JPH1124257A - Photosensitive polyimide precursor composition and pattern forming method by using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the photosensitive polyimide precursor composition and the pattern forming method superior in photosensitive characteristics to (i) line and capable of obtaining a pattern good in pattern forms in even low quantity of exposed light and superior in storage stability and also in hardened film characteristics. SOLUTION: This photosensitive polyimide precursor composition contains the photosensitive polyimide precursor having structural units each represented by the formula (in which R<1> is a tetravalent organic group; R<2> is a photosensitive group; each of R<3> -R<6> is, independently, an H atom or a univalent organic group and at least 2 of them is a univalent organic group), and a titanocene compound, and a dye compound having an absorption of 450-600 nm, and the pattern is formed by irradiating a coat film formed by using the photosensitive polyimide precursor composition through a prescribed pattern mask with light of (i) line and developing this coat film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive polyimide precursor composition and a method for producing a pattern suitable as a material for a protective film such as a surface coat film of a semiconductor element and an interlayer insulating film of a thin film multilayer wiring board.

[0002]

2. Description of the Related Art Polyimide or a precursor thereof which also has photopatterning properties by itself is called photosensitive polyimide, and is used for a surface protective film of a semiconductor or the like. Several photosensitive methods are known for photosensitive polyimide. A typical example is Japanese Patent Publication No. 55-4
No. 1422, which is an ester of a polyamic acid with hydroxyacrylate, or a compound such as an amino acrylate which is mixed with a polyamic acid proposed in Japanese Patent Application Laid-Open No. 54-145794. It is known to introduce a photosensitive group through a salt bond. These materials have a drawback in that the sensitivity of the film formed by spin coating or the like is lower than that of a conventional ultraviolet curable paint or dry film resist because the polyamic acid itself is rigid.

In recent years, along with the high integration of semiconductors,
Processing rules tend to become smaller and smaller. For this reason, a 1: 1 projection exposure machine called mirror projection and a reduced projection exposure machine called a stepper have been used instead of the conventional contact / proximity exposure machine using parallel rays. Recently, i-line steppers have become mainstream, and sensitivity at i-line is required. On the other hand, there is a disadvantage that the varnish changes in viscosity during storage and the photosensitive characteristics are reduced in a state of being dissolved in a polar solvent during storage. Therefore, high sensitivity in the film state, particularly i
There was a problem that it was impossible to achieve both high sensitivity by line exposure and storage stability in a solution state during storage.

[0004]

The invention according to claim 1 has excellent i-line photosensitive characteristics, can obtain a pattern having a good shape even at a low exposure dose, has excellent storage stability, and has excellent cured film characteristics. An object of the present invention is to provide an excellent photosensitive polyimide precursor composition. A second aspect of the present invention provides a photosensitive polyimide precursor composition having further excellent sensitivity in addition to the object of the first aspect of the present invention. The third aspect of the present invention is to provide a method for producing a pattern which is excellent in i-line photosensitive characteristics, can obtain a pattern having a good shape even at a low exposure dose, and can obtain a cured film having excellent cured film characteristics.

[0005]

The present invention provides a compound represented by the general formula (I):

Embedded image (Wherein, R ¹ is a tetravalent organic group, R ² is a photosensitive group, R ³ ,
R ⁴ , R ^5, and R ⁶ are each independently a hydrogen atom or a monovalent organic group, and at least two of these four are monovalent organic groups). Photosensitive polyimide precursor, titanocene compound and 450 nm to 60
The present invention relates to a photosensitive polyimide precursor composition containing a dye compound having an absorption at 0 nm.

