JPH1138619A - Photosensitive polyimide precursor composition and pattern forming method by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance photosensitive characteristics and storage stability and process stability and hardened film characteristics by incorporating a specified photosensitive polyimide precursor and a titanocene compound, and a compound selected from each specified hydroquinone compound and catechol compound and benzoquinone compound in the composition. SOLUTION: The polyimide precursor composition contains the photosensitive polyimide precursor having structural units represented by formula I, the titanocene compound, and one of the compounds selected from the hydroquinone compound represented by formula II and catechol compound represented by formula III and the benzoquinone compound represented by formulae IV, and in formulae I-IV, R<1> is a tetravalent organic group; R<2> is a photosensitive group; R<3> is a divalent organic group; each of R<4> -R<7> is an H atom or a 1-5C alkyl or phenyl group or the like; each of R<8> -R<11> is an H atom or a 1-5C alkyl or phenyl group; and each of R<12> and R<13> is an H or halogen atom or a 1-5C alkyl or phenyl or heterocyclic group or the like.

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, as the integration of semiconductors has increased, the processing rules have tended to become smaller. For this reason, a conventional contact / proximity exposure machine using parallel rays is referred to as mirror projection 1:
One projection exposure machine and a reduced projection exposure machine called a stepper have been used. 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. For this reason, there is a problem that it is not possible to achieve both high sensitivity in a film state, particularly high sensitivity by i-ray exposure, and storage stability in a solution state during storage. In addition, in the process of irradiating active light from a mask on which a pattern is drawn on the coating film of these photosensitive materials and developing and removing the unirradiated portions, a process of manufacturing a relief pattern has poor process stability.
There were also problems such as a limitation in resolution and poor dimensional accuracy.

[0004]

SUMMARY OF THE INVENTION The invention according to claim 1 is excellent in photosensitive properties, a pattern of a good shape can be obtained even at a low exposure dose, excellent in storage stability and process stability, and has excellent cured film properties. 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, and R ³ is 2
A photosensitive polyimide precursor having a structural unit represented by the following formula (II), a titanocene compound, and the following general formula (II)

Embedded image (Wherein R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom,
Which represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, a nitro group, a halogen atom or a heterocyclic ring);

Embedded image (Wherein R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are a hydrogen atom, a carbon atom 1
Catechol compounds represented by the following general formulas (IV): alkyl groups, phenyl groups, nitro groups, halogen atoms or heterocyclic rings

Embedded image (Wherein, R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, a nitro group, a halogen atom or a heterocyclic ring). The present invention relates to a photosensitive polyimide precursor composition containing a compound.

[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 preferably a tetracarboxylic acid residue capable of forming a polyimide resin by reacting with a diamine. From the viewpoints of mechanical properties, heat resistance and adhesiveness of the polyimide film to be obtained, 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, organic groups having a total carbon number of 6 to 30 including an aromatic ring (benzene ring, naphthalene ring, etc.) are more preferable. In the polyimide precursor molecule, in the plurality of repeating units, all R ^{1 s} may be the same or different.

[0008]

Embedded image

[0009]

Embedded image

In the photosensitive polyimide precursor, the photosensitive group represented by R ² is a group which is eliminated by light irradiation, a group which can be duplicated or copolymerized by light irradiation, etc. A group having a double bond is preferable because good photosensitivity can be easily imparted.

The binding of the photosensitive group may be through a covalent bond, but is preferably a compound having a photosensitive group via an ester bond, an amide bond or a urea bond, and particularly preferably a polymerizable unsaturated divalent compound via an ester bond. Those having a heavy bond are preferable because of their excellent photosensitive properties. In particular

Embedded image (Wherein R ¹⁴ is a divalent organic group). Examples of R ¹⁴ include an alkylene group and an arylene group, and those having 1 to 10 carbon atoms are preferable.

