JPH0850354A - Photosensitive composition for i-line - Google Patents

Abstract

PURPOSE:To obtain a photosensitive compsn. capable of forming a patter with i-line a certain film thickness or above and capable of being put to practical use by using a polymer having specified divalent groups as a precursor of arom. polyimide and imparting a specified absorbance. CONSTITUTION:This photosensitive compsn. contains a precursor of arom. polyimide having repeating units represented by formula I and >=1.5mol/kg concn. of amido bonds, a photopolymn. initiator and a solvent. In the formula I, X is a tetravalent org. group having a chemical structure formed by combining tetravalent F-free arom. groups through a single bond or an ether bond, -COR and -COR' are at o-positions, each of R and R' is -OR1, R and R1 of them is a residue other than -OH and Y is an F-free divalent org. group having a chemical structure formed by combining F-free divalent arom. groups represented by formula II through a single bond or an ether bond. A film of this compsn. has a specified absorbance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel photosensitive composition useful for manufacturing electric / electronic materials such as semiconductor devices and multilayer wiring boards. More specifically, the present invention relates to a photosensitive composition suitable for forming a polyimide pattern by image formation using a short-wavelength light source which will be predominant in semiconductor manufacturing processes in the future.

[0002]

2. Description of the Related Art Polyimide resins have been attracting attention as materials for microelectronics because of their high thermal and chemical stability, low dielectric constant and excellent planarization ability. These are widely used as materials for semiconductor surface protection films, interlayer insulating films, multichip modules, and the like. By the way, in order to form a desired pattern from a normal polyimide resin film by using a lithography technique, a photoresist and a photomask are used on the polyimide film which has been formed, and after forming a photoresist pattern, An indirect method of patterning a polyimide resin by an etching method is used.

However, in this method, a photoresist pattern is formed, the polyimide resin is etched using the photoresist pattern as a mask, and the photoresist pattern that is no longer needed must be removed thereafter, resulting in a complicated process. In addition, it is necessary to use a toxic substance such as hydrazine, and there are disadvantages such that only a pattern with low resolution can be obtained by indirect pattern formation. Therefore, in recent years, a method of introducing a photopolymerizable sensitive group into a polyimide precursor and directly forming a pattern has been studied, and a compound having a double bond is bonded through an ester bond, an amide bond, an ionic bond, or the like. The polyamic acid derivative is insolubilized with a photoinitiator,
After development, a method of removing the photosensitive group component by heating and converting it into a polyimide having heat stability has been proposed [Yamaoka, Table, "Polyfile", Vol. 27, No. 2, 14-18 (1990)]. This technology
It is generally called photosensitive polyimide.

By the way, the demand for the degree of integration of semiconductor elements such as ICs, LSIs, and VLSIs is increasing year by year.
At the same time, it has become necessary to develop technology that enables fine processing. And as one of the techniques, as a light beam for exposure when forming a photoresist pattern, a normal G
Instead of a line (wavelength 436 nm), an attempt has been made to use a light beam of a short wavelength which can be expected to have a high resolution, for example, an i-line having a wavelength of 365 nm, and it has been quite successful for ordinary photoresists. Therefore, it is expected that all exposure apparatuses in semiconductor manufacturing plants will use i-line as a light source in the future.

However, in the case of a photosensitive polyimide precursor composition, unlike ordinary photoresists, the polyimide precursor, which is the main component, has a relatively large absorbance for i-line, and the polyimide coating film after heat treatment has Often used for applications requiring a film thickness of 6 μm or more in terms of physical properties, and taking into account shrinkage due to volatile components of photosensitive groups during heat treatment, a relatively thick coating film thickness of about 12 μm or more during exposure. Therefore, when using the one currently used, the i-line does not reach the bottom of the coating film sufficiently, the underside of the coating film is insufficiently cured, and the pattern is scooped from the bottom portion. It is known that it is difficult to use the i-line as a light source in order to obtain a polyimide having a certain thickness or more because it flows. ["IEEE / SEMI Advanced Semico Doctor Manufacturing Conference (C. Schcket, et a
l. , Advanced Semiconductor
Manufacturing Conferenc
e) ", Proceedings, pp. 72-74 (1990)].

For this reason, when the i-line is used, the thin film patterns are stacked several times in order to obtain a sufficient film thickness, which is not practical because the accuracy is not improved and the process is complicated. . Further, as a polyimide precursor having a high i-ray transmittance of the coating film, one having fluorine has been known so far [[Journal of Applied Polymer Science (T. Omote, T. Yamaoka.
a. and K. kosei, J .; Appld. Pol
ymer Sci. ), 38, 389-402 (1989)]. However, polyimide containing fluorine in the main skeleton obtained after heat-curing this precursor is another material used in combination when forming a semiconductor device or a multilayer wiring board, such as a base inorganic material, a coating layer epoxy resin, or wiring. However, it has a drawback that it has low adhesiveness with metal and lacks practicality. For this reason, it has been the actual situation that no photosensitive polyimide precursor composition capable of forming a pattern by using i-line has been obtained so far.

[0007]

SUMMARY OF THE INVENTION In view of such circumstances, the present invention provides a photosensitive polyimide precursor composition capable of forming a pattern by i-line with a film thickness of a certain value or more and being practically used. It was done for the purpose.

[0008]

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted various researches on a photosensitive polyimide precursor composition capable of forming a pattern by i-line, and as a result, have a plurality of specific chemical structures and / or Alternatively, when a photosensitive polyimide precursor composition containing a polyimide precursor having a specific amide bond concentration and prepared so that the film obtained after coating and drying exhibits a specific absorbance is used, a good pattern is formed by i-line. Moreover, it was found that the polyimide obtained after thermosetting the pattern shows excellent coating film physical properties and also has good adhesive strength with epoxy resin, inorganic material and metal, and shows excellent water resistance. Based on this, the present invention has been completed.

That is, the present invention provides (A) general formula (I)
And a amide bond concentration of 1.
An aromatic polyimide precursor having a concentration of 5 mol / kg or more (hereinafter referred to as "polyimide precursor"),

[0010]

[Chemical 3]

[In the formula, X is an aromatic group containing no tetravalent fluorine atom or an aromatic group containing no 2 to 4 fluorine atoms in the form of a single bond, an ether bond, a thioether bond, a carbonyl bond, a methylene bond or a sulfoxide. A tetravalent organic group having a chemical structure bonded through at least one bond selected from a bond and a sulfone bond, wherein a -COR group, a -COR 'group and a -CONH- group are mutually present. In the ortho position, R and R'are independently -OR ₁ -NHR ₂ ,-.
^{_{O - N + R 3 R 4}} R 5 R 6 or -OH (provided that, R _1,
R ₂ and R ₃ are not limited to one type,
An organic group having an ethylenically unsaturated bond in at least a part thereof, R ₄ , R ₅ and R ₆ are each hydrogen or a hydrocarbon group having 1 to 6 carbon atoms), and at least a part thereof is R or R in the repeating unit. 'Is a residue other than -OH, and Y is a divalent aromatic group containing no fluorine atom or 2 to 6 aromatic groups having a single bond, an ether bond, a thioether bond, a carbonyl bond, a methylene bond, or 2 , 2-propylene bond, sulfoxide bond, and sulfone bond, having a chemical structure interconnected via at least one bond selected from the group,
It is a divalent organic group that does not contain a fluorine atom.)

In the photosensitive composition containing (B) a photopolymerization initiator and (C) a solvent, (iii-1) Y in the above polyimide precursor is represented by the general formula (II).

[0013]

[Chemical 4] (In the formula, R ₇ is an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and n is 0.
An integer of 3), and the absorbance at a wavelength of 365 nm of the film of the photosensitive composition formed after coating and drying the above-mentioned photosensitive composition is 10 μm per film thickness. A photosensitive composition characterized by being 1.5 or less.

The polyimide precursor used as the component (A) in the composition of the present invention is represented by the above general formula (I). Examples of the X and Y aromatic groups of the general formula (I) include groups having a benzene ring, a naphthalene ring, and an anthracene ring,
It is preferable because the polyimide coating film obtained by heating and curing the photosensitive composition of the present invention has high heat resistance. For the same reason, as the aromatic bonding group, a single bond, an ether bond,
One or more selected from a carbonyl bond and a sulfone bond are preferable.

--COR group or --COR 'of the general formula (I)
The group is an ester group represented by the general formula (V-1) —CO—OR ₁ ... (V-1) (wherein R ₁ has the same meaning as described above). As the ester group, a 2-acryloyloxyethyloxycarbonyl group, a 2-methacryloyloxyethyloxycarbonyl group, a 2- (1-acryloyloxy) propyloxycarbonyl group, a 2- (1-
(Methacroyloxy) propyloxycarbonyl group, 2
-It is necessary to contain a group having an ethylenically unsaturated bond such as a methacrylaminoethyloxycarbonyl group, a 3-methacryloyloxy-2-hydroxypropyloxycarbonyl group, and an acrylaminomethyloxycarbonyl group. Ethoxycarbonyl group, methoxycarbonyl group, 2-methoxyethoxycarbonyl group, 2
It may include a group having no ethylenically unsaturated bond such as an ethoxyethoxycarbonyl group.

