JP2000221677A - Positive photosensitive resin composition and pattern forming method using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the positive photosensitive resin composition developable in an aqueous alkali solution and high in resolution by incorporating a specified polyimide precursor and a diazo-naphthoquinone type photosensitive agent and a component capable of causing cross-linking reaction or self-heat-polymerization reaction with the specified group of this polyimide precursor. SOLUTION: The photosensitive composition contains (a) the polyimide precursor represented by the formula, (b) the naphthoquionone type photosensitive agent, and (c) the component capable of causing the cross-linking reaction or self-heat-polymerization reaction with the Z-group of this polyimide precuror. In the formula, X is a tetravalent aromatic group; Y is a divalent aromatic group; Z is a carboxyl, hydroxyl, amino, sulfonamide, or amide group; R is an H atom or a 1-6C alkyl group; and (m) is 0, 1, 2, or 3. The component (c) is mixed to the polyimide in an amount of 1-15 weight % of the polyimide precursor and the component (c) is at least one kind among melamine, styrene, epoxy, phenylacetylene, acrylates, methacrylates, and bismaleimides.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a positive photosensitive resin composition using a polyimide precursor and a method for forming a pattern thereof.

[0002]

2. Description of the Related Art Polyimide is excellent in heat resistance, mechanical strength, and electrical insulation, and is therefore applied to semiconductor devices and the like that require high reliability.

[0003] The application of polyimide to semiconductor devices involves the application of a passivation film, a buffer coat film, an α-ray shielding film, an interlayer insulating film, etc. to the conductive portions of the upper and lower conductor layers and external lead wires. Fine processing such as through holes for connection is required. Therefore, a chemical etching process of a polyimide film using a photoresist as a mask is generally performed.

However, the patterning of such a polyimide film requires application and peeling of a photoresist, which complicates the process. In addition, the transfer of the relief pattern via the resist causes a reduction in dimensional accuracy. For this reason, a negative photosensitive polyimide that can be developed with an organic solvent is commercially available as a photosensitive polyimide that has a short process and can be finely processed.

However, recently, from the viewpoint of improving the efficiency of equipment and the global environment, a positive photosensitive polyimide which can be developed with an aqueous alkali solution for which a disposal method has been established and has a higher resolution than a negative type has been required. It became so.

[0006] The polyimide precursor structure serving as the base of such a photosensitive polyimide is an important factor that has a great influence on the dissolution characteristics during development. Also, the alkaline solution is
As compared with the conventional organic solvent, the dissolving power for such a resin material is inferior. In addition, swelling, peeling, cracks, and the like are likely to occur in exposed portions and unexposed portions. However, the relationship between such dissolution characteristics and the structure of the polyimide precursor has not yet been fully understood.

[0007] As the negative type of the prior art, a method using a photo-crosslinking agent (JP-A-2-163743, JP-A-3-16374).
157657) and a method using a photobase generator (JP-A-5-197148) are known.
The former method using a photocrosslinking agent is mainly used.

In the case of a positive type, a polyimide precursor having a photosensitive group introduced (Japanese Patent Publication No. 1-59571)
And those to which a photosensitive group is added.

In the latter case of adding a photosensitive group, a polyimide precursor and a diazonaphthoquinone sulfonic acid ester which generates a carboxylic acid upon irradiation with light (JP-A-4-168441)
And JP-A-4-204738), and those obtained by adding a dihydroxypyridine derivative to a polyimide precursor (JP-A-6-43648).

[0010]

However, it is difficult to accurately form a pattern having a size of 10 μm square or less with the above-mentioned prior art. For example, in the case of a hole pattern of 10 μm square or less, at the time of imidization by a heating step after development,
The positive photosensitive film melts to fill the hole pattern, or the pattern cross section is greatly deformed, thereby lowering the resolution during development.

In the conventional negative photosensitive polyimide, since the pattern is formed by photocrosslinking of the exposed portion, there was no reduction in resolution due to melting during thermal imidization. Therefore, a cross-linking agent was examined based on the negative type knowledge. As a result, the carboxyl group, hydroxyl group, amino group,
It was considered that melting could be prevented by adding a compound that causes a crosslinking reaction or a self-polymerization reaction with a sulfonamide group or an amide group to the positive photosensitive resin composition.

An object of the present invention is to provide a high-resolution positive photosensitive resin composition which can be developed with an aqueous alkali solution.

Another object of the present invention is to provide a pattern forming method using the above-mentioned positive photosensitive resin composition.

[0014]

The gist of the present invention to achieve the above object is as follows.

