JP3261138B2 - Polyimide resin film for multi-layer wiring of semiconductor, interlayer insulating film or surface protection film, and semiconductor device using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor device having a multilayer wiring structure using a polyimide resin film which is suitable for an interlayer insulating film for a semiconductor multilayer wiring or a surface protective film.

[0002]

2. Description of the Related Art Conventionally, a polyimide resin has a higher flatness than an inorganic insulating film such as silicon dioxide formed by a chemical vapor deposition method or the like. Widely used for interlayer insulating films and surface protection films. Its usage is performed as follows. First, a circuit element is formed on a wafer, a glass plate, a metal, etc., and a solution of a polyamic acid, which is a precursor of a polyimide resin, is applied on a semiconductor substrate having a predetermined portion thereof exposed, and heat treatment is performed. Part or all of the acid is imidized. Next, a photoresist is formed in a desired pattern, and the photoresist is immersed in an etching solution to dissolve and remove unnecessary portions, and the photoresist is peeled. When the film is partially imidized and etched, heat treatment is performed again to completely cure the film. 2 to completely cure conventional polyimide resin
A temperature of 50 ° C. or higher is required.

However, in the case of an image sensor formed of a-Si (amorphous silicon) or a semiconductor substrate having a built-in compound semiconductor, an interlayer between an electrode material and a semiconductor element is prevented due to the prevention of reaction between the semiconductor element and the heat resistance of the semiconductor element itself. Since the formation temperature of the material used for the insulating film and the surface protection film needs to be about 250 ° C. or less, the conventional polyimide resin film is used in a heat treatment at 250 ° C. or less that does not completely imidize. Therefore, unreacted polyamic acid remains in the interlayer insulating film and the surface protective film, and there is a problem that the corrosion of the conductor layer is liable to occur and the moisture resistance reliability is poor.

As a method of completely curing at 250 ° C. or lower, polyimide which is completely imidized or polyamideimide which is partially imidized is dissolved in a polar solvent such as N-methylpyrrolidone or γ-butyllactone. These solutions are used, but in any case, etching is not possible after curing, or a special etching solution or etching step is required, which is not practical.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a polyimide resin film which can be completely cured at a temperature of 250 ° C. or less and can be subjected to wet etching. An object of the present invention is to provide an interlayer insulating film or a surface protective film for a multilayer wiring and a semiconductor device using the same and having excellent moisture resistance reliability.

[0006]

According to the present invention, a polyimide resin film for an interlayer insulating film or a surface protection film of a semiconductor multilayer wiring according to the present invention is represented by the following formula (a):

[0007]

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(Wherein, R ₁ represents a trivalent organic group obtained by removing a hydroxyl group from a compound having three hydroxyl groups in a molecule), and a hexacarboxylic trianhydride represented by the following formula: 3 to 35 mol%, and (b) Formula 2:

[0009]

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(Wherein n is an integer of 2 to 16) containing at least 50 mol% of the tetracarboxylic dianhydride and the total amount of the tetracarboxylic dianhydride as the carboxylic anhydride. A carboxylic anhydride containing 97 to 65 mol% with respect to: (c) Formula 3:

[0011]

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(Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen; an alkyl group selected from a methyl group, an ethyl group, an isopropyl group and a butyl group; A methoxy group, an ethoxy group and an alkoxy group selected from a butoxy group, wherein at least one of R ₁ , R ₂ , R ₃ and R ₄ is a group other than hydrogen; X is -CH ₂ -, -
_{C (CH 3) 2 -,} - C (CF 3) 2 -, - O -, - C (=
O) -, - shows a or -S- or a single bond) - SO ₂
An aromatic diamine, m-xylenediamine,
A solution containing a polyimide resin precursor obtained by reacting a diamine containing at least 0.5 mol% of a compound selected from 2,4-diaminotoluene or 2,6-diaminotoluene in an organic polar solvent. Is applied to a semiconductor substrate and subjected to a dehydration ring-closing reaction, and is a polyimide resin film for an interlayer insulating film for a semiconductor multilayer wiring or a surface protective film. Further, a polyimide-based resin film obtained by applying a solution containing the polyimide-based resin precursor described above to a semiconductor substrate and performing a dehydration ring-closing reaction is used as an interlayer insulating film or a surface protective film for semiconductor multilayer wiring. Semiconductor device.

(A) The hexacarboxylic acid trianhydride represented by the formula 1 can be obtained by reacting a compound having three hydroxyl groups with trimellitic anhydride chloride to form an ester bond. A compound having three hydroxyl groups as described above, and benzene (dimethylbenzoic acid chloride) having, as substituents, two methyl groups and one -CO-Cl group having ortho positions relative to each other, such as 3,4-dimethylbenzoic acid chloride. Is reacted to form an ester bond, and then the methyl group is oxidized to a carboxyl group and then dehydrated.

The hexacarboxylic acid trianhydride thus obtained is, for example, of the formula 1:

[0015]

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(Wherein, in the formula 1, R ₁ represents a trivalent organic group obtained by removing a hydroxyl group from a compound having three hydroxyl groups in the molecule).

The hexacarboxylic acid trianhydride of the present invention can be easily prepared from a compound having three hydroxyl groups in a molecule and trimellitic anhydride chloride in an organic solvent in the presence of a tertiary amine. It is preferable to obtain by reacting. Compounds having three hydroxyl groups in the molecule include glycerin, trimethylolethane, trimethylolpropane, 1,2,6-hexanetriol, 2,4-dihydroxy-3-hydroxymethylpentane, 2,6-bis (hydroxy Methyl) butan-3-ol, 3-methylpentane-1,3,5-triol, 1,3,5-trihydroxybenzene, 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene , 2,4
5-trihydroxybutylphenone, 2,3,4-trihydroxybenzaldehyde, 1,3,5-tris [1
-(4-hydroxyphenyl) isopropyl] benzene, 2,6-bis [(2-hydroxy-5-methylphenyl) methyl] -4-methylphenol, 2,3,4-
And trihydroxyacetophenone. It is preferable to use such a proportion that trimellitic anhydride chloride is 3 mol per 1 mol of the compound having three hydroxyl groups in the molecule. Examples of the organic solvent include benzene, toluene, xylene, tetrahydrofuran, 1,4-dioxane, diethyl ether, 1,2-dichloroethane, chlorobenzene, dichloromethane and the like, and two or more kinds may be used as a mixture. It is better to use the organic solvent dried with molecular sieves or the like. Examples of the tertiary amine include pyridine, triethylamine, and tributylamine, and two or more tertiary amines may be used in combination. The tertiary amine is preferably used in an amount equivalent to 1 to 2 times the amount of trimellitic anhydride chloride. The reaction temperature and the reaction time are not particularly limited, but are preferably 50 ° C. or lower and within 3 hours. If the reaction temperature and the reaction time are out of this range, an oligomer-like substance may be generated and the yield may be reduced.

