KR20180004609A - A resist stripper composition, method for manufacturing a display device and display device - Google Patents

Abstract

The present invention relates to a resist stripper composition comprising: (a) an amino alkyl silane-based compound having a structure represented by chemical formula 1; (b) alkanol amine; and (c) a polar organic solvent, to a method for manufacturing a display substrate manufactured by using the same and a display substrate manufactured by the method. The resist stripper composition of the present invention has excellent corrosion resistance and high peeling strength.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a resist stripping liquid composition, a method of manufacturing a display substrate using the resist stripping liquid composition,

The present invention relates to a resist stripping liquid composition to which an aminoalkylsilane compound having excellent galvanic and crevice corrosion resistance is applied, a method of manufacturing a display substrate using the same, and a display substrate therefor.

In recent years, efforts to increase the number of pixels per unit area have continued as the demand for realizing a high resolution of a display substrate has increased. 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 copper having a lower resistivity than aluminum is now being used as a wiring material. Accordingly, the required performance of the stripping solution used in the stripping process, which is a resist stripping process, is increasing. Specifically, a considerable level of exfoliating property with respect to corrosion inhibiting ability against metal wiring is required. In particular, corrosion resistance to copper as well as aluminum is required, and in order to secure price competitiveness, economic efficiency such as increase in the number of processed substrates is also required. In response to the needs of such industries, new technologies are being published.

For example, Korean Patent Registration No. 10-1557778 discloses a resist stripper composition containing an alkanolamine, an organic solvent and the like, but does not improve the anticorrosion properties of a metal film or a metal wiring including a metal such as molybdenum .

Korean Patent No. 10-1557778

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a resist stripping liquid composition which exhibits excellent anti-corrosive effect on a metal film or metal wiring including molybdenum and exhibits high stripping force, And a display substrate therefor.

In order to achieve the above object,

(A) an aminoalkylsilane compound having a structure represented by the following formula (1); (b) an alkanolamine; And (c) a polar organic solvent.

The present invention provides a method of manufacturing a display substrate including a step of cleaning a display substrate using the resist stripping liquid composition.

The present invention also provides a display substrate manufactured by the above manufacturing method.

The resist stripping liquid composition according to the present invention causes corrosion in aluminum, copper, tungsten, molybdenum, titanium and a lower metal film or metal wiring containing the same by using an aminoalkylsilane compound having excellent solubility in deionized water and a polar solvent And has an effect of exhibiting a high peeling force.

The present invention relates to a resist stripping liquid composition, a method of manufacturing a display substrate manufactured using the same, and a display substrate therefor.

The resist stripping composition according to the present invention comprises (a) an aminoalkylsilane compound; (b) an alkanolamine; Copper, tungsten, molybdenum, titanium and the underlying metal film or metal wiring comprising the same, and (c) a polar organic solvent, in particular by using an aminoalkylsilane compound having excellent solubility in deionized water and a polar solvent. It does not cause corrosion and has an effect of exhibiting high peeling force. The resist stripping liquid composition according to the present invention may further contain (d) a corrosion inhibitor.

Hereinafter, the contents of the present invention will be described in detail according to the constitution.

(a) an aminoalkylsilane compound

The aminoalkylsilane compound (a) used in the present invention has a structure represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

R ₁ , R ₂ and R ₃ are each independently an alkyl group having 1 to 4 carbon atoms;

R ₄ is an alkylene group having 1 to 5 carbon atoms;

R ₅ and R ₆ are, each independently, when one is hydrogen atom, an alkoxy group having 1 to 5 carbon atoms alkyl group, a hydroxyl group or 1 to 4 carbon atoms of, R ₅ hydroxyl or alkoxy groups R ₆ is hydrogen An atom or an alkyl group, and when R ₆ is a hydroxy group or an alkoxy group, R ₅ is a hydrogen atom or an alkyl group.

