JP2002099083A - Photosensitive resin composition, method of producing pattern, and electronic part - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition having good i-ray transmissiveness and excellent in resolution, provide a method of producing pattern which is capable of forming a pattern having good resolution by i-ray exposure, and provide an electronic part which possesses a pattern with high resolution and has good reliability after polyimide is formed. SOLUTION: This photosensitive resin composition contains a polyimide precursor having repeating units represented by general formula (1) [Wherein, A represent a divalent organic group; R1 and R2 each independently represent hydroxyl group or a monovalent organic group; R3 and R4 each independently represent hydrogen atom or a 1-10 alkyl group; n represents an integer of 5-20.]. The method of producing this pattern includes a process wherein the photosensitive resin composition is applied onto the supporting substrate and dried, a process of exposure, a process of development, and a process of heat treatment. This electronic part possesses a layer of the pattern obtained by the method of producing the pattern.

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. More specifically, using a polyimide precursor having a high i-line permeability, by heat treatment, it can be changed to a polyimide-based heat-resistant polymer and the like as a surface protective film of an electronic component such as a semiconductor element, an interlayer insulating film, and the like. The present invention relates to a negative or positive 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 and a surface protective film material which have conventionally been formed using inorganic materials. It has been used taking advantage of. However, forming a circuit pattern on a semiconductor integrated circuit or a printed circuit board is complicated by forming a resist material on the base material surface, exposing a predetermined portion, removing unnecessary portions by etching, and cleaning the substrate surface. Since pattern formation is performed through various steps, 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.

[0003] As these materials, for example, heat-resistant light-sensitive materials based on photosensitive polyimide, cyclized polybutadiene and the like have been proposed. In particular, photosensitive polyimide is, for example, excellent in heat resistance. Particular attention has been paid to its ease of removal.

As such a photosensitive polyimide, a system comprising a polyimide precursor and a dichromate (JP-B-49-17374) was first proposed. However, this material has practical photosensitivity and has advantages such as high film-forming ability, but lacks storage stability and has disadvantages such as chromium ions remaining in polyimide. Did not reach.

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 of mixing a functional group and a photosensitive group in the polyimide precursor. A method of reacting with a functional group of a compound having a compound to impart a photosensitive group (JP-A-56-24343,
JP-A-60-100143) and the like have been proposed. However, these photosensitive polyimide precursors use a basic skeleton as an aromatic monomer and have excellent heat resistance and mechanical properties, but due to the absorption of the polyimide precursor itself, light transmission in the ultraviolet region is low. Low. Therefore, in the method using these photosensitive polyimide precursors, the photochemical reaction in the exposed portion cannot be performed sufficiently effectively, and the sensitivity is low.
There is a problem that the shape of the pattern deteriorates.

In recent years, as the integration of semiconductors has increased, processing rules have become smaller, and higher resolutions have been required. For this reason, a 1: 1 projection exposure machine called a mirror projection and a reduction projection exposure machine called a stepper have been used instead of a conventional contact / proximity exposure machine using parallel rays.

The stepper utilizes a high-power oscillation line of an ultra-high pressure mercury lamp and monochromatic light such as an excimer laser. Until now, the stepper has used g-li
Although a g-line stepper using visible light (wavelength: 435 nm) called ne has been mainstream, it is necessary to shorten the wavelength of the stepper to be used in order to further meet the demand for finer processing rules. Therefore, the exposure equipment used is from a g-line stepper (wavelength: 435 nm) to an i-line stepper (wavelength: 435 nm).
365 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 reasons described above, and in particular, have low transparency. i
Line (wavelength: 365 nm) has almost no transmittance.
Good patterns cannot be obtained with a line stepper. Also,
In order to support LOC (lead-on-chip), which is a high-density mounting method for semiconductor devices, a thicker polyimide film is required for surface protection. Becomes even more serious. 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.

[0009]

The object of the present invention is to provide a photosensitive resin composition having good i-line transmittance and excellent resolution. The second, third and fourth aspects of the present invention provide a photosensitive resin composition capable of forming a negative pattern in addition to the objects of the first aspect of the present invention. A fifth aspect of the present invention provides a photosensitive resin composition capable of developing and patterning with an aqueous alkali solution, in addition to the objects of the first aspect of the present invention. The inventions of claims 6 and 7 provide a photosensitive resin composition capable of forming a positive pattern in addition to the objects of the invention of claim 5.

The inventions according to claims 8 and 9 provide a method for producing a pattern capable of forming a pattern with good resolution by i-line exposure. According to the tenth and eleventh aspects of the present invention, there is provided an electronic component having a high-resolution pattern and having good reliability after polyimide formation.

[0011]

According to the present invention, there is provided a compound represented by the general formula (1):

Embedded image (In the formula, A represents a divalent organic group, R ¹ and R ² each independently represent a hydroxyl group or a monovalent organic group, and R ³ and R ⁴ each independently represent a hydrogen atom or a carbon atom having 1 to 10 carbon atoms. Wherein n is an integer of 5 to 20). The photosensitive resin composition comprises a polyimide precursor having a repeating unit represented by the following formula:

[0012] The present invention, R ¹ in the general formula (1)
And R ² is a photosensitive resin composition in which at least one of R ¹ and R ² is a monovalent organic group having a carbon-carbon unsaturated double bond. Further, the present invention relates to the photosensitive resin composition further containing a photopolymerization initiator. The present invention also relates to the photosensitive resin composition further containing an addition polymerizable compound having a carbon-carbon unsaturated double bond.

Further, the present invention provides a compound represented by the above general formula (1).
A in the polyimide precursor is a carboxyl group or
A divalent organic group having a phenolic hydroxyl group, or
Is R ¹And R^TwoAt least one of which is a hydroxyl group
The present invention relates to a fat composition. Further, the present invention further provides an acid by light.
The photosensitive resin composition containing the compound generated
You. The present invention also relates to a compound which generates an acid by the light.
Is a photosensitive resin composition which is an o-quinonediazide compound
About.

The present invention also relates to a method for producing a pattern, comprising the steps of applying and drying the photosensitive resin composition according to any of the above on a supporting substrate, exposing, developing, and heating. . The present invention also relates to a method for producing a pattern, wherein the exposing step is performed using i-line as an exposure light source.

The present invention also relates to an electronic component having a layer having a pattern obtained by the above-mentioned manufacturing method. The present invention also relates to an electronic component in which the layer of the pattern is a surface protective film or an interlayer insulating film.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The polyimide precursor of the present invention is a polymer compound having a repeating unit represented by the above general formula (1).
The polyimide precursor has high transparency.

Although the ratio of the repeating unit represented by the general formula (1) to all the repeating units is not particularly limited, the transmittance of the polyimide precursor at the i-line (365 nm) and the heat resistance after imidization are as follows. It is preferable that the setting is made to match the required characteristics. Specifically, the content is preferably 10 to 100 mol% with respect to all the repeating units.

