JPH1130859A - Photosensitive polyimide precursor composition and image forming method by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the photosensitive polyimide precursor composition developable in an aqueous solution, superior in photosensitive characteristics, high in sensitivity, good in pattern form even in low exposure, superior in resolution, high in film endurance, and also in hardened film characteristics by incorporating the polyimide precursor having a photosensitive group and an acid and containing a titanocene compound. SOLUTION: This photosensitive composition contains the photosensitive polyimide precursor having a photosensitive group and an acidic group and containing the titanocene compound. This polyimide precursor has structural units represented by the formula in which R<1> is a tetravalent organic group; R<2> is a tri- or tetra-valent organic group; R<3> is a photosensitive group; A is an acidic group; and (n) is 1 or 2, thus permitting the obtained polyimide precursor composition to be developed in an aqueous solution and enhanced in sensitive characteristics and sensitivity and good in pattern forms even in low exposure and superior in resolution and film endurance and hardened film characteristics.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimide precursor suitable as a material for a protective film such as a surface coat film of a semiconductor element or an interlayer insulating film of a thin-film multilayer wiring board, and a photosensitive polyimide precursor composition containing the same. And a method for manufacturing a pattern.

[0002]

2. Description of the Related Art Conventionally, as a photosensitive polyimide precursor composition, an olefin aromatic tetracarboxylic acid dianhydride described in JP-B-5-67026 is reacted with an olefin unsaturated alcohol to form an olefin aromatic tetracarboxylic acid. Synthesis of carboxylic acid diester, polymerization of this compound and diamine by dehydration condensation reaction using carbodiimides, including polyimide precursor with covalent bond to introduce photosensitive group,
No. 63-31939, polyamic acid obtained by reacting an aromatic tetracarboxylic dianhydride with an aromatic diamine, an amine compound having a photosensitive group is ion-bonded, and a photosensitive group is introduced. Are known.

[0003] Each of these is applied to a substrate in the form of a varnish dissolved in an appropriate organic solvent, dried to form a film, and then irradiated with ultraviolet rays through an appropriate photomask to cure the exposed portion by photocuring. Type photosensitive composition, which is developed and rinsed with an organic solvent to form a relief /
That's what gets the pattern.

However, when an organic solvent is used as a developing solution at the time of pattern formation, swelling of an exposed portion tends to occur at the time of development, and it is difficult to obtain a high-resolution pattern.
In addition, when an organic solvent is used, there is also a problem that the health of workers is adversely affected and waste liquid treatment is troublesome.

Therefore, as a material which can be developed with an aqueous liquid, which solves the above problems, for example, a positive polymer in which a naphthoquinonediazidosulfonylamide group is introduced into a carboxyl group of polyamic acid has been proposed ( JP-A-6-258835). This polymer has a feature that the exposed portion is solubilized in a basic aqueous solution because a naphthoquinonediazidosulfonylamide group is changed to a carboxyl group by light irradiation, and is known as a positive photosensitive polyimide precursor. However, at present, such a positive photosensitive polyimide precursor having high sensitivity, excellent pattern shape, and performance for practical use has not been obtained. On the other hand, as the negative type photosensitive polyimide precursor composition, at the present time, a high-resolution pattern is obtained, and a composition which can be developed with a basic aqueous solution has not been obtained.

[0006]

SUMMARY OF THE INVENTION The invention according to claim 1 can be developed with an aqueous liquid, has excellent photosensitive characteristics, particularly excellent i-line photosensitive characteristics, has high sensitivity, and has good sensitivity even at a low exposure dose. An object of the present invention is to provide a photosensitive polyimide precursor composition having a shape pattern, excellent resolution, high residual film ratio, and excellent cured film characteristics. A second aspect of the present invention provides a photosensitive polyimide precursor composition having excellent developability in an aqueous solution, in addition to the object of the first aspect. A third aspect of the present invention is to provide a photosensitive polyimide precursor composition having more excellent photosensitivity and the like in the object of the first aspect of the present invention. Claims 4 and 5
The described invention can be developed with an aqueous liquid, and has excellent photosensitive characteristics, particularly excellent in i-line photosensitive characteristics, high sensitivity, a pattern with a good shape even at a low exposure dose, and excellent resolution. ,
It is an object of the present invention to provide a pattern manufacturing method which can obtain a cured film having a high residual film ratio and excellent cured film characteristics, can further reduce the production steps, and can reduce the production cost.

