JPH0540340A - Formation of polyimide pattern - Google Patents

Abstract

PURPOSE:To obtain such a pattern that the temp. of heat treatment to make imide rings can be decreased, the residual stress in pattern can be reduced and that the pattern has excellent mechanical characteristics even with low heat treatment temp. CONSTITUTION:A base material having a photosensitive layer containing a photopolymn. initiator and a photosensitive polyimide precursor having the recurring unit expressed by formula I is exposed to light to form images, developed and heat treated to form the polyimide pattern. In formula, X is a chemical structure of aromatic tetracarboxylic acid excluding carboxyl group, Y is a chemical structure of aromatic diamine excluding amino group, and R is an unsatd. compound residue having ethylenic linkage at the end.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polyimide patterning method using a polyimide precursor, which is suitable for manufacturing electronic materials such as semiconductor devices and multilayer wiring boards.

[0002]

2. Description of the Related Art As a photoresist used for manufacturing electronic parts such as IC and LSI, a photosensitive resin composition containing a photosensitive component such as a quinonediazide compound, a vinyl cinnamate, an acroyl compound and a cinnamylidene compound is widely used. Used recently, mechanical strength, heat resistance,
Due to their excellent physical properties such as thermal stability and processability, photoresists containing photosensitive polyimide as a photosensitive component have been receiving attention.

This photosensitive polyimide is generally prepared by photopolymerizing or photocrosslinking a polyimide precursor having photosensitivity, developing it to remove unexposed portions, and forming a pattern.
The imide is cyclized by heat treatment, and the precursor has a chemical structure in which a photosensitive group is bonded to polyamic acid by an ester bond or an ionic bond.

[0004]

However, this photosensitive polyimide tends to have a higher heat treatment temperature for imide cyclization than ordinary non-photosensitive polyimide because of the necessity of volatilizing the photosensitive group. Therefore, it is unsuitable when it is used as a photoresist in a field where the heat treatment temperature is limited such as aluminum wiring or compound semiconductor material, and when it is used as an interlayer insulating film of a multilayer wiring board. In order to reduce the thermal strain generated in the constituent body, it is better that the heat treatment temperature is lower, and therefore, a method of lowering the heat treatment temperature of the photosensitive polyimide has been demanded.

[0005]

As a result of various studies on lowering the heat treatment temperature of the photosensitive polyimide, the present inventors have used a photosensitive polyimide precursor having a specific chemical structure and initiated photopolymerization on it. It was found that the object can be achieved by adding a thermal polymerization initiator together with an agent and subjecting it to imide cyclization by heat treatment, and based on this finding, the present invention has been accomplished.

That is, the present invention has the general formula

[Chemical 2] (X in the formula represents the chemical structure of the aromatic tetracarboxylic acid excluding the carboxyl group, and Y represents the chemical structure of the aromatic diamine excluding the amino group.
Is an unsaturated compound residue having a terminal ethylene bond,
The two -CO-R groups in X are bound to the carbonyl group forming the amide group backbone in the ortho position), a photosensitive polyimide precursor having a repeating unit represented by the formula, a photopolymerization initiator, and thermal polymerization. A substrate having a photosensitive layer composed of a photosensitive resin composition containing an initiator as an essential component is subjected to imagewise exposure, and after development, heat treatment is performed to perform imide cyclization of the polyimide precursor. A method for patterning a polyimide is provided.

X in the general formula (I) represents a chemical structure obtained by removing four carboxyl groups from an aromatic tetracarboxylic acid. Here, the aromatic tetracarboxylic acid means an aromatic compound. An aromatic group, that is, a compound having a chemical structure in which a carboxyl group is directly bonded to a completely unsaturated carbocycle or heterocycle.

Examples of such an aromatic tetracarboxylic acid include those belonging to the following groups. (1) One composed of one monocyclic or condensed cyclic aromatic ring. For example, pyromellitic acid, 1,2,7,8-naphthalene tetracarboxylic acid, 1,2,8,9-anthracene tetracarboxylic acid, 2,3,5,6-pyridine tetracarboxylic acid, 2,3,6. 7-quinoline tetracarboxylic acid and the like.

