KR20120089873A - Resist stripper composition and method of stripping resist using the same - Google Patents

Abstract

PURPOSE: A resist stripper composition and a method for stripping resist using the same are provided to easily verify the dissolved degree of resist per stripper tank and the replacing timing of the stripper. CONSTITUTION: A resist stripper composition includes 0.1 to 10 weight% of a free radical eliminating agent represented by chemical formula 1, 5 to 30 weight% of a basic compound represented by chemical formula 2, 55 to 94 weight% of a solvent, and 0.01 to 5 weight% of an anticorrosive agent. The solvent includes a protic polar solvent and an aprotic polar solvent. In chemical formula 1, R1 and R2 are respectively C1 to C10 alkyl groups, C2 to C10 alkenyl groups, C1 to C10 hydroxyl alkyl groups, carboxylic groups and hydroxyl group substituted or non-substituted C1 to C10 alkoxy group substituted C1 to C10 alkyl groups, phenyl groups, or benzyl groups. In chemical formula 2, R3, R4, R5 are respectively hydrogen atoms, amino group substituted or non-substituted C1 to C10 alkyl groups, C1 to C4 alkyl group substituted amino group substituted C1 to C10 alkyl groups, C2 to C10 alkenyl groups, C1 to C10 hydroxyl alkyl groups, carboxylic group and hydroxyl group substituted or non-substituted C1 to C10 alkoxy group substituted C1 to C10 alkyl groups, C1 to C4 alkyl group substituted or non-substituted amino groups, phenyl groups, or benzyl groups.

Description

Resist stripper composition and method for stripping resist using same {Resist stripper composition and method of stripping resist using the same}

The present invention relates to a resist stripping liquid composition and a method for peeling a resist using the same.

Recently, as the demand for high resolution implementation of flat panel displays increases, efforts have been made to increase the number of pixels per unit area. In accordance with this trend, a reduction in the wiring width is also required, and in order to cope with this, the process conditions are becoming more severe, such as the introduction of a dry etching process. In addition, due to the larger size of the flat panel display device, an increase in signal speed in the wiring is also required. Accordingly, copper having a lower specific resistance than aluminum has been put into practical use as a wiring material. In keeping with this, the required performance for the stripping solution used in the stripping step, which is a resist removal step, is also increasing. Specifically, a considerable level of peeling characteristics are required for the removal force on the etching residue and the corrosion inhibiting force on the metal wiring, which occur after the dry etching process. In particular, corrosion resistance to copper as well as aluminum is required, and in order to secure price competitiveness, economics such as increasing the number of substrates are required.

In response to such industry demands, new technologies are being disclosed. For example, Korean Patent Laid-Open Publication No. 10-2006-0028523 proposes a photoresist stripper which does not cause corrosion of metal wiring including alcohol amine, glycol ether, N-methylpyrrolidone and a chelating agent. However, even when the resist is not peeled off, the chelating agent changes the color of the peeling liquid by its own characteristics, so that the color change of the peeling liquid depending on the degree of dissolution of the resist in the peeling process cannot be visually confirmed. Cause problems.

Korean Patent Laid-Open No. 10-2006-0024478 discloses a photoresist stripper composition comprising a cyclic amine, a solvent, a corrosion inhibitor and a stripping accelerator. It is described that the stripper composition has no additional corrosion on metal wiring even if the isopropyl alcohol (IPA) rinse step is omitted, and in particular, has a feature of greatly improving the peeling force. However, the stripper composition has a disadvantage in that the stripping force composition is insufficient in the peeling force to the resist generated under the harsh conditions such as dry etching residue by using only the cyclic amine as the stripping agent.

The present invention is to solve the problems of the prior art as described above, and excellent in resist pattern and dry and wet etching residue removal ability, not only excellent corrosion protection of metal wiring including aluminum and / or copper, It is an object of the present invention to provide a resist stripper composition and a method of stripping a resist using the same, wherein the color change of the stripping solution by the corrosion inhibitor is also prevented and the number of treatments of the substrate is improved.

The present invention, based on the total weight of the composition, (a) 0.1 to 10% by weight free radical remover represented by the formula (1), (b) 5 to 30% by weight of the basic compound represented by the formula (2), (c) proton polarity Provided is a resist stripper composition comprising 55 to 94% by weight of a solvent comprising a solvent and an aprotic polar solvent and (d) 0.01 to 5% by weight of a corrosion inhibitor:

[Formula 1]

Where

R1 and R2 are each independently substituted with an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, a carboxyl group and a carboxyl group substituted with carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms. It is a 1-10 alkyl group, a phenyl group, or a benzyl group.

[Formula 2]

Where

R3, R4 and R5 are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms substituted or unsubstituted with an amino group, an alkyl group having 1 to 10 carbon atoms substituted with an amino group substituted with an alkyl group having 1 to 4 carbon atoms, and having 2 to 10 carbon atoms Alkyl group, C1-C10 hydroxyalkyl group, carboxyl group, C1-C10 alkyl group substituted or unsubstituted C1-C10 alkoxy group substituted or unsubstituted or C1-C4 alkyl group substituted or unsubstituted amino group , Phenyl group, or benzyl group.

