KR100497587B1 - Photoresist stripping solution and a method of stripping photoresists using the same - Google Patents

Abstract

The present invention relates to (a) hydroxylamines, (b) aromatic hydroxy compounds, (c) benzotriazole compounds, (d) amines having an acid dissociation constant (pKa) in an aqueous solution at 25 ° C of 7.5 to 13, and (e A photoresist stripping solution containing a water-soluble organic solvent and / or (f) water, and a photoresist stripping method using the same, and in particular, a stripping of a photoresist film and a deterioration film suitably used for the production of a liquid crystal panel device. It is to provide a photoresist stripper composition excellent in properties, excellent in corrosion resistance of a substrate on which both a metal wiring and an inorganic material layer are formed, and a photoresist stripping method using the same.

Description

Photoresist stripping solution and photoresist stripping method using the same {PHOTORESIST STRIPPING SOLUTION AND A METHOD OF STRIPPING PHOTORESISTS USING THE SAME}

The present invention relates to a photoresist stripper and a photoresist stripper using the same. More specifically, the photoresist stripping solution and the photoresist stripper excellent in the anticorrosive property to the substrate and the use of the photoresist film and the modified film which are suitably used for the manufacture of semiconductor devices such as IC and LSI or liquid crystal panel devices. It relates to a photoresist stripping method.

In semiconductor devices such as ICs and LSIs, and liquid crystal panel devices, a photoresist is uniformly coated on a conductive metal film such as a tin oxide film formed by vapor deposition on a substrate, or an insulating film such as a SiO ₂ film, which is selectively exposed and developed. After the treatment, a photoresist pattern is formed, the conductive metal film or the insulating film is selectively etched using the pattern as a mask, a microcircuit is formed, and the undesired photoresist layer is removed by a stripping solution.

In recent years, photoresist stripping liquid compositions using alkanolamines have been used as stripping solutions for peeling the photoresist layer (Japanese Patent Laid-Open No. 62-49355, No. 63-208043, etc.).

However, in the manufacturing process of today's semiconductor devices and liquid crystal devices, in addition to the above method, it has also become necessary to peel off the photoresist film provided with the photoresist layer by dry etching, ashing, ion implantation, or the like. By these treatments, the photoresist film after the treatment becomes a deteriorated film. In recent years, these treatment conditions have become more severe, and since the deteriorated film becomes a film having inorganic properties from the organic film, the conventional peeling liquid using alkanolamines is insufficient in the peelability of the deteriorated film.

In recent years, the peeling liquid composition for resists containing hydroxylamine as a peeling liquid for photoresists which is more excellent in the peelability of a deterioration film | membrane is proposed to this.

In addition, in the current photolithography technique, the technique of peeling off the photoresist film is required to meet the severer conditions in response to the miniaturization of the pattern, the progress of the multilayering of the substrate, and the change of the material formed on the substrate surface.

In particular, in the manufacture of liquid crystal display devices, since metal substrates and substrates having inorganic material layers such as annealing polysilicon films and amorphous silicon films are used, corrosion of both of these metal wirings and inorganic material layers is prevented. The development of the peeling liquid which can peel without generating is required.

As a peeling liquid composition for resist containing the said hydroxylamine, For example, the peeling liquid composition for resist which pKa mixed 7.5-13 amine, hydroxylamine, water-soluble organic solvent, an anticorrosive agent, and water in specific amount (Japanese Patent Publication) No. 2911792), a peeling liquid composition for resists (Japanese Patent Laid-Open No. 11-119444) and the like in which a specific amount of hydroxylamines, water, specific amines, specific water-soluble organic solvents, and aromatic hydroxy compounds are blended. Can be. In addition, a stripping solution for positive photoresist (Japanese Patent Publication No. 7-120937) containing a nitrogen-containing organic hydroxy compound, a specific aromatic hydroxy compound, a desired triazole compound and a water-soluble organic solvent is also proposed. . Each of these peeling liquid compositions is excellent in the peelability of the photoresist film and the deteriorated film, and has an excellent anticorrosive effect on the corrosion of the metal wiring board which is a problem of the peeling solution using hydroxylamines. The metal wiring and the polysilicon The correspondence to the board | substrate with which inorganic material layers, such as a film | membrane and an amorphous silicon film, were formed was not examined.

Therefore, particularly in the field of using SiO ₂ substrates used in liquid crystal display devices and the like, it is excellent in the corrosiveness of the substrate formed by forming both metal wiring and an inorganic material layer such as a polysilicon film, and in the peelability of the photoresist layer and the deterioration film. Excellent stripping solution is required.