As the polyimide precursor, the general formula (V-
When the one having only the ester group represented by 1) is used, the resulting photosensitive composition has good storage stability and is a polyimide film obtained against fluctuations in process conditions such as fluctuations in patterning process time. It is more preferable because it has a wide process latitude such that the pattern does not change.

The --COR group or --COR 'of the general formula (I)
When the group is represented by an amide group represented by the general formula (V-2) —CO—NHR ₂ ... (V-2) (wherein R ₂ has the same meaning as described above), the amide group is Is N- (2-
Acryloyloxyethyl) -aminocarbonyl group, N
It is necessary to contain a group having an ethylenically unsaturated bond such as-(2-methacryloyloxyethyl) -aminocarbonyl group, and other than this, methylaminocarbonyl group, ethylaminocarbonyl group, N- (2-ethoxy) It may contain a group having no ethylenically unsaturated bond such as an ethyl) aminocarbonyl group.

--COR group or --COR 'of the general formula (I)
Group is formulas (V-3) -CO-O - · N + R 3 R 4 R 5 R 6 ··· (V-3) (R 3 in the formula, R _4, R ₅ and R ₆ are the And a substituted ammonium addition salt type carboxylic acid residue represented by the following), the substituted ammonium addition salt type carboxylic acid residue may be a methacryloxyethyl / trimethylammonium addition salt type carboxylic acid residue. , Acryloyloxyethyl / dimethylammonium addition salt type carboxylic acid residue, and the like, it is necessary to contain a group having an ethylenically unsaturated bond, and in addition to this, R ₃ , R ₄ ,
All of R ₅ and R ₆ may include a hydrogen atom or a group which is a hydrocarbon group.

The -COR group or -COR 'group of all the repeating units of the polyimide precursor resistance does not have to be the group represented by the above (V-1) to (V-3), but the -COR group in the repeating unit. It suffices that a part of the group or —COR ′ group is the above group and the other is a carboxylic acid group. In the composition of the present invention, the polyimide precursor used as the component (A) needs to have an amide bond concentration of 1.5 mol / kg or more. The amide bond concentration as referred to herein is the molecular weight of the repeating unit in the polyimide precursor, or when the polyimide precursor has several types of repeating units, 2000 is divided by the average molecular weight calculated from the respective molecular weights and mole fractions. This is a value, which is a parameter representing the number of moles of amide groups present in 1 kg of the polyimide precursor. When the amide bond concentration is less than 1.5 mol / kg, the heat resistance is significantly reduced.

The aromatic polyimide precursor polymer used as the component (A) in the composition of the present invention is already known as a precursor of a heat-resistant polymer compound, and known methods such as Lubner (R. Rubner) et al. ["Photographic Science and
Engineering (Photograph. Sci.
Eng. ) ”, No. 23, p. 303 (1979)],
The method of M. T. Pottiger et al. ["38th Electronic Components Conference (38th. Electronic Com
fonts Conf. ) ”, P. 315 (198)
8)], the method of L. Minnema et al. [“Polymer Engineering and Science (Po
lym. Eng. Sci) ", Vol. 28, No. 12, page 815 (1988)", Davis et al. [Chem. & Engineering News (Chem. & Eng. News), September 1983]. 26th issue, page 23] and the like. In addition, it can also be produced by the methods described in JP-A-61-272022, JP-A-3-220558, JP-B-59-52822 and JP-A-3-4226.

According to these methods, the polyimide precursor has an aromatic tetracarboxylic dianhydride represented by the general formula (IV) (hereinafter referred to as ATC dianhydride) and a general formula (V
It is produced by using the aromatic diamino compound represented by II) as a part of the raw material.

[0022]

Embedded image

H ₂ N--Y--NH ₂ ... (VII) (wherein Y is the same as above) A compound having a group containing a fluorine atom such as a fluorine group and a trifluoromethyl group is used as the polyimide precursor of the present invention. When used as a body material, the polyimide containing a fluorine atom obtained after heat-curing the photosensitive composition has poor adhesiveness to other materials used in combination and is not preferable.

In order to obtain the photosensitive composition of the present invention, it is necessary to use a polyimide precursor under specific conditions. However, this condition is not a single condition, but a condition selected from a plurality of conditions. Either one kind or a combination of two or more kinds can be used in the present invention as long as other conditions of the composition are satisfied. Specifically, the polyimide precursor needs to satisfy at least one of (i) to (iii-4). Amide bond concentration is 1.5 mol / kg
The above is required and the amide concentration is 2.42 mol / k.
When it is at most g, the composition of the present invention can be obtained regardless of the structure. Further, the lower the concentration of the amide bond in the polyimide precursor, the lower the i-ray absorption value of the polymer coating film formed and the higher the water resistance of the polyimide film after heat treatment. Further, it is more preferable to use a polyimide precursor having an amide bond concentration of 2.0 to 2.45 mol / kg in the polyimide precursor, since it is possible to obtain a polyimide film having higher mechanical strength and heat resistance. .

Further, in the present invention, as long as the absorbance of the film of the photosensitive composition of the present invention at a wavelength of 365 nm is 1.5 or less per 10 μm of film thickness, it is represented by the general formula (VI) other than the above. When ATC dianhydride is optionally mixed with the above-mentioned ATC dianhydride, or in combination with a specific aromatic diamino compound described below, and / or when used as an aromatic polyimide precursor having a specific amide bond concentration. Can be used alone.

Specific examples of such compounds include pyromellitic dianhydride, 2,3,5,6-naphthalenetetracarboxylic dianhydride and 3,3 ', 4,4'-benzophenonetetracarboxylic acid. Dianhydride, 3,3 ', 4,4'
-Biphenyltetracarboxylic dianhydride, 2, 3, 5,
6-pyridine tetracarboxylic dianhydride, 2, 3, 6,
7-quinoline tetracarboxylic dianhydride, 3,3 ′,
4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3', 4,4'-diphenyl sulfoxide tetracarboxylic dianhydride Other compounds such as 1,2,8,9-anthracene tetracarboxylic acid dianhydride, 1,4-bis (3,4-dicarboxylphenylsulfonyl) benzene dianhydride,
1,4-bis (3,4-dicarboxylphenylthio)
Benzene dianhydride, 3,3 ", 4,4" -terphenylphenylcarboxylic dianhydride, 4-phenylbenzophenone-3,3 ", 4,4" -tetracarboxylic dianhydride,
1,4-bis (3,4-dicarboxylbenzoyl)-
Benzene dianhydride, 3,3 ′ ″, 4,4 ′ ″-quatylphenyltetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxylphenoxy) benzophenone dianhydride, 4 , 4'bis (3,4-dicarboxylphenoxy) diphenyl sulfoxide dianhydride can also be used.

In the case of producing a polyimide precursor, an aromatic diamino compound in which Y is a divalent group represented by the above general formula (II) is used. Specific preferred examples of such aromatic diamino compounds include metaphenylenediamine, 3,5-diaminotoluene, 2,4-diaminotoluene, and 2,4-diaminomesitylene. Further, as long as the absorbance of the film of the photosensitive composition of the present invention at 365 nm is 1.5 or less per 10 μm, the fragrance represented by the general formula (VII) other than the aromatic diamino compound having the above specific chemical structure. Group diamino compound optionally mixed with aromatic diamino compound having the above-mentioned specific chemical structure, or combined with ATC anhydride having the above-mentioned specific chemical structure, and / or polyimide having a specific amide bond concentration. When used as a precursor, it can be used alone.

Specific preferred examples of such aromatic diamino compounds include 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide,
3,4'-diaminodiphenyl ether, 1,4-phenylenediamine, 2,7-naphthalenediamine, 3,
3'-dimethyl-4,4'-diaminobiphenyl, 3,
3'-dimethoxy-4,4'-diaminobiphenyl,
3,3'-dichloro-4,4'-diaminobiphenyl,
1,4-bis (4-aminophenoxy) benzene, 1,
3-bis (4-aminophenoxy) benzene, 5,8-
Diaminoquinoline, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-diaminodiphenylmethane, bis [4- (4-aminophenoxy) phenyl] ether, 1,4-bis (4-aminophenyl) Benzene, 9,10-bis (4-aminophenyl) anthracene, 4,4'-bis (4-aminophenoxy) diphenylmethane, 4,4'-bis (4-aminophenoxy) diphenyl sulfide, bis [2- (4 -Aminophenyl) -benzothiazolyl] oxide, bis [2- (4-
Aminophenyl) -benzimidazolyl] sulfoxide, bis [2- (4-aminophenyl) -benzoxazolyl], 4- (4-aminophenylsulfonyl)-
4'-aminobiphenyl, 4,4'-bis (4-aminophenyl) diphenyl ether, 1,4-di- (4-aminobenzoyloxy) butane and the like can be mentioned.

Among these various aromatic diamino compounds, an aromatic diamino compound in which Y is the above-mentioned divalent group is used to produce a polyimide precursor, which is obtained after heat curing from the obtained photosensitive composition. The heat resistance, strength, and water resistance of the resulting polyimide coating film are good, and are therefore more preferable. Among the aromatic diamino compounds listed here, bis [4
-(3-aminophenoxy) phenyl] sulphone,
3,3'-diaminodiphenyl sulfone, 1,3-bis (3-aminophenoxy) benzene, 4,4'-bis (3-aminophenoxy) biphenyl and bis [4-
(4-aminophenoxy) phenyl] sulfone, 4,
4'-diaminobenzophenone, 4,4'-bis [4-
The use of (4-aminophenoxy) phenoxy) diphenyl sulfone and 4,4′-diaminodiphenyl sulfoxide and 4,4′-diaminodiphenyl sulfone is more preferable from the viewpoint of the physical properties of the same polyimide coating film as described above.