(2) General formula

[Chemical 3] (X ₁ in the formula is —CH ₂ —, —CO—, —SO ₂ —, —
O -, - S- or -C _{(CF 3) 2} - a and, a is one represented by a 0 or 1). For example 3,3 ', 4
4'-diphenyltetracarboxylic acid, 3,3 ', 4
4'-diphenyl ether tetracarboxylic acid, 3,
3 ', 4,4'-benzophenone tetracarboxylic acid,
3,4,3 ', 4'-diphenylmethane tetracarboxylic acid, 3,3', 4,4'-diphenyl sulfoxide tetracarboxylic acid and the like.

Next, Y in the general formula (I) represents a chemical structure in which two amino groups are removed from the aromatic diamine. Here, the aromatic diamine is an aromatic diamine. It means a compound having a chemical structure in which an amino group is directly bonded to a carboxylic group, that is, a completely unsaturated carbocycle or heterocycle.

Examples of such aromatic diamines include those belonging to the following groups. (1) One composed of one monocyclic or condensed cyclic aromatic ring. For example, 1,4-phenylenediamine, 2,7-
Naphthalenediamine, 3,5-diaminopyridine, 5,
8-diaminoquinoline and the like.

(2) General formula

[Chemical 4] (Y ₁ in the formula is —CH ₂ —, —CO—, —SO ₂ —, —
O -, - S- or -C _{(CF 3) 2} - a and, b is one represented by a 0 or 1). For example 3,4 'or 4,4'-diaminodiphenyl, 3,4' or 4,4 '
-Diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfoxide, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 4,4 '
-Diaminodiphenyl sulfide, etc.

(3) General formula

[Chemical 5] (Y ₁ and b in the formula have the same meanings as described above). For example, 4,4'-bis (3 or 4-aminophenoxy) diphenyl sulfoxide, 4,4'-bis (3 or 4-aminophenoxy) diphenylmethane,
4,4'-bis (3 or 4-aminophenoxy) diphenyl ether, 4,4'-bis (3 or 4-aminophenoxy) diphenyl sulfide and the like.

(4) General formula

[Chemical 6] (Y ₁ and b in the formula have the same meanings as described above, and Z is —S
-, -O- or -NH-). For example, bis [2- (4-aminophenyl) -benzothiazolyl] oxide, bis [2- (4-aminophenyl)-
Benzimidazolyl] sulfoxide, bis [2- (4-
Aminophenyl) -benzoxazolyl] and the like.

(5) Others 1,3 or 1,4-bis (4-aminophenoxy) benzene, 1,4-di- (4-aminobenzoyloxy) butane, formula

[Chemical 7] Such as diamine. The aromatic ring in these aromatic tetracarboxylic acids and aromatic diamines may be further substituted with an alkyl group having 1 to 6 carbon atoms.

Next, R in the general formula (I) is an unsaturated compound residue having a terminal ethylene bond, and examples of such a residue include groups belonging to the following groups. (1) General formula

[Chemical 8] (R ₁ in the formula is a hydrocarbon group which may be interrupted by an oxygen atom or a nitrogen atom, R ₂ is a hydrogen atom or a methyl group, and d is 0 or 1). For example, allyloxy group, 2-acryloyloxyethyloxy group, 2-methacryloyloxypropyloxy group and the like.

(2) General formula

[Chemical 9] (R ₁ , R ₂ and d in the formula have the same meanings as described above). For example, 2-acryloyloxyethylamino group, 2-methacryloyloxyethylamino group, 2
-Acryloyloxypropylamino group and the like.

(3) General formula

[Chemical 10] (R ₁ , R ₂ and d in the formula have the same meanings as described above). For example, 2-hydroxy-3-methacryloyloxypropyloxy group, 2-hydroxy-3-acryloyloxypropyloxy group, 2-hydroxy-
4-pentenyloxy group and the like.

(4) General formula

[Chemical 11] (Wherein R ₁ , R ₂ and d have the same meanings as described above,
R ₃ , R ₄ and R ₅ are each a hydrogen atom or a carbon number of 1 to 4
Which is an alkyl group of). For example, 2-acryloyloxyethyl dimethyl ammonium group, 2
-Methacryloyloxypropyl / trimethylammonium group etc.

