JP2002308986A - Photopolymer composition and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photopolymer composition containing a polyimide precursor having ethylenic double bonds reactive to an actinic radiation such as an ultraviolet radiation in side chains, being developable with an aqueous alkali solution, and having negative pattern forming properties. SOLUTION: The composition is the one comprising a solvent containing (A) the polyimide precursor comprising repeating units of the formulae (wherein R<3> and R<4> are each an ethylenically unsaturated organic group), (B) a photopolymerization initiator, a sensitizer, and an inhibitor intended for storage stability, and (C) a photosensitizer, wherein the repeating units of formulae (2) and (3) constitute at least 0.15 mol% of those of polyimide precursor (A).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimide-based photosensitive polymer composition used as an electrical or electronic insulating material in the manufacture of semiconductor devices and the like.
More specifically, the photosensitive resin composition is formed on a semiconductor element such as an IC or LSI, and is applied to the formation of an insulating protective film that requires processing of a fine pattern.

[0002]

2. Description of the Related Art In recent years, polyimide resins have been developed in the fields of electricity and electronics, including semiconductors, due to their high heat resistance, chemical resistance, electrical insulation, low dielectric constant, and the like. , IC, LSI and VLSI chips are used as interlayer insulating films and surface protective films. However, in the conventional pattern forming method, after a polyimide precursor is applied on a wafer and dried to form a polyimide resinized film, pattern etching using a photoresist must be performed. In addition, a harmful hydrazine solution had to be used as a polyimide etching solution.

[0003] For this reason, attempts to introduce a photosensitive group into a polyimide precursor to enable pattern formation with the polyimide itself have been made by various material manufacturers, and are in the practical stage in some product fields. However, photosensitive polyimides currently in practical use can be broadly classified into those in which photosensitive groups are introduced into the polyimide precursor through ionic bonds and those in which photosensitive groups are introduced through ester bonds. A dedicated organic solvent must be used as a developing solution when performing the process. Most of these organic solvents are treated as industrial waste, and no consideration is given to environmental protection. However, all the photoresists used in the semiconductor field have been developed with an alkaline aqueous solution, so that the waste liquid can be treated and discharged in a safe state.

Similarly, there is a strong demand for developing a photosensitive polyimide capable of forming a pattern with an aqueous alkaline solution, and the material maker has a mission to protect the environment.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyimide precursor which can be developed with an alkaline aqueous solution and has a negative pattern forming ability excellent in pattern forming ability. And a method for producing the same.

[0006]

The present inventors have made intensive studies to achieve the above-mentioned object, and as a result, a novel negative-type photosensitive resin composition having a composition described later and a method for synthesizing the same have been disclosed. Have been achieved, and the present invention has been completed.

That is, the present invention provides (A) a polyimide precursor comprising a repeating unit (1) and (2) or (3) represented by the following formula:

Embedded image(However, in the formula, R¹Is a tetravalent aromatic group, a plurality of aromatic groups
A tetravalent organic group having a single bond or a plurality of aromatic rings
-O-, -CO-, -SO_Two-Or -CH_TwoNegative
A combined tetravalent organic group,^TwoIs divalent aromatic
Group, a divalent organic group in which a plurality of aromatic rings are single-bonded, or
Plural aromatic rings are -O-, -CO-, -SO _Two-Young
Is -CH_TwoA divalent organic group linked by-^Three,
R^FourRepresents an organic group having an ethylenically unsaturated bond,
(B) Photopolymerization initiator, sensitizer and storage stability
Consisting of a solvent containing the inhibitor and the photosensitive agent (C),
(A) Among the polyimide precursors, the repeating unit of (A) (1)
Characterized in that the position portion is 0.15 mol% or more.
G-shaped photosensitive resin composition and stable production of this composition
Is the way.

Another aspect of the present invention is to provide (A) a polyimide precursor comprising repeating units (1) and (2) represented by the following formula:

Embedded image(However, in the formula, R¹Is a tetravalent aromatic group, a plurality of aromatic groups
A tetravalent organic group having a single bond or a plurality of aromatic rings
-O-, -CO-, -SO_Two-Or -CH_TwoNegative
A combined tetravalent organic group,^TwoIs divalent aromatic
Group, a divalent organic group in which a plurality of aromatic rings are single-bonded, or
Plural aromatic rings are -O-, -CO-, -SO _Two-Young
Is -CH_TwoA divalent organic group linked by-^Three,
R^FourRepresents an organic group having an ethylenically unsaturated bond,
(B) Photopolymerization initiator, sensitizer and storage stability
Consisting of a solvent containing the inhibitor and the photosensitive agent (C),
(A) Of polyimide precursors, repeating units of (A) and (2)
-Type photosensitive resin set with 0.15 mol% or more
A method for producing a product, comprising:¹Backbone tetracarboxylic acid or
Is the repeating unit of (A) (2) in the anhydride.
And R^ThreeAnd R^FourEster with alcohol
And reacting the solution after the esterification reaction with R^Two
Add all the backbone diamine and add diphenyl (2,3-dihydro
-2-thioxo-3-benzoxazole) phosphonate
Or its derivative or diphenyl (2,3-dihydro-2-thio)
Oxo-3-benzothiazole) phosphonate or
As a dehydrating condensing agent, after the esterification reaction
R¹Residual carboxyl groups in backbone tetracarboxylic acids
And R^TwoPolycondensation with the amino group of the skeleton diamine (A)
(2) Polyimide precursor product composed of repeating units
And reacting the above (A) (2) repeating unit portion
Repeating (A) (1) on the polyimide precursor product
R as a unit¹Add backbone tetracarboxylic acid
Existence R^TwoPolycondensation with the amino group of the skeleton diamine (A)
(1) Polyimide precursor product composed of repeating units
And (A) (1) reacting the repeating unit portion
The dehydrating condensing agent from the polyimide precursor product
Including the process of precipitating polyimide precursor
This is a method for producing a photopolymer composition.

Hereinafter, the present invention will be described in detail.

The acid component serving as the R ¹ skeleton of the polyimide precursor (A) used in the present invention includes, for example, pyromellitic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ', 4'-biphenyltetracarboxylic acid, 3,3', 4,4'-benzophenonetetracarboxylic acid, 4,4'-oxydiphthalic acid, 3,3 ', 4
4'-diphenylsulfonetetracarboxylic acid, 2,2-
Bis (3,4-dicarboxyphenyl) hexafluoropropane, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid,
1,4,5,8-naphthalenetetracarboxylic acid, 1,
2,3,4-cyclobutanetetracarboxylic acid, 1,2,2
3,4-butanetetracarboxylic acid, 1,2,4,5-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 3,3 ', 4,4'-bicyclohexyltetracarboxylic Acid, 2,3,5-tricarboxycyclopentylacetic acid, 3,4-dicarboxy-
Examples thereof include 1,2,3,4-tetrahydronaphthalene-1-succinic acid and anhydrides thereof, and these can be used alone or in combination.

The acid component has a proportion in which the repeating unit of the above formula 1 is a carboxylic acid, that is, (A) (1), within a range of not less than 0.15 mol% based on the weight of the polymer. A compound having an ethylenically unsaturated bond can be reacted with an ester bond or an amide bond.

Examples of the compound having R ³ and R ⁴ skeletons introduced by an ester bond include pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol acrylate dimethacrylate, pentaerythritol diacrylate methacrylate, glycerol diacrylate, glycerol dimethacrylate. Glycerol acrylate methacrylate, trimethylolpropane diacrylate, 1,3-diacryloylethyl-5-hydroxyethylisocyanurate, ethylene glycol-modified pentatrierythritol triacrylate, propylene glycol-modified pentaerythritol triacrylate, trimethylolpropane diacrylate, trimethylol Propane dimethacrylate, 2-hydro Siethyl acrylate, 2-hydroxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, and the like, and these may be used alone or in combination. Can be used.