In particular, the present invention provides a photoresist stripping solution which is particularly excellent in the peelability of a photoresist layer and a deterioration film formed on a substrate formed by forming both a metal wiring and an inorganic material layer such as a polysilicon film, and excellent in corrosion resistance of the substrate. And a photoresist stripping method using the same.

Namely, the present invention provides an amino acid having a dissociation constant (pKa) of 7.5 to 13 in an aqueous solution of (a) hydroxylamine, (b) aromatic hydroxy compound, (c) benzotriazole compound, (d) 25 ° C., and It relates to a release liquid for photoresists comprising (e) a water-soluble organic solvent and / or (f) water.

In addition, the present invention,

(I) providing a photoresist layer on the substrate;

(II) selectively exposing the photoresist layer,

(III) developing the photoresist layer after exposure to provide a photoresist pattern;

(IV) etching the substrate with the photoresist pattern as a mask, and

(V) Process of peeling the photoresist pattern after an etching process from a board | substrate using the said peeling liquid for photoresists.

It relates to a photoresist stripping method comprising a.

In addition, the present invention,

(I) providing a photoresist layer on the substrate;

(II) selectively exposing the photoresist layer,

(III) developing the photoresist layer after exposure to provide a photoresist pattern;

(IV) etching the substrate with the photoresist pattern as a mask,

(V) plasma ashing the photoresist pattern, and

(VI) Process of peeling the photoresist quality film after plasma ashing from a board | substrate using the said peeling liquid for photoresists,

It relates to a photoresist stripping method comprising a.

Hereinafter, the peeling liquid for photoresists of this invention is demonstrated in detail.

Hydroxylamines as the component (a) are represented by the following general formula (II):

(In formula, R <^6> , R <^7> respectively independently represents a hydrogen atom and the lower alkyl group of 1-6 carbon atoms.)

Represented by

Here, as the lower alkyl group having 1 to 6 carbon atoms, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group and neo Pentyl groups, tert-pentyl groups, hexyl groups, isohexyl groups, 3-methylpentyl groups, 2, 2-dimethylbutyl groups or 2, 3-dimethylbutyl groups and the like are exemplified. R ⁶ and R ⁷ may be the same or different.

Specific examples of the hydroxylamines include hydroxylamine (NH ₂ OH), N-methylhydroxylamine, N, N-dimethylhydroxylamine, N, and N-diethylhydroxylamine. Of these, hydroxylamine (NH ₂ OH), N, N-diethylhydroxylamine and the like are particularly preferably used. (a) A component can use 1 type (s) or 2 or more types.

The aromatic hydroxy compound as the component (b) is mainly intended to obtain an anticorrosive effect, specifically, phenol, clesol, xylenol, pyrocatechol (= 1, 2-dihydroxybenzene), tert-butylcate Kohl, resorcinol, hydroquinone, pyrogallol, 1, 2, 4-benzenetriol, salicylic alcohol, p-hydroxybenzyl alcohol, o-hydroxybenzyl alcohol, p-hydroxyphenethyl alcohol, p- Aminophenone, m-aminophenone, diaminophenone, aminoresorcinol, p-hydroxybenzoic acid, o-hydroxybenzoic acid, 2, 4-dihydroxybenzoic acid, 2, 5-dihydroxybenzoic acid, 3, 4-dihydroxy benzoic acid, 3, 5- dihydroxy benzoic acid, a gallic acid, etc. are mentioned. Among them, pyrocatechol, tert-butylcatechol, pyrogallol and gallic acid are suitably used. (b) A component can use 1 type (s) or 2 or more types.

As a benzotriazole type compound as (c) component, it is following Chemical formula 1:

[Wherein, Q is a hydrogen atom, a hydroxyl group, a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms (however, the structure may have an amide bond, an ester bond), an aryl group, or the following general formula:

(Wherein, R ³ represents an alkyl group having carbon atoms 1 to 6; R ^4, R ⁵ represents a hydroxyalkyl group or an alkoxyalkyl group of hydrogen, hydroxyl, or a carbon atom number of 1-6, each independently)

Represents a group represented by; R ¹ and R ² each independently represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, a carboxyl group, an amino group, a hydroxyl group, a cyano group, a formyl group, a sulfonylalkyl group, or a sulfo group]

The compound represented by it is used preferably.

