JP2001194784A - Photosensitive polyimide precursor composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive polyimide precursor composition having good suitability to patterning, giving a cured film excellent in adhesion to a sealing resin and producible in a short producing step without carrying out the reprecipitation of a polymer and to obtain a method for producing the composition. SOLUTION: The photosensitive polyimide precursor composition is obtained by reacting (a) a polymer or oligomer having a structural unit of formula 1 (where R1 is a tri- or tetravalent >=2C organic group; R2 is a divalent >=2C organic group; R3 is H, an alkali metal ion, an ammonium ion or at least one of 1-30C organic groups, 30-100 mol% of R3 is H; and (n) is 1 or 2) with (b) a vinyl ether compound of formula 2 (where R4 is a 1-30C organic group and 50-100 mol% R4 is an organic group containing a photosensitive group).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a semiconductor device,
It relates to a polyimide precursor composition useful for the production of electric and electronic materials such as a multilayer wiring board, and more specifically, has a good pattern workability, and has excellent adhesion to a sealing resin of a cured film, The present invention relates to a photosensitive polyimide precursor composition that can be produced in a short production step without passing through a polymer precipitation step, and a method for producing the same.

[0002]

2. Description of the Related Art Due to its excellent heat resistance, electrical properties and mechanical properties, polyimides have been widely put to practical use in protective films for semiconductor chips and wiring, interlayer insulating films for multilayer wiring boards, stress buffer coats, and the like. Further, since the photosensitive polyimide itself has pattern processability, the process can be simplified as compared with a case where a normal non-photosensitive polyimide is patterned using a resist or the like.

For example, as described in JP-B-55-41422, an ester containing a photosensitive group-containing alcohol such as 2-hydroxyethyl methacrylate is condensed with a carboxyl group on the side chain of a polyamic acid. A composition containing a polymer as a main component has good pattern processability, and also has good storage stability of the composition. The most commonly used method for producing this polymer is to react an acid dianhydride with an alcohol, and then polymerize the resulting dicarboxylic diester and diamine using DCC (Japanese Patent Application Laid-Open No. -22853
No. 7). However, this production method has a disadvantage that the production step is lengthened because a polymer precipitation step is required. In addition, the obtained polymer has a problem that the photosensitive group is not easily detached when cured, and the adhesion to the sealing resin is poor.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned drawbacks of the prior art. It is an object of the present invention to have good pattern workability and adhesion of a cured film to a sealing resin. It is an object of the present invention to provide a photosensitive polyimide precursor composition which is excellent in the above process and can be produced in a short production step without going through a polymer precipitation step.

[0005]

The present invention provides:
(A) a photosensitive polyimide precursor obtained by reacting a polymer or oligomer having a structural unit represented by the general formula (1) with (b) a vinyl ether compound represented by the general formula (2) A composition.

[0006]

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(R ¹ represents a trivalent or tetravalent organic group having at least two or more carbon atoms, and R ² represents a divalent organic group having at least two or more carbon atoms.
³ is hydrogen, alkali metal ion, ammonium ion,
Alternatively, it represents at least one selected from organic groups having 1 to 30 carbon atoms, of which 30 to 100 mol% is composed of hydrogen. n represents 1 or 2. )

[0008]

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(R ⁴ represents an organic group having 1 to 30 carbon atoms,
Of these, 50 to 100 mol% represents an organic group containing a photosensitive group. )

[0010]

DETAILED DESCRIPTION OF THE INVENTION The present invention is a photosensitive polyimide precursor composition obtained by reacting a vinyl ether compound containing a photosensitive group with a side chain carboxyl group of a polyamic acid to form an ester.

The polyimide precursor composition in the present invention may be in a polymer solution state,
It may be in the form of a film after being applied to a substrate and dried.

The polyimide precursor of the present invention has the general formula (1)
And a polymer (hereinafter, referred to as a "polyimide polymer") having an imide ring or other cyclic structure by heating or using a suitable catalyst.

In the general formula (1), R ¹ is at least 2
A trivalent or tetravalent organic group having at least two carbon atoms, and from the heat resistance of the polyimide polymer, a tetravalent group containing an aromatic ring or an aromatic heterocyclic ring and having 6 to 30 carbon atoms. preferable. Preferred specific examples of R ¹ include:
3,3 ′, 4,4′-biphenyltetracarboxylic acid,
3,3 ′, 4,4′-diphenylethertetracarboxylic acid, 3,3 ′, 4,4′-diphenylhexafluoropropanetetracarboxylic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 3, 3 ′, 4,4′-diphenylsulfonetetracarboxylic acid, pyromellitic acid,
Examples include, but are not limited to, residues such as butanetetracarboxylic acid and cyclopentanetetracarboxylic acid. From the viewpoint of the heat resistance of the polyimide polymer, particularly preferred specific examples include 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-diphenylethertetracarboxylic acid, and 3,3 ', 4,4'-diphenylhexafluoropropanetetracarboxylic acid, 3,
3 ′, 4,4′-benzophenonetetracarboxylic acid,
Residues such as 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid and pyromellitic acid are exemplified.

In the present invention, the polyimide precursor is R ¹
May be one type or a copolymer composed of two or more types.