The molecular weight of the polyimide precursor of the present invention is not particularly limited.
It is preferably 00,000. The weight-average molecular weight can be measured by gel permeation chromatography and converted using a standard polystyrene calibration curve.

In the general formula (1), R ¹ and R ² are each independently a hydroxyl group or a monovalent organic group, and different groups can be used according to desired functions. Specific examples of each will be described later.

In the above formula (1), R ³ and R ⁴ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, Examples include a pentyl group, a cyclopentyl group, a hexyl, a cyclohexyl group, and a decyl group.

In the general formula (1), A can react with tetracarboxylic dianhydride or a derivative thereof.
A divalent organic group derived from a diamine represented by the general formula H ₂ N-A-NH ₂ , which generally has a halogen atom on its ring,
A hydrocarbon group, a halogenated hydrocarbon group, a hydroxyl group, an aromatic ring such as a naphthalene ring which may have a substituent such as a carboxyl group, or an aromatic ring such as a naphthalene ring; And a divalent organic group having a structure linked via a group, a sulfone group, a carbonyl group, a thioether group, a methylene group, an alkylidene group, a halogenated alkylidene group, a sulfonyl group, or the like.

The diamine represented by the above general formula H ₂ N—A—NH ₂ is not particularly limited, and is, for example, 4,4′-diamine.
(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'-) diaminodiphenyl sulfide, paraphenylenediamine, metaphenylenediamine, p-xylylenediamine, m-xylylenediamine, o-tolidine, o-tolidine sulfone, ,
4'-methylene-bis- (2,6-diethylaniline), 4,4'-methylene-bis- (2,6-diisopropylaniline), 2,4-diaminomesitylene,
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, 2,
2-bis (4-aminophenyl) propane and the like can be mentioned, and these can be used alone or in combination of two or more.

Among the diamines, a diamine which provides a polyimide precursor having high heat resistance and high transparency is represented by the general formula (2)

Embedded image (Wherein, R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group, a fluorine atom or a fluoroalkyl group, and two or more thereof are an alkyl group, a fluorine atom or a fluoroalkyl group )).

In the above general formula (2), in R ⁵ , R ⁶ , R ⁷ and R ⁸ , the alkyl group is preferably one having 1 to 5 carbon atoms, and among them, a methyl group, an ethyl group and a propyl group are more preferable. preferable. As the fluoroalkyl group, a perfluoroalkyl group having 1 to 5 carbon atoms is preferable, and among them, a trifluoromethyl group and a pentafluoroethyl group are more preferable.

When the diamine represented by the above general formula (2) is used for the purpose of improving the i-ray transmittance and the mechanical and thermal properties of the polyimide film, the amount of the diamine used is 10 times the total amount of the diamine. It is preferable to set it in the range of 100 mol%.

In order to improve the adhesion to the substrate, the following general formula (3)

Embedded image (In the formula, R ⁹ and R ¹⁰ each independently represent a divalent hydrocarbon group, a plurality of R ¹¹ each independently represent a monovalent hydrocarbon group, and t is an integer of 1 or more.) An aliphatic diamine such as diaminopolysiloxane represented by the formula (1) can also be used.

In the above general formula (3), examples of the divalent hydrocarbon group represented by R ⁹ and R ¹⁰ include those having 1 carbon atom.
To 10 alkylene groups and phenylene groups;
Examples of the monovalent hydrocarbon group represented by ¹¹ include an alkyl group having 1 to 10 carbon atoms and a phenyl group.

The polyimide precursor represented by the general formula (1) is, for example, a compound represented by the following general formula (4)

Embedded image (Wherein, R ³ and R ⁴ each independently represent a hydrogen atom or a carbon atom
Indicates 10 alkyl group, n and the alkylene group containing tetracarboxylic dianhydride or its derivative represented by a is) integer 5-20, and the diamine represented by _{H 2 N-A-NH 2} , If necessary, it can be produced using other compounds forming a side chain as raw materials.

Examples of the derivatives of tetracarboxylic dianhydride include tetracarboxylic diester, tetracarboxylic diester dichloride and the like.

The outline of one example of the method for producing the alkylene group-containing tetracarboxylic dianhydride represented by the general formula (4) will be described.

For example, a 4-halogenated phthalic anhydride or a dicarboxylic acid is esterified to give a compound of the general formula (5)

Embedded image (Wherein, two R ¹² each independently represent an alkyl group having 1 to 10 carbon atoms, and X represents an iodine atom, a bromine atom or a chlorine atom), and a halogenated phthalic acid diester represented by the following formula: 1/2 equivalent of the general formula (6)

Embedded image (Wherein, R ³ and R ⁴ each independently represent a hydrogen atom or a carbon atom
Is an alkyl group of 10 to 10, m is an integer of 1 to 16) and a diacetylene represented by the general formula (7):

Embedded image (Wherein, R ³ and R ⁴ each independently represent a hydrogen atom or a carbon atom
An acetylene group-containing aromatic tetracarboxylic acid ester represented by the following formula: wherein R 4 represents an alkyl group having 1 to 10 carbon atoms, and each of four R ¹² independently represents an alkyl group having 1 to 10 carbon atoms; Can be obtained.

Next, the ester site of the acetylene group-containing aromatic tetracarboxylic acid ester is hydrolyzed to give a compound of the general formula (8)

Embedded image (Wherein, R ³ and R ⁴ each independently represent a hydrogen atom or a carbon atom
Acetylene group-containing aromatic tetracarboxylic acid represented by the formula (9), wherein m is an integer of 1 to 16), and then the acetylene moiety is hydrogenated to alkylene to form a compound represented by the general formula (9)

Embedded image (Wherein, R ³ and R ⁴ each independently represent a hydrogen atom or a carbon atom
An alkyl group of 10 to 10 and n is an integer of 5 to 20), and the resulting alkylene group-containing aromatic tetracarboxylic acid is subjected to dehydration and ring closure to obtain a compound represented by the above general formula (4). Alkylene group-containing tetracarboxylic dianhydride can be obtained.

In the production of the polyimide precursor of the present invention, an alkylene group-containing tetracarboxylic dianhydride represented by the above general formula (4) or a derivative thereof is required as an essential component. Other tetracarboxylic dianhydrides or derivatives thereof can be used to the extent that the properties and the like are not reduced.

The tetracarboxylic dianhydride is not particularly restricted but includes, for example, oxydiphthalic acid, pyromellitic acid, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, 3,3', 4 4,4'-biphenyltetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-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
Dianhydride of tetracarboxylic acid such as -hexafluoro-2,2-bis {4 '-(2,3- or 3,4-dicarboxyphenoxy) phenyl} propane;
0)

Embedded image (Wherein, a plurality of R ¹³ each independently represent a monovalent hydrocarbon group, and s is an integer of 1 or more), such as an aromatic tetracarboxylic acid dianhydride. They can be used alone or in combination of two or more.