The resist stripper composition may further include 3 to 15% by weight of deionized water based on the total weight of the composition.

In addition,

(I) depositing a conductive metal film on a flat panel display substrate,

(II) forming a resist film on the conductive metal film;

(III) selectively exposing the resist film;

(IV) developing the resist film after exposure to form a resist pattern;

(V) etching the conductive metal film using the resist pattern as a mask; And

(VI) after the etching process, a method of removing the resist comprising the step of peeling the remaining resist from the substrate using the resist stripper composition of the present invention.

In addition,

It provides the manufacturing method of the flat panel display apparatus including the process of peeling the resist of the board | substrate for flat panels using the resist stripping liquid composition of this invention.

The present invention provides a flat panel display device comprising a substrate for a flat panel manufactured using the resist stripper composition.

The resist stripper composition of the present invention is excellent in resist pattern and dry and wet etching residue removal ability, and excellent in corrosion protection of metal wiring including aluminum and / or copper, so that a fine pattern is applied to achieve a high resolution pattern. It can be usefully used in the manufacturing process of the display apparatus and the manufacturing process of the flat panel display apparatus in which aluminum and / or copper wiring was used. In addition, since the color change of the stripping solution by the corrosion inhibitor is prevented, it is possible to provide a transparent resist stripping liquid composition, so that the degree of dissolution in the solution of the resist can be visually checked during the stripping process, and thus the degree of resist dissolution for each stripping tank and stripping. The liquid replacement time can be easily determined. In addition, it is possible to process a large number of substrates, which greatly contributes to cost reduction.

The present invention, based on the total weight of the composition, (a) 0.1 to 10% by weight free radical remover represented by the formula (1), (b) 5 to 30% by weight of the basic compound represented by the formula (2), (c) proton polarity A resist stripper composition comprising 55 to 94% by weight of a solvent comprising a solvent and an aprotic polar solvent and (d) 0.01 to 5% by weight of a corrosion inhibitor:

 [Formula 1]

Where

R1 and R2 are each independently substituted with an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, a carboxyl group and a carboxyl group substituted with carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms. It is an alkyl group, a phenyl group, or a benzyl group of 1-10.

[Formula 2]

Where

R3, R4 and R5 are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms substituted or unsubstituted with an amino group, an alkyl group having 1 to 10 carbon atoms substituted with an amino group substituted with an alkyl group having 1 to 4 carbon atoms, and having 2 to 10 carbon atoms Alkyl group, C1-C10 hydroxyalkyl group, carboxyl group, C1-C10 alkyl group substituted or unsubstituted C1-C10 alkoxy group substituted or unsubstituted or C1-C4 alkyl group substituted or unsubstituted amino group , Phenyl group, or benzyl group.

The resist stripper composition may further include 3 to 15% by weight of deionized water based on the total weight of the composition.

Hereinafter, the present invention will be described in detail.

The free radical scavenger represented by the following formula (1) included in the resist stripper composition of the present invention not only inhibits corrosion of metal wires, but also includes a corrosion inhibitor such as alkyl gallates in the stripper. It serves to prevent the color change of the peeling liquid by oxidation before the peeling process. Therefore, even if a corrosion inhibitor which changes the color of the stripping liquid by oxidation is contained in the stripping liquid, the color change of the stripping liquid due to such a reaction is suppressed, so that the degree of dissolution in the solution of the resist can be easily visually checked during the stripping process. To be able.

[Formula 1]

Where

R1 and R2 are each independently substituted with an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, a carboxyl group and a carboxyl group substituted with carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms. It is an alkyl group, a phenyl group, or a benzyl group of 1-10.

The alkyl group included in the substituent above may be linear or branched chain.

In Formula 1, R1 and R2 are each independently an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.

Representative free group removers represented by the general formula (1) include dimethyl hydroxyl amine, diethyl hydroxyl amine, dibutyl hydroxyl amine and the like.

The free radical remover is preferably included in an amount of 0.1 to 10% by weight, more preferably 0.3 to 5% by weight. When satisfying the above-described range, it is possible to effectively perform the method of metal wiring by oxidation to help other corrosion inhibitors, it is possible to effectively block the color change by the oxidation of the corrosion inhibitors. When the free radical remover is included in less than 0.1% by weight, it is difficult to obtain the effect of preventing the corrosion of the metal and the effect of preventing the color change, and if it exceeds 10% by weight, it is not economical because there is no increase in the effect of the increase and the relative of the basic compound and the polar solvent Due to the reduction, the removal of residues by dry / wet etching may be reduced or the number of treated sheets may be reduced.

(B) The basic compound represented by Chemical Formula 2 included in the resist stripper composition of the present invention may be deteriorated or crosslinked under various process conditions such as dry or wet etching, ashing, or ion implant processing. It penetrates strongly into the polymer matrix of the resist and serves to break the bonds present in or between molecules. This action of the basic compound creates an empty space in the structurally vulnerable portion of the resist remaining on the substrate, transforming the resist into an amorphous polymer gel mass so that the resist attached to the substrate can be easily removed. .

