JPH10228105A - Photosensitive composition, photosensitive material, production of relief pattern and production of polyimide pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive compsn. having excellent photosensitive characteristics and storage stability, high resolution and good process stability by incorporating a resorcinol compd., a titanocene compd. and an addition polymerizable compd. having a specified or higher boiling point. SOLUTION: This compsn. contains a resorcinol compd. expressed by formula I, a titanocene compd. expressed by formula II and an addition polymerizable compd. having >=100 deg.C boiling point at normal pressure. Further, the compsn. contains a dye compd. having absorption in 450 to 600nm region. In the formula I, R<1> to R<4> are independently hydrogen atoms, 1 to 5C alkyl groups, phenyl groups, etc., or heterocyclic groups. In the formula II, R<5> to R<14> are independently hydrogen atoms, halogen atoms, 1 to 20C alkoxy groups or heterocyclic groups. Thereby, the obtd. photosensitive compsn. shows excellent photosensitive characteristics and storage stability, high resolution and good process stability.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive composition, a photosensitive material, a method for producing a relief pattern, and a method for producing a polyimide pattern.

[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. The sensitivity can be increased by adding an oxime ester compound, a phenylglycine compound, or the like to improve this. However, on the other hand, there is a disadvantage that the viscosity changes and the photosensitive characteristics are reduced in a state of being dissolved in a polar solvent during storage. For this reason, there was a problem that it was not possible to achieve both high sensitivity in a film state and storage stability in a solution state during storage. Also, 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, the process stability is poor, and the resolution is limited. There was also a problem such as there.

[0003]

The object of the present invention is to provide a photosensitive composition exhibiting excellent photosensitive characteristics and storage stability, and having high resolution and good process stability. The invention described in claim 2 provides a photosensitive composition having more excellent storage stability in addition to the effects of the invention described in claim 1. The third aspect of the present invention is to provide a photosensitive material which exhibits excellent photosensitive characteristics, storage stability and heat resistance, and has high resolution and good process stability. The invention described in claim 4 provides a photosensitive material having more excellent storage stability in addition to the effects of the invention described in claim 3. The invention described in claim 5 provides a photosensitive material exhibiting more excellent photosensitive characteristics in addition to the effects of the invention described in claim 3 or 4. The invention according to claim 6 provides a method for producing a relief pattern which exhibits excellent heat resistance, adhesion and chemical resistance and can provide a polyimide pattern having a good shape. The invention according to claim 7 provides a method for producing a polyimide pattern having excellent heat resistance, adhesion and chemical resistance and having a good shape.

[0004]

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

Embedded image (Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom,
A resorcinol 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);

Embedded image (Wherein, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ ,
R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a halogen atom, an alkoxy group having 1 to 20 carbon atoms or a heterocyclic ring)
At a normal pressure and a titanocene compound represented by the formula:
The present invention relates to a photosensitive composition containing the addition polymerizable compound having the above boiling point. In addition, the present invention further comprises 450 to
The present invention relates to the photosensitive composition containing a dye compound having an absorption at 600 nm.

Further, the present invention provides a compound represented by the following general formula (I):

Embedded image (Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom,
A resorcinol 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);

Embedded image (Wherein, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ ,
R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a halogen atom, an alkoxy group having 1 to 20 carbon atoms or a heterocyclic ring)
And a photosensitive material comprising a compound having a carbon-carbon double bond capable of being dimerized or polymerized by actinic radiation and an amino group or a quaternized salt thereof. In addition, the present invention further comprises 450 to
The present invention relates to the photosensitive material containing a dye compound having an absorption at 600 nm. The present invention also relates to the above-mentioned light-sensitive material further containing a bisazide compound.

The present invention also relates to a method for producing a relief pattern, which comprises irradiating a coating of the photosensitive composition or the photosensitive material with actinic rays in a pattern and developing and removing unirradiated portions. Further, the present invention relates to a method for producing a polyimide pattern, wherein the relief pattern obtained by the above-mentioned production method is heated.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the photosensitive composition of the present invention will be described. The photosensitive composition of the present invention is a composition that can be used for various photosensitive applications, for example, various photoresist materials, materials applied to photosensitive films, and the like. The photosensitive composition of the present invention has the general formula (I)
A resorcinol compound represented by the formula, a titanocene compound represented by the general formula (II), and an addition polymerizable compound having a boiling point of 100 ° C. or more at normal pressure.