[1] (a) Formula [I]

[0016]

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(Wherein, X is a tetravalent aromatic group, Y is a divalent aromatic group, Z is a carboxyl group, a hydroxyl group, an amino group, a sulfonamide group, an amide group, R is hydrogen or a carbon atom having 1 to 1 carbon atoms.
An alkyl group of 6 and m represents an integer of 0 to 3), a (b) diazonaphthoquinone-based photosensitizer, and (c) a crosslinking reaction with the Z group of the formula [I], or A positive photosensitive resin composition comprising a component that causes a thermal polymerization reaction.

[2] A positive photosensitive resin composition in which the component (c) is blended in an amount of 1 to 15% by weight based on the polyimide precursor.

[3] A positive photosensitive resin composition wherein the component (c) is at least one of melamine, styrene, epoxy, phenylacetylene, acrylates, methacrylates, and bismaleimides.

[4] (a) a polyimide precursor represented by the formula [I], (b) a diazonaphthoquinone-based photosensitizer, and (c) a crosslinking reaction with the Z group of the formula [I], or self-thermal polymerization. A step of blending at least 30% by weight of a solvent with the positive photosensitive resin composition containing a component causing a reaction and applying the mixture to a substrate of an electronic device, and a photosensitive resin applied by prebaking the substrate A step of forming the composition into a film, a step of irradiating the film with an electromagnetic wave through a photomask, a step of developing the film with an alkali developer, a step of forming a pattern, and a step of heating the patterned film to form a polyimide. A method for forming a pattern of a positive photosensitive resin, comprising:

The polyimide precursor constituting the positive photosensitive resin composition of the present invention is a base polymer which becomes a polyimide having excellent heat resistance after heat curing, and the diazonaphthoquinone compound becomes indenecarboxylic acid upon exposure. It is an indispensable photosensitizer for forming a positive type photoreceptor that increases the dissolution rate of an exposed portion in an aqueous alkaline solution.

A positive pattern is formed from the difference between the dissolution rates of the exposed and unexposed portions. The compounding amount is preferably 5 to 25% by weight based on the polyimide precursor. If it is less than 5%, the dissolution rate is not sufficiently increased, and if it exceeds 25% by weight, light absorption is large and it is necessary to increase the exposure.

At the end, 1 to 15% by weight of a component which causes a crosslinking reaction with a carboxyl group, a hydroxyl group, an amino group, an amide group or a sulfonamide group of the polyimide precursor or a thermal polymerization reaction by itself is blended.

These can prevent the hole pattern after exposure and development from melting at the time of thermal curing, and can form a high-resolution pattern.

[0025]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Polyimide precursors are roughly classified into polyamic acids and polyamic esters. Polyamic acid is obtained by reacting an acid dianhydride with a diamine in a solvent.

On the other hand, the polyamic acid ester is prepared by preparing a tetracarboxylic diester from a tetracarboxylic dianhydride and an alcohol, chlorinating the carboxylic acid with a chlorinating agent, passing through an acid chloride, and reacting with a diamine. can get.

In addition, a tetracarboxylic diester is DB
There is also a method of condensing with a diamine using a condensing agent such as OP [2,3-dihydro-2-thioxo-3-benzoxazolyl) sulfonate] or DCC (dicyclohexylcarbodiimide).

As the tetracarboxylic dianhydride, a tetracarboxylic dianhydride generally used for a photosensitive polyimide can be used, but ODPA is not preferred in terms of melting.

As the tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride, 3,3', 4'-tetraphenyl dianhydride is preferred in view of the transparency and solubility of the base polymer.
Biphenyltetracarboxylic dianhydride, 3,3 ', 4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',
4'-benzophenonetetracarboxylic dianhydride, 2,2
-Bis (3,4-dicarboxyphenyl) hexafluoropropanoic acid dianhydride.

The alcohol to be reacted with the tetracarboxylic dianhydride includes methanol, ethanol, propanol, butanol, pentanol, hexanol and the like, and includes primary, secondary and tertiary alcohols and those having a hydroxyl group.