The hexacarboxylic trianhydride thus obtained is represented by the formula 1

[0019]

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(Wherein, R ₁ represents a trivalent organic group obtained by removing a hydroxyl group from a compound having three hydroxyl groups in the molecule).

Specific examples of the hexacarboxylic trianhydride include 1,2,3-tris (trimellitic anhydride) glyceride, 1,1,1-tris (methyl trimellitate anhydride) propane, 1,1 , 1-tris (methyl trimellitate anhydride) ethane, and the like.

The hexacarboxylic acid trianhydride is used in an amount of 3 to 35 mol% based on the total amount of the acid anhydride.
It is preferable to use 30 mol%. If it is less than 3 mol%, the effect of crosslinking is small, and if it is more than 35 mol%, gelation occurs during the synthesis of the polyimide, and uniform varnish cannot be obtained. If the total amount of hexacarboxylic acid trianhydride is within the above range, two or more kinds may be used as a mixture.

(B) Examples of the acid dianhydride represented by the formula 2 include 1,2-bis (trimellitic anhydride) ethylene ester, 1,3-bis (trimellitic anhydride) trimethylene ester, 4-bis (trimellitic anhydride)
Tetramethylene ester, 1,5-bis (trimellitic anhydride) pentamethylene ester, 1,6-bis (trimellitic anhydride) hexamethylene ester, 1,8-bis (trimellitic anhydride) octamethylene ester,
There are 1,10-bis (trimellitic anhydride) decamethylene ester, 1,16-bis (trimellitic anhydride) hexadecamethylene ester and the like.
Two or more can be used in combination.

These are used at least 50 mol% in the tetracarboxylic dianhydride (b), preferably at least 50 mol% in the acid anhydride. If the amount of the acid dianhydride represented by the above formula (2) is too small, the curing temperature will increase.

(B) Examples of the tetracarboxylic dianhydride which may be used in combination with the acid dianhydride represented by the formula 2 include pyromellitic dianhydride, 3,3 ', 4,4'-diphenyltetracarboxylic acid Acid dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,2 ', 3,3'
Diphenyltetracarboxylic dianhydride, 2,2-bis (3,4, -dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9, 10-perylenetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5 8-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-
1,4,5,8-tetracarboxylic dianhydride, 2,7-
Dichloronaphthalene-1,4,5,8, tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8 , 9,10-tetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-
Dicarboxyphenyl) methane dianhydride, bis (3,4
-Dicarboxyphenyl) methane dianhydride, bis (3,
4-dicarboxyphenyl) sulfone dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,
4,3 ', 4'-benzophenonetetracarboxylic dianhydride, 2,3,2', 3'-benzophenonetetracarboxylic dianhydride, 2,3,3 ', 4'-benzonephenonetetracarboxylic acid Dianhydride, pyrazine-2,3,5
6-tetracarboxylic dianhydride, thiophene-2,3
4,5-tetracarboxylic dianhydride, ethylene tetracarboxylic dianhydride, decahydronaphthalene-1,4,4
5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-
1,2,5,6-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride,
Pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, bicyclo- [2,2,2] -oct (7) -ene-
2,3,5,6-tetracarboxylic dianhydride, 2,3
3 ', 4'-biphenyltetracarboxylic dianhydride,
3,4,3 ', 4'-biphenyltetracarboxylic dianhydride, 2,3,2', 3'-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride Product, bis (3,4-dicarboxyphenyl) methylphenylsilane dianhydride, bis (3,4
-Dicarboxyphenyl) diphenylsilane dianhydride,
Bis (2,3-dicarboxyphenyl) dimethylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenyl) ) -1,1,3,3-
Tetramethyldicyclohexane dianhydride, p-phenylbis (trimellitic acid monoester anhydride), 4,
4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 2,2-bis (2,3-dicarboxyphenyl) hexafluoropropane dianhydride,
2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis [4- (3
4-dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride, 1,4-bis (2-hydroxyhexafluoropropyl) benzenebistrimellitic dianhydride, 1,3-bis (2-hydroxyhexafluoropropyl) benzene Bistrimellitic dianhydride, (trifluoromethyl) pyromellitic dianhydride, bis (trifluoromethyl) pyromellitic dianhydride, 5,5 '
-Bis (trifluoromethyl) -3,3 ', 4,4'-
Biphenyltetracarboxylic dianhydride, 2,2 ', 5
5'-tetrakis (trifluoromethyl) -3,3 ',
4,4'-biphenyltetracarboxylic dianhydride, 5,
5'-bis (trifluoromethyl) -3,3 ', 4
4'-diphenylethertetracarboxylic dianhydride,
5,5'-bis (trifluoromethyl) -3,3 ',
4,4'-benzophenonetetracarboxylic dianhydride,
Bis {(trifluoromethyl) dicarboxyphenoxy} benzene dianhydride, bis (trifluoromethyl)
Dicarboxyphenoxy (biphenyl dianhydride, bis (trifluoromethyl) dicarboxyphenoxy)
(Trifluoromethyl) benzene dianhydride, bis {(trifluoromethyl) dicarboxyphenoxy} bis (trifluoromethyl) biphenyl dianhydride, bis {(trifluoromethyl) dicarboxyphenoxy} diphenyl ether dianhydride, bis ( Dicarboxyphenoxy)
(Trifluoromethyl) benzene dianhydride, bis (dicarboxyphenoxy) bis (trifluoromethyl) benzene dianhydride, bis (dicarboxyphenoxy) tetrakis (trifluoromethyl) benzene dianhydride, bis (dicarboxyphenoxy) Examples include bis (trifluoromethyl) biphenyl dianhydride and bis (dicarboxyphenoxy) tetrakis (trifluoromethyl) biphenyl dianhydride.

As the specific aromatic diamine, a diamine represented by the following formula 3 is preferably used.

[0027]

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In the formula 3, R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen, an alkyl group such as a methyl group, an ethyl group, an isopropyl group or a butyl group, a fluorine-substituted alkyl group, a methoxy group, ethoxy group, an alkoxy group or a halogen or butoxy group (chlorine, bromine, fluorine or iodine), at least one of R _1, R _2, R ₃ and R ₄
Number is a group other than hydrogen, X is, -CH ₂ -, - C
(CH ₃ ) _2- , -C (CF ₃ ) _2- , -O-, -C (=
O) -, - shows a or -S- or a bond - SO _2. In formula 3, at least one of R ₁ and R ₂ and at least one of R ₃ and R ₄ are particularly preferably a group other than hydrogen.