[0006] The present invention further relates to a method for controlling the pressure of 100
The present invention relates to the photosensitive polyimide precursor composition containing an addition polymerizable compound having a boiling point of not lower than ° C. Furthermore, the present invention provides a pattern formed by irradiating a coating formed using the photosensitive polyimide precursor resin composition with an i-line through a mask having a predetermined pattern, and then developing the coating. Related to manufacturing method.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The polyimide precursor used in the photosensitive polyimide precursor composition of the present invention is generally a polyamic acid having a structural unit consisting of a tetracarboxylic acid residue and a diamine residue or a derivative thereof. The sex group is bonded to a tetracarboxylic acid residue. In the structural unit represented by the general formula (I), the tetravalent organic group represented by R ¹ is generally a residue of a tetracarboxylic acid, and the mechanical properties, heat resistance, and adhesiveness of a polyimide film obtained by curing. In view of the above, a tetravalent organic group having 4 or more carbon atoms is preferable, an organic group having 4 to 30 carbon atoms is more preferable, and an organic group containing an aromatic ring is preferable. Preferred examples thereof are shown in the following structural formula group. In the polyimide precursor molecule, in the plurality of repeating units, all R ^{1 s} may be the same or different. R ¹ is preferably a residue of a tetracarboxylic dianhydride capable of reacting with a diamine to form a polyimide resin.

[0008]

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[0009]

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In the photosensitive polyimide precursor, the photosensitive group represented by R ² is a group capable of leaving upon irradiation with light, a group capable of dimerization or copolymerization upon irradiation with light, and the like. A group having a saturated double bond is preferable because good photosensitivity can be easily imparted. The bond of the photosensitive group may be via a covalent bond or an ionic bond. In particular

Embedded image (Wherein, R ⁷ is a divalent organic group). R ⁷ includes an alkylene group, an arylene group and the like, and preferably has 1 to 10 carbon atoms.

In the structural unit represented by the general formula (I), R ³ , R ⁴ , R ⁵ and R ⁶ are a hydrogen atom or a monovalent organic group, and at least two of these four are monovalent. Organic group. In particular, those in which a monovalent organic group is separately present in two aromatic rings are preferable. As the monovalent organic group, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group and a propyl group, a halogen, an alkyl halide and the like are preferable.

Preferred examples of the diamine residue in this structural unit are shown below.

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The polyimide precursor used in the present invention may contain a structural unit represented by the general formula (II) together with a structural unit represented by the general formula (I). this is,

Embedded image (Wherein, R ⁸ is a tetravalent organic group, R ⁹ is a divalent organic group, R ¹⁰
Is a monovalent organic group or a hydroxyl group, and does not include the structural unit represented by the general formula (I)).

Specific examples of the tetravalent organic group represented by R ⁸ include the same as the organic group represented by R ¹ , and preferred examples thereof are also the same, and the same applies to the monovalent organic group represented by R ^10. Specific examples of the group include the same photosensitive group as the organic group represented by R ² , and in addition, an alkoxy group such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, and an n-butoxy group; It may contain an aryloxy group such as an oxy group, an alkylamino group, a dialkylamino group, an anilino group, a toluidino group, and the like.

In the general formula (II), R ⁹ is a divalent organic group, and the mechanical properties of the polyimide film obtained by curing are as follows:
Those containing an aromatic ring or silicon are preferred from the viewpoint of heat resistance, adhesiveness and the like. When a plurality of structural units represented by the general formula (II) are present in a molecule, a plurality of R ² may be the same or different. R ⁹ is preferably a residue of a diamine compound capable of forming a polyimide resin by reacting with tetracarboxylic dianhydride, and is preferably an organic group having 6 to 30 carbon atoms, particularly an aromatic ring. The organic group preferably contains

Preferred examples of R ⁹ are as follows.

[0017]

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[0018]

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[0019]

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[0020]

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In the polyimide precursor of the present invention, the ratio of the structural units represented by the general formulas (I) and (II) is 10 to 100 in terms of mole percentage of each structural unit.
Mol% and (II) are preferably from 90 to 0 mol%, since high sensitivity and a good pattern shape can be obtained.
Is more preferably 20 to 50 mol%, and (II) is more preferably 80 to 50 mol%.

Further, a polyimide precursor side chain, ie, R ³
And ¹⁰ to 100 mol% of the total group represented by R10 and R10 is preferably a photosensitive group. When having a group other than the photosensitive group, from the viewpoint of film properties, it is preferable to use an alkyl group having 4 or less carbon atoms, and a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group are Particularly preferred.

