KR20080057325A - Process for producing substrate with metal wiring - Google Patents

Abstract

A process for producing a substrate bearing a metal wiring, which comprises (a) a step in which a positive photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a compound having a quinonediazide group, and (C) a solvent is applied to a substrate to form a coating film, (b) a step in which the coating film is dried under vacuum to form a photosensitive layer, (c) a step in which the photosensitive layer is pattern-wise exposed to light and then developed to form a resist pattern in a reversed taper form, (d) a step in which a metal is vapor-deposited on the substrate having the resist pattern in a reversed taper form obtained in the step (c), and (e) a step in which both of the resist pattern in a reversed taper form and the vapor-deposited metal film formed thereon are removed by a lifting-off operation from the substrate which has undergone metal vapor deposition in the step (d). The target substrate can be inexpensively produced with satisfactory productivity from a substrate having a reversed-taper-form resist pattern obtained from a common positive photoresist.

Description

Manufacturing method of board with metal wiring {PROCESS FOR PRODUCING SUBSTRATE WITH METAL WIRING}

This invention relates to the manufacturing method of the board | substrate with a metal wiring useful for manufacture of flat panel displays, such as a liquid crystal display (LCD), an organic electroluminescent (organic EL) display, a plasma display panel (PDP). In more detail, this invention relates to the method of obtaining the board | substrate which has a reverse taper-shaped resist pattern using a positive photosensitive resin composition, and using it to manufacture the said board | substrate with a metal wiring by the lift-off method.

When forming metal wiring on a board | substrate by the lift-off method, the resist material which can form the resist pattern which has an inverse taper shape in cross section is used normally.

For example, when a conductor pattern is formed by a lift-off method, (1) a resist film is formed on a board | substrate using a negative photosensitive resin composition, (2) the resist film is exposed to pattern shape, And developing to form a negative resist pattern (negative image), (3) depositing a metal on the entire surface of the substrate including the negative resist pattern image to form a deposited film, and (4) the whole substrate is immersed in a solution, The conductor pattern is formed on a board | substrate by a series of processes of swelling-dissolving a negative resist pattern. In the said process (4), the vapor deposition film on a negative resist pattern is also removed, and the vapor deposition film on a board | substrate remains in a pattern form.

FIG.1 (a), FIG.1 (b) and FIG.1 (c) are explanatory drawing which shows an example of the pattern formation process by the lift-off method.

In the said process (2), as shown in FIG.1 (a), if the negative resist pattern 2 of the reverse taper shape is formed on the board | substrate 1, the whole board | substrate in a next process (3) When the metal vapor deposition film is formed in the surface, as shown to FIG. 1 (b), the vapor deposition film 3 and the vapor deposition film 3 'are formed independently on the board | substrate 1 and the negative resist pattern 2, respectively. . Therefore, when the negative resist pattern 2 is removed in step (4), the deposited film 3 'on it is also removed, and as shown in FIG. 1 (c), the deposition film 3 is formed on the substrate 1. Only the pattern remains.

In the case where the resist pattern has a cross-sectional shape such as a rectangular shape, a forward taper shape, a skirt shape, and the like, in the step (3), when the metal vapor deposition film is formed on the entire surface of the substrate, the vapor deposition film is also formed on the resist pattern side surface. And a vapor deposition film on a resist pattern are formed continuously. Therefore, when the resist pattern is removed in step (4), not only the vapor deposition film formed thereon but also a part or all of the vapor deposition film on the substrate continuous therewith is peeled off.

Conventionally, a negative photoresist is mainly used as a photoresist which can form an inverse taper resist pattern. For example, it contains at least 1 type of the component which crosslinks by exposure by (X) light ray or heat processing following exposure, (Y) alkali-soluble resin, and (Z) light ray to expose, and is alkaline The negative photosensitive composition for pattern formation by the lift-off method characterized by using aqueous solution as a developing solution (for example, refer patent document 1) is known.

However, the method of using a negative photoresist has a problem that post-exposure bake treatment is required or a long exposure time is required, and productivity is low and the photoresist itself is relatively expensive.

On the other hand, in the past, the tapered resist pattern has been considered difficult to be formed in a conventional positive photoresist. Then, the method of forming an inverse taper resist pattern is proposed by studying a resist composition, a process, etc. For example, a method of forming an inverse tapered resist pattern using a positive type resist of an image reversal type, and further forming a film pattern by a lift-off method (see Patent Document 2, for example) A method of forming an inverse tapered resist pattern even in a positive resist composition using a roughened transparent substrate and using diffuse reflection of light according thereto (see Patent Document 3, for example), and a ring on the positive resist film. A pattern formation method (for example, refer to Patent Document 4) according to the lift-off method which simplifies the peeling operation by laminating a rubberized negative resist film is proposed.