As the diamine represented by the formula 3,
3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminodiphenylmethane, 3,3'diethoxy-4 , 4'-diaminodiphenylmethane, 3,3'-difluoro-4,
4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'diaminodiphenylmethane, 3,3'-dibromo-4,4'-diaminodiphenylmethane, 3,3 '
-Di (trifluoromethyl) -4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenyl ether, 3,3'-diisopropyl-
4,4'-diaminodiphenyl ether, 3,3'-dimethoxy-4,4'-diaminodiphenyl ether,
3,3'-diethoxy-4,4'-diaminodiphenyl ether, 3,3'-difluoro-4,4'-diaminodiphenyl ether, 3,3'-dichloro-4,4'-
Diaminodiphenyl ether, 3,3'-dibromo-
4,4'-diaminodiphenyl ether, 3,3'-di (trifluoromethyl) -4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 3,3'-dimethoxy -4, 4 '
-Diaminodiphenyl sulfone, 3,3'-diethoxy-4,4'-diaminodiphenyl sulfone, 3,3'-
Difluoro-4,4'-diaminodiphenyl sulfone,
3,3'-dichloro-4,4'-diaminodiphenylsulfone, 3,3'-dibromo-4,4'-diaminodiphenylsulfone, 3,3'-di (trifluoromethyl)
-4,4'-diaminodiphenylsulfone, 3,3'-
Dimethyl-4,4'-diaminodiphenylpropane,
3,3'-dimethoxy-4,4'-diaminodiphenylpropane, 3,3'-diethoxy-4,4'-diaminodiphenylpropane, 3,3'-difluoro-4,4 '
-Diaminodiphenylpropane, 3,3'-dichloro-
4,4'-diaminodiphenylpropane, 3,3'-dibromo-4,4'-diaminodiphenylpropane,
3'-di (trifluoromethyl) -4,4'-diaminodiphenylpropane, 3,3'-dimethyl-4,4'diaminodiphenyl sulfide, 3,3'-dimethoxy-
4,4'-diaminodiphenyl sulfide, 3,3'-diethoxy-4,4'-diaminodiphenyl sulfide,
3,3'-difluoro-4,4'-diaminodiphenyl sulfide, 3,3'-dichloro-4,4'-diaminodiphenyl sulfide, 3,3'-dibromo-4,4 '
-Diaminodiphenyl sulfide, 3,3'-di (trifluoromethyl) -4,4'-diaminodiphenyl sulfide, 3,3'-dimethyl-4,4'-diaminodiphenylhexafluoropropane, 3,3'-dimethoxy -4,4'-diaminodiphenylhexafluoropropane, 3,3'-diethoxy-4,4'-diaminodiphenylhexafluoropropane, 3,3'-difluoro-
4,4'-diaminodiphenylhexafluoropropane, 3,3'-dichloro-4,4'-diaminodiphenylhexafluoropropane, 3,3'-dibromo-4,
4'-diaminodiphenylhexafluoropropane,
3,3'-di (trifluoromethyl) -4,4'-diaminodiphenylhexafluoropropane, 3,3'-dimethyl-4,4'-diaminobenzophenone, 3,3 '
-Dimethoxy-4,4'-diaminobenzophenone,
3,3'-diethoxy-4,4'-diaminobenzophenone, 3,3'-difluoro-4,4'-diaminobenzophenone, 3,3'-dichloro-4,4'-diaminobenzophenone, 3,3'- Dibromo-4,4'-diaminobenzophenone, 3,3'-di (trifluoromethyl) -4,4'-diaminobenzophenone, 3,3'-
Dimethylbenzidine, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3',
5,5'-tetraisopropyl-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetramethoxy-4,4'-diaminodiphenylmethane, 3,3',
5,5'-tetraethoxy-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetrafluoro-
4,4'-diaminodiphenylmethane, 3,3 ', 5
5'-tetrachloro-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetrabromo-4,4'-
Diaminodiphenylmethane, 3,3 ', 5,5'-tetra (trifluoromethyl) -4,4'-diaminodiphenylmethane, 3,3', 5,5'-tetramethyl-4,
4'-diaminodiphenyl ether, 3,3 ', 5
5'-tetraethyl-4,4'-diaminodiphenyl ether, 3,3 ', 5,5'-tetramethoxy-4,
4'-diaminodiphenyl ether, 3,3 ', 5
5'-tetraethoxy-4,4'-diaminodiphenyl ether, 3,3 ', 5,5'-tetrafluoro-4,
4'-diaminodiphenyl ether, 3,3 ', 5
5'-tetrachloro-4,4'-diaminodiphenyl ether, 3,3 ', 5,5'-tetrabromo-4,4'
-Diaminodiphenyl ether, 3,3 ', 5,5'-
Tetra (trifluoromethyl) -4,4'-diaminodiphenyl ether, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylsulfone, 3,3',
5,5'-tetramethoxy-4,4'-diaminodiphenylsulfone, 3,3 ', 5,5'-tetraethoxy-
4,4'-diaminodiphenyl sulfone, 3,3 ',
5,5'-tetrafluoro-4,4'-diaminodiphenylsulfone, 3,3 ', 5,5'-tetrachloro-
4,4'-diaminodiphenyl sulfone, 3,3 ',
5,5'-tetrabromo-4,4'-diaminodiphenylsulfone, 3,3 ', 5,5'-tetra (trifluoromethyl) -4,4'-diaminodiphenylsulfone,
3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylpropane, 3,3', 5,5'-tetramethoxy-4,4'-diaminodiphenylpropane,
3 ', 5,5'-tetraethoxy-4,4'-diaminodiphenylpropane, 3,3', 5,5'-tetrafluoro-4,4'-diaminodiphenylpropane, 3,
3 ', 5,5'-tetrachloro-4,4'-diaminodiphenylpropane, 3,3', 5,5'-tetrabromo-4,4'-diaminodiphenylpropane, 3,3 ',
5,5'-tetra (trifluoromethyl) -4,4'-
Diaminodiphenylpropane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylsulfide, 3,3', 5,5'-tetramethoxy-4,4'-
Diaminodiphenyl sulfide, 3,3 ', 5,5'-
Tetraethoxy-4,4'-diaminodiphenyl sulfide, 3,3 ', 5,5'-tetrafluoro-4,4'
-Diaminodiphenyl sulfide, 3,3 ', 5,5'
-Tetrachloro-4,4'-diaminodiphenyl sulfide, 3,3 ', 5,5'-tetrabromo-4,4'-
Diaminodiphenyl sulfide, 3,3 ', 5,5'-
Tetra (trifluoromethyl) -4,4'-diaminodiphenylsulfide, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylhexafluoropropane, 3,3', 5,5'- Tetramethoxy-4,4 '
-Diaminodiphenylhexafluoropropane, 3,
3 ', 5,5'-tetraethoxy-4,4'-diaminodiphenylhexafluoropropane, 3,3', 5
5'-tetrafluoro-4,4'-diaminodiphenylhexafluoropropane, 3,3 ', 5,5'-tetrachloro-4,4'-diaminodiphenylhexafluoropropane, 3,3', 5,5 ' -Tetrabromo-4,
4'-diaminodiphenylhexafluoropropane,
3,3 ', 5,5'-tetra (trifluoromethyl)-
4,4'-diaminodiphenylhexafluoropropane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminobenzophenone, 3,3', 5,5'-tetramethoxy-4,4'- Diaminobenzophenone, 3,
3 ', 5,5'-tetraethoxy-4,4'-diaminobenzophenone, 3,3', 5,5'-tetrafluoro-4,4'-diaminobenzophenone, 3,3 ', 5
5'-tetrachloro-4,4'-diaminobenzophenone, 3,3 ', 5,5'-tetrabromo-4,4'-diaminobenzophenone, 3,3', 5,5'-tetra (trifluoromethyl) -4,4'-diaminobenzophenone, 3,3 ', 5,5'-tetraisopropyl-
4,4'-diaminodiphenylmethane, 3,3'-diisopropyl-5,5'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diisopropyl-5
5'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-diisopropyl-5,5'-dimethyl-
4,4'-diaminodiphenyl ether, 3,3'-diisopropyl-5,5'-diethyl-4,4'-diaminodiphenyl ether, 3,3'-diisopropyl-
5,5'-dimethyl-4,4'-diaminodiphenylpropane, 3,3'-diisopropyl-5,5'-diethyl-4,4'-diaminodiphenylpropane, 3,3 '
-Diisopropyl-5,5'-dimethyl-4,4'-diaminodiphenylsulfone, 3,3'-diisopropyl-5,5'-diethyl-4,4'-diaminodiphenylsulfone, 3,3'-bis (tri Fluoromethyl) benzidine, 2,2′-bis (trifluoromethyl) -4,
4'-diaminodiphenyl ether, 3,3'-bis (trifluoromethyl) -4,4'-diaminodiphenyl ether, 3,3 ', 5,5'-tetrakis (trifluoromethyl) -4,4'-diaminodiphenyl ether , 3,3'-bis (trifluoromethyl) -4,4 '
-Diaminobenzophenone and the like, and two or more kinds may be used in combination.