The alkyl group having 1 to 4 carbon atoms may be in the form of a chain or a branched chain if it has 3 or more carbon atoms.

As the kind of the aminoalkylsilane compound represented by the formula (1), (2-aminoethyl) triethoxysilane, (3-aminopropyl) trimethoxysilane, (3-aminopropyl) triethoxy Silane, etc. These may be used singly or in combination of two or more.

Further, in the present invention, a compound such as (3-aminopropyl) silanetriol may be further added to the aminoalkylsilane compound (a).

The aminoalkylsilane compound (a) of the present invention is excellent in the ability to prevent corrosion of metals that can occur during resist stripping, and is particularly suitable for galvanic corrosion and crevice corrosion in aluminum, molybdenum, and alloys containing copper and molybdenum And it is experimentally confirmed that the power is excellent.

The amount of the aminoalkylsilane compound (a) represented by Formula 1 is preferably 0.001 to 3 wt%, more preferably 0.005 to 1 wt% based on the total weight of the composition. If the amount is less than 0.001% by weight, corrosion may occur in the metal wiring in the rinsing process by peeling or deionized water. If the amount is more than 3% by weight, improvement in corrosion prevention effect due to increase in the content of the corrosion inhibitor can not be obtained economically .

(b) an alkanolamine

The alkanolamine of the present invention strongly penetrates into the polymer matrix of the modified or crosslinked resist under various process conditions such as dry or wet etching, ashing or ion implant processing, The resist attached to the upper part of the substrate is easily removed by deforming the resist into amorphous polymer gel state by forming an empty space in the structurally weak part in the resist remaining on the substrate, .

Examples of the alkanolamine include monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, 2-aminoethanol, 2- (ethylamino) ethanol, 2- (methylamino) ethanol, N-methyldiethanolamine, N-dimethylaminoethanol, N, N-diethylaminoethanol, 2- (2-aminoethylamino) -1-ethanol, 1-amino-2-propanol, (Methoxymethyl) diethanolamine, (hydroxyethyloxymethyl) diethylamine, methyl (methoxymethyl) aminoethanol, methyl (butoxymethyl) (2-aminoethoxy) ethanol, 1- (2-hydroxyethyl) piperazine, 1- (2-hydroxyethyl) methylpiperazine, N- , And N- (3-hydroxypropyl) morpholine. These may be used alone or in combination of two or more.

The content of the alkanolamine (b) in the present invention is preferably 0.1 to 20% by weight, more preferably 0.5 to 10% by weight based on the total weight of the entire composition. If the amount is less than 0.1% by weight, the resist removing ability may be lowered. If the amount of the alkanolamine is more than 20% by weight, the effect of improving the resist removing ability due to the increase of the alkanolamine may not be obtained, which is not economical. .

(c) a polar organic solvent

The polar organic solvent (c) used in the present invention includes a protonic polar solvent and an aprotic polar solvent, which may be used alone or in combination of two or more. 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 admixture of two or more.

Preferable examples of the aprotic polar solvent include pyrrolidone compounds such as N-methylpyrrolidone 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, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N - (2-hydroxyethyl) acetamide, N, N-dimethylpropionamide, 3- methoxy-N, N-dimethylpropionamide, 3- (2-ethylhexyloxy) -N, N-dimethylpropionamide , And 3-butoxy-N, N-dimethylpropionamide. These may be used alone or in combination of two or more.

The polar organic solvent (c) serves to dissolve the gelled resist polymer. In addition, since the removal of the peeling liquid by the water during rinsing of the deionized water after the resist peeling is facilitated, the peeling liquid and the resorption / Minimize reattachment. The polar organic solvent (c) preferably has neither too high nor too low a boiling point for proper peeling power, and may be used in combination. The polar organic solvent may be added according to the performance required in the peeling process.

The content of the (c) polar organic solvent is preferably 80 to 99.8% by weight based on the total weight of the entire composition. If the amount is less than 80% 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, when the amount of the alkanolamine is more than 99.8% by weight, the content of the alkanolamine (b) may be relatively decreased and the peeling force may be lowered.