However, these methods have disadvantages such as complicated operation and difficulty in forming a resist pattern having a good shape.

[Patent Document 1] Japanese Patent Application Laid-Open No. 10-213902

[Patent Document 2] Japanese Patent Application Laid-Open No. 8-120443

[Patent Document 3] Japanese Patent Application Laid-Open No. 9-185174

[Patent Document 4] Japanese Patent Application Laid-Open No. 9-283414

Disclosure of the Invention

Under the circumstances, the present invention uses a substrate having a reverse tapered resist pattern obtained by a simple operation by a general-purpose, low-cost positive photoresist, and inexpensively high productivity using a substrate with a metal wiring by a lift-off method. It is made for the purpose of providing a method for producing.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to achieve the said objective, the present inventors apply | coated on a board | substrate using a positive photosensitive resin composition, and forms a coating film, and this coating film is dried under reduced pressure easily, and an inverse tapered resist pattern is easily carried out. The present invention was found to be capable of forming the present invention and to achieve the object, and to complete the present invention based on this finding.

That is, the present invention,

(1) Process of apply | coating positive photosensitive resin composition containing (A) alkali-soluble resin, (B) quinonediazide group containing compound, and (C) solvent on (a) board | substrate, and forming a coating film, (b ) A step of forming the photosensitive layer by drying the coating film under reduced pressure, (c) developing the inverse tapered resist pattern by developing the photosensitive layer after pattern exposure, and (d) the inverse obtained by the step (c). A step of depositing a metal on the substrate having a tapered resist pattern, and (e) removing the reverse tapered resist pattern and the metal deposited film thereon from the substrate deposited with the metal in the step (d) by a lift-off operation. The manufacturing method of the board | substrate with a metal wiring which has a process to make,

(2) The manufacturing method as described in said (1) which performs the reduced-pressure drying in (b) process on the conditions of 5 to 4,000 Pa of arrival pressures, and

(3) Process of apply | coating positive photosensitive resin composition containing (A) alkali-soluble resin, (B) quinonediazide group containing compound, and (C) solvent on (a) board | substrate, and forming a coating film, ( b) a substrate having an inverse tapered resist pattern, which has a step of drying the coating film under reduced pressure to form a photosensitive layer; and (c) pattern exposing the photosensitive layer and then developing the inverse tapered resist pattern. It is to provide a method for producing.

According to this invention, the board | substrate with a metal wiring can be manufactured with high productivity at low cost.

1 (a), 1 (b) and 1 (c) are explanatory diagrams showing an example of a pattern forming process according to the lift-off method, and FIGS. 2 (a) and 2 (b) are cross-sectional shapes of the resist pattern; It is explanatory drawing which shows this different example. In the drawings, reference numeral 1 is a substrate, 2 a negative resist pattern, and 3 and 3 'are vapor deposition films.

Implement the invention  Best form for

The manufacturing method of the board | substrate with a metal wiring of this invention has the (a) process, (b) process, (c) process, (d) process, and (e) process shown below.

In addition, in this specification, as shown in FIG.2 (a), with an inverse taper resist pattern, in the cross-sectional shape of the resist pattern on a board | substrate, the angle (alpha) which arises between a resist pattern and a board | substrate is 0 degrees <(alpha) < Refers to a resist pattern that can satisfy 90 °.

[(a) process]

This process is a process of apply | coating positive type photosensitive resin composition containing (A) alkali-soluble resin, (B) quinonediazide group containing compound, and (C) solvent on a board | substrate, and forming a coating film.

Alkali-soluble resin of the said (A) component will not be specifically limited if it is resin which is soluble in the developing solution which consists of alkaline aqueous solution etc .. As said resin, resin used for the well-known photosensitive resin composition, for example, a novolak resin, a resol resin, an acrylic resin, polyvinyl alcohol, a styrene-acrylic acid copolymer, a hydroxy styrene polymer, a polyvinyl hydroxy benzoate, etc. Can be mentioned. Especially, novolak resin is preferable. These resin may be used individually by 1 type, and may be used in combination of 2 or more type.

The said novolak resin is a novolak-type phenol resin obtained by condensing a phenol compound and an aldehyde compound.

The phenol compound used for producing the novolak resin may be a monovalent phenol or a divalent or higher polyhydric phenol such as resorcinol.