In the general formula (I), R ³ is preferably a residue of a diamine capable of forming a polyimide resin by reacting with a tetracarboxylic acid or a derivative thereof (an acid anhydride, a diester or the like). From the viewpoints of mechanical properties, heat resistance and adhesiveness of the polyimide film obtained by the above method, it is preferred that the polyimide film is an organic group containing 6 to 30 carbon atoms, including an aromatic ring or silicon. When a plurality of structural units represented by the general formula (I) exist in a molecule, a plurality of R ³ may be the same or different.

Preferred examples of R ³ are as follows.

[0014]

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[0015]

Embedded image

[0016]

Embedded image

In the present invention, units other than the structural unit represented by the above general formula (I), specifically, R2
Instead of a non-photosensitive group, for example, an alkyloxy group,
An aryloxy group or an OH group may be partially included. In this case, the proportion of the structural unit represented by the general formula (I) is preferably 30 to 100 mol%, particularly 50 to 100 mol% in terms of mol percentage, since a high sensitivity and a good pattern shape can be obtained. preferable. Further, in the case of having a group other than the photosensitive group, from the viewpoint of film properties, it is preferable to use an alkyloxy group having 4 or less carbon atoms, and a methyloxy group, an ethyloxy group, an n-propyloxy group, an isopropyloxy group, An n-butyloxy group is particularly preferred.

The molecular weight of the polyimide precursor in the present invention may be 1 in terms of weight average molecular weight from the viewpoint of film properties and the like.
It is preferably from 10,000 to 700,000, and from 10,000 to
200,000 is more preferred. The weight average molecular weight is G
PC (gel permeation chromatography)
And can be calculated in terms of polystyrene.

The photosensitive 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, and then acid chloride with thionyl chloride. Then, it can be synthesized by a method of reacting with a diamine, or a method of reacting the tetracarboxylic acid half ester with a diamine using a carbodiimide as a condensing agent.

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 represented by the following general formula (V)

Embedded image (Wherein, R ¹⁵ and R ¹⁶ 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 ³ in the structural unit represented by the general formula (I) 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 are used, and these are used alone or in combination of two or more.

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

Embedded image (Wherein, R ¹⁷ and R ¹⁸ each represent a divalent hydrocarbon group and may be the same or different, and R ¹⁹ and R ²⁰ each represent a monovalent hydrocarbon group, and may each 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 30 mol% based on all the diamine components. As R ¹⁷ and R ¹⁸ , 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, a bonding group thereof, and the like. Examples of R ¹⁹ and R ²⁰ 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. When this diamine is used, it is preferable to use 1 to 30 mol% of all the diamine components. These diamines are used alone or in combination of two or more.

The compound having a photosensitive group used to introduce an ester bond includes, for example, hydroxyalkyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxypropyl methacrylate, hydroxymethyl acrylate, hydroxymethyl methacrylate and the like. Preferred are (meth) acrylates. These are used alone or in combination of two or more.

The photosensitive polyimide precursor composition of the present invention contains a titanocene compound. Examples of the titanocene compound include compounds represented by the following general formula (VII):

Embedded image (Wherein, R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ ,
R ²⁸ , R ^29, and R ³⁰ 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.

Specific compounds include 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 0.1 to 100 parts by weight of the polyimide precursor.
10.0 parts by weight, preferably 0.3 to 5.0 parts by weight.
It is more preferred to be parts by weight.

In the present invention, a compound selected from the group consisting of the hydroquinone compound represented by the general formula (II), the catechol compound represented by the general formula (III) and the benzoquinone compound represented by the general formula (IV) is used. Used.

Examples of the hydroquinone compound include:
Hydroquinone, methylhydroquinone, chlorohydroquinone, t-butylhydroquinone, 2,3-dimethylhydroquinone, 2,5-bis (1,1,3,3-tetramethylbutyl) -hydroquinone, trimethylhydroquinone, tetrafluorohydroquinone, phenylhydroquinone , Nitrohydroquinone, thienylhydroquinone, furylhydroquinone and the like. These may be used in combination of two or more.