A "hydrocarbon group" is an organic group consisting of carbon atoms and hydrogen atoms. In the present invention, in each definition of the groups Q, R ¹ and R ^2, the hydrocarbon group may be either an aromatic hydrocarbon group or an aliphatic hydrocarbon group, or may have a saturated or unsaturated bond, and may be any linear or branched chain. It may be. As a substituted hydrocarbon group, a hydroxyalkyl group, an alkoxylalkyl group, etc. are mentioned, for example.

In the above formula (1), particularly as Q, the following formula:

(Wherein R ³ , R ⁴ and R ⁵ are the same as defined above)

The group represented by is preferable. Among these, in said formula, it is preferable to respectively independently select the C1-C6 hydroxyalkyl group or the alkoxyalkyl group as R <^4> , R <^5> . In addition, when at least one of R ⁴ and R ⁵ is an alkyl group having 1 to 6 carbon atoms, the properties of the benzotriazole-based compound having such a composition are insufficient in water solubility, but other components capable of dissolving the compound are peeled off. It is preferably used when present in the liquid.

In Formula 1, Q is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (ie, a methyl group, an ethyl group, a propyl group, an isopropyl group), a hydroxyalkyl group having 1 to 3 carbon atoms, a hydroxyl group, or the like. Used.

Specific examples of the benzotriazole-based compound include benzotriazole, 5, 6-dimethylbenzotriazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 1-aminobenzotriazole, and 1-phenylbenzotriazole. , 1-hydroxymethylbenzotriazole, 1-benzotriazolecarboxylic acid methyl, 5-benzotriazolecarboxylic acid, 1-methoxybenzotriazole, 1- (2, 2-dihydroxyethyl) benzo Triazole, 1- (2, 3-dihydroxypropyl) benzotriazole, or 2,2 '-{[(4-methyl-) sold by Chiba, Specialty Chemicals as "irugamet" series 1H-benzotriazol-1-yl) methyl] imino} bisethanol, 2, 2 '-{[(5-methyl-1H-benzotriazol-1-yl) methyl] imino} bisethanol, 2, 2 '-{[(4-methyl-1H-benzotriazol-1-yl) methyl] imino} bisethane, or 2,2'-{[(4-methyl-1H-benzotriazol-1-yl ) Methyl] imino} bispropane etc. are mentioned. Among these, benzotriazole, 1-hydroxybenzotriazole, 1-methoxybenzotriazole, 1- (2, 2-dihydroxyethyl) benzotriazole, 1- (1, 2-dihydroxypropyl ) Benzotriazole, 1- (2, 3-dihydroxypropyl) benzotriazole, 2, 2 '-{[(4-methyl-1H-benzotriazol-1-yl) methyl] imino} bisethanol And 2,2 '-{[(5-methyl-1H-benzotriazol-1-yl) methyl] imino} bisethanol, etc., on which both metal wirings and inorganic material layers such as polysilicon films are formed. The anticorrosive effect, the peeling effect, and the like are preferably used.

(c) A component can use 1 type (s) or 2 or more types.

The amines as the component (d) are anticorrosive effects on a substrate on which metal wiring (eg, Al, Al alloy, etc.) and an inorganic material layer (eg, polysilicon film, amorphous silicon film, etc.) are formed. Use a dissociation constant (pKa) of 7.5 to 13. Thus, as amines, 1 or more types chosen from alkanolamines, polyalkylene polyamines, aliphatic amines, aromatic amines, and cyclic amines are used preferably.

Specific examples of the alkanolamines include monoethanolamine, diethanolamine, triethanolamine, 2- (2-aminoethoxy) ethanol, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N -Dibutylethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N-methyldiethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, etc. are mentioned.

Specific examples of the polyalkylene polyamines include diethylenetriamine, triethylenetetraamine, propylenediamine, N, N-diethylethylenediamine, 1,4-butanediamine, N-ethyl-ethylenediamine, 1, 2- Propanediamine, 1, 3-propanediamine, 1, 6-hexadiamine, etc. are mentioned.

As aliphatic amines, 2-ethyl-hexylamine, dioctylamine, tributylamine, tripropylamine, triallylamine, heptylamine, cyclohexylamine, etc. are mentioned.

Benzylamine, diphenylamine, etc. are mentioned as aromatic amines.

Examples of the cyclic amines include piperazine, N-methyl-piperazine, methyl-piperazine, hydroxylethylpicerazine, and the like.

Among them, monoethanolamine, 2- (2-aminoethoxy) ethanol, diethylenetriamine, triethylenetetraamine, cyclohexylamine, piperazine and the like are preferably used.