As a specific example of a monovalent phenol compound, For example, Phenol; cresol of o-cresol, p-cresol, m-cresol; Xylenols such as 3,5-xylenol, 2,5-xylenol, 2,3-xylenol and 3,4-xylenol; 2-ethylphenol, 3-ethylphenol, 4-ethylphenol, 2-propylphenol, 3-propylphenol, 4-propylphenol, 2-t-butylphenol, 3-t-butylphenol, 4-t-butylphenol , 3,5-diethylphenol, 2,5-diethylphenol, 2-t-butyl-4-methylphenol, 2-t-butyl-5-methylphenol, 6-t-butyl-3-methylphenol, Alkyl phenols such as 2,3,5-trimethylphenol and 2,3,5-triethyl phenol; alkoxy such as p-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol, 2,3-dimethoxyphenol, 2,5-dimethoxyphenol and 3,5-dimethoxyphenol Phenol; Aryl phenols such as 2-phenylphenol, 3-phenylphenol and 4-phenylphenol; alkenylphenols such as o-isopropenylphenol, p-isopropenylphenol, 2-methyl-4-isopropenylphenol and 2-ethyl-4-isopropenylphenol; Etc. can be mentioned.

As a specific example of a polyhydric phenol compound, Resorcinol, 2-methyl resorcinol, 4-methyl resorcinol, 5-methyl resorcinol, 2-methoxy resorcinol, 4-methoxy resorcinol; Hydroquinone; Catechol, 4-t-butylcatechol, 3-methoxycatechol; 4,4'- dihydroxybiphenyl, bisphenol A; Pyrogallol; Floroglycinol; Etc. can be mentioned.

Of these phenolic compounds, o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol are preferred.

A phenol compound may be used individually by 1 type, and may be used in combination of 2 or more type.

The aldehyde compound condensed with the phenol compound may be any of aliphatic aldehydes, alicyclic aldehydes and aromatic aldehydes.

Specific examples of aliphatic aldehyde include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, n-butylaldehyde, isobutylaldehyde, trimethylacetaldehyde, n-hexylaldehyde, acrolein, crotonaldehyde and the like.

Specific examples of the alicyclic aldehyde include cyclohexanealdehyde, cyclopentanealdehyde, furfural, furyl acrolein, and the like.

Specific examples of the aromatic aldehyde include benzaldehyde, o-tolualdehyde, m-tolualdehyde, p-tolualdehyde, p-ethylbenzaldehyde, 2,4-dimethylbenzaldehyde, 2,5-dimethylbenzaldehyde, 3,4-dimethylbenzaldehyde, 3 , 5-dimethylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-anisaldehyde, m-anisaldehyde, p Anisaldehyde, terephthalaldehyde, phenylacetaldehyde, α-phenylpropionaldehyde, β-phenylpropionaldehyde, cinnamon aldehyde and the like.

These aldehyde compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

Condensation reaction of a phenol compound and an aldehyde compound may be performed by a well-known method in presence of an acidic catalyst in manufacture of a novolak resin. As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid, p-toluenesulfonic acid and the like can be used. The condensation reaction product obtained by such a reaction can be used as a novolak resin as it is.

Alkali-soluble resin can remove and use a low molecular weight component separately. As a method of removing a low molecular weight component, the liquid-liquid fractionation method which separates resin from two types of solvents which have different solubility, the method of removing a low molecular weight component by centrifugation, a thin film distillation method, etc. are mentioned, for example. have.

For example, in the case of the said novolak resin, the obtained condensation reaction product is made into a good solvent, for example, alcohol solvents, such as methanol and ethanol; Ketone solvents such as acetone and methyl ethyl ketone; Alkylene glycol solvents such as ethylene glycol monoethyl ether acetate; Ether solvents such as tetrahydrofuran; And so on. Subsequently, it is injected in water and precipitated, and the novolak resin from which the low molecular weight component was removed can be obtained.

The alkali-soluble novolak resin used preferably in this invention has the weight average molecular weight normally 2,000-20,000, Preferably it is 2,500-12,000, More preferably, it is 3,000-8,000. In addition, a weight average molecular weight can be measured according to the gel permeation chromatography (GPC) method using tetrahydrofuran (THF) as an eluent, using monodisperse polystyrene as a standard sample.

As a quinone diazide group containing compound of (B) component in the positive photosensitive resin composition used for this invention, the well-known photosensitive agent currently used by the quinone diazide- novolak-type resin resist can be used.

The quinone diazide group-containing compound generally has an acid halide such as naphthoquinone diazide sulfonic acid chloride or benzoquinone diazide sulfonic acid chloride and a functional group capable of condensation reaction with this (hydroxyl group, amino group, etc., preferably hydroxyl group). Preference is given to quinonediazidesulfonic acid esters obtained by reacting compounds.

As the acid halide, specifically, 1,2-naphthoquinone diazide-5-sulfonyl chloride, 1,2-naphthoquinone diazide-4-sulfonyl chloride, 1,2-naphthoquinone diazide-6 -Sulfonyl chloride, etc. are mentioned as a preferable thing.