Examples of the photopolymerization initiator used as the component (B) of the photosensitive composition of the present invention include benzophenone and
Methyl o-benzoylbenzoate, 4-benzoyl-4 '
Benzophenone derivatives such as methyldiphenylketone, dibenzylketone and fluorenone, acetophenone derivatives such as 2,2′-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone and 1-hydroxycyclohexylphenylketone, thioxanthone,
Thioxanthone derivatives such as 2-methylthioxanthone, 2-isopropylthioxanthone and diethylthioxanthone, benzyl derivatives such as benzyl, benzyl dimethyl ketal, benzyl-β-methoxyethyl acetal, benzoin derivatives such as benzoin and benzoin methyl ether, 2,6-diethyl (4-azidobenzylidene)
Azides such as -4-methylcyclohexanone and 2,6'-di (4-azidobenzylidene) cyclohexanone,
1-phenyl-1,2-butanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propane Zion-2- (O
-Ethoxycarbonyl) oxime, 1-phenyl-1,
2-propanedione-2- (O-benzoyl) oxime, 1,3-diphenyl-propanetrione-2- (O
-Ethoxycarbonyl) oxime, 1-phenyl-3-
Ethoxy-propanetrione-2- (O-benzoyl)
Although oximes such as oximes are used, oximes are preferable in terms of photosensitivity. The addition amount of these photopolymerization initiators is preferably 1 to 15 parts by weight with respect to 100 parts by weight of the polyimide precursor polymer.

The solvent used as the component (C) in the photosensitive composition of the present invention is preferably a polar solvent from the viewpoint of solubility, and examples thereof include N, N'-dimethylformamide, N-methylpyrrolidone and N-acetyl-2-. Pyrrolidone, N,
N′-dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone and the like are used, and these can be used alone or in combination of two or more. These solvents are added in an amount of 100 to 4 with respect to 100 parts by weight of the aromatic polyimide precursor depending on the coating film thickness and the viscosity.
It can be used in the range of 100 parts by weight.

To the photosensitive composition of the present invention, in addition to the above-mentioned essential components (A) to (C), if desired, a compound having a reactive carbon-carbon double bond may be added to improve photosensitivity. You can also Examples of such a compound include 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate having an addition mole number of 2 to 20, pentaerythritol diacrylate, dipentaerythritol hexaacrylate. , Trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, methylenebisacrylamide, N-methylolacrylamide and the above acrylates or corresponding methacrylates, methacrylamides and the like. These compounds are preferably added in the range of 1 to 30 parts by weight per 100 parts by weight of the polyimide precursor.

If desired, a sensitizer for improving photosensitivity can be added to the photosensitive composition of the present invention. Examples of such sensitizers include Michler's ketone, 4,
4'-bis (diethylamino) benzophenone, 2,5
-Bis (4'-diethylaminobenzylidene) cyclopentanone, 2,6-bis (4'-diethylaminobenzylidene) cyclohexanone, 2,6-bis (4'-dimethylaminobenzylidene) -4-methylcyclohexanone, 2,6- Bis (4'-diethylaminobenzylidene) -4-methylcyclohexanone, 4,4'-bis (dimethylamino) chalcone, 4,4'-bis (diethylamino) chalcone, 2- (4'-dimethylaminocinnamylideneindanone , 2- (4'-dimethylaminobenzylideneindanone, 2- (p-4'-dimethylaminobiphenyl) -benzothiazole, 1,3-bis (4
-Dimethylaminobenzylidene) acetone, 1,3-bis (4-diethylaminobenzylidene) acetone, 3,
3'-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3
-Ethoxycarbonyl-7-dimethylaminocoumarin,
3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N-ethylethanolamine, N-phenyldiethanolamine, Np -Tolyldiethanolamine, N-phenylethanolamine,
4-morpholinobenzophenone, 4-dimethylaminobenzoic acid isoamyl, 4-diethylaminobenzoic acid isoamyl, 2-mercaptobenzimidazole, 1-phenyl-5-mercapto-1,2,3,4-tetrazole,
2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2- (p-dimethylaminostyryl) naphtho (1,2-d) thiazole, 2 Examples thereof include-(p-dimethylaminobenzoyl) styrene. From the viewpoint of sensitivity, it is preferable to use a compound having a mercapto group and a compound having a dialkylaminophenyl group in combination. These are used alone or in combination of 2 to 5 kinds, and the addition amount thereof is 0.1 to 100 parts by weight of the polyimide precursor.
10 parts by weight is preferred.

If desired, an adhesive aid may be added to the photosensitive composition of the present invention to improve the adhesiveness to the substrate. Examples of this adhesion aid include γ-aminopropyltrimethoxysilane and N- (β-aminoethyl) -γ-
Aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltri Methoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N- (3-diethoxymethylsilylpropyl) succinimide, N- [3- (triethoxysilyl) propyl] Phthalamic acid, benzophenone-3,3'-bis (3-triethoxysilyl) propylaminocarbonyl-4,4'-dicarboxylic acid, benzene-1,4-bis (3-triethoxysilyl) propylaminocarbonyl Such as 2,5-dicarboxylic acid is used. The addition amount of these is the above-mentioned polyimide precursor 10
The range of 0.5 to 10 parts by weight is preferable with respect to 0 parts by weight.

If desired, a thermal polymerization inhibitor can be added to the photosensitive composition of the present invention in order to improve the viscosity of the composition solution during storage and the stability of photosensitivity. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol,
Phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino)
Phenol, N-nitroso-N-phenylhydroxyamine ammonium salt, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N (1
-Naphthyl) hydroxylamine ammonium salt, bis (4-hydroxy-3,5-tert-butyl-phenylmethane), etc. are used in an amount of 0.005-5 based on 100 parts by weight of the polyimide precursor. A range of parts by weight is preferred.

The photosensitive composition of the present invention, in order to enable pattern formation by i-line, has an absorbance of i-line, ie, a ray having a wavelength of 365 nm, of a film after coating and drying formed therefrom of 1. It should be 5 or less. If the absorbance is higher than this, the required amount of light cannot reach the bottom of the film, resulting in incomplete pattern formation. Such absorbance is (A)
It can be prepared by appropriately adjusting the amounts of the essential components (1) to (C) and other components added as desired. The photosensitive composition of the present invention can be obtained by mixing the essential components (A) to (C) and other components. Then, the polyimide coating film can be obtained from the composition by the following method.

The photosensitive composition of the present invention can be applied onto a substrate by, for example, a method of applying with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, or a method of spraying with a spray coater. it can. The obtained coating film is dried by air drying, heat drying with an oven or a hot plate, vacuum drying, or the like. The coating film thus obtained is exposed by an ultraviolet light source or the like using an exposure device such as a contact aligner, a mirror projection, or a stepper. From the viewpoint of pattern resolution and handleability, the light source wavelength is preferably i-line, and a stepper is preferable as an apparatus. Development is
Any known method can be selected from conventionally known photoresist developing methods, such as a rotary spray method, a paddle method, and a dipping method with ultrasonic treatment.

The developer used is preferably a combination of a good solvent and a poor solvent for the polymer precursor. As the good solvent, N-methylpyrrolidone, N-
Acetyl-2-pyrrolidone, N, N′-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone and the like, and poor solvents such as toluene, xylene, methanol, ethanol and isopropyl alcohol. And water are used. The ratio of the poor solvent to the good solvent is adjusted by the solubility of the polyimide precursor used. It is also possible to use each solvent in combination.

For a composition containing a high carboxylic acid content, a developer prepared by adding the above solvent to an aqueous solution of an organic base such as choline hydroxide or tetramethylammonium hydroxide, if necessary. Is used. The pattern film of the polyimide precursor composition thus obtained is converted into a polyimide by heating to volatilize the photosensitive component. The heat conversion can be performed by a hot plate, an oven, or a temperature rising type oven in which a temperature program can be set. Air may be used as the atmospheric gas at the time of heat conversion, and an inert gas such as nitrogen or argon can be used.

[0040]

EXAMPLES The present invention will be described in more detail with reference to Examples, Reference Examples and Comparative Examples, but the scope of the present invention is not limited to these. The characteristics in each example were measured as follows. (1) Amide bond concentration The amide bond concentration is calculated according to the following formula. In the above formula, [M] _C represents the molecular weight of the tetracarboxylic acid unit, which is obtained by subtracting the atomic weight 32 of two oxygen atoms from the molecular weight of the tetracarboxylic dianhydride used as a raw material. When two or more tetracarboxylic dianhydrides are used, the average molecular weight calculated from the molecular weight of each tetracarboxylic dianhydride and the molar ratio used is used. [M] _A represents the molecular weight of a diamine unit, which is obtained by subtracting the atomic weight 2 of two hydrogen atoms from the molecular weight of the aromatic diamino compound used as a raw material. When two or more aromatic diamino compounds are used, the average molecular weight calculated from the molecular weight of each diamino compound and the number of moles used is used.