The organic solvent used in the production of the polyimide precursor of the present invention is not particularly limited as long as the produced polyimide precursor can be completely dissolved, but a polar solvent is preferred in terms of good solubility. , 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, and these organic solvents may be used alone. Alternatively, two or more types can be used in combination.

When the photosensitive resin composition of the present invention is of a negative type, at least a part, preferably 20 to 100 mol%, of R ¹ and R ^{2 in} the above general formula (1) is substituted with a carbon-carbon unsaturated diamine. It is preferable to use a monovalent organic group having a heavy bond.

As such a monovalent organic group, a group represented by the following general formula having a carbon-carbon unsaturated double bond group via an ionic bond, an ester bond, an amide bond or the like is preferred. Can be

Embedded image (In the formula, X represents a divalent hydrocarbon group, R represents a hydrogen atom or a methyl group, and Z ¹ , Z ² and Z ³ each independently represent a hydrogen atom or a monovalent hydrocarbon group.)

In the above formula, X represents 1 carbon atom.
Preferred are alkylene groups of 10 to 10. As Z ¹ , Z ² and Z ³ , a hydrogen atom or an alkyl group having 1 to 5 carbon atoms is preferable.
It is preferable that one has a hydrogen atom and the other two have an alkyl group.

Among the above methods, the method for introducing a carbon-carbon unsaturated double bond through an ionic bond is preferably a method using an acrylic compound having an amino group such as a derivative having an amino group of acrylic acid or methacrylic acid. . Such compounds include, for example, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminopropyl methacrylate, N, N-diethylaminopropyl methacrylate, N, N-dimethylaminoethyl Acrylate, N, N-diethylaminoethyl acrylate, N,
Examples include N-dimethylaminopropyl acrylate, N, N-diethylaminopropyl acrylate, N, N-dimethylaminoethyl acrylamide, N, N-dimethylaminoethyl acrylamide and the like. These can be used alone or in combination of two or more.

When the carbon-carbon unsaturated double bond is introduced via an ionic bond, the amount of the acrylic compound having an amino group is determined by the amount of the polyamic acid before the introduction (ie,
In the general formula (1), R ¹ and R ² are both hydroxyl groups), preferably 1 to 200% by weight, more preferably 5 to 150% by weight. If the amount is less than 1% by weight, the photosensitivity tends to be inferior, and if it exceeds 200% by weight, the heat resistance and the mechanical properties of the film tend to be inferior. With this method,
When producing an ion-bonding type polyimide precursor, the tetracarboxylic dianhydride and the diamine are mixed and subjected to a ring-opening polyaddition reaction to form a polyamic acid, and then the acrylic compound having an amino group is mixed. Good.

When a carbon-carbon unsaturated double bond is introduced via an ester bond, a polyamic acid ester is synthesized. As a method of synthesizing this compound, for example, a tetracarboxylic dianhydride is reacted with an unsaturated alcohol to synthesize a tetracarboxylic diester compound, which is subsequently converted into a tetracarboxylic diester dihalide, and further, a diamine and It can be obtained by reacting.

Hereinafter, an example of a method for synthesizing the polyamic acid ester will be described more specifically. First, a tetracarboxylic diester compound can be obtained by mixing the tetracarboxylic dianhydride represented by the general formula (4) and an unsaturated alcohol compound in an organic solvent in the presence of a base.

As the unsaturated alcohol compound, hydroxyalkyl acrylate or methacrylate is preferable, and from the viewpoint of easy availability, those having an alkyl chain having 1 to 10 carbon atoms are more preferable. Examples of such unsaturated alcohol compounds include hydroxymethyl acrylate, hydroxymethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, and the like.

In the synthesis of the tetracarboxylic acid diester, the ratio (molar ratio) of the tetracarboxylic dianhydride to the unsaturated alcohol compound is 1/2 to 1/2.
The range is preferably 5 and most preferably 1/2. The ratio (molar ratio) of tetracarboxylic dianhydride to base is 1 / 0.001 to 1/3 for the former / the latter.
And more preferably 1 / 0.005 to １ ／. The reaction temperature is 10-60 ° C
Is preferable, and the reaction time is preferably 3 to 24 hours.

Then, a tetracarboxylic diester dihalide is synthesized, and this method is known. For example, it can be obtained by reacting a tetracarboxylic diester dissolved in an organic solvent by dropwise addition of thionyl chloride. Ratio of tetracarboxylic acid diester to thionyl chloride (molar ratio)
Is preferably in the range of 1 / 1.1 to 1 / 2.5 for the former / latter, and more preferably in the range of 1 / 1.5 to 1 / 2.2. The reaction temperature is preferably -20 to 40C, and the reaction time is preferably 1 to 10 hours.

The polyamic acid ester is prepared by dissolving a dehalogenating agent such as pyridine and a diamine in an organic solvent, dropping a tetracarboxylic diester dihalide dissolved in the organic solvent, and then reacting the resulting mixture with water. It can be obtained by putting it in a solvent, filtering the precipitate and drying. The ratio (molar ratio) of the total amount of the diamine and the tetracarboxylic diester dihalide was 0.6 / 1 in the former / the latter.
To 1 / 0.6, preferably 0.7 / 1 to 1/0.
A range of 7 is more preferred. The reaction temperature is preferably -20 to 40C, and the reaction time is preferably 1 to 10 hours. The ratio of the dehalogenating agent to the tetracarboxylic diester dihalide is 1.8 / 1-2.
The range of 1 is preferable, and the range of 1.9 / 1 to 2.1 / 1 is more preferable.

R ¹ and R ² in the polyimide precursor may have a form in which a hydrocarbon group is bonded via a nitrogen atom. In this case, the compound has a repeating unit represented by the general formula (1). The polyimide precursor becomes a polyamic acid amide.

The production method is such that a monoamine compound, for example, an alkyl group having 1 to 1 carbon atoms, is used instead of the unsaturated alcohol compound in the synthesis of the polyamic acid ester.
10, aminoalkyl methacrylate having 1 to 10 carbon atoms of an alkyl group, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, isobutylamine,
1-pentylamine, 2-pentylamine, 3-pentylamine, isoamylamine, 1-hexylamine, 2
-Hexylamine, 3-hexylamine, morpholine,
It can be synthesized by using aniline, benzylamine or the like.

In the case of producing a negative photosensitive resin composition in the photosensitive resin composition of the present invention, a photopolymerization initiator can be contained, if necessary, together with the polyimide precursor.

Examples of the photopolymerization initiator include Michler's ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 2-te
rt-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) oxyiminopropan-1-one, 3,3,4,4-tetra (tert-butylperoxycarbonyl) benzophenone, 3,3-carbonylbis (7-diethylaminocoumarin), bis (cyclopentadienyl) ) -Bis- [2,6-difluoro-3- (pyr-1-yl) phenyl] titanium, azide compounds and the like. These can be used alone or in combination of two or more.

The amount of the photopolymerization initiator to be used is preferably 0.01 to 30% by weight, based on the amount of the polyimide precursor having a repeating unit represented by the general formula (1). More preferably, the content is set to 05 to 10% by weight. 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 negative photosensitive resin composition may contain an addition polymerizable compound having a carbon-carbon unsaturated double bond, if necessary.