In addition, since it may heat at the time of peeling process, when it is set as the peeling liquid for photoresists, it is preferable that flash point is 30 degreeC or more, especially 50 degreeC or more from a viewpoint of stability. In view of this and the stability of the liquid composition when the stripping solution is used continuously, triethylene tetraamine, monoethanolamine, diethanolamine, 2- (2-aminoethoxy) ethanol and the like are particularly preferable. (d) A component can use 1 type (s) or 2 or more types.

In the peeling liquid of this invention, it adds to the said (a)-(d) component, and contains water-soluble organic solvent and / or water as (f) component as (e) component.

As the water-soluble organic solvent of the component (e), any organic solvent that is miscible with water may be used as long as it dissolves the components (a), (b), (c) and (d). Thus, as water-soluble organic solvent, sulfoxides, such as dimethyl sulfoxide; Sulfones such as dimethyl sulfone, diethyl sulfone, bis (2-hydroxyethyl) sulfone and tetramethylene sulfone; Amides such as N, N-dimethylformamide, N-methylformamide, N, N-dimethylacetoamide, N-methylacetoamide, N, and N-diethylacetoamide; N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, N-hydroxyethyl-2- Lactams such as pyrrolidone; Imidazolidinones, such as 1, 3-dimethyl-2-imidazolidinone, 1, 3-diethyl-2-imidazolidinone, and 1, 3-diisopropyl-2-imidazolidinone; Ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol mono Polyhydric alcohols, such as diethylene glycol monoalkyl ether (alkyl is a C1-C6 lower alkyl group), such as ethyl ether, diethylene glycol monopropyl ether, and diethylene glycol monobutyl ether, and its derivative (s) are mentioned. . Among these, 1 or more types chosen from dimethyl sulfoxide, N-methyl- 2-pyrrolidone, and diethylene glycol monobutyl ether are used suitably as further peeling performance. Among them, dimethyl sulfoxide is particularly excellent in the anticorrosive effect on the substrate. (e) A component can use 1 type (s) or 2 or more types.

Although the water of (f) component may inevitably be contained in the other component in the peeling liquid of this invention, you may add further and adjust the compounding quantity.

The compounding quantity of each component is the following in the photoresist stripping liquid of this invention containing said (a)-(d) component and (e) component and / or (f) component.

30 weight% is preferable and, as for the upper limit of the compounding quantity of (a) component, 20 weight% is especially preferable. Moreover, 2 weight% is preferable and, as for a minimum, 5 weight% is especially preferable.

20 weight% is preferable and, as for the upper limit of the compounding quantity of (b) component, 15 weight% is especially preferable. Moreover, 0.5 weight% is preferable and, as for a minimum, 1 weight% is especially preferable.

20 weight% is preferable and, as for the upper limit of the compounding quantity of (c) component, 15 weight% is especially preferable. Moreover, 0.01 weight% is preferable and, as for a minimum, 0.1 weight% is especially preferable.

80 weight% is preferable and, as for the upper limit of the compounding quantity of (d) component, 70 weight% is especially preferable. Moreover, 2 weight% is preferable and, as for a minimum, 5 weight% is especially preferable. It is preferable to determine and use an optimal compounding quantity suitably according to each intrinsic dissociation constant (pKa) value within the said compounding quantity range.

80 weight% is preferable and, as for the upper limit of the compounding quantity of (e) component, 70 weight% is especially preferable. Moreover, 15 weight% is preferable and, as for a minimum, 25 weight% is especially preferable.

In addition, the component (f) occupies the remainder.

In the present invention, the components (a) to (d), and the components (e) and / or (f) fall within the above-described compounding ratio range, so that the inorganic material layers such as photoresist peelability, metal wiring, and polysilicon film can be used. Better effect of anticorrosiveness can be achieved.

Especially among these, by carrying out the compounding quantity of (b) component and (c) component in the said range, corrosion prevention to a metal wiring and an inorganic material layer can be achieved more effectively.

The peeling liquid of this invention is added to the said (a)-(d) component, and (e) component and / or (f) component, and improves the permeability of this peeling liquid, and peels to a photoresist film more. In order to further improve, on demand, the following general formula (3):

(Wherein R ⁸ represents an alkyl group having 6 to 20 carbon atoms)

You may mix | blend 1 or more types of compound chosen from N-alkyl- 2-pyrrolidone represented by these, and acetylene alcohol-alkylene oxide adduct.

N-alkyl-2-pyrrolidone and acetylene alcohol-alkylene oxide adducts are surfactants and are themselves known substances.