Diamines include m-diaminodiphenylsulfone, p-diaminodiphenylsulfone, m-diaminodiphenylether, 4,4'-diamino-3,3'-dicarboxydiphenylmethane, m-xylylenediamine,
-Xylylenediamine, 2,2-bis (3-aminophenyl) hexafluoropropane, 3,3'-difluoro-4,4'-diaminobiphenyl, 3,3 ', 5,5'-tetrafluoro-4,4 '-Diaminobiphenyl, fluoro-4
-Phenylenediamine, 3,5-difluoro-4-phenylenediamine, trifluoro-4-phenylenediamine, trifluoromethyl-4-phenylenediamine,
3,5-ditrifluoromethyl-4-phenylenediamine, tetrafluoro-4-phenylenediamine, 2,2 ′
-Di (trifluoromethyl) -4,4'-diaminobiphenyl, octafluoro-4,4'-diaminobiphenyl, tetramethyl-4-phenylenediamine, tetraethyl-
4-phenylenediamine, tetrapropyl-4-phenylenediamine, trimethyl-4-phenylenediamine,
Triethyl-4-phenylenediamine, tripropyl 4
Phenylenediamine, 3,3 ′, 5′-trimethyl-4,
4'-diaminobiphenyl, 3,3 ', 5'-triethyl-
4,4'-diaminobiphenyl, 3,3 ', 5'-tripropyl-4,4'-diaminobiphenyl, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 2,2'- Dimethyl-4,4'-diaminibiphenyl,
4,4'-diamino-3-carboxamide-diphenyl ether, 4,4'-diamisulfonamide-diphenyl ether and the like.

In polyimide, a self-adhesive diamine having excellent adhesiveness to a silicon substrate is 1,1.
3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (3-aminophenyl) tetramethyldisiloxane, 1,3-bis (3-aminopropyl) tetraphenyldisiloxane, 1,3- Bis (3-aminophenyl) tetraphenyldisiloxane and the like, and the amount of these self-adhesive diamines is 3 to 7% of the diamine component of the polyimide precursor, so that the decrease in mechanical strength of the polyimide film is small, Has little effect on development characteristics.

Examples of the chlorinating agent include thionyl chloride, phosphorus trichloride, phosphorus pentachloride and the like.

Examples of polar solvents include N-methyl-2-pyrrolidone, N, N'-dimethylacetamide, dimethylformamide, dimethylsulfoxide, acetonitrile, diglyme, γ-butyrolactone, phenol, toluene, dioxane, tetrahydrofuran, sulfolane, hexamethyl And phosphoramide.

The naphthoquinonediazide-based photosensitizers include
The compound is not particularly limited as long as it is a compound containing a naphthoquinonediazide group in the molecule.

Usually, the naphthoquinonediazide compound is used as a naphthoquinonediazidesulfonic acid ester.
This is obtained by a condensation reaction between naphthoquinonediazide sulfonic acid chloride and a compound having a phenolic hydroxyl group.

The naphthoquinonediazidesulfonic acid constituting the naphthoquinonediazidesulfonic acid chloride includes 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride and 1,2-naphthoquinone-2-diazide-4-.
And sulfonic acid chloride.

Specifically, 1,3-bis {3- [4- (1,
2-naphthoquinone-2-diazido-4-sulfoxy) phenyl] ureidomethyl-benzene, 1- [4- (1,2
-Naphthoquinone-2-diazido-4-sulfoxy) phenyl] -3-phenylurea, 1-benzyl-3- [4-
(1,2-Naphthoquinone-2-diazido-4-sulfoxy) phenyl] urea, 2-amino-4,6-bis (1,2-
Urea compounds such as naphthoquinone-2-diazido-4-sulfoxy) pyrimidine, 4,4'-bis (1,2-naphthoquinone-2-diazido-4-sulfonylamino) diaminodiphenyl ether, 4- (1,2-naphthoquinone -2
-Diazido-4-sulfonylamino) -1- (1,2-naphthoquinone-2-diazido-4-sulfonyloxy) benzene, N-methyl-1,2-bis (1,2-naphthoquinone-2-diazide-4 -Sulfonylamino) ethane, 2
-(1,2-naphthoquinone-2-diazido-4-sulfonylamino) -1- (1,2-naphthoquinone-2-diazido-4-sulfonyloxy) ethane or 1,3-bis {3-
[4- (1,2-Naphthoquinone-2-diazido-5-sulfoxy) phenyl] ureidomethyl-benzene, 1-
[4- (1,2-naphthoquinone-2-diazido-5-sulfoxy) phenyl] -3-phenylurea, 1-benzyl-3- [4- (1,2-naphthoquinone-2-diazide-5
Urea compounds such as -sulfoxy) phenyl] urea, 2-amino-4,6-bis (1,2-naphthoquinone-2-diazido-5-sulfoxy) pyrimidine and 4,4′-bis (1,
2-naphthoquinone-2-diazido-5-sulfonylamino) diaminodiphenyl ether, 4- (1,2-naphthoquinone-2-diazido-5-sulfonylamino) -1-
(1,2-naphthoquinone-2-diazido-5-sulfonyloxy) benzene, N-methyl-1,2-bis (1,2-naphthoquinone-2-diazido-5-sulfonylamino) ethane, 2- (1, 2-naphthoquinone-2-diazide-5
Sulfonylamino) -1- (1,2-naphthoquinone-2-
Diazide-5-sulfonyloxy) ethane and the like.