[M] _S represents the total molecular weight of the side chain substituents (R) and (R ′) existing in the carbonyl group portion bonded to the aromatic ring of the precursor polymer, and the same substituents are bonded. In that case, the molecular weight of the substituent may be multiplied by 2,
When two or more kinds of substituents are present, the average molecular weight calculated from the molecular weight of each substituent and the molar ratio used is multiplied by 2. In the above calculation, the atomic weight of carbon is 12, the atomic weight of nitrogen is 14, the atomic weight of oxygen is 16, and the atomic weight of sulfur is 3.
2. This is a value obtained by calculating the atomic weight of hydrogen as 1. In the formula, 2000 is a coefficient for calculating the number of moles of the amide bond existing in 1 kg of the polyimide precursor.

(2) Absorbance of polyimide precursor coating film A solution of the polyimide precursor in N-methylpyrrolidone was added to about 1
After spin coating on a quartz plate having a thickness of mm, it is dried in an oven at 80 ° C. for 40 minutes to form a coating film having a thickness of 10 μm. Then, the absorbance at 365 nm of this coating film was measured using a UV spectroscope (UV-240 type, manufactured by Shimadzu Corp.), and the absorbance was represented by the following formula. Absorbance = log ₁₀ I ₀ / I (In the formula, I ₀ is the intensity of incident light and I is the intensity of light transmitted through the film.) (3) Absorbance of coating film of photosensitive composition Same as (2) above Was measured by the method.

(4) Viscosity number of polyimide precursor Polyimide precursor in N-methylpyrrolidone (1 g / d
l) Viscosity number (ηsp / c) of auto viscometer
It measured at 30 degreeC with AVL-2C (made by Sun Denshi). (5) Viscosity of Photosensitive Composition A solution of the composition sample was treated with an E-type viscometer (manufactured by Tokyo Keiki, VISC).
ONIC-EMD type) was used for measurement at 23 ° C. (6) Tensile strength and elongation of polyimide coating film In each example, the coating film on the wafer was treated in the same manner except that the entire surface was exposed without using a photomask and was not developed. Peel the resulting polyimide coating from the wafer,
Its tensile strength and elongation are ASTM D-882-88.
Was measured according to.

(7) Peeling Test The adhesiveness of the polyimide coating film with the epoxy resin was measured as follows. A pin having a diameter of 2 mm was bonded to the polyimide coating film on the silicon wafer after the heat treatment by using an epoxy resin adhesive (Showa Polymer Co., Ltd., Araldite Standard). This sample was subjected to a peeling test using a take-off tester (manufactured by Quad Group, Sebastian 5 type). Rating: peel strength 7kg / mm ² or more ... adhesion good 6-5kg / mm ² ··· usable 5kg / mm ² less than ... bad

(8) Water resistance test A polyimide coating film on a silicon wafer after heat treatment was kept in boiling water for 48 hours, dried in an oven at 50 ° C. for 2 hours, and then subjected to a peeling test similar to the above. It was Rating: peel strength 7 kg / mm ² or more ... adhesion good 6-3kg / mm ² ··· Usable 3 kg / mm ² less than ... poor (9) ATC dianhydride used as a raw material preparation example It is represented by the following symbols. The following structural formula represents X in the structural formula (IV).

[0046]

[Chemical 6]

[0047]

[Chemical 7]

The aromatic diamino compounds used in Production Examples are represented by the following symbols. The following structural formula represents Y in the structural formula (I).

Embedded image

[0049]

[Chemical 9]

[0050]

[Chemical 10]

[0051]

[Chemical 11]

[0052]

[Chemical 12]

[0053]

[Chemical 13]

(Production Example 1) (X-1) 16.1 g, (X-11) 10.9 were placed in a 500 ml separable flask.
g, (E-1) 27.0 g and γ-butyrolactone 6
Charge 0 ml and pyridine 1 while stirring under ice cooling.
7.0 g was added. After stirring at room temperature for 16 hours, a solution of 41.2 g of dicyclohexylcarbodiimide in 40 ml of γ-butyrolactone was added over 30 minutes under ice cooling, and subsequently 35.0 g of (Y-1) was suspended in 70 ml of γ-butyrolactone. Was added in 60 minutes. After stirring for 3 hours under ice-cooling, 5 ml of ethanol was added, and the mixture was stirred for 1 hour, and the solid matter generated in the above process was removed by filtration. The reaction solution was added to 10 l of ethanol, the formed precipitate was filtered off, and then dried in vacuum. Thus, the polyimide precursor (A1-1) was manufactured. Table 5 shows the viscosity number, amide bond concentration, and absorbance of (A1-1).

(Production Example 2) 62.0 g of (X-2) and 462 ml of N, N'-dimethylacetamide (hereinafter referred to as DMAc) were placed in a 500 ml separable flask, and while stirring, 68.4 g of (Y-2). DMA including
100 ml of c was added, and the mixture was stirred at room temperature for 16 hours, and then 43.4 g under ice cooling (E-2) was added, and the mixture was stirred for 3 hours.
The reaction solution was added to 10 l of ethanol, and the formed precipitate was filtered and then dried in vacuum. Thus, the polyimide precursor (A2-1) was manufactured. Table 5 shows the viscosity number, amide bond concentration, and absorbance of (A2-1).

(Production Example 3) 76.8 g of (Y-3) was added to N-
Dissolved in 450 g of methylpyrrolidone (X-3) 71.6
g was added and reacted at 50 ° C. for 6 hours. To this (E-
3) A solution of 74.0 g dissolved in 110 g of N-methylpyrrolidone was slowly added at room temperature to obtain a solution of a polyimide precursor (A3-1). Table 5 shows the amide bond concentration and absorbance of (A3-1).

(Production Example 4) 121.1 g of (Y-4) was added to N
-Dissolved in 687 g of methylpyrrolidone, (X-8) 8
8.2 g was added, and the mixture was stirred at room temperature for 12 hours. next,
(E-4) 85.3 g was added, and the mixture was stirred at 70 ° C. for 36 hours. Thus, a solution of the polyimide precursor (A4-1) was manufactured. The amide bond concentration of this (A4-1),
The absorbance is shown in Table 5.

(Production Example 5) 72.9 g of (X-4) was added to N-
Dissolved in 200 g of methylpyrrolidone, (E-1) 5.2
g and the mixture was heated at 100 ° C. for 1 hour. This was cooled to 50 ° C., 44.4 g of (Y-5) was added together with 110 g of N-methylpyrrolidone, and the mixture was stirred at 50 ° C. for 5 hours. Then, 76.0 g of trifluoroacetic anhydride was added together with 280 ml of tetrahydrofuran, and the mixture was stirred at 50 ° C. for 2 hours.
Stir the time. At this time, insoluble solid components were precipitated. Next, (E-1) (52.0 g) was added, and the mixture was stirred at 50 ° C. for 5 hours to dissolve the solid component and obtain a uniform solution. This solution was added to 10 l of water, and the formed precipitate was filtered, washed with water, and dried in vacuum. Thus, the polyimide precursor (A5-1) was manufactured. Table 5 shows the viscosity number, amide bond concentration, and absorbance of this (A5-1).

(Production Examples 6 to 17) ATC shown in Table 1
Polyimide precursors (A1-2) to (A1-17) in the same manner as in Production Example 1 except that the amounts of the dianhydride, aromatic diamino compound and R-containing compound shown in Table 1 were used, respectively.
Was manufactured. Table 5 shows the viscosity number, amide bond concentration, and absorbance of the obtained polyimide precursor. (Production Examples 18 to 25) A polyimide precursor was prepared in the same manner as in Production Example 3 except that the amounts of the ATC dianhydride, aromatic diamino compound and other compound shown in Table 2 were used. The bodies (A3-2) to (A3-9) were produced. The amide bond concentration of the obtained polyimide precursor,
The absorbance is shown in Table 6.

(Production Examples 26 to 28) AT shown in Table 2
Polyimide precursor (A5-A5) was prepared in the same manner as in Production Example 5, except that C dianhydride was used in the amounts shown in Table 2.
2) to (A5-4) were produced. Table 6 shows the viscosity number, the amide bond concentration, and the absorbance of the thus obtained polyimide precursor. (Production Examples 29 and 30) A polyimide precursor (A1)
-14) and (A1-15) were produced. Table 6 shows the viscosity number, the amide bond concentration, and the absorbance of the thus obtained polyimide precursor.

(Production Example 31) In a separable flask having a volume of 500 ml, 31.0 g of (X-2) and 17.0 g of pyridine were added.
g, and 60 ml of γ-butyrolactone were added, and 27.0 g of (E-1) was added while stirring. The solution was heated to 40 ° C., kept for 4 hours, stirred at room temperature for 16 hours, and then 41.2 g of γ-dicyclohexylcarbodiimide.
A solution of 40 ml of butyrolactone was added for 30 minutes under ice cooling, and subsequently 40.4 g of (Y-8) was added to 80 ml of γ-.
The suspension in butyrolactone was added over 60 minutes. After stirring for 3 hours under ice-cooling, 5 ml of ethanol was added and further stirred for 1 hour. The solid solution produced by the above process was removed by filtration, and the reaction solution was added to 10 liters of ethanol, and the formed precipitate was filtered off. Dried. Thus, the polyimide precursor (A1-16) was manufactured.
Table 6 shows the viscosity number, amide bond concentration, and absorbance of this (A1-16).