In the above general formula (1), R ² is at least 2
It is a divalent organic group having at least two carbon atoms. In view of the heat resistance of the polyimide polymer, R ² is preferably a divalent group containing an aromatic ring or an aromatic heterocyclic ring and having 6 to 30 carbon atoms. Preferred specific examples of R ² include paraphenylenediamine, metaphenylenediamine, methylparaphenylenediamine, methylmetaphenylenediamine, dimethylparaphenylenediamine, dimethylmetaphenylenediamine, trimethylparaphenylenediamine, trimethylmetaphenylenediamine, and tetramethyldiphenylenediamine. Methyl paraphenylenediamine, tetramethyl metaphenylenediamine, trifluoromethyl paraphenylenediamine, trifluoromethyl metaphenylenediamine, bis (trifluoromethyl) paraphenylenediamine, bis (trifluoromethyl) metaphenylenediamine, methoxyparaphenylenediamine, Methoxymetaphenylenediamine, trifluoromethoxyparaphenylenediamine, trifluoromethoxymetaphe Diamine, fluoroparaphenylenediamine, fluorometaphenylenediamine, chloroparaphenylenediamine, chlorometaphenylenediamine, bromoparaphenylenediamine, bromometaphenylenediamine, carboxyparaphenylenediamine, carboxymetaphenylenediamine, methoxycarbonylparaphenylenediamine, methoxy Carbonyl metaphenylenediamine, diaminodiphenylmethane, bis (aminomethylphenyl) methane,
Bis (aminotrifluoromethylphenyl) methane, bis (aminoethylphenyl) methane, bis (aminochlorophenyl) methane, bis (aminodimethylphenyl)
Methane, bis (aminodiethylphenyl) methane, diaminodiphenylpropane, bis (aminomethylphenyl) propane, bis (aminotrifluoromethylphenyl) propane, bis (aminoethylphenyl) propane, bis (aminochlorophenyl) propane, bis (amino Dimethylphenyl) propane, bis (aminodiethylphenyl) propane, diaminodiphenylhexafluoropropane, bis (aminomethylphenyl) hexafluoropropane, bis (aminotrifluoromethylphenyl) hexafluoropropane, bis (aminoethylphenyl) hexafluoropropane Bis (aminochlorophenyl) hexafluoropropane, bis (aminodimethylphenyl) hexafluoropropane, bis (aminodiethylphenyl) Safluoropropane, diaminodiphenylsulfone, bis (aminomethylphenyl) sulfone, bis (aminoethylphenyl) sulfone, bis (aminotrifluoromethylphenyl) sulfone, bis (aminodimethylphenyl) sulfone, bis (aminodiethylphenyl) sulfone, Diaminodiphenyl ether, bis (aminomethylphenyl) ether, bis (aminotrifluoromethylphenyl) ether, bis (aminoethylphenyl) ether, bis (aminodimethylphenyl) ether, bis (aminodiethylphenyl)
Ether, dimethylbenzidine, bis (trifluoromethyl) benzidine, dichlorobenzidine, bis (aminophenoxy) benzene, bis (aminophenoxyphenyl) propane, bis (aminophenoxyphenyl) hexafluoropropane, bis (aminophenoxyphenyl) ether, bis (Aminophenoxyphenyl) methane, bis (aminophenoxyphenyl) sulfone, 3,
5-diaminobenzoic acid methacryloyl ethyl ester,
3,5-diaminobenzoic acid acroyl ethyl ester,
Examples include, but are not limited to, residues such as 2,4-diaminobenzoic acid methacryloyl ethyl ester and 2,4-diaminobenzoic acid acroyl ethyl ester, and residues of hydrogenated compounds thereof.

The polyimide precursor according to the present invention comprises R ²
May be composed of one of these, or may be a copolymer composed of two or more.

Further, in order to improve the adhesiveness of the polyimide-based polymer, it is possible to copolymerize an aliphatic group having a siloxane bond as R ² as long as the heat resistance is not reduced. A preferred specific example is bis (3
-Aminopropyl) tetramethyldisiloxane and the like, but are not limited thereto.

In the general formula (1), R ³ is hydrogen, an alkali metal ion, an ammonium ion, or a compound having 1 carbon atom.
Represents at least one kind of structure selected from organic groups of 30 to 30, in which 30 to 100 mol% is composed of hydrogen. Carbon number 1
As the organic group of ~ 30, an aliphatic organic group is preferable, and the organic group to be contained includes, but is not limited to, a hydrocarbon group, a hydroxyl group, a carbonyl group, a carboxyl group, a urethane group, a urea group and an amide group. Not done. Preferred specific examples include, but are not limited to, methyl, ethyl, isopropyl, butyl, t-butyl and the like. More preferably, 50 to 100 mol% of R ³ is hydrogen, and even more preferably, 80 to 100 mol%. As the proportion of hydrogen increases, the number of reaction points with the vinyl ether compound represented by the general formula (2) also increases, so that there is an advantage that the pattern processing performance of the composition is improved. R ³ may be a single species or a mixture of two or more species.

The polyimide precursor in the present invention may be composed of only the structural unit represented by the general formula (1), or may be a copolymer or a blend with another structural unit. . At that time, it is preferable that the content of the structural unit represented by the general formula (1) is 80% or more. The type and amount of the structural unit used for copolymerization or blending are preferably selected within a range that does not significantly impair the heat resistance of the polyimide-based polymer obtained by the final heat treatment.

These polyimide precursors can be any of various known
Synthesized by the method ^ThreeIs hydrogen
Is the acylation reaction between tetracarboxylic dianhydride and diamine.
It can be said that it is preferable to synthesize by reaction. Acid two
It can also be synthesized by the reaction of anhydride and diisocyanate,
Be careful as this may lead to an increase in the imidization rate of the polymer
is necessary. As the polymerization solvent used at that time,
N-methyl-2-pyrrolidone, N, N-dimethylaceto
Amide, N, N-dimethylformamide, dimethyl sulf
Mainly composed of foxide, hexamethyl phosphorotriamide, etc.
Polar solvent or γ-butyrolactone as a main component.
Solvents and the like are preferably used.