[Formula 2]

Where

R3, R4 and R5 are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms substituted or unsubstituted with an amino group, an alkyl group having 1 to 10 carbon atoms substituted with an amino group substituted with an alkyl group having 1 to 4 carbon atoms, and having 2 to 10 carbon atoms Alkyl group, C1-C10 hydroxyalkyl group, carboxyl group, C1-C10 alkyl group substituted or unsubstituted C1-C10 alkoxy group substituted or unsubstituted or C1-C4 alkyl group substituted or unsubstituted amino group , Phenyl group, or benzyl group.

The alkyl group included in the substituent above may be linear or branched chain.

Examples of the basic compound represented by Formula 2 include primary amines such as methylamine, ethylamine, monoisopropylamine, n-butylamine, sec-butylamine, isobutylamine, t-butylamine, and pentylamine; Secondary such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, methylethylamine, methylpropylamine, methylisopropylamine, methylbutylamine, methylisobutylamine Amines; Tertiary amines such as trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, dimethylethylamine, methyldiethylamine and methyldipropylamine; Choline, monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, 2-aminoethanol, 2- (ethylamino) ethanol, 2- (methylamino) ethanol, N-methyl diethanolamine, N, N-dimethyl Ethanolamine, N, N-diethylaminoethanol, 2- (2-aminoethylamino) -1-ethanol, 1-amino-2-propanol, 2-amino-1-propanol, 3-amino-1-propanol, Alkanolamines such as 4-amino-1-butanol and dibutanolamine; (Butoxymethyl) diethylamine, (methoxymethyl) diethylamine, (methoxymethyl) dimethylamine, (butoxymethyl) dimethylamine, (isobutoxymethyl) dimethylamine, (methoxymethyl) diethanolamine , (Hydroxyethyloxymethyl) diethylamine, methyl (methoxymethyl) aminoethane, methyl (methoxymethyl) aminoethanol, methyl (butoxymethyl) aminoethanol, 2- (2-aminoethoxy) ethanol Alkoxyamines; 1- (2-hydroxyethyl) piperazine, 1- (2-aminoethyl) piperazine, 1- (2-hydroxyethyl) methylpiperazine, N- (3-aminopropyl) morpholine, 2-methyl Cyclic amines having a ring such as piperazine, 1-methylpiperazine, 1-amino-4-methylpiperazine, 1-benzyl piperazine, 1-phenyl piperazine, and the like. More than one species may be used together.

In particular, monoethanolamine, triethanolamine, 1-amino- 2-propanol, 2- (2-aminoethoxy) ethanol, N-methylethanolamine, N-methyldiethanolamine, N, N-dimethylethanol amine, N , N-diethylaminoethanol and 2- (2-aminoethylamino) -1-ethanol are preferable.

(B) The basic compound represented by the formula (2) is preferably included in 5 to 30% by weight, more preferably in 7 to 20% by weight based on the total weight of the composition. When included in the content as described above, the resist stripper composition of the present invention can exhibit a desirable peeling properties without the problem of insufficient resist stripping effect or a sharp increase in the corrosion rate for aluminum and copper wiring. Specifically, when the (b) basic compound is contained in less than 5% by weight, the removal performance of the deteriorated or cross-linked resist is inferior, and when included in excess of 30% by weight may cause corrosion of the metallization.

The solvent containing (c) a protic polar solvent and an aprotic polar solvent included in the resist stripper composition of the present invention serves to dissolve the resist polymer gelled by the (b) basic compound, and further, after resist stripping, DI It facilitates the removal of the stripping solution by water in the rinse process and serves to minimize the reprecipitation of the resist dissolved in the stripping solution.

Specific examples of the proton polar solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, di Ethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monoisopropyl ether, triethylene glycol monobutyl ether, polyethylene glycol monomethyl ether, polyethylene Glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and the like. This combination of two or more may be used together.

Specific examples of the aprotic polar solvent include pyrrolidone compounds such as N-methylpyrrolidone (NMP) and N-ethylpyrrolidone; Imidazolidinone compounds, such as 1,3-dimethyl- 2-imidazolidinone and 1,3-dipropyl- 2-imidazolidinone; lactone compounds such as γ-butyrolactone; Sulfoxide compounds such as dimethyl sulfoxide (DMSO) and sulfolane; Phosphate compounds such as triethyl phosphate and tributyl phosphate; Carbonate compounds such as dimethyl carbonate and ethylene carbonate; Formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N- (2-hydroxyethyl) acetamide, 3-methoxy Amide compounds such as -N, N-dimethylpropionamide, 3- (2-ethylhexyloxy) -N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, and the like. These can be used individually or in mixture of 2 or more types.

(C) The solvent containing the protic polar solvent and the aprotic polar solvent is preferably included in the 55 to 94% by weight, more preferably in the 60-80% by weight based on the total weight of the composition. When included in the content range as described above is advantageous for the expression of the removal performance of the modified or cross-linked resist polymer by etching, etc., and at the same time advantageous in increasing the number of treatment. In addition, the problem of relatively low basic compound content can be avoided.