The molecular weight of the polyimide precursor in the present invention is, in terms of film characteristics and the like, 10% by weight-average molecular weight.
000 to 200,000 is preferred. The weight average molecular weight is
It can be measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene.

The photosensitive polyimide precursor used in the present invention, when a photosensitive group is introduced by ionic bonding, is obtained by reacting a tetracarboxylic dianhydride with a diamine to obtain a polyamic acid, and then forming an amine or a photosensitive group-containing amine. A method of reacting the quaternary salt, when a photosensitive group is introduced by a covalent bond, a reaction is performed by mixing a tetracarboxylic dianhydride and a hydroxy group-containing compound to produce a half ester of tetracarboxylic acid, It can be synthesized by a method of acid chloride with thionyl chloride and then reacting with a diamine, or a method of reacting the tetracarboxylic acid half ester with a diamine using a carbodiimide as a condensing agent. Of these, the method of introducing a photosensitive group by ionic bonding is preferred because it is simple and can impart good photosensitivity.

The tetracarboxylic dianhydride includes:
For example, oxydiphthalic acid, pyromellitic acid, 3,
3 ', 4,4'-benzophenonetetracarboxylic acid,
3,3 ', 4,4'-biphenyltetracarboxylic acid,
1,2,5,6-naphthalenetetracarboxylic acid, 2,
3,6,7-naphthalenetetracarboxylic acid, 1,4
5,8-naphthalenetetracarboxylic acid, 2,3,5,6
-Pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, sulfonyldiphthalic acid, m-terphenyl-3,3 ', 4,4'-tetracarboxylic acid,
p-terphenyl-3,3 ', 4,4'-tetracarboxylic acid, 1,1,1,3,3,3-hexafluoro-2,
2-bis (2,3- or 3,4-dicarboxyphenyl) propane, 2,2-bis (2,3- or 3,4-dicarboxyphenyl) propane, 2,2-bis {4'-
(2,3- or 3,4-dicarboxyphenoxy) phenyl} propane, 1,1,1,3,3,3-hexafluoro-2,2-bis {4 ′-(2,3- or 3, 4-dicarboxyphenoxy) phenyl} propane, the following general formula (III)

Embedded image (Wherein, R ¹¹ and R ¹² each represent a monovalent hydrocarbon group, and may be the same or different, and s is an integer of 1 or more). Examples include tetracarboxylic dianhydrides such as acids, which are used alone or in combination of two or more. Among them, a tetracarboxylic acid giving the structure shown as a preferable example of R ¹ in the general formula (I) is preferable.

The diamine providing the diamine residue R2 in the structural unit represented by the general formula (I) includes 2,2 '
-Dialkyl-4,4'-diaminobenzidine, 2,
2 ', 6,6'-tetraalkyl-4,4'-diaminobenzidine (the alkyl group is a methyl group, an ethyl group or an isopropyl group) is preferred.

Other diamines include 4,4'-
(Or 3,4'-, 3,3'-, 2,4'-, 2,2 '
-) Diaminodiphenyl ether, 4,4'- (or 3,4'-, 3,3'-, 2,4'-, 2,2'-) diaminodiphenylmethane, 4,4'- (or 3,4 '
-, 3,3'-, 2,4'-, 2,2'-) diaminodiphenylsulfone, 4,4'- (or 3,4'-, 3,
3'-, 2,4'-, 2,2'-) diaminodiphenyl sulfide, paraphenylenediamine, metaphenylenediamine, p-xylylenediamine, m-xylylenediamine, o-tolidine, o-tolidine sulfone, ,
4'-methylene-bis- (2,6-diethylaniline), 4,4'-methylene-bis- (2,6-diisopropylaniline), 2,4-diaminomesitylene,
5-diaminonaphthalene, 4,4'-benzophenonediamine, bis- {4- (4'-aminophenoxy) phenyl} sulfone, 1,1,1,3,3,3-hexafluoro-2,2-bis ( 4-aminophenyl) propane,
2,2-bis {4- (4'-aminophenoxy) phenyl} propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetramethyl-4,4 '-Diaminodiphenylmethane, bis @ 4-
(3'-aminophenoxy) phenyl disulfone, 2,
2-bis (4-aminophenyl) propane, and the like, which are used alone or in combination of two or more.

