JPH11316459A - Photosensitive composition, photosensitive material, production of relief pattern and production of polyimide pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance photosensitive characteristic and life stability, to ensure high resolution and to improve process stability by incorporating a specified picrylhydrazine, titanocene compound and an addition polymerizable compd. SOLUTION: This photosensitive composition contains 1,1-diaryl-2- picrylhydrazyl represented by formula I, a titanocene compound represented by formula II and an addition polymerizable compound. In the formula I, R is halogen or a monovalent organic group and (m) and (n) are each an integer of 0-5. In the formula II, R<1> -R<10> are each H, halogen, 1-20C alkoxy or a heteroring. 1,1-diaryl-2-picrylhydrazyl is preferably 1,1-diphenyl-2-picrylhydrazyl. The preferred amount of 1,1-diaryl-2-picrylhydrazyl used is 0.01-1 pt.wt., more preferably 0.01-0.5 pt.wt. per 100 pts.wt. polyimide precursor.

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 according to claim 2 provides a photosensitive composition having more excellent storage stability in addition to the object of the invention according to 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. A fourth aspect of the present invention provides a photosensitive material having more excellent storage stability, in addition to the objects of the third aspect of the present invention. The invention according to claim 5 provides a photosensitive material exhibiting more excellent photosensitive characteristics in addition to the objects 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 represents a halogen atom or a monovalent organic group,
m and n each independently represent an integer of 0 to 5), 1,1-diaryl-2-picrylhydrazyl represented by the following general formula (II)

Embedded image (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R
⁹ and R ¹⁰ 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 composition containing an addition polymerizable compound.

[0005] Further, the present invention further provides a method for producing a substrate having a wavelength of 450 to 600 nm.
The present invention relates to the above-mentioned photosensitive composition containing a dye compound having absorption in water.

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

Embedded image (Wherein, R represents a halogen atom or a monovalent organic group,
m and n each independently represent an integer of 0 to 5), 1,1-diaryl-2-picrylhydrazyl represented by the following general formula (II)

Embedded image (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R
⁹ and R ¹⁰ each independently represent a hydrogen atom, a halogen atom, an alkoxy group having 1 to 20 carbon atoms or a heterocyclic ring) and a carbon-carbon double bond that can be dimerized or polymerized by actinic radiation. A photosensitive material comprising a polyimide precursor having the formula:

The present invention also relates to the above light-sensitive material, further comprising a dye compound having an absorption at 450 to 600 nm. Further, the present invention 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 the photosensitive composition or the coating film of the photosensitive material with actinic rays in a pattern and developing and removing the 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.

[0009]

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)
1,1-diaryl-2-picrylhydrazyl represented by the following formula, a titanocene compound represented by the general formula (II), and an addition polymerizable compound are contained as essential components.

The 1,1-diaryl-2-picrylhydrazyl represented by the general formula (I) in the present invention is preferably 1,1-diphenyl-2-picrylhydrazyl. , Other, as a substituent represented by R, a halogen atom such as chlorine and fluorine, an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group,
A hydrocarbon group having 1 to 20 carbon atoms, such as an aryl group such as a phenyl group, or an alkoxy group having 1 to 20 carbon atoms, such as a methoxy group, an ethoxy group, or a propoxy group, is substituted by 1 to 5 in each phenyl group. What was done. Different substituents may be mixed. 1,
There is no particular limitation on the amount of 1-diaryl-2-picrylhydrazyl used, but in the photosensitive composition of the present invention, the solid content excluding 1,1-diaryl-2-picrylhydrazyl (excluding the solvent) The same applies hereinafter.) 10
It is preferably from 0.01 to 3 parts by weight, more preferably from 0.05 to 1 part by weight, per 0 parts by weight.
If the amount is less than 0.01 part by weight, the resolution and the process stability tend not to be improved. If the amount exceeds 3 parts by weight, the sensitivity tends to decrease and the pattern shape tends to deteriorate.

The titanocene compound represented by the general formula (I) 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 used is not particularly limited, but is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the solid content excluding the titanocene compound in the photosensitive composition of the present invention. Is preferred. The proportion of the 1,1-diaryl-2-picrylhydrazyl and the titanocene compound is not particularly limited, but it is preferable to use the titanocene compound in the same amount or more as the 1,1-diaryl-2-picrylhydrazyl. . In addition, from the viewpoint of photocurability, the total content of the 1,1-diaryl-2-picrylhydrazyl and the titanocene compound in the photosensitive composition is used as an addition polymerizable compound described later and as necessary. The amount is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of the high molecular weight organic polymer.

As the addition-polymerizable compound contained in the photosensitive composition of the present invention, those having a boiling point of 100 ° C. or more at normal pressure are preferable, such as 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 (meta) ) 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-
Preferred examples include acrylic acid or methacrylic acid ester compounds such as dimethylacrylamide and N-methylolacrylamide, acrylamide-based compounds, styrene and derivatives thereof. These are used alone or in combination of two or more.

If the solvent has a boiling point lower than 100 ° C. at normal pressure, the addition polymerizable compound tends to be volatilized when the solvent contained in the system is removed by drying or the like or when irradiating with an actinic ray. There is. 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 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,
Phenolphthalein, 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, Preferred are 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 polyvalent carboxylic 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, Examples include polyamic acid esters and polyamic acid amides.

The polyamic acid is not particularly restricted but includes, for example, those obtained by addition polymerization using tetracarboxylic dianhydride and a diamine compound as materials. As the tetracarboxylic dianhydride, for example,
Pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4
4'-biphenyltetracarboxylic dianhydride, 1,2,2
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 Anhydride, 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-dicarboxy) Phenyl) 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 ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent an alkyl group having 1 to 6 carbon atoms, and p and q 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.

[0021] 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 use amount of these photoinitiators is not particularly limited, but in the photosensitive composition of the present invention, the content 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 includes the above-mentioned 1,1-diaryl-2-picrylhydrazyl, the titanocene compound represented by the above formula (I), and actinic radiation. Contains a polyimide precursor having a carbon-carbon double bond which can be dimerized or polymerized 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.

Carbon dimerizable or polymerizable by actinic radiation
As a polyimide precursor having a carbon double bond, for example, a vinyl group, an acryloyl group, a methacryloyl group, or the like is introduced into a side chain of the polyimide precursor via a covalent bond such as an ester bond, an amide bond, and a urea bond. A covalent bond type, a polyamic acid as described above, a dimerizable or polymerizable carbon-carbon double bond and an amino group or a quaternized salt thereof, which are introduced into the carboxyl group of the polyamic acid by an ionic bond. And a compound having the following formula: From the viewpoint of the ease of volatilization of the photosensitive group at the time of ring closure of the thermal imide and the ease of manufacturing the photosensitive material,
An ionic bond type is preferred.

In the light-sensitive material of the present invention, the amount of 1,1-diaryl-2-picrylhydrazyl used is preferably 0.01 to 1 part by weight based on 100 parts by weight of the polyimide precursor. More preferably, it is 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, and if it exceeds 1 part by weight, sensitivity is lowered and pattern shape is deteriorated. In the light-sensitive material of the present invention, the content of the titanocene compound represented by the general formula (I) is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the polyimide precursor. 0.
If it is less than 01 parts by weight, the photocurability tends to be low,
If it exceeds 0 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 photocurable polyimide precursor in which a double bond has been introduced as a side chain into the polyamic acid via this ionic bond to form a polyimide precursor. Examples of this compound include the following compounds.

[0027]

Embedded image

[0028]

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. The amount is preferably 0.05 to 5 parts by weight based on 100 parts by weight of the polyimide precursor from the viewpoint of stability, handleability, and the like. 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.

[0030]

Embedded image

[0031]

Embedded image

When a bisazide compound is used, the content of the polyimide precursor 1 is determined in terms of heat resistance, photocurability and the like.
It is preferably 0.01 to 10 parts by weight based on 00 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 is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the polyimide precursor from the viewpoint of heat resistance, photocurability and the like.

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 depends on heat resistance, photocurability and the like.
It is preferably 0.01 to 10 parts by weight based on 00 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, its use amount is not particularly limited, but from the viewpoint of coatability and the like, the amount is such that the solid content (components other than the organic solvent) of the photosensitive material is 5 to 95 parts by weight. Preferably 10 to 50% by weight
More preferably, the amount is such that 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 applied to a substrate such as a silicon wafer, a metal substrate, a glass substrate, a ceramic substrate or the like by an immersion method, a spray method, a screen printing method, a spin coating method 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,
Examples include monochromatic light such as electron beams and X-rays. After the irradiation, a desired relief pattern is obtained by dissolving and removing the unirradiated portion with an appropriate developer.

The developer is not particularly limited, but may be, 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-mentioned 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.

[0038]

The present invention will be described below with reference to examples. Examples 1 and 2 and Comparative Example 1 4,4'-diaminodiphenylsulfone and 3,3 ',
N-methyl-polyamide acid obtained by reacting 4,4'-biphenyltetracarboxylic dianhydride with equimolar amount
10 g of 2-pyrrolidone solution (solid content 20% by weight), 1.8 g of dimethylaminoethyl methacrylate, bis (cyclopentadienyl) -bis [2,6-difluoro-3-
(Pyri-1-yl) phenyl] titanium 0.1 g, 4,
0.02 g of 4'-bisazide-3,3'-biphenyl,
After blending 1,1-diphenyl-2-picrylhydrazyl and a dye compound, the mixture was stirred and mixed to obtain a photosensitive material. After filtering through a filter, the sample was taken out into a glass sample bottle and left in a yellow room at room temperature to perform a storage stability test. Table 1 shows the viscosities of the photosensitive resins immediately after blending and after 7 days from standing.

These photosensitive materials are spin-coated on a silicon wafer and placed on a hot plate at 100 ° C. for 200 hours.
After heating for 2 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 exposure amount at which the residual film ratio (value obtained by dividing the film thickness by the initial film thickness) becomes 90% and the minimum mask dimension of the pattern opened at that time are shown in Table 1 as a resolution. Indicated.

[0040]

[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.

[0042]

[Table 2]

[0043]

[Table 3]

For the wafer obtained in Example 1,
This is carried out under nitrogen atmosphere at 100 ° C. for 15 minutes and at 200 ° C. for 2 minutes.
Heating was performed at 350 ° C. for 60 minutes for 0 minute 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.

[0045]

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 H01L 21/312 H01L 21/30 502R 571

Claims (7)

[Claims] 1. A compound represented by the following general formula (I) (Wherein, R represents a halogen atom or a monovalent organic group,
m and n each independently represent an integer of 0 to 5), and 1,1-diaryl-2-picrylhydrazyl represented by the following general formula (II): (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R
⁹ and R ¹⁰ each independently represent a hydrogen atom, a halogen atom, an alkoxy group having 1 to 20 carbon atoms or a heterocyclic ring) and an addition polymerizable compound. 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 represents a halogen atom or a monovalent organic group,
m and n each independently represent an integer of 0 to 5), 1,1-diaryl-2-picrylhydrazyl; a compound represented by the following general formula (II): (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R
⁹ and R ¹⁰ each independently represent a hydrogen atom, a halogen atom, an alkoxy group having 1 to 20 carbon atoms or a heterocyclic ring) and a carbon-carbon double bond that can be dimerized or polymerized by actinic radiation. A photosensitive material comprising a polyimide precursor having the formula: 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. A method of irradiating a photosensitive composition according to claim 1 or 2 or a coating film of the photosensitive material according to claim 3, 4 or 5 with actinic rays in a pattern, and developing and removing unirradiated portions. A method for producing a relief pattern that is a feature. 7. A method for producing a polyimide pattern, comprising heating the relief pattern obtained by the method according to claim 6.