KR20130128952A

KR20130128952A - A resist stripper composition for flat panel display

Info

Publication number: KR20130128952A
Application number: KR1020120053186A
Authority: KR
Inventors: 신혜라; 김성식; 김정현
Original assignee: 동우 화인켐 주식회사
Priority date: 2012-05-18
Filing date: 2012-05-18
Publication date: 2013-11-27

Abstract

The present invention (a) an organic phosphate represented by the following formula (1): (b) an alkali compound; (c) water-soluble polar solvents; And (d) relates to a resist stripper composition for a flat panel display comprising deionized water.
[Formula 1]

(Wherein R1 is an alkyl, alkenyl group or hydroxyalkyl group having 3 or more carbon atoms)
Moreover, this invention relates to the manufacturing method of the flat panel display board | substrate including the process of washing | cleaning a flat panel display board | substrate using the said resist stripper composition for display.

Description

Resist stripper composition for flat panel displays {A RESIST STRIPPER COMPOSITION FOR FLAT PANEL DISPLAY}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resist stripper composition having excellent residue removal capability of resist by dry / wet etching in the manufacturing process of a flat panel display substrate.

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, a reduction in wiring width is 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. In particular, 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 generated 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 the needs of such industries, new technologies are being published.

For example, Korean Patent Laid-Open Publication No. 10-2006-0028523 provides a photoresist stripper that does not cause corrosion of metal wiring including alcohol amine, glycol ether, N-methylpyrrolidone and a chelating agent. However, according to the present invention, even when the chelating agent does not peel off the resist, the color of the peeling liquid is changed 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 is visually confirmed. Causes problems that make it impossible.

In addition, Korean Patent Registration No. 10-0429920 provides a stripping solution composition comprising a nitrogen-containing organic hydroxy compound, a water-soluble organic solvent, water, and a benzotriazole-based compound. However, according to the present invention, although the anticorrosive performance of copper and copper alloy is excellent, there is a problem that the anticorrosive performance for aluminum and aluminum alloy is lowered.

KR 2006-0028523 A KR 0429920 B

The present invention is to solve the above problems, excellent in removing the residue of the resist by dry / wet etching during the manufacturing process of the flat panel display substrate, a Cu, Al simultaneous method resist stripper composition for flat panel display The purpose is to provide.

In order to achieve the above object,

The present invention (a) an organic phosphate represented by the following formula (1): (b) an alkali compound; (c) water-soluble polar solvents; And (d) deionized water, to provide a resist stripper composition for a flat panel display.

[Formula 1]

(Wherein R 1 is an alkyl, alkenyl or hydroxyalkyl group having 3 or more carbon atoms)

In addition, the present invention provides a method for manufacturing a flat panel display substrate comprising the step of cleaning the flat panel display substrate using the resist stripper composition for flat panel display.

The resist stripper composition for flat panel displays according to the present invention not only has excellent residue removal ability of the resist by dry / wet etching, but also has anticorrosion property against Cu and Al. In addition, when using the resist stripper composition for panel display of the present invention, it is possible to reduce the failure rate of the flat panel display device to reduce the cost required for the overall manufacturing process.

Hereinafter, the resist stripping liquid composition for a flat panel display according to the present invention will be described in detail.

The resist stripper composition for a flat panel display according to the present invention comprises (a) an organic phosphate represented by the following general formula (1): (b) an alkali compound; (c) water-soluble polar solvents; And (d) deionized water.

[Formula 1]

(a) organophosphates

In the present invention, the type of organic phosphoric acid represented by the following Chemical Formula 1 is preferably propylphosphonic acid, butyl phosphonic acid, t-butyl phosphonic acid, pentyl phosphonic acid, hexyl phosphonic acid, heptyl phospho Nic acid, octyl phosphonic acid, n-dodecyl phosphonic acid, etc. are mentioned. These may be used alone or in combination of two or more.

[Formula 1]

(Wherein, R1 is an alkyl, alkenyl group, hydroxyalkyl group having 3 or more carbon atoms.)

The compound of Chemical Formula 1 serves to prevent corrosion of metal wires including aluminum and / or copper, and particularly has excellent solubility in water and polar solvents and does not remain on the surface of the substrate, but is used in the prior art. Unlike the agent, no color change of the stripper composition is caused.