Examples of such addition-polymerizable compounds include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and trimethylolpropane. Diacrylate, 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-
Vinyl toluene, 4-vinyl pyridine, N-vinyl pyrrolidone, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,3-acryloyloxy-2-hydroxypropane, 1,3-methacryloyloxy-2-hydroxypropane, methylene Bisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide and the like can be mentioned. These can be used alone or in combination of two or more.

The amount of the addition polymerizable compound to be used is preferably 1 to 200% by weight based on the amount of the polyimide precursor having a repeating unit represented by the general formula (1). When the amount is less than 1% by weight, the photosensitive characteristics including solubility in a developer tend to be inferior.
If it exceeds, the mechanical properties of the film tend to be poor.

Further, the negative photosensitive resin composition may contain a radical polymerization inhibitor or a radical polymerization inhibitor in order to enhance the stability during storage.

Examples of the radical polymerization inhibitor or the radical polymerization inhibitor include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol,
o-dinitrobenzene, p-dinitrobenzene, m-dinitrobenzene, phenanthraquinone, N-phenyl-
1-naphthylamine, N-phenyl-2-naphthylamine, cuperon, phenothiazine, 2,5-toluquinone,
Examples include tannic acid, parabenzylaminophenol, nitrosamines and the like. These can be used alone or in combination of two or more.

The amount of the radical polymerization inhibitor or the radical polymerization inhibitor is 0.01 to 30 with respect to the amount of the polyimide precursor having a repeating unit represented by the general formula (1).
% By weight, more preferably 0.05 to 10% by weight. If this amount is less than 0.01% by weight, the stability during storage tends to be poor,
If it exceeds 0% by weight, the light sensitivity and the mechanical properties of the film tend to be poor.

When the photosensitive resin composition of the present invention is a positive photosensitive resin composition having an alkali developability, or
In the case of preparing an alkali-developable negative photosensitive resin composition, one of the methods for imparting alkali solubility to a polyimide precursor is to substitute a residue represented by A in the general formula (1) with a phenolic hydroxyl group or a carboxyl group. There is a method of forming a divalent organic group having a group.

In this case, a plurality of A in the polyimide precursor having a repeating unit represented by the general formula (1) may have both a phenolic hydroxyl group and a carboxyl group. The number of phenolic hydroxyl groups or carboxyl groups of the divalent organic group represented by A may be at least one, and is preferably 1 to 3.

Specific examples of diamines having these structures include 2,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 2,5-diaminoterephthalic acid, and bis (4 -Amino-3-carboxyphenyl) methylene, 4,4'-diamino-3,3'-dicarboxybiphenyl, 4,4'-diamino-5,5 '
-Dicarboxy-2,2'-dimethylbiphenyl, 1,
3-diamino-4-hydroxybenzene, 1,3-diamino-5-hydroxybenzene, 3,3'-diamino-
4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-
Amino-3-hydroxyphenyl) sulfone, bis (3
-Amino-4-hydroxyphenyl) hexafluoropropane, bis (4-amino-3-hydroxyphenyl)
Hexafluoropropane, bis (4-amino-3-carboxyphenyl) methane and the like can be mentioned.

According to this method, when an alkali-developable positive photosensitive resin composition or an alkali-developable negative photosensitive resin composition is used, the amount of the diamine giving A is the total amount of the diamine. Is preferably 50 to 100% by mol.

When imparting alkali developability to the photosensitive resin composition, as described above, the residue represented by A in the general formula (1) is replaced with a divalent organic group having a phenolic hydroxyl group or a carboxyl group. In addition to the above method, there is a method in which at least one of the groups represented by R ¹ and R ² is a hydroxyl group. When alkali developability is imparted by this method, it is preferable that 50 to 100 mol% of the groups represented by R ¹ and R ² in the polyimide precursor be hydroxyl groups.

When a positive photosensitive resin composition is produced, for example, when a diamine having a phenolic hydroxyl group or a carboxyl group is used as A in the general formula (1), R ¹ and R ² in the polyimide precursor are used. R ² is a monovalent hydrocarbon group (preferably having 1 to 10 carbon atoms) via an oxygen atom.
Is preferred, and is also a polyamic acid ester, so that an alcohol compound is substituted and a carbon-carbon unsaturated double bond is introduced via the above-described ester bond. Synthetic methods can be employed.

The alcohol compound used in this case includes, for example, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, 1-pentanol, -Pentanol, 3-pentanol, isoamyl alcohol, 1-hexanol, 2-hexanol, alkyl alcohols having 1 to 10 carbon atoms such as 3-hexanol and the like, and these may be used alone or in combination of two or more. Can be used.

When producing a positive photosensitive resin composition, a compound which generates an acid by light is generally used together with the polyimide precursor. The compound that generates an acid by light is a photosensitive agent, and has a function of generating an acid and increasing the solubility of the irradiated portion in an aqueous alkaline solution.
Examples of the type include an o-quinonediazide compound, an aryldiazonium salt, a diaryliodonium salt, and a triarylsulfonium salt, and are not particularly limited. Among them, the o-quinonediazide compound is more preferable because of its high sensitivity.

The o-quinonediazide compound is, for example, o
-It is obtained by subjecting a quinonediazide sulfonyl chloride to a condensation reaction with a hydroxy compound, an amino compound and the like in the presence of a dehydrochlorination catalyst.

Examples of the o-quinonediazidosulfonyl chloride include benzoquinone-1,2-diazido-4-sulfonylchloride and naphthoquinone-1,2-
Diazide-5-sulfonyl chloride, naphthoquinone-
1,2-diazido-4-sulfonyl chloride and the like can be mentioned.

As the hydroxy compound, for example,
Hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane,
2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxy Benzophenone, 2,3,4,2 ', 3'-pentahydroxybenzophenone, 2,3,4,3', 4 ', 5'-hexahydroxybenzophenone, bis (2,3,4-trihydroxyphenyl) methane , Bis (2,3,4-trihydroxyphenyl) propane, 4b, 5,9b, 10-tetrahydro-1,3,6,8-tetrahydroxy-5,
Examples thereof include 10-dimethylindeno [2,1-a] indene, tris (4-hydroxyphenyl) methane, and tris (4-hydroxyphenyl) ethane.

As the amino compound, for example, p-
Phenylenediamine, m-phenylenediamine, 4,
4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, o
-Aminophenol, m-aminophenol, p-aminophenol, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis (3-amino- 4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-
Hydroxyphenyl) sulfone, bis (3-amino-4)
-Hydroxyphenyl) hexafluoropropane, bis (4-amino-3-hydroxyphenyl) hexafluoropropane and the like.