In order to improve the adhesiveness, the following general formula (IV)

Embedded image (Wherein, R ¹³ and R ¹⁴ each represent a divalent hydrocarbon group, which may be the same or different, and R ¹⁵ and R ¹⁶ each represent a monovalent hydrocarbon group, each of which may be the same or different. Often, t is an integer of 1 or more), and it is preferable to use a diamine such as diaminopolysiloxane,
At this time, the amine is preferably used in an amount of 0.1 to 20 mol% based on all the diamine components. R ¹³ and R ¹⁴ are an alkylene group such as a methylene group, an ethylene group, a propylene group,
Examples thereof include an arylene group such as a phenylene group, and a bonding group thereof. Examples of R ¹⁵ and R ¹⁶ include an alkyl group such as a methyl group and an ethyl group, and an aryl group such as a phenyl group.

In order to improve heat resistance, 4,4'-diaminodiphenyl ether-3-sulfonamide,
4'-diaminodiphenylether-4-sulfonamide, 3,4'-diaminodiphenylether-3'-sulfonamide, 3,3'-diaminodiphenylether-4-sulfonamide, 4,4'-diaminodiphenylether-3-carboxamide, 3,4'-diaminodiphenyl ether-4-carboxamide, 3,4'-diaminodiphenyl ether-3'-carboxamide,
A diamine compound having a sulfonamide group or a carboxamide group such as 3,3'-diaminodiphenyl ether-4-carboxamide can also be used. These diamines are used alone or in combination of two or more.

Examples of the compound having an amino group and a photosensitive group used for introducing an ionic bond include, for example,
N, N-dimethylaminoethyl methacrylate, N, N
-Diethylaminoethyl methacrylate, N, N-dimethylaminopropyl methacrylate, N, N-diethylaminopropyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, N, N-dimethylaminopropyl acrylate N-diethylaminopropyl acrylate, N, N-dimethylaminoethyl acrylamide,
N, N-dimethylaminoethylacrylamide and the like are preferred. These are used alone or in combination of two or more.

The amount of the compound having an amino group and a photosensitive group is preferably 1 to 200% by weight, and more preferably 5 to 150% by weight based on the amount of the polyimide precursor before introducing the photosensitive group. % Is more preferable. If the amount is less than 1% by weight, the photosensitivity tends to be inferior, and if it exceeds 200% by weight, the heat resistance and the mechanical properties of the film tend to be inferior.

The photosensitive polyimide precursor composition of the present invention contains a titanocene compound. As an example of the titanocene compound, the following general formula (V)

Embedded image (Wherein, R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ ,
R ²⁴ , R ^25, and R ²⁶ each independently represent a hydrogen atom, a halogen atom, an alkoxy group having 1 to 20 carbon atoms or a heterocyclic ring), and are preferably excellent in sensitivity.

As a specific compound, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2
-(1H-pyrrol-1-yl) propyl) phenyl]
Titanium, bis (cyclopentadienyl) -bis [2,6
-Difluoro-3- (2- (1H-pyrrol-1-yl) methyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (pyrrol-1-yl) phenyl] titanium, Bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2,5-dimethylpyrrol-1-yl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro- 3- (2,5-diethylpyrrol-1-yl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2,5-diisopropylpyrrol-1-yl) phenyl] Titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3-
(2,5-bisdimethylaminopyrrol-1-yl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2,5-dimethyl-3-)
Methoxypyrrole-1-yl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3-methoxyphenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro- 3-isopropoxyphenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3-n-propoxyphenyl] titanium and the like.