It is preferable that the compound of Formula 1 is 0.01 wt% to 3 wt% with respect to the total amount of the composition, and in case of 0.01 wt% or less, a decrease in metal anticorrosion ability occurs and the coating remains on the surface of the metal wiring when it contains more than 3 wt%. It can cause problems.

(b) alkali compounds

In the present invention, the alkali compound is preferably potassium hydroxide, sodium hydroxide, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, Carbonates, phosphates, ammonia and amines, and the like, and these may be used alone or in combination of two or more.

Examples of 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-aminoethoxy) ethanol and the like Alkoxyamine; 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 alkali compounds strongly penetrate into the polymer matrix of the deteriorated or crosslinked resist under various process conditions such as dry or wet etching, ashing or ion implant processing, and thus may be used in or between molecules. To break existing bonds. An empty space is formed in the structurally weak portion of the resist remaining on the substrate to deform the resist into an amorphous polymer gel mass so that the resist attached to the top of the substrate can be easily removed.

The alkali compound is preferably 2% to 20% by weight, more preferably 5% to 15% by weight based on the total weight of the composition. If it is less than 2% by weight, a problem of resist peeling force decreases, and if it is more than 20% by weight, a rapid corrosion rate improvement may be caused for a metal wiring made of aluminum or an aluminum alloy and copper or a copper alloy.

(c) water-soluble polar solvent

In the present invention, the water-soluble polar solvent includes a proton polar solvent and an aprotic polar solvent, and these may be used alone or in combination. Preferred 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 Alkylene glycol monoalkyl ethers, such as glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and te La hydroxy and the like hydroperoxide furyl alcohol, one kinds of these may be used alone or in combinations of two or more.

Preferred examples of the aprotic polar solvent include pyrrolidone compounds such as N-methyl pyrrolidone (NMP) and N-ethyl pyrrolidone; 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 dimethylsulfoxide (DMSO) and sulfolane; Phosphate compounds such as triethyl phosphate, tributyl phosphate and the like; Carbonate compounds such as dimethyl carbonate and ethylene carbonate; 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 water-soluble polar solvent serves to dissolve the resist polymer gelled by the alkali-based compound, and also facilitates the removal of the stripping solution by water in the rinsing process of deionized water after the stripping of the resist to remove the stripping solution and the dissolved resist. Minimize adsorption / reattachment. It is preferable that the water-soluble polar solvent is not too high or low in boiling point for proper peeling force, and can be mixed.

The water-soluble polar solvent is preferably 50% to 93% by weight, more preferably 60% to 85% by weight based on the total amount of the composition. When included in the content range as described above is also 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 the effect of increasing the number of treatment.

(d) deionized water

In the present invention, deionized water improves the activation rate of the alkali-based compound to increase the peeling rate, and compared to the composition containing no deionized water, the effect of improving the removal ability of the resist crosslinked or modified by the dry / wet etching process. You can get it.

The organic contaminants and the resist stripping solution remaining on the substrate in the rinsing process by deionized water mixed with the water-soluble polar solvent can be quickly and completely removed, which is advantageous in terms of cost.

Deionized water is preferably included 5 to 40% by weight based on the total weight of the composition. If it is less than 5% 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 40% by weight, the dissolution capacity of the resist is reduced to reduce the number of treatments. May cause corrosion

(e) corrosion inhibitors

In the present invention, the corrosion inhibitor serves to suppress corrosion of the metal wiring. In order to improve the corrosion protection of the metal, benzotriazole derivatives represented by the following Chemical Formula 2 may be further added.

(2)

(In the formula, R2, R3 and R4 are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an allyl group, an aryl group, an amino group, an alkylamino group, a nitro group, a cyano group, a mercapto group, an alkyl mercapto group, Monovalent group having a hydroxyl group, a hydroxyalkyl group, a carboxyl group, a carboxyalkyl group, an acyl group, an alkoxy group or a heterocycle)

Specific examples of the benzotriazole derivatives include 2,2 '-[[[benzotriazole] methyl] imino] bisethanol, 2,2'-[[[methyl-1 hydrogen-benzotriazol-1-yl] Methyl] imino] bismethanol, 2,2 '-[[[ethyl-1 hydrogen-benzotriazol-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] bismethylamine, 2,2 '-[[[amine-1 hydrogen-benzotriazol-1-yl] methyl] imino ] Bisethanol etc. are mentioned.