The o-quinonediazidosulfonyl chloride and the hydroxy compound or amino compound are preferably blended so that the total of the hydroxy group and the amino group is 0.5 to 1 equivalent relative to the o-quinonediazidosulfonyl chloride. The ratio between the dehydrochlorination catalyst and o-quinonediazide sulfonyl chloride is preferably in the range of 0.95 / 1 to 1 / 0.95. The reaction temperature is preferably from 0 to 40C, and the reaction time is preferably from 1 to 10 hours.

The reaction solvent is not particularly limited as long as it is a solvent which dissolves o-quinonediazidosulfonyl chloride and a hydroxy compound or an o-quinonediazidosulfonyl chloride and an amino compound and does not cause an undesired side reaction during the condensation reaction. For example, solvents such as dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether, and N-methylpyrrolidone are used. Examples of the catalyst for dehydrochlorination include sodium carbonate, sodium hydroxide, sodium hydrogencarbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, pyridine and the like.

From the viewpoint of the film thickness and sensitivity after development, the component that generates an acid by light is based on 100 parts by weight of the polyimide precursor having the repeating unit represented by the general formula (1).
Preferably 5 to 100 parts by weight, more preferably 10 to 4 parts by weight
0 parts by weight are used.

The photosensitive resin composition of the present invention can be obtained in a solution state by dissolving a polyimide precursor having a repeating unit represented by the above general formula (1) in a solvent and then dissolving other components. it can.

As the solvent, for example, N-methyl-
2-pyrrolidone, N, N-dimethylformamide, N,
N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphoramide, tetramethylene sulfone,
An aprotic polar solvent such as γ-butyrolactone, cyclohexanone, and cyclopentanone is 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, vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane,
γ-methacryloxypropyltrimethoxysilane and the like can be mentioned. Examples of the aluminum chelate compound include tris (acetylacetonate) aluminum,
Acetyl acetate aluminum diisopropylate and the like can be mentioned.

The photosensitive resin composition of the present invention is applied to a 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 most of the solvent is removed. By heating and drying, a coating film having no tackiness can be obtained. There is no particular limitation on the thickness of this coating film, but from the viewpoint of circuit characteristics and the like, 4 to 50 μm
Is preferably, more preferably from 6 to 40 μm, particularly preferably from 10 to 40 μm,
It is extremely preferred that it is 20 to 35 μm. On this coating film, after exposure to a pattern by irradiating actinic rays or actinic rays through a mask on which a desired pattern is drawn, the unexposed portion or the exposed portion is developed and dissolved with an appropriate developing solution, By removing, a desired relief pattern can be obtained.

The photosensitive resin composition of the present invention is suitable for i-line exposure using an i-line stepper or the like.
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, X-rays, and an electron beam can also be used.

As the developing solution, for example, a good solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and a lower alcohol, ketone, water, aromatic Examples thereof include a mixed solvent with a poor solvent such as an aromatic hydrocarbon and an alkaline developer. When the polyimide precursor has alkali solubility, an alkaline solution can be used.
Examples of the alkaline solution include aqueous solutions of sodium hydroxide, potassium hydroxide, sodium silicate, tetramethylammonium hydroxide and the like. The concentration of the alkaline solution is preferably 5% by weight or less, more preferably 1.5 to 3.0% by weight. Among them, the most preferable developer is an aqueous solution of 1.5 to 3.0% by weight of tetramethylammonium hydroxide.

Further, a surfactant or the like may be added to the above-mentioned developer for use. These are respectively developer 1
The amount is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, per 100 parts by weight.

After the development, it is preferable to rinse with water or a poor solvent, if necessary, and to dry at about 100 ° C. to make the pattern stable. The obtained relief pattern can be made into a pattern of a highly heat-resistant polyimide film by heating. The heating temperature at this time is 150
To 500 ° C, more preferably 200 to 400 ° C. If the heating temperature is lower than 150 ° C., the mechanical and thermal properties of the polyimide film tend to decrease, and if it exceeds 500 ° C., the mechanical and thermal properties of the polyimide film tend to decrease. The heating time at this time is preferably set to 0.05 to 10 hours. If the heating time is less than 0.05 hours, 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 specifically, surface protective 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 pattern of a highly heat-resistant polyimide film formed using the composition as a surface protective film or an interlayer insulating film, and may have various structures. Can be.

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 1 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 3 is formed on the exposed circuit element. ing. An interlayer insulating film layer 4 such as a polyimide resin is formed on the semiconductor substrate 1 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 layer 4 by spin coating, and a predetermined portion of the interlayer insulating film layer 4 is formed by a known photolithography technique. The window 6A is provided so that the surface is exposed (step (b)). The interlayer insulating film layer 4 of 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 first conductor layer 3 exposed from the window 6B
The photosensitive resin layer 5 is completely removed using an etching solution that corrodes only the photosensitive resin layer 5 without corroding the photosensitive resin layer 5 (step (c)).

Further, using a known photo engraving 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 having three or more layers is formed, the above steps are repeated to form each layer.

Next, a surface protective film layer 8 is formed. In the example of this figure, the photosensitive resin composition is applied as a surface protective film layer by a spin coating method and dried, and a window 6 is formed on a predetermined portion.
After irradiating light from above the mask on which the pattern for forming C is drawn, development is performed with an alkaline aqueous solution to form a relief pattern, which is heated to form a polyimide film pattern. The pattern of this polyimide film is formed by applying an external stress, α
The semiconductor device is protected from wires and the like, and the obtained semiconductor device has excellent reliability. In the above example, the interlayer insulating film layer can be formed using the photosensitive resin composition of the present invention.

[0088]

The present invention will be described below with reference to examples.

Synthesis Example 1 [1,10-bis [3,4-di (carboxy) phenyl] -decane dianhydride [In the formula (4), R ³ and R ⁴
There are both hydrogen atoms, n = 10, compound] Synthesis] (1) 4-bromophthalic acid dimethyl ester [in the general formula (5) of the two R ^{1 2} are both methyl group, X is a compound a bromine atom] in the Synthesis Using a three-necked flask equipped with a stirrer, thermometer, and condenser, 40.79 g of 4-bromophthalic dianhydride (0.79 g) was used.
18 mol), a mixed solution of 177.55 g (5.54 mol) of methanol and 17.62 g (0.18 mol) of concentrated sulfuric acid were heated under reflux for 8 hours. After the methanol was distilled off under reduced pressure, the remaining mixture was allowed to cool to room temperature, and then poured into 200 g of ice water. The mixture was extracted with 600 ml of ethyl acetate (200 ml × 3), and the organic layer was washed with saturated sodium hydrogen carbonate and then with saturated saline. After drying over anhydrous magnesium sulfate,
After concentration under reduced pressure, 4-bromophthalic acid dimethyl ester was obtained (46.30 g, 0.170 mol, 94% yield).

