KR20150024482A - A resist stripper composition - Google Patents

Abstract

상기 화학식 1에서, R₁ 및 R₂는 C1~C5의 알킬기이다.The present invention relates to a resist stripping liquid composition comprising (a) a primary amino alcohol represented by the following general formula (1) and (b) a polar organic solvent:
(Formula 1)

In Formula 1, R ₁ and R ₂ are C1-C5 alkyl groups.

Description

Resist stripper composition {A RESIST STRIPPER COMPOSITION}

The present invention relates to a resist stripper composition which maximizes the solubility of a solidified resist as well as minimizing corrosion of a film quality including copper and aluminum metal in a manufacturing process of a flat panel display substrate without a separate corrosion inhibitor .

In recent years, efforts have been made to increase the number of pixels per unit area as the demand for high resolution implementation of flat panel displays increases. In accordance with this trend, reduction of the wiring width is required, and in order to cope with this, the dry etching process has been introduced, and the process conditions have become increasingly severe. In addition, due to the enlargement of the flat panel display device, an increase in the signal speed in the wiring is also required, and a wiring material having a low resistivity such as aluminum or copper has been put to practical use. Accordingly, the required performance of the stripping solution used in the stripping process, which is a resist stripping process, is increasing. Specifically, there is a demand for corrosion inhibiting ability for copper as well as aluminum, while maintaining a considerable level of peeling force for metal wiring. Particularly, in order to secure price competitiveness, development of a peeling liquid which minimizes corrosion of copper and aluminum is demanded without a separate corrosion inhibitor. In addition, in order to improve the number of processed substrates and provide a peeling solution having excellent economical efficiency, it is also necessary to develop a peeling solution that maximizes the solubility of the solidified resist.

Korean Patent Laid-Open No. 2006-0117666 discloses a resist composition comprising (a) a water-soluble organic amine compound, (b) a quantitative alkylene glycol monoalkyl ether compound, (c) a polar aprotic solvent, and (d) Stripper compositions are disclosed. However, when the corrosion inhibitor is not included, the composition of the present invention has a disadvantage in that it is not only extremely corrosive to copper and aluminum, but also solubility of the resist is low.

Accordingly, there is a need to develop a resist stripping liquid composition that solves the above problems of the prior art.

Korea Patent Publication No. 2006-0117666

In order to solve the above problems, the present invention aims to provide a resist stripper composition which not only minimizes corrosion of film quality including copper and aluminum metal but also maximizes the solubility of a solidified resist without any additional corrosion inhibitor have.

In order to achieve the above object, the present invention provides a resist stripping liquid composition comprising: (a) a primary amino alcohol represented by the following general formula (1): and (b) a polar organic solvent:

(Formula 1)

In the above formula (1), R ₁ and R ₂ are C1-C5 alkyl groups

In addition, the present invention provides a method of manufacturing a flat panel display substrate including a step of cleaning the flat panel display substrate using the resist stripping liquid composition.

The resist stripper composition of the present invention has the effect of minimizing the corrosion to the film quality including copper and aluminum metal, and maximizing the solubility of the solidified resist without any additional corrosion inhibitor.

In addition, when the resist stripper composition of the present invention is used, it is not necessary to additionally add a corrosion inhibitor, thereby reducing the cost of the entire manufacturing process.

Fig. 1 is a photograph of a resist of the remaining amount remaining on the filter paper as a result of the dissolution test for Example 3 with a digital camera. Fig.
Fig. 2 is a photograph of a resist of the remaining amount remaining on the filter paper as a result of the dissolution test for Comparative Example 2 with a digital camera.

Hereinafter, the present invention will be described in more detail.

The present invention relates to a resist stripping liquid composition comprising (a) a primary amino alcohol represented by the following general formula (1) and (b) a polar organic solvent:

(Formula 1)

In the above formula (1), R ₁ and R ₂ are C1-C5 alkyl groups

With the above structure, the resist stripper composition of the present invention has the effect of maximizing the solubility of the solidified resist as well as minimizing the corrosion to the film quality including copper and aluminum metal without any additional corrosion inhibitor And confirmed the present invention.

The resist stripping solution composition of the present invention may further comprise (c) a basic compound, (d) a corrosion inhibitor, or a mixture thereof.

Hereinafter, the constitution of the present invention will be described in detail by constituent elements.