The photosensitive imide precursor having a repeating unit represented by the general formula (I) can be produced, for example, by the following method. (1) When R is a group represented by the general formula (VI), a tetracarboxylic acid dianhydride represented by the general formula (II) and a general formula

[Chemical formula 12] An alcohol represented by the formula (wherein R ₁ , R ₂ and d have the same meaning as described above) in an inert solvent, and then in the presence of a condensing agent such as thionyl chloride or dicyclohexylcarbodiimide, The general formula (III)
A photosensitive polyimide precursor is obtained by polycondensation with a diamine represented by Then, the condensing agent is removed from the reaction mixture thus obtained, and further subjected to ion exchange treatment to remove impurities, and then this is poured into water or alcohol to precipitate a precursor. The precipitate is separated by filtration, dried, dissolved in a required solvent, and necessary additives are added to prepare a photosensitive composition.

(2) When R is a group represented by the general formula (VII) The dianhydride of the tetracarboxylic acid represented by the general formula (II) and the diamine represented by the general formula (III) are not mixed with each other. A polyamic acid is produced by polycondensation in an active solvent, and then a polyamic acid of the general formula

[Chemical 13] An isocyanate represented by the formula (R ₁ , R ₂ and d have the same meaning as described above) is reacted to prepare a photosensitive polyimide precursor solution. Next, this solution is purified in the same manner as described above, and necessary additives are added to obtain a photosensitive composition.

(3) When R is a group represented by the general formula (VIII): The tetracarboxylic acid dianhydride represented by the general formula (II) and the diamine represented by the general formula (III) are not mixed with each other. A polyamic acid is prepared by polycondensation in an active solvent, which is

[Chemical 14] An epoxy compound represented by the formula (wherein R ₁ , R ₂ and d have the same meanings as described above) is reacted to prepare a photosensitive polyimide precursor solution. Next, this solution is purified in the same manner as described above, and necessary additives are added to obtain a photosensitive composition.

(4) When R is a group represented by the general formula (IX), the dianhydride of the tetracarboxylic acid represented by the general formula (II) and the diamine represented by the general formula (III) are not mixed with each other. A polyamic acid is produced by polycondensation in an active solvent, and then a salt having a fourth compound residue represented by the general formula (IX) is reacted with this to prepare a photosensitive polyimide precursor solution.

Next, this solution is purified in the same manner as described above, and necessary additives are added to obtain a photosensitive composition. The photopolymerization initiator of the photosensitive composition used in the method of the present invention,
For example, benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone,
Benzophenone derivatives such as dibenzyl ketone and fluorenone, acetophenone derivatives such as 2,2′-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, thioxanthone, 2-methylthioxanthone,
Thioxanthone derivatives such as 2-isopropylthioxanthone and diethylthioxanthone, benzyl derivatives such as benzyl, benzyldimethylketal and benzyl-β-methoxyethylacetal, benzoin derivatives such as benzoin and benzoin methyl ether, 2,6-di (4'-diazidobenzal) ) -4-Methylcyclohexanone, 2,6'-di (4'-diazidobenzal) cyclohexanone and other azides, 1-phenyl-1,2-butanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-propane Dione-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- (o-benzoyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl Sulfonyl-3-ethoxy - although oximes such as propane trione-2-(o-benzoyl) oxime is used, oximes in terms of photosensitivity are preferred. The addition amount of these photopolymerization initiators is preferably 1 to 15 parts by weight with respect to 100 parts by weight of the precursor polymer.

The thermal polymerization initiator contained in the photosensitive composition used in the method of the present invention is stable at the drying temperature after coating for forming a coating film and is efficient at the heat treatment temperature for imidization. Radicals that generate radicals are preferred, and in this respect, the 10-hour half-life temperature is 100 to
A thermal polymerization initiator in the range of 200 ° C is preferable. Examples of such thermal polymerization initiators include alkylazo compounds such as 2,2'-azobis (2,4,4-trimethylpentane) and 2,2'-azobis (2-methylpropane), cumene hydroperoxide, diisopropyl Benzene hydroperoxide, dicumyl peroxide, ter
t-Butyl cumyl peroxide, 1,3-di (tert)
Examples include organic peroxides such as -butylperoxyisopropyl) benzene.