These are used alone or in combination of two or more. The content in the composition is preferably 0.1 to 10.0 parts by weight, more preferably 0.3 to 5.0 parts by weight, based on 100 parts by weight of the polyimide precursor.

The dye compound contained in the photosensitive polyimide precursor composition of the present invention has an absorption at 450 to 600 nm. Preferred examples thereof include phenolphthalene, phenol red, neal red, pyrogallol red, pyrogallol violet, disperse red 1, disperse red 13, disperse red 1
9, Day sparse orange 1, Day sparse orange 3, Day sparse orange 13, Day sparse orange 25, Day sparse blue 3, Day sparse blue 1
4, eosin B, rhodamine B, quinalizarin, 5- (4
-Dimethylaminobenzylidene) rhodanine, aurin tricarboxyside, aluminone, alizarin, pararosaniline, emodin, thionine and methylene violet, more preferably phenolphthalene, disperse red 1 and neil red . These are used alone or in combination of two or more. As the content in the composition, from the viewpoint of storage stability, based on 100 parts by weight of the polyimide precursor,
It is preferably 0.1 to 3.0 parts by weight, and 0.3 to 3.0 parts by weight.
More preferably, it is 1.5 parts by weight.

In the present invention, it is preferable to use an addition polymerizable compound having a boiling point of 100 ° C. or more at normal pressure. When the boiling point is lower than 100 ° C. at normal pressure, when the solvent contained in the system is removed by drying or the like or when irradiating with an actinic ray, the addition polymerizable compound tends to volatilize and the properties tend to deteriorate. The addition polymerizable compound is preferably soluble in an organic solvent.

As the addition polymerizable compound having a boiling point of 100 ° C. or more at normal pressure, polyhydric alcohols and α, β-
A compound obtained by condensing an unsaturated carboxylic acid, for example, ethylene glycol di (meth) acrylate (meaning diacrylate or dimethacrylate, the same applies hereinafter),
Triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,2-propylene glycol di (meth) acrylate, di ( 1,2
-Propylene glycol) di (meth) acrylate, tri (1,2-propylene glycol) di (meth) acrylate, tetra (1,2-propylene glycol) di (meth) acrylate, dimethylaminoethyl (meth)
Acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate,
Diethylaminopropyl (meth) acrylate, 1,4
-Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, etc.), styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone , 2-hydroxyethyl (meth) acrylate, 1,3- (meth) acryloyloxy-2-hydroxypropane, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, neopentylglycol di (meth) acrylate, Pentaerythritol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tetramethylolpropanetetra (meth)
Acrylates and the like can be mentioned, and these are used alone or in combination of two or more. When using these,
The amount is preferably 1 to 100 parts by weight, more preferably 3 to 50 parts by weight, based on 100 parts by weight of the polyimide precursor. When deviating from the range of 1 to 100 parts by weight,
The desired effect tends to decrease, and also tends to adversely affect the developability.

Examples of the organic solvent used in the photosensitive polyimide composition of the present invention include acetone, methyl ethyl ketone, diethyl ketone, toluene, chloroform, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol and 2-butanol. , T-butanol, ethylene glycol monomethyl ether, xylene, tetrahydrofuran, dioxane, cyclopentanone, N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N-benzyl-2 -Pyrrolidone, γ-butyrolactone, dimethyl sulfoxide, ethylene carbonate, propylene carbonate, sulfolane, hexamethylene phosphortriamide, N-acetyl-ε-caprolactam, Preferred examples include dimethylimidazolidinone, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether. These may be used alone or as a mixed system. The content in the composition is not particularly limited, but 10 parts by weight based on 100 parts by weight of the polyimide precursor.
0 to 300 parts by weight, preferably 150 to 20 parts by weight.
More preferably, it is 0 parts by weight.