As the diamine component serving as the R ² skeleton of the polyimide precursor (A) used in the present invention, for example, m-phenylenediamine, p-phenylenediamine, 2,4-
Diaminotoluene, 2,5-diaminotoluene, 2,6
-Diaminotoluene, 3,5-diaminotoluene, 1-
Methoxy-2,4-diaminobenzene, 1,4-diamino-2-methoxy-5-methylbenzene, 1,3-diamino-4,6-dimethylbenzene, 3,5-diaminobenzoic acid, 2,5-diamino Benzoic acid, 1,2-diaminonaphthalene, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,
7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,3-diaminonaphthalene, 2,6-diaminonaphthalene, 1,4-diamino-2-methylnaphthalene,
1,5-diamino-2-methylnaphthalene, 1,3-diamino-2-phenylnaphthalene, 2,2-bis (4-
Aminophenyl) propane, 1,1-bis (4-aminophenyl) ethane, 4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5 ′ -Tetramethyl-4,
4'-diaminodiphenylmethane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'
-Diaminodiphenylmethane, 4,4'-methylenebis (cyclohexylamine), 4,4'-methylenebis (3,3-dimethyl-cyclohexylamine), 2,
4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'-diaminobenzanilide, 3,3'-
Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, bis (4-aminophenyl) diethylsilane, bis (4-aminophenyl) diphenylsilane, bis (4-
(Aminophenyl) -N-methylamine, bis (4-aminophenyl) -N-phenylamine, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 2,6-diaminopyridine, 3,5-diamino Pyridine, 4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3, 3'-dihydroxy-4,4 '
-Diaminobiphenyl, o-toluidinesulfone,
4,4'-bis (4-aminophenoxy) biphenyl,
2,2-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 1,4-bis (4-
Aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 9,10-bis (4-aminophenyl) anthracene, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis ( 4-aminophenyl) hexafluoropropane, 2,2-bis (3-aminophenyl) hexafluoropropane, 1,1-bis (4-aminophenyl) -1-phenyl-2,2,2-
Trifluoroethane, 2,2-bis (3-amino-4-
Hydroxyphenyl) hexafluoropropane, 2,2
-Bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, etc., and these may be used alone or in combination of two or more. Can be used. In addition, these compounds are preferably used in an equimolar amount to the above ester compound, but can be used in a range of 0.5 to 1.5 times mol according to the purpose of use, final viscosity, and molecular weight. .

Next, the dehydrating condensing agent used in the polycondensation reaction between the ester compound and the diamine component in the present invention will be described.

When the esterification reaction product and the diamine component are reacted by a polycondensation method, the reaction is usually carried out using an acid chloride. In the electric and electronic fields including semiconductor devices, free chlorine ions are produced. Polymerization by the acid chloride method is not preferred because it causes poor reliability. DCC used as a dehydrating condensing agent
Carbodiimide derivatives have problems such as simultaneous side reactions, gelation of the polyimide precursor, toxicity, and the like, and it is difficult to completely remove urea generated as a by-product. Therefore, it is used for cooling a reaction system, adding a dehydrating condensing agent in several portions, or breaking a molar balance between an acid component and a diamine component. As a result, not only is strict process control required in manufacturing,
Problems such as a decrease in the molecular weight of the synthesized polyimide precursor, a decrease in resolution, and a deterioration in film characteristics occur.

However, the dehydrating condensing agent used in the present invention is:
Since the above-mentioned drawbacks are completely solved and stable production is possible under mild conditions, a polyimide precursor having high resolution and high film properties can be obtained. That is, in the polycondensation reaction of the ester compound and the diamine component, the dehydration condensing agent used in the present invention selectively generates an amide bond, so that simultaneous occurrence of side reactions hardly occurs and gelation of the polyimide precursor does not occur. It has the feature that it can be made high molecular weight. Further, the unreacted portion of the dehydrating condensing agent or the decomposed product thereof present after the completion of the polymerization reaction is dissolved in a lower alcohol such as methanol or ethanol, so that it can be easily removed from the polyimide precursor.

The dehydrating condensing agent used in the present invention as described above includes diphenyl (2,3-dihydro-2-thioxo-3-benzoxazole) phosphonate and derivatives thereof, and diphenyl (2,3-dihydro-2-benzodiazole). Thioxo-3-benzothiazole) phosphonate and derivatives thereof, and these can be used alone or in combination of two or more. These compounding ratios are in the range of 1 to 3 moles, preferably 2
It can be used in a range of up to 2.5 moles.

Examples of the polymerization solvent for the resin composition used in the present invention include aprotic polar solvents such as N-methylpyrrolidone, N, N'-dimethylacetamide, N, N'-dimethylformamide, cyclohexanone and cyclohexanone. Pentanone and the like can be mentioned, and these can be used alone or in combination of two or more.

Next, the preparation of a polyimide precursor solution containing a photopolymerization initiator, a sensitizer, a storage stabilizer and a photosensitizer will be described.