The amount of these thermal polymerization initiators added is preferably in the range of 0.05 to 5 parts by weight with respect to 100 parts by weight of the precursor polymer. A compound having a reactive carbon-carbon double bond for improving photosensitivity can be added to the photosensitive composition used in the present invention. Examples of such compounds 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. , 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 precursor polymer.

Next, a sensitizer for improving photosensitivity can be added to the photosensitive composition used in the method of the present invention. Examples of such sensitizers include Michler's ketone, 4,4'-bis (diethylamino) benzophenone, 2,5-bis (4'-diethylaminobenzal) cyclopentane, and 2,6-bis (4'-diethylaminobenzene. Monkey) cyclohexanone, 2,6-bis (4'-dimethylaminobenzal) -4-methylcyclohexanone,
2,6-bis (4'-diethylaminobenzal) -4-
Methylcyclohexanone, 4,4'-bis (dimethylamino) chalcone, 4,4'-bis (diethylamino) chalcone, p-dimethylaminocinnamylideneindanone, p-dimethylaminobenzylideneindanone, 2-
(P-Dimethylaminophenylbiphenylene) -benzothiazole, 2- (p-dimethylaminophenylvinylene) benzothiazole, 2- (p-dimethylaminophenylvinylene) isonaphthothiazole, 1,3-bis (4'-dimethylamino) Benzal) acetone, 1,3-
Bis (4'-diethylaminobenzal) 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, N- p-tolyldiethanolamine, N-phenylethanolamine,
4-morpholinobenzophenone, dimethylaminobenzoic acid isoamyl, diethylaminobenzoic acid isoamyl, 2
-Mercaptobenzimidazole, 1-phenyl-5-
Examples thereof include mercapto-1H-tetrazole and 2-mercaptobenzothiazole. These alone or 2
It is used in a combination of 5 to 5 kinds, and the addition amount thereof is preferably 0.1 to 15 parts by weight with respect to 100 parts by weight of the precursor polymer.

Further, an adhesion aid may be added to the photosensitive composition used in the method of the present invention in order to improve the adhesion to the substrate. Examples of this adhesion aid include γ-aminopropyldimethoxysilane, N- (β-aminoethyl)
-Γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3- Piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N- (3-diethoxymethylsilylpropyl) succinimide, N- [3-
(Triethoxysilyl) propyl] phthalamic acid, benzophenone-3,3'-bis (N- [3-triethoxysilyl] propylamido) -4,4'-dicarboxylic acid, benzene-1,4-bis (N- [3-Triethoxysilyl] propylamido) -2,5-dicarboxylic acid or the like is used. The amount of these adhesion promoters added is preferably in the range of 0.5 to 10 parts by weight with respect to 100 parts by weight of the precursor polymer.

Further, a thermal polymerization inhibitor may be added to the photosensitive composition used in the method 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 and 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-phenylhydroxylamine ammonium salt, N-nitroso-
N (1-naphthyl) hydroxylamine ammonium salt or the like is used. The addition amount is preferably in the range of 0.005 to 5 parts by weight with respect to 100 parts by weight of the precursor polymer.

The solvent in the photosensitive composition used in the method of the present invention is preferably a polar solvent from the viewpoint of solubility,
For example, N, N'-dimethylformamide, N-methylpyrrolidone, N-acetyl-2-pyrrolidone, N, N'-
Dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α
-Acetyl-γ-butyrolactone and the like are used, and they can be used alone or in combination of two or more.

In the method of the present invention, the method for applying the photosensitive composition onto the substrate is, for example, a spin coater,
Bar coater, blade coater, curtain coater,
A method of applying with a screen printer or a method of spraying with a spray coater can be used. As the method for drying the coating film, methods such as air drying, heat drying using an oven or a hot plate, and vacuum drying are used.
The coating film thus obtained is exposed to X-rays or ultraviolet rays through a photomask or a stepper projection exposure apparatus. Among these, ultraviolet rays are preferable from the viewpoint of handleability, and a high pressure mercury lamp, an ultrahigh pressure mercury lamp, etc. are used as the light source, and the latter is preferable from the viewpoint of illuminance.