[0007]

SUMMARY OF THE INVENTION The present invention relates to a photosensitive polyimide precursor having a photosensitive group and an acidic group, and a photosensitive polyimide precursor composition containing a titanocene compound. In the present invention, the photosensitive polyimide precursor having a photosensitive group and an acidic group may be a compound represented by the general formula (I):

Embedded image (Wherein, R ¹ is a tetravalent organic group, R ² is a trivalent or tetravalent organic group, R ³ is a photosensitive group, A is an acidic group, n is 1 or 2
The present invention relates to the photosensitive polyimide precursor composition having a structural unit represented by the following formula: The present invention also provides
The present invention further relates to the polyimide precursor composition containing a coumarin compound.

The present invention also provides a method for irradiating a film formed using the photosensitive polyimide precursor resin composition with light through a mask having a predetermined pattern, and then irradiating the film with a basic aqueous solution. The present invention relates to a pattern manufacturing method characterized by developing. Furthermore, the present invention relates to the above-mentioned pattern production method, wherein the light to be irradiated is i-line.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The polyimide precursor used in the photosensitive polyimide precursor composition of the present invention has a photosensitive group and an acidic group. Is necessary to obtain a polyimide precursor having Polyimide precursor is generally a polyamic acid or a derivative thereof having a structural unit consisting of a tetracarboxylic acid residue and a diamine residue, but the photosensitive group may be bonded to the tetracarboxylic acid residue, It may be bonded to a residue, and an acidic group may be similarly bonded to a tetracarboxylic acid residue or a diamine residue.

An example of a polyimide precursor in which a photosensitive group is bonded to a tetracarboxylic acid residue and an acidic group is bonded to a diamine residue is a polyimide precursor which does not participate in the formation of an amide bond by reaction with a diamine. Utilizing two carboxyl groups, an ester bond, a photosensitive group is introduced through an amide bond or the like, and a polyimide precursor to which an acidic group is bonded as a side chain of the diamine is exemplified. An example of a polyimide precursor in which an acidic group is bonded to a tetracarboxylic acid residue and a photosensitive group is bonded to a diamine residue is one that does not participate in the formation of an amide bond by reaction with a diamine or Before the polyimide in which two carboxyl groups remain as is and a photosensitive group is introduced into the side chain of the diamine residue via an ester bond, an amide bond, an ether bond, an amino bond, or the like. Body, and the like. As a method for introducing a photosensitive group into a side chain of a diamine residue, a hydroxyl group, a carboxyl group, a diamine having a functional group such as an amino group is reacted with a compound having a group reactive with the functional group and a compound having a photosensitive group. And the like.

Among these, the photosensitive polyimide precursor used in the present invention exhibits good tourist characteristics and developability in a basic aqueous solution, so that a photosensitive group is bonded to a tetracarboxylic acid residue and a diamine residue is present. Those having an acidic group bonded to the group are preferable, and those having the structural unit represented by the above general formula (I) are more preferable because of easy production. In the structural unit represented by the general formula (I), the tetravalent organic group represented by R ¹ is a tetracarboxylic acid capable of reacting with a diamine to form a polyimide resin, an anhydride thereof, a mono- or di-esterified product, It is preferably a residue of a derivative such as a mono- or diamidated compound,
From the viewpoints of mechanical properties, heat resistance, and adhesiveness of the polyimide film obtained by curing, it is preferably a tetravalent organic group having 4 or more carbon atoms. Preferred examples thereof are shown in the following structural formula group. Among the tetravalent organic groups having 4 or more carbon atoms, a total of 6 to 3 carbon atoms including an aromatic ring (benzene ring, naphthalene ring, etc.)
More preferably, it is 0. In the polyimide precursor molecule, in the plurality of repeating units, all R ^{1 s} may be the same or different.