The compounding amount of the diazonaphthoquinone type photosensitive agent is 5 to 25% by weight based on the polyimide precursor.

The following compounds can be used as a compound that causes a crosslinking reaction or a self-polymerization reaction with a carboxyl group, a hydroxyl group, an amino group, a sulfonamide group, or an amide group of the polyimide precursor.

Melamine, as a compound capable of undergoing a crosslinking reaction,
Specifically, hexamethoxymethyl melamine or a bifunctional epoxy, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, polyglycol type epoxy resin, glycidyl ester type epoxy resin, bifunctional And isocyanates.

Compounds that cause a self-polymerization reaction include N, N'-
(4,4'-diphenyl-methane) bismaleimide, bis
(3-ethyl-5-methyl-4-maleimidophenyl) methane, 2,2'-bis [4- (4-maleimidophenoxy)
Phenyl] propane, methacrylic acid methyl ester, methacrylic acid ethyl ester, methacrylic acid propyl ester, methacrylic acid butyl ester, methacrylic acid hydroxyethyl ester, etc., methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate Phenylacetylene, styrene, 4-divinylbenzene and the like.

These were added to the polyimide precursor in an amount of 1 to 1
5% by weight, preferably 5 to 10% by weight is blended. If the amount is less than 1% by weight, the prevention of melting is insufficient, and if it exceeds 15% by weight, the exposure amount may need to be increased.

The compound that undergoes a crosslinking reaction with the carboxyl group, hydroxyl group, amino group, sulfonamide group, or amide group of the above polyimide precursor or self-polymerizes does not react at the time of prebaking or exposure, but only at the time of thermal imidization. React
It is desirable to prevent melting. Therefore, a catalyst, a reaction accelerator and the like can be added within the conditions satisfying the above.

The terminal group of the polyimide precursor also greatly affects the solubility. In the case of an amine terminal, the diamine component is increased such that the mixing ratio of the acid dianhydride and the diamine is 10 to 11. In the case of a carboxylic acid terminal, the amount of the acid dianhydride component is increased. This gives one of any molecular weight and terminal group.

Examples of the alkali developing solution include quaternary ammonium hydroxide aqueous solutions such as tetraammonium hydroxide and tetraethylammonium hydroxide, and amine aqueous solutions such as ethanolamine and propylamine. Among them, a 2.38% aqueous solution of tetraammonium hydroxide is most common.

When the polyimide comprising the positive photosensitive resin composition of the present invention is used for an electric or electronic device, it can be used as a varnish dissolved in a polar solvent.

Resin concentration of the above varnish (abbreviated as NV)
Is selected depending on the required film thickness and coating performance,
% By weight is preferred. If it exceeds 45% by weight, the varnish viscosity becomes high, and problems such as control of the film thickness and retention of bubbles occur. 3%
If it is less than 3, a uniform polyimide layer having a thickness of 3.0 μm or more cannot be obtained.

The average molecular weight (weight average molecular weight: represented by Mw) of the polyamic acid / polyamic acid ester copolymer of the present invention is determined by GPC (Gel Permeation Chromatography).
Is preferably 5000 to 60,000 in terms of polystyrene.

If the Mw is less than 5000, the mechanical strength of the polyimide is insufficient and the polyimide is not practical. When Mw exceeds 60,000, the development time is prolonged, and a favorable positive relief pattern cannot be obtained.

The positive photosensitive resin composition is spin-coated on a glass plate or a silicon wafer or the like, and
A film is formed by pre-baking at 0 ° C. to evaporate the solvent to some extent. I through a photomask having a fine pattern
After irradiation with a line (monochromatic light of 365 nm), the exposed portion is etched in an alkaline aqueous solution to form a fine relief pattern.

After washing with water, it is thermally imidized to obtain a polyimide. Thermal imidization temperature after development is 200-450 ° C,
Preferably it is 300-400 degreeC.

The above positive photosensitive resin composition of the present invention comprises:
It can be developed with an alkaline aqueous solution, and a polyimide film having a high-resolution positive relief pattern can be formed. Thus, an electronic device using the positive photosensitive resin composition can be obtained.

A positive electrode comprising a polyimide precursor and a diazonaphthoquinone photosensitizer, and a component which causes a crosslinking reaction with a carboxyl group, a hydroxyl group, an amino group, an amide group or a sulfonamide group of the polyimide precursor, or a polymerization reaction by itself. The photosensitive resin composition of the present invention can be developed with an aqueous alkali solution, and a polyimide film having a good positive relief pattern having no difference between the resolution during development and the resolution during thermal imidization can be obtained.