Examples of the photopolymerization initiator (B) used in the present invention include benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenylketone, dibenzylketone, and 2,2'-diethoxy. Acetophenone, acetophenone derivatives such as 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone, thioxanthone, 2-methyloxanthon, 2-isopropylthioxanthone, diethylthioxanthone, benzyl, benzyldimethylketal, benzoin, benzoinmethyl Ether, 2,6 '
-Di (4'-diazidobenzal) cyclohexanone,
2,6'-di (4'-diazidobenzal) -4-methylcyclohexanone, 2,6'-di (4'-diazidobenzal) -4-ethylcyclohexanone, 2,6'-di (4'-diazidobenzal) -4 -Butylcyclohexanone, 2,6'-di (4'-diazidobenzal) -4-
Azide compounds such as (t-butyl) cyclohexanone, 1
-Phenyl-1,2-butadione-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-2- (o-ethoxycarbonyl) oxime, 1-
Phenyl-propanedione-2- (o-benzoyl) oxime, 1,3-diphenylpropanetrione-2-
(O-ethoxycarbonyl) oxime, 1-phenyl-
Oximes such as 3-ethoxy-propanetrione-2- (o-benzoyl) oxime, N-phenylglycine,
Glycine derivatives such as N- (P-ethyl) phenylglycine and N- (P-methyl) phenylglycine are listed, and these can be used alone or in combination of two or more. The compounding ratio is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the composition.

The photopolymerization initiator in the present invention is not limited to the above compounds as long as it generates reactive radicals efficiently at 365 nm and 436 nm in ultraviolet rays.

The sensitizer used in the present invention includes, for example, Michler's ketone, 4,4'-bis (diethylaminobenzophenone), 2,5-bis (4'-diethylaminobenzal) cyclopentanone, 2,6-bis ( 4'-diethylaminobenzal) cyclohexanone, 2,6-bis (4'-dimethylaminobenzal) -4-methylcyclohexanone, 2,6-bis (4'-diethylaminobenzal) -4-methylcyclohexanone, 4'-bis (diethylamino) chalcone, 4,4'-bis (dimethylamino) chalcone, p-dimethylaminocinnamylideneindanone, p-dimethylaminobenzylideneindanone, 2- (p-dimethylaminophenylbiphenylene)- Benzothiazole, 2- (p-dimethylaminophenylvinylene)- Nzochiazoru, 1,3-bis (4'-dimethylamino benzal) acetone, 3,3 '
-Carbonyl-bis (7-diethylaminocoumarin),
3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin,
3-methoxycarbonyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethanolamine, N-phenylethanolamine, NP-tolyldiethanolamine, N-phenylmethanolamine, 4-morphoninobenzophenone dimethylamino isoamyl benzoate,
2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole,
Examples thereof include 1-phenyl-5-mercapto-1H-tetrazole and the like, and these can be used alone or as a mixture of two or more. The amount of the resin composition is 100
It is preferably 0.1 to 10 parts by weight based on part by weight. Also,
By using these sensitizers in accordance with the wavelength to be used and further in accordance with the required sensitivity, the resolution at each wavelength can be improved.

The polymerization inhibitor used in the present invention is for improving the storage stability of the resin, and specific examples thereof include hydroquinone derivatives such as hydroquinone, methylhydroquinone and butylquinone. These can be used alone or in combination of two or more. The addition amount is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the resin composition.

The solvent used for dissolution in the present invention includes, for example, N-methylpyrrolidone, N, N '
Aprotic polar solvents such as -dimethylacetamide, N, N'-dimethylformamide, cyclohexanone,
Cyclopentanone and the like can be mentioned, and these can be used alone or in combination of two or more.

Next, a method for producing the polymer composition according to the present invention will be described.

In the polymer composition of the present invention, the ratio of the repeating unit represented by the above polyimide precursor (2), that is, the ester of R ³ and R ⁴ , is 0.15 mol per polymer weight. % Is required,
An important invention was also required for the synthesis method. When the ratio is less than 0.15 mol%, the polyimide does not exhibit sufficient solubility in an aqueous alkaline solution used for pattern formation, and a polyimide pattern with high resolution cannot be obtained.

The polymer used in the present invention is generally called a polyimide precursor, and is synthesized by a dehydration polycondensation method between an aromatic or aliphatic dicarboxylic acid and an aromatic or aliphatic diamine. . However, the above formula 2
When a tetraacid, a dianhydride or a dianhydride and an esterified product of an active ethylene compound are simultaneously used as a compound having an R ¹ skeleton in the reaction with a diamine compound,
It was clear that gelation by three-dimensional crosslinking progressed from the low reaction selectivity.

Then, the present inventor succeeded in synthesizing a polymer without three-dimensional crosslinking by improving the reaction selectivity by the following method.

In the above formula, R ³ and R ⁴ in the above formula 2 are -OH
It is necessary to divide the dianhydride to be reacted with the compound having an active ethylene group by the number of moles so that the ratio is 0.15 mol% or more per polymer weight.