Examples of the specific aromatic diamine other than the diamine represented by Formula 3 include m-xylenediamine, 2,4
-Diaminotoluene, 2,6-diaminotoluene and the like.

The amount of the specific aromatic diamine (c) used is 0.5 to 100 mol% based on the total amount of the diamine.
used. If the amount is less than 0.5 mol%, gelation occurs during the synthesis of polyimide, and uniform varnish cannot be obtained.

The diamine which may be used in combination with the specific aromatic diamine is 4- (4-aminophenyl) -3
-Aminobenzoic acid, 2,2-bis (4-aminophenyl) propane, 2,6-diaminopyridine, bis (4-
Aminophenyl) diethylsilane, bis- (4-aminophenyl) diphenylsilane, bis- (4-aminophenyl) ethylphosphine oxide, bis- (4-aminophenyl) -N-butylamine, bis- (4-aminophenyl) -N-methylamine, N- (3-aminophenyl) -4-aminobenzamide, 3,3'-diaminodiphenylmethane, 3,3'-diaminodiphenylether, 3,3'-diaminodiphenylsulfone, 3,
3'-diaminodiphenylpropane, 3,3'-diaminodiphenylsulfide, p-phenylenediamine, m
-Phenylenediamine, m-xylenediamine, 2,4
-Diaminotoluene, 2,6-diaminotoluene, 4,
4'-diaminodiphenylpropane, 4,4'-diaminodiphenylmethane, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylsulfide, 4,
4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,4-bis (β-amino-t-butyl) toluene, bis (p- β-
Amino-t-butyl-phenyl) ether, bis (p-
β-methyl-γ-amino-pentyl) benzene, bis-
p- (1,1-dimethyl-5-aminopentyl) benzene, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis {4- (2-aminophenoxy) phenyl} hexafluoropropane 2,2-bis {4- (3-aminophenoxy) phenyl} hexafluoropropane, 2,2-bis {4- (4-aminophenoxy) phenyl} hexafluoropropane, 2,2-bis (3-carbamoyl -4-aminophenyl) hexafluoropropane, 2,2-bis {4- (3-carbamoyl-4-aminophenoxy) phenyl} hexafluoropropane, 2,2-bis (3-sulfamoyl-4-aminophenyl) hexa Fluoropropane, 2,2-bis {4- (3-sulfamoyl-4-aminophenoxy)
Phenyl @ hexafluoropropane, 2,2-bis (3
-Carboxy-4-aminophenyl) hexafluoropropane, 2,2-bis {4- (3-carboxy-4-aminophenoxy) phenyl} hexafluoropropane,
Diamines having a perfluoroisopropyl residue such as 1,3-bis [2- {4- (4-aminophenoxy) phenyl} hexafluoroisopropyl] benzene can be mentioned, and p-bis (3-carboxy-4- Aminophenoxy) tetrafluorobenzene, 4,4'-bis (3-carboxy-4-aminophenoxy) octafluorobiphenyl, 4,4'-diaminooctafluorobiphenyl, 1,2-bis (3-carboxy-4-amino Phenyl) tetrafluoroethane, 1,3-bis (3-
(Carboxy-4-aminophenyl) hexafluoropropane, 1,5-bis (3carboxy-4-aminophenyl) decafluoropentane, diaminobenzotrifluoride, bis (trifluoromethyl) phenylenediamine, diaminotetra (trifluoromethyl) benzene,
Diamino (pentafluoroethyl) benzene, 2,2 '
-Bis (trifluoromethyl) benzidine, 2,2'-
Bis (trifluoromethyl) -4,4'-diaminodiphenyl ether, bis (aminophenoxy) di (trifluoromethyl) benzene, bis (aminophenoxy) tetrakis (trifluoromethyl) benzene, bis [(trifluoromethyl) aminophenoxy Benzene, bis [(trifluoromethyl) aminophenoxy] biphenyl, bis {[(trifluoromethyl) aminophenoxy] phenyl} hexafluoropropanehexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine , Tetramethylene diamine, propylene diamine, 3
-Methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 2,11-diaminododecane,
1,2-bis (3-aminopropoxy) ethane, 2,2
-Dimethylpropylenediamine, 3-methoxy-hexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,5-dimethylheptamethyldiamine, 5-
Methylnonamethylenediamine, 2,17-diaminoicosadecane, 1,4-diaminocyclohexane, 1,1
0-diamino-1,10-dimethyldecane, 1,12-
There are diaminooctadecane and the like, and two or more kinds may be used in combination. Among these diamines, aromatic diamines are preferred in terms of heat resistance.

If necessary, a diaminoamide compound or a diaminosulfonamide compound can be used as a part of the diamine. Examples of the diaminoamide compound or diaminosulfonamide compound include those represented by the following formulas 4, 5, 6, and 7.

[0034]

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[0035]

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[0036]

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[0037]

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In the formulas 4, 5, 6, and 7, Y represents SO ₂ or CO, and one amino group and Y—NH ₂ group are located at ortho positions to each other. Also,
In Formula 4, X means O, CH ₂ , SO ₂ , S or CO.