The photosensitive polyimide precursor composition of the present invention may further contain a photoinitiator as shown below, if necessary. Such photoinitiators include, for example,
Michler's ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 2-t-butylanthraquinone, 2-ethylanthraquinone, 4,4'-bis (PN, N-diethylamino) benzophenone, acetophenone, benzophenone, thioxanthone, , 2-Dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, benzyl,
Diphenyl disulfide, phenanthrenequinone, 2-
Isopropylthioxanthone, riboflavin tetrabutyrate, N-phenyldiethanolamine, 2- (o-
Ethoxycarbonyl) oxyimino-1,3-diphenylpropanedione, 1-phenyl-2- (o-ethoxycarbonyl) oxyiminopropan-1-one, 3,
3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, N- (p-cyanophenyl) glycine, N- (p-methylsulfonylphenyl) glycine and the like. The amount of these photoinitiators used is not particularly limited, but when used, the polyimide precursor 10
It is preferably added in an amount of 0.1 to 50 parts by weight, more preferably 0.3 to 20 parts by weight, based on 0 parts by weight.

The photosensitive polyimide precursor composition of the present invention may optionally contain a sensitizer as shown below. Examples of the sensitizer include various coumarin compounds, benzalacetophenone, 4'-N, N-dimethylaminobenzalacetophenone, 4'-acetoaminobenzal-
4-methoxyacetophenone and the like. Of these, the use of a coumarin compound is preferable because the patternability, particularly the pattern shape and the resolution, are improved.

Coumarin compounds include 7-N, N-diethylaminocoumarin, 3,3'-carbonylbis (7
-N, N-diethylamino) coumarin, 3,3'-carbonylbis (7-N, N-dimethoxy) coumarin, 3-
Thienylcarbonyl-7-N, N-diethylaminocoumarin, 3-benzoylcoumarin, 3-benzoyl-7-
N, N-methoxycoumarin, 3- (4'-methoxybenzoyl) coumarin, 3,3'-carbonylbis-5,7
-(Dimethoxy) coumarin, 7-diethylamino-3-
Tenonyl coumarin, 7-methoxy-3-benzoyl coumarin, 3,3'-carbonylbis- (7-methoxycoumarin), 3,3'-carbonylbis- (7-ethoxycoumarin), 3- (4-cyanobenzoyl ) -5,7-Dimethoxycoumarin, 3- (2-benzothiazoyl) -7
-(Diethylaminocoumarin), 3- (2-benzimidazoyl) -7- (diethylamino) coumarin, 7-diethylamino-4-methylcoumarin, 4,6-dimethyl-7-ethylaminocoumarin and the like. It is not limited to.

The use amount of the sensitizer is not particularly limited, but when used, it is preferably incorporated in an amount of 0.01 to 50 parts by weight based on 100 parts by weight of the polyimide precursor.
The range is more preferably from 0.05 to 20 parts by weight. In the case of a coumarin compound, the amount is preferably 0.01 to 5.0 parts by weight based on 100 parts by weight of the polyimide precursor,
More preferably, the content is 0.05 to 3.0 parts by weight.

The photosensitive polyimide precursor composition of the present invention may contain other additives, for example, additives such as a plasticizer and an adhesion promoter. The pattern production method of the present invention uses the photosensitive polyimide precursor composition of the present invention obtained as described above to form a polyimide film made of a cured product of the composition by a photolithography technique. In the pattern manufacturing method of the present invention, first, a film made of the photosensitive polyimide precursor composition of the present invention is formed on the surface of a supporting substrate. Here, in order to improve the adhesiveness between the coating or the polyimide coating after heat curing and the supporting substrate, the surface of the supporting substrate may be previously treated with an adhesion aid.

The coating comprising the photosensitive polyimide precursor composition can be formed, for example, by forming a varnish film of the photosensitive polyimide precursor composition and then drying it. The varnish film can be formed by a means appropriately selected from means such as spin coating using a spinner, dipping, spray printing, and screen printing, depending on the viscosity of the varnish. The thickness of the film can be adjusted by the application conditions, the solid content concentration of the present composition, and the like. In addition, the film formed on the support is peeled off from the support to form a sheet made of the polyimide precursor composition, and the sheet is attached to the surface of the support substrate to form the film described above. May be.

