KR20130019729A

KR20130019729A - Cleaning solution composition for flat display device and cleaning method of flat panel display

Info

Publication number: KR20130019729A
Application number: KR1020110081864A
Authority: KR
Inventors: 방순홍; 윤효중; 신혜라
Original assignee: 동우 화인켐 주식회사
Priority date: 2011-08-17
Filing date: 2011-08-17
Publication date: 2013-02-27

Abstract

PURPOSE: A cleaning liquid composition for manufacturing a flat panel display is provided to have excellent particle removing force and to have excellent anti-corrosion effect for aluminum or aluminum alloy which is formed on a substrate. CONSTITUTION: A cleaning composition for a flat panel display comprises an oxyalkylamine compound indicated in chemical formula 1, an organophosphorus compound or a salt thereof, a sulfur-containing compound, a water-soluble polar solvent, and water. In chemical formula 1, n is an integer from 1-5; R1 is an alkyl, acryl, hydroxyalkyl, aryl, alkoxyalkyl, thiol-containing alkyl, or ether-containing substituent; each of R2 and R3 is an alkyl, acryl, hydroxyalkyl, aryl, aminoalkyl, alkoxy alkyl, hydroxyl, or amino group. When each of R2 and R3 has a C1-8, R2 and R3 can form a cyclic structure together with nitrogen which is bonded with R2 and R3.

Description

CLEANING SOLUTION COMPOSITION FOR FLAT DISPLAY DEVICE AND CLEANING METHOD OF FLAT PANEL DISPLAY}

The present invention relates to a cleaning liquid composition for a flat panel display device and a cleaning method for the flat panel display device.

Flat panel display devices, like semiconductor devices, are manufactured through processes such as film formation, exposure, and etching. However, during the manufacturing process, adhesion contamination due to very small particles having a size of 1 μm or less of various organic or inorganic substances occurs on the substrate surface. If such contamination is not cleaned, pinholes or pits of the film, disconnection or bridges of the wires are generated, and the production yield of the product is reduced.

Therefore, a cleaning process for removing contaminants takes place between each process. As the cleaning liquid used for the cleaning, Korean Patent Laid-Open Publication No. 2008-7003568 discloses a releasing agent composition for a semiconductor device composed of organic amine, organic phosphonic acid, linear sugar alcohol and residual water, but in a wiring made of copper or copper alloy. No ability to

In addition, the Republic of Korea Patent Publication No. 2002-0064489 relates to a combination of alkanol amine and an organic solvent, lacking the ability to remove organic contaminants and particles, precipitation problems when used for a long time in the case of catechol or gallic acid, a polyhydroxy benzene-based chelate compound May occur.

In addition, Korean Patent Laid-Open Publication No. 2006-7015165 is a cleaning liquid consisting of an organic acid, an organic alkali component, a surfactant, and water, and the cleaning liquid is a solution in an acidic range, and the removal of small organic matter and inorganic particles of 1 μm or less in the initial stage of cleaning. Insufficient sex, and there is a problem that does not exhibit an anticorrosive effect other than copper wiring.

Republic of Korea Patent Publication No