Examples of the resorcinol compound represented by the general formula (I) include resorcinol, 2-methylresorcinol, 4-ethylresorcinol, 4-hexylresorcinol, 4-dodecylresorcinol,
4-chlororesorcinol, 4-bromoresorcinol, orcinol, olivetol, 5-methoxyresorcinol, 2,5-dimethylresorcinol, 4,6
-Dichlororesorcinol, 2,4,6-tribromoresorcinol and the like. These are used alone or in combination of two or more. The amount of the resorcinol compound used is not particularly limited, but is preferably 0.01 to 3 parts by weight based on 100 parts by weight of the solids excluding the resorcinol compound in the photosensitive composition of the present invention. , 0.05 to 1 part by weight.

The titanocene compound represented by the general formula (II) includes, for example, bis (cyclopentadienyl)
-Bis [2,6-difluoro-3- (2- (1H-pyrrol-1-yl) ethyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3
-(2- (1H-pyrrol-1-yl) propyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2- (1H-pyrrole-
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- Bisdimethylaminopyrrole-1-yl) phenyl] titanium, bis (cyclopentadienyl)
-Bis [2,6-difluoro-3- (2,5-dimethyl-3-methoxypyrrol-1-yl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3-methoxy] Phenyl] 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 amount of the titanocene compound to be used is not particularly limited. However, in the photosensitive composition of the present invention, the amount is 0.1 to 10 parts by weight based on 100 parts by weight of the solid content excluding the titanocene compound. Is preferred. The ratio of the resorcinol compound and the titanocene compound used is not particularly limited, but it is preferable to use the titanocene compound in the same amount or more as the resorcinol compound. In addition, the total content of the resorcinol compound and the titanocene compound in the photosensitive composition from the viewpoint of photocurability is used as an addition-polymerizable compound having a boiling point of 100 ° C. or more at normal pressure to be described later and as needed. Total amount of high molecular weight organic polymer 1
It is preferably 0.1 to 10 parts by weight with respect to 00 parts by weight.

The addition polymerizable compound having a boiling point of 100 ° C. or more at normal pressure in the photosensitive composition of the present invention is, for example, obtained by condensing a polyhydric alcohol with an α, β-unsaturated carboxylic acid. (Eg, 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, pentaerythritol tetra (meth) acrylate, etc.), styrene, divinylbenzene,
4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl (meth) acrylate, 1,3- (meth) acryloyloxy-2-hydroxypropane, methylenebisacrylamide, N, N-
Dimethyl acrylamide, N-methylol acrylamide and the like can be mentioned, and these are used alone or in combination of two or more.

If the boiling point is lower than 100 ° C. at normal pressure, the addition polymerizable compound volatilizes when the solvent contained in the system is removed by drying or the like or when irradiating with an actinic ray. Because. The addition polymerizable compound is preferably soluble in an organic solvent. The amount of these addition polymerizable compounds used is not particularly limited, but in the photosensitive composition of the present invention, from the viewpoint of photocurability, 5 per 100 parts by weight of the total amount with the high molecular weight organic polymer described below. It is preferably from 9 to 99.9 parts by weight.

The photosensitive composition of the present invention may contain 4
A dye compound having an absorption at 50 to 600 nm may be contained, and such a dye compound may be 450 to 600 nm
There is no particular limitation as long as it has absorption, for example,
Phenolphthalene, phenol red, neal red, pyrogallol red, pyrogallol violet,
Disperse Red 1, Disperse Red 13, Disperse Red 19, Disperse Orange 1, Disperse Orange 3, Disperse Orange 13, Disperse Orange 25, Disperse Blue 3, Disperse Blue 14, Eosin B, Lodamin B, Quinalizarin, 5- (4-dimethylaminobenzylidene) rhodanine, aurin tricarboxyside, aluminone, alizarin, pararosaniline, emodin, thionine, methylene violet and the like. These are used alone or in combination of two or more. The amount of these compounds used is not particularly limited, but is preferably 0.1 to 5 parts by weight based on 100 parts by weight of the solid content excluding the dye compound in the photosensitive composition of the present invention. The proportion of the dye compound and the titanocene compound used is preferably the same or larger than that of the dye compound from the viewpoint of photocurability and stability in the yellow room.