(2) 1,10-bis [3,4-di (methoxycarbonyl) phenyl] -1,9-decadiyne [In the general formula (7), R ³ and R ⁴ are both a hydrogen atom and four R ¹² Are methyl groups, m = 6)] 4-bromophthalic acid dimethyl ester 1.00 g (36.6) using a four-necked flask equipped with a stirrer, thermometer, condenser, and nitrogen inlet tube. Mmol), 0.245 g (18.3 mmol) of 1,9-decadiyne, 10.34 g (141 mmol) of diethylamine, 0.0846 g (0.08 g) of palladium tetrakis (triphenylphosphine) palladium
732 mmol), cuprous iodide (CuI) 0.013
9 g (0.0732 mmol) of the mixture was heated under reflux for 4 hours under a nitrogen atmosphere. After cooling the mixture to room temperature, the solid was filtered off and the solid was washed with ethyl acetate. The mixture of the washing liquid and the filtrate was concentrated under reduced pressure, and the oily substance obtained was purified by silica gel column chromatography to give 1,10
-Di [3,4-di (methoxycarbonyl) phenyl]-
1,9-decadiyne was obtained (yield 0.86 g, 16.6).
Mmol, 91% yield).

(3) 1,10-bis [3,4-di (carboxy) phenyl] -1,9-decadiyne [In the general formula (8), R ³ and R ⁴ are both hydrogen atoms and m = 6. Synthesis of Compound] Using a three-necked flask equipped with a stirrer, a thermometer, and a condenser, 50.32 g of 1,10-bis [3,4-di (methoxycarbonyl) phenyl] -1,9-decadiyne ( 9
7.0 mmol), 35.87 g of potassium hydroxide (54
After refluxing a mixture of 32.8 mmol) and 322.85 g of water under heating for 13 hours, methanol produced as a by-product was distilled off under reduced pressure. After cooling, 50 ml of concentrated hydrochloric acid was added dropwise with stirring, and the resulting white solid was separated by filtration and dried under reduced pressure to obtain 1,10-bis [3,4-di (carboxy) phenyl] -1,9-decadiyne. (Yield 41.29 g, 89.3 mmol,
Yield 92%).

(4) 1,10-bis [3,4-di (carboxy) phenyl] -decane [R in the general formula (9)
Wherein R ³ and R ⁴ are both hydrogen atoms and n = 10] 1,10-bis [3,4-di (carboxy) phenyl]
22.71 g (49.1 mmol) of 1,9-decadiine, 1.14 g of activated carbon supporting 10% by weight of palladium (hereinafter referred to as 10% Pd / C) and 1200 ml of methyl alcohol were added to the autoclave, and the mixture was added at room temperature. The hydrogenation was performed at a hydrogen pressure of 1.0 kg / cm ² . 10% Pd / C was filtered off, and the filtrate was concentrated under reduced pressure to obtain 1,10-bis [3,4-di (carboxy) phenyl] -decane (yield 21.09 g, 44.8 mmol, yield). 91
%).

(5) 1,10-bis [3,4-di (carboxy) phenyl] -decane dianhydride [a compound of the formula (4) wherein R ³ and R ⁴ are both hydrogen atoms and n = 10] Synthesis of 1,10-bis [3,4-di (carboxy) phenyl]
14.41 g (30.6 mmol) of decane are added under reduced pressure to 1
By keeping at 60 ° C. for 6 hours, 1,10-bis [3
4-di (carboxy) phenyl] -decane dianhydride was obtained (13.04 g, 30.0 mmol, 98 yield).
%).

IR of the obtained acid anhydride,¹H-NMR etc.
The analysis data of is shown below. The measuring instrument used for the analysis
The vessel is shown below. IR spectrum: JIR-100, manufactured by JEOL Ltd.¹ H-NMR: R-250 MS manufactured by Hitachi, Ltd .; m / z 434 IR (KBr method); 2924 cm^-1, 2853cm^-1, 18
50cm^-1, 1767cm ^-1, 1262cm^-1, 887cm^-1,
737cm^{-1 1} H-NMR (solvent: CDCl_Three); Δ: 1.16 to 1.45 (m, 12H), δ: 1.67 (quintet, 4H), δ: 2.81 (t, 4H), δ: 7.69 (d, 2H), δ: 7.81 (s, 2H), δ: 7.92 (d, 2H)

(Negative photosensitive resin composition) Synthesis Examples 2 to 5 Using a four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a drying tube, the diamine component shown in Table 1 was N-
Methyl-2-pyrrolidone (hereinafter referred to as NMP) 22.5
g, and the acid components shown in Table 1 were added to this solution and reacted at room temperature for 24 hours to obtain a polyimide precursor. Further, this solution was heated at 70 ° C. for 5 hours, and the viscosity was adjusted to 80 poise (solid content: 25% by weight) to obtain polyimide precursor solutions (PA-1 to PA-4). The amounts of the diamine component and the acid component used are shown in Table 1.

The viscosity was measured using an E-type viscometer (Toki Sangyo Co., Ltd.)
, EHD type) at a temperature of 25 ° C and a rotation speed of 2.
It was measured at 5 min ^-1 . The weight-average molecular weight was determined by high performance liquid chromatography (L-6000, manufactured by Hitachi, Ltd.).
Form), column (Gelpack GL-, manufactured by Hitachi Chemical Co., Ltd.)
S3300MDT-5, UV detector (L-4000, manufactured by Hitachi, Ltd.), data processing device (Chromatopack C-R44, manufactured by Shimadzu Corporation), and an eluent (THF / DMF = 50/50 (volume ratio), LiB
r 0.03 mol / L, H ₃ PO ₄ 0.06 mol / L),
The measurement was performed under the condition of a measurement wavelength (270 nm). An infrared absorption spectrum (JIR-100, manufactured by JEOL Ltd.) of the dried polyimide precursor solution (PA-1 to PA-4) was measured by the KBr method. In each case, absorption of C = O of the amide group was observed at around 1600 cm ^-1 and absorption of NH at around 3300 cm ^-1 .

[0097]

[Table 1]

<Abbreviations> DBPA: 1,10-bis [3,4-di (carboxy)]
Phenyl] -decane dianhydride ODPA: oxydiphthalic dianhydride DDE: 4,4'-diaminodiphenyl ether DMAP: 2,2'-dimethyl-4,4'-diaminobiphenyl

Examples 1-2 and Comparative Examples 1-2 Each of the polyimide precursors (PA-
1-PA-4), 0.027 g of 2,6-bis (4'-azidobenzal) -4-carboxycyclohexanone (CA) and 4,4'-bis (diethylamino) benzophenone (EAB) .027 g and 0.054 g of 1-phenyl-2- (o-ethoxycarbonyl) oxyiminopropan-1-one (PDO) were added, and dimethylaminopropyl methacrylate (MDAP) equivalent to the carboxyl group of the polyimide precursor was added.
, And mixed with stirring to obtain Examples 1-2 and Comparative Examples 1-2.
To obtain a uniform negative photosensitive resin composition.