First, a compound having an active ethylene group and R
^A dianhydride having ^one skeleton is reacted with an aprotic polar solvent such as N-methylpyrrolidone or N, N'-dimethylacetamide in the presence of a base catalyst. As the base catalyst, organic amines such as triethylamine, triethanolamine and triphenylamine are desirable.

Next, the whole amount of the diamine compound having an R ² skeleton is dissolved in the reaction system, and the dehydration condensing agent diphenyl (2,3
-Dihydro-2-thioxo-3-benzoxazole)
Phosphonate and its derivatives, diphenyl (2,3-
The reaction proceeds completely with dihydro-2-thioxo-3-benzothiazole) phosphonate and its derivatives.
Since the polymerization intermediate at this time is obviously rich in diamine compounds, it is expected that the reaction terminal of the polymerization intermediate is present with an amino group. After confirming that the reaction has completely progressed, the remaining dianhydride is reacted with the amino group at the reaction terminal to obtain an acid molar concentration of 0.15 mol% or more in the polymer and high reaction selectivity. It becomes possible to synthesize a polymer.

The polymer synthesized by the above method can be purified by a general reprecipitation method.
The reaction solution is poured into a large amount of methanol or a water / methanol mixed solvent to solidify only the polymer. Next, after washing with a large amount of methanol or a mixed solvent of water / methanol in the same manner, drying by aeration or drying under reduced pressure can obtain only the polymer. The resulting polymer is GPC
As a result of measuring the molecular weight, molecular weight distribution, state of gelation, etc. by (gel permeation chromatography),
The number average molecular weight was 10,000 to 50,000, the molecular weight distribution was 2.2 to 3.5, and the gelation ratio was 0%.

Next, a method of using the resin composition obtained by the present invention will be described.

When application to a semiconductor device is considered, this resin composition is first coated on a target wafer using a spin coater, and then the coating film is dried at 90 to 130 ° C. An active ultraviolet ray having a wavelength of 365 nm or 436 nm is irradiated through a mask having a pattern drawn on the obtained coating film. Next, this coating film is applied to an alkaline aqueous solution, for example, sodium hydroxide, potassium hydroxide,
Inorganic alkaline aqueous solutions such as sodium carbonate, potassium carbonate and ammonia; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-propylamine; tertiary amines such as triethylamine and methyldimethylamine; dimethyl Using an aqueous solution of an alcohol amine such as ethanolamine or triethanolamine, or a quaternary amine such as tetramethylammonium hydroxide or tetraethylammonium hydroxide, only the unirradiated portion of the active light beam is dissolved and developed, and rinsed with pure water. As a developing system, a system such as spray, paddle, immersion, and ultrasonic wave can be considered. Thereby, a desired positive pattern can be obtained on the target wafer. Further, by heat-treating the coating film, the resin composition can be imidized to form a polyimide film having excellent film properties.

[0035]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be specifically described based on embodiments.

Example 1 First, 51.9 g of pyromellitic dianhydride, 65.0 g of 2-hydroxyethyl methacrylate, and 530.N-methylpyrrolidone were placed in a reaction flask equipped with a dry air inlet tube.
0 g, and 0.5 g of hydroquinone.
6 g of triethylamine was added dropwise over 30 minutes. This reaction system was reacted at room temperature for 3 hours. After completion of the reaction, 63.3 g of paraphenylenediamine and 11.8 g of 1,3-bis (γ-aminopropyl) -1,1,3,3-tetramethyldisiloxane were added, and the mixture was further stirred for 1 hour.
1.6 g of diphenyl (2,3-dihydro-2-thioxo-3-benzoxazole) phosphonate was added in three portions to carry out a polymerization reaction. After the reaction is completed 51.
9 g of pyromellitic dianhydride was added and reacted at room temperature for 12 hours.

The obtained slurry resin was stirred and washed in 10 L of methanol which was stirred at a high speed, and then dried by drying under reduced pressure. When the molecular weight of this polyimide precursor was measured by GPC (gel permeation chromatography), the number average molecular weight in terms of styrene was 20,000, which proved to be a sufficient high molecular weight. G
No abnormal peak on the polymer side was clearly observed from the PC chart, indicating that the polymer was not gelled. The acid mole% of the obtained polymer is 2.1.

100 parts by weight of this polyimide precursor, 2 parts by weight of benzophenone, 20 parts by weight of tetraethylene glycol dimethacrylate, and 1 part by weight of hydroquinone were dissolved in 300 parts by weight of N-methylpyrrolidone to obtain a photosensitive resin composition.