[0012]

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[0013]

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In the photosensitive polyimide precursor, an acidic group, that is, a group represented by A in the general formula (I) is not particularly limited, but a sulfonic acid group (-
SO ₃ H), a sulfinic acid group (—SO ₂ H), a carboxyl group (—COOH), or a phenolic hydroxyl group is preferable because of good solubility. Among these, a carboxyl group and a hydroxyl group are particularly preferable because the synthesis of the polyimide precursor is easy.

In the general formula (I), the group R ² to which the acidic group A is bonded is preferably a diamine residue capable of forming a polyimide resin by reacting with a tetracarboxylic acid or a derivative thereof. From the viewpoint of the mechanical properties, heat resistance and adhesiveness of the polyimide film obtained by the above method, it is preferably a trivalent or tetravalent organic group containing an aromatic ring, and the mechanical properties and heat resistance of the polyimide film obtained by curing. From the viewpoint of adhesion and adhesiveness, a trivalent or tetravalent organic group having a total of 6 to 30 carbon atoms including an aromatic ring is more preferable. Specific preferred examples are shown in the following structural formula groups. Note that all R ² in the molecule may be the same or different.

[0016]

Embedded image (However, Z is

Embedded image Indicates)

In the photosensitive polyimide precursor, a photosensitive group, and a group represented by R ³ in the structural unit represented by the general formula (I), include, for example, a group capable of leaving upon irradiation with light,
It is a group that can be dimerized or copolymerized by light irradiation, and a group having a polymerizable unsaturated double bond is particularly preferable because good photosensitivity can be easily imparted.

As the group having a polymerizable unsaturated double bond, for example, the following general formula:

Embedded image (However, R ⁴ , R ^5, and R ⁶ are each independently selected from hydrogen, an alkyl group, a phenyl group, a vinyl group, and a propenyl group, and R ⁷ represents a divalent organic group.) The organic group to be used is preferable because it can impart high-sensitivity photosensitivity. The alkyl group preferably has 1 to 4 carbon atoms. The divalent organic group represented by R ⁷ is preferably an alkylene group having 1 to 20 carbon atoms such as a methylene group, an ethylene group, and a propylene group.

In particular, a methacryloyloxyalkyl group and an acryloyloxyalkyl group (alkyl having 1 to 20 carbon atoms) not only realize high sensitivity,
Since the synthesis is easy, it is suitable for the present invention.

The polyimide precursor used in the present invention may contain the structural unit represented by the general formula (II) together with the 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 monovalent organic group represented by R ¹⁰ is the same. Specific examples of the group include a group in which the organic group represented by R ³ is bonded via an oxygen atom, and preferred groups are also the same, but methoxy, ethoxy, n
-It may contain an alkoxy group such as a propoxy group, an isopropoxy group or an n-butoxy group, an aryloxy group such as a benzyloxy group, an alkylamino group, a dialkylamino group, an anilino group, a toluidino group, or the like. In the case of these other groups, those having 1 to 20 carbon atoms in total are preferred.

R ⁹ is a divalent organic group, and preferably contains an aromatic ring or silicon from the viewpoints of mechanical properties, heat resistance, adhesiveness and the like of the polyimide film obtained by curing. In the case of those containing an aromatic ring, those having 6 to 30 carbon atoms are preferable,
In the case of those containing silicon, those having silicon atoms having 1 to 10 (poly) siloxane bonds are preferred. When a plurality of structural units represented by the general formula (II) are present in a molecule, a plurality of R ⁹ may be the same or different.

Preferred examples of R ⁹ are as follows.

[0024]

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[0025]

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[0026]

Embedded image

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% because the balance between developability in a basic aqueous solution and a good pattern shape is excellent, and (I) is preferably from 80 to 100 mol%.
(II) is more preferably 20 to 0 mol%. Further, it is preferable that 10 to 100 mol% of the photosensitive group be the photosensitive group in the polyimide precursor side chain, that is, the total of the groups represented by R ³ and R ¹⁰ . 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 preferably 10,000 to 200,000 in terms of weight average molecular weight from the viewpoint of the properties of the cured film after imidization.
5,000-50,000 is more preferred. The weight average molecular weight can be measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene.