In the above general formula (2), R ⁴ has 1 to 30 carbon atoms.
Of which 50 to 100 mol% represents an organic group containing a photosensitive group. Preferably 70 to 100 mol%
And most preferably 85 to 100 mol%. It can be said that the higher the concentration of the photosensitive group, the better the improvement in pattern processability. As the organic group having 1 to 30 carbon atoms, an aliphatic organic group is preferable, and examples of the contained organic group include a hydrocarbon group, a hydroxyl group, a carbonyl group, a carboxyl group, a urethane group, a urea group, and an amide group. It is not limited to these. Specific examples of preferred general formula (2) include, but are not limited to, those represented by the following structural formulas.

[0022]

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It can be said that the vinyl ether compound represented by the general formula (2) is preferably added and reacted after the formation of the polymer or oligomer represented by the general formula (1). The preferred amount to be added is 20 to 500 mol%, more preferably 40 to 400 mol%, and most preferably 100 to 300 mol%, based on the structural unit of the general formula (1). If the amount is larger than this amount, the mechanical properties of the cured polyimide film will be reduced. If the amount is smaller than this amount, sufficient pattern processing performance cannot be obtained, so care must be taken.

When the compound represented by the general formula (1) and the vinyl ether compound represented by the general formula (2) are reacted in a solution, the reaction temperature is 0 to 70 ° C., preferably 10 to 60 ° C. ° C, most preferably from 20 to 50 ° C. Above this range, modification of the photosensitive group occurs,
Care must be taken when the ratio is smaller than this range, since the reaction does not proceed sufficiently. The reaction time is preferably selected from 1 hour to 240 hours depending on the reaction temperature. Further, the reaction is not necessarily required to be performed in the solution, and the solution is reacted during the film forming process by adjusting the drying temperature and the drying time when the solution is applied to the substrate and dried before exposure, or in the solution. The reaction which has occurred to some extent can further proceed. The preferable range of the drying temperature is 40 to 15
0 ° C., the preferable time is 1 minute to several hours, but is not particularly limited.

It is preferable to add an acid catalyst to the composition in order to accelerate the esterification reaction in the solution or during the film forming process. Specific examples include, but are not limited to, phosphoric acid, toluenesulfonic acid, and toluenesulfonic acid pyridine salt.

The preferred range of the acid catalyst is 1 ppm to 10000 ppm, more preferably 10 ppm to 1000 ppm, based on the weight of the polymer. If the amount is larger than the above range, the polymer is decomposed.

Further, from the viewpoint of improving the film thickness retention after development and the pattern resolution, the photosensitive polyimide precursor composition may contain an amine compound represented by the general formula (3). R ⁵ , R ⁶ and R ^{7 in the} general formula (3) have 1 to 30 carbon atoms.
Of which at least one is an organic group containing a photosensitive group. As the organic group having 1 to 30 carbon atoms, an aliphatic organic group is preferable, and examples of the contained organic group include a hydrocarbon group, a hydroxyl group, a carbonyl group, a carboxyl group, a urethane group, a urea group, and an amide group. It is not limited to these. The content at this time is preferably from 20 to 200 mol% based on the structural unit of the general formula (1). If the ratio is smaller than this range, the film thickness retention after development is reduced. If the ratio is beyond this range, the resolution is lowered and the elongation of the polyimide film after heat curing is lowered. It is more preferably in the range of 30 to 150 mol%, and still more preferably in the range of 40 to 100 mol%. Preferred specific examples of the general formula (3) include dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl methacrylate, dimethylaminobutyl methacrylate, dimethylamino methacrylate Hexyl, N- (2-dimethylaminoethyl) methacrylamide, N- (3-dimethylaminopropyl) methacrylamide, N- (2-diethylaminoethyl) methacrylamide, N- (3-diethylaminopropyl) acrylamide, N- ( 2-dimethylaminoethyl) acrylamide, N- (3-dimethylaminopropyl) acrylamide, N- (2-diethylaminoethyl) acrylamide, N- (3-diethylaminopropyl) acryl Mido, acryloylmorpholine, methacryloylmorpholine, acryloylpiperidine, methacryloylpiperidine, allylamine, diallylamine, triallylamine, methallylamine, vinylpyridine, ethyltrimethylammonium methacrylate, 2-hydroxypropyltrimethylammonium methacrylate, para (or meth) azide Dimethylaminoethyl benzoate, diethylaminoethyl para (or meta) azidobenzoate, dimethylaminopropyl para (or meta) azidobenzoate, diethylaminopropyl para (or meta) azidobenzoate, para (or meta) azide Sulfonylbenzoic acid dimethylaminoethyl ester, para (or meta) azidosulfonylbenzoic acid diethyl Aminoethyl ester, para (or meta) Ajidosuruhoniru acid dimethylaminopropyl ester, para (or meta) but such Ajidosuruhoniru compound represented benzoic acid diethylaminopropyl ester include, but are not limited to. The additive compound may be a single compound or a mixture of two or more compounds.

Further, when the composition of the present invention is used for alkali development, the carboxyl group concentration of the polymer in the prebaked film having a thickness of 10 μm is based on the structural unit in order to improve the pattern processing performance with an alkali developer. It is preferably 10 to 150 mol%. If the ratio is smaller than this range, there is almost no solubility in an alkali developing solution, and if the ratio is larger than this range, the film loss at the time of development increases. Also more preferably, 20 to 14
0 mol%, most preferably 30 to 130 mol%.