Next, the film is irradiated with light (usually using ultraviolet light) through a photomask having a predetermined pattern. This exposure step can be performed using a contact / proximity exposure machine using an ultra-high pressure mercury lamp, a mirror projection exposure machine, a g-ray stepper, an i-ray stepper, other ultraviolet rays, a visible light source, X-rays, an electron beam, or the like. it can. In particular, the photosensitive polyimide precursor composition of the present invention comprises:
Since it has excellent light transmittance to a line, it is suitable for an i-line stepper.

Next, the unexposed portion is dissolved and removed with a developer to obtain a desired relief pattern. This developing step can be performed using a normal photoresist developing device or the like. As the developer, for example, a good solvent (N, N
-Dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.), a mixed solvent of the above good solvent and a poor solvent (lower alcohol, ketone, water, aromatic hydrocarbon, etc.), a basic solution ( Aqueous solution of tetramethylammonium hydroxide, aqueous solution of triethanolamine, etc.).

After the development, it is preferable to perform rinsing with water or a poor solvent, if necessary, and to dry at about 100 ° C. to make the pattern stable. In addition, the relief pattern is heated to close the imide ring by heating to form a patterned highly heat-resistant polyimide film.
The heating temperature at this time is preferably from 150 to 500 ° C, more preferably from 200 to 400 ° C. If the heating temperature is lower than 150 ° C., the mechanical properties and thermal properties of the polyimide film tend to decrease,
If the temperature exceeds 0 ° C., the mechanical properties and thermal properties of the polyimide film tend to decrease. The heating time at this time is
It is preferable to set it to 0.05 to 10 hours. If the heating time is less than 0.05 hours, the mechanical and thermal characteristics of the polyimide film tend to decrease, and if it exceeds 10 hours, the mechanical and thermal characteristics of the polyimide film tend to decrease.

As described above, the photosensitive resin composition of the present invention can be used for a surface protective film for a semiconductor, an interlayer insulating film of a multilayer wiring board, and the like. In addition, a polyimide pattern is obtained on a substrate on which a passivation film is formed by the above-described method, and further, the passivation film is etched and processed using the polyimide pattern as a mask. Can also.

Here, the processing of the passivation film usually means that SiO, S
This is a process for opening a conduction portion of a passivation film formed using an inorganic substance such as iN. Note that the polyimide pattern remaining on the passivation film prevents physical influence from the sealing agent and functions as a surface protection film. In addition, as the processing of the passivation film, the processing of removing the passivation film on the bonding pad and the compensation circuit by dry etching is preferable from the viewpoint of improving yield. The relief pattern formed by the development is then washed with a rinsing liquid to remove the developing solvent. Preferable examples of the rinsing liquid include methanol, ethanol, isopropyl alcohol, and water having good miscibility with the developing liquid.

In the relief pattern obtained by the above-mentioned treatment, there is a relief pattern in which the polyimide precursor of the present invention is partially imidized. This relief pattern is
By performing the heat treatment at a temperature selected from the range of ° C to 450 ° C, a resin pattern made of polyimide can be obtained with high resolution. Since this resin pattern has high heat resistance and excellent mechanical properties, the surface protection film of the semiconductor element,
It is used as an interlayer insulating film or the like of a thin multilayer wiring board.

[0051]

The present invention will be described below with reference to examples. Synthesis of Polyimide Precursor (Synthesis Examples 1 to 3) Table 1 was placed in a 100 ml flask equipped with a stirrer and a thermometer.
And N-methyl-2-pyrrolidone shown in (1) was added and dissolved by stirring at room temperature under nitrogen flow. The acid component shown in Table 1 was added to this solution, and the mixture was stirred for 5 hours to obtain a viscous polyamic acid. Was obtained. Further, this solution was heated at 70 ° C. for 5 hours, and the viscosity was 80 poise (solid content: 25% by weight).
To obtain polyamic acid solutions (PI-1 to 3).
The amounts of the diamine component, acid component, and N-methyl-2-pyrrolidone used are shown in Table 1.