Specific examples of the diaminoamide compound include:
4,4'-diaminodiphenyl ether-3-sulfonamide, 3,4'-diaminodiphenyl ether-4-
Sulfonamide, 3,4'-diaminodiphenylether-3'-sulfonamide, 3,3'-diaminodiphenylether-4-sulfonamide, 4,4'-diaminodiphenylmethane-3-sulfonamide, 3,4'-
Diaminodiphenylmethane-4-sulfonamide, 3,
4'-diaminodiphenylmethane-3'-sulfonamide, 3,3'-diaminodiphenylmethane-4-sulfonamide, 4,4'-diaminodiphenylsulfon-3
-Sulfonamide, 3,4'-diaminodiphenylsulfone-4-sulfonamide, 3,4'-diaminodiphenylsulfone-3'-sulfonamide, 3,3'-diaminodiphenylsulfone-4-sulfonamide, 4,
4'-diaminodiphenylsulfide-3-sulfonamide, 3,4'-diaminodiphenylsulfide-
4-sulfonamide, 3,3'-diaminodiphenylsulfide-4-sulfonamide, 3,4'-diaminodiphenylsulfide-3'-sulfonamide, 1,
4-diaminobenzene-2-sulfonamide, 4,4 '
-Diaminodiphenyl ether-3-carbonamide,
3,4'-diaminodiphenyl ether-4-carbonamide, 3,4'-diaminodiphenyl ether-3 '
-Carbonamide, 3,3'-diaminodiphenylether-4-carbonamide, 4,4'-diaminodiphenylmethane-3-carbonamide, 3,4'-diaminodiphenylmethane-4-carbonamide, 3,4'-diaminodiphenylmethane -3'-carbonamide, 3,
3'-diaminodiphenylmethane-4-carbonamide, 4,4'-diaminodiphenylsulfone-3-carbonamide, 3,4'-diaminodiphenylsulfone-
4-carbonamide, 3,4'-diaminodiphenylsulfone-3'-carbonamide, 3,3'-diaminodiphenylsulfone-4-carbonamide, 4,4'-diaminodiphenylsulfide-3-carbonamide,
3,4'-diaminodiphenylsulfide-4-carbonamide, 3,3'-diaminodiphenylsulfide-4-carbonamide, 3,4'-diaminodiphenylsulfide-3'-sulfonamide, 1,4-diaminobenzene- 2-carbonamide and the like. Two or more of these diaminoamide compounds or diaminosulfonamide compounds can be used in combination.

The diaminoamide compound or diaminosulfonamide compound is used in an amount of 30 mol% or less in the diamine. If this is too large, the curing temperature will increase.

Further, diaminosiloxane may be used as a part of the diamine. As the diaminosiloxane, for example, those represented by the following formula 8 can be used.

[0042]

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Wherein R is a divalent hydrocarbon group;
R 'represents a monovalent hydrocarbon group, R and R' may be the same or different, and n is an integer of 1 or more.

Specific examples of the diaminosiloxane include those represented by the following formulas 9, 10, 11, and 12.

[0045]

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[0046]

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[0047]

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[0048]

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From the viewpoint of the adhesiveness of the polyimide resin to the surface of the semiconductor element and the heat resistance, it is preferable that diaminosiloxane be 0.1 to 50 mol% of the diamine component.

In order to obtain a precursor of a polyimide resin, the acid anhydride and the diamine (including the diaminoamide compound or diaminosiloxane added as necessary) are used in such a manner that they are substantially in equimolar or substantially equal amounts. It is obtained by reacting them.

This reaction is preferably performed in an organic solvent, such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-diethylformamide. An organic polar solvent such as dimethylsulfoxide and hexamethylphosphoramide is preferable because the precursor is easily dissolved, and an aromatic solvent such as toluene, cresol, and phenol is used to such an extent that the dissolution of the precursor is not hindered. The organic polar solvent may be used in combination with the organic polar solvent.

The above reaction is preferably carried out by dissolving the diamine in an organic solvent and then adding hexacarboxylic trianhydride and an acid dianhydride at a temperature of 80 ° C. or lower, preferably 0 to 50 ° C. As a result, a polyamic acid or a polyamic acid in which a part is dehydrated to form a ring and imidized (collectively referred to as “a precursor of a polyimide resin”) is obtained.

When the specific aromatic diamine is 0.5 to 50 mol%, especially 0.5 to 40 mol%, based on the total amount of the diamine, the acid dianhydride and the specific aromatic diamine are used. Reacting a diamine other than the aromatic diamine, and then reacting by adding the specific aromatic diamine,
Thereafter, it is preferable to react hexacarboxylic trianhydride. The specific aromatic diamine is added in an amount of 0.1 to the total amount of the diamine.
When 5 to 50 mol% is used, great care must be taken to prevent gelation during the reaction. However, according to the above method, the reaction can be easily performed without worrying about gelation.

The polyimide resin film of the present invention is obtained by heat-treating the precursor of the polyimide resin at a temperature of 150 to 250 ° C., preferably 180 to 230 ° C. to remove the solvent, and dehydrating and ring closing.

The semiconductor device according to the present invention uses the above-mentioned polyimide resin film as an interlayer insulating film for multilayer wiring or a surface protective film. An example of a manufacturing process of the semiconductor device will be described below.

FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure. In FIG. 1, a semiconductor substrate 1 such as a Si substrate, a glass plate, or a metal plate having a circuit element is covered with a protective film 2 such as a silicon oxide film except for a predetermined portion of the circuit element. One conductor layer 3 is formed. The above-mentioned polyamic acid is applied on the semiconductor substrate by a spinner method or the like, and the solvent is removed by heat treatment and the polyamic acid is dehydrated and closed to form a polyimide resin film as the interlayer insulating film 4 (step (a)). ).

Next, a cyclized rubber-based or phenol novolak-based photosensitive resin layer 5 is formed on the interlayer insulating film 4 by a spinner method, and a predetermined portion of the interlayer insulating film 4 is exposed by a known photolithography technique. Window 6A is provided as described above (step (b)).

The interlayer insulating film 4 of the window 6A is made of hydrazine,
The window 6B is selectively etched by a chemical etching means using an organic alkali solution such as a mixed solution of hydrazine and polyamine and a tetramethylammonium hydroxide solution as an etching solution. Next, the photosensitive resin layer 5 is completely removed by using an etching solution that does not corrode the first conductor layer 3 exposed from the window 6B but corrodes only the photosensitive resin layer 5 (step (c)).

Further, the second conductor layer 7 is formed by using a known metal film forming method and a photolithography technique, and the electrical connection with the first conductor layer 3 is completely performed (step (d)). When a multilayer wiring structure having three or more layers is formed, the above steps are repeated to form each layer. That is, a step (a) of forming an interlayer insulating film to be an insulating layer on the conductor layer, and a step (b) of selectively removing a predetermined portion of the coating and opening a window to expose a lower conductor layer. , (C) and step (d) of forming an upper conductor extending over the coating and connected to a predetermined portion of the lower conductor layer.