The solvent (c) comprising a protonic polar solvent and an aprotic polar solvent may include a protonic polar solvent and an aprotic polar solvent in a weight ratio of 2: 6 to 6: 2, and 2.5: 5.5 to 4: 4. More preferably included in the weight ratio of.

(D) Corrosion inhibitor included in the resist stripper composition of the present invention serves to suppress corrosion of the metal wiring.

 The kind of the corrosion inhibitor is not particularly limited, and benzotriazole, tolitriazole, methyl totritriazole, 2,2 '-[[[benzotriazole] methyl, which provides a corrosion protection effect on Cu wirings ] Imino] bisethanol, 2,2 '-[[[methyl-1 hydrogen-benzotriazol-1-yl] methyl] imino] bismethanol, 2,2'-[[[ethyl-1 hydrogen benzotria] Zol-1-yl] methyl] imino] bisethanol, 2,2 '-[[[methyl-1 hydrogen-benzotriazol-1-yl] methyl] imino] bisethanol, 2,2'-[[ [Methyl-1 hydrogen-benzotriazol-1-yl] methyl] imino] biscarboxylic acid, 2,2 '-[[[methyl-1 hydrogen-benzotriazol-1-yl] methyl] imino] bismethyl Azole compounds such as amines, 2,2 '-[[[amine-1 hydrogen-benzotriazol-1-yl] methyl] imino] bisethanol;

Quinone compounds such as 1,2-benzoquinone, 1,4-benzoquinone, 1,4-naphthoquinone and anthraquinone, which provide a corrosion protection effect against Al wiring; Catechol; Alkyl gallate compounds such as pyrogallol, methyl gallate, propyl gallate, dodecyl gallate, octyl gallate and gallic acid; And cyclic diketone compounds such as 2-methyl-1,3-cyclohexadione, 1,2-cyclopentadione, dimedone, and the like.

The said corrosion inhibitor can be used individually by 1 type or in mixture of 2 or more types.

In particular, the corrosion inhibitor includes at least one corrosion inhibitor for Al wiring and at least one corrosion inhibitor for Cu wiring, which is effective in preventing corrosion of metal wiring. That is, when one or more Al wiring corrosion inhibitors and one or more Cu wiring corrosion inhibitors are included as described above, the synergistic effect is exerted, and the corrosion protection effect on both the Al wiring and the Cu wiring includes only the Al wiring corrosion inhibitor, and It is improved compared with the case where only the corrosion inhibitor for Cu wiring is included. That is, the anticorrosive effect on each of Cu and Al wirings is enhanced.

The Al wiring corrosion inhibitor and at least one Cu wiring corrosion inhibitor It may be included in a weight ratio of 2: 8 to 8: 2.

The (d) corrosion inhibitor is preferably included in 0.01 to 5% by weight, more preferably 0.05 to 4% by weight based on the total weight of the composition. If the amount is less than 0.01 wt%, corrosion may occur in the metal wiring made of aluminum or aluminum alloy and copper or copper alloy in the peeling or DI rinse process. It may cause contamination or increase the viscosity of the resist stripping solution to reduce the convenience.

In addition, in the case where the at least one Al wiring corrosion inhibitor and at least one Cu wiring corrosion inhibitor are included in the above, even if the Al wiring corrosion inhibitor and the Cu wiring corrosion inhibitor are included in each of 1.0 wt% or less, Anticorrosive effect can be obtained.

The resist stripper composition of the present invention may further include (e) deionized water. When deionized water is added, the removal rate of the resist is increased by improving the activation of the basic compound (b), and the organic contaminants and resist stripping solution remaining on the substrate during the rinsing process using the deionized water (c) It is quickly and completely removed, further improving the residue removal ability formed by dry etching in harsh conditions.

 The deionized water (e) is preferably included in 3 to 15% by weight, more preferably in 7 to 12% by weight relative to the total weight of the composition. If it is less than 3% by weight, the removal ability of the resist crosslinked or deteriorated by the dry / wet etching process is reduced, and if it is more than 15% by weight, the dissolution capacity of the resist is reduced to reduce the number of treatments. May cause corrosion.

The resist stripping composition of the present invention may be prepared by mixing the above-mentioned compound in an advantageous amount in an advantageous amount.

This invention also provides the resist peeling method characterized by using the resist stripping liquid composition of this invention. The peeling method of the said resist,

(I) depositing a conductive metal film on a flat panel display substrate,

(II) forming a resist film on the conductive metal film;

(III) selectively exposing the resist film;

(IV) developing the resist film after exposure to form a resist pattern;

(V) etching the conductive metal film using the resist pattern as a mask; And

(VI) after the etching process, a step of peeling the remaining resist from the substrate using the resist stripper composition of the present invention.

In the peeling method of the present invention, a dry etching process such as an etchback process or a chemical mechanical polishing (CMP) process is performed without proceeding a resist pattern forming process using a mask, and then the exposed resist film is viewed. The method of peeling with the peeling liquid composition of this invention is included.