As a cross-linking agent, peroxide is required for bismaleimide, and a catalyst such as an acid generator is required for hexatetramethoxymethylmelamine, but it is necessary to add a catalyst such that the dissolution rate after prebaking is not significantly changed. It is possible.

The polyimide film of the positive photosensitive resin composition of the present invention can be used for an interlayer insulating film, a passivation film, and an insulating film for a multilayer printed circuit board of a semiconductor device. In the electronic device, a microcomputer, a memory, a gate array, a logic, and the like can be cited, and as their mounting forms, PGA, QFP, SOJ, SOP, TSOP,
There are TQFP, ZIP, BGA, CSP, COB and the like.

[0057]

EXAMPLES The positive photosensitive polyimide of the present invention which can be developed with an aqueous alkali solution will be specifically described with reference to Examples.
Table 1 shows the positive photosensitive compositions of Examples and Comparative Examples.

[0058]

[Table 1]

The compounds used in Examples and Comparative Examples and their abbreviations are shown below.

ODPA: 3,3 ′, 4′-diphenylethertetracarboxylic dianhydride, PMDA: pyromellitic dianhydride, DSDA: 3,3 ′, 4′-biphenyltetracarboxylic dianhydride, BPDA: 3,3 ′, 4′-biphenyltetracarboxylic dianhydride, BADA: 3,5-diaminobenzoic acid, DADM: 4,4′-diamino-3,3′-dicarboxydiphenylmethane, DHDM: 4,4 ′ -Dihydro-3,3'-diamino-diphenylmethane, DDSO: 4,4'-diamino-diphenylsulfone, TMPDA: 2,6-tetramethyl-1,4-phenylenediamine, XYDA: 4,4'-xylylenediamine , DDEC: 4,4'-diamino-3-carboxamide-diphenyl ether, MeOH: methyl alcohol, n-BuOH: 1-butanol, t BuOK: Potassium -t- butoxide, THF: tetrahydrofuran, NMP: N-methyl-2-pyrrolidone, MS: NMPN and γ- butyrolactone pair with a mixed solvent at a weight ratio of 9, DNQ3: tetrahydroxy - 1,2 benzophenone
AMP-Q: 4- (1,2-naphthoquinone-2-diazido-5-sulfonylamino) -1- (1,2-naphthoquinone-2 -Diazido-5-sulfonyloxy) benzene, DE-Q: 4,4'-bis (1,2-naphthoquinone-2-diazido-5-sulfonylamino) diphenyl ether, BMI: 2,2'-bis [4- ( 4-maleimidophenoxy) phenyl] propane, BG: glycidyl methacrylate (manufactured by NOF Corporation), H3M: hexamethoxymethylmelamine, YX4000: tetramethylbiphenol type epoxy resin (manufactured by Yuka Shell Epoxy).

[Production Example 1] 9.3 g (0.03 mol) of polyamic acid ester ODPA was dried with n-BuO
H. After adding 20 g of H and refluxing for 1 hour, excess n-Bu
OH is distilled off to obtain 3,3 ′, 4′-diphenylethertetracarboxylic acid dibutyl ester (ODPBu).

8.6 g of thionyl chloride (0.07
2 mol), and refluxed for 1 hour. Excessive thionyl chloride was removed under reduced pressure, and dibutyl ester dichloride of 3,3 ′, 4′-diphenylethertetracarboxylic acid (ODPBu) was added.
Cl).

4.3 g (0.0285 mol) of DABA,
After adding and dissolving 18 g of NMP, the NMP solution of dibutyl ester dichloride of 3,3 ′, 4′-diphenylethertetracarboxylic acid was slowly added dropwise over 1 hour while maintaining the temperature at 5 ° C. or lower, and stirring was continued for 3 hours. Was. Thereafter, the reaction solution was poured into 3 liters of water, vigorously stirred, and the precipitate was separated by filtration. After thoroughly washing this,
The resultant was dried under reduced pressure at 40 ° C. for 72 hours to obtain a target white polyamic acid ester.