Specific examples of N-alkyl-2-pyrrolidone represented by Formula 3 include N-hexyl-2-pyrrolidone, N-heptyl-2-pyrrolidone, N-octyl-2-pyrrolidone, and N-nonyl -2-pyrrolidone, N-decyl-2-pyrrolidone, N-undecyl-2-pyrrolidone, N-dodecyl-2-pyrrolidone, N-tridecyl-2-pyrrolidone, N-tetradecyl-2-pyrrolidone, N-pentadecyl-2-pyrrolidone, N-hexadecyl-2-pyrrolidone, N-heptadecyl-2-pyrrolidone, N-octadecyl-2 -Pyrrolidone, etc. are mentioned. Among these, N-octyl-2-pyrrolidone and N-dodecyl-2-pyrrolidone are marketed as "SURFADONE LP 100" and "SURFADONE LP 300" (all are manufactured by ISP Japan), respectively. It is used appropriately.

In the acetylene alcohol-alkylene oxide adduct, as the acetylene alcohol forming the adduct, the following general formula (4):

Wherein R ⁹ represents a hydrogen atom or Represents; R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)

The compound represented by is used preferably. Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, isohexyl group, 3-methylpentyl group, 2, 2-dimethylbutyl group, 2, 3-dimethylbutyl group, etc. are mentioned.

This acetylene alcohol is marketed as a series of, for example, "spinor", "orupin" (all manufactured by Air Product and Chemicals Inc.) and the like, and is suitably used. Among these, in terms of its physical properties, "spinor 104", "spinor 82" or a mixture thereof is very appropriately used. In addition, "Orufin B", "Orufin P", "Orufin Y", etc. can also be used.

As the alkylene oxide added to the acetylene alcohol, ethylene oxide, propylene oxide or a mixture thereof is preferably used.

In the present invention, as the acetylene alcohol alkylene oxide adduct,

Wherein R ¹⁴ represents a hydrogen atom or Represents; R ¹⁵ , R ¹⁶ , R ¹⁷ , and R ¹⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)

The compound represented by is used preferably. Here, (n + m) represents an integer from 1 to 30, and the properties such as solubility in water, surface tension and the like slightly change depending on the adduct of this ethylene oxide.

The acetylene alcohol alkylene oxide adduct is commercially available as a series of "Sapnor" (manufactured by Air Product and Chemicals Inc.), or a series of "acechirenor" (manufactured by Kawabane Fine Chemical Co., Ltd.). It is used properly. Among these, in consideration of changes in properties such as solubility in water and surface tension due to the addition of ethylene oxide, `` safinor 440 '' (n + m = 3.5) and `` safnor 465 '' (n + m = 10). ), `` Sapinor 485 '' (n + m = 30), `` acethyrenor EL '' (n + m = 4), `` acethyrenor EH '' (n + m = 10), or mixtures thereof are suitably used. have. In particular, a mixture of "acethylenor EL" and "acethyrenor EH" is preferably used. Among these, the thing which mixed "acethylenor EL" and "acethyrenor EH" in the ratio of 2: 8-4: 6 (weight ratio) is used especially preferably.

In the peeling solution of this invention, the upper limit of the compounding quantity of the compound which can be added in order to improve the permeability of these peeling liquids is preferable, and is especially 0.5 weight%. Moreover, 0.01 weight% is preferable and a minimum is 0.015 weight% especially.

The peeling solution for photoresists of the present invention can be advantageously used for photoresists that can be developed with an aqueous alkali solution containing negative and positive photoresists. Such photoresists include (i) a positive photoresist containing a naphthoquinone diazide compound and a novolak resin, (ii) a compound that generates an acid upon exposure, and a solubility in an aqueous alkali solution that is decomposed by an acid. Positive photoresist containing an increasing compound and an alkali-soluble resin, (iii) A positive photoresist containing an alkali-soluble resin having a compound in which an acid is generated by exposure and a group that is decomposed by an acid and has increased solubility in an aqueous alkali solution. Although the resist and (iv) negative photoresist containing the compound which generate | occur | produces an acid by light, a crosslinking agent, and alkali-soluble resin, etc. are mentioned, It is not limited to these.

The photoresist stripping method of the present invention forms a photoresist pattern obtained by a lithography method, selectively etches a conductive metal film or an insulating film as a mask, forms a microcircuit, and then peels the photoresist pattern. And the case where the photoresist pattern after the etching process is subjected to plasma ashing, and the deteriorated film (photoresist residue), metal deposition, etc. after the plasma ashing can be divided.