The polyimide precursor used in the present invention is prepared by mixing and reacting a tetracarboxylic dianhydride and a hydroxy group-containing compound to produce a half ester of tetracarboxylic acid, followed by acid chloride with thionyl chloride. It can be synthesized by a method of reacting with a diamine, a method of reacting the tetracarboxylic acid half ester with a diamine using a carbodiimide as a condensing agent, or the like.

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 R ² in the structural unit represented by the general formula (I) includes 3,5-
Diaminobenzoic acid, 4,4'-dihydroxy-3,3 '
-Diaminobiphenyl, 3,4-diaminobenzoic acid,
3,3'-dihydroxy-4,4'-diaminobiphenyl, 2,3-diamino-4-hydroxypyridine, 2,
2-bis (4-hydroxy-3-aminophenyl) hexafluoropropane, 2,4-diaminophenol,
2,4-diaminobenzoic acid, 3-carboxy-4,4 '
-Diaminodiphenyl ether, 3,3'-dicarboxy-4,4'-diaminodiphenyl ether, 3-carboxy-4,4'-diaminodiphenylmethane, 3,
3'-dicarboxy-4,4'-diaminodiphenylmethane, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3 ', 5,5'-tetracarboxy-
4,4'-diaminobiphenyl, 3-carboxy-4,
4'-diaminodiphenylsulfone, 3,3'-dicarboxy-4,4'-diaminodiphenylsulfone, 1,
1,1,3,3,3-hexafluoro-2,2-bis (3-carboxy-4-aminophenyl) propane and the like.

The diamine providing the diamine residue R ⁹ in the structural unit represented by the general formula (II) includes 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 addition, as a diamine providing a diamine residue R ⁹ in the structural unit represented by the general formula (II), 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.) It is also possible to use a diamine such as diaminopolysiloxane. R
^{Examples of 13} and R ¹⁴ include an alkylene group such as a methylene group, an ethylene group and a propylene group, an arylene group such as a phenylene group, and a bonding group thereof, and R ¹⁵ and R ¹⁶ include a methyl group, an ethyl group, and the like. And an aryl group such as a phenyl group. When these are used, it is preferable to use 1 to 30 mol% based on all amine components.

As the diamine providing the diamine residue R ⁹ in the structural unit represented by the general formula (II), 4,4′-diaminodiphenylether-3-sulfonamide, 3,4 ′ -Diaminodiphenyl ether-4-sulfonamide, 3,4'-diaminodiphenyl ether-3'-sulfonamide, 3,3 '
-Diaminodiphenyl ether-4-sulfonamide,
4,4'-diaminodiphenylether-3-carboxamide, 3,4'-diaminodiphenylether-4-
Diamine compounds having a sulfonamide group or a carboxamide group, such as carboxamide, 3,4'-diaminodiphenyl ether-3'-carboxamide, and 3,3'-diaminodiphenyl ether-4-carboxamide, can also be used. When these are used, it is preferable to use 1 to 30 mol% based on all amine components. These diamines providing the diamine residue R ⁹ in the structural unit represented by the general formula (II) may be used alone or in combination of two or more.

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), from the viewpoint of patternability.

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 may be 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.

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, dimethylsulfoxide, ethylene carbonate, propylene carbonate, sulfolane, hexamethylenephosphortriamide, 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 it has excellent patternability, particularly pattern shape and resolution, and has a high residual film rate and high sensitivity.