The developer used for the development is preferably a combination of a good solvent and a poor solvent for the above-mentioned polymer, and the good solvent includes N-methylpyrrolidone, N-acetyl-2-pyrrolidone, N, N. '-Dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc.
As the poor solvent, toluene, xylene, methanol, isopropyl alcohol, water or the like is used.
The ratio of the poor solvent to all the solvents is 1 to 50% (volume / volume), and several kinds of each solvent can be used in combination.

The developing method can be arbitrarily selected from conventionally used methods such as a spray method involving rotation, a paddle method, and a dipping method involving ultrasonic treatment. In the method of the present invention, it is necessary to subject the pattern thus obtained to a heat treatment for imide cyclization. This heat treatment can be performed using an oven, a tube furnace, a conveyor furnace, a hot plate, etc., and the heat treatment temperature is in the range of 250 to 500 ° C., especially 400
C. or less is preferable. At this time, if necessary, 100 to 25
Pre-heat treatment can also be performed at a temperature in the range of 0 ° C.

[0034]

The method of forming a polyimide pattern of the present invention has many advantages over the conventional prior art. That is, according to the method of the present invention, it is possible to lower the heat treatment temperature, thereby expanding the range of use in fields of application such as semiconductor protective films and multilayer wiring structure insulating films,
Since the temperature change during the heat treatment becomes smaller, the residual stress generated due to the difference in thermal expansion coefficient between the base material and the polyimide material after the heat treatment can be reduced. Furthermore, sufficient mechanical properties can be obtained even at a lower heat treatment temperature,
This mechanical property can be evaluated and used as a measure of film physical properties.

[0035]

The present invention will be described in more detail with reference to Reference Examples, Examples and Comparative Examples. Reference Example 1 In a 500 ml separable flask, 3, 3, ', 4,
4'-benzophenone tetracarboxylic acid anhydride 16.1
g, 10.9 g of pyromellitic dianhydride, 27.0 g of 2-hydroxyethyl methacrylate and 100 ml of γ-butyrolactone were charged, and 17.0 g of pyridine was added while stirring under ice cooling. 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, 19.0 g of 4,4′-diaminodiphenyl ether was added over 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 reaction solution in which the precipitate was filtered was added to 10 l of ethanol, and the generated precipitate was filtered and then dried in vacuum. This polymer is designated as P-1. The intrinsic viscosity of P-1 in N-methylpyrrolidone at 30 ° C. and 1 g / dl was 0.17.

Reference Example 2 A 500 ml separable flask was charged with 21.8 g of pyromellitic dianhydride, 27.0 g of 2-hydroxyethyl methacrylate and 100 ml of γ-butyrolactone, and 17.0 g of pyridine was stirred under ice cooling. added. After stirring for 16 hours at room temperature, γ-butyrolactone 4 containing 41.2 g of dicyclohexylcarbodiimide 4
0 ml of the solution was added over 30 minutes under ice cooling, followed by the formula

[Chemical 15] 39.0 g of a diamine having the structure of was added over 60 minutes.
Then, after stirring for 3 hours under ice cooling, 5m of ethanol
1 was added, and the mixture was stirred for 1 hour, and the reaction solution obtained by filtering the precipitate was added to 10 l of ethanol. The generated precipitate was filtered and then vacuum dried. This polymer is designated as P-2. P-2 in N-methylpyrrolidone at 30 ° C., 1 g /
The intrinsic viscosity in dl was 0.34.

Reference Example 3 In a 1 l separable flask, 3,3 ', 4,4'-
64.4 g of benzophenone tetracarboxylic acid anhydride and 462 ml of N, N'-dimethylacetamide (hereinafter referred to as DMAc) were added, 100 ml of DMAc containing 28.0 g of diaminomesitylene was added with stirring, and the mixture was stirred at room temperature for 16 hours and then cooled with ice, 31 g of 2-isocyanatoethyl methacrylate was added, and the mixture was stirred for 3 hours. This polymer is designated as P-3. The intrinsic viscosity of P-3 in N-methylpyrrolidone at 30 ° C and 1 g / dl is 0.
It was 24.