As an example in the case of peeling the photoresist film after the former etching process,

(I) providing a photoresist layer on the substrate;

(II) selectively exposing the photoresist layer,

(III) developing the photoresist layer after exposure to provide a photoresist pattern;

(IV) etching the substrate with the photoresist pattern as a mask, and

(V) Process of peeling the photoresist pattern after an etching process from a board | substrate using the photoresist peeling liquid of the said invention.

The photoresist peeling method containing these is mentioned.

Moreover, as an example in the case of peeling a deterioration film, metal deposition, etc. after the latter plasma ashing process,

(I) providing a photoresist layer on the substrate;

(II) selectively exposing the photoresist layer,

(III) developing the photoresist layer after exposure to provide a photoresist pattern;

(IV) etching the substrate with the photoresist pattern as a mask,

(V) plasma ashing the photoresist pattern, and

(VI) Process of peeling the photoresist deterioration film after plasma ashing from a board | substrate using the peeling liquid for photoresists of the said invention.

The photoresist peeling method containing these is mentioned.

In the present invention, in particular, in the peeling of the photoresist formed on the substrate on which the metal wiring and the inorganic material layer are formed, the peeling property of the photoresist film and the altered film and the anticorrosive property of the substrate are excellent.

Examples of the metal wiring include aluminum (Al); Aluminum alloys (Al alloys) such as aluminum-silicon (Al-Si) and aluminum-silicon-copper (Al-Si-Cu); Pure titanium (Ti); Titanium alloys (Ti alloys) such as titanium nitride (TiN) and titanium tungsten (TiW); Pure copper (Cu) etc. can be mentioned, It is not limited to these.

As an inorganic material layer, especially in the case of liquid crystal element manufacture, although the layer which consists of semiconductor materials, such as a polysilicon film and an amorphous silicon film, is mentioned, It is not limited to these examples. In the conventional stripping solution, it was difficult to achieve both the peelability of the photoresist and the corrosion resistance of the substrate having the metal wiring and the layer made of these inorganic materials, but in the present invention, both of these effects could be achieved.

In the latter peeling method, after plasma ashing, a photoresist residue (photoresist-denatured film) or metal deposition generated during etching of a metal film adheres and remains on the substrate surface as a residue. These residues are contacted with the peeling liquid of this invention, and the residue on a board | substrate is peeled off. Originally, plasma ashing is a method of removing the photoresist pattern, but since the photoresist pattern remains as a part of the altered film by plasma ashing in many cases, the present invention is particularly effective as a complete removal of the photoresist altered film in such a case.

Formation, exposure, development, and etching of the photoresist layer are all conventional means and are not particularly limited. Although etching can use both wet etching and dry etching, the peeling liquid of this invention can be used especially suitably for peeling of the photoresist film after wet etching. Especially in glass substrates used for liquid crystal panel elements and the like, an acidic etching solution such as phosphoric acid, nitric acid, acetic acid or the like is preferably used as the etching solution (enchant).

In addition, after the developing step (III) and the peeling step (V) or (VI), rinsing and drying using distilled water, lower alcohol, and the like conventionally performed may be performed.

Moreover, depending on the kind of photoresist, you may perform the post-exposure heat processing which is the post exposure bake normally performed with a chemically amplified type photoresist. In addition, you may perform the post-baking after forming a photoresist pattern.

The peeling treatment is usually performed by an immersion method or a shower method. The peeling time should just be sufficient time peeled, and it is although it does not specifically limit, Usually, it is about 10 to 20 minutes.

EXAMPLE

Although an Example demonstrates this invention further in detail, this invention is not limited by these examples. In addition, a compounding quantity is weight% unless there is particular notice.

Examples 1 to 8, Comparative Examples 1 to 7

On a SiO ₂ substrate on which Al wiring and an amorphous silicon film were formed, a positive photoresist TFR-890 PM (manufactured by Tokyo Kogyo Co., Ltd.) was applied with a spinner, prebaked at 110 ° C. for 90 seconds, and the film was filmed. A photoresist layer having a thickness of 2.5 μm was formed. This photoresist layer was exposed through a mask pattern, and developed as a 2.38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution to form a photoresist pattern. Subsequently, the post-baking was performed at 145 degreeC for 240 second.

Next, the dry etching process was performed for the board | substrate which has the photoresist pattern formed on said conditions.

The photoresist pattern was subjected to plasma ashing with oxygen gas, but there was an ashing residue (photoresist deterioration film).