The viscosity was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., E
HD type), temperature is 25 ° C, rotation speed is 2.5rpm
Was measured. Further, those obtained by drying a solution of the obtained respective polyimide precursor, by KBr method, infrared absorption spectrum (JEOL Co., JIR-100 type) was measured, both, 1600 cm ^-1 Around the C =
O absorption and N-H absorption were confirmed at around 3300 cm ^-1 .

[0053]

[Table 1]

Examples 1-5 and Comparative Examples 1-2 N-methyl-2 of the polyamic acid obtained in Synthesis Examples 1-3
-Pyrrolidone solution (solid content 25% by weight), 1.8 g of 3-diaminopropyl methacrylate, bis (cyclipentadienyl) -bis (2,6-difluoro-3- (1H-
After mixing 0.1 g of pyruyl) phenyl) titanium, 0.02 g of 7-diethylamino-3-thenonylcoumarin and a coloring compound, the mixture was taken out into a glass sample bottle, and left at room temperature in a yellow room to conduct a storage stability test. went. Table 2 shows the viscosities of the photosensitive resin immediately after the arrangement and 7 days after standing.

The obtained photosensitive resin composition solution was dropped and spin-coated on a silicon wafer. Next, the mixture was heated at 100 ° C. for 200 seconds using a hot plate, and the solvent was dried to obtain a photosensitive coating film. The film thickness after drying was 23 microns. The coating film was exposed with an i-line stepper through a photomask. This was further heated at 100 ° C. for 60 seconds, and immersion developed using a mixed solution of N-methyl-2-pyrrolidone / methyl alcohol (4/1 (volume ratio)). Further, it was rinsed with isopropanol. The pattern shape after development was measured and observed, and the exposure amount at which the residual film ratio (the value obtained by dividing the film thickness by the initial film thickness) was 90% was defined as sensitivity as shown in Table 2.
It was shown to. This is carried out at 100 ° C. for 15 minutes and at 200 ° C. for 2 minutes.
Heated at 350 ° C. for 60 minutes for 0 minute to obtain a final cured film thickness of 1
A good polyimide relief pattern of 0 microns was obtained. An infrared absorption spectrum of a part of the obtained polyimide relief pattern was measured by the KBr method. As a result, characteristic absorption of the imide was confirmed at around 1780 cm ^-1 .

[0056]

[Table 2]

[0057]

The photosensitive polyimide precursor composition according to claim 1 is excellent in i-line photosensitive characteristics, can obtain a good-shaped pattern even at a low exposure dose, and has good storage stability and cured film characteristics. It is excellent. The photosensitive polyimide precursor composition according to claim 2 has the effect of the invention according to claim 1,
It is more excellent in sensitivity. According to the third aspect of the present invention, a pattern having a good shape can be obtained even with a low exposure amount, and a cured film having excellent cured film characteristics can be obtained.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // C08G 73/10 C08G 73/10 (72) Inventor Hideo Hagiwara 4-3-1-1, Higashicho, Hitachi City, Ibaraki Prefecture Hitachi Chemical Semiconductor & Liquid Crystal Materials Division Development Center

Claims (3)

[Claims] 1. A compound of the general formula (I) (Wherein, R ¹ is a tetravalent organic group, R ² is a photosensitive group, R ³ ,
R ⁴ , R ^5, and R ⁶ are each independently a hydrogen atom or a monovalent organic group, and at least two of these four are monovalent organic groups). Photosensitive polyimide precursor, titanocene compound and 450 nm to 60
A photosensitive polyimide precursor composition containing a dye compound having an absorption at 0 nm. 2. The photosensitive polyimide precursor composition according to claim 1, further comprising an addition polymerizable compound having a boiling point of 100 ° C. or higher at normal pressure. 3. A film formed using the photosensitive polyimide precursor resin composition according to claim 1 or 2 is irradiated with i-line through a mask having a predetermined pattern, and then the film is developed. A pattern manufacturing method characterized by the above-mentioned.