Reference Example 4 110 g of 4,4'-diaminodiphenyl ether was added to N
-Dissolved in 770 g of methylpyrrolidone, 120 g of pyromellitic anhydride was added, and the reaction was carried out for 6 hours. This solution 5
2.5 g of diethylaminoethyl methacrylate to 0 g
Was dissolved in 50 g of N-methylpyrrolidone. This polymer solution is designated as P-4. The intrinsic viscosity of P-4 in N-methylpyrrolidone at 30 ° C. and 1 g / dl was 0.32.

Reference Example 5 4,4'-Diamino-3,3 ', 5,5'-tetraethyldiaminomethane (86.2 g) was dissolved in 400 ml of N-methylpyrrolidone to prepare 3,3', 4,4'- 88.2 g of biphenyl tetracarboxylic acid dianhydride was added, and the mixture was stirred at room temperature for 12 hours. Next, 85.3 g of glycidyl methacrylate was added, and the mixture was stirred at 70 ° C. for 36 hours. This polymer solution is designated as P-5. The intrinsic viscosity of P-5 in N-methylpyrrolidone at 30 ° C. and 1 g / dl is 0.28.
Met. Examples will be shown below, and the abbreviations for each component in the examples mean the following.

(1) Photopolymerization Initiator Abbreviation Compound I-1 Benzophenone I-2 Benzyl I-3 2-Isopropylthioxanthone I-4 1,3-Diphenylpropanetrione-2- (O-Ethoxycarbonyloxime) I -5 1-phenyl-3-ethoxypropanetrione-2- (O-benzoyl) oxime

(2) Thermal Polymerization Initiator Symbol Compound T-1 2,2'-azobis (2,4,4-trimethylpentane) T-2 2,2'-azobis (2-methylpropane) T- 3 Diisopropylbenzene hydroperoxide T-4 tert-butylcumyl peroxide T-5 1,3-di (tert-butylperoxyisopropylbenzene)

(3) Compound Having Reactive Carbon-Carbon Double Bond Abbreviation Compound M-1 Tetraethylene glycol diacrylate M-2 Pentaerythritol diacrylate M-3 Methylene methylenebisacrylamide M-4 N-Methylolacrylamide M- 5 Trimethylolpropane triacrylate

(4) Sensitizer abbreviation compound S-1 3-acetyl-7-dimethylaminocoumarin S-2 3-ethoxycarbonyl-7-dimethylaminocoumarin S-3 3-benzyloxycarbonyl-7-dimethylamino Coumarin S-4 3-Methoxycarbonyl-7-diethylaminocoumarin S-5 3-Ethoxycarbonyl-7-diethylaminocoumarin S-6 N-phenyl-N'-ethylethanolamine S-7 N-phenyldiethanolamine S-8 N -P-tolyldiethanolamine S-9 N-phenylethanolamine S-10 4-morpholinobenzophenone S-11 2-mercaptobenzimidazole S-12 1-phenyl-5-mercapto-1H-tetrazole S-13 2-mercaptobenzone Zothiazole

(5) Adhesion aid Abbreviation Compound A-1 γ-glycidoxypropylmethyldimethoxysilane A-2 3-methacryloxypropyltrimethoxysilane A-3 3-methacryloxypropylmethyldimethoxysilane A-4 N -[3- (Triethoxysilyl) propyl] phthalamide acid A-5 Benzophenone-3,3'-bis [N- (3-triethoxysilyl) propylamide] -4,4'-dicarboxylic acid

(6) Thermal polymerization inhibitor abbreviation compound Z-1 N-nitrosodiphenylamine Z-2 bis (4-hydroxy-3,5-di-tert-butyl-phenyl) methane Z-3 2,6-di -Tert-butyl-p-methylphenol Z-4 2-nitroso-1-naphthol Z-5 N-nitroso-N-phenylhydroxylamine ammonium salt