Examples of the catechol compound include catechol, 3-methylcatechol, 4-methylcatechol, 3-methoxycatechol, 3-fluorocatechol, 4-t-butylcatechol, 3,3,3 ', 3'-
Tetramethyl-1,1'-spirobisindene 5,
5 ', 6,6'-tetrol, 3,4-dihydroxyphenyl glycol, 3,5-diisopropylcatechol, 3,5-di-t-butylcatechol, tetrachlorocatechol, tetrabromocatechol and the like.
These may be used in combination of two or more.

Examples of the benzoquinone compound include p
-Benzoquinone, 2,5-dimethyl-p-benzoquinone, 2,5-diethyl-p-benzoquinone, 2,5-diphenyl-p-benzoquinone, 2,5-dinitro-p-
Benzoquinone, 2,5-dichloro-p-benzoquinone,
Preferred are 2,5-dibromo-p-benzoquinone, 2,5-difuryl-p-benzoquinone, 2,5-dithienyl-p-benzoquinone and the like. These may be used in combination of two or more.

Each of the above compounds may be used in combination of two or more compounds. These compounds are added in an amount of 0.01 to 100 parts by weight of components (solid content) other than the compounds.
It is preferably used in an amount of from 1 to 1 part by weight, more preferably from 0.01 to 0.5 part by weight. If the amount is less than 0.01 part by weight, the effect of improving the resolution and process stability tends to be hardly seen. If the amount exceeds 1 part by weight, the sensitivity tends to decrease and the pattern shape tends to deteriorate.

The photosensitive polyimide precursor composition of the present invention preferably further uses a dye compound, particularly a dye compound having an absorption at 450 nm to 600 nm. Thereby, the storage stability can be further improved. Preferred examples thereof include phenolphthalene, phenol red, neal red, pyrogallol red, pyrogallol violet, disperse red 1, disperse red 1
3, disperse red 19, disperse orange 1, disperse orange 3, disperse orange 1
3, day sparse orange 25, day sparse blue 3, day sparse blue 14, eosin B, rhodamine B, quinalizarin, 5- (4-dimethylaminobenzylidene) rhodanine, aurin tricarboxyside, aluminon, alizarin, pararosaniline, emodin , Thionin and methylene violet, and more preferred are Disperse Red 1, phenolphthalene, and Neil Red. These are used alone or in combination of two or more. From the viewpoint of storage stability, the content in the composition is preferably from 0.1 to 3.0 parts by weight, preferably from 0.3 to 1.5 parts by weight, based on 100 parts by weight of the polyimide precursor. Is more preferable.

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.

Examples of the addition polymerizable compound having a boiling point of 100 ° C. or more at normal pressure include polyhydric alcohol 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. As the sensitizer, for example, benzal acetophenone,
4'-N, N-dimethylaminobenzalacetophenone, 4'-acetoaminobenza-4-methoxyacetophenone and the like. There is no particular limitation on the amount of the sensitizer used, but when used, the polyimide precursor 100
It is preferably added in an amount of 0.01 to 50 parts by weight, more preferably 0.05 to 20 parts by weight, based on parts by weight.

The light-sensitive material may contain a bisazide compound. Examples of the bisazide compound include

Embedded image

Embedded image And the like. The bisazide compound is preferably used in a range of 0.01 to 10 parts by weight based on 100 parts by weight of the polyimide precursor.

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 method for producing a pattern of the present invention is preferable from the viewpoint of using the photosensitive polyimide precursor composition of the present invention obtained as described above and improving the cured product of the composition by a photolithography technique. 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.

Some of the relief patterns obtained by the above-mentioned treatment have the polyimide precursor of the present invention 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.