Next, a surface protection film 8 is formed. The protective film 8 is formed by applying the above-mentioned polyimide resin precursor on the uppermost conductive layer of a semiconductor device having a multilayer wiring structure in the same manner as the formation of the interlayer insulating film 4 to form a polyimide resin liquid. The window 6C is formed in the portion to be manufactured (step (e)). The conductor layer can be protected from external moisture, foreign matter, and the like by the surface protection film 8.

In the semiconductor device of the present invention, the polyimide resin film described above may be used for either interlayer insulation or surface protection of the semiconductor device, or for both interlayer insulation and surface protection of the semiconductor device. Good.

[0062]

EXAMPLES The present invention will be described below with reference to examples, but the scope of the present invention is not limited by these examples.

Example 1 254.0 g (1.00 mol) of 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane was placed in a four-necked flask equipped with a thermometer, a stirring device and a drying tube. ) And 2500 g of N, N-dimethylacetamide were added and stirred until a homogeneous solution was obtained. Cool the contents on ice, about 5 ° C
At a temperature of 1,4-bis (trimellitic anhydride) octamethylene ester 444.6 g (0.90 mol) and 1,1
2,3-tris (trimellitic anhydride) glyceride 5
4.2 g (0.10 mol) of the mixture were slowly added.
Thereafter, the reaction was carried out at 5 ° C. for 5 hours to obtain a polyamic acid solution.

This solution is spin-coated at 4000 rpm on the silicon oxide film 2 and the semiconductor substrate 1 of a glass plate using aluminum as the first conductor layer 3 in the step (a) of FIG. 1 in the oven
Heat treatment was performed at 30 to 140 ° C. for 30 minutes to form an interlayer insulating film layer 4. Next, in order to selectively remove only a predetermined portion of the insulating film layer 4, a phenol-volak resin-based photosensitive resin (positive photoresist, AZ-1350J, manufactured by Hoechst) layer 5 is provided on the layer 4. After forming by spinning at 3000 rpm and exposing by a known photographic etching technique,
Tetramethylammonium hydroxide aqueous solution developer (N
The resist was developed with MD-3 (manufactured by Tokyo Ohka Kogyo Co., Ltd.), and this solution was used as an etching solution at 25 ° C. for 2 minutes to selectively etch the insulating film layer 4 to form a window 6B. And the first conductor layer 3 was exposed at this portion. Thereafter, the photosensitive resin layer 5 was completely removed by immersion treatment at room temperature for 2 minutes using a resist stripping solution (acetone) that etches only the photosensitive resin layer 5 without corroding the first conductor layer 3.

Next, the interlayer insulating film layer 4 is subjected to
By treating at 0 ° C. for 60 minutes, a completely cured polyimide resin film having a thickness of about 3 μm was obtained. Further, the second aluminum is formed by using a known vacuum deposition method, a sputtering method and a photolithography technique.
The conductor layer 7 was formed, and the electrical connection with the first conductor layer 3 was completed. Further, on the obtained multilayer wiring structure, a polyamic acid solution was spin-coated on the second conductor layer 7 at a rotation speed of 4000 rpm, and a surface protective film layer 8 was formed in the same manner as the formation of the interlayer insulating film layer 4. Then, a semiconductor device was manufactured. The second conductor layer 7 is not exposed because the surface protective film layer 8 is not subjected to the window opening (selective etching of the polyimide resin film) as shown in step (e) of FIG. Further, the semiconductor substrate is not sealed (packaged) thereafter.

Example 2 In Example 1, tetracarboxylic dianhydride was added to 1,10
-Bis (trimellitic anhydride) decamethylene ester 3
A polyamic acid solution was synthesized in the same manner as in Example 1, except that the mixture was changed to a mixture of 13.2 g (0.60 mol) and 65.4 g (0.30 mol) of pyromellitic dianhydride. Heat treatment 2 after etching of polyimide resin
A semiconductor device was manufactured by forming an interlayer insulating film and a surface protective film in the same manner as in Example 1 except that the temperature was changed from 60 minutes at 30 ° C. to 60 minutes at 250 ° C.

Comparative Example 1 A polyamic acid solution was synthesized in the same manner as in Example 2 except that only 196.2 g (0.90 mol) of pyromellitic dianhydride was used as the acid dianhydride. Using this, a semiconductor device was manufactured.

Example 3 180.0 g of 4,4'-diaminodiphenyl ether was placed in a four-necked flask equipped with a thermometer, a stirring device and a drying tube.
(0.90 mol) and N-methyl-2-pyrrolidone 20
Add 00 g and stir until a homogeneous solution is obtained. The content was ice-cooled, and 369.0 g (0.90 mol) of 1,2-bis (trimellitic anhydride) ethylene ester was gradually added at a temperature of about 5 ° C. After reacting at 5 ° C. for about 2 hours, 22.6 g (0.10 mol) of 3,3′-dimethyl-4,4′-diaminodiphenylmethane was added at room temperature, and the mixture was stirred for 30 minutes. 44.9 g (0.07 mol) ethane (methyl trimellitate) ethane
Was added and stirred at room temperature for 3 hours to obtain a polyamic acid solution. Using this, a semiconductor device was manufactured in the same manner as in Example 1.

Comparative Example 2 200.0 g of 4,4'-diaminodiphenyl ether was placed in a four-necked flask equipped with a thermometer, a stirring device and a drying tube.
(1.00 mol), and N-methyl-2-pyrrolidone 2
000 g was added and stirred until a homogeneous solution was obtained. The contents were cooled on ice and, at a temperature of about 5 ° C., 369.0 g (0.90 mol) of 1,2-bis (trimellitic anhydride) ethylene ester and 1,1,1-tris (methyl trimellitate anhydride) A mixture of 44.9 g (0.07 mol) of ethane was slowly added. Gelation occurred about 10 minutes after the addition was completed.

Example 4 79.2 g of 4,4'-diaminodiphenylmethane was placed in a four-necked flask equipped with a thermometer, a stirring device and a drying tube.
(0.40 mol), 186.0 g of 3,3 ', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane
(0.60 mol) and N, N-dimethylacetamide 2
500 g was added and stirred until a homogeneous solution was obtained. The contents were cooled on ice and 469.8 g of 1,10-bis (trimellitic anhydride) decamethylene ester (0.
90 mol) and 45.9 g (0.07 mol) of 1,1,1-tris (methyl trimellitate anhydride) propane were gradually added. Thereafter, the reaction was carried out at 5 ° C. for 5 hours to obtain a polyamic acid solution. Using this, a semiconductor device was manufactured in the same manner as in Example 1.