The obtained composition was applied on a 6-inch silicon wafer using a spin coater, and then applied at 90 ° C.
The film thickness was adjusted to 20 μm by drying on a baking plate. Next, a 300 mj line / space pattern was formed on the surface of the coating film using mirror projection.
/ Cm ² . Further, the surface of the coating film was subjected to paddle development for 10 seconds with a 2.38% aqueous solution of TMAH (tetramethylammonium hydroxide), followed by rinsing with pure water. Observation of the obtained pattern with an optical microscope revealed that the pattern had a resolution of up to 10 μm line / space. Further, the pattern is formed at 150 ° C. for 1 hour, at 250 ° C. for 1 hour, at 350 ° C.
For 1 hour to complete the imidization of the coating film. After heat shock at 280 ° C. for 30 seconds, the obtained polyimide pattern was cured by PCT (121 ° C., 2 atm).
Even after the treatment for 00 hours, it was firmly adhered to the wafer, and did not peel off even in a normal tape peeling test.

Example 2 First, 3 was added to a reaction flask equipped with a dry air introduction tube.
After adding 62.9 g of 3 ', 4,4'-benazophenonetetracarboxylic dianhydride, 53.4 g of 2-hydroxyethyl methacrylate, 574.2 g of N-methylpyrrolidone and 0.5 g of hydroquinone, 41. 5 g of triethylamine was added dropwise over 30 minutes. This reaction system was reacted at room temperature for 3 hours. After completion of the reaction, 38.0 g of paraphenylenediamine and 1,3-bis (γ-aminopropyl) -1,1,3,3-tetramethyldisiloxane 9.
After adding 7 g and further stirring for 1 hour, 157.3 g of diphenyl (2,3-dihydro-2-thioxo-3-benzoxazole) phosphonate was added in three portions to carry out a polymerization reaction. After the reaction, 62.9 g of 3,
3 ', 4,4'-Benazophenonetetracarboxylic dianhydride was added and reacted at room temperature for 12 hours.

The obtained slurry resin was stirred and washed in 10 L of methanol which was stirred at a high speed, and then dried under reduced pressure. When the molecular weight of this polyimide precursor was measured by GPC (gel permeation chromatography), it was found that the number average molecular weight in terms of styrene was 18,000, which was a sufficient high molecular weight. G
No abnormal peak on the polymer side was clearly observed from the PC chart, indicating that the polymer was not gelled. The acid mole% of the obtained polymer is 0.17.

100 parts by weight of this polyimide precursor, 2 parts by weight of benzophenone, 20 parts by weight of tetraethylene glycol dimethacrylate, and 1 part by weight of hydroquinone were dissolved in 300 parts by weight of N-methylpyrrolidone to obtain a photosensitive resin composition.

The obtained composition was applied on a 6-inch silicon wafer using a spin coater, and then applied at 90 ° C.
The film thickness was adjusted to 20 μm by drying on a baking plate. Next, a 300 mj line / space pattern was formed on the surface of the coating film using mirror projection.
/ Cm ² . Further, the surface of the coating film was developed with a 2.38% aqueous solution of TMAH (tetramethylammonium hydroxide) for 15 seconds, and then rinsed with pure water. Observation of the obtained pattern with an optical microscope revealed that the pattern had a resolution of up to 10 μm line / space. Further, the pattern was subjected to a heat treatment at 150 ° C. for 1 hour, 250 ° C. for 1 hour, and 350 ° C. for 1 hour to complete the imidization of the coating film. The obtained polyimide pattern is firmly adhered to the wafer even after a heat shock at 280 ° C. for 30 seconds and a PCT (121 ° C., 2 atm) for 300 hours, and peels off even in a normal tape peeling test. I never did.

Comparative Example 1 First, 2,2 'was added to a reaction flask equipped with a dry air introduction tube.
-Bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride 71.7 g, 2-hydroxyethyl methacrylate 44.1 g, N-methylpyrrolidone 6
After adding 08.7 g and 0.5 g of hydroquinone,
34.3 g of triethylamine were added dropwise over 30 minutes. This reaction system was reacted at room temperature for 3 hours. After the completion of the reaction, 31.4 g of paraphenylenediamine and 8.0 g of 1,3-bis (γ-aminopropyl) -1,1,3,3-tetramethyldisiloxane were added, and the mixture was further stirred for 1 hour. 0 g of diphenyl (2,3-dihydro-2
(Thioxo-3-benzoxazole) phosphonate was added in three portions to carry out a polymerization reaction. After completion of the reaction, 71.7 g of 2,2'bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride was further added, and the mixture was reacted at room temperature for 12 hours.