Moreover, as a compound which has a hydroxyl group which can be condensed-reacted with an acid halide, used preferably in this invention, For example, 2,3,4- trihydroxy benzophenone, 2,4,4'- trihydride Hydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2', 3,4,4'-pentahydroxy Polyhydroxy benzophenones such as benzophenone; Gallic acid esters such as methyl gallate, ethyl gallate and propyl gallate; Polyhydroxy bisphenyl alkanes such as 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (2,4-dihydroxyphenyl) propane; Tris (4-hydroxyphenyl) methane, 1,1,1-tris (4-hydroxy-3-methylphenyl) ethane, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxy-3-methylphenyl) -1- (4-hydroxyphenyl) ethane, bis (4-hydroxy-3-methylphenyl) -2-hydroxy-4-methoxyphenylmethane, 4,4 ' Polyhydroxytrisphenylalkanes such as-(1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) bisphenol; 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-methyl-4-hydroxyphenyl) ethane, 1,1,3,3- Polyhydroxy tetrakisphenyl alkane such as tetrakis (4-hydroxyphenyl) propane; α, α, α ', α'-tetrakis (4-hydroxyphenyl) -3-xylene, α, α, α', α'-tetrakis (4-hydroxyphenyl) -4-xylene, polyhydroxytetrakisphenylxylene such as α, α, α ', α'-tetrakis (3-methyl-4-hydroxyphenyl) -3-xylene; 2,6-bis (2,4-dihydroxybenzyl) -p-cresol, 2,6-bis (2,4-dihydroxy-3-methylbenzyl) -p-cresol, 4,6-bis (4-hydroxybenzyl) resorcin, 4,6-bis (4-hydroxy-3-methylbenzyl) resorcin, 4,6-bis (4-hydroxybenzyl) -2-methyllezocin, 4, Trimers of phenol compounds such as 6-bis (4-hydroxy-3-methylbenzyl) -2-methyllezocin and formaldehyde; Tetramer of the said phenol compound and formaldehyde; Novolak resin; Etc. can be mentioned.

The compound which has the above acid halide and hydroxyl group can be used individually by 1 type or in combination of 2 or more types.

For example, the reaction of an acid halide with a compound having a hydroxyl group is usually a basic condensing agent such as triethanolamine, alkali carbonate or hydrogen carbonate in an organic solvent such as dioxane, N-methylpyrrolidone or dimethylacetamide. It is carried out in the presence of. The esterification rate of the obtained quinone diazide sulfonic acid ester becomes like this. Preferably it is 50 mol% or more, More preferably, it is 60 mol% or more. In addition, esterification rate is determined by the compounding ratio of the compound which has an acid halide and a hydroxyl group.

The compounding quantity of the quinonediazide group containing compound of this (B) component is 5-50 mass parts normally per 100 mass parts of alkali-soluble resin of the said (A) component, Preferably it is 15-40 mass parts, More preferably, 20 It is-40 parts by mass. If this compounding quantity is in the said range, the positive photosensitive resin composition which the formation property of an inverse taper type resist pattern is more favorable, and excellent in the balance of resist characteristics, such as effective sensitivity, a residual film ratio, and resolution, can be obtained.

The solvent of (C) component in the positive photosensitive resin composition used for this invention will not be specifically limited if alkali-soluble resin and a quinonediazide group containing compound are melt | dissolved. For example, an alkylene glycol solvent, an ether solvent, an ester solvent, a hydrocarbon solvent, a ketone solvent, an amide solvent, etc. can be used.

These solvents can be used individually by 1 type or in combination of 2 or more types.

What is necessary is just to set content of a solvent suitably in consideration of solid content of the photosensitive resin composition mentioned later.

Specific examples of the alkylene glycol solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and the like. Glycol alkyl ethers; Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether; Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; Etc. can be mentioned.

Tetrahydrofuran etc. are mentioned as a specific example of an ether solvent.

Specific examples of the ester solvents include ethyl acetate, n-butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, and γ-butyrolactone.

As a specific example of a hydrocarbon solvent, aromatic hydrocarbons, such as toluene and xylene, etc. are mentioned.

As a specific example of a ketone solvent, methyl ethyl ketone, 2-heptanone, cyclohexanone, etc. are mentioned.

Specific examples of the amide solvents include N, N-dimethylacetamide, N-methylpyrrolidone, and the like.

The positive type photosensitive resin composition used for this invention contains various well-known additives as needed, for example, surfactant, the adhesion promoter for improving the adhesiveness of the composition and a board | substrate, dye, a sensitivity promoter, a plasticizer, a stabilizer, etc. You can.