(a) a primary amino alcohol represented by formula

The resist stripper composition of the present invention is characterized by containing a primary amino alcohol represented by the following general formula (1).

(Formula 1)

Thus, the primary amino alcohol represented by the general formula (1) is strongly resistant to a polymer matrix of a resist modified or crosslinked under various process conditions such as dry or wet etching, ashing, or ion implant processing. And breaks bonds existing in molecules or between molecules. It has been found that a vacant space is formed in a structurally weak portion in a resist remaining on a substrate so that the resist attached to the upper portion of the substrate can be easily removed by deforming the resist into an amorphous polymer gel lump state. In addition, since it is less corrosive to metal films including copper and aluminum, corrosion to the metal film can be minimized, and the solubility of a resist polymer gelled in a small amount can be maximized. (B) The dissolution power can be realized to increase the processing capacity of the substrate to which the resist is applied.

Wherein R ₁ and R ₂ are primary aminoalcohols of an alkyl group having 1 to 5 carbon atoms. Examples thereof include 3-amino-2-butanol, 2-amino-3-pentanol, 2-amino-3-hexanol, 4-octanol, and the like, which may be used singly or in combination of two or more.

The content of the primary amino alcohol represented by the formula (1) is preferably 1 to 40% by weight based on the total weight of the composition. If the content is less than 1% by weight, the effect of increasing the solubility is difficult to obtain and the peeling force is weakened have. If it exceeds 40% by weight, the effect of increasing the solubility of the composition due to the increase of the content is insufficient.

(b) a polar organic solvent

The polar organic solvent (b) serves to dissolve the resist polymer gelled together with the primary amino alcohol (a) represented by the formula (1), and further, Thereby minimizing re-adsorption / re-adhesion of the exfoliation liquid and the dissolved resist. It is preferable that the polar organic solvent does not have a boiling point too high or low for an appropriate peeling force, and may be mixed and used. The polar organic solvent may be added according to the performance additionally required in the peeling process

The polar organic solvent (b) used in the present invention includes a protonic polar solvent and an aprotic polar solvent, which may be used alone or in combination. Preferable examples of the protonic 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, polypropylene glycol, Alkylene glycol monoalkyl ethers such as polyethylene glycol monomethyl ether, polyethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether and tripropylene glycol monomethyl ether; Recycled monomethyl ether acetate, and tetrahydroperfuryl alcohol. These solvents may be used alone or in combination of two or more.

Preferable 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? -butyrolactone; Sulfoxide compounds such as dimethylsulfoxide (DMSO) and sulfolane; Phosphate compounds such as triethyl phosphate, tributyl phosphate and the like; Carbonate compounds such as dimethyl carbonate, ethylene carbonate, and the like; N, N-dimethylacetamide, N- (2-hydroxyethyl) acetamide, 3-methoxypyridine, N, N-dimethylformamide, Amide compounds such as N, N-dimethylpropionamide, 3- (2-ethylhexyloxy) -N, N-dimethylpropionamide and 3-butoxy-N, N-dimethylpropionamide, These can be used alone or in admixture of two or more.

The content of the polar organic solvent (b) is preferably 60 to 99% by weight based on the total weight of the entire composition. If the amount is less than 60% by weight, the solubility may be lowered, and re-adsorption / redeposition of the resist may occur in the rinsing step with deionized water. On the other hand, if it exceeds 99% by weight, the content of the primary amino alcohol represented by the formula (1) may be relatively decreased, and the peeling force may be lowered.

(c) a basic compound

In addition to the resist stripping composition of the present invention, (c) a basic compound may be included. The basic compound (c) is used together with (a) the primary amino alcohol represented by the general formula (1) to strongly penetrate into a polymer matrix of a resist which is denatured or crosslinked to break bonds existing in the molecule or between molecules And forms a vacant space in a structurally weak portion in the resist remaining on the substrate, thereby deforming the resist into amorphous polymer gel mass to quickly remove the resist attached on the substrate.

The basic compound (c) to be further contained is preferably a basic compound such as KOH, NaOH, Tetramethyl ammonium hydroxide (TMAH), Tetraethyl ammonium hydroxide (TEAH), carbonate, phosphate, ammonia and amines. Two or more species may be used together.