The peeling method may be a deposition method, a spraying method, or a deposition and spraying method. When peeling by immersion, spraying, or spraying and spraying, the temperature as peeling conditions is usually 15 to 100 ° C, preferably 30 to 70 ° C, and the deposition, spraying, or deposition and spraying time is usually 30 seconds to 40 minutes, Preferably from 1 to 20 minutes, but not strictly applied in the present invention, it can be modified by easy and suitable conditions by those skilled in the art.

The resist stripper composition of the present invention and the stripping method using the same can be used not only for removing general resists, but also for removing resists and etching residues that have been modified or cured by etching gas and high temperature.

In addition,

It provides the manufacturing method of the flat panel display apparatus including the process of peeling the resist of the board | substrate for flat panels using the resist stripping liquid composition of this invention.

The present invention provides a flat panel display device comprising a substrate for a flat panel manufactured using the resist stripper composition.

The flat panel display device manufactured by the above manufacturing method has excellent quality since the resist is completely removed during the manufacturing process and the corrosion of the metal wire including aluminum and / or copper hardly occurs.

Hereinafter, the present invention will be described in more detail using examples and comparative examples. However, the following examples and comparative examples are intended to illustrate the present invention, the present invention is not limited by the following can be variously modified and changed.

Example  1-17 and Comparative Example 1 ~ 9: Resist Stripper  Preparation of the composition

The resist stripper composition was prepared by mixing the components and contents shown in Table 1 below.

division (a)
Free radical
Remover (b)
Basic
compound (c)
menstruum (d)
Corrosion inhibitor (e)
Deionized water Example 1 DEHA 2 MEA 15 NMP 50 BDG 29 MG 2 BTA 2 Example 2 DEHA 2 MEA 15 NMP 50 BDG 29 C.H.D 2 BTA 2 Example 3 DEHA 2 MEA 15 NMP 50 BDG 29 C.P.D 2 BTA 2 Example 4 DEHA 2 MEA 15 NMP 50 BDG 29 C.H.D 2 BZFG 2 Example 5 DEHA 2 MEA 15 NMP 50 BDG 29 C.P.D 2 BZFG 2 Example 6 DEHA 2 MEA 15 NMP 40 BDG 29 MG 2 10 BTA 2 Example 7 DEHA 2 MEA 15 NMP 40 BDG 29 Cat. 2 10 BTA 2 Example 8 DEHA 2 MEA 15 NMP 40 BDG 29 MG 2 10 BZFG 2 Example 9 DEHA 2 MEA 15 NMP 40 MDG 29 MG 2 10 BZFG 2 Example 10 DEHA 2 MEA 15 DMSO 40 BDG 29 MG 2 10 BZFG 2 Example 11 DEHA 2 DEA 15 NMP 40 BDG 29 MG 2 10 BZFG 2 Example 12 DEHA 2 MDEA 15 NMP 40 BDG 29 MG. 2 10 BZFG 2 Example 13 DEHA 2 HEP 15 NMP 40 BDG 29 MG 2 10 BZFG 2 Example 14 DEHA 2 MEA 15 NMP 40 BDG 31 MG 2 10 - - Example 15 DEHA 2 MEA 15 NMP 40 BDG 32.5 MG 0.5 10 - - Example 16 DEHA 2 MEA 15 NMP 40 BDG 32.5 - - 10 BZFG 0.5 Example 17 DEHA 2 MEA 15 NMP 40 BDG 32 MG 0.5 10 BZFG 0.5 Comparative Example 1 - - MEA 15 NMP 40 BDG 31 MG 2 10 BZFG 2 Comparative Example 2 - - MEA 15 NMP 40 BDG 33 - - 10 BZFG 2 Comparative Example 3 - - MEA 15 NMP 40 BDG 33 MG 2 10 - - Comparative Example 4 - - MEA 15 NMP 42 BDG 39 MG 2 - BZFG 2 Comparative Example 5 - - MEA 15 NMP 71 - - MG 2 10 BZFG 2 Comparative Example 6 - - MEA 15 - - BDG 71 MG 2 10 BZFG 2 Comparative Example 7 - - - - NMP 50 BDG 36 MG 2 10 BZFG 2 Comparative Example 8 DEHA 12 HEP 15 NMP 35 BDG 24 MG 2 10 BZFG 2 Comparative Example 9 DEHA 4 HEP 15 NMP 35 BDG 24 MG 2 18 BZFG 2

Unit: weight%

MEA: monoethanolamine

DEA: diethanolamine

MDEA: N-methyldiethanolamine

HEP: hydroxyethyl piperazine

DMSO: Dimethyl Sulfoxide

NMP: N-methylpyrrolidone

BDG: diethylene glycol monobutyl ether

MDG: diethylene glycol monomethyl ether

MG: methyl gallate

C.H.D: 2-methyl-1,3-cyclohexadione

C.P.D: 1,2-cyclopentadione

BTA: Benzotriazole

Cat .: Catechol

BZFG: Cobratec BZ-FG (manufactured by PMC)