As surfactant which can be used by this invention, a silicone type surfactant, a fluorine type surfactant, and a hydrocarbon type surfactant are mentioned. These surfactant may be used individually by 1 type, and may be used in combination of 2 or more type.

As silicone type surfactant, surfactant which has a siloxane bond is mentioned. As a specific example, SH28PA, SH29PA, SH30PA, polyether modified silicone oil SF8410, copper SF8427, copper SH8400, ST80PA, ST83PA, ST86PA [above, manufactured by Toray Dow Corning Silicone company]; KP321, KP323, KP324, KP340, KP341 [above, Shin-Etsu Silicone company make]; TSF400, TSF401, TSF410, TSF4440, TSF4445, TSF4446 (above, the TOSHIBA silicone company make) etc. are mentioned.

As a fluorine type surfactant, surfactant which has a fluorocarbon chain is mentioned. As a specific example, Florinert [brand name] FC-430, the same FC-431 [above, Sumitomo 3M company make]; Suplon [brand name] S-141, copper S-145, copper S-381, copper S-393 [above, Asahi Glass Co., Ltd. product]; F-Top [brand name] EF301, copper EF303, copper EF351, copper EF352 [above, product made by Jemuco Corporation]; Megapack [brand name] F171, copper F172, copper F173, R-30 [above, Dai Nippon Ink Chemical Co., Ltd. product] etc. are mentioned.

Moreover, the silicone type surfactant which has a fluorine atom (fluorocarbon chain) can also be used. Specific examples thereof include Mega Pack R08, F470, F471, F472SF, F475, and the like.

As a hydrocarbon type surfactant, surfactant which has a polyoxyethylene chain is mentioned. Specific examples thereof include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate Etc. can be mentioned.

The usage-amount of these surfactant is 100-5,000 mass ppm with respect to a positive photosensitive resin composition, Preferably it is 200-2,000 mass ppm. If surfactant is used in this range, application | coating nonuniformity will not generate | occur | produce in a coating film, and it is preferable.

As an adhesion promoter, a melamine compound and a silane compound are mentioned, for example.

As a specific example of a melamine compound, Cymel-300, 303 (made by Japan Cytec Industries Co., Ltd.); MW-30MH, MW-30, MS-11, MS-001, MX-750, MX-706 (above, Sanwa Chemical Co., Ltd.), etc. are mentioned. The usage-amount of a melamine compound is 20 mass parts or less normally with respect to 100 mass parts of alkali-soluble resin, Preferably it is 0.5-18 mass parts, More preferably, it is 1-15 mass parts.

In addition, as a specific example of a silane compound, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl tris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxy silane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyl Trimethoxysilane etc. are mentioned.

The use amount of the silane compound is usually 2 parts by mass or less, preferably 0.001 to 1 part by mass, and more preferably 0.005 to 0.8 part by mass with respect to 100 parts by mass of the alkali-soluble resin.

Examples of the dyes include triphenylmethane dyes, cyanine dyes, diazo dyes, styryl dyes, and the like.

As a sensitivity promoter, the compound which has a hydroxyl group quoted as a structural component of the said photosensitive agent can be used. As a specific example of a sensitivity accelerator, polyhydroxy benzophenone, gallic acid ester, polyhydroxy bisphenyl alkane, polyhydroxy trisphenyl alkane, polyhydroxy tetrakisphenyl alkane, etc. are mentioned. Especially, polyhydroxy trisphenyl alkane, polyhydroxy benzophenone, etc. are especially preferable.

The positive type photosensitive resin composition used for this invention is a solvent which contains additives, such as said alkali-soluble resin, a quinonediazide group containing compound, and also a surfactant, an adhesion promoter, a dye, a sensitivity promoter, a plasticizer, and a stabilizer as needed. It can be prepared by mixing with and dissolving the mixture using various mixers or dispersers. There is no limitation such as the mixing order of each component.

Although solid content content (component content other than a solvent) of the positive photosensitive resin composition used for this invention is not specifically limited, Usually, 6-30 mass%, Preferably 7-25 mass%, More preferably, 8- It adjusts to 20 mass%. By setting the solid content in this range, the coating film can be formed without causing application unevenness.

The substrate used in the step (a) is not particularly limited, and known substrates such as silicon substrates, glass substrates, ITO film-forming substrates, chromium film-forming substrates, and resin substrates may be mentioned. Especially, in the method of this invention, the large size board | substrate, which has a square thru | or rectangular shape normally, and whose length of at least one side is 800 mm or more, Preferably the length of the at least one side is 1,000 mm or more is used preferably.

As the method of apply | coating the positive photosensitive resin composition mentioned above on these board | substrates, any of the coating methods currently performed may be sufficient, for example, a spray method, a roll coat method, the rotation coating method, the spinless slit coat method Various methods, such as these, can be used.