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 coating 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 basic aqueous solution to obtain a desired relief pattern. This developing step can be performed using a normal photoresist developing device or the like. In the pattern forming method of the present invention, a basic aqueous solution is used as a developer. The developer may be an aqueous solution of one compound or an aqueous solution of two or more compounds as long as the aqueous solution exhibits basicity. The basic aqueous solution is usually a solution in which a basic compound is dissolved in water.
The concentration of the basic compound is usually from 0.1 to 50% by weight, preferably from the influence on the supporting substrate and the like, and is preferably from 0.1 to 3% by weight.
More preferably, it is 0% by weight. The developer is
To improve the solubility of the polyimide precursor, methano-
, Ethanol, propanol, isopropyl alcohol
And a water-soluble organic solvent such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide.

Examples of the basic compound include hydroxides or carbonates of alkali metals, alkaline earth metals or ammonium ions, amine compounds, and the like. Specifically, 2-dimethylaminoethanol, 3
-Dimethylamino-1-propanol, 4-dimethylamino-1-butanol, 5-dimethylamino-1-pentanol, 6-dimethylamino-1-hexanol, 2
-Dimethylamino-2-methyl-1-propanol, 3
-Dimethylamino-2,2-dimethyl-1-propano-
2-diethylaminoethanol, 3-diethylamino-1-propanol, 2-diisopropylaminoethanol, 2-di-n-butylaminoethanol, N, N
-Dibenzyl-2-aminoethanol, 2- (2-dimethylaminoethoxy) ethanol, 2- (2-diethylaminoethoxy) ethanol, 1-dimethylamino-2
-Propanol, 1-diethylamino-2-propano-
, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N
-T-butyldiethanolamine, N-lauryldiethanolamine, 3-diethylamino-1,2-propanediol, triethanolamine, triisopropanolamine, N-methylethanolamine, N-ethylethanolamine, Nn-butylethanolamine, N
-T-butylethanolamine, diethanolamine,
Diisopropanolamine, 2-aminoethanol, 3
-Amino-1-propanol, 4-amino-1-butanol, 6-amino-1-hexanol, 1-amino-2
-Propanol, 2-amino-2,2-dimethyl-1-
Propanol, 1-aminobutanol, 2-amino-1
-Butanol, N- (2-aminoethyl) ethanolamine, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 3-amino-1, 2-propanediol, 2-amino-2-hydroxymethyl-1,3-propanediol, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate , Ammonium hydrogen carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium hydroxide, aminomethanol, 2-
Aminoethanol, 3-aminopropanol, 2-aminopropanol, methylamine, ethylamine, propylamine, isopropylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, trimethylamine, triethylamine, tripropylamine, triisopropylamine It is preferable to use other compounds as long as they are soluble in water and the aqueous solution exhibits basicity.

The relief pattern formed by 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-described treatment, there is a case where the polyimide precursor of the present invention is partially imidized. By heating this relief pattern at a temperature selected from the range of 150 ° C. to 450 ° C., a resin pattern made of polyimide can be obtained with high resolution. This resin pattern
Since it has high heat resistance and excellent mechanical properties, it is used as a surface protective film of a semiconductor element, an interlayer insulating film of a thin multilayer wiring board, and the like.

[0051]

The present invention will be described below with reference to examples. Examples 1-5 and Comparative Examples 1-2 (1) Synthesis of polyimide precursor Synthesis of acid chloride 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) was placed in a 200 ml four-necked flask. ) 9.4
2 g (0.032 mol), 8.32 g (0.064 mol) of 2-hydroxyethyl methacrylate (HEMA),
5.06 g (0.064 mol) of pyridine, 0.03 g of t-butylcatechol, N-methyl-2-pyrrolidone (N
(MP) and stirred at 60 ° C. to form a clear solution in 2 hours. After stirring this solution at room temperature for 7 hours, the flask was cooled with ice and 9.88 g of thionyl chloride was added.
(0.083 mol) was added dropwise in 10 minutes. Thereafter, the mixture was stirred at room temperature for 1 hour to obtain a solution containing acid chloride.