DEHA: diethyl hydroxylamine

Test Example  One: Stripper Color change

In order to confirm the color change of the resist stripper composition, the respective components were mixed in the same composition as in Examples 1 to 14 and Comparative Examples 1 to 9, and then opened for 24 hours in a state where the stripper and the air were in contact with each other. The color change was observed while stirring at 50 ° C. using a stirrer until the solid reagent in the solution was completely dissolved. According to the degree of color of the stripping solution at the time of observation was given a grade from 1 to 5, 1 is closer to the transparent and to indicate that the deep red toward 5, the results are shown in Table 2 below.

division Color change division Color change Example 1 One Comparative Example 1 5 Example 2 One Comparative Example 2 One Example 3 One Comparative Example 3 5 Example 4 One Comparative Example 4 4 Example 5 One Comparative Example 5 5 Example 6 One Comparative Example 6 4 Example 7 2 Comparative Example 7 3 Example 8 One Comparative Example 8 One Example 9 One Comparative Example 9 One Example 10 One Example 11 One Example 12 One Example 13 One Example 14 One

As confirmed in Table 2, no color change was observed in Examples 1 to 14 and Comparative Example 2 (only using a corrosion inhibitor not causing color change) and Comparative Example 8 and Comparative Example 9 (including free radical remover). In Comparative Example 1, Comparative Example 3, and Comparative Examples 4-7, although there was a difference of a dark degree, a color change was observed. From these results, it was confirmed that chelating agents (eg, alkyl gallates) used as corrosion inhibitors have the greatest influence on the color change, and even when such corrosion inhibitors are used, color change is prevented when the free radical remover is contained. .

Experimental Example  2: Evaluation of peeling performance and number of sheets

(1) Peeling performance evaluation

In order to confirm the peeling effect of the resist stripper composition, after forming a Mo / Al, Cu / Mo-Ti layer using a thin film sputtering method on a glass substrate according to a conventional method, after forming a photoresist pattern, Substrates in which metal films were etched by etching and dry etching were prepared, respectively. After keeping the temperature of the composition for resist stripping constant at 50 ° C, the object was deposited for 10 minutes to evaluate the peel force. Thereafter, washing was performed with pure water for 1 minute to remove the stripping solution remaining on the substrate, and the substrate was completely dried using nitrogen to remove the pure water remaining on the substrate after the cleaning. Denatured or cured resist and dry etching residue removal performance of the substrate was confirmed using a scanning electron microscope (SEM, Hitach S-4700), the results are shown in Table 3 below.

[Very good: ◎, Good: ○, Normal: △, Poor: ×]

(2) Evaluation of the number of substrate treatment sheets

To evaluate the number of substrate treatment sheets of the resist stripper composition, the photoresist was dissolved in a stripper composition in which 1 to 5% by weight of solidified photoresist (photoresist solidified by removing all solvents through heat treatment at 130 ° C. for 1 day) was sequentially dissolved. After the resist pattern was formed, the Mo / Al and Cu / Mo-Ti wiring boards, which were etched by the metal film by wet etching and dry etching, were immersed in a stripper composition having a temperature of 50 ° C. for 10 minutes, and then washed and dried. Through the scanning electron microscope (SEM, Hitach S-4700) was confirmed the time of the residue issuance. The results are shown in Table 3 below.

[Very good: ◎, Good: ○, Normal: △, Poor: ×]

division Peeling performance Processing Sheet Performance
(Solidified resist concentration) Wet
Etching deflation
Etching 1 wt% 2 wt% 3 wt% 4 wt% 5 wt% Example 1 ◎ ○ ◎ ◎ ◎ ○ △ Example 2 ◎ ○ ◎ ◎ ◎ ○ △ Example 3 ◎ ○ ◎ ◎ ◎ ○ △ Example 4 ◎ ○ ◎ ◎ ◎ ○ △ Example 5 ◎ ○ ◎ ◎ ◎ ○ △ Example 6 ◎ ◎ ◎ ◎ ◎ ○ X Example 7 ◎ ◎ ◎ ◎ ◎ △ X Example 8 ◎ ◎ ◎ ◎ ◎ ○ X Example 9 ◎ ◎ ◎ ◎ ◎ ○ X Example 10 ◎ ◎ ◎ ◎ ◎ ○ X Example 11 ◎ ◎ ◎ ◎ ◎ △ X Example 12 ◎ ◎ ◎ ◎ ◎ △ X Example 13 ◎ ◎ ◎ ◎ ◎ △ X Example 14 ◎ ◎ ◎ ◎ ◎ △ X Comparative Example 1 ◎ ◎ ◎ ◎ ◎ ○ X Comparative Example 2 ◎ ◎ ◎ ◎ ◎ ○ X Comparative Example 3 ◎ ◎ ◎ ◎ ◎ ○ X Comparative Example 4 ◎ △ ◎ △ △ △ X Comparative Example 5 ◎ △ ○ △ △ X X Comparative Example 6 ◎ △ ○ △ △ X X Comparative Example 7 △ X △ X X X X Comparative Example 8 ◎ ◎ ◎ ◎ ○ X X Comparative Example 9 ◎ ◎ ◎ ◎ △ X X

As shown in Table 3, the resist stripper compositions of Examples 1 to 14, Comparative Examples 1 to 3, and Comparative Examples 8 to 9 were not only excellent in resist stripping ability by wet etching but also resist and etching residues subjected to dry etching. All showed good performance for removal. However, the peeling liquid composition of Comparative Example 7, which did not contain a basic compound, was poor in the ability to remove all of the resist after wet or dry etching, and did not include deionized water (Comparative Example 4) or a protic polar solvent or an aprotic polar solvent. It was found that the peeling liquid composition of only one of the solvents (Comparative Examples 5 to 6) had a very low removal force of the resist treated by dry etching as compared with the peeling liquid composition of Examples 1 to 14.