(d) Corrosion inhibitor

The composition of the present invention may further contain (d) a corrosion inhibitor. Specifically, the corrosion inhibitor of the present invention may be a monocarboxylic acid such as formic acid, acetic acid, or propionic acid; Dicarboxylic acids such as acetic acid, malic acid, malonic acid, succinic acid, gluconic acid, adipic acid, pimelic acid, maleic acid, fumaric acid and glutaconic acid; Tricarboxylic acids such as trimellitic acid and tricarvaleric acid; Organic acids such as hydroxyacetic acid, lactic acid, salicylic acid, malic acid, tartaric acid, citric acid, gluconic acid and oxycarboxylic acid; Maleic amide esters, maleic amide esters, maleic amide esters, fumaric amide esters, oxalic amide esters, malonic amide esters, glutaric amide esters, acetic amide esters, lactic amide esters, Organic acid amide esters such as tartaric amide esters, tartaric amide esters, tartaric amide esters, tartaric amide esters, tartaric amide esters, tartaric amide esters, tartaric amide esters, tartaric amide esters, 2,2 '- [[[[[benzotriazole] methyl] imino] bisethanol, 2,2' - [[[methyl-1-hydrogen-benzotriazole Yl] methyl] imino] bisethanol, 2,2 '- [[[ethyl-1-hydrogen-benzotriazol- Methyl-imino] biscarboxylic acid [methyl-1-hydrogen-benzotriazol-1-yl] methyl] imino] bisethanol and 2,2 '- [[ Methyl] imino] bismethylamine and 2,2 '- [[[amine-1-hydrogen-benzotriazol-1-yl] Methyl] -4,5-dihydro-1H-benzo [1,2,3] triazole, 4 Methyl-4,5,6,7-tetrahydro-1H benzo [1,2,3] triazole, 5-methyl-4,5,6,7-tetrahydro-1H- benzo [1,2,3 ] Triazole, 5,6-dimethyl-4,5,6,7-tetrahydro-1H- benzo [1,2,3] triazole, 4,6-dimethyl-4,5,6,7-tetrahydro -1H-benzo [1,2,3] tri Azole and 5-methyl-1-hydrogen-azole compounds such as benzotriazole; 2,6-dimethylphenol, 2,4,6-trimethylphenol, 2,6-diethylphenol, 2,6-diethyl-4-methylphenol, 4-methylphenol, 2,6-di-t-butylphenol, 2,4,6-tri-t-butylphenol and 2,6- ; But is not limited thereto. These may be used alone or in combination of two or more.

The content of (d) the corrosion inhibitor of the present invention may be 0.001 to 1.0% by weight based on the total weight of the composition. When the amount of the corrosion inhibitor is less than 0.001% by weight, there is a problem that slight corrosion occurs on the copper surface. When the corrosion inhibitor is contained in an amount exceeding 1.0% by weight, corrosion prevention effect due to the increase is not obtained.

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 display.

That is, the present invention includes a method of manufacturing a display substrate including a step of cleaning a display substrate using the resist stripping liquid composition of the present invention and a display substrate manufactured by the manufacturing method.

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.

EXAMPLES AND COMPARATIVE EXAMPLES Preparation of resist stripper composition

The components shown in Table 1 below were mixed in the composition ratios to prepare resist stripper compositions of Examples and Comparative Examples.