[0041]

The present invention will be described below with reference to examples. Examples 1 to 3 and Comparative Example 1 3,3 ', 4,4'- obtained by reacting 1 equivalent of 3,3', 4,4'-biphenyltetracarboxylic dianhydride with 2 equivalents of 2-hydroxyethyl methacrylate Biphenyltetracarboxylic acid di (2-hydroxyethyl methacrylate)
0.50 mol of ester and 1 equivalent of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride were added to methanol 2
2.20 mol of thionyl chloride is condensed with a mixture of 0.50 mol of 3,3 ', 4,4'-biphenyltetracarboxylic acid dimethyl ester reacted with an equivalent amount and 1.00 mol of 4,4'-diaminodiphenyl ether. Of N-methyl-2-pyrrolidone solution of polyamic acid ester obtained by reacting as an agent, 10 g (solid content: 20% by weight), tetra (1,2-propylene glycol) diacrylate 0.1 g
50 g, bis (cyclopentadienyl) -bis [2,6
-Difluoro-3- (pyrrol-1-yl) phenyl]
After mixing 0.1 g of titanium, 0.02 g of 4,4'-bisazide-3,3'-biphenyl, a catechol compound and a coloring compound, take out the sample in a glass sample bottle and store it in a yellow room at room temperature at room temperature. A stability test was performed. Table 1 shows the viscosities of the photosensitive resins immediately after blending and after 7 days from standing.

After the photosensitive resin is spin-coated on a silicon wafer, it is placed on a hot plate at 100 ° C. for 20 minutes.
The solvent was dried by heating for 0 seconds to obtain a photosensitive coating film. The film thickness after drying was 20 microns. Pattern exposure was performed on the coating film via a photomask with a mirror projection exposure machine using an ultra-high pressure mercury lamp as a light source. After that, immersion development was carried out with a mixed solution of N-methyl-2-pyrrolidone and methyl alcohol (volume ratio: 4/1), followed by rinsing with ethanol. 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% is shown in Table 1 as sensitivity. Table 1 shows the minimum mask dimension of the pattern opened at that time as the resolution.
Tables 2 and 3 show the resolution of the photosensitive materials of Example 1 and Comparative Example 1 when the time from application to exposure and the time from exposure to development were changed.

[0043]

[Table 1]

[0044]

[Table 2]

[0045]

[Table 3]

Examples 4 to 6 The same procedures as in Example 1 were carried out except that the catechol compound and the coloring compound were changed to those shown in Table 4. The results are shown in Tables 4, 5 and 6.

[0047]

[Table 4]

[0048]

[Table 5]

[0049]

[Table 6]

Examples 7 to 9 The same procedures as in Example 1 were carried out except that the catechol compound and the coloring compound were changed to those shown in Table 7. The binding is shown in Tables 7, 8 and 9.

[0051]

[Table 7]

[0052]

[Table 8]

[0053]

[Table 9]

The wafers of Examples 1 to 9 were placed in a nitrogen atmosphere at 100 ° C. for 15 minutes and at 200 ° C. for 20 minutes.
And heated at 350 ° C. for 60 minutes to obtain a final cured film. A good polyimide pattern having a final cured film thickness of 10 microns was obtained. As shown in the examples, the photosensitive composition of the present invention has better photosensitive characteristics than the composition of the comparative example.

[0055]

The photosensitive polyimide precursor composition according to claim 1 has excellent photosensitive characteristics, a pattern having a good shape can be obtained even at a low exposure dose, and storage stability, process stability and cured film characteristics are also obtained. It is excellent. The photosensitive polyimide precursor composition according to the second aspect is more excellent in sensitivity in addition to the effects of the first aspect. According to the third aspect of the present invention, a pattern having a good shape can be obtained even with a low exposure dose, and a cured film having excellent cured film characteristics can be obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/027 502 G03F 7/027 502 7/029 7/029 7/037 501 7/037 501 H01L 21/027 H01L 21/312 B 21/312 21/30 502R 21/768 21/90 S

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, and R ³ is 2
A photosensitive polyimide precursor having a structural unit represented by the formula (II), a titanocene compound, and a compound represented by the following general formula (II): (Wherein R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom,
A hydroquinone compound represented by an alkyl group having 1 to 5 carbon atoms, a phenyl group, a nitro group, a halogen atom or a heterocyclic ring), represented by the following general formula (III): (Wherein R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are a hydrogen atom, a carbon atom 1
A catechol compound represented by the following general formula (IV): (Wherein, R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, a nitro group, a halogen atom or a heterocyclic ring). A photosensitive polyimide precursor composition containing a compound. 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.