Corrosion inhibitor of the formula (2) is preferably included in an amount of 0.01 to 3% by weight, more preferably 0.01 to 2% by weight relative to the total weight of the composition. If it is less than 0.01% by weight, corrosion may occur in the metal wiring made of aluminum or aluminum alloy and copper or copper alloy in the stripping or deionized water rinsing process. Peel force may occur.

Although the dipping method is common as a method of removing a resist using the resist stripping liquid composition for flat panel displays of this invention, other methods, for example, the method by a spraying method, can also be used. As a 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 only washing with water is sufficient.

The resist stripper composition for flat panel displays of the present invention can be usefully used in the process of removing the resist for semiconductor or electronic products, especially flat panel displays.

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

Example 1 to 6 and Comparative Example 1 to 5: flat For panel display Resist Peeling liquid Preparation of the composition

The components shown in Table 1 below were mixed at the corresponding composition ratios to prepare resist stripper compositions for flat panels of Examples 1-6 and Comparative Examples 1-5.

a
Organophosphates b
Basic compound C
Water soluble organic solvent d
Deionized water E
Corrosion inhibitor Kinds Component (% by weight) Kinds Component (% by weight) Kinds Component (% by weight) Component (% by weight) Kinds Component (% by weight) Example 1 OPA 1.0 MEA 10 NMP
BDG 48
30 10 e-1 - Example 2 OPA 2.0 DEA 10 NMP
BDG 47
30 10 e-1 1.0 Example 3 OPA 2.0 DEA 10 NMP
BDG 47
20 20 e-1 1.0 Example 4 OPA 1.0 MDEA 10 NMP
BDG 58
20 10 e-1 1.0 Example 5 HPA 1.0 HEP 10 NMP
EDG 58
20 10 e-1 - Example 6 HPA 1.0 HEP 10 NMP
EDG 48
20 20 e-1 1.0 Comparative Example 1 OPA - MEA 10 NMP
BDG 50
20 20 e-1 - Comparative Example 2 OPA 1.0 - NMP
BDG 48
30 20 e-1 1.0 Comparative Example 3 OPA 2.0 DEA 20 NMP
BDG - 78 e-1 1.0 Comparative Example 4 OPA - DEA 10 NMP
BDG 49
20 20 e-1 1.0 Comparative Example 5 HEDP 2.0 DEA 10 NMP
BDG 47
30 10 e-1 -

OPA: octylphosphonic acid

HPA: hexylphosphonic acid

HEDP: 1-hydroxyethylidene-1,1-diphosphonic acid

MEA: Monoethanolamine

DEA: diethanolamine

MDEA: N-methyldiethanolamine

HEP: hydroxyethylpiperazine

NMP: N-methylpyrrolidone

BDG: diethylene glycol monobutyl ether

EDG: diethylene glycol monoethyl ether

e-1: 2,2 '-[[[ethyl-1H-benzotriazol-1-yl] methyl] imino] bisethanol

Experimental Example : flat For panel display Resist Peeling liquid Evaluation of the properties of the composition

1) Peeling force evaluation of peeling liquid

In order to confirm the peeling effect of the resist stripping composition, after forming a Mo / Al, Cu / Ti layer by using a thin film sputtering method on a glass substrate according to a conventional method, after forming a photoresist pattern, wet etching and Substrates were prepared by etching the metal film by dry etching. After the temperature of the resist stripping composition was kept constant at 50 ° C, the object was dipped 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), and the results are shown in Table 2 below, very good ◎, good ○, poor Is indicated by x.

2) Evaluation of peeling liquid metal wiring anticorrosion

To evaluate the corrosion protection ability of the resist stripper composition against metal wiring, a substrate exposed with Mo / Al and Cu / Ti wiring was used. The stripper composition was kept at 50 ° C. and the substrate was immersed for 30 minutes. Then, washing and drying were performed using a scanning electron microscope (SEM, Hitach S-4700). The results are shown in Table 2 below, with very good ◎, good ○, and poor x.

division Peel force Anticorrosion Al Cu Example 1 ◎ ◎ ○ Example 2 ◎ ◎ ◎ Example 3 ◎ ◎ ◎ Example 4 ○ ◎ ◎ Example 5 ○ ◎ ○ Example 6 ○ ◎ ◎ Comparative Example 1 ○ X X Comparative Example 2 X ○ ◎ Comparative Example 3 X ○ ○ Comparative Example 4 ○ X ○ Comparative Example 5 ○ X X

From the test results in Table 2, the compositions of Examples 1 to 6, which are the peeling liquid compositions of the present invention, are not only excellent in resist removal ability, but also anticorrosive to aluminum and copper, as compared to the compositions of Comparative Examples 1 to 5, respectively. It was confirmed that it is excellent.