) APTES: (3-aminopropyl) triethoxysilane

APSTO: (3-aminopropyl) silanetriol

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

MAE: 2- (methylamino) ethanol

MDEA: N-methyldiethanolamine

IME: imidazolidine Ethanol

NMF: N-methylformamide

NEF: N-ethylformamide

NMP: N-methylpyrrolidone

MDG: diethylene glycol monomethyl ether

EDG: diethylene glycol monoethyl ether

BDG: diethylene glycol monobutyl ether

MTG: triethylene glycol monomethyl ether

TTA: tolyltriazole

MTBT: 6-methyl-4,5,6,7-tetrahydro-1H-benzo [1,2,3] triazole

EXPERIMENTAL EXAMPLE 1 Evaluation of Photoresist Peelability of Peeling Solution

In order to confirm the peeling effect of the resist stripping solution composition, a positive photoresist (DWG-520: our PR) was applied on a glass substrate in an amount of 1.7 .mu.m and hard bake was performed at 170.degree. C. for 10 minutes in a hot plate. After the resist stripper solution composition was maintained at a constant temperature of 50, the substrate was immersed at intervals of 30 seconds to evaluate the peeling force. Then, the substrate was cleaned with DIW for 1 minute to remove the peeling liquid remaining on the substrate, and the substrate was completely dried with nitrogen to remove the DIW remaining on the substrate after cleaning. The evaluated substrate was visually inspected and the time for completely removing the resist was measured. The results are shown in Table 2 below. The shorter the time, the better the peeling effect.

≪ Experimental Example 2 >

Mo / Mo, MoTi, MoW, MoNb, Mo / Al, and Cu / X layers were formed on a glass substrate by a thin film sputtering method according to a conventional method in order to evaluate the corrosion- ), A photoresist pattern was formed, and then a substrate on which a metal film was etched by a wet etching method was prepared. The stripping liquid composition was maintained at a constant temperature of 60 ° C using a simple strip spray evaluation apparatus, and the substrate was subjected to a spray strip at a pressure of ² kgf / cm ² for 2 minutes. Then, the strip was cleaned using a simple DIW cleaning spraying apparatus, The completed substrate was subjected to spray cleaning at a pressure of ² kgf / cm < ² > for 3 minutes at room temperature. The substrate which had been cleaned was dried using N ² , and the process from the strip process to DIW washing and drying was repeated three times, and the substrate was evaluated using an electron microscope (SEM, Hitachi S-4700) . The results are shown in Table 2 below. No corrosion was observed according to the degree of corrosion of each metal, and corrosion was observed microscopically. However, there was no problem in application of the membrane, and corrosion was observed. △, corrosion was observed very badly and membrane quality was not applicable.

With reference to the above experimental results, the resist stripping composition of the present invention was found to be resistant to corrosion of aluminum, copper, tungsten, molybdenum, titanium and metal wiring containing the same by using an aminoalkylsilane compound having excellent solubility in deionized water and polar solvents It is possible to confirm that it has a high peeling force effect without causing it to occur.

Claims (13)

(a) an aminoalkylsilane compound having a structure represented by the following formula (1);
(b) an alkanolamine; And
(c) a polar organic solvent.
[Chemical Formula 1]