The term “prebaked film having a thickness of 10 μm” in the present invention is defined as a film obtained by applying a composition varnish to a substrate and heat-treating it at 80 ° C. for 3 minutes using a hot plate.

Further, in order to improve the pattern processing performance with an alkali developer, the imidation ratio of the polymer in the prebaked film having a thickness of 10 μm is preferably 0 to 0.4. If the ratio is larger than this range, care must be taken because the solubility of the composition in an alkali developing solution is significantly reduced and a pattern may not be formed. More preferably, it is 0 to 0.3, and most preferably 0 to 0.2.

Hereinafter, a method for obtaining the imidation ratio Ia and the carboxyl group concentration Ca will be described. Carboxyl group concentration C
In the measurement of a, first, a sample varnish is applied on a silicon wafer by a spin coating method, and heat-treated at 80 ° C. for 3 minutes using a hot plate to form a prebaked film having a thickness of 10 μm. This film is dissolved in a solvent for nuclear magnetic resonance spectrum (NMR) measurement (dimethyl-d6 sulfoxide). The solution was subjected to ¹ H-NMR measurement to determine the peaks corresponding to the hydrogen of the carboxyl group of the polyamic acid and the hydrogen bonded to the aromatic carbon of the polyamic acid.
Calculating an integral value of ¹ H. Let the integral of both be C
Assuming that the number of hydrogens bonded to aromatic carbons per structural unit of polyamic acid used in the measurement is 1, M, and C, the carboxyl group concentration Ca (mol%) is represented by Ca
= (M × C1 / C2) × 100.

The value of the imidation ratio Ia is determined by measuring the absorbance at a wave number due to an imide group of a polyimide precursor composition (hereinafter, referred to as a sample varnish) as a sample by transmission infrared spectrum (IR) measurement. calculate. As the vibration wave number due to the imide group used for the absorbance measurement,
Usually 1750-1800 cm ^-1 or 1350-14
Using the wave number of 00 cm ⁻¹ , the absorbance of the imide group is calculated. Hereinafter, details of the calculation method will be described.

First, a sample varnish is applied on a silicon wafer by a spin coating method. Next, the film is baked at 80 ° C. for 3 minutes to form a prebaked film having a thickness of 10 μm, and the absorbance I of the imide group is determined by IR measurement. Next, the film is heat-treated (cured) at 350 ° C. for 2 hours in a nitrogen stream in an oven to allow imidization to proceed by 100%. This, 100
% For imidized allowed samples subjected to IR measurement, determine the absorbance I ₁ wavenumber due to imide groups.

At this time, the equation showing the relationship between the absorbance I of the imide group and the imidization ratio Ia is Ia = I / I ₁ .

As shown in FIG. 1, the absorbance of a peak due to an imide group was measured by drawing an auxiliary line connecting both ends of the peak to be obtained and a line perpendicular to the horizontal axis of the IR spectrum from the peak apex. And the length X between the intersection and the peak apex is defined as the absorbance.

In order to obtain higher sensitivity and higher resolution in the pattern after development, it is preferable to contain a photoinitiator and a photosensitizer. The method used is not limited, such as using each of these two or using both at the same time.

The photoinitiator suitable for the present invention includes aromatic amines such as N-phenyldiethanolamine, N-phenylglycine and Michler's ketone, and 3-phenyl-5.
-A cyclic oxime compound represented by isoxazolone,
Linear oxime compounds represented by 1-phenylpropanedione-2- (O-ethoxycarbonyl) oxime, benzophenones, benzophenone derivatives such as methyl o-benzoylbenzoate, dibenzyl ketone and fluorenone, thioxanthon, 2-methylthioxanthone, 2-
Thioxanthone derivatives such as isopropylthioxanthone; and the like, but are not limited thereto.

Examples of sensitizers suitable for the present invention include aromatic monoazides such as azidoanthraquinone and azidobenzalacetophenone, coumarin compounds such as 3,3'-carbonylbis (diethylaminocoumarin), benzanthrone and phenanthrenequinone. In some cases, aromatic ketones such as those generally used for photocurable resins and those used as charge transfer agents for electrophotography can be preferably used.

The photoinitiator and the sensitizer are added to the polymer in an amount of 0.1%.
It is preferably added in an amount of 01 to 30% by weight, more preferably 0.1 to 20% by weight. If the ratio is outside this range, the photosensitivity is lowered and the mechanical properties of the polymer are lowered. These photoinitiators and sensitizers alone,
Alternatively, two or more kinds can be used in combination.

In order to improve the adhesion between the coating film of the composition of the present invention or the polyimide film after the heat treatment and the support, an adhesion aid may be appropriately used.

Examples of the adhesion aid include oxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-
Organic silicon compounds such as methacryloxypropyltrimethoxysilane, or aluminum chelate compounds such as aluminum monoethylacetoacetate diisopropylate and aluminum tris (acetylacetonate) or titanium chelate compounds such as titanium bis (acetylacetonate) are preferable. Used. Further, other additives may be contained in such a range that the adhesion to the substrate, the sensitivity and the heat resistance are not significantly reduced.

Next, the method of using the composition of the present invention will be described. The composition of the present invention can be patterned by a known fine processing technique using actinic radiation.

First, the composition of the present invention is coated on a suitable support. Examples of the material of the support include, but are not limited to, metal, glass, semiconductor, metal oxide insulating film, and silicon nitride.

As a coating method, means such as spin coating using a spinner, spray coating using a spray coater, dipping, printing, and roll coating are possible. The thickness of the applied film can be adjusted depending on the application means, the solid content concentration and the viscosity of the composition, but is usually applied in the range of 0.1 to 150 μm.