Among these methods, the spinless slit coat method is preferable. In the spinless slit coat method, the slit does not come into contact with the substrate by moving the slit for supplying the positive photosensitive resin composition, and the photosensitive resin composition is applied.

The coating according to the spinless slit coat method includes a spinless coater (manufactured by Tokyo Oka Industry Co., Ltd.), a table coater (manufactured by Jugairo Kogyo Co., Ltd.), a linear coater (manufactured by Dainippon Screen Manufacturer), a head coater (manufactured by Hirata Kogyo Co., Ltd.), slit A commercial coater such as a die coater (manufactured by Toray Engineering Co., Ltd.) or a toray slit coater (manufactured by Toray Corporation) may be used.

In this way, the coating film of the positive photosensitive resin composition is formed on a board | substrate.

[(b) process]

This process is a process of forming a photosensitive layer by drying under reduced pressure the coating film formed on the board | substrate in the said (a) process.

Drying under reduced pressure can be carried out using a known vacuum drying apparatus. The conditions of the vacuum drying are defined by the time until the attained pressure and the pressure condition of the apparatus reach the attained pressure. Drying under reduced pressure is usually performed at room temperature under a pressure of 5 to 4,000 Pa, preferably 10 to 1,000 Pa, and more preferably 20 to 300 Pa. If the attained pressure is less than 5 Pa, it is not practical, and if it exceeds 4,000 Pa, the reverse tapered resist pattern tends to be hard to be formed. In addition, in this specification, a "pressure reduction" means reducing a pressure to 13,000 Pa or less. There is no restriction | limiting in particular in the time required for pressure reduction drying, What is necessary is just to set arbitrarily in consideration of a film thickness, the magnitude | size of a board | substrate, the solvent amount of the photosensitive resin composition, the exhaust capacity of a pressure reduction pump, the volume of a reduced pressure part, etc. 30 minutes, Preferably it is for 5 seconds-10 minutes, More preferably, it is for 5 seconds-5 minutes, Especially preferably, it is for 30 seconds-2 minutes.

The coating film dried under reduced pressure is prebaked as needed, and it is set as the photosensitive layer without fluidity. The said prebaking is normally performed by heating at 60-120 degreeC for about 10 to 600 second. The thickness of this photosensitive layer is about 0.5-5 micrometers normally, Preferably it is 0.8-4 micrometers.

[(c) process]

This process is a process of pattern-exposing the photosensitive layer formed at the said (b) process, and developing and forming an inverse taper resist pattern.

Specifically, actinic light is irradiated to the photosensitive layer through a mask pattern normally, and the latent image pattern of a predetermined shape is formed in a photosensitive layer (pattern exposure). This latent image pattern is then developed with an alkaline developer to form a desired resist pattern.

The kind of actinic light used by this invention is not specifically limited, For example, visible light, an ultraviolet-ray, an ultraviolet-ray, X-rays, etc. are mentioned, Especially a visible light and an ultraviolet-ray are preferable. The amount of light to be irradiated can be arbitrarily set in consideration of the purpose of use of the photosensitive layer, the thickness of the film, and the like.

The alkali developer used for the development of the latent image pattern is not particularly limited. Specific examples of the alkaline component used in the developer include tetramethylammonium hydroxide, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide and the like. These developing solutions are normally used as 0.1-5 mass% aqueous solution.

After development of the pattern, it is usually washed with water and further air dried with compressed air or compressed nitrogen. Subsequently, if desired, the pattern is heated by a heating device such as a hot plate or an oven at a predetermined temperature, for example, 100 to 250 ° C. for a predetermined time, for example, on a hot plate, for about 2 to 60 minutes, in an oven. The target resist pattern can be obtained by heating (post-baking) for about 90 minutes.

The resist pattern thus obtained has an inverse tapered cross-sectional shape.

[(d) process]

This process is a process of depositing a metal with respect to the board | substrate which has the reverse taper resist pattern obtained by the said (c) process.

The deposition of the metal may be performed by depositing the metal in the vertical direction with respect to the entire surface of the substrate having the inverse tapered resist pattern. As a result, a metal vapor deposition film is formed on the entire surface of the substrate. Examples of the metal to be deposited include platinum (Pt), gold (Au), palladium (Pd), chromium (Cr), nickel (Ni), aluminum (Al), silver (Ag), tantalum (Ta), Metals such as tungsten (W), copper (Cu), titanium (Ti), indium (In), tin (Sn), magnesium (Mg), or alloys containing these metal elements. These metals can be used individually or in mixture of 2 or more types, respectively.