(In the formula 1,
R ₁ , R ₂ and R ₃ are each independently an alkyl group having 1 to 4 carbon atoms;
R ₄ is an alkylene group having 1 to 5 carbon atoms; And
R ₅ and R ₆ are, each independently, when one is hydrogen atom, an alkoxy group having 1 to 5 carbon atoms alkyl group, a hydroxyl group or 1 to 4 carbon atoms of, R ₅ hydroxyl or alkoxy groups R ₆ is hydrogen An atom or an alkyl group, and when R ₆ is a hydroxy group or an alkoxy group, R ₅ is a hydrogen atom or an alkyl group. The method according to claim 1,
(d) a corrosion inhibitor.
3. The method of claim 2,
Wherein the corrosion inhibitor is a Cu corrosion inhibitor.
The method according to claim 1,
Wherein the aminoalkylsilane compound (a) is at least one of (2-aminoethyl) triethoxysilane, (3-aminopropyl) trimethoxysilane and (3-aminopropyl) triethoxysilane. Peeling liquid composition.
5. The method according to any one of claims 1 to 4,
The (b) alkanolamine may be selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, 2-aminoethanol, 2- (ethylamino) ethanol, 2- , N, N-dimethyl ethanolamine, N, N-diethylaminoethanol, 2- (2-aminoethylamino) -1- (Methoxymethyl) aminoethanol, methyl (methoxymethyl) diethanolamine, (hydroxyethyloxymethyl) diethylamine, methyl (2-hydroxyethyl) piperazine, 1- (2-hydroxyethyl) methylpiperazine, N- (2-hydroxyethyl) ) Morpholine and N- (3-hydroxypropyl) morpholine.
5. The method according to any one of claims 1 to 4,
Wherein the polar organic solvent (c) is at least one of a protonic polar solvent and an aprotic polar solvent.
The method according to claim 6,
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 monoisoprene Propylene glycol monobutyl 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 tetrahydroperfuryl alcohol. By weight of the resist stripper composition.
The method according to claim 6,
The aprotic polar solvent may be selected from the group consisting of N-methylpyrrolidone (NMP), N-ethylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, (DMSO), sulfolane, triethylphosphate, tributylphosphate, dimethyl carbonate, ethylene carbonate, formamide, N-methylformamide, N, Amide, N-methylacetamide, N, N-dimethylacetamide, N- (2-hydroxyethyl) acetamide, 3- methoxy-N, N-dimethylpropionamide, 3- ) -N, N-dimethylpropionamide and 3-butoxy-N, N-dimethylpropionamide.
3. The method of claim 2,
(d) The corrosion inhibitor is selected from the group consisting of formic acid, acetic acid, propionic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, fumaric acid, glutaconic acid, trimellitic acid, tricarbalic acid, Maleic acid esters, malonic amide esters, maleic amide esters, fumaric amide esters, oxalic amide esters, malonic amide esters, maleic anhydride esters, But are not limited to, glutaric amide esters, acetic amide esters, lactic amide esters, citric amide esters, tartaric amide esters, gluconic amide esters, Dihydro-benzotriazol-1-yl] methyl] imino] bis (2,2 '- [[ Methanol, 2,2 '- [[[ethyl-1-hydrogen-benz Methyl] imino] bisethanol, 2,2 '- [[[methyl hydrogen-benzotriazol- Methyl] imino] biscarboxylic acid, 2,2 '- [[[methyl-1-hydrogen-benzotriazol- Methyl-1-hydrogen-benzotriazole, 6-methyl-4, 5-dihydro- 5,6,7-tetrahydro-1H-benzo [1,2,3] triazole, 4-methyl-4,5,6,7-tetrahydro-1H benzo [1,2,3] triazole, 5 -Methyl-4,5,6,7-tetrahydro-1H-benzo [1,2,3] triazole, 5,6-dimethyl-4,5,6,7-tetrahydro-1H- benzo [ 2,3] triazole, 4,6-dimethyl-4,5,6,7-tetrahydro-1H- benzo [1,2,3] triazole, 5-methyl-1-hydrogen-benzotriazole, 2 Dimethylphenol, 2,4,6-trimethylphenol, 2,6-diethylphenol, 2,6-diethyl-4-methylphenol, 2,6-dipropylphenol, 2,6- 4-methylphenol, 2,6-di-t-butylphenol, 2,4,6-tri- t-butylphenol, and 2,6-di-t-butyl-4-methylphenol.
3. The composition of claim 1 wherein, relative to the total weight of the composition,
(a) 0.001 to 3.0% by weight of an aminoalkylsilane compound;
(b) 0.1 to 20.0% by weight of an alkanolamine compound; And
(c) 80.0 to 99.8% by weight of a polar organic solvent.
11. The method of claim 10,
(d) 0.001 to 1.0% by weight of a corrosion inhibitor.
A method of manufacturing a display substrate comprising the step of cleaning a display substrate using the resist stripping liquid composition according to any one of claims 1 to 4.
A display substrate manufactured by the manufacturing method of claim 12.