(Production Example 32) 35.0 g of (Y-1) was added to 70 ml of γ-butyrolactone by using the amounts of ATC dianhydride and aromatic diamino compound shown in Table 2 respectively. Instead of adding suspended ones (Y-5)
A polyimide precursor (A1-17) was produced in the same manner as in Production Example 1 except that 160 ml γ-butyrolactone solution containing 23.6 g was added. Table 6 shows the viscosity number, amide bond concentration, and absorbance of this (A1-17). (Production Example 33) A polyimide precursor (A2-2) was prepared in the same manner as in Production Example 2 except that the amounts of the ATC dianhydride, amino compound and other compound shown in Table 2 were used. ) Was manufactured. The viscosity number of this (A2-2),
Table 6 shows the amide bond concentration and the absorbance.

(Production Example 34) (Y-7) 160.6 g
Was dissolved in 770 g of N-methylpyrrolidone, and (X-1
1) 120 g was added and reacted at 50 ° C. for 6 hours. A solution prepared by dissolving 2.5 g of (E-9) in 50 g of N-methylpyrrolidone was added to 50 g of this solution to obtain a polyimide precursor (A3-10). Table 6 shows the viscosity number, amide bond concentration, and absorbance of (A3-10). (Production Examples 35 to 43) ATC dianhydride shown in Table 3,
Polyimide precursors (A1-18) to (A1-26) were produced in the same manner as in Production Example 32 except that the amounts of the aromatic diamino compound and other compounds shown in Table 3 were used. Table 7 shows the viscosity number, amide bond concentration, and absorbance of the polyimide precursor.

(Production Example 44) (Y-20) 22.8 g,
Dissolved in 150 g of N-methylpyrrolidone, (X-3) 3
5.8g was added and it was made to react at 50 degreeC for 6 hours. A solution prepared by dissolving 37.2 g of (E-3) in 66 g of N-methylpyrrolidone was slowly added at room temperature to obtain a polyimide precursor solution (A3-11). Table 7 shows the viscosity number, amide bond concentration, and absorbance of (A3-11). (Production Examples 45 to 48) ATC dianhydride shown in Table 3,
Table 3 shows aromatic diamino compounds and other compounds, respectively.
In the same manner as in Production Example 32 except that the amount shown in
Polyimide precursors (A1-28) to (A1-31) were produced. Viscosity number of polyimide precursor, amide bond concentration,
The absorbance is shown in Table 7.

(Production Examples 49 to 50) AT shown in Table 3
Polyimide precursor solutions (A4-2) and (A4-3) were produced by the same synthetic method as in Reference Example 4 except that the amounts of C dianhydride and aromatic diamino compound shown in Table 3 were used. Table 7 shows the viscosity number, amide bond concentration, and absorbance of the polyimide precursor solution. (Production Examples 51 and 52) A polyimide precursor solution (A3-12) was prepared using the same synthetic method as in Production Example 44 except that the other compounds shown in Table 3 were used in the amounts shown in Table 3.
(A3-13) was produced. Table 7 shows the viscosity number, amide bond concentration, and absorbance of the polyimide precursor solution.

(Production Examples 53 to 58) AT shown in Table 4
Polyimide precursors (A1-32) to (A1-37) were produced by the same synthetic method as in Production Example 43 except that the amounts of C dianhydride and aromatic diamino compound shown in Table 4 were used. Table 8 shows the viscosity number, amide bond concentration, and absorbance of the polyimide precursor. (Production Examples 59 and 60) Polyimide precursors (A5-5) and (A5A) were prepared in the same manner as in Production Example 5 except that the compounds shown in Table 4 were used as the ATC dianhydride in the amounts shown in Table 4.
5-6) was produced. Table 8 shows the viscosity number, the amit bond concentration, and the absorbance of the polyimide precursor. (Production Example 61) A polyimide precursor (A1) was prepared in the same manner as in Production Example 32 except that the amounts of the ATC dianhydride, aromatic diamino compound and other compound shown in Table 4 were respectively used. -38) was produced. Table 8 shows the viscosity number, amide bond concentration, and absorbance of the polyimide precursor.

Examples will be shown below, and the abbreviations for the components in the examples are as follows. (Photopolymerization Initiator (Component B)) I-1 Benzophenone I-2 Benzyl I-3 2-Isopropylthioxanthone I-4 1,3-Diphenylpropanetrione-2-
(O-Ethoxycarbonyl) oxime I-5 1-Phenyl-3-ethoxypropanetrione-2- (O-benzoyl) oxime (Compound having reactive carbon-carbon double bond) M-1 Tetraethylene glycol dimethacrylate M -2 pentaerythritol diacrylate M-3 methylene bisacrylamide M-4 N-methylol acrylamide M-5 trimethylol propane triacrylate

(Sensitizer) S-1 Michler's ketone S-2 4,4'-bis (diethylamino) benzophenone S-3 2- (p-dimethylaminostyryl) benzoxazole S-4 2- (p-dimethylaminobenzoyl) ) Styrene S-5 N-phenyldiethanolamine S-6 Np-tolyldiethanolamine S-7 N-phenylethanolamine S-8 2-mercaptobenzimidazole S-9 1-phenyl-5-mercapto-1,2,
3,4-tetrazole S-10 2-mercaptobenzothiazole

(Adhesion Aid) F-1 γ-glycidoxypropylmethyldimethoxysilane F-2 3-methacryloxypropyltrimethyoxysilane F-3 3-methacryloxypropylmethyldimethoxysilane F-4 N- [3- (Triethoxysilyl) propyl] phthalamic acid F-5 benzophenone-3,3'-bis [N- (3
-Triethoxysilyl) propylamide] -4,4'-
Dicarboxylic acid (thermal polymerization inhibitor) Z-1 N-nitrosodiphenylamine Z-2 bis (4-hydroxy-3,5-tert-)
Butylphenyl) methane Z-3 2,6-di-tert-butyl-p-methylphenol Z-4 2-nitroso-1-naphthol

Reference Example 1 Polyimide precursor (A1-
1) 50 g, (I-1) 2 g, (M-1) 6 g, (S-
1) 0.05 g, (S-5) 1 g, (S-8) 1.5
g, (F-1) 1 g and (Z-1) 0.05 g, N
-Methylpyrrolidone was dissolved in 75 g to prepare a photosensitive composition (W-1). The coating film of this composition had an absorbance of 1.5 and a viscosity of 73.5 poise. This composition was spin-coated on a 3-inch silicon wafer and dried to form a coating film having a thickness of 13 μm. An i-line stepper EPA20 is applied to this coating film using a reticle with a test pattern.
An energy of 800 mJ / cm ² was irradiated with 01iI (manufactured by Canon). Then, this wafer was spray-developed with γ-butyrolactone and xylene (50/50 (%)) and rinsed with isopropyl alcohol, and a sharp pattern having a resolution of 10 μm line / space was obtained.

This wafer was placed in an inert oven under a nitrogen atmosphere at 140 ° C. for 1 hour and then at 300 ° C.
A polyimide film having a thickness of 7 μm was obtained by heat-treating for 1 hour. In both the peeling test and the water resistance test, the epoxy resin was broken at a stress of 8 kg / mm ² , and the film had good adhesive strength and water resistance. The tensile strength of the polyimide film is 14
It was kg / mm ² and the elongation was 30%.

Reference Example 2 Polyimide precursor (A2-
1) 20 g, (I-2) 0.3 g, (M-2) 0.5
g, (S-2) 0.02 g, (S-9) 0.1 g, (F
-3) 0.15 g and 0.01 g of (Z-2) methane were dissolved in 40 g of N-methylpyrrolidone to prepare a photosensitive composition (W-2). The coating film of this composition had an absorbance of 1.5 and a viscosity of 44 poise. Next, this composition was spin-coated on a 3-inch silicon wafer and dried to obtain a coating film having a thickness of 13 μm. This coating film was exposed to energy of 400 mJ / cm ² from an i-line light source through an reticle by an i-line stepper exposure machine NSR1505i (manufactured by Nikon Corporation). This wafer was then treated with tetramethylammonium hydroxide / methanol / water (0.3 / 2.
7/97 (% by volume)), paddle development and rinsing with water gave a sharp pattern with a resolution of 10 μm lines / space.

This was baked on a hot plate at 200 ° C. for 10 minutes, placed in a vertical curing furnace, and heat-treated at 350 ° C. for 1 hour in a nitrogen atmosphere to obtain a 7 μm-thick polyimide pattern. This film has a stress of 8 kg in both the peeling test and the water resistance test.
The epoxy resin broke at the point of / mm ² and both the adhesive strength and the water resistance were good. The polyimide coating film had a tensile strength of 20 kg / mm ² and an elongation of 9%.

Reference Example 3 Polyimide precursor (A3-
To 77 g of the solution of 1), 0.2 g of (I-3), (M-3)
0.8 g, (S-3) 0.02 g, (S-6) 0.3
g, (S-10) 0.15 g, (F-3) 0.1 g and (Z-3) 0.01 g were dissolved to give a photosensitive composition (W-
3) was prepared. The absorbance of the coating film of this composition is 0.8,
The viscosity was 55.0 poise. Then, this composition
1 inch by spin coating on inch silicon wafer and drying
A 7 μm thick coating film was obtained. A photo mask is passed through this coating film, and a PLA50LF exposure machine (made by Canon) is used to make an i-line band pass filter UVD36C (made by Toshiba Colored Glass).
Was exposed with an energy of 1000 mJ / cm ² . This wafer is N, N'-dimethylacetamide /
After spray development with a developer of ethanol (80/20 (vol%)) and rinsing with isopropyl alcohol, a sharp pattern with a resolution of 10 μm lines / spaces was obtained.