Subsequently, the photoresist deterioration film peeling process was performed with respect to the board | substrate after the said process by the dipping method at 40 degreeC using the peeling liquid of each composition shown in Table 1, respectively. The board | substrate after peeling process was fully rinsed with distilled water, and the peelability of the deterioration film | membrane, the state of corrosion of an Al wiring, and the corrosion state of an amorphous silicon film at this time were evaluated by observation of the scanning electron microscope (SEM) photograph. The results are shown in Table 2.

In addition, the peelability of the deteriorated film, the corrosion state of the Al wiring and the amorphous silicon film were respectively evaluated as follows.

[Releasability of Photoresist Altered Film]

A: no peeling residue of photoresist deterioration film

B: Exfoliation residue of photoresist deterioration film

[Corrosion status of Al wiring, amorphous silicon film]

A: Corrosion not confirmed

B: Corrosion confirmed

TABLE 1

Composition of Photoresist Stripping Solution (wt%) (a) Component (b) ingredients (c) component (d) component (e) Ingredient (f) ingredients Other Ingredients Example 1 HA (10) PCA (4.5) BT-GL (0.5) MEA (5) BDG (60) Water (20) - Example 2 HA (10) PCA (4.5) BT-IR (0.5) AEE (5) DMSO (60) Water (20) - Example 3 HA (15) PCA (5) BT-GL (1) MEA (64) - Water (15) - Example 4 HA (15) PCA (5) BT-IR (0.5) AEE (64.5) - Water (15) - Example 5 HA (15) PCA (5) BT (0.5) TET (10) DMSO (54.5) Water (15) - Example 6 DEHA (10) PCA (5) BT (1) MEA (64) BDG (20) - - Example 7 HA (10) PCA (5) BT-GL (0.5) MEA (5) NMP (59) Water (20) PI (0.5) Example 8 HA (15) PCA (4.3) BT-GL (0.5) MEA (10) NMP (55) Water (15) AT (0.2) Comparative Example 1 HA (15) PCA (5) - TET (10) DMSO (55) Water (15) - Comparative Example 2 HA (15) PCA (10) - MEA (30) DMSO (30) Water (15) - Comparative Example 3 HA (15) PCA (5) - MEA (65) - Water (15) - Comparative Example 4 HA (15) PCA (5) - AEE (65) - Water (15) - Comparative Example 5 HA (10) PCA (5) - MEA (5) BDG (60) Water (20) - Comparative Example 6 - PCA (5) BT-GL (0.5) MEA (9.5) DMSO (60) Water (25) - Comparative Example 7 HA (10) - BT-GL (0.5) MEA (9.5) DMSO (60) Water (20) -

In addition, in Table 1, HA is hydroxylamine; DEHA is N, N-diethylhydroxylamine; MEA is monoethanolamine (pKa = 9.52 in 25 degreeC aqueous solution); AEE is 2- (2-aminoethoxy) ethanol (pKa = 9.42 in 25 degreeC aqueous solution); TET is triethylenetetraamine (pKa = 9.74 in 25 degreeC aqueous solution); BDG is diethylene glycol monobutyl ether; DMSO is dimethyl sulfoxide; NMP is N-methyl-2-pyrrolidone; PCA is pyrocatechol; BT-GL is 1- (1, 2-dihydroxypropyl) benzotriazole; BT-IR represents 2, 2 '-{[(4-methyl-1H-benzotriazol-1-yl) methyl] imino} bisethanol; BT benzotriazole; PI is a pyrrolidone-based activator (N-octyl-2-pyrrolidone); AT represents an acetylene alcohol alkylene oxide adduct (a mixture of "acethylenor EL": "acethyrenor EH" = 3: 7 (mixed weight ratio)), respectively.

TABLE 2

Corrosion State of Amorphous Silicon Layer Corrosion state of AI wiring Peelability of Photoresist Alternating Film Example 1 A A A Example 2 A A A Example 3 A A A Example 4 A A A Example 5 A A A Example 6 A A A Example 7 A A A Example 8 A A A Comparative Example 1 B A A Comparative Example 2 B A A Comparative Example 3 B A A Comparative Example 4 B A A Comparative Example 5 A A B Comparative Example 6 A A B Comparative Example 7 A C -

As is clear from the results in Table 2, in Examples 1 to 8, it was confirmed that the metal wiring and the inorganic material layer were excellent in both anticorrosive properties and excellent in peelability of the photoresist deterioration film. On the other hand, in neither of Comparative Examples 1-7, the effect which was excellent in the anticorrosive property of both metal wiring and an inorganic material layer, and the peelability of a photoresist quality film was not acquired.