In addition, from the results of the treatment sheet performance evaluation shown in Table 3, the resist stripper composition of Examples 1 to 14 and Comparative Examples 1 to 3, since the residue starts to occur on the substrate when the solid resist content is 4% by weight or more. In addition, it was confirmed that it has a very good treatment yield performance. However, when the deionized water and the free radical scavenger are not included as in Comparative Example 4, or when only one of the protonic polar solvent or the aprotic polar solvent is included as in Comparative Examples 5 to 6, the solid resist content is 2 weights. From the percentage, residue was generated on the substrate, indicating poor performance of the number of sheets. In addition, the peeling liquid composition of Comparative Example 7 containing no basic compound showed very poor treatment yield performance, and the content of the polar solvent was reduced according to the increase in the content of other components (free radical remover, deionized water). The number of treatments at 9 degrees was reduced.

Experimental Example  3: of metal wiring Corrosion protection  evaluation

Evaluation of the anti-corrosion ability of the resist stripper composition on the metal wiring was performed using a substrate exposed to Mo / Al and Cu / Mo-Ti wiring.

The substrate was immersed in a stripper composition having a constant temperature maintained at 60 ° C. for 30 minutes, and then the substrate was washed and dried, and observed using a scanning electron microscope (SEM, Hitach S-4700). Table 4 shows as follows.

[Very good: ◎, Good: ○, Normal: △, Poor: ×]

division Anticorrosion for metal wiring division Anticorrosion for metal wiring Mo / Al Cu / Mo-Ti Mo / Al Cu / Mo-Ti Example 1 ◎ ◎ Comparative Example 1 ◎ ○ Example 2 ◎ ◎ Comparative Example 2 X ○ Example 3 ◎ ◎ Comparative Example 3 ○ X Example 4 ◎ ◎ Comparative Example 4 ◎ ◎ Example 5 ◎ ◎ Comparative Example 5 ◎ ○ Example 6 ◎ ◎ Comparative Example 6 ◎ ○ Example 7 ◎ ◎ Comparative Example 7 ◎ ◎ Example 8 ◎ ◎ Comparative Example 8 ◎ ◎ Example 9 ◎ ◎ Comparative Example 9 ◎ ◎ Example 10 ◎ ◎ Example 11 ◎ ◎ Example 12 ◎ ◎ Example 13 ◎ ◎ Example 14 ◎ △ Example 15 ○ × Example 16 × ○ Example 17 ◎ ◎

From the results in Table 4, it can be seen that the peeling liquid compositions of Examples 1 to 14 of the present invention showed excellent corrosion protection against the metal wiring in the peeling liquid itself or the rinse process. On the other hand, as for the peeling liquid compositions of Comparative Example 2 and Comparative Example 3, when the free radical remover is not contained compared with Example 14, the fall of the corrosion prevention force was confirmed. On the other hand, the release liquid composition of Example 14 was confirmed that the anti-corrosion performance is also improved by containing the free radical remover. In addition, it was confirmed that the peeling liquid composition of Comparative Examples 1 to 6, in which the free radical remover was not included, also decreased the corrosion preventing ability of the metal wiring as compared to the peeling liquid composition of Examples 1 to 14.

On the other hand, from the results of the corrosion protection test of the peeling liquid composition of Examples 15 to 17 it was able to confirm the synergistic effect on the corrosion protection appeared when the Al and Cu anticorrosive agent together. That is, in the case of the exfoliating liquid compositions of Examples 15 and 16, in which a small amount of Al preservatives or Cu preservatives were used alone, good anticorrosion performance was shown only for Al or Cu wirings, respectively, but a small amount of Al preservatives and Cu The peeling liquid composition of Example 17 using a corrosion inhibitor together showed very good corrosion protection for both Al and Cu wiring.

On the other hand, in Comparative Example 7, since no basic compound was included, the problem of metal wiring corrosion did not occur.