Comparative Example 3 In Example 4, 522.0 g (1.00 mol) of 1,10-bis (trimellitic anhydride) decamethylene ester, which is an acid dianhydride, was used without using an acid trianhydride. A polyamic acid solution was synthesized in the same manner as in Example 4 except that it was used, and a semiconductor device was manufactured using the same. However, when a peeling solution (acetone) for the photosensitive resin layer 5 was used, a crack was formed on the interlayer insulating layer 4. There has occurred.

Test Example 1 A moisture resistance test was performed using the semiconductor devices manufactured in Examples 1 to 4 and Comparative Example 1 as samples. In this test, the sample was 121
The sample was allowed to stand at a temperature of 2 ° C. and a vapor pressure of 2 atm, and the progress of corrosion of the aluminum wiring layer as a conductor layer was observed for each sample with a microscope over time. Table 1 shows the results.

[0073]

[Table 1]

In Table 1, the progress of the corrosion was evaluated as follows. A: There was no corrosion of the aluminum wiring in the semiconductor device. B: Corrosion was about 5 to 10%. C: Corrosion was about 30 to 50%. D: Corrosion was observed throughout the semiconductor device. E: The aluminum wiring layer was dissolved.

These results indicate that the semiconductor devices of the present invention in Examples 1 to 4 have better moisture resistance than the semiconductor device of Comparative Example 1.

The polyamic acid used in Examples 1 to 4 was completely imidized at 230 to 250 ° C. to form a polyimide resin film. The polyamic acid used in Comparative Example 1 was heat-treated at 250 ° C. Shows that imidization is not completely performed, and unreacted polyamic acid remains.

When the polyimide resin used in Comparative Example 1 was heat-treated at 350 ° C. using a semiconductor substrate such as a Si wafer of a monolithic IC, the moisture resistance of the semiconductor substrate was determined in Examples 1-4. The results were almost the same.

Further, in Examples 1 to 4, a uniform polyamic acid solution was obtained, whereas in Comparative Example 2 (without using a specific aromatic diamine), gelling occurred, and a uniform varnish was not obtained. Further, Examples 1 to 4 are more excellent in solvent resistance than Comparative Example 3 (without using hexacarboxylic trianhydride).

Example 5 246,4 g (0.97 mol) of 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane was placed in a four-necked flask equipped with a thermometer, a stirring device and a drying tube. ),
1,3-bis (3-aminopropyl) -1,1,3,3
-7.5 g (0.03 mol) of tetramethyldisiloxane
And 2500 g of N, N-dimethylacetamide were added and stirred until a homogeneous solution was obtained. Cool the contents with ice, and
444.6 g (0.90 mol) of 1,8-bis (trimellitic anhydride) octane ester and 1,2,3
-Tris (trimellitic anhydride) triglyceride 54.
2 g (0.10 mol) of the mixture were added slowly. Thereafter, the reaction was performed at 5 ° C. for 5 hours to obtain a silicon polyamic acid type intermediate solution. Using this, a semiconductor device was manufactured in the same manner as in Example 1.

Example 6 In Example 5, 313.2 g of 1,10-bis (trimellitic anhydride) decamethylene ester was used as the acid dianhydride.
(0.60 mol) and 65.4 g of pyromellitic dianhydride
(0.30 mol), except that the mixture was synthesized in the same manner as in Example 1 except that the mixture was changed to a mixture of (0.30 mol).
Using this, an interlayer insulating film and a surface protection film were formed in the same manner as in Example 1 except that the heat treatment after the etching treatment of the polyimide resin was changed from 230 ° C. for 60 minutes to 250 ° C. for 60 minutes. The device was made.

Comparative Example 4 The same procedure as in Example 6 was repeated except that only 196.2 g (0.90 mol) of pyromellitic dianhydride was used as the acid dianhydride. Was synthesized, and a semiconductor device was fabricated using the same as in Example 1.

Example 7 In Example 5, the diaminosiloxane 1,3-
A polyamic acid solution was synthesized using the same diamine and acid dianhydride as in Example 5, except that bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane was not used. Using this, an interlayer insulating film and a surface protection film were formed in the same manner as in Example 1 to fabricate a semiconductor device.

Example 8 174.0 g of 4,4'-diaminodiphenyl ether was placed in a four-necked flask equipped with a thermometer, a stirring device and a drying tube.
(0.87 mol), 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane7.
5 g (0.03 mol) and 2000 g of N-methyl-2-pyrrolidone were added and stirred until a homogeneous solution was obtained. The content was cooled on ice and 369.0 g (0.90 g) of 1,2-bis (trimellitic anhydride) ethylene ester was added at a temperature of about 5 ° C.
Mol) was added slowly. After reacting at 5 ° C. for about 2 hours, 22.6 g (0.10 mol) of 3,3′-dimethyl-4,4′-diaminodiphenylmethane was added at room temperature, and the mixture was stirred for 30 minutes. 44.9 g (0.07 mol) of (methyl trimellitate) ethane was added, and the mixture was stirred at room temperature for 3 hours to obtain a polyamic acid solution. Using this, a semiconductor device was manufactured in the same manner as in Example 1.

Comparative Example 5 194.0 g of 4,4'-diaminodiphenyl ether was placed in a four-necked flask equipped with a thermometer, a stirring device and a drying tube.
(0.97 mol), 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane7.
5 g (0.03 mol) and 2000 g of N-methyl-2-pyrrolidone were added and stirred until a homogeneous solution was obtained. The content was cooled on ice and 369.0 g (0.90 g) of 1,2-bis (trimellitic anhydride) ethylene ester was added at a temperature of about 5 ° C.
Mol) and 44.9 g (0.07 mol) of 1,1,1-tris (methyl trimellitate anhydride) ethane. Gelation occurred about 10 minutes after the addition was completed.

Example 9 73.3 g of 4,4'-diaminodiphenylmethane was placed in a four-necked flask equipped with a thermometer, a stirring device and a drying tube.
(0.37 mol), 3,3'5,5'-tetraethyl-
186.0 g of 4,4'-diaminodiphenylmethane
(0.60 mol) 1,3-bis (3-aminopropyl)
7.5 g of -1,1,3,3-tetramethyldisiloxane
(0.03 mol) and N, N-dimethylacetamide 2
500 g was added and stirred until a homogeneous solution was obtained. The contents were cooled on ice and 469.8 g of 1,10-bis (trimellitic anhydride) decamethylene ester (0.
90 mol) and 45.9 g (0.07 mol) of 1,1,1-tris (methyl trimellitate anhydride) propane were gradually added. Thereafter, the reaction was carried out at 5 ° C. for 5 hours to obtain a polyamic acid solution. Using this, a semiconductor device was manufactured in the same manner as in Example 1.

Comparative Example 6 In Example 8, 522.0 g (1.00 mol) of 1,10-bis (trimellitic anhydride) decamethylene ester, which is an acid dianhydride, was used without using an acid trianhydride. A polyamic acid solution was synthesized in the same manner as in Example 4 except that it was used, and a semiconductor device was manufactured using the same. However, when a peeling solution (acetone) for the photosensitive resin layer 5 was used, a crack was formed on the interlayer insulating layer 4. There has occurred.