[Production Example 2] 26 g of NMP was added to 6.85 g (0.05 mol) of polyamic acid / polyamic acid ester copolymer and dissolved, and 8.2 g of ODPA (0.0265 mol) was obtained.
l) was added and stirred slowly for 8 hours. This was kept at 5 ° C. or lower, and 14.0 g (0.0265 mol) of the above-mentioned acid chloride solution (dibutyl ester dichloride (ODPBuCl) of 3,3 ′, 4′-diphenylethertetracarboxylic acid) was added.
And NMP (25 g)) were slowly added dropwise over 1 hour,
The mixture was stirred for 1 hour. Thereafter, the reaction solution was poured into 3 liters of water, stirred vigorously, and the precipitate was separated by filtration. This was sufficiently washed with water and dried under reduced pressure at 40 ° C. for 72 hours to obtain a desired white polyamic acid / polyamic acid ester copolymer.

[Production Example 3] 20 g of a THF solution containing 3.1 g of acid chloride ODPA using t-butyl ester was dissolved at 5 ° C.
, And slowly add a THF solution of t-BuOK
After stirring at room temperature for a period of time, di-t-butyl ester of 3,3 ′, 4′-diphenylethertetracarboxylic acid (ODPtB
u).

Using this, a polyamic acid ester or a polyamic acid / polyamic acid ester copolymer was obtained according to Production Examples 1 and 2.

Although the notation of BAT is omitted in Table 1 below, 5 mol of diamine component is used in all Examples and Comparative Examples.
1% incorporated BAT.

The resolution is represented by a value of the minimum size that can be developed by developing a positive pattern having a side of 100 to 1 μm square through a photomask.

The positive pattern size was 100 μm.
Square, 90 μm square, 80 μm square, 70 μm square, 60 μm
Square, 50 μm square, 40 μm square, 30 μm square, 20 μm
Square, 10 μm square, 8 μm square, 6 μm square, 5 μm square, 4 μ
m square, 3 μm square, 2 μm square, 1 μm square.

Example 1 2.5 g of DDEQ, 0.5 g of YX4000 and 23.2 g of a mixed solvent MS were added to 10 g of the polyamic acid ester obtained in Production Example 1, and mixed solvent MS was added with sufficient stirring to dissolve the mixture. (0 μm) to obtain a positive photosensitive resin composition.

This composition was applied on an untreated silicon wafer and spin-coated at 2500 rpm for 40 seconds. This is pre-baked on a hot plate at 80 ° C for 10 minutes,
A coating film having a thickness of 5.8 μm was obtained.

An i-line (365 nm) was irradiated with light from an ultra-high pressure mercury lamp through a photomask having a fine pattern on the coating film.
Irradiation was performed at a dose of 500 mJ / cm ² using a band-pass filter and a light-shielding mask.

After the exposure, 5 ° C. was added to an aqueous alkaline solution (a 2.38% by weight aqueous solution of tetramethylammonium hydroxide) at 23 ° C.
It was immersed for 0 to 160 seconds and developed. Then, use pure water for 30
After rinsing for 2 seconds, a relief pattern without erosion in the unexposed area was obtained. The resolution was 5 μm square.

This was heated on a hot plate at 120.degree. C./3 minutes + 200.degree. C./3 minutes + 350.degree. C./6 minutes to imidize it to obtain a 3.5 .mu.m thick polyimide film. The resolution after thermal imidization was 5 μm square. There was no change in resolution after development and after thermal imidization, and it was confirmed that melting was prevented.

Example 2 According to Example 1, a positive resin composition having the composition shown in Table 1 was prepared. The resolution after development was 6 μm square, the film thickness after thermal imidization was 2.8 μm, the resolution was 6 μm square, and no melting occurred.

Examples 3 to 6 Positive resin compositions having the compositions shown in Table 1 were prepared according to Production Example 3 and Example 1. In all cases, the resolution after development was equivalent to the resolution after thermal imidization, and no melting occurred during thermal imidization. The film thickness after thermal imidization is 2.8 to 4.3 μm.

Example 7 A positive resin composition having the composition shown in Table 1 was prepared according to Example 1. PMD (Bu)
And the mixing ratio of ODP (Bu) is 3/7. The resolution after development was equivalent to that after thermal imidization, and no melting occurred during thermal imidization. The film thickness after thermal imidization is 4.0μ
m.

Example 8 A positive resin composition having the composition shown in Table 1 was prepared according to Production Example 2 and Example 1.
The resolution after development and the resolution after thermal imidization are the same,
No melting occurred during thermal imidization. The film thickness after thermal imidization is 3.6 μm.

Example 9 A positive resin composition having the composition shown in Table 1 was prepared according to Production Example 2 and Example 1.
The resolution after development and the resolution after thermal imidization are the same,
No melting occurred during thermal imidization. The film thickness after thermal imidization is 3.3 μm.