Next, the substrate coated with the polyimide precursor is dried to obtain a polyimide precursor composition film. Drying is
Use an oven, hot plate, infrared, etc.
To 150 ° C., preferably 60 to 120 ° C.
It is more preferable to carry out within the range. The drying time is preferably from one minute to several hours.

Next, exposure is performed using a mask having a desired pattern. The exposure amount is 50 to 1000 mJ /
A range of cm ² is preferred. A particularly preferred range is 100 to
It is 600 mJ / cm ² . By using an appropriate sensitizer, exposure can be performed using an exposure machine such as an i-line stepper, a g-line stepper, a mask aligner, and a mirror projection.

The resolution of the pattern at the time of development is improved,
When the allowable range of the developing conditions is increased, a step of performing a baking process before the development may be adopted. The temperature is preferably in the range of 50 to 180 ° C., particularly preferably 60 to 180 ° C.
A range of 150 ° C. is more preferred. The time is preferably from 10 seconds to several hours. If the ratio is out of this range, the reaction may not proceed or all the regions may not be dissolved.

Next, a relief pattern is obtained by dissolving and removing the unirradiated portion with a developing solution. A suitable developer can be selected according to the structure of the polyimide precursor, but when used in alkali development, ammonia, tetramethylammonium hydroxide, an alkaline aqueous solution such as diethanolamine and the like can be preferably used. . When used in organic development, N-methyl-2-pyrrolidone, N-
Acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphortriamide, γ-butyrolactone, cyclopentanone, cyclohexanone, etc. alone or methanol, ethanol, isopropyl alcohol , Water, methyl carbitol, ethyl carbitol, toluene, xylene, ethyl lactate, ethyl pyruvate, propylene glycol monomethyl ether acetate, methyl-3-methoxypropionate,
A mixed solution with ethyl-3-ethoxypropionate, 2-heptanone, ethyl acetate and the like can also be preferably used.

In the development, the above-mentioned developer is applied to the coating film surface as it is.
Alternatively, emit in the form of a mist, immerse in a developer,
Alternatively, it can be performed by a method such as applying ultrasonic waves while dipping.

Next, it is preferable to wash the relief pattern formed by development with a rinsing liquid. Water or an organic solvent is used as the rinsing liquid, but when rinsing with an organic solvent, methanol, ethanol, isopropyl alcohol, ethyl lactate, ethyl pyruvate, propylene glycol monomethyl ether acetate, methyl -3-Methoxypropionate, ethyl-3-ethoxypropionate, 2-heptanone, ethyl acetate and the like are preferably used.

The polymer of the relief pattern obtained by the above treatment is a precursor of a heat-resistant polyimide-based polymer, and becomes a heat-resistant polymer having an imide ring or other cyclic structure by heat treatment. The heat treatment is preferably performed at 135 to 500 ° C.,
More preferably, it is performed at 450 ° C. The heat treatment is usually performed stepwise or continuously while increasing the temperature.

[0052]

EXAMPLES Examples are shown below, but the present invention is not limited to these examples. The following (1)-about evaluation
The item (4) was performed.

(1) Evaluation of Varnish (1-a) Calculation of Carboxyl Group Concentration Ca (Mole%) First, a sample varnish was applied on a silicon wafer by a spin coating method, and a hot plate (apparatus was Dainippon Co., Ltd.) SKW-636 manufactured by Screen Manufacturing Co., Ltd. at 80 ° C.
By performing a partial heat treatment, a prebaked film having a thickness of 10 μm was prepared.
This film was analyzed by nuclear magnetic resonance spectroscopy (apparatus: JASCO Corporation)
Was dissolved in a measuring solvent (dimethyl-d6 sulfoxide). The solution was subjected to ¹ H-NMR measurement, and the integrated value of ¹ H was calculated for peaks corresponding to the hydrogen of the carboxyl group of the polyamic acid and the hydrogen bonded to the aromatic carbon of the polyamic acid. The integrated values of the two are respectively C1 and C2, and the number of hydrogen bonded to aromatic carbon per structural unit of the polyamic acid used for the measurement is M
Then, the formula expressing the carboxyl group concentration Ca (mol%) is Ca = (M × C1 / C2) × 100.

(1-b) Method for calculating imidation ratio Ia First, a sample varnish is applied on a silicon wafer by a spin coating method. Then, bake for 3 minutes on a hot plate at 80 ° C. (the device is SK manufactured by Dainippon Screen Mfg. Co., Ltd.)
W-636), and finally a pre-baked film having a thickness of 10 μm was formed. IR measurement (Equipment: manufactured by Horiba Ltd., F
T-720), the absorbance I of the imide group having a wave number of 1350 to 1400 cm ^-1 is determined. Next, the film is heat-treated (cured) at 350 ° C. for 2 hours in a nitrogen stream in an oven to allow imidization to proceed by 100%. This, 100
% For imidized allowed samples subjected to IR measurement, determine the absorbance I ₁ wavenumber due to imide groups.

[0055] In this case, the following equation indicating the relationship between absorbance I and imidization Ia of the imide groups, from Ia = I / I _1, to calculate the imidization Ia.

(2) Evaluation of pattern processing performance A varnish was spin-coated on a silicon wafer,
3 minutes on a hot plate at 0 ° C (apparatus: SKW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.)
m was prepared. This film was exposed under the following two conditions.

(2-a) In the case of i-line exposure The light was exposed at an exposure of 400 mJ / cm ² using an i-line stepper (DSW-8000 manufactured by GCA).

(2-b) In the case of full wavelength exposure: Mask aligner (PLA-501 manufactured by Canon Inc.)
Exposure was performed using F). Exposure measured at i-line is 20
It was 0 mJ / cm ² .