Test Example 2 Using the semiconductor devices manufactured in Examples 5 to 9 and Comparative Example 4, samples were subjected to a moisture resistance test by two methods. One was a moisture resistance adhesion test by a grid test, and the other was a corrosion resistance test of an aluminum wiring layer as a conductor layer under a moisture resistance test.

The cross-cut test was carried out in accordance with JIS K 5400. A knife was used to make a 1 mm-long scratch from the surface of the polyimide resin film to the surface of the semiconductor substrate at intervals of 1 mm from the surface of the polyimide resin film.
I made 100 squares at the corner. Next, a cellophane tape (manufactured by Sekisui Chemical Co., Ltd.) is closely adhered to the surface of the polyimide resin film on which the grids are formed, and then the cellophane tape is peeled off at a stretch, and the grid-like polyimide remaining on the semiconductor substrate is removed. The number of resin films was counted. If the adhesive strength between the polyimide resin film and the semiconductor substrate is weak, the polyimide resin film is peeled off from the semiconductor substrate with the polyimide resin film adhered to the cellophane tape. The test was conducted at the initial stage and the moisture resistance test (121 ° C,
(Leaving at a vapor pressure of 2 atm)).

For the corrosion resistance, the manufactured semiconductor device was left under a humidity resistance test (121 ° C., vapor pressure 2 atm), and the progress of corrosion of the aluminum wiring layer as a conductor layer was shown in Table 2 for each semiconductor device. The observation was performed with a microscope every time.

Table 2 shows the results of the moisture resistance and corrosion resistance tests.
Shown in

[0091]

[Table 2]

The evaluation methods in Table 2 are as follows. Moisture resistance The number (n / 100) remaining in a grid test. Corrosion resistance The degree of corrosion was indicated in stages A to E. A: There was no corrosion of the aluminum wiring in the semiconductor device. B: Corrosion was about 5 to 10%. C: Corrosion was about 30 to 50%. D: Corrosion was observed throughout the semiconductor device. E: The aluminum wiring layer was dissolved.

These results show that the semiconductor devices of the present invention in Examples 5 to 9 have better humidity resistance reliability than the semiconductor device of Comparative Example 4. This is because the polyamic acid silicon type intermediate used in Examples 5 to 9 is 23
Although the polyimide-based resin film is formed completely by imidization at 0 to 250 ° C., the polyamide silicon type intermediate used in Comparative Example 4 is not completely imidized by heat treatment at 250 ° C., and unreacted polyamide Indicates that the acid remains. The polyimide resin used in Comparative Example 4 was used for a semiconductor substrate such as a Si wafer of a monolithic IC.
When heat treatment was performed at 50 ° C., the moisture resistance of the semiconductor substrate was almost the same as the result of Example 1.

The polyamide acid used in Example 7 has a lower moisture resistance adhesive strength than that of Examples 5 to 6 and 8 to 9 after 100 hours or more passed under a humidity test (121 ° C., 2 atm). It also shows that the corrosiveness is slightly inferior.

In Examples 5 to 9, a uniform polyamic acid solution was obtained, whereas in Comparative Example 5 (without the use of a specific aromatic diamine), a gel was formed and a uniform varnish was not obtained. Further, Examples 5 to 9 are more excellent in solvent resistance than Comparative Example 6 (without using hexacarboxylic trianhydride).

In the above embodiments, aluminum is used as the conductor layer of the semiconductor device. However, the present invention is not limited to aluminum.

[0097]

The composition according to claim 1 has a temperature of 250 ° C.
A polyimide resin film that can be completely cured by the following heat treatment and that can be wet-etched is obtained.

The semiconductor device according to claim 2 can have a highly reliable multi-layer wiring structure having excellent moisture resistance, and a semiconductor substrate in which a compound semiconductor such as Si, Ga, As or the like of a monolithic IC or LSI is built. It can be applied to

[Brief description of the drawings]

FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Semiconductor substrate 2 ... Protective film 3 ... First conductor layer 4 ... Interlayer insulating film 5 ... Photosensitive resin layer 6A, 6B, 6C ... Window 7 ... Second conductor layer 8 ... Surface protective film layer

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Shinji Takeda 48th Wadai, Tsukuba, Ibaraki Prefecture Hitachi Chemical Co., Ltd.Tsukuba Development Laboratory Co., Ltd. (56) References JP-A-4-261430 (JP, A) JP-A-3-59034 (JP, A) JP-A-3-59031 (JP, A) JP-A-2-138341 ( JP, A) JP-A-3-140328 (JP, A) JP-A-48-7116 (JP, A) JP-A-58-162637 (JP, A) JP-A-58-162658 (JP, A) 50-50362 (JP, A) JP-A-3-58982 (JP, A) JP-A-3-75727 (JP, A) JP-A-3-145751 (JP, A) JP-A-3-1455753 (JP , A) (58) Field surveyed (Int.Cl. ⁷ , DB name) H01L 21/312 C 08G 73/10 H01L 21/768

Claims (2)

(57) [Claims] (A) Formula 1: embedded image (Wherein, R ₁ represents a trivalent organic group obtained by removing a hydroxyl group from a compound having three hydroxyl groups in a molecule), with respect to the total amount of the carboxylic anhydride.
３５35 mol%, and (b) Formula 2: (Wherein, n represents an integer of 2 to 16) containing at least 50 mol% of the tetracarboxylic dianhydride represented by the formula (1), wherein the tetracarboxylic dianhydride is based on the total amount of the carboxylic anhydride. A carboxylic anhydride containing 97 to 65 mol%; (c) Formula 3: (Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen; an alkyl group selected from a methyl group, an ethyl group, an isopropyl group and a butyl group; wherein hydrogen of the alkyl group is substituted with fluorine. A fluorine-substituted alkyl group; or an alkoxy group selected from a methoxy group, an ethoxy group and a butoxy group, wherein at least one of R ₁ , R ₂ , R ₃ and R ₄ is a group other than hydrogen; CH ₂ —, —C (CH ₃ ) ₂ —, —C (CF ₃ )
_{2 -, - O -, -} C (= O) -, - SO 2 - or -S
An aromatic diamine represented by the formula:
-Containing a polyimide resin precursor obtained by reacting a diamine containing at least 0.5 mol% of a compound selected from xylene diamine, 2,4-diaminotoluene or 2,6-diaminotoluene in an organic polar solvent A polyimide-based resin film for an interlayer insulating film for semiconductor multilayer wiring or a surface protective film obtained by applying the resulting solution to a semiconductor substrate and subjecting it to a dehydration ring-closing reaction. 2. A solution containing the polyimide-based resin precursor according to claim 1, applied to a semiconductor substrate, and a polyimide-based resin film obtained by a dehydration and ring-closing reaction is applied to a semiconductor interlayer insulating film for multilayer wiring or A semiconductor device used as a surface protective film.