This was heat-treated in an inert oven in a nitrogen atmosphere at 140 ° C. for 1 hour and 300 ° C. for 1 hour to give 8 μm.
An m-thick polyimide pattern was obtained. This film is
In both the peeling test and the water resistance test, the epoxy resin broke at a stress of 8 kg / mm ² , and both the adhesive strength and the water resistance were good. The polyimide coating film had a tensile strength of 12 kg / mm ² and an elongation of 70%.

Reference Example 4 Polyimide precursor (A4-
To 33.3 g of the solution of 1), 0.6 g of (I-4), (M-
4) 0.8 g, (S-4) 0.03 g, (S-7) 0.
2 g, (S-8) 0.1 g, (F-4) 0.1 g and (Z-4) 0.01 g were dissolved to obtain a photosensitive composition (W-
4) was prepared. The absorbance of the coating film of this composition is 1.5,
The viscosity was 38 poise.

This composition was spin-coated on a 3-inch silicon wafer and dried to obtain a coating film having a thickness of 13 μm. An i-line stepper FPA using a pattern reticle on this coating film
800 mJ / cm ^{2 with} 2000 iI (made by Canon)
Exposure. This wafer was choline hydroxide / ethanol / water (0.5 / 9.5 / 90 (vo
(1%)) and then rinsed with water after paddle development, a sharp pattern with a resolution of 10 μm lines / spaces was obtained. This was heat-treated in an inert oven in a nitrogen atmosphere at 140 ° C. for 1 hour and 300 ° C. for 1 hour to obtain a polyimide pattern having a thickness of 7 μm. In both the peeling test and the heat resistance test, the epoxy resin of this film broke at a stress of 8 kg / mm ² , and the adhesive strength and water resistance were good. Also,
The polyimide coating film had a tensile strength of 18 kg / mm ² and an elongation of 12%.

(Reference Example 5) Polyimide precursor (A5-
1) 50 g, (I-5) 2 g, (M-5) 3 g, (S-
3) 0.1 g, (S-9) 0.5 g, (F-5) 1 g and (Z-4) 0.02 g were added to N-methylpyrrolidone 7
It was dissolved in 5 g to prepare a photosensitive composition (W-5). The coating film of this composition had an absorbance of 1.0 and a viscosity of 47.0 poise. This composition was spin-coated on a 3-inch silicon wafer and dried to obtain a coating film having a thickness of 19 μm. 600mJ by i-line stepper FPA2001iI (manufactured by Canon) using a reticle with a test pattern on this coating film
It was exposed with an energy of / cm ² . When this wafer was rinsed with a paddle developer and isopropyl alcohol with a cyclohexanone / xylene (70/30 (vol%)) developer, a sharp pattern with a resolution of 15 μm lines / space was obtained.

This wafer was heat-treated in an inert oven in a nitrogen atmosphere at 140 ° C. for 1 hour and 350 ° C. for 2 hours to obtain a polyimide pattern having a thickness of 10 μm.
In both the peeling test and the water resistance test, the epoxy resin broke at a stress of 8 kg / mm ² , and the film had good adhesive strength and water resistance. Also,
The polyimide coating film had a tensile strength of 18 kg / mm ² and an elongation of 18%.

Reference Examples 6 to 18 Various polyimide precursors shown in Table 9: 50 g, (I-5) 2 g, (M-5) 3
g, (S-3) 0.3 g, (S-9) 0.5 g, (F-
5) 1 g and (Z-4) 0.02 g were dissolved in N-methylpyrrolidone 75 g to prepare photosensitive compositions (W-6) to (W-6).
-18) was prepared. The viscosity of these compositions and the absorbance of the coating film are shown in Table 9. These compositions were spin-coated on a 3-inch silicon wafer and dried. Table 9 shows the film thickness of the obtained coating film. These coating films were exposed with an energy of 800 mJ / cm ² by an i-line stepper FPA2001iI (manufactured by Canon) using a reticle with a test pattern. This wafer was paddle-developed with a cyclohexanone / xylene (70/30 (vol%)) developing solution, rinsed with isopropyl alcohol, and the obtained resolutions are shown in Table 9. These wafers were placed in an inert oven under a nitrogen atmosphere at 140 ° C. for 1 hour for 35 hours.
A heat treatment was performed at 0 ° C. for 2 hours to obtain a polyimide pattern. Table 9 shows the results of the peeling test, the water resistance test, the tensile strength, the elongation, and the film thickness of the polyimide coating film.

Reference Examples 19 to 26 Using 77 g of various polyimide precursor solutions shown in Table 10, photosensitive compositions (W-19) to (W-26) were prepared in the same manner as in Reference Example 3. . Table 10 shows the viscosities of these compositions and the absorbance of coating films.
Shown in A coating film was formed using these compositions in the same manner as in Reference Example 3, and the resolution and the peeling test of the polyimide coating film after heat treatment, the results of the water resistance test, and the tensile strength, elongation, and film thickness were determined. It shows in Table 10.

Reference Examples 27 to 28 Polyimide precursors (50 g) shown in Table 10, (I-5) 2 g, (M-5) 3
g, (S-3) 0.1 g, (S-9) 0.5 g, (F-
5) 1 g and 0.02 g of (Z-4) are dissolved in 75 g of N-methylpyrrolidone to prepare a photosensitive composition (W-27).
(W-28) was prepared. Table 10 shows these viscosities and the absorbance of the coating film. The resolution of the pattern obtained by treating with these compositions in the same manner as in Example 1, the peeling test of the coating film of the polyimide after heat curing, the water resistance test and the film thickness, the tensile strength, and the elongation were evaluated. It shows in Table 10.

Comparative Examples 1 and 2 50 g of the polyimide precursor shown in Table 10, 2 g of (I-5), 3 g of (M-5),
(S-3) 0.05 g, (S-9) 0.5 g, (F-
5) 1 g and (O-4) 0.02 g were dissolved in 75 g of N-methylpyrrolidone to prepare photosensitive compositions (WR-1) and (WR-2). Table 10 shows the viscosities of these compositions and the absorbance of coating films. Next, when these compositions were treated in the same manner as in Reference Example 6, the composition of Comparative Example 1 had a line /
Space lines flowed, and in Comparative Example 2, the lines flowed due to the stronger inverted trapezoidal pattern cross-sectional shape, and there were practical problems. Table 10 shows the peeling test, the water resistance test, the film thickness, the tensile strength, and the elongation of the heat-cured polyimide coating film.

(Comparative Example 3) Polyimide precursor (A1-
A photosensitive composition (WR-3) was prepared in the same manner as in Comparative Example 1 except that the polyimide precursor (A1-14) was used instead of 7). The viscosity of this composition was 66.3 poise and the absorbance of the coating film was 0.41. This composition was spin-coated on a 3-inch silicon wafer and dried to 27 μm.
A thick coating film was obtained. In the pattern obtained by treating this coating film in the same manner as in Reference Example 1, the swelling of the exposed portion was strong and the line / space could not be resolved. This film has a stress of 8 kg / m in both the peeling test and the water resistance test.
At the time of m ² , the epoxy resin had good breakage, adhesive strength and water resistance. The tensile strength of the polyimide coating film is 9
It was kg / mm ² and the elongation was 120%.

(Reference Example 29) Polyimide precursor (A1-
17) 50 g, (I-1) 2 g, (M-1) 6 g, (S
-1) 0.05 g, (S-5) 1 g, (S-10) 1.
A composition (W-29) was prepared by dissolving 5 g, (F-1) 1 g and (Z-1) 0.05 g in N-methylpyrrolidone 75 g. The composition had a viscosity of 78 poise and a coating film absorbance of 1.5. A 13 μm-thick coating film was formed from this composition in the same manner as in Reference Example 1, developed, and rinsed with xylene. A sharp pattern with a resolution of 10 μm lines / spaces was obtained. This wafer was heat treated in the same manner as in Reference Example 1 to obtain a polyimide pattern having a thickness of 7 μm. In both the peeling test and the water resistance test, the film had good epoxy resin fracture, adhesive strength and water resistance at a stress of 8 kg / mm ² . The tensile strength of this polyimide coating film is 15
It was kg / mm ² and the elongation was 14%.

(Example 30) Polyimide precursor (A2-
2) 55.6 g, (I-2) 0.3 g, (M-2) 0.
5 g, (S-2) 0.02 g, (S-9) 0.1 g,
0.15 g of (F-2) and 0.01 g of (Z-2) were dissolved to prepare a photosensitive composition (W-30). The viscosity of this composition was 129 poise and the absorbance of the coating film was 1.5.
A 13 μm-thick coating film was formed from this composition in the same manner as in Reference Example 2 and developed. As a result, a sharp pattern having a resolution of 10 μm lines / spaces was obtained. This wafer was heat treated in the same manner as in Reference Example 2 to obtain a 7 μm thick polyimide pattern. In the peeling test, this film broke at 5 to 6 kg / mm ² ,
In the water resistance test, the peel strength was reduced to 3 kg / mm ² . The tensile strength of this polyimide coating is 17k.
The value was g / mm ² and the elongation was 10%.