The vapor deposition of the metal may be performed using a commercially available vacuum vapor deposition apparatus. Although it does not specifically limit as vapor deposition conditions, For example, what is necessary is just to select suitably in the range of 1 * 10 <^-3> -1 * 10 <^-6> Pa, and a deposition rate of 0.1-10 nm / sec. What is necessary is just to set vapor deposition time suitably according to the film thickness of a metal vapor deposition film.

Although it does not specifically limit as film thickness of a metal vapor deposition film, Usually, it is 5-1,000 nm.

[(e) process]

This step is a step of removing the reverse tapered resist pattern and the metal vapor deposition film thereon from the substrate deposited in the step (d) by a lift-off operation.

When the metal vapor deposition film is formed in the whole surface of a board | substrate by the said (d) process, as shown, for example in FIG.1 (b), a metal vapor deposition film is formed independently on a board | substrate and an inverse tapered resist pattern, respectively. Therefore, when the resist pattern and the metal deposition film thereon are removed together by the lift-off operation, the metal deposition film having a predetermined pattern remains on the substrate. The remaining metal deposited film constitutes metal wiring.

The lift-off operation may be performed according to a known method. For example, the board | substrate with which the metal vapor deposition film obtained by the process (d) was formed was dimethyl sulfoxide, N-methylpyrrolidone, acetone, dimethylacetamide, propylene glycol methyl ether, and monoethanolamine at the temperature of 23-150 degreeC. In the? -butyrolactone or a mixed solvent thereof, or in a commercially available resist stripping solution, it is usually immersed for about 1 to 30 minutes, and the resist pattern and the metal deposition film thereon may be removed together. When immersing a board | substrate, you may perform stirring as needed.

The desired board | substrate with a metal wiring is obtained by the above. In this invention, since the board | substrate with which the inverse taper resist pattern obtained by simple operation is used by the general-purpose cheap positive photoresist is used, the board | substrate with a metal wiring can be manufactured in low cost, and high productivity.

Moreover, this invention applies the positive type photosensitive resin composition containing (A) alkali-soluble resin, (B) quinonediazide group containing compound, and (C) solvent on (a) board | substrate as one aspect, and is a coating film. Forming a photosensitive layer by drying the coating film under reduced pressure and (c) subjecting the photosensitive layer to pattern exposure, followed by developing to form a reverse tapered resist pattern. A method for producing a substrate having a resist pattern is provided. Such a method has a (c) process from the said (a) process demonstrated about the manufacturing method of the board | substrate with a metal wiring of this invention, and can be easily performed in accordance with the said description regarding those processes. The board | substrate which has the reverse taper resist pattern obtained by this invention is used not only as a lift-off resist pattern in the manufacturing method of the board | substrate with a metal wiring of this invention, but also as a partition material etc. of an organic electroluminescent display apparatus. It is preferably used.

Next, although an Example demonstrates this invention still in detail, this invention is not limited at all by these examples.

Example 1

(1) Preparation of Positive Photosensitive Resin Composition

17.7 parts by mass of a novolak resin (weight average molecular weight = about 5500) obtained by condensation polymerization of m-cresol / p-cresol mixed cresol (mass mixing ratio = 5: 5) and formaldehyde in the presence of oxalic acid Silicone surfactant having 4.3 parts by mass of a quinonediazide group-containing compound having an esterification rate of 70 mol% obtained from 4'-tetrahydroxybenzophenone and 1,2-naphthoquinonediazide-5-sulfonic acid chloride, and having a siloxane bond. SH29PA "[made by Toray Dow Corning Silicone Co., Ltd.] 0.05 mass part and 107.4 mass parts of propylene glycol monomethyl ether acetates (PGMEA) were mixed, and the positive photosensitive resin composition (resist solution) was obtained.

(2) Formation of Reverse Tapered Resist Pattern

The resist solution obtained by said (1) was apply | coated on the glass substrate using the slit coater, and drying under reduced pressure was performed at room temperature (23 degreeC) for 25 second on the conditions of 266 Pa of arrival pressures. Subsequently, it heated (prebaked) on the hotplate at 110 degreeC for 150 second and normal pressure, and formed the photosensitive layer (resist film) of 2.1 micrometers of film pressures. The latent image pattern was obtained by exposing with the mirror projection aligner "MPA7000" [product name: Canon company] using the mask of the line-and-space pattern of 10 micrometers of line widths from this resist film. Exposure amount was made into the amount of energy which the line width of a line turns into 10 micrometers. After exposure, the substrate was developed with a 2.38% by mass tetramethylammonium hydroxide aqueous solution for 70 seconds to obtain a substrate having a resist pattern.

The cross section of the resist pattern on the substrate was observed (magnification: 15,000 times) by a scanning electron microscope ("JSM-5400" manufactured by Nippon Electronics Co., Ltd.). As a result, as shown in FIG.