Example 1 (P-1) 50 g, (I-1) 2 g, (T-1) 0.3
g, (M-1) 6g, (S-1) 0.2g, (S-6)
1g, (S-11) 1.5g, (A-1) 1g, (Z-
1) 0.05 g was dissolved in 100 g of N-methylpyrrolidone to obtain a composition varnish. This varnish was spin-coated on a 3 ″ silicon wafer and dried to obtain a coating film having a thickness of 20 μm.
300mJ / mm ^{2 with} 1F exposure machine (manufactured by Canon)
Exposure. Γ-butyrolactone / xylene [50/50 (vol / vol%)]
After spray development with the developing solution of No. 1 and rinsing with xylene, a sharp pattern was obtained. This wafer was placed in an inert oven at 140 ° C. under a nitrogen atmosphere.
Heat treatment was performed at 1 ° C. for 1 hour and 300 ° C. for 1 hour to obtain a polyimide pattern. Further, the residual stress obtained from the warp of the wafer which was processed in the same manner as above without using a photomask and without developing was 3.6 kg / mm ² , and the film was peeled from the wafer and the physical properties of the film were measured. Tensile strength 1
The value was 7 kg / mm ² and the elongation was 24%, which was a value that was not a problem in practical use.

Example 2 (P-2) 50 g, (I-2) 3 g, (T-2) 0.2
g, (M-2) 5g, (S-7) 0.5g, (S-1
2) 1g, (A-2) 1.5g, (Z-2) 1g N-
It was dissolved in 100 g of methylpyrrolidone to obtain a composition varnish. This varnish was spin-coated on a 3 ″ silicon wafer and dried to obtain a 20-micron-thick coating film. This coating film was passed through a reticle with a reduction projection stubber exposure machine NSR-1505G2A (manufactured by Nikon Corporation) to pass the g-line (436 nm). )
Exposure was performed with a light source at an energy of 500 mJ / mm ² . This wafer is treated with N-methylpyrrolidone / xylene / water [4
8/46/6 (vol / vol%)] of the developing solution, and after puddling with isopropyl alcohol, a sharp pattern was obtained. The wafer was baked at 200 ° C. for 10 minutes on a hot plate, and further heat-treated at 350 ° C. for 1 hour in a nitrogen atmosphere in a curing oven to obtain a polyimide pattern. The residual stress obtained from the warp of the wafer that was treated in the same manner as above without using the reticle and without development was 1.7 kg / mm ² , and when the film was peeled from the wafer and the film physical properties were measured, The strength was 20 kg / mm ² , and the elongation was 13%, which were values practically no problem.

Example 3 (P-3) 55.6 g, (I-3) 0.2 g, (T-
3) 0.04 g, (M-3) 0.8 g, (S-2) 0.
05g, (S-8) 0.3g, (S-13) 0.15
g, (A-3) 0.1 g, and (Z-3) 0.01 g were dissolved to obtain a composition varnish. This varnish was spin-coated on a 3 ″ silicon wafer and dried to obtain a 10-micron-thick coating film.
Exposure was performed with an energy of 600 mJ / mm ² by a 1F exposure machine (manufactured by Canon). This wafer was treated with N, N′-dimethylacetamide / ethanol [80/20 (vol /
After developing by spraying with a developing solution of [vol%)] and rinsing with isopropyl alcohol, a sharp pattern was obtained. This wafer was heat-treated in an inert oven at 140 ° C. for 1 hour and 300 ° C. for 1 hour to obtain a polyimide pattern. Further, the residual stress obtained from the warp of the wafer which was subjected to the same treatment as above without using a photomask and without development was 3.6 kg / mm ² , and the film was peeled from the wafer and the physical properties of the film were measured. The tensile strength was 15 kg / mm ² , and the elongation was 23%, which were values practically no problem.

Example 4 (P-4) 71.4 g, (I-4) 0.6 g, (T-
4) 0.015g, (M-4) 0.8g, (S-3)
0.05g, (S-9) 0.2g, (S-11) 0.1
g, (A-4) 0.1 g, and (Z-4) 0.01 g were dissolved to obtain a composition varnish. This varnish was spin-coated on a 3 ″ silicon wafer and dried to obtain a 10-micron-thick coating film.
Exposure was performed with an energy of 400 mJ / mm ² by a 1F exposure machine (manufactured by Canon). This wafer was treated with N, N′-dimethylacetamide / ethanol [80/20 (vol /
After developing by spraying with a developing solution of [vol%)] and rinsing with isopropyl alcohol, a sharp pattern was obtained. This wafer 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. The residual stress obtained from the warp of a wafer which was subjected to the same treatment as above without using a photomask and without development was 3.3 kg / m 2.
m ² and the film was peeled from the wafer and the film physical properties were measured. Tensile strength 14 kg / mm ² , elongation 21
%, Which is a value that is practically acceptable.