(Reference Example 31) Polyimide precursor (A3-
A photosensitive composition (W-31) was prepared in the same manner as in Reference Example 3 using the polyimide precursor (A3-10) instead of 1). The viscosity of this composition was 50 poise and the absorbance of the coating film was 1.4. A 17 μm-thick coating film was formed from this composition in the same manner as in Reference Example 3 and developed.
A sharp pattern with a resolution of μm lines / spaces was obtained. This wafer was heat treated in the same manner as in Reference Example 3 to obtain a polyimide pattern having a thickness of 9 μm. In both the peeling test and the water resistance test, the epoxy resin ruptured at a stress of 8 kg / mm ² in this film.
Both the adhesive strength and water resistance were good. The polyimide coating film has a tensile strength of 16 kg / mm ² and an elongation of 10%.
Met.

(Example 34, Comparative Examples 32, 33, 35,
36 and Comparative Examples 4-6) Various polyimide precursors shown in Table 11 and other components were added to N-methylpyrrolidone 75 g.
To prepare compositions (W-32) to (W-36) and (WR-4) to (WR-6). Table 12 shows these viscosities and the absorbance of the coating film. These compositions were spin-coated on a 3-inch silicon wafer and dried.
Table 12 shows the thickness of the obtained coating film. Using the reticle with the test pattern on this coating, i-line stepper FPA2
Exposure was performed with the exposure energy of 00liI (manufactured by Canon) shown in Table 11. This wafer was paddle-developed with a developing solution of cyclohexanone / xylene (70/30 (vol%)), rinsed with the solvent shown in Table 11, and the obtained resolutions are shown in Table 12. In each of the reference examples, a sharp pattern was obtained. These wafers were heated at 140 ° C. for 1 hour under a nitrogen atmosphere for 35 hours using an inert open.
Heat treatment was performed at 0 ° C. for 2 hours to obtain a polyimide pattern having a thickness shown in Table 12. Table 12 shows the results of the peeling test, the water resistance test, the tensile strength, and the elongation of this polyimide coating film.
Shown in

Reference Examples 37 to 40 Various polyimide precursors shown in Table 13: 50 g, (I-1) 2 g, (M-1)
6 g, (S-1) 0.05 g, (S-5) 1 g, (S-
8) 1.5 g, (F-1) 1 g, (Z-1) 0.05 g
Was dissolved in 75 g of N-methylpyrrolidone to give a composition (W-
37) to (W-40) were prepared. Table 13 shows these viscosities and the absorbance of the coating film.

These compositions were spin-coated on a 3-inch silicon wafer and dried. Table 13 shows the thickness of the obtained coating film. This coating film was exposed using a reticle with a test pattern under the exposure conditions of i-line stepper shown in Table 13. When this wafer was spray-developed with a developer of γ-butyrolactone / xylene (50/50 (vol%)) and rinsed with xylene, a sharp pattern was obtained in each case. These resolutions are shown in Table 13. This wafer was heat-treated in an inert oven in a nitrogen atmosphere at 140 ° C. for 1 hour, 300 ° C. for 1 hour to remove the polyimide coating film from the peeling test, the water resistance test result and the coating film, the tensile strength and the elongation. Is shown in Table 13.

(Reference Examples 41 and 42) To 33.3 g of the polymer precursor shown in Table 13, 0.6 g of (I-4) and (M
-4) 0.8 g, (S-4) 0.03 g, (S-7)
0.2 g, (S-8) 0.1 g, (F-4) 0.1 g,
The photosensitive composition (W-4
1) and (W-42) were prepared. Table 13 shows the viscosities of these compositions and the absorbance of coating films. When this composition was treated in the same manner as in Reference Example 5 except that the exposure energy was changed to 500 mJ / cm ² , a sharp pattern was obtained in each case. These resolutions are shown in Table 13. This wafer was heat-treated in an inert oven in a nitrogen atmosphere at 140 ° C. for 1 hour, 350 ° C. for 1 hour, and a polyimide coating film obtained by peeling test, water resistance test result and coating film, tensile strength, elongation Is shown in Table 13.

Reference Examples 43 to 45 To 77 g of the polymer precursor shown in Table 13, 0.2 g of (I-3) and (M-3)
0.8 g, (S-3) 0.02 g, (S-6) 0.3
g, (S-10) 0.15 g, (F-3) 0.1 g,
(Z-3) 0.01 g was dissolved to obtain a photosensitive composition (W-4
3) to (W-45) were prepared. Table 13 shows the viscosities of these compositions and the absorbance of coating films.

These compositions were spin-coated on a 3-inch silicon wafer and dried. Table 13 shows the thickness of the obtained coating film. This coating film was exposed through a reticle with an i-line light source under the exposure conditions shown in Table 13. This wafer is N,
N'-dimethylacetamide / ethanol = 80/20
(Vol%)), a spray developing solution and isopropyl alcohol were used for rinsing. As a result, sharp patterns were obtained. These resolutions are shown in Table 13. This wafer was heat-treated in an nitrogen atmosphere at 140 ° C. for 1 hour and at 350 ° C. for 1 hour using an inert open to obtain a polyimide pattern having a thickness shown in Table 13. Table 13 shows the results of the peeling test, the water resistance test, the tensile strength, and the elongation of this polyimide coating film.

(Reference Example 46) Polyimide precursor (A1-
31) 50 g, (I-1) 2 g, (M-1) 6 g, (S
-1) 0.05 g, (S-5) 1 g, (S-10) 1.
5 g, (F-1) 1 g and (Z-1) 0.05 g
-Methylpyrrolidone dissolved in 75 g to give a photosensitive composition (W
-46) was prepared. The viscosity of this composition is 43 poise,
The absorbance of the coating film was 1.5. This composition was spin-coated on a 3-inch silicon wafer and dried to obtain a coating film having a thickness of 13 μm. I-line stepper exposure machine NSR
-1505i (manufactured by Nikon)
Exposure was performed with a linear light source at an energy of 600 mJ / cm ² .
Γ-butyrolactone / xylene = 50 /
After spray development with 50 (vol / vol%) developing solution and rinsing with xylene, a sharp pattern with a resolution of 10 μm lines / spaces was obtained.
This wafer was heat-treated in an nitrogen atmosphere at 140 ° C. for 1 hour, 300 ° C. for 1 hour using an inert open to 7 μm.
An m-thick polyimide pattern was obtained. This film is
In both the peeling test and the water resistance test, the epoxy resin had good fracture, adhesive strength and water resistance at the stress of 8 kg / mm ² . The polyimide coating film had a tensile strength of 14 kg / mm ² and an elongation of 15%.

Reference Examples 47 and 48 50 g of polymer precursors shown in Table 14, 2 g of (I-5), and (M-5) 3
g, (S-3) 0.1 g, (S-9) 0.5 g, (F-
5) 1 g and (Z-4) 0.02 g were dissolved in N-methylpyrrolidone to prepare photosensitive compositions (W-47) to (W-48).
Was prepared. Table 14 shows the viscosities of these compositions and the absorbance of coating films. This composition was spin-coated on a 3-inch silicon wafer and dried. Table 14 shows the thickness of the obtained coating film. Apply this coating to i-line stepper NSR-150
The 5i (Nikon), for the W-47 i-line light source through a reticle for 500mJ / cm ^2, W-48 were exposed with an energy of 600 mJ / cm ^2. Cyclohexanone / xylene = 70/30
After paddle development with a (vol / vol%) developing solution and rinsing with isopropyl alcohol, a sharp pattern was obtained in each case. The resolutions are shown in Table 14. This wafer was heat-treated in an inert oven in a nitrogen atmosphere at 140 ° C. for 1 hour and 350 ° C. for 1 hour to obtain a polyimide pattern having a thickness shown in Table 14. Table 14 shows the results of the peeling test, the water resistance test, the tensile strength, and the elongation of this polyimide coating film.

Reference Example 49 Polyimide precursor (A1-
A photosensitive composition (W-49) was prepared in the same manner as in Reference Example 46 except that (31) was replaced with (A1-34). The composition had a viscosity of 44 poise and a coating film absorbance of 1.0. This composition was exposed to light having an exposure energy of 200 mJ / cm ^2.
A coating film having a thickness of 20 μm was obtained by treating in the same manner as in Reference Example 46 except that it was changed to 15 μm.
A sharp pattern with a resolution of m lines / spaces was obtained. This wafer was heat treated in the same manner as in Reference Example 46 to obtain a polyimide pattern having a thickness of 11 μm. This film has a stress of 8 kg / in both peeling test and water resistance test.
At the time of mm ² , the epoxy resin was broken and the adhesiveness and water resistance were good. The polyimide coating film had a tensile strength of 14 kg / mm ² and an elongation of 30%.