After exposure, baking for 1 minute on a hot plate at 60 ° C. (apparatus: SKW-6 manufactured by Dainippon Screen Mfg. Co., Ltd.)
36) Then, development was performed under the following three conditions.

(2-c) Developing condition 1 Developed with a developer of cyclohexanone / methanol = 49/1 (weight ratio), rinsed with propylene glycol monomethyl ether acetate, and dried.

(2-d) Developing condition 2 Developed with a developing solution of N-methyl-2-pyrrolidone / propylene glycol monomethyl ether acetate / water = 9/1/1 (weight ratio), and then rinsed with 2-propanol. Let dry.

(2-e) Developing condition 3 The film was developed with an aqueous solution of 2.38% tetramethylammonium hydroxide, rinsed with pure water and dried.

After drying, the following two types of pattern evaluation were performed.

(2-f) Pattern Size Observing a pattern of 100 μm × 100 μm, it is good if the pattern does not have a reverse taper and the size is in the range of 90 to 110 μm. A taper having a reverse taper or a size out of the above range is defective.

(2-g) Retention of film thickness after development If the film thickness after development / the film thickness before development = 0.7 or more, it is good.
If it was less than 0.7, it was determined to be defective.

(3) Adhesion to Sealing Resin A pre-baked film was formed on a bare silicon wafer in the same manner as in the evaluation (2). This film was put into an oven and cured at 140 ° C. for 30 minutes and then at 300 ° C. for 1 hour to obtain a polyimide film. Cure was performed in nitrogen. Sealing resin TM20-100 manufactured by Toray Industries, Inc. on the polyimide film
Was formed into a column having a height of 5 mm and a diameter of 5 mm by transfer molding. "Tensilon" (RTM-10
0; manufactured by Orientec Co., Ltd.) to determine the strength at which the sealing resin was peeled off from the polyimide film. At this time, if the strength at break exceeds 40 MPa, it is good.
If it is less than 0 MPa, it is defective.

(4) Time Required for Production The total time from the introduction of the first diamine to the completion of the preparation of the photosensitive polyimide precursor composition was measured.

In the synthesis examples and examples, abbreviations of polyimide raw materials are used in the following manner. 4,4'-DAE: 4,4'-diaminodiphenyl ether m-BAPS: bis [4- (3-aminophenoxy) phenyl] sulfone SiDA: bis (3-aminopropyl) tetramethyldisiloxane PMDA: pyromellitic anhydride BTDA: 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride ODPA: 3,3', 4,4'-diphenylethertetracarboxylic dianhydride NPG: N-phenylglycine BOX: bis (α- Isonitrosopropiophenone oxime) isophthal NNAP: 1-nitroso-2-naphthol CmA: 7-diethylamino-3-benzoylcoumarin DEM: diethylaminoethyl methacrylate HEMA: 2-hydroxyethyl methacrylate NMP: N-methyl-2- Pyrrolidone γ-BL: cancer Butyrolactone.

Synthesis Example 1 (Vinyl ether monomer MBV
Synthesis of E) 58.0 g (0.5 mol) of hydroxybutyl vinyl ether in a 1-liter four-necked flask under a stream of dry air
Was dissolved in 100 g of ethyl acetate at 20 ° C. To this solution, 50.6 g (0.5 mol) of triethylamine was added, and the mixture was placed in an ice bath to lower the temperature to 10 ° C. or lower.
52.3 g (0.5 g) of methacrylic acid chloride was added to 0.0 g.
) Was added dropwise over 1 hour while maintaining the temperature at 10 ° C or lower. After stirring for another 1 hour in an ice bath, the flask was returned to room temperature and further stirred for 3 hours. After 3 hours, the precipitate was separated by filtration, and 200 g of ethyl acetate and 100 parts of a saturated aqueous solution of sodium hydrogencarbonate were added to the obtained filtrate.
g was added and shaken vigorously with a separatory funnel. After removing the aqueous phase, the ethyl acetate phase was further washed three times with 200 g of pure water, and only the ethyl acetate phase was separated. The obtained ethyl acetate phase was dried over anhydrous sodium sulfate, the inorganic salts were separated by filtration, and 0.5 g of phenothiazine was added to the filtrate, and the ethyl acetate was removed by evaporation. The obtained solution was distilled under reduced pressure to obtain a target vinyl ether monomer.
This monomer was designated as MBVE.

Synthesis Example 2 (Vinyl ether monomer MEV)
Synthesis of E) 58.0 g of hydroxybutyl vinyl ether of Synthesis Example 1
To hydroxyethyl vinyl ether 44.0 g (0.5
Mol), and the same procedure as in Synthesis Example 1 was carried out. The obtained monomer was designated as MEVE.

Synthesis Example 3 (Vinyl ether monomer ABV
Synthesis of E) The procedure of Synthesis Example 1 was repeated except that 52.3 g of methacrylic chloride in Synthesis Example 1 was changed to 45.3 g (0.5 mol) of acrylic acid chloride. ABVE
And

Synthesis Example 4 (Vinyl ether monomer MCH
Synthesis of MVE) 58.0 g of hydroxybutyl vinyl ether of Synthesis Example 1
To cyclohexanedimethanol monovinyl ether 8
The same procedure as in Synthesis Example 1 was carried out except that the amount was changed to 5.0 g (0.5 mol). The obtained monomer was designated as MCHMVE.

Synthesis Example 5 (Vinyl ether monomer MMV)
Synthesis of E) 58.0 g of hydroxybutyl vinyl ether of Synthesis Example 1
To 66.0 g of diethylene glycol monovinyl ether
(0.5 mol) in the same manner as in Synthesis Example 1.
The obtained monomer was MMVE.