(3) formation of metal deposition patterns

Subsequently, an aluminum film having a film thickness of 200 nm was vacuum deposited on the entire surface of the substrate obtained in the above (2) by a commercial vacuum evaporation apparatus (manufactured by Albakg Technician) at a vacuum degree of 1 × 10 ⁻⁴ Pa and a deposition rate of 4 nm / second. The board | substrate which deposited this aluminum film was immersed in dimethyl sulfoxide of 40 degreeC for 1 minute, and the resist pattern and the aluminum film on it were peeled off. As a result of observing (magnification: 200 times) the pattern of the metal vapor deposition film with the optical microscope with respect to the board | substrate after peeling, the resist pattern peels without a residue and the desired pattern of metal vapor deposition film (metal wiring) is formed on the board | substrate. Was observed. That is, the board | substrate with a desired metal wiring was obtained.

In the 1st table | surface, the evaluation result of the cross-sectional shape of a resist pattern and the pattern shape of the metal vapor deposition film after peeling is shown with the arrival pressure and processing time at the time of a vacuum drying process. About the cross-sectional shape of a resist pattern, the case where the inverse taper type resist pattern is formed was favorable, and the case where the forward taper type resist pattern was formed was evaluated as defect, respectively. Regarding the pattern shape of the metal deposited film after peeling, it is preferable that the resist pattern is peeled off without residue, and the desired pattern of the metal deposited film is formed on the substrate. The resist pattern does not peel off smoothly, and residues remain, or the resist Even when the pattern was peeled off, each of the cases where the pattern of the desired metal deposited film was not formed by peeling to the metal deposited film to be left on the substrate was evaluated as defective.

Example 2, 3

Except having changed the achieved pressure at the time of pressure reduction drying, the board | substrate with a metal wiring was obtained by the method similar to Example 1, respectively.

The evaluation results of the attained pressure and the treatment time during the vacuum drying treatment, the cross-sectional shape of the resist pattern, and the pattern shape of the metal deposited film after peeling are shown in the first table.

Comparative Example 1

A substrate with a metal wiring was obtained in the same manner as in Example 1 except that the reduced pressure drying was not performed.

The evaluation results of the cross-sectional shape of the resist pattern and the pattern shape of the metal vapor deposition film after peeling are shown in the first table.

Comparative Example 2

The board | substrate with a metal wiring was obtained by the method similar to Example 1 except having changed the achieved pressure at the time of pressure reduction drying.

The evaluation results of the attained pressure and the treatment time during the vacuum drying treatment, the cross-sectional shape of the resist pattern, and the pattern shape of the metal deposited film after peeling are shown in the first table.

In Examples 1 to 3 in which the predetermined pressure reduction test process was performed from the first table to form the photosensitive layer, the resist pattern on the substrate became an inverse taper shape, and a good metal deposited film pattern was formed, while such a reduced pressure drying process was not performed. In Comparative Examples 1 and 2, it is understood that a forward tapered resist pattern is formed and the metal deposited film pattern is defective.

Good cross-sectional shape of resist pattern: reverse tapered shape, bad: forward tapered shape

Metal deposition film pattern shape after peeling Good: Good pattern formation, bad: Bad pattern formation

According to the present invention, a method of manufacturing a substrate with a metal wiring at a high productivity at low cost by a lift-off method using a substrate having a reverse tapered resist pattern obtained by a simple operation by a general-purpose positive type photoresist. This is provided.

Claims (3)

(a) Process of apply | coating positive photosensitive resin composition containing (A) alkali-soluble resin, (B) quinonediazide group containing compound, and (C) solvent on a board | substrate, and forming a coating film, (b) drying the coating film under reduced pressure to form a photosensitive layer, (c) a step of pattern-exposing the photosensitive layer and then developing to form an inverse tapered resist pattern, (d) depositing a metal on the substrate having an inverse tapered resist pattern obtained by the step (c); and (e) The manufacturing method of the board | substrate with a metal wiring which has a process of removing the reverse taper-shaped resist pattern and the metal vapor deposition film on it from the board | substrate vapor-deposited by the said (d) process by lift-off operation. The method of claim 1, (b) The manufacturing method which performs drying under reduced pressure in a process on the conditions of 5 to 4,000 Pa of reached pressures. (a) Process of apply | coating positive photosensitive resin composition containing (A) alkali-soluble resin, (B) quinonediazide group containing compound, and (C) solvent on a board | substrate, and forming a coating film, (b) drying the coating film under reduced pressure to form a photosensitive layer, and (c) The method of manufacturing a substrate having an inverse tapered resist pattern, which has a step of developing the inverse tapered resist pattern by developing the pattern after exposing the photosensitive layer.

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