Each of the obtained negative photosensitive resin compositions was filtered through a filter and spin-coated on a silicon wafer by dropping. Then, using a hot plate, 100
After heating at 150 ° C. for 150 seconds to form a 23 μm coating film,
The pattern was masked and exposed with an i-line stepper. this,
The mixture was further heated at 100 ° C. for 60 seconds, and paddle-developed using a mixed solution of N-methyl-2-pyrrolidone / water (75/25 (weight ratio)).
Heating was performed at 00 ° C. for 30 minutes and at 350 ° C. for 60 minutes to obtain a polyimide pattern. An infrared absorption spectrum of a part of the obtained polyimide pattern was measured by the KBr method. As a result, characteristic absorption of the imide was confirmed at around 1780 cm ^-1 .

Each of the polyimide precursors (P
The transmittance of A-1 to PA-4) and the resolution of the pattern on the silicon wafer obtained above were evaluated by the following methods. The evaluation results are shown in Table 2. The transmittance was measured by spin-coating the obtained resin solution of each of the polyimide precursors (PA-1 to PA-5) at 85 ° C. for 3 minutes, and further at 105 ° C.
The coating film (20 μm) obtained by drying at 3 ° C. for 3 minutes was measured with a spectrophotometer. (Measurement wavelength: 365 nm)
Using the through hole test pattern, evaluation was made as the minimum size of the developable through hole.

The polyimide patterns of Examples 1 to 3 had good pattern shapes reflecting good resolution, but the polyimide patterns of Comparative Examples 1 and 2 had poor resolution. Reflecting the fact, it had an undesirable pattern shape.

[0103]

[Table 2]

(Positive Photosensitive Resin Composition) Example 3 1,10-bis [3,4-di (carboxy)) was placed in a flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a drying tube.
[Phenyl] -decane dianhydride 34.76 g and n-butyl alcohol 59.30 g were added, and the mixture was stirred at 95 ° C for 5 hours. Excess n-butyl alcohol is distilled off under reduced pressure,
1,10-bis [3,4-di (carboxy) phenyl]
-Decane 34.76-di (n-butyl) ester was obtained. Next, 95.17 g of thionyl chloride was placed in the flask,
70.00 g of toluene was added and reacted at 40 ° C. for 3 hours. Excess thionyl chloride was azeotroped with toluene under reduced pressure and removed. 186 g of N-methylpyrrolidone was added to obtain a solution (α) of 1,10-bis [3,4-di (carboxy) phenyl] -decane-di (n-butyl) ester dichloride.

Next, 95 g of N-methylpyrrolidone was added to a 0.5-liter flask equipped with a stirrer, a thermometer and a Dimroth condenser, and 3,5-diaminobenzoic acid was added.
28 g, 4,4'-diaminodiphenyl ether 5.1
After adding 3 g and dissolving with stirring, 12.66 g of pyridine was added.
And keeping the temperature at 0 to 5 ° C., the solution (α) of 1,10-bis [3,4-di (carboxy) phenyl] -decane-di (n-butyl) ester dichloride is added for 1 hour. After dropping, stirring was continued for 1 hour. The solution was poured into 4 liters of water, the precipitate was collected, washed, and dried under reduced pressure to obtain a polyamic acid n-butyl ester (hereinafter, referred to as polymer I). The weight average molecular weight was 27,000.

30 g of Polymer I was dissolved in 54 g of NMP with stirring, 0.9 g of 3-isocyanatopropyltriethoxysilane was added, and the mixture was further stirred for 12 hours.
7.5 g of a compound obtained by reacting 3,4,4'-tetrahydroxybenzophenone and naphthoquinone-1,2-diazido-5-sulfonyl chloride at a molar ratio of 1/3 was dissolved. This solution was filtered under pressure using a 3 μm-pore Teflon (registered trademark) filter to obtain a positive photosensitive resin composition.

The obtained positive photosensitive resin composition was spin-coated on a silicon wafer using a spinner, and dried by heating at 125 ° C. for 3 minutes on a hot plate.
An 8 μm positive photosensitive resin composition film was obtained. An i-line reduction projection exposure apparatus (LD-5 manufactured by Hitachi, Ltd.)
Using 010i), exposure was performed at 700 mJ / cm ² through a mask having a 100 to 3 μm equal-width line / interval pattern. Next, paddle development was performed for 70 seconds using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide as a developing solution.
After washing with pure water, a relief pattern was obtained. The film thickness after development was 8.5 μm. The minimum opening size was 5 μm. Next, this relief pattern was heated at 350 ° C. for 1 hour in a nitrogen atmosphere to obtain a 5.6 μm-thick polyimide film pattern.

Example 4 A thermometer equipped with a thermometer, a stirrer, a nitrogen inlet tube and a drying tube was used.
In a 5-liter flask, 1,10-bis [3,4-
Di (carboxy) phenyl] -decane dianhydride 34.7
6 g and n-butyl alcohol 59.3 g were added,
And reacted for 5 hours. Excess n-butyl alcohol is distilled off under reduced pressure to give 1,10-bis [3,4-di (carboxy) phenyl] -decane-di (n-butyl).
The ester was obtained. Then, thionyl chloride 9 was added to the flask.
5.17 g and 70.00 g of toluene were added,
Allowed to react for hours. Excess thionyl chloride was azeotroped with toluene under reduced pressure and removed. 186 g of NMP was added to obtain a solution (β) of 1,10-bis [3,4-di (carboxy) phenyl] -decane-di (n-butyl) ester dichloride.

Next, 95 g of N-methylpyrrolidone was added to a 0.5 liter flask equipped with a stirrer, a thermometer and a Dimroth condenser, and bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added to 19.76.
g, 4,4'-diaminodiphenyl ether 5.13 g
Was added and stirred and dissolved, and 12.66 g of pyridine was added, and the temperature was maintained at 0 to 5 ° C., and 6,6′-dimethyl-3,3 ′, 4,4′-biphenyltetracarboxylic acid di ( n-butyl) ester dichloride solution (β)
After dropwise addition over time, stirring was continued for 1 hour. The solution was poured into 4 liters of water, the precipitate was collected, washed, and dried under reduced pressure to obtain a polyamic acid-n-butyl ester (hereinafter, referred to as polymer II). The weight average molecular weight is 29,000
Met.

30 g of Polymer II was dissolved in 54 g of NMP with stirring, 0.12 g of 3-isocyanatopropyltriethoxysilane was added, and the mixture was further stirred for 6 hours. Tris (4-hydroxyphenyl) methane and naphthoquinone-
1,2-diazide-5-sulfonyl chloride was added to 1/2.
6 g of the compound reacted at a molar ratio of 5 was dissolved. This solution was filtered under pressure using a Teflon filter having a pore size of 3 μm to obtain a positive photosensitive resin composition.

The obtained positive photosensitive resin composition was spin-coated on a silicon wafer by using a spinner, and dried by heating at 90 ° C. for 3 minutes on a hot plate.
A film of a positive photosensitive resin composition having a thickness of μm was obtained. An i-line reduction projection exposure apparatus (LD-5, manufactured by Hitachi, Ltd.)
Using 010i), exposure was performed at 600 mJ / cm ² through a mask having a 100 to 3 μm uniform width line / interval pattern. Subsequently, paddle development was performed for 60 seconds using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide as a developing solution.
After washing with pure water, a relief pattern was obtained. The film thickness after development was 8.6 μm. The minimum opening size was 5 μm. Next, this pattern was heated at 350 ° C. in a nitrogen atmosphere.
For 1 hour to obtain a 5.4 μm-thick polyimide film pattern.