Claims (12)

Regarding the total weight of the composition, (a) 0.1 to 10% by weight free group remover represented by the following formula (1), (b) 5 to 30% by weight of the basic compound represented by the following formula (2), (c) proton polar solvent and aprotic A resist stripper composition comprising 55 to 94% by weight of a solvent comprising a polar solvent and 0.01 to 5% by weight of a corrosion inhibitor:
[Formula 1]

In this formula,
R1 and R2 are each independently substituted with an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, a carboxyl group and a carboxyl group substituted with carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms. It is an alkyl group, a phenyl group, or a benzyl group of 1-10.
(2)

In this formula,
R3, R4 and R5 are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms substituted or unsubstituted with an amino group, an alkyl group having 1 to 10 carbon atoms substituted with an amino group substituted with an alkyl group having 1 to 4 carbon atoms, and having 2 to 10 carbon atoms Alkyl group, C1-C10 hydroxyalkyl group, carboxyl group, C1-C10 alkyl group substituted or unsubstituted C1-C10 alkoxy group substituted or unsubstituted or C1-C4 alkyl group substituted or unsubstituted amino group , Phenyl group, or benzyl group. The resist stripper composition of claim 1, wherein the composition further comprises 3 to 15 wt% of deionized water based on the total weight of the composition. The resist stripping agent according to claim 1, wherein (a) the free radical remover represented by Formula 1 is one or two or more selected from the group consisting of dimethylhydroxylamine, diethylhydroxylamine and dibutylhydroxylamine. Liquid composition. The method of claim 1, wherein (b) the basic compound represented by the formula (2) is methylamine, ethylamine, monoisopropylamine, n-butylamine, sec-butylamine, isobutylamine, t-butylamine, pentylamine, Dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, methylethylamine, methylpropylamine, methylisopropylamine, methylbutylamine, methylisobutylamine, trimethylamine, Triethylamine, tripropylamine, tributylamine, tripentylamine, dimethylethylamine, methyldiethylamine, methyldipropylamine, choline, monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, 2-amino Ethanol, 2- (ethylamino) ethanol, 2- (methylamino) ethanol, N-methyl diethanolamine, N, N-dimethylethanolamine, N, N-diethylaminoethanol, 2- (2-aminoethylamino ) -1-ethanol, 1-amino- 2-propanol, 2- Amino-1-propanol, 3-amino-1-propanol, 4-amino-1-butanol, dibutanolamine, (butoxymethyl) diethylamine, (methoxymethyl) diethylamine, (methoxymethyl) dimethyl Amine, (butoxymethyl) dimethylamine, (isobutoxymethyl) dimethylamine, (methoxymethyl) diethanolamine, (hydroxyethyloxymethyl) diethylamine, methyl (methoxymethyl) aminoethane, methyl (meth Methoxymethyl) aminoethanol, methyl (butoxymethyl) aminoethanol, 2- (2-aminoethoxy) ethanol, 1- (2-hydroxyethyl) piperazine, 1- (2-aminoethyl) piperazine, 1 -(2-hydroxyethyl) methylpiperazine, N- (3-aminopropyl) morpholine, 2-methylpiperazine, 1-methylpiperazine, 1-amino-4-methylpiperazine, 1-benzyl piperazine And 1-phenyl piperazine; and a resist stripper composition according to claim 1 or 2 or more. The method according to claim 1, wherein the solvent (c) containing a protic polar solvent and an aprotic polar solvent, the protic polar solvent and aprotic polar solvent is characterized in that it is included in a weight ratio of 2: 6 ~ 6: 2 A resist stripping liquid composition. The method of claim 5, wherein the proton polar solvent is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monoisopropyl ether, triethylene glycol monobutyl ether, polyethylene glycol monomethyl ether, 1 type selected from the group consisting of polyethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate Is two or more kinds;
The aprotic polar solvent is N-methyl pyrrolidone (NMP), N-ethyl pyrrolidone, 1,3-dimethyl- 2-imidazolidinone, 1,3-dipropyl-2-imidazolidinone, γ-butyrolactone, dimethyl sulfoxide (DMSO), sulfolane, triethyl phosphate, tributyl phosphate, dimethyl carbonate, ethylene carbonate, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N- (2-hydroxyethyl) acetamide, 3-methoxy-N, N-dimethylpropionamide, 3- (2-ethylhexyloxy)- A resist stripping liquid composition, characterized in that one or two or more selected from the group consisting of N, N-dimethylpropionamide, and 3-butoxy-N, N-dimethylpropionamide. The resist stripper according to claim 1, wherein (d) the corrosion inhibitor is at least one member selected from the group consisting of an azole compound, a quinone compound, a catechol, an alkyl gallate compound, and a cyclic diketone compound. Composition. The method according to claim 7, wherein the (d) corrosion inhibitor comprises at least one selected from azole compounds and at least one selected from quinone compounds, catechol, alkyl gallate compounds and cyclic diketone compounds Resist stripper composition, characterized in that. The resist stripper composition according to claim 1, wherein the resist stripper composition is used for resist stripping of a flat panel substrate on which metal wiring containing aluminum or copper is formed. (I) depositing a conductive metal film on a flat panel display substrate,
(II) forming a resist film on the conductive metal film;
(III) selectively exposing the resist film;
(IV) developing the resist film after exposure to form a resist pattern;
(V) etching the conductive metal film using the resist pattern as a mask; And
(VI) peeling the resist after the etching process, using the resist stripper composition of claim 1; A method of manufacturing a flat panel display device comprising the step of peeling a resist of a substrate for a flat panel using the resist stripper composition of claim 1. A flat panel display device comprising a substrate for a flat panel manufactured using the resist stripper composition of claim 1.