Claims

(a) organophosphates represented by the following formula (1):
(b) an alkaline compound;
(c) water-soluble polar solvents; And
(d) A resist stripper composition for flat panel displays comprising deionized water.
[Formula 1]

The method of claim 1,
(e) A resist stripping liquid composition for a flat panel display, further comprising a corrosion inhibitor represented by the following formula (2).
(2)

(In the formula, R2, R3 and R4 are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an allyl group, an aryl group, an amino group, an alkylamino group, a nitro group, a cyano group, a mercapto group, an alkyl mercapto group, Monovalent group which has a hydroxyl group, a hydroxyalkyl group, a carboxyl group, a carboxyalkyl group, an acyl group, an alkoxy group, or a heterocyclic ring.)

The method according to claim 1, wherein the total amount of the composition is
(a) 0.01 wt% to 3 wt% of organic phosphoric acid represented by Formula 1;
(b) 2 wt% to 20 wt% of an alkali compound;
(c) 50% to 93% by weight of a water-soluble polar solvent; And
(d) 5 to 40 weight% of deionized water, The resist stripping liquid composition for flat panel displays characterized by the above-mentioned.

3. The method of claim 2,
(E) A resist stripper composition for a flat panel display comprising (e) 0.01 wt% to 3 wt% of a corrosion inhibitor represented by the formula (2).

3. The method according to claim 1 or 2,
The (a) organic phosphates include propylphosphonic acid, butylphosphonic acid, t-butylphosphonic acid, pentylphosphonic acid, hexylphosphonic acid, heptylphosphonic acid, octylphosphonic acid, n-dodecylphosphate A resist stripper composition for a flat panel display, characterized in that any one or a mixture of two or more selected from the group consisting of phonic acid.

3. The method according to claim 1 or 2,
The (b) alkali compound is potassium hydroxide, sodium hydroxide, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, carbonate, phosphate, A resist stripping liquid composition for a flat panel display, characterized in that any one or a mixture of two or more selected from the group consisting of ammonia, alkylamine, allylamine, alkanolamine, alkoxyamine and cyclic amine.

3. The method according to claim 1 or 2,
The water-soluble polar solvent (c) 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, polyethylene glycol mono Alkylene glycol monoalkyl ethers such as butyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, tetrahydroperfu Alcohol, N-methyl pyrrolidone (NMP), N-ethyl pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dipropyl-2-imidazolidinone, γ-butyro Lactone, dimethyl sulfoxide (DMSO), sulfolane, triethyl phosphate, tributyl phosphate, dimethyl carbonate, ethylenecarbonato, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N- Methylacetamide, N, N-dimethylacetamide, N- (2-hydroxyethyl) acetamide, 3-methoxy-N, N-dimethylpropionamide, 3- (2-ethylhexyloxy) -N, A resist stripping liquid composition for a flat panel display, characterized in that any one or a mixture of two or more selected from the group consisting of N-dimethylpropionamide and 3-butoxy-N, N-dimethylpropionamide.

3. The method of claim 2,
(E) The corrosion inhibitor is 2,2 '-[[[benzotriazole] methyl] imino] bisethanol, 2,2'-[[[methyl-1 hydrogen-benzotriazol-1-yl] methyl] Imino] bismethanol, 2,2 '-[[[ethyl-1 hydrogen-benzotriazol-1-yl] methyl] imino] bisethanol, 2,2'-[[[methyl-1 hydrogen-benzotria Zol-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] bismethylamine, 2,2 '-[[[amine-1 hydrogen-benzotriazol-1-yl] methyl] imino] bis Resist stripper composition for a flat panel display, characterized in that any one or a mixture of two or more selected from the group consisting of ethanol.

The manufacturing method of the flat panel display substrate containing the process of washing a flat panel display substrate using the resist stripping liquid composition for flat panel displays of Claim 1 or 2.