The amines include primary amines such as methylamine, ethylamine, monoisopropylamine, n-butylamine, sec-butylamine, isobutylamine, t-butylamine and pentylamine; Examples of the secondary amine such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, methylethylamine, methylpropylamine, methylisopropylamine, methylbutylamine and methylisobutylamine Amine; Tertiary amines such as diethylhydroxyamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, dimethylethylamine, methyldiethylamine and methyldipropylamine; But are not limited to, choline, monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, 2-aminoethanol, 2- (ethylamino) ethanol, 2- (methylamino) ethanol, Amino-2-propanol, 2-amino-1-propanol, 3-amino-1-propanol, Alkanolamines such as 4-amino-1-butanol and dibutanolamine; (Methoxymethyl) dimethylamine, (methoxymethyl) dimethylamine, (butoxymethyl) dimethylamine, (isobutoxymethyl) dimethylamine, (methoxymethyl) diethanolamine (Methoxymethyl) aminoethanol, methyl (butoxymethyl) aminoethanol, 2- (2-iminoethoxy) - Alkoxyamines such as 1-ethanol and 2- (2-aminoethoxy) ethanol; Hydroxylamines such as diethylhydroxylamine, dipropylhydroxylamine and N-ethyl-N-methylhydroxylamine; 1- (2-hydroxyethyl) piperazine, 1- (2-aminoethyl) piperazine, 1- Methylpiperazine, 1-amino-4-methylpiperazine, 1-benzylpiperazine, 1-phenylpiperazine, N-methylmorpholine, 4-ethylmorpholine, N-formylmorpholine, N - (2-hydroxyethyl) morpholine, N- (3-hydroxypropyl) morpholine and the like.

The amount of the basic compound (c) is preferably 0.1 to 20% by weight based on the total weight of the composition, and if it is less than 0.1% by weight, (a) If it is more than 1 wt%, the degree of corrosion of the metal film including copper and aluminum becomes worse.

(d) Corrosion inhibitor

In addition to the resist stripping composition of the present invention, (d) a corrosion inhibitor may be included.

(D) corrosion inhibitors which may be further included include benzotriazole, tolithriazole, methyltolytriazole, 2,2 '- [[[benzotriazole] methyl] imino] bisethanol, 2,2' - [[ethyl-1-hydrogen benzotriazol-1-yl] methyl] imino] Dihydrobenzotriazol-1-yl] methyl] imino] bisethanol, 2,2 '- [[[methyl- - [[methyl-1-hydrogen-benzotriazol-1-yl] methyl] imino] bismethylamine, 2,2 '- [[[ -1 hydrogen-benzotriazol-1-yl] methyl] imino] bis-ethanol and 1,2-benzoquinone, 1,4-benzoquinone, 1,4-naphthoquinone, anthraquinone The same quinone compounds and alkyl gallates such as catechol, pyrogallol, methyl gallate, propyl gallate, dodecylgallate, octylgallate, The acids, etc., and these may be used alone or by mixing two or more.

The corrosion inhibitor is preferably used in an amount of 0.001 to 10 wt% based on the total weight of the composition. If the amount of the corrosion inhibitor is less than 0.001 wt%, it is difficult to obtain a corrosion inhibiting effect of a film quality including copper and aluminum. It is inefficient economically since it is impossible to obtain an increase in the corrosion prevention effect due to the increase in the amount of water.

As a method for removing the resist using the resist stripping liquid composition for a flat panel display of the present invention, a dipping method is generally used, but other methods such as a spraying method may also be used. As the cleaning agent after treatment with the composition according to the present invention, it is not necessary to use an organic solvent such as alcohol, and it is sufficient to wash with water.

The resist stripping liquid composition of the present invention can be usefully used in a process for removing a semiconductor or an electronic product, particularly a resist for a flat panel display.

Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

Example  1 to 6 and Comparative Example  1-4. Resist Peeling liquid  Composition manufacturing

The components shown in Table 1 below were mixed at the composition ratios to prepare resist stripper compositions for flat panel displays of Examples 1 to 6 and Comparative Examples 1 to 4.

