the polyimide precursor and other components in a solvent. Examples of the solvent include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphoramide, tetramethylsulfone, γ-butyrolactone, cyclohexanone, cyclopentane Aprotic polar solvents such as nonone are used alone or in combination of two or more.

The photosensitive resin composition of the present invention may further contain an organic silane compound, an aluminum chelate compound, a silicon-containing polyamic acid and the like in order to enhance the adhesion of the cured film to the substrate. Examples of the organic silane compound include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, and the like. Examples of the aluminum chelate compound include aluminum tris (acetylacetate) and aluminum acetylacetate diisopropylate.

The photosensitive resin composition of the present invention is applied onto a base material 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 most of the solvent is removed. By heating and drying, a coating film having no tackiness can be obtained. Although there is no particular limitation on the thickness of this coating film, from the viewpoint of circuit characteristics and the like, it is 4 to 50 μm.
m, more preferably 6 to 40 μm, particularly preferably 10 to 40 μm, and most preferably 20 to 35 μm.

After exposing the coating film to a pattern by irradiating actinic rays or actinic rays through a mask on which a desired pattern is drawn, the unexposed portion is developed and dissolved with an appropriate developing solution, By removing, a desired relief pattern can be obtained.

Since the photosensitive resin composition of the present invention can form a film having a low residual stress, it can be applied to a large-diameter wafer such as a silicon wafer having a diameter of 20 cm or more, especially 30 cm (12 inches) or more. It is suitable. The coating film is exposed to actinic rays or actinic rays through a mask on which a desired pattern is drawn, exposed in a pattern, and the unexposed or exposed portions are developed and dissolved with an appropriate developer to remove and remove. Thereby, a desired pattern can be obtained.

The photosensitive resin composition of the present invention is suitable for exposure to i-ray monochromatic light using an i-ray stepper or the like. For example, a contact / proximity exposure machine using an ultra-high pressure mercury lamp, a mirror projection exposure machine, a g-ray stepper, other ultraviolet rays, a visible light source, an X-ray, an electron beam, and the like can be used.

As a developing solution, for example, a good solvent (N, N-dimethylformamide, N, N
N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.), mixed solvents of the above-mentioned good solvents and poor solvents (lower alcohols, ketones, water, aromatic hydrocarbons, etc.), and aqueous alkali solutions. As the alkaline aqueous solution,
For example, an aqueous solution of tetramethylammonium hydroxide, an aqueous solution of triethanolamine and the like can be mentioned. After the development, rinsing is preferably performed with water or a poor solvent to stabilize the pattern. Also, by heating this relief pattern, a patterned high heat-resistant polyimide can be formed.

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 0.1 to 10
Preferably, it is time. If the heating time is less than 0.1 hour, the mechanical and thermal characteristics of the polyimide film tend to decrease, and if it exceeds 10 hours, the mechanical and thermal characteristics of the polyimide film tend to decrease.

The photosensitive resin composition of the present invention can be used for electronic parts such as semiconductor devices and multilayer wiring boards, and more specifically, for surface protection films and interlayer insulating films of semiconductor devices and multilayer wiring boards. It can be used for forming an interlayer insulating film and the like. 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.

As an example of the electronic component of the present invention, an example of a semiconductor device manufacturing process will be described below. FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure. In the figure, a semiconductor substrate such as a Si substrate having a circuit element is covered with a protective film 2 such as a silicon oxide film except for a predetermined portion of the circuit element, and a first conductor layer is formed on the exposed circuit element. . A film 4 of a 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, 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 resin composition by a spin coating method, dried, irradiated with light from a mask on which a pattern for forming a window 6C is formed on a predetermined portion, and then exposed to an alkaline aqueous solution. To form a pattern and heat to form a resin film of a relief pattern. This resin film protects the conductor layer from external stress, α rays, etc.
The obtained 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.

[0055]

The present invention will be described below with reference to examples. Synthesis Examples 1-3 and Synthesis Examples 4-5 (1) In a 200 ml four-necked flask, 0.03 mol of the acid anhydride shown in Table 1 and 7.81 g (0.06 mol) of 2-hydroxyethyl methacrylate (HEMA). , 4.75 g (0.06 mol) of pyridine, 0.01 of hydroquinone
g, N, N'-dimethylacetamide (DMAc) 70
Then, the mixture was stirred at 60 ° C. and turned into a clear solution in 1 hour. The solution was stirred at room temperature for the next 12 hours,
The flask was cooled with ice and 8.57 g of thionyl chloride (0.
072 mol) was added dropwise in 10 minutes. Thereafter, the mixture was stirred at room temperature for 1 hour to obtain a solution containing acid chloride.

(2) Synthesis of Polyimide Precursor Another 200 ml four-necked flask was charged with 0.03 mol of the diamine shown in Table 1, 5.06 g (0.064 mol) of pyridine, 0.01 g of hydroquinone, and 50 ml of DMAc. The acid chloride solution obtained in the above (1) was slowly dropped over 1 hour while cooling the flask with ice (10 ° C. or lower) and stirring. Thereafter, the mixture was stirred at room temperature for 1 hour, poured into 1 liter of water, and the precipitated polymer was collected by filtration, washed twice, and dried in vacuum. This polymer powder was dissolved in γ-butyrolactone (γ-BL), the viscosity was adjusted to 80 poise, and a polyimide precursor solution (PAE-1 to PAE-5) was obtained.

The dried polyimide precursor solution (PAE-1 to PAE-5) was dried with KB
The infrared absorption spectrum (manufactured by JEOL Ltd.,
(JIR-100 type) were measured.
The absorption of C = O of the amide group around 00 cm ^-1 and 3300
The absorption of NH was confirmed at around cm ^-1 .