The photosensitive composition of the present invention may contain one or more high molecular weight organic polymers, if necessary. By adding a high molecular weight organic polymer in the photosensitive composition,
Properties such as adhesion to a substrate, chemical resistance, and film properties can be improved. The amount of the high molecular weight organic polymer is preferably from 0.1 to 70 parts by weight based on 100 parts by weight of the total amount of the high molecular weight organic polymer and the addition polymerizable compound from the viewpoint of photocurability. The weight average molecular weight of the high molecular weight organic polymer is preferably from 10,000 to 700,000. The weight average molecular weight can be measured by gel permeation chromatography and using a standard polystyrene calibration curve.

Examples of the high molecular weight organic polymer include copolyesters (polyhydric alcohols (eg, diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylolpropane, neopentyl glycol, etc.) and polycarboxylic acids (eg, terephthalic acid, Copolyesters manufactured from isophthalic acid, sebacic acid, adipic acid, etc.), vinyl polymers (methacrylic acid, acrylic acid, methacrylic acid or alkyl esters of acrylic acid, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (Meth) acrylate, 2-
Hydroxyethyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2
-Dimethylaminoethyl (meth) acrylate, homopolymer or copolymer of vinyl monomer such as 2-ethylhexyl (meth) acrylate, etc.), polyformaldehyde, polyurethane, polycarbonate, polyamide, cellulose ester (methylcellulose, ethylcellulose, etc.), polyamic acid, Polyamic acid esters and the like can be mentioned.

The polyamic acid is not particularly limited,
For example, those obtained by addition polymerization using tetracarboxylic dianhydride and a diamine compound as materials are mentioned. Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-
Biphenyltetracarboxylic dianhydride, 1,2,5,6
-Naphthalenetetracarboxylic dianhydride, 2,3,6
7-naphthalenetetracarboxylic dianhydride, 2,3
5,6-pyridinetetracarboxylic dianhydride, 1,4
5,8-naphthalenetetracarboxylic dianhydride, 3,
4,9,10-perylenetetracarboxylic dianhydride,
4,4'-sulfonyldiphthalic dianhydride, m-terphenyl-3,3 ", 4,4" -tetracarboxylic dianhydride, p-terphenyl-3,3 ", 4,4"- Tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2
-Bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl)
Propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 1,1,1,3,3
3-hexafluoro-2,2'-bis [4- (2,3-
Dicarboxyphenoxy) phenyl] propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,
2'-bis [4- (3,4-dicarboxyphenoxy)
[Phenyl] propane dianhydride.

Examples of the diamine compound include p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 1,5-diaminonaphthalene, benzidine, 3,3'-dimethylbenzidine, , 3'-Dimethoxybenzidine, 4,4 '
(Or 3,4'-, 3,3'-, 2,4 '-)-diaminodiphenylmethane, 4,4' (or 3,4'-, 3,
3'-, 2,4 '-)-diaminodiphenyl ether,
4,4 '(or 3,4'-, 3,3'-, 2,4'-)
Diaminodiphenylsulfone, 4,4 '(or 3,
4 '-, 3,3'-, 2,4 '-)-diaminodiphenyl sulfide, 4,4'-benzophenone diamine,
3,3'-benzophenonediamine, 4,4'-di (4
-Aminophenoxy) phenylsulfone, 4,4'-
Bis (4-aminophenoxy) biphenyl, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 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, 4,4'-di (3-aminophenoxy) phenylsulfone, 3,3'-diaminodiphenylsulfone,
Aromatic diamines such as 2,2'-bis (4-aminophenyl) propane, 2,6-diaminopyridine, 2,4-diaminopyrimidine, 2,4-diamino-s-triazine, 2,7-diaminobenzofuran; 2,7-diaminocarbazole, 3,7-diaminophenothiazine, 2,
5-diamino-1,3,4-thiadiazole, 2,4-
Heterocyclic diamines such as diamino-6-phenyl-s-triazine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, 2,2-dimethylpropylenediamine, the following general formula (III)

Embedded image (Wherein, R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent an alkyl group having 1 to 6 carbon atoms, and m and n each independently represent 1
And an aliphatic diamine such as diaminopolysiloxane. The above tetracarboxylic dianhydride and diamine compound are used alone or in combination of two or more.

The photosensitive composition of the present invention may contain a sensitizer if necessary. Examples of the sensitizer 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, benzalacetophenone, 4'-N, N-dimethylaminobenzalacetophenone, 4'-acetoaminobenzal -4-methoxyacetophenone and the like. These are used alone or in combination of two or more. The amount of these sensitizers is not particularly limited, but in the photosensitive composition of the present invention, 0.1 to 0.1 parts by weight of the solid content excluding the sensitizer.
Preferably, the amount is from 10 to 10 parts by weight.

The photosensitive composition of the present invention may contain a photoinitiator, 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, 2,2-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-methylsulfonyl) Phenyl) glycine and the like. These photoinitiators are used alone or in combination of two or more. The amount of these photoinitiators used is not particularly limited, but in the photosensitive composition of the present invention, the amount is preferably 0.1 to 10 parts by weight based on 100 parts by weight of solids excluding the photoinitiator. preferable.

The photosensitive composition of the present invention can contain an organic solvent, if necessary. Examples of such an organic solvent include acetone, methyl ethyl ketone, toluene, chloroform, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, ethylene glycol monomethyl ether, xylene, and tetrahydrofuran. , Dioxane, N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, γ-butyrolactone, dimethylsulfoxide, ethylene carbonate, propylene carbonate, sulfolane and the like. These organic solvents are used alone or in combination of two or more. The use amount of these organic solvents is not particularly limited, but is preferably such that the solid content is 5 to 95% by weight in the photosensitive composition of the present invention from the viewpoint of coatability and the like. More preferably, the amount is 50% by weight.

The photosensitive composition of the present invention may contain other additives, for example, additives such as a plasticizer and an adhesion promoter.

The light-sensitive material of the present invention is different from the above-mentioned light-sensitive composition, and comprises a resorcinol compound represented by the general formula (I), a titanocene compound represented by the general formula (II), a polyamic acid, A compound having a carbon-carbon double bond capable of being dimerized or polymerized by actinic radiation and an amino group or a quaternized salt thereof is contained as an essential component. This photosensitive material is preferably used for an interlayer insulating film or a surface protective film of a semiconductor device, for example, and can form a good polyimide film by curing.

As the polyamic acid, the above-mentioned polyamic acid can be used. In the light-sensitive material of the present invention, the amount of the resorcinol compound represented by the general formula (I) is 0.01 to 100 parts by weight of the polyamic acid.
To 1 part by weight, more preferably 0.01 to 0.5 part by weight. If the amount is less than 0.01 part by weight, the effect of resolution and process stability tends to be small,
If the amount exceeds 1 part by weight, the sensitivity is lowered and the pattern shape is deteriorated. In the light-sensitive material of the present invention, the content of the titanocene compound represented by the general formula (II) is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the polyamic acid. If it is less than 0.01 part by weight, the photocurability tends to be low, and if it exceeds 10 parts by weight, the heat resistance tends to be poor.

The compound having a carbon-carbon double bond which can be dimerized or polymerized by actinic radiation and an amino group or a quaternized salt thereof is a carboxyl group of the polyamic acid and an amino group or a quaternized salt thereof. And a double bond is introduced as a side chain into the polyamic acid via the ionic bond to form a photocurable polyamic acid. Examples of this compound include the following compounds.

[0025]

Embedded image

[0026]

Embedded image

The amount of the compound to be used is preferably an amount that is equimolar to the carboxyl group of the polyamic acid ± 10 mol% from the viewpoint of photocurability, heat resistance and the like. This amount is usually 30 parts by weight per 100 parts by weight of the polyamic acid.
１２０120 parts by weight. Further, the light-sensitive material of the present invention may contain the above-mentioned dye compound having absorption at 450 to 600 nm, if necessary. This amount is, from the viewpoint of stability, handleability, etc., based on 100 parts by weight of the polyamic acid.
It is preferably 0.1 to 3 parts by weight.

The light-sensitive material of the present invention may contain a bisazide compound if necessary. Examples of such a bisazide compound include the following compounds.

[0029]

Embedded image

[0030]

Embedded image

When a bisazide compound is used, the content of the bisazide compound is preferably 100 or less in terms of heat resistance and photocurability.
It is preferably 0.01 to 10 parts by weight based on parts by weight. Further, the light-sensitive material of the present invention may contain a photoinitiator. Such photoinitiators include those described above. When a photoinitiator is used, the amount of the photoinitiator is preferably 100 or less in terms of heat resistance and photocurability.
It is preferably 0.1 to 10 parts by weight based on parts by weight.

Further, the light-sensitive material of the present invention may contain a sensitizer. Such sensitizers include those described above. When a sensitizer is used, the amount of the sensitizer to be used is preferably 100 or less in terms of heat resistance and photocurability.
It is preferably 0.01 to 10 parts by weight based on parts by weight.

Further, the light-sensitive material of the present invention may contain an organic solvent. Examples of such organic solvents include those described above. When an organic solvent is used, the amount used is not particularly limited, but is preferably an amount such that the solid content of the photosensitive material is 5 to 95 parts by weight from the viewpoint of coatability and the like. More preferably, the amount is 50% by weight. Further, the light-sensitive material of the present invention may contain additives such as a plasticizer and an adhesion promoter.

The photosensitive composition and the photosensitive material of the present invention are coated on a substrate such as a silicon wafer, a metal substrate, a glass substrate, a ceramic substrate or the like by dipping, spraying, screen printing, spin coating, or the like. When an organic solvent is contained, a coating film having no tackiness can be obtained by heating and drying most of the organic solvent. The coating film is irradiated with actinic rays in a pattern. For example, actinic light is irradiated through a mask on which a pattern is drawn. The actinic rays to be irradiated include ultraviolet rays, far ultraviolet rays, visible light,
There are an electron beam and an X-ray. After the irradiation, a desired relief pattern is obtained by dissolving and removing the unirradiated portion with an appropriate developer.

The developing solution is not particularly limited. For example, a flame-retardant solvent such as 1,1,1-trichloroethane, an alkaline aqueous solution such as an aqueous sodium carbonate solution, N, N-dimethylformamide, N, N-dimethyl Acetamide, N
Good solvents such as -methyl-2-pyrrolidone, and mixed solvents of these good solvents with poor solvents such as lower alcohols, water and aromatic hydrocarbons are used. After the development, rinsing may be performed with a poor solvent or the like, if necessary, and the pattern may be dried at about 100 ° C. to make the pattern stable.

By heating the thus obtained relief pattern at, for example, 80 to 400 ° C. for 5 to 300 minutes, imide ring closure can be performed to obtain a polyimide pattern. Using the above-described relief pattern or polyimide pattern as a mask, a passivation film formed using an inorganic substance such as SiO or SiN can be processed by dry etching. Further, it can be used as an interlayer insulating film or a surface protective film of a semiconductor device.

[0037]

The present invention will be described below with reference to examples. Examples 1-4 and Comparative Example 1 N-methyl-2-pyrrolidone solution of polyamic acid obtained by reacting 4,4'-diaminodiphenyl ether with pyromellitic dianhydride in equimolar amount 10 g (solids 2
0% by weight), 1.8 g of 2-dimethylaminoethyl methacrylate, bis (cyclopentadienyl) -bis [2,
6-difluoro-3- (pyrrol-1-yl) phenyl] titanium 0.1 g, 4,4'-bisazide-3,3 '
After blending 0.02 g of biphenyl, a resorcinol compound and a dye compound, the mixture was stirred and mixed to obtain a light-sensitive material.
This was taken out into a glass sample bottle and left at room temperature in a yellow room to perform a storage stability test. Table 1 shows the viscosities of the photosensitive materials immediately after blending and after 7 days from standing.

Further, these photosensitive materials are spin-coated on a silicon wafer and placed on a hot plate at 100 ° C. for 20 minutes.
After heating for 0 seconds, the solvent was dried to obtain a photosensitive coating film. The film thickness after drying was 23 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. Thereafter, immersion development was performed with a mixed solution of N-methyl-2-pyrrolidone and methyl alcohol (volume ratio: 4/1). Further, it was rinsed with isopropanol. The pattern shape after development is measured and observed, and the residual film ratio (the value obtained by dividing the film thickness by the initial film thickness) is 90%.
Table 1 shows the exposure amount and the minimum mask dimension of the pattern opened at that time as the resolution.

[0039]

[Table 1]

Tables 2 and 3 show the resolution of the photosensitive material of Example 1 when the standing time from coating to exposure and from exposure to development was changed.

[0041]

[Table 2]

[0042]

[Table 3]

The wafer obtained in Example 1 was 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 and photosensitive material of the present invention are superior in storage stability and photosensitive characteristics to those of the comparative examples, and have high resolution and good process stability.

[0044]

The photosensitive composition according to the first aspect exhibits excellent photosensitive properties and storage stability, and has high resolution and good process stability. The photosensitive composition according to the second aspect has the effect of the invention according to the first aspect and is more excellent in storage stability. The photosensitive material according to claim 3 is
It shows excellent photosensitive characteristics, storage stability and heat resistance, and has high resolution and good process stability. Claim 4
The photosensitive material described above has the effects of the invention according to claim 3,
It is more excellent in storage stability. The light-sensitive material according to the fifth aspect has the effects of the invention according to the third or fourth aspect and exhibits more excellent light-sensitive properties. According to the method for producing a relief pattern according to the sixth aspect, a relief pattern which exhibits excellent heat resistance, adhesion and chemical resistance and can provide a polyimide pattern having a good shape can be obtained. According to the method for producing a polyimide pattern according to claim 7, a polyimide pattern having excellent heat resistance, adhesion and chemical resistance and having a good shape can be obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/027 504 G03F 7/027 504 7/038 505 7/038 505 7/40 501 7/40 501 H01L 21/027 H01L 21 / 312 B 21/312 21/30 502R 569F

Claims (7)

[Claims] 1. A compound represented by the following general formula (I) (Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom,
A resorcinol compound represented by an alkyl group, a phenyl group, a nitro group, a halogen atom or a heterocyclic ring), represented by the following general formula (II): (Wherein, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ ,
R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a halogen atom, an alkoxy group having 1 to 20 carbon atoms or a heterocyclic ring)
At a normal pressure and a titanocene compound represented by the formula:
A photosensitive composition containing an addition polymerizable compound having the above boiling point. 2. The photosensitive composition according to claim 1, further comprising a dye compound having an absorption at 450 to 600 nm. 3. The following general formula (I): (Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom,
A resorcinol 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 (II): (Wherein, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ ,
R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a halogen atom, an alkoxy group having 1 to 20 carbon atoms or a heterocyclic ring)
A photosensitive material comprising a titanocene compound represented by the formula: polyamic acid, a compound having a carbon-carbon double bond dimerizable or polymerizable by actinic radiation and an amino group or a quaternized salt thereof. 4. The light-sensitive material according to claim 3, further comprising a dye compound having an absorption at 450 to 600 nm. 5. The light-sensitive material according to claim 3, further comprising a bisazide compound. 6. The photosensitive composition according to claim 1 or 2, or a coating film of the photosensitive material according to claim 3 or 4, is irradiated with actinic rays in a pattern, and the unirradiated portion is developed and removed. Method of producing relief patterns. 7. A method for producing a polyimide pattern, comprising heating the relief pattern obtained by the method according to claim 6.