division (a) an amino alcohol of formula (b) a polar organic solvent (c) a basic compound (d) Corrosion inhibitor Kinds content
(weight%) Kinds content
(weight%) Kinds content
(weight%) Kinds content
(weight%) Example 1 3A4O 10 NMP 90 - - - - Example 2 2A3H 10 NMF 90 - - - - Example 3 3A4O 10 NMP
BDG 60
30 - - - - Example 4 3A4O 10 NMP
EDG 50
30 MDEA 10 - - Example 5 3A4O 10 NMP
EDG 54.5
30 AEE 5 BTA 0.5 Example 6 3A4O 10 NMP
EDG 54
30 MEA 5 BTA
MG 0.5
0.5 Comparative Example 1 - - NMP
EDG 60
30 MDEA 10 - - Comparative Example 2 - - NMP
EDG 64.5
30 AEE 5 BTA 0.5 Comparative Example 3 - - NMP
EDG 64
30 MEA 5 BTA
MG 0.5
0.5 Comparative Example 4 - - NMP
EDG 65
30 MEA 5 - -

3A4O: 3-amino-4-octanol

2A3H: 2-amino-3-hexanol

NMP: N-methylpyrrolidone

NMF: N-methylformamide

BDG: diethylene glycol monobutyl ether

EDG: diethylene glycol monoethyl ether

MDEA: N-methyldiethanolamine

AEE: 2- (2-Iminoethoxy) -1-ethanol

MEA: Monoethanolamine

BTA: benzotriazole

MG: methyl gallate

Experimental Example : Resist Peeling liquid  Evaluation of composition characteristics

Experimental Example  One. Exfoliation Peel force  evaluation

In order to confirm the peeling effect of the resist stripping composition, a Mo / Al or Cu / Ti layer is formed on a glass substrate by a thin film sputtering method, and then a photoresist pattern is formed. A substrate on which a metal film was etched by a dry etching method was prepared. After the resist stripping composition was maintained at a constant temperature of 50 캜, an object was immersed for 1 minute to evaluate the stripping force. Then, the substrate was cleaned with pure water for 1 minute to remove the peeling liquid remaining on the substrate, and the substrate was completely dried with nitrogen to remove pure water remaining on the substrate after cleaning. The denaturation or curing resist and dry etching residue removal performance of the substrate were confirmed using a scanning electron microscope (SEM, Hitachi S-4700), and the results are shown in Table 2, Quot; and " bad "

Experimental Example  2. Peeling liquid  Metal wiring Revolution  evaluation

The evaluation of the corrosion inhibiting ability of the resist stripping solution composition on the metal wiring was carried out by using a substrate on which Mo / Al and Cu / Ti wiring lines were exposed, maintaining the stripping solution composition at a constant temperature of 50 캜, immersing the substrate for 30 minutes , Followed by washing, drying, and evaluation using a scanning electron microscope (SEM, Hitachi S-4700). The results are shown in Table 2 below. Excellent results are shown as " good ", good results are shown as "?&Quot;

Experimental Example  3. Exfoliation Resist solvency  evaluation

As one of the methods for expressing the performance of the resist stripping solution, how much of the substrate on which the resist is applied can be peeled off is referred to as the processing number / processing capacity evaluation. 5% by weight of the resist (solidified by removing all the solvent through heat treatment for 3 days at 130? For 3 days) was dissolved at 50? For 1 hour under the same conditions of 500 rpm, and the remaining amount was filtered with filter paper And the solubility was calculated as% after the weight was measured. It can be determined that the higher the value, the higher the resist solubility and the higher the number of processed / treated capacities. The results are shown in Table 2, Figs. 1 and 2.

division Peel force Revolution Solubility (%) Al Cu Example 1 ○ ◎ ◎ 98.5% Example 2 ○ ◎ ◎ 98.6% Example 3 ○ ◎ ◎ 98.5% Example 4 ○ ○ ○ 98.7% Example 5 ◎ ◎ ◎ 98.7% Example 6 ◎ ◎ ◎ 98.6% Comparative Example 1 X ○ ○ 82.5% Comparative Example 2 ◎ ◎ ◎ 83.0% Comparative Example 3 ◎ ◎ ◎ 81.9% Comparative Example 4 ◎ X X 82.4%

From the results of the tests of Table 2, it can be seen that the compositions of Examples 1 to 6, which are the release liquid compositions of the present invention, are superior in terms of resist removal performance as compared with the compositions of Comparative Examples 1 to 4, And the solubility in solidified resist was also excellent.