Synthesis Example 6 (Vinyl ether monomer MOB
Synthesis of VE) 58.0 g (0.5 mol) of hydroxybutyl vinyl ether in a 1-liter four-necked flask under a stream of dry air
Was dissolved in 100 g of ethyl acetate at 20 ° C. To this solution, 1.00 g of n-butyltin laurate was added, and the mixture was placed in an ice bath to adjust the temperature to 10 ° C. or lower, and 50.0 g of ethyl acetate was added.
Nikarinzu MOI (manufactured by Showa Denko KK) 77.6 g
(0.5 mol) was added dropwise over 1 hour while maintaining the temperature at 10 ° C. or lower. After stirring for another hour in an ice bath, the flask was brought to room temperature and
Stirred for hours. After 12 hours, the solution was added to ethyl acetate 2
Then, 00 g and 100 g of a saturated aqueous solution of sodium hydrogen carbonate were added, and the mixture was vigorously shaken with a separating funnel. After removing the aqueous phase,
The ethyl acetate phase was further washed three times with 200 g of pure water, and only the ethyl acetate phase was separated. The obtained ethyl acetate phase was dried over anhydrous sodium sulfate, the inorganic salt was separated by filtration, 0.1 g of phenothiazine was added to the filtrate, and the ethyl acetate was removed by evaporation to obtain the desired vinyl ether monomer. This monomer was named MOBVE.

Synthesis Example 7 In a 1-liter four-necked flask, m-
BAPS 41.1 g (0.095 mol), SiDA1.
24 g (0.005 mol) is added to γ-BL 132 g at 20 ° C.
And dissolved. Thereafter, 6.54 g of PMDA (0.03 g)
0 mol), 9.67 g (0.030 mol) of BTDA, O
12.4 g (0.040 mol) of DPA was added and reacted at 55 ° C. for 4 hours. After 4 hours, the solution was returned to room temperature in 1 hour, 46 g of MBVE was added, and the mixture was stirred at 50 ° C. for 2 hours. BOX 2.13 g, NPG 2.13 g,
0.03 g of NNAP was added and diluted with γ-BL to obtain a varnish having a final viscosity of 5 poise (measured at 25 ° C.). This varnish was designated as varnish A.

Synthesis Example 8 The same procedure as in Synthesis Example 7 was carried out except that MBVE was not added. The obtained varnish was designated as varnish B.

Synthesis Example 9 MBVE of Synthesis Example 7 was converted to cyclohexyl vinyl ether 3
The procedure was performed in the same manner as in Synthesis Example 7 except that the amount was changed to 2 g. The varnish obtained was used as varnish C.

Synthesis Example 10 MBVE of Synthesis Example 7 was converted to cyclohexyl vinyl ether 1
The procedure was performed in the same manner as in Synthesis Example 7, except that the amount was changed to 6 g and 23 g of MBVE. The obtained varnish was designated as varnish D.

Synthesis Example 11 Synthesis Example 7 was carried out in the same manner as in Synthesis Example 7 except that MBVE was changed to 33 g of HEMA. The obtained varnish was designated as varnish E.

Synthesis Example 12 In a 1-liter four-necked flask, m-
BAPS 41.1 g (0.095 mol), SiDA1.
24 g (0.005 mol) is added to γ-BL 132 g at 20 ° C.
And dissolved. Thereafter, 6.54 g of PMDA (0.03 g)
0 mol), 9.67 g (0.030 mol) of BTDA, O
12.4 g (0.040 mol) of DPA was added and reacted at 55 ° C. for 4 hours. After 4 hours, the solution was returned to room temperature in 1 hour, 46 g of MBVE was added, and the mixture was stirred at 50 ° C. for 2 hours. BOX 2.13 g, NPG 2.13 g,
0.03 g of NNAP and 18.5 g of DEM were added, and γ-
Diluted with BL to a final viscosity of 5 poise (measured at 25 ° C)
Varnish was obtained. This varnish was used as varnish F.

Synthesis Example 13 Synthesis Example 13 was carried out in the same manner as in Synthesis Example 7 except that MBVE was changed to 39 g of MEVE. The obtained varnish was used as varnish G.

Synthesis Example 14 The same procedure was performed as in Synthesis Example 7 except that MBVE in Synthesis Example 7 was changed to 43 g of ABVE. The obtained varnish was designated as varnish H.

Synthesis Example 15 Synthesis Example 7 was carried out in the same manner as in Synthesis Example 7 except that MBVE was changed to 60 g of MCHMVE. The obtained varnish was designated as varnish I.

Synthesis Example 16 Synthesis Example 7 was carried out in the same manner as in Synthesis Example 7 except that MBVE was changed to 50 g of MMVE. The obtained varnish was designated as varnish J.

Synthesis Example 17 The procedure of Synthesis Example 7 was repeated except that 46 g of MBVE was changed to 35 g. The obtained varnish was designated as varnish K.

Synthesis Example 18 In a 1-liter four-necked flask,
4′-DAE 19.0 g (0.095 mol), SiDA
1.24 g (0.005 mol) is added to NMP 100 g for 20
Dissolved at ° C. Thereafter, 6.54 g of PMDA (0.0
30 mol), BTDA 9.67 g (0.030 mol),
12.4 g (0.040 mol) of ODPA was added, and 55 ° C.
For 4 hours. After 4 hours, the solution was returned to room temperature in 1 hour and stirred at room temperature for 8 hours. B in this solution
OX 1.47 g, NPG 1.47 g, NNAP 0.02
g, CmA 0.25 g and DEM 37 g were added.
To obtain a varnish having a final viscosity of 15 poise (measured at 25 ° C.). This varnish was designated as varnish L.