Example 5 (P-5) 21.7 g, (I-5) 0.4 g, (T-
5) 0.02 g, (M-5) 0.6 g, (S-4) 0.
03g, (S-10) 0.15g, (S-12) 0.2
g, (A-5) 0.3 g, (Z-5) 0.005 g and N-methylpyrrolidone 7.3 g were added and dissolved to obtain a composition varnish. This varnish was spin-coated on a 3 ″ silicon wafer and dried to obtain a 20-micron-thick coating film. A reduced projection stepper exposure machine NSR-1505G2A was applied to this coating film.
(Manufactured by Nikon Corporation), g-line (436
(nm) light source with an energy of 600 mJ / mm ² . Cyclohexanone / xylene / isopropyl alcohol [70/20/10 (vol / vo
1%)] and spray development followed by rinsing with isopropyl alcohol gave a sharp pattern. 200 this wafer with a hot plate
After baking at 10 ° C. for 10 minutes and further heat treatment at 250 ° C. for 1 hour in a nitrogen atmosphere using an inert oven, a polyimide pattern was obtained. The residual stress obtained from the warp of the wafer that was processed in the same manner as above without using the reticle and without development was 3.4 kg / mm ² , and when the film was peeled from the wafer and the film properties were measured, The strength was 13 kg / mm ² , and the elongation was 19%, which was a value that was not a problem in practical use.

Comparative Example 1 A film prepared by using the polymer (P-1) and using the same composition as in Example 1 except that (T-1) was not used was peeled from the wafer and the physical properties of the film were measured. , Tensile strength 11
It showed kg / mm ² and an elongation of 15%.

Comparative Example 2 A film prepared by using the polymer (P-2) and using the same composition as in Example 2 except that (T-2) was not used was peeled from the wafer and the physical properties of the film were measured. The physical properties of the film were such that the tensile strength was 7 kg / mm ² , and the elongation was 6%, which was not practical.

Comparative Example 3 The same composition as in Example 1 was used except that the polymer (P-1) was not used and (T-1) was not used. The heat treatment was carried out in an inert oven under a nitrogen atmosphere at 140 ° C. for 1 hour. The residual stress obtained from the warp of the wafer treated in the same manner as in Example 1 except that the temperature was changed to 400 ° C. for 1 hour was 4.2 kg / mm ² , and the film was peeled from the wafer to measure the film physical properties. The tensile strength was 22 kg / mm ² and the elongation was 26%.

Comparative Example 4 Polymer (P-2) was used, the same composition as in Example 2 was used except that (T-2) was not used, and the heat treatment conditions were baking on a hot plate at 200 ° C. for 10 minutes, followed by vertical type. The residual stress obtained from the warp of the wafer which was treated in the same manner as in Example 2 except that the temperature was changed to 450 ° C. for 1 hour in a curing furnace was 2.2 kg / mm ² , and the film was peeled from the wafer. Then, the physical properties of the film were measured, and the tensile strength was 2
It exhibited 7 kg / mm ² and an elongation of 10%.

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Claims (1)

[Claims] 1. A general formula: (X in the formula represents the chemical structure of the aromatic tetracarboxylic acid excluding the carboxyl group, and Y represents the chemical structure of the aromatic diamine excluding the amino group.
Is an unsaturated compound residue having a terminal ethylene bond,
The two -CO-R groups in X are bound to the carbonyl group forming the amide group backbone in the ortho position), a photosensitive polyimide precursor having a repeating unit represented by the formula, a photopolymerization initiator, and thermal polymerization. A substrate having a photosensitive layer composed of a photosensitive resin composition containing an initiator as an essential component is subjected to imagewise exposure, and after development, heat treatment is performed to perform imide cyclization of the polyimide precursor. A method for patterning a polyimide.