Claims (8)

(a) a primary amino alcohol represented by the following formula
(b) a polar organic solvent.
(Formula 1)

In Formula 1, R ₁ and R ₂ are C1-C5 alkyl groups.
The method of claim 1, wherein, relative to the total weight of the composition,
(A) 1 to 40% by weight of a primary amino alcohol represented by the general formula (1): and
And (b) 60 to 99% by weight of the polar organic solvent.
The method according to claim 1,
(A) the primary amino alcohol represented by the general formula (1) is at least one selected from the group consisting of 3-amino-2-butanol, 2-amino-3-pentanol, Amino-3-heptanol and 3-amino-4-octanol.
The method according to claim 1,
The polar organic solvent may be a protonic polar solvent, apolar polar solvent or a mixture thereof,
Wherein the protonic polar solvent is selected from the group consisting of 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 mono Isopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monoisopropyl ether, triethylene glycol monobutyl ether, polyethylene glycol, polypropylene glycol, polyethylene glycol mono Methyl ether, polyethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and tetrahydrofuran It is at least one selected from a group consisting of furyl alcohol,
The aprotic polar solvent may be at least one selected from the group consisting of N-methylpyrrolidone (NMP), N-ethylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, , dimethylsulfoxide (DMSO), sulfolane, triethylphosphate, tributylphosphate, dimethylcarbonate, ethylene carbonate, formamide, N-methylformamide, N, N-dimethylformamide, N-dimethylacetamide, N, N-dimethylacetamide, N- (2-hydroxyethyl) acetamide, 3- methoxy- N, N-dimethylpropionamide, and 3-butoxy-N, N-dimethylpropionamide.
The method according to claim 1,
(C) a basic compound, (d) a corrosion inhibitor, or a mixture thereof.
The method of claim 5,
The basic compound (c) is at least one selected from the group consisting of KOH, NaOH, Tetramethyl ammonium hydroxide (TMAH), Tetraethyl ammonium hydroxide (TEAH), carbonate, phosphate, ammonia,
The amines may be selected from the group consisting of methylamine, ethylamine, monoisopropylamine, n-butylamine, sec-butylamine, isobutylamine, t-butylamine, pentylamine, dimethylamine, diethylamine, dipropylamine, diisopropyl Examples of the amine compound include aliphatic amines such as amine, dibutylamine, diisobutylamine, methylethylamine, methylpropylamine, methylisopropylamine, methylbutylamine, methylisobutylamine, diethylhydroxyamine, trimethylamine, Monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, 2-aminoethanol, 2- (ethylamino) ethylamine, diethylamine, diethylamine, Ethanol, 2- (methylamino) ethanol, N-methyldiethanolamine, N, N-dimethylethanolamine, N, N-diethylaminoethanol, 2- Amino-2-propanol, 2-amino-1-propanol, 3-amino- (Butoxymethyl) dimethylamine, (methoxymethyl) dimethylamine, (methoxymethyl) dimethylamine, (methoxymethyl) dimethylamine, (Methoxymethyl) aminoethanol, methyl (methoxymethyl) aminoethanol, methyl (methoxymethyl) aminoethanol, methyl (methoxymethyl) (2-aminoethoxy) ethanol, diethylhydroxylamine, dipropylhydroxylamine, N-ethyl-N-methyl (2-aminoethyl) piperazine, 1- (2-hydroxyethyl) methylpiperazine, N- (3-aminopropyl) morpholine Methylpiperazine, 1-amino-4-methylpiperazine, 1-benzylpiperazine, 1-phenylpiperazine, N-methylmorpholine, 4-ethylmorpholine, N- N- (2-hydroxyethyl) morpholine and N- (3- De-hydroxypropyl) resist stripper composition, characterized in that at least one selected from the group consisting of morpholine.
The method of claim 5,
(D) the corrosion inhibitor is selected from the group consisting of benzotriazole, tolythriazole, methyltolytriazole, 2,2 '- [[[benzotriazole] methyl] imino] bisethanol, 2,2' - [[[ Methyl-1H-benzotriazol-1-yl] methyl] imino] bis-methanol, 2,2 '- [[ , 2 '- [[[methyl-1H-benzotriazol-1-yl] methyl] imino] Yl] methyl] imino] bismethylamine, 2,2 '- [[[amine-1-hydrogen- Benzoquinone, 1,4-naphthoquinone, anthraquinone, catechol, pyrogallol, methyl gallate, Wherein the resist stripping liquid composition is at least one selected from the group consisting of propyl gallate, propyl gallate, dodecyl gylate, octyl gylate, and gallic acid.
A method for manufacturing a flat panel display substrate, comprising the step of cleaning a flat panel display substrate using the resist stripping liquid composition according to any one of claims 1 to 7.

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