Example 10 Production Example 2 and Example 1
A positive resin composition having the composition shown in Table 1 was prepared according to the procedure shown in Table 1. The resolution after development and the resolution after thermal imidization are the same,
No melting occurred during thermal imidization. The film thickness after thermal imidization is 3.9 μm.

Example 11 Production Example 2 and Example 1
A positive resin composition having the composition shown in Table 1 was prepared according to the procedure shown in Table 1. The resolution after development and the resolution after thermal imidization are the same,
No melting occurred during thermal imidization. The film thickness after thermal imidization is 3.1 μm.

Example 12 Production Example 2 and Example 1
A positive resin composition having the composition shown in Table 1 was prepared according to the procedure shown in Table 1. The resolution after development and the resolution after thermal imidization are the same,
No melting occurred during thermal imidization. The film thickness after thermal imidization is 2.6 μm.

Example 13 Production Example 2 and Example 1
A positive resin composition having the composition shown in Table 1 was prepared according to the procedure shown in Table 1. The resolution after development and the resolution after thermal imidization are the same,
No melting occurred during thermal imidization. The film thickness after thermal imidization is 3.0 μm.

Example 14 A resin-sealed semiconductor device is shown as an example of an electronic device using the positive photosensitive resin composition of the present invention. FIG. 1 is a schematic cross-sectional view showing a manufacturing process of a semiconductor device using the positive photosensitive resin composition of the present invention.

As shown in FIG. 1A, the LSI chip 1
Are formed on the tab 3 on which is mounted a 50 .mu.m square bonding pad. Next, as shown in FIG. 1 (b), the rotation speed was adjusted so that the thickness of the polyimide film became 3.5 μm, and the positive photosensitive resin composition 4 of the present invention was spin-coated.

Next, in FIG. 1C, after preliminary drying at 80 ° C. for 10 minutes, a photomask was placed, and i-line was irradiated at 500 mJ / cm ² through a band-pass filter. Further, the resultant was immersed in a 2.38% by weight aqueous solution of tetraammonium hydroxide for about 1.5 minutes to form a 50 μm square through hole 50.

FIG. 1D shows a bonding pad 2 in which a through hole 50 is formed and a lead frame 7 connected by a bonding wire 6, and the whole is packaged with an epoxy-based sealing agent 8, and the resin sealing of the present invention is performed. A semiconductor device was fabricated.

Example 15 is a schematic sectional view showing a process for producing a copper / polyimide thin film multilayer wiring board using the positive photosensitive resin composition of the present invention.

As shown in FIG. 2A, the positive photosensitive resin composition 12 of Example 1 is formed on a thick-film multilayer wiring board 11 by spin coating and pre-baking.
Exposure through Next, as shown in FIG. 2B, development and thermal imidization are performed to obtain a polyimide layer 15 having a mask opening 14 having a thickness of 10 μm.

Next, as shown in FIG. 2C, a copper film is formed by a method used in the manufacture of semiconductors and the like, and then photo-etched to form a copper wiring 16. Further, as shown in FIG. 2D, the above operation was repeated three times to prepare a copper / polyimide thin film multilayer wiring board.

Comparative Example 1 A polyimide film was obtained in the same manner as in Example 1 except that YX4000 was not added.
As a result, the resolution after development was 4 μm square, but it melted during thermal imidization, and the resolution after thermal imidization decreased to 10 μm square.

In Comparative Example 1 and Example 1, there was a difference in the melting resolution depending only on the presence or absence of YX4000. Incidentally, the film thickness after thermal imidization is 4.1 μm.

Comparative Example 2 A polyimide film was obtained in the same manner as in Example 4 except that H3M was not added. As a result, the resolution after development was 3 μm square, but it melted during thermal imidization, and the resolution after thermal imidization decreased to 20 μm square.

In Comparative Example 2 and Example 4, melting occurred and the resolution was reduced only by the presence or absence of H3M. The film thickness after thermal imidization is 3.5 μm.

Comparative Example 3 A polyimide film was obtained in the same manner as in Example 9 except that YX4000 was not blended.
As a result, the resolution after development was 3 μm square, but it melted during thermal imidization, and the resolution after thermal imidization decreased to 10 μm square.

In Comparative Example 3 and Example 9, melting was caused only by the presence or absence of YX4000, and the resolution was reduced. The film thickness after thermal imidization is 4.0 μm.

[0097]

The positive photosensitive resin composition of the present invention can form a polyimide layer having a high-resolution relief pattern by exposure through a photomask, development with an alkaline aqueous solution, imidization by heating, and the like. it can.

In particular, since no melting occurs during thermal imidization, a high-resolution polyimide film can be obtained.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view showing a manufacturing process of a semiconductor device using a positive photosensitive resin composition of the present invention.