Synthesis of Polyimide Precursor (Polyamic Acid Ester) In another 200 ml four-necked flask, 4.72 g (0.031 mol) of 3,5-diaminobenzoic acid and 5.0 parts of pyridine were added.
6 g (0.064 mol), t-butylcatechol 0.0
3 g of N-methyl-2-pyrrolidone (NMP) (50 ml) was added to the flask, and the acid chloride solution obtained above was slowly added dropwise over 1 hour while cooling the flask with ice and stirring (keeping the temperature at 10 ° C. or lower). Thereafter, the mixture was stirred at room temperature for 1 hour, poured into 1 liter of water, and the precipitated polymer was collected by filtration, washed twice with water, and dried under vacuum.
g were obtained. When the weight average molecular weight of this polyamic acid ester was measured by GPC (gel permeation chromatography), it was 44,000 in terms of polystyrene.
Met.

(2) Preparation of polyimide precursor composition 10 g of the obtained polymer was dissolved in 16 g of γ-butyrolactone and 2 g of cyclopentanone, and 2.5 g of tetraethylene glycol diacrylate and a photosensitive agent shown in Table 1 were blended. Thereafter, the solution was filtered under pressure using a filter having a pore size of 3 μm to obtain a photosensitive polyimide precursor composition in the form of a solution.

(3) Pattern formation The photosensitive polyimide precursor composition prepared in (2) is spin-coated on a silicon wafer, and
Heating at 200 ° C. for 200 seconds gave a 15 μm thick coating. After this coating film was exposed with an i-line stepper, immersion development was performed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide. Further rinse with water. The pattern shape after development was measured and observed, and the resolution and pattern shape are shown in Table 1.

[0055]

[Table 1]

Examples 6 to 10 Using the patterns obtained in Examples 1 to 5, under a nitrogen atmosphere, 100 ° C. for 30 minutes, 200 ° C. for 30 minutes, 35
Heating was performed at 0 ° C. for 60 minutes to obtain a polyimide pattern. The thickness of the obtained polyimide pattern was 10 μm, and a good polyimide pattern was obtained. From Table 1, it can be seen that the photosensitive material of the present invention has better photosensitive characteristics than the composition of the comparative example.

[0057]

The photosensitive polyimide precursor composition according to claim 1 is developable with an aqueous liquid, has excellent photosensitive characteristics, especially excellent i-line photosensitive characteristics, has high sensitivity, and can be used even at a low exposure dose. A pattern having a good shape is obtained, the resolution is excellent, the residual film ratio is high, and the cured film characteristics are also excellent. The photosensitive polyimide precursor composition according to claim 2 is excellent in developability in an aqueous solution in addition to the effects of the invention according to claim 1. The photosensitive polyimide precursor composition according to the third aspect is more excellent in the photosensitive characteristics and the like in the effects of the invention according to the first aspect. According to the method for producing a pattern according to claims 4 and 5, a pattern having a good shape which can be developed with an aqueous solution, has excellent photosensitive characteristics, particularly excellent in i-line photosensitive characteristics, and has high sensitivity and a low exposure amount can be obtained. As a result, a cured film having excellent cured film characteristics can be obtained, and the production process can be shortened, and the production cost can be reduced.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Makoto Kaji 4-3-1-1, Higashicho, Hitachi City, Ibaraki Pref. Hitachi Chemical Co., Ltd.

Claims (5)

[Claims] 1. A photosensitive polyimide precursor composition comprising a photosensitive polyimide precursor having a photosensitive group and an acidic group and a titanocene compound. 2. A photosensitive polyimide precursor having a photosensitive group and an acidic group is represented by the general formula (I): (Wherein, R ¹ is a tetravalent organic group, R ² is a trivalent or tetravalent organic group, R ³ is a photosensitive group, A is an acidic group, n is 1 or 2
The photosensitive polyimide precursor composition according to claim 1, which has a structural unit represented by: 3. The photosensitive polyimide precursor composition according to claim 1, further comprising a coumarin compound. 4. A film formed using the photosensitive polyimide precursor resin composition according to claim 1, 2 or 3, which is irradiated with light through a mask having a predetermined pattern, and then the film is formed into a base. A pattern production method characterized by developing using a neutral aqueous solution. 5. The pattern manufacturing method according to claim 4, wherein the light to be irradiated is i-ray.