Reference Examples 50 and 51 50 g of polyimide precursors shown in Table 14, (I-5) 2 g, (M-5) 3
g, (S-3) 0.1 g, (S-9) 0.5 g, (F-
5) 1 g and (Z-4) 0.02 g were dissolved in N-methylpyrrolidone to prepare photosensitive compositions (W-50) and (W-5).
1) was prepared. Table 14 shows these viscosities and the absorbance of the coating film. Exposure energy of these compositions is set to W-5.
200 mJ / cm ² for 0, 500 for W-51
A sharp pattern was obtained by the same process as in Reference Example 5 except that mJ / cm ² was used. Table 14 shows the resolution. This wafer was heat-treated at 140 ° C. for 1 hour, 350 ° C. for 1 hour in a nitrogen atmosphere using an inert open, and a polyimide coating film peeling test, water resistance test results, film thickness, tensile strength, and elongation were obtained. It shows in Table 14.

(Reference Example 52) Polyimide precursor (A1-
A photosensitive composition (W-52) was prepared in the same manner as in Reference Example 46 except that (A1-37) was used instead of 31) and 80 g of N-methylpyrrolidone was used. The viscosity of this composition was 30 poise and the absorbance of the coating film was 1.2. This composition was treated in the same manner as in Reference Example 46 to obtain a coating film having a thickness of 13 μm, and the resolution after development was measured. As a result, a sharp pattern having a resolution of 10 μm lines / spaces was obtained.
This wafer was heat treated in the same manner as in Reference Example 46 to obtain a 7 μm thick polyimide pattern. In both the peeling test and the water resistance test, this film broke the epoxy resin at a stress of 8 kg / mm ² , and had good adhesive strength and water resistance. The tensile strength of this polyimide coating is 14
It was kg / mm ² and the elongation was 25%.

(Reference Examples 53 and 54) Photosensitive compositions (W-53) and (W-54) were prepared in the same manner as in Reference Example 6 except that 50 g of various polyimide precursors shown in Table 15 were used.
Was prepared. Table 15 shows the viscosities of these compositions and the absorbance of the coating films. These compositions were processed in the same manner as in Reference Example 6 to obtain a pattern resolution, the peeling test of the polyimide coating film after heat curing, the result of the water resistance test and the film thickness, the tensile strength, The elongation is shown in Table 15.

(Comparative Example 7) Polymer precursor (A1-8)
In place of (A1-38), a photosensitive composition (WR-7) was prepared in the same manner as in Reference Example 6. The composition had a viscosity of 60.2 poise and a coating film absorbance of 2.0.
Then, these compositions were treated as in Reference Example 6 to give 1
When a coating film of 2 μm was obtained and the resolution after development was measured,
Due to the strong inverted trapezoidal pattern cross-sectional shape, lines of lines / spaces flowed, which was a practical problem. From this wafer, a 7 μm thick polyimide pattern was obtained in the same manner as in Reference Example 6. This film broke at a stress of 5 kg / mm ² in the peel test and 3 kg in the water resistance test.
/ Mm ² or less. The tensile strength of this polyimide coating film was 14 kg / mm ^2, and the degree was 30%.

<Other Physical Property Tests> Various physical properties of the photosensitive composition and the polyimide coating film obtained therefrom were measured, and the results are shown in Tables 16 to 17. Measuring method,
The evaluation is as follows. (1) Storage stability test Photosensitive compositions (W-1) to (W-54) and (WR-1) to produced in Reference Examples 1 to 54 and Comparative Examples 1 to 6 respectively.
(WR-6) was kept in the open at 40 ° C. for 5 days. The thermal stability of the composition was examined by measuring the change in viscosity after holding and the ability to form a pattern.

Evaluation: No change in viscosity of ± 5% or more, application and pattern formation possible before holding ... Good (○) Viscosity change of up to ± 25% is recognized, but application is possible by changing the number of application rotations. , Pattern formation is possible ... No problem in practical use (△) Viscosity change exceeding ± 25% is observed, but coating is impossible ... Poor (×)

(2) Effect of long-term development Under the same conditions as in Reference Examples 1 to 54 and Comparative Examples 4 and 6, the photosensitive compositions (W-1) to (W-54), (WR-4) and (WR-4) and (WR-4) and (WR-1) were used. WR-6) was used for coating and exposure, and then 3 more than the development performed in Reference Examples 1 to 54 and Comparative Examples 4 and 6.
After development for a long time of 0%, a pattern was obtained by rinsing. Evaluation: A sharp pattern was obtained ・ ・ ・ Good (○) Slight pattern swelling ・ ・ ・ No practical problem (△) Slight swelling in exposed area, Melts and does not resolve ... Bad (×)

(3) Heat resistance test of polyimide coating film The polyimide films obtained in Reference Examples 1 to 28 and Comparative Example 3 were (i) placed in a solder bath at 280 ° C. for 20 seconds, and (ii) 300. 2 metal levers heated to ℃
The change of the film when pressed for 2 seconds was observed. Evaluation: (i) No change ··· Good (○) Shrinkage occurred, some swelling · No practical problems (△) Melting, Impossible to recover ・ ・ ・ ・ ・ ・ ・ ・ (Poor) (ii) No major change ・ ・ ・ ・ ・ ・ ・ ・ ・ Good (○) Marks are generated ・ ・ ・--- No problem in practical use (△) Holes are produced --- Poor (×)

(4) Elongation of Polyimide Film Reference Examples 8, 27, 28, 30 and 54, Comparative Examples 1 and 2
The polyimide films obtained in 1 and 7 were each held in boiling water for 48 hours and then dried in an oven at 50 ° C. for 2 hours, and the elongation of the film was measured. Reference examples 8 and 2
The elongation of the films from 7 and 28 after boiling is 90 each.
% Is 85%, 27% is 30%, 65% is 65%,
Almost no change in the elongation of the film in boiling water was observed. In each of Reference Examples 30 and 54, 10% is 5
%, 30% fell to 15%. Comparative Example 1 and 7
Then, 30% decreased to 22% and 30% decreased to 10%. In Comparative Example 2, 8% was 2% or less, and elongation could not be measured.

[0106]

[Table 1]

[0107]

[Table 2]

[0108]

[Table 3]

[0109]

[Table 4]

[0110]

[Table 5]

[0111]

[Table 6]

[0112]

[Table 7]

[0113]

[Table 8]

[0114]

[Table 9]

[0115]

[Table 10]

[0116]

[Table 11]

[0117]

[Table 12]

[0118]

[Table 13]

[0119]

[Table 14]

[0120]

[Table 15]

[0121]

[Table 16]

[0122]

[Table 17]

[0123]

According to the photosensitive composition of the present invention, it is possible to obtain a polyimide pattern with high resolution by an i-line exposure process which will be generalized in the photolithography process in the manufacture of semiconductor devices. Therefore, a polyimide coating film can be easily obtained without using a non-photosensitive polymer that uses a complicated and toxic substance as in the conventional case. In addition, the polyimide film obtained after heat conversion from the photosensitive composition of the present invention is excellent in water resistance and adhesion to a substrate.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display location G03F 7/027 514 7/031 H01L 21/027 21/312 B

Claims (3)

[Claims] 1. An aromatic polyimide precursor having (A) a repeating unit represented by the general formula (I) and having an amide bond concentration of 1.5 mol / kg or more, [Wherein X is an aromatic group containing no tetravalent fluorine atom or 2
~ Chemistry in which aromatic groups not containing 4 fluorine atoms are bonded via at least one bond selected from a single bond, an ether bond, a thioether bond, a carbonyl bond, a methylene bond, a sulfoxide bond and a sulfone bond. A tetravalent organic group having a structure, which is a -COR group or -CO
The R ′ group and the —CONH— group are in the ortho positions with respect to each other, and
And R'are independently -OR ₁ -NHR ₂ , -O ^- N ⁺ R
₃ R ₄ R ₅ R ₆ or —OH (provided that R ₁ , R ₂ and R
₃ are each independently and not necessarily one type, and an organic group having an ethylenically unsaturated bond in at least a part thereof, R ₄ , R
₅ and R ₆ are each hydrogen or a hydrocarbon group having 1 to 6 carbon atoms)
And at least a part of R or R ′ in the repeating unit.
Is a residue other than -OH, Y is a divalent aromatic group containing no fluorine atom or 2 to 6 aromatic groups each having a single bond, an ether bond, a thioether bond, a carbonyl bond, a methylene bond, 2, It is a divalent organic group containing no fluorine atom, having a chemical structure interconnected via at least one bond selected from 2-propylene bond, sulfoxide bond and sulfone bond] (B) Light In a photosensitive composition containing a polymerization initiator and a solvent (C), (iii-1) Y in the above aromatic polyimide precursor polymer.
Is represented by the general formula (II): (In the formula, R ₇ is an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and n is 0.
An integer of 3), and the absorbance at a wavelength of 365 nm of the film of the photosensitive composition formed after coating and drying the above-mentioned photosensitive composition is 10 μm per film thickness. A photosensitive composition which is 1.5 or less. 2. An aromatic group having 2 to 4 X's in the general formula (I) are linked to each other through at least one bond selected from a single bond, an ether bond, a carbonyl bond and a sulfone bond. 4. A tetravalent organic group having a chemical structure
The photosensitive composition of. 3. The following steps: (A) a step of applying a photosensitive composition containing an aromatic polyimide precursor (a), a photopolymerization initiator (b) and a solvent (c) to a substrate, (B) exposure process of coating film using i-line as a light source,
(C) a step of removing a non-exposed portion with a developing solution, and (D) a heat treatment step of the obtained pattern, wherein the photosensitive composition is a photosensitive composition according to claim 1 to form a polyimide pattern. Method.