The obtained slurry resin was stirred and washed in 10 L of methanol which was stirred at a high speed, and then dried by drying under reduced pressure. When the molecular weight of this polyimide precursor was measured by GPC (gel permeation chromatography), the number average molecular weight in terms of styrene was 15,000, which proved to be a sufficient high molecular weight. G
No abnormal peak on the polymer side was clearly observed from the PC chart, indicating that the polymer was not gelled. The acid mole% of the obtained polymer is 0.14.

100 parts by weight of this polyimide precursor, 2 parts by weight of benzophenone, 20 parts by weight of tetraethylene glycol dimethacrylate, and 1 part by weight of hydroquinone were dissolved in 300 parts by weight of N-methylpyrrolidone to obtain a photosensitive resin composition.

After applying the obtained composition to a 6-inch silicon wafer using a spin coater,
The film thickness was adjusted to 20 μm by drying on a baking plate. Next, a 300 mj line / space pattern was formed on the surface of the coating film using mirror projection.
/ Cm ² . Further, the surface of this coating film was developed with a 2.38% aqueous solution of TMAH (tetramethylammonium hydroxide) for 60 seconds, but the film was peeled off and could not be dissolved. Subsequently, the substrate was rinsed with pure water. Observation of the obtained pattern with an optical microscope revealed that there was undissolved residue in the dissolution part of the pattern,
The resolution was insufficient. Further, this pattern is
For 1 hour, 250 ° C. for 1 hour, and 350 ° C. for 1 hour to complete the imidization of the coating film. The obtained polyimide pattern is firmly adhered to the wafer even after a heat shock at 280 ° C. for 30 seconds and a PCT (121 ° C., 2 atm) for 300 hours, and peels off even in a normal tape peeling test. I never did.

Comparative Example 2 First, 80.7 g of pyromellitic dianhydride, 101.1 g of 2-hydroxyethyl methacrylate, and N-methylpyrrolidone 39 were placed in a reaction flask equipped with a dry air inlet tube.
After adding 6.4 g and 0.5 g of hydroquinone, 78.6.
g of triethylamine was added dropwise over 30 minutes. This reaction system was reacted at room temperature for 3 hours. After the reaction was completed, 36.0 g of paraphenylenediamine and 9.2 g of 1,3-bis (γ-aminopropyl) -1,1,3,3-tetramethyldisiloxane were added, and the mixture was further stirred for 1 hour, and then stirred for 29 hours. 9
g of diphenyl (2,3-dihydro-2-thioxo-3)
(Benzoxazole) phosphonate was added in three portions to carry out a polymerization reaction.

The obtained resin in the form of a slurry was washed by stirring in 10 L of methanol which was rapidly stirred, and then dried by drying under reduced pressure. When the molecular weight of this polyimide precursor was measured by GPC (gel permeation chromatography), it was found that the number average molecular weight in terms of styrene was 23,000, which was a sufficient high molecular weight. G
No abnormal peak on the polymer side was clearly observed from the PC chart, indicating that the polymer was not gelled. The acid mole% of the obtained polymer is 0.0.

100 parts by weight of this polyimide precursor, 2 parts by weight of benzophenone, 20 parts by weight of tetraethylene glycol dimethacrylate, and 1 part by weight of hydroquinone were dissolved in 300 parts by weight of N-methylpyrrolidone to obtain a photosensitive resin composition.

After applying the obtained composition to a 6-inch silicon wafer using a spin coater,
The film thickness was adjusted to 20 μm by drying on a baking plate. Next, a 300 mj line / space pattern was formed on the surface of the coating film using mirror projection.
/ Cm ² . Further, the coating film surface was developed with a 2.38% aqueous solution of TMAH (tetramethylammonium hydroxide) for 60 seconds, but could not be dissolved. Subsequently, the substrate was rinsed with pure water. When the film thickness of the dissolution part of the obtained pattern is measured, it is 2
It was found that a film thickness of 0 μm remained and was not melted. Further, the pattern was subjected to a heat treatment at 150 ° C. for 1 hour, 250 ° C. for 1 hour, and 350 ° C. for 1 hour to complete the imidization of the coating film. The obtained polyimide pattern is
After heat shock at 280 ° C. for 30 seconds, PCT (121
(At 2 ° C., 2 atm) for 300 hours, it was firmly adhered to the wafer, and did not peel off even in a normal tape peeling test.