As described above, according to the present invention, the photoresist stripping solution excellent in the anticorrosive property of the substrate on which both the metal wiring and the inorganic material layer are formed, the peeling property of the photoresist layer and the deteriorated film, and the photoresist stripping method using the same are Is provided. In particular, the present invention is suitably used for peeling a photoresist layer and a deterioration film formed on a substrate used for the production of a liquid crystal panel element.

Claims (14)

(a) hydroxylamines, (b) aromatic hydroxy compounds, (c) benzotriazole compounds, (d) amines having an acid dissociation constant (pKa) in an aqueous solution at 25 ° C of 7.5 to 13, and (e) water-soluble. An organic solvent and / or (f) water-containing photoresist stripping solution, wherein (a) component is from 2 to 30% by weight, (b) component is from 0.5 to 20% by weight, ( c) 0.01 to 20% by weight of component, 2 to 80% by weight of component (d), 15 to 80% by weight of component (e), and (f) residual weight to bring the total amount of the composition to 100% by weight. Peeling liquid for photoresists comprised by%. The method according to claim 1, wherein the component (c) is represented by the following formula 1: [Formula 1] [Wherein, Q is a hydrogen atom, a hydroxyl group, a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms (however, may have an amide bond or ester bond in its structure), an aryl group, or the following general formula: (Wherein, R ³ represents an alkyl group having 1 to 6 carbon atoms; R ⁴ and R ⁵ each independently represent a hydrogen atom, a hydroxyl group, or a hydroxyalkyl group or an alkoxyalkyl group having 1 to 6 carbon atoms) Represents a group represented by; R ¹ and R ² each independently represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, a carboxyl group, an amino group, a hydroxyl group, a cyano group, a formyl group, a sulfonylalkyl group, or a sulfo group] A peeling liquid for photoresists which is a compound represented by The compound of claim 2, wherein Q is represented by the following formula: Wherein R ³ , R ⁴ , and R ⁵ are the same as defined in claim 2, respectively. A peeling solution for photoresists which is a group represented by, a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or a hydroxyl group. The peeling liquid for photoresists of Claim 1 whose (d) component is 1 or more types chosen from alkanolamines, polyalkylene polyamines, aliphatic amines, and cyclic amines. The peeling liquid for photoresists of Claim 1 whose (e) component is 1 or more types chosen from diethylene glycol monoalkyl ether, N-methyl- 2-pyrrolidone, and dimethyl sulfoxide. delete The peeling liquid for photoresists of Claim 1 in which 15-80 weight% of (e) components are mix | blended in peeling liquid whole quantity. The method according to claim 1, further comprising: [Formula 3] (Wherein R ⁸ represents an alkyl group having 6 to 20 carbon atoms) A peeling liquid for photoresists comprising at least one compound selected from N-alkyl-2-pyrrolidone and acetylene alcohol and alkylene oxide adducts. The acetylene alcohol alkylene oxide adduct of claim 8 is represented by the following general formula (5). [Formula 5] Wherein R ¹⁴ represents a hydrogen atom or Represents; R ¹⁵ , R ¹⁶ , R ¹⁷ , and R ¹⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) A peeling liquid for photoresists which is a compound represented by The photoresist stripper according to claim 1, which is used for peeling a photoresist provided on a substrate on which a metal wiring and an inorganic material layer are formed. (I) providing a photoresist layer on the substrate; (II) selectively exposing the photoresist layer, (III) developing the photoresist layer after exposure to provide a photoresist pattern; (IV) etching the substrate with the photoresist pattern as a mask, and (V) Process of peeling the photoresist pattern after an etching process from a board | substrate using the peeling liquid for photoresists in any one of Claims 1-10. Photoresist stripping method comprising a. The photoresist stripping method according to claim 11, wherein a substrate on which metal wiring and an inorganic material layer are formed is used. (I) providing a photoresist layer on the substrate; (II) selectively exposing the photoresist layer, (III) developing the photoresist layer after exposure to provide a photoresist pattern; (IV) etching the substrate with the photoresist pattern as a mask, (V) plasma ashing the photoresist pattern, and (VI) Process of peeling off the deterioration film | membrane after plasma ashing from a board | substrate using the peeling liquid for photoresists in any one of Claims 1-10. Photoresist stripping method comprising a. The photoresist stripping method according to claim 13, wherein a substrate on which metal wiring and an inorganic material layer are formed is used.