Synthesis Example 19 In a 1-liter four-necked flask,
4′-DAE 19.0 g (0.095 mol), SiDA
1.24 g (0.005 mol) is added to 100 g of γ-BL.
Dissolved at 0 ° C. Thereafter, 29.8 g of ODPA (0.
096 mol) and reacted at 55 ° C. for 4 hours. After 4 hours, the solution was returned to room temperature in 1 hour, 35 g of MBVE was added, and the mixture was stirred at 50 ° C. for 2 hours. B in this solution
OX 1.47 g, NPG 1.47 g, NNAP 0.02
g and 0.25 g of CmA were added and diluted with γ-BL to obtain a varnish having a final viscosity of 15 poise (measured at 25 ° C.). This varnish was used as varnish M.

Synthesis Example 20 The same procedure was performed as in Synthesis Example 19 except that 35 g of MBVE in Synthesis Example 19 was changed to 43 g. The varnish obtained was named Varnish N.

Synthesis Example 21 The same procedure was performed as in Synthesis Example 19, except that 35 g of MBVE in Synthesis Example 19 was changed to 11 g. The obtained varnish was designated as varnish O.

Synthesis Example 22 The reaction temperature of the polymer of Synthesis Example 19 was changed from 55 ° C. to 95 ° C.
The same procedures as in Synthesis Example 19 were conducted except that MBVE in Synthesis Example 19 was changed to 35 g in 11 g. The obtained varnish was designated as varnish P.

Synthesis Example 23 The reaction temperature of the polymer of Synthesis Example 19 was changed from 55 ° C. to 80 ° C.
The same procedures were performed as in Synthesis Example 19 except that MBVE in Synthesis Example 19 was changed from 35 g to 22 g. The varnish obtained was used as Varnish Q.

Synthesis Example 24 The same procedures as in Synthesis Example 7 were conducted except that MBVE in Synthesis Example 7 was changed to 68 g of MOBVE. The obtained varnish was designated as varnish R.

Synthesis Example 25 PMD was placed in a two-liter four-necked flask under a stream of dry air.
A52.3 g (0.261 mol), ODPA49.6 g
(0.16 mol), HEMA 62.4 g (0.48 mol), ethanol 14.7 g (0.32 mol), γ-B
Add L320g and stir pyridine 6 under ice-cooling.
4.2 g were added. After completion of the heat generation, the mixture was allowed to cool to room temperature and left for 16 hours, and then 166 g of dicyclohexylcarbodiimide was obtained.
Was dissolved in 120 g of γ-BL under ice-cooling for 40 minutes while stirring, followed by 4,4′-DAE74.
A suspension of 5 g (0.372 mol) in 150 g of γ-BL was added over 60 minutes while stirring under ice-cooling. After stirring at room temperature for 2 hours, 30 g of ethanol was added and the mixture was stirred for 1 hour, 250 g of dimethylacetamide and 400 g of tetrahydrofuran were added, and the reaction solution obtained by removing the precipitate by filtration was added to 15 liters of ethanol.
The resulting precipitate was separated by filtration and dried under vacuum to obtain a polymer powder. BOX3.00g, NPG to 100g of this powder
3.00 g, CmA 0.50 g, and NNAP 0.05 g were added, and diluted with NMP to a final viscosity of 15 poise (25 poise).
Varnish). This varnish was used as varnish S.

Examples 1 to 16 and Comparative Examples 1 to 6 Varnishes A to S were evaluated in (1) to (3) described above. Varnishes evaluation results are shown respectively proportion of among light-sensitive group R ^4, pattern processing conditions, patterning evaluation result, adhesion evaluation result, the manufacturing time in Table 1.

[0095]

[Table 1]

[0096]

According to the present invention, it has good pattern processability, excellent adhesion of the cured film to the sealing resin, and can be manufactured in a short manufacturing process without re-precipitation of the polymer. A photosensitive polyimide precursor composition and a method for producing the same can be obtained.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a method for determining absorbance due to an imide group from an IR spectrum.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 21/027 H01L 21/30 502R

Claims (4)

[Claims] 1. A method comprising the steps of: (a) reacting a polymer or oligomer having a structural unit represented by the general formula (1) with (b) a vinyl ether compound represented by the general formula (2). Photosensitive polyimide precursor composition. Embedded image (R ¹ represents a trivalent or tetravalent organic group having at least 2 or more carbon atoms, R ² represents a divalent organic group having at least 2 or more carbon atoms. R ³ represents hydrogen, alkali Represents at least one selected from a metal ion, an ammonium ion, or an organic group having 1 to 30 carbon atoms, of which 30 to 100 mol% consists of hydrogen, and n represents 1 or 2. (R ⁴ represents an organic group having 1 to 30 carbon atoms, of which 50 to 1
00 mol% represents an organic group containing a photosensitive group. ) 2. The photosensitive polyimide precursor composition according to claim 1, comprising an amine compound represented by the general formula (3). (R ⁵ , R ⁶ , and R ⁷ are organic groups having 1 to 30 carbon atoms, at least one of which is an organic group containing a photosensitive group.) 3. The carboxyl group concentration of the polymer in the prebaked film having a thickness of 10 μm is 10 to 1 with respect to the structural unit.
The photosensitive polyimide precursor composition according to claim 1, wherein the content is 50 mol%. 4. The photosensitive polyimide precursor composition according to claim 1, wherein the imidation ratio of the polymer in the prebaked film having a thickness of 10 μm is from 0 to 0.4.