FIG. 2 shows the results of using a positive photosensitive resin composition of the present invention for copper /
It is a schematic cross section which shows the manufacturing process of a polyimide thin film multilayer wiring board.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... LSI chip, 2 ... Bonding pad, 3 ... Tab, 4 ... Positive photosensitive resin composition, 5 ... Polyimide layer,
50 through hole, 6 bonding wire, 7 lead frame, 8 sealant, 11 thick film multilayer wiring board,
12: Positive photosensitive resin composition, 13: Photomask,
14 ... mask opening, 15 ... polyimide layer, 16 ... copper wiring.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 35/00 C08L 35/00 49/00 49/00 63/00 63/00 A 79/08 79/08 A 101/16 101/02 101/02 G03F 7/004 501 G03F 7/004 501 7/022 7/022 7/039 501 7/039 501 7/40 501 7/40 501 H01L 21/312 D H01L 21 / 027 C08L 61/32 21/312 101/00 // C08L 61/32 H01L 21/30 502R (72) Inventor Takao Miwa 7-1-1, Omikamachi, Hitachi City, Hitachi City, Ibaraki Prefecture Within Hitachi Research Laboratory, Hitachi, Ltd. 72) Inventor Takumi Ueno 7-1-1, Omika-cho, Hitachi City, Ibaraki Prefecture Inside Hitachi, Ltd.Hitachi Research Laboratory (72) Inventor Shinji Yamada 7-1-1, Omika-cho, Hitachi City, Ibaraki Prefecture Hitachi, Ltd. Hitachi Research Laboratory (72) Inventor Masataka Nunomura 13-1, Higashicho, Hitachi City, Ibaraki Prefecture F-term in Hitachi Chemical DuPont Microsystems Co., Ltd. (Reference) 2H025 AA02 AA10 AA13 AA20 AB16 AC01 AD03 BE01 CB25 CC20 EA10 FA01 FA03 FA17 FA29 2H096 AA25 BA10 BA20 DA01 EA02 GA08 HA01 4J002 AA00X BC01X BC03X BG04X BG05X BG06X BG07X BH02X BM00X CC18X CD00X CD01X CD05X CM04W ER007 EV246 FD14X FD147 FD206 GP03 GQ01 GQ05 HA03 5F007 AA10 AC04

Claims (4)

[Claims] (A) Formula (I): ## STR1 ## (Where X is a tetravalent aromatic group, Y is a divalent aromatic group, Z
Is a carboxyl group, a hydroxyl group, an amino group, a sulfonamide group, an amide group, R is hydrogen or an alkyl group having 1 to 6 carbon atoms, and m is an integer of 0 to 3). A positive photosensitive resin composition comprising: a naphthoquinone-based photosensitive agent; and (c) a component which causes a crosslinking reaction or a self-thermal polymerization reaction with the Z group of the formula [I]. (A) Formula (I): (Where X is a tetravalent aromatic group, Y is a divalent aromatic group, Z
Is a carboxyl group, a hydroxyl group, an amino group, a sulfonamide group, an amide group, R is hydrogen or an alkyl group having 1 to 6 carbon atoms, and m represents an integer of 0 to 3). 5 to 25% by weight of a diazonaphthoquinone-based photosensitizer based on the precursor, and (c) a component which causes a crosslinking reaction with the Z group of the formula (I) or a self-thermal polymerization reaction,
A positive photosensitive resin composition, which is contained in an amount of 1 to 15% by weight based on the polyimide precursor. 3. The method according to claim 1, wherein the component (c) is melamine, styrene,
3. The positive photosensitive resin composition according to claim 1, which is at least one of epoxy, phenylacetylene, acrylates, methacrylates, and bismaleimides. (A) Formula (I): (Where X is a tetravalent aromatic group, Y is a divalent aromatic group, Z
Is a carboxyl group, a hydroxyl group, an amino group, a sulfonamide group, an amide group, R is hydrogen or an alkyl group having 1 to 6 carbon atoms, and m is an integer of 0 to 3). A positive photosensitive resin composition containing a naphthoquinone-based photosensitizer and a component (c) which causes a crosslinking reaction or a self-thermal polymerization reaction with the Z group of the formula [I], and at least 30% by weight of the resin composition Applying the solvent to a substrate of an electronic device, applying the solvent to a substrate of an electronic device, forming a film of the applied photosensitive resin composition by prebaking the substrate, irradiating the film with an electromagnetic wave through a photomask, Forming a pattern with an alkaline developer and heating the patterned film to form a polyimide, the method comprising the steps of: