JPH05224419A - Forming method for polyimide fine pattern - Google Patents

Abstract

PURPOSE:To expand usable range in the use field such as an insulating film between semiconductor layers or surface protecting layer in need of fine machining by using a photosensitive polyimide precursor having a specific chemical structure and by using a developer having a specific solubility in the developing processing. CONSTITUTION:A photosensitive layer made of a photosensitive resin compound containing essentially a photosensitive polyimide precursor having a repeating unit expressed by a formula and a photopolymerization initiator is provided on a substrate. In the formula, X has a chemical structure, in which carboxyl group is removed from aromatic tetracarboxylic acid, Y has a chemical structure, in which amino group is removed from aromatic diamine, R is the residue of an unsaturated compound having ethylene bond at the terminal. And the photosensitive layer is exposed to form an image by energy beam of practically <400nm wave length and is developing processed with a developer having the solubility of >5.0 seconds dissolving time per 1mum photosensitive layer and is heat processed to imide cyclize the polyimide precursor.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improved method for forming a polyimide fine pattern. More specifically, the present invention utilizes a polyimide precursor having a specific structure, which is suitable for the production of electronic materials such as semiconductor devices and multilayer wiring boards, and substantially utilizes energy rays having a wavelength of 400 nm or less, particularly i-line stepper. The present invention relates to a method for forming a polyimide fine pattern by performing an exposure process with.

[0002]

2. Description of the Related Art In recent years, since polyimide is excellent in mechanical strength, heat resistance, thermal stability, etc., polyimide patterns have been used for manufacturing electronic materials such as semiconductor devices and multilayer wiring boards. It's coming.

As a method for forming this polyimide pattern, for example, (1) a non-photosensitive polyimide layer or a polyimide precursor layer is provided on a substrate, a photoresist is patterned on the surface, and then this photoresist pattern is formed. Etching the polyimide layer or the polyimide precursor layer by using as an etching mask to form a polyimide pattern, or (2) providing a photosensitive layer mainly composed of a photosensitive polyimide precursor on a substrate, and activating light There is known a method of irradiating the film with an image to expose it for image formation, then developing it to form a pattern, and then heat-treating it to form an imide cyclization. However, the method (1) requires a long patterning step. However, the method (2) is usually used because it has the drawback of low resolution. In this method, the photosensitive polyimide precursor is generally 4
Since the active light having a wavelength of 00 nm or less is strongly absorbed, the g-line (436 nm) and the h-line (408 n
Ultraviolet rays including m) are used.

However, in recent years, in the semiconductor manufacturing process, the i-line (365n
m) is desired, and the need to use i-line stepper has also arisen in the patterning of the photosensitive polyimide precursor. However, due to restrictions on the polymer skeleton and process conditions, it is possible to use i-line exposure. No photosensitive polyimide precursor has been found so far.

[0005]

Under these circumstances, the present invention is suitable for the production of electronic materials such as semiconductor devices and multilayer wiring boards, and has a wavelength of substantially 400 nm or less, particularly i. The purpose of the present invention is to provide a method for forming a polyimide fine pattern by performing exposure processing using a line stepper.

[0006]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have used a photosensitive polyimide precursor having a specific chemical structure, and have a specific solubility for development processing. It was found that the purpose can be achieved by using a developing solution having the above-mentioned characteristics, and the present invention has been completed based on this finding.

That is, the present invention is based on the general formula (A)

[Chemical 2] (X in the formula represents the chemical structure of the aromatic tetracarboxylic acid excluding the carboxyl group, and Y represents the chemical structure of the aromatic diamine excluding the amino group.
Is an unsaturated compound residue having a terminal ethylene bond,
The two -CO-R groups in X are bonded to the carbonyl group forming the amide group backbone in the ortho position) and a photosensitive polyimide precursor having a repeating unit represented by (B) a photopolymerization initiator. After providing a photosensitive layer composed of a photosensitive resin composition containing as an essential component, the photosensitive layer is subjected to imagewise exposure with an energy ray having a wavelength of substantially 400 nm or less, and then the dissolution time per 1 μm of the photosensitive layer. Provides a method for forming a fine pattern of polyimide, which comprises subjecting the polyimide precursor to imide cyclization after development with a developer having a solubility of 5.0 seconds or more.

In the photosensitive resin composition used in the method of the present invention, a photosensitive polyimide precursor having a repeating unit represented by the general formula (I) is used as the component (A). X in the general formula (I) represents a chemical structure in which four carboxyl groups have been removed from an aromatic tetracarboxylic acid. Here, the aromatic tetracarboxylic acid means an aromatic group. That is, it means a compound having a chemical structure in which a carboxyl group is directly bonded to a completely unsaturated carbon ring or heterocycle.

Examples of such an aromatic tetracarboxylic acid include those belonging to the following groups. (1) One composed of one monocyclic or condensed cyclic aromatic ring. For example, pyromellitic acid, 1,2,7,8-naphthalene tetracarboxylic acid, 1,2,8,9-anthracene tetracarboxylic acid, 2,3,5,6-pyridine tetracarboxylic acid, 2,3,6. 7-quinoline tetracarboxylic acid and the like.

(2) General formula

[Chemical 3] (X ₁ in the formula is —CH ₂ —, —CO—, —SO ₂ —, —
O -, - S- or -C _{(CF 3) 2} - a and, a is one represented by a 0 or 1). For example 3,3 ', 4
4'-diphenyltetracarboxylic acid, 3,3 ', 4
4'-diphenyl ether tetracarboxylic acid, 3,
3 ', 4,4'-benzophenone tetracarboxylic acid,
3,4,3 ', 4'-diphenylmethane tetracarboxylic acid, 3,3', 4,4'-diphenyl sulfoxide tetracarboxylic acid and the like.

Next, Y in the general formula (I) represents a chemical structure obtained by removing two amino groups from an aromatic diamine. Here, the aromatic diamine is an aromatic diamine. It means a compound having a chemical structure in which an amino group is directly bonded to a carboxylic group, that is, a completely unsaturated carbocycle or heterocycle.

Examples of such aromatic diamines include those belonging to the following groups. (1) One composed of one monocyclic or condensed cyclic aromatic ring. For example, 1,4-phenylenediamine, 2,7-
Naphthalenediamine, 3,5-diaminopyridine, 5,
8-diaminoquinoline and the like.

(2) General formula

[Chemical 4] (Y ₁ in the formula is —CH ₂ —, —CO—, —SO ₂ —, —
_{O -, - S -, -} C (CF 3) 2 -, - C (CF 3) 2
-, A divalent organic residue having a divalent aromatic residue or a siloxane bond, and b is 0 or 1.).

For example, 3,4 'or 4,4'-diaminodiphenyl, 3,4' or 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfoxide, 4,4'-diaminobenzophenone, 4,4 ′ -Diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, etc.

(3) General formula

[Chemical 5] (Y ₁ and b in the formula have the same meanings as described above). For example, 4,4'-bis (3 or 4-aminophenoxy) diphenyl sulfoxide, 4,4'-bis (3 or 4-aminophenoxy) diphenylmethane,
4,4'-bis (3 or 4-aminophenoxy) diphenyl ether, 4,4'-bis (3 or 4-aminophenoxy) diphenyl sulfide and the like.

(4) General formula

[Chemical 6] (Y ₁ and b in the formula have the same meanings as described above, and Z is —S
-, -O- or -NH-). For example, bis [2- (4-aminophenyl) -benzothiazolyl] oxide, bis [2- (4-aminophenyl)-
Benzimidazolyl] sulfoxide, bis [2- (4-
Aminophenyl) -benzoxazolyl] and the like.

(5) Others 1,3 or 1,4-bis (4-aminophenoxy) benzene, 1,4-di- (4-aminobenzoyloxy) butane, formula

[Chemical 7] Such as diamine. The aromatic ring in these aromatic tetracarboxylic acids and aromatic diamines may be further substituted with an alkyl group having 1 to 6 carbon atoms.

Next, R in the general formula (I) is an unsaturated compound residue having a terminal ethylene bond, and examples thereof include groups belonging to the following groups. (1) General formula

[Chemical 8] (R ₁ in the formula is a hydrocarbon group which may be interrupted by an oxygen atom or a nitrogen atom, R ₂ is a hydrogen atom or a methyl group, and d is 0 or 1). For example, allyloxy group, 2-acryloyloxyethyloxy group, 2-methacryloyloxypropyloxy group and the like.

(2) General formula

[Chemical 9] (R ₁ , R ₂ and d in the formula have the same meanings as described above). For example, 2-acryloyloxyethylamino group, 2-methacryloyloxyethylamino group,
2-acryloyloxypropylamino group and the like.

(3) General formula

[Chemical 10] (R ₁ , R ₂ and d in the formula have the same meanings as described above). For example, 2-hydroxy-3-methacryloyloxypropyloxy group, 2-hydroxy-3-
Acryloyloxypropyloxy group, 2-hydroxy-4-pentenyloxy group, etc.

The photosensitive resin composition containing the photosensitive imide precursor having the repeating unit represented by the general formula (I) can be prepared, for example, by the following method. (1) When R is a group represented by the general formula (VI): a dianhydride of a tetracarboxylic acid represented by the general formula (II);

[Chemical 11] Reacting with an alcohol represented by the formula (R ₁ , R ₂ and d have the same meaning as described above) in an inert solvent,
Then, in the presence of a condensing agent such as thionyl chloride or dicyclohexylcarbodiimide, the above-mentioned general formula (II
A photosensitive polyimide precursor is obtained by polycondensation with a diamine represented by I). Next, the condensing agent is removed from the reaction mixture thus obtained, and further subjected to ion exchange treatment to remove impurities, which is then poured into water or alcohol to precipitate a precursor. The precipitate is separated by filtration, dried, dissolved in a required solvent, and necessary additives are added to prepare a photosensitive resin composition.

(2) When R is a group represented by the general formula (VII) The dianhydride of tetracarboxylic acid represented by the general formula (II) and the diamine represented by the general formula (III) are not mixed with each other. A polyamic acid is produced by polycondensation in an active solvent, and then a polyamic acid of the general formula

[Chemical 12] An isocyanate compound represented by the formula (R ₁ , R ₂ and d have the same meaning as described above) is reacted to prepare a photosensitive polyimide precursor solution. Next, this solution is purified in the same manner as described above, and necessary additives are added to obtain a photosensitive resin composition.

(3) When R is a group represented by the general formula (VIII): The tetracarboxylic acid dianhydride represented by the general formula (II) and the diamine represented by the general formula (III) are not mixed with each other. A polyamic acid is prepared by polycondensation in an active solvent, which is

[Chemical 13] An epoxy compound represented by the formula (R ₁ , R ₂ and d in the formula have the same meanings as described above) is reacted to prepare a photosensitive polyimide precursor solution. Next, this solution is purified in the same manner as described above, and necessary additives are added to obtain a photosensitive resin composition.

Next, this solution is purified in the same manner as described above, and necessary additives are added to obtain a photosensitive resin composition.

Examples of the photopolymerization initiator of the component (B) in the photosensitive resin composition used in the method of the present invention include benzophenone, methyl o-benzoylbenzoate,
Benzophenone derivatives such as 4-benzoyl-4'-methyldiphenylketone, dibenzylketone and fluorenone, acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl Ketone, thioxanthone, 2-methylthioxanthone, 2-
Thioxanthone derivatives such as isopropylthioxanthone and diethylthioxanthone, benzyl derivatives such as benzyl, benzyldimethylketal and benzyl-β-methoxyethylacetal, benzoin, benzoin derivatives such as benzoin methyl ether, 2,6-di (4 '
-Diazidobenzal) -4-methylcyclohexanone,
Azides such as 2,6'-di (4'-diazidobenzal) cyclohexanone, 1-phenyl-1,2-butanedione-2- (o-methoxycarbonyl) oxime, 1-
Phenyl-propanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione-2-
(O-Ethoxycarbonyl) oxime, 1-phenyl-
Propanedione-2- (o-benzoyl) oxime,
Although oximes such as 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime and 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxime are used, Oximes are preferable from the viewpoint. The addition amount of these photopolymerization initiators is preferably 1 to 15 parts by weight with respect to 100 parts by weight of the precursor polymer.

The photosensitive resin composition used in the present invention includes
If necessary, an unsaturated compound having an ethylenic double bond or a sensitizer for improving photosensitivity, an adhesion aid for improving adhesion to a substrate, or improving stability over time such as viscosity or high sensitivity. For this purpose, a polymerization inhibitor or the like can be added.

Examples of the unsaturated compound having an ethylenic double bond include 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, and the number of added moles of 2 to 20.
Polyethylene glycol diacrylate, pentaerythritol diacrylate, dipentaerythritol hexaacrylate, tetramethylolmethane tetraacrylate, methylenebisacrylamide, N-methylolacrylamide, and methacrylates and methacrylamides corresponding to these acrylates and acrylamides. These compounds are preferably added in the range of 1 to 30 parts by weight per 100 parts by weight of the precursor polymer.

Examples of the sensitizer include Michler's ketone, 4,4'-bis (diethylamino) benzophenone and 2,5-bis (4'-diethylaminobenzal).
Cyclopentane, 2,6-bis (4'-diethylaminobenzal) cyclohexanone, 2,6-bis (4'-dimethylaminobenzal) -4-methylcyclohexanone, 2,6-bis (4'-diethylaminobenzal) )-
4-methylcyclohexanone, 4,4'-bis (dimethylamino) chalcone, 4,4'-bis (diethylamino) chalcone, p-dimethylaminocinnamylideneindanone, p-dimethylaminobenzylideneindanone,
2- (p-dimethylaminophenylbiphenylene) -benzothiazole, 2- (p-dimethylaminophenylvinylene) benzothiazole, 2- (p-dimethylaminophenylvinylene) isonaphthothiazole, 1,3-bis (4'- Dimethylaminobenzal) acetone, 1,3
-Bis (4'-diethylaminobenzal) acetone,
3,3'-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin,
3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'- Ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, dimethylaminobenzoic acid isoamyl, diethylaminobenzoic acid isoamyl, 2-mercaptobenzimidazole, 1-phenyl-5- Examples thereof include mercapto-1H-tetrazole and 2-mercaptobenzothiazole. These are used alone or in combination of 2 to 5 kinds, and the addition amount thereof is 0.1 to 1 with respect to 100 parts by weight of the precursor polymer.
5 parts by weight is preferred.

Next, as an adhesion aid, for example, γ-aminopropyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ
-Glycidoxypropylmethyldimethoxysilane, γ-
Mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3
-Glycidoxypropylmethylsilane, N- (3-diethoxymethylsilylpropyl) succinimide, N-
[3- (triethoxysilyl) propyl] phthalamic acid, benzophenone-3,3'-bis [N- (3-triethoxysilyl) propylamide] -4,4'-dicarboxylic acid, benzene-1,4-bis [N- (3-triethoxysilyl) propylamide] -2,5-dicarboxylic acid or the like is used. The amount of these adhesion promoters added is preferably in the range of 0.5 to 10 parts by weight with respect to 100 parts by weight of the precursor polymer.

Further, as the polymerization inhibitor, for example, hydroquinone, N-nitrosodiphenylamine, p-ter
t-Butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso- 8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1
-Naphthol, 2-nitroso-5- (N-ethyl-N-
Sulfopropylamino) phenol, N-nitroso-
N-phenylhydroxylamine ammonium salt, N-
Nitroso-N (1-naphthyl) hydroxylamine ammonium salt or the like is used. The addition amount is preferably in the range of 0.005 to 5 parts by weight with respect to 100 parts by weight of the precursor polymer.

The solvent in the photosensitive resin composition used in the method of the present invention is preferably a polar solvent from the viewpoint of solubility. For example, N, N'-dimethylformamide, N-methylpyrrolidone, N-acetyl-2- Pyrrolidone, N,
N′-dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone and the like are used, and they can be used alone or in combination of two or more kinds.

In the method of the present invention, the method for applying the photosensitive resin composition onto the substrate may be, for example, a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, or a spray coater. A method such as spray coating can be used.
As the method for drying the coating film, methods such as air drying, heat drying using an oven or a hot plate, and vacuum drying are used.

The photosensitive layer thus formed on the substrate is subjected to image forming exposure, and this image forming exposure irradiates an energy ray having a wavelength of substantially 400 nm or less through a photomask. Done by. The energy rays having a wavelength of substantially 400 nm or less are obtained by using, for example, ultraviolet rays from a high-pressure mercury lamp or an ultra-high-pressure mercury lamp, an h-line (408 nm) and a g-ray with an optical filter such as a bandpass filter.
Obtained by cutting wavelengths above 400 nm, such as the line (436 nm). Specifically, by combining an ultra-high pressure mercury lamp with a colored glass filter UV-D36C (manufactured by Toshiba Glass Co., Ltd.), ultraviolet rays and i-line stepper FPA2000i (manufactured by Canon Inc.) and NSR-1505i (Nikon Inc.) that cut wavelengths exceeding 400 nm are combined. And an X-ray exposure device using an excimer laser light source.

After the image-forming exposure is carried out in this way, a developing treatment is carried out. In the present invention, however, the developing solution has a solubility of 5.0 seconds or more per 1 μm of the photosensitive layer. The one that has is used. The developing solution having such a solubility comprises, for example, a combination of a good solvent for the photosensitive polyimide precursor and a poor solvent used as necessary, and the photosensitive polyimide precursor is placed on a silicon wafer. When the photosensitive layer obtained by coating and drying is immersed in the solvent at a liquid temperature of 23 ° C. in a stationary state, the dissolution time at the end point at which the coating film is completely dissolved and the coating film disappears is 5 μm per film thickness. It is obtained by adjusting the time to be 0 seconds or more.

The good solvent used in this developer is:
For example, N-methylpyrrolidone, N-acetyl-2-pyrrolidone, N, N′-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α
-Acetyl-γ-butyrolactone and the like, and the poor solvent includes toluene, xylene, methanol, isopropyl alcohol and water.

As the developing method, any known method can be selected from conventionally known photoresist developing methods such as a rotary spray method, a paddle method, a dipping method and a dipping method involving ultrasonic treatment. Of these, the paddle method is preferable. Especially when a film thickness of 5 μm or more is practically 400 n
The paddle method is preferable when exposing with an energy ray having a wavelength of m or less.

An example of the operation of the paddle method will be described. First, the base material is rotated at a speed of 10 to 50 rpm, and an amount of the developing solution spread over the entire surface of the base material is dropped. At this time, when the substrate has a large area, it is desirable to use a spray or a fan-shaped nozzle. Next, when the developing solution spreads on the base material, the supply of the developing solution is stopped, the rotation is continued at the same number of revolutions, and then the rotation of the base material is increased to shake off the developing solution. When the film thickness is thick, the above operation is repeated. Then, when the unexposed portion is removed, the rinse liquid is dropped or sprayed onto the base material, and the base material is rotated at a high speed to shake off the developing solution and the rinse liquid.

In the method for forming a polyimide pattern of the present invention, it is possible to use plural kinds of developing solutions. Further, it is effective to operate the developing rinse again after the developing / rinsing, or to perform the developing / rinsing again after the developing rinse after once drying at a temperature of 50 to 110 ° C. It is desirable to appropriately determine the type and solubility of the developing solution, or the process conditions according to the substrate area, the exposure wavelength, the required resolution, or the like.

In the method of the present invention, a heat treatment is carried out after the development treatment, but this heat treatment is a imide cyclization or a volatilization of additives, and this treatment produces a polyimide pattern having excellent mechanical and thermal physical properties. can get. As the heat treatment method, there is a method using an oven, a tube furnace, an infrared furnace, a conveyor furnace, a microwave furnace, a hot plate, etc., and these methods are usually carried out in a relatively low temperature range of 250 to 500 ° C. At this time, first 10
Preliminary heat treatment at a low temperature of 0 to 250 ° C. for 30 minutes to 2 hours and heat treatment at 250 to 500 ° C. can improve the pattern shape and the quality of the polyimide film.

[0040]

The method of forming a polyimide pattern of the present invention has many advantages over the conventional prior art. That is, according to the method of the present invention, it is possible to expose and pattern the photosensitive polyimide precursor by an energy ray having a wavelength of substantially 400 nm or less, particularly an i-ray stepper exposure, and a semiconductor interlayer insulating film that requires fine processing or The range of use in a field of application such as a surface protective film or an interlayer insulating film of a multichip module is expanded, which can contribute to speeding up and high reliability of electronic devices.

The technique of the present invention can be applied not only to the polyimide precursor but also to a photosensitive material having strong absorption at the exposure wavelength.

That is, when patterning a photosensitive material having a light transmittance of 3% or less at an exposure wavelength in a photosensitive layer having a film thickness of 5 μm or more, the dissolution time per 1 μm of the photosensitive layer is 5.0 seconds or more. A pattern having a good film thickness can be obtained by performing development processing with a developing solution having a solubility.

[0043]

The present invention will be described in more detail with reference to Reference Examples, Examples and Comparative Examples, but the present invention is not limited to these Examples.

Reference Example 21.8 g of pyromellitic anhydride, 27.0 g of 2-hydroxyethyl methacrylate and 16.5 g of pyridine were dissolved in 100 ml of γ-butyrolactone, and the mixture was reacted at room temperature for 15 hours and then stirred. While adding 23.8 g of thionyl chloride dropwise. Furthermore, 16 g of 4,4′-diaminodiphenyl ether was added to γ-butyrolactone 5
What was made into a slurry with 0 ml was added dropwise under ice cooling, stirred for 2 hours, and then added dropwise with stirring to 10 l of ion-exchanged water. Then, the precipitate was filtered, washed with water, and then vacuum dried to obtain a pale yellow powder. The polymer of this powder is designated as P-1.

Example 50 g of P-1 obtained in the reference example, 2 g of benzophenone, 2
A varnish composition was prepared by dissolving 1 g of isopropylthioxanthone, 2 g of tetraethylene glycol diacrylate and 0.2 g of 3-methacryloxypropyltrimethoxysilane in 70 g of N-methylpyrrolidone. This varnish was spin coated on a 6 inch silicon wafer,
It was dried on a hot plate at 0 ° C. to obtain a 20 μm thick coating film.

On the other hand, 950 ml of cyclopentanone and 50 ml of ethanol were mixed to prepare a developing solution-1, a portion of which was placed in a beaker and the temperature was adjusted to 23 ° C., after which the previously prepared 20 μm thick coating film was attached. A silicon wafer was placed and left standing. When the time taken for the coating film to dissolve from the silicon wafer to disappear was measured visually, it was 250 seconds,
The dissolution time per 1 μm of the photosensitive layer was 12.5 seconds.

Next, a 6-inch silicon wafer with a coating film of 20 μm thick was attached to a Canon i-line stepper FPA.
The exposure was performed at -2000i at an exposure dose of 400 mJ / cm ² . After the exposure, it was dipped in Developer-1 for 250 seconds, then dipped in isopropyl alcohol for rinsing, and then air blown and air dried. When the obtained pattern was observed, a good pattern with a line and space of 20 μm was obtained.

Comparative Example The wafer exposed by the i-line stepper obtained in the example was treated with 500 ml of N-methylpyrrolidone and 500 xylene.
Immerse in developer-2 consisting of a mixture with ml for 60 seconds, then rinse with isopropyl alcohol,
Air dried with air blow. The obtained pattern was severely undercut, and a fine line pattern of 30 μm or less flowed out. The solubility of this developer-2 at 23 ° C. per 1 μm of film thickness was 3.2 seconds.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location H01L 21/027 H05K 3/06 6921-4E

Claims (1)

[Claims] 1. A general formula of (A) embedded image on a substrate. (X in the formula represents the chemical structure of the aromatic tetracarboxylic acid excluding the carboxyl group, and Y represents the chemical structure of the aromatic diamine excluding the amino group.
Is an unsaturated compound residue having a terminal ethylene bond,
The two -CO-R groups in X are bonded to the carbonyl group forming the amide group backbone in the ortho position) and a photosensitive polyimide precursor having a repeating unit represented by (B) a photopolymerization initiator. After providing a photosensitive layer composed of a photosensitive resin composition containing as an essential component, the photosensitive layer is subjected to imagewise exposure with an energy ray having a wavelength of substantially 400 nm or less, and then the dissolution time per 1 μm of the photosensitive layer. Is subjected to a development treatment with a developing solution having a solubility of 5.0 seconds or more and then subjected to a heat treatment to imide cyclize the polyimide precursor to form a polyimide fine pattern.