[0052]

Conventionally, the unexposed portion was dissolved using a special organic solvent at the time of forming a negative type pattern. However, in the present invention, an alkaline aqueous solution is used for forming a pattern. It is possible to form a pattern having a resolution. This is extremely effective for eliminating a large amount of organic solvent waste. Further, in the present invention, the method for synthesizing such a resin composition is based on a completely new idea, and it can be easily understood that the invention is a unique and excellent invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) H01L 21/027 H01L 21/30 502R F-term (Reference) 2H025 AA03 AA04 AB16 AC01 AD01 BC69 BJ10 CA27 CC01 CC03 FA03 FA17 4J027 AD03 BA19 CB10 CC05 CD10 4J043 PA04 PA09 PA19 PC015 PC08 QB31 QB33 RA06 RA35 SA06 SA43 SA47 SA62 SA72 SB01 TA14 TA22 TB01 UA022 UA032 UA041 UA042 UA05 UA 121 UA1 UA1 UA1 UA1 UA1 UA1 UA1 UA1 UA1 UA2 UB301 UB302 UB311 UB401 UB402 VA011 VA012 VA021 VA022 VA031 VA041 VA051 VA061 VA062 VA081 VA091 VA092 XA16 XB20 YA06 ZA46 ZB50

Claims (2)

[Claims] (A) A repeating unit of the following formula (1) and (2)
Or a polyimide precursor composed of (3) and(However, in the formula, R¹Is a tetravalent aromatic group, a plurality of aromatic groups
A tetravalent organic group having a single bond or a plurality of aromatic rings
-O-, -CO-, -SO_Two-Or -CH_TwoNegative
A combined tetravalent organic group,^TwoIs divalent aromatic
Group, a divalent organic group in which a plurality of aromatic rings are single-bonded, or
Plural aromatic rings are -O-, -CO-, -SO _Two-Young
Is -CH_TwoA divalent organic group linked by-^Three,
R^FourRepresents an organic group having an ethylenically unsaturated bond,
(B) Photopolymerization initiator, sensitizer and storage stability
Consisting of a solvent containing the inhibitor and the photosensitive agent (C),
(A) Among the polyimide precursors, (A) (2) and
(3) The repeating unit portion is 0.15 mol% or more.
And a negative photosensitive resin composition. (A) a repeating unit (1) or (2) of the following formula:
A polyimide precursor composed of:(However, in the formula, R¹Is a tetravalent aromatic group, a plurality of aromatic groups
A tetravalent organic group having a single bond or a plurality of aromatic rings
-O-, -CO-, -SO_Two-Or -CH_TwoNegative
A combined tetravalent organic group,^TwoIs divalent aromatic
Group, a divalent organic group in which a plurality of aromatic rings are single-bonded, or
Plural aromatic rings are -O-, -CO-, -SO _Two-Young
Is -CH_TwoA divalent organic group linked by-^Three,
R^FourRepresents an organic group having an ethylenically unsaturated bond,
(B) Photopolymerization initiator, sensitizer and storage stability
Consisting of a solvent containing the inhibitor and the photosensitive agent (C),
(A) Of polyimide precursors, repeating units of (A) and (2)
-Type photosensitive resin set with 0.15 mol% or more
A method for producing a product, comprising:¹Backbone tetracarboxylic acid or
Is the repeating unit of (A) (2) in the anhydride.
And R^ThreeAnd R^FourEster with alcohol
And reacting the solution after the esterification reaction with R^Two
Add all the backbone diamine and add diphenyl (2,3-dihydro
-2-thioxo-3-benzoxazole) phosphonate
Or its derivative or diphenyl (2,3-dihydro-2-thio)
Oxo-3-benzothiazole) phosphonate or
As a dehydrating condensing agent, after the esterification reaction
R¹Residual carboxyl groups in backbone tetracarboxylic acids
And R^TwoPolycondensation with the amino group of the skeleton diamine (A)
(2) Polyimide precursor product composed of repeating units
And reacting the above (A) (2) repeating unit portion
Repeating (A) (1) on the polyimide precursor product
R as a unit¹Add backbone tetracarboxylic acid
Existence R^TwoPolycondensation with the amino group of the skeleton diamine (A)
(1) Polyimide precursor product composed of repeating units
And (A) (1) reacting the repeating unit portion
The dehydrating condensing agent from the polyimide precursor product
Including the process of precipitating polyimide precursor
A method for producing a photopolymer composition.