Comparative Example 3 In a flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a drying tube, 23.54 g of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and n-butyl alcohol 5
9.30 g was added, and the mixture was stirred and reacted at 95 ° C. for 5 hours.
Excess n-butyl alcohol is distilled off under reduced pressure,
3 ', 4,4'-biphenyltetracarboxylic acid di (n-
(Butyl) ester was obtained. Next, 95.17 g of thionyl chloride and 70.00 g of toluene were added to the flask, and 4
The reaction was performed at 0 ° C. for 3 hours. Excess thionyl chloride was azeotroped with toluene under reduced pressure and removed. 186 g of N-methylpyrrolidone was added to obtain a solution (γ) of 3,3 ′, 4,4′-biphenyltetracarboxylic acid di (n-butyl) ester dichloride.

Next, 95 g of N-methylpyrrolidone was added to a 0.5-liter flask equipped with a stirrer, thermometer and Dimroth condenser, and 3,5-diaminobenzoic acid was added.
28 g, 4,4'-diaminodiphenyl ether 5.1
After adding 3 g and dissolving with stirring, 12.66 g of pyridine was added.
And keeping the temperature at 0 to 5 ° C,
A solution (γ) of 4,4′-biphenyltetracarboxylic acid di (n-butyl) ester dichloride was added dropwise over 1 hour, and stirring was continued for 1 hour. The solution was poured into 4 liters of water, the precipitate was collected, washed, and dried under reduced pressure to obtain a polyamic acid n-butyl ester (hereinafter, referred to as polymer III). The weight average molecular weight was 26,000.

30 g of Polymer III was dissolved in 54 g of NMP with stirring, 0.9 g of 3-isocyanatopropyltriethoxysilane was added, and the mixture was further stirred for 12 hours.
7.5 g of a compound obtained by reacting 3,4,4'-tetrahydroxybenzophenone and naphthoquinone-1,2-diazido-5-sulfonyl chloride at a molar ratio of 1/3 was dissolved. This solution was filtered under pressure using a Teflon filter having a pore size of 3 μm to obtain a positive photosensitive resin composition.

The obtained positive photosensitive resin composition was spin-coated on a silicon wafer using a spinner, and dried by heating at 125 ° C. for 3 minutes on a hot plate to obtain 9.8.
A film of a positive photosensitive resin composition having a thickness of μm was obtained. An i-line reduction projection exposure apparatus (LD-50 manufactured by Hitachi, Ltd.)
Using 10i), exposure was performed at 1000 mJ / cm ² through a mask having a 100 to 3 μm equal-width line / space pattern. Next, paddle development was performed for 90 seconds using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide as a developing solution.
After washing with pure water, a relief pattern was obtained. The film thickness after development was 8.0 μm. The minimum opening size is 20 μm
Met. Next, this pattern is formed under a nitrogen atmosphere at 400
Heat treatment was performed at 1 ° C. for 1 hour to obtain a 5.2 μm-thick polyimide film pattern.

As can be seen from the above Examples and Comparative Examples, the Examples of the present invention are excellent in sensitivity to i-line, short in development time, and excellent in resolution after development. On the other hand, the comparative example has a low resolution after development.

[0117]

According to the present invention, the photosensitive resin composition according to the present invention has good i-ray transmittance and excellent resolution. The photosensitive resin compositions according to claims 2 to 4 have the effects of the invention according to claim 1 and can form a negative pattern. The photosensitive resin composition according to the fifth aspect is the first aspect.
According to the invention described above, the pattern can be formed by developing with an aqueous alkali solution. The photosensitive resin composition according to claim 6 has the effects of the invention according to claim 5,
A positive pattern can be formed.

According to the method for manufacturing a pattern according to the seventh and eighth aspects, a pattern having good resolution can be formed by i-line exposure. The electronic component according to the ninth and tenth aspects has a high-resolution pattern and has good reliability after polyimide formation.

[Brief description of the drawings]

FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 semiconductor substrate 2 protective film 3 first conductor layer 4 interlayer insulating film layer 5 photosensitive resin layer 6A, 6B, 6C window 7 second conductor layer 8 surface protective film layer

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/027 514 G03F 7/027 514 7/028 7/028 7/40 7/40 H01L 21/027 H01L 21/312 B 21/312 D 21/30 502R F-term (reference) 2H025 AA02 AB15 AB16 AB17 AC01 AD01 AD03 BC12 BC69 BE00 BE01 BE07 BE10 BG00 CA00 CB25 CB45 FA17 FA29 2H096 AA25 AA26 AA27 BA04 BA06 BA10 BA11 GA04 HA01 4007 EE036 EE056 EL096 EN106 EN116 EQ037 EU076 EV297 EV306 FD156 FD207 GP03 5F058 AA10 AC02 AC07 AC08 AF04 AG01 AH02 AH03

Claims (11)

[Claims] 1. A compound of the general formula (1) (Wherein, A represents a divalent organic group, R ¹ and R ² each independently represent a hydroxyl group or a monovalent organic group, and R ³ and R ⁴ each independently represent a hydrogen atom or a carbon number of 1-10. Wherein n is an integer of 5 to 20). A photosensitive resin composition comprising a polyimide precursor having a repeating unit represented by the following formula: 2. The photosensitive resin composition according to claim 1, wherein at least one of R ¹ and R ^{2 in} the general formula (1) is a monovalent organic group having a carbon-carbon unsaturated double bond. 3. The method according to claim 1, further comprising a photopolymerization initiator.
Or the photosensitive resin composition according to 2. 4. The photosensitive resin composition according to claim 1, further comprising an addition polymerizable compound having a carbon-carbon unsaturated double bond. 5. In a polyimide precursor having a repeating unit represented by the general formula (1), A is a divalent organic group having a carboxyl group or a phenolic hydroxyl group, or R ¹
And at least one of R ² is a hydroxyl group, according to claim 1 photosensitive resin composition. 6. The photosensitive resin composition according to claim 5, further comprising a compound capable of generating an acid by light. 7. The photosensitive resin composition according to claim 6, wherein the compound that generates an acid by light is an o-quinonediazide compound. 8. Production of a pattern comprising a step of applying and drying the photosensitive resin composition according to claim 1 on a supporting substrate, a step of exposing, a step of developing, and a step of heat treatment. Law. 9. The method for producing a pattern according to claim 8, wherein the step of exposing is performed using i-line as an exposure light source. 10. An electronic component having a pattern layer obtained by the method according to claim 8. Description: 11. The electronic component according to claim 10, wherein the pattern layer is a surface protective film or an interlayer insulating film.