Examples 1 to 3 and Comparative Examples 1 to 2 10 g of the powder of each of the polyimide precursors (PAE-1 to PAE-5) obtained in Synthesis Examples 1 to 3 and Synthesis Examples 4 to 5 was subjected to γ-
It was dissolved in 15 g of butyrolactone (γ-BL), and 100 mg of Michler's ketone and 200 mg of 1,3-diphenyl-1,2,3-propanetrione-2- (o-ethoxycarbonyl) oxime were added and dissolved. And the uniform photosensitive resin composition solution used for Comparative Examples 1-2 was obtained.

The obtained photosensitive resin composition solution was filtered through a filter, and each of the solutions was spin-coated on a silicon wafer. Next, using a hot plate, the coating was heated at 100 ° C. for 150 seconds to form a 23 μm coating film, and then subjected to pattern masking and exposure with an i-line stepper. After exposure, γ-
Paddle development was performed using a mixed solution of butyrolactone and butyl acetate, and this was heated at 350 ° C. for 60 minutes to obtain a polyimide relief pattern. For a part of the obtained polyimide relief pattern, by KBr method,
Upon measuring the infrared absorption spectrum, 1780 cm ⁻¹
Characteristic absorption of the imide was confirmed in the vicinity.

The transmittance of each of the polyimide precursors (PAE-1 to PAE-5) obtained in Synthesis Examples 1 to 5, the residual stress on the silicon wafer, and the resolution of the relief pattern were evaluated by the following methods. Table 2 shows the evaluation results.
The transmittance was determined for each of the obtained polyimide precursors (PAE-1 to PAE-1).
PAE-5) is spin-coated with a resin solution and dried at 85 ° C. for 2 hours.
And dried at 105 ° C. for 2 minutes, and the coating film (20 μm) obtained was measured with a spectrophotometer. Residual stress is 5
A polyimide film was formed on an inch wafer, and measured with a stress measuring device (FLX-2320 type, manufactured by Tencor Corporation). The resolution was evaluated as the minimum size of a developable through hole using a through hole test pattern.

The relief patterns obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were prepared at 4000 ° C. in a nitrogen atmosphere at 6 ° C.
Heating was performed for 0 minutes to obtain a polyimide pattern.

[0062]

[Table 1]

[0063]

[Table 2] Molecular weight measurement conditions (GPC method) Detector: L4000 UV Detector (manufactured by Hitachi, Ltd.), detection wavelength: 270 nm Pump: L6000 Pump (manufactured by Hitachi, Ltd.) Data processing: C-R4A Chromatopac (Shimazu Corporation) Column): Gelpack GL-S300 MDT-5 (Hitachi Chemical Industries, Ltd.)
Eluent: THF / DMF = 1/1 (volume ratio), LiBr (0.03 mol / dm ³ ), H ₃
PO ₄ (0.06mol / dm ³ )

[0064]

The polyimide of the present invention and its precursor are
It achieves both good i-line permeability and low residual stress after imidization. The photosensitive resin composition of the present invention has both good i-line transmittance in the polyimide precursor and low glass transition temperature after imidization, and the silicon wafer on which the polyimide film is formed has low residual stress. A simple pattern can be formed.

According to the method for producing a pattern of the present invention,
With high i-line transmittance, a pattern with high sensitivity, high resolution and good shape can be manufactured by i-line exposure, and a polyimide film having low stress and excellent heat resistance after imidization can be formed. Further, the electronic component of the present invention is a pattern having a high resolution and a good shape, has a polyimide film excellent in heat resistance and the like, and has extremely low residual stress, and thus 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: 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 F term (reference) 2H025 AA00 AA10 AB16 AC01 AD01 BC32 BC42 BC69 CA01 CA18 CA27 CA39 CB25 FA03 FA15 FA29 2H096 AA25 AA26 BA06 BA20 EA02 GA03 HA01 4J043 PA04 PA19 QB23 QB26 QB31 RA34 SA54 TA43 SA TA27 UA121 UA122 UA131 UA132 UA142 UA151 UA152 UA252 UA261 UA262 UA362 UB011 UB021 UB022 UB061 UB062 UB121 UB122 UB132 UB151 UB152 UB281 UB301 UB302 UB322 UB351 UB352 Z12B04 ZUBA ZB32A04A

Claims (7)

[Claims] 1. A compound of the general formula (1) (Wherein R ¹ and R ² are each independently a hydrogen atom or a monovalent organic group, and R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or a hydrocarbon group and have at least 1 Is a hydrocarbon group, and the two bonds indicated by the arrows may be mutually oppositely bonded) and a structural unit represented by the general formula (2): (Wherein R ¹ and R ² are each independently a hydrogen atom or a monovalent organic group, and R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a group containing a hydrogen atom or a fluorine atom. At least one is a group containing a fluorine atom, and the two bonds indicated by arrows may be mutually oppositely bonded). 2. A compound of the general formula (3) (Wherein R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or a hydrocarbon group and at least one is a hydrocarbon group), and a general formula (4) Embedded image (Wherein, R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a group containing a hydrogen atom or a fluorine atom, and at least one is a group containing a fluorine atom) A polyimide comprising: 3. A photosensitive resin composition comprising the polyimide precursor according to claim 1. 4. A method for producing a pattern, comprising the steps of: applying the photosensitive resin composition according to claim 3 on a support substrate and drying; exposing; developing; and heating. 5. The method according to claim 4, wherein the step of exposing is performed using i-line as an exposure light source. 6. An electronic component having a layer of a pattern obtained by the method according to claim 4. 7. An electronic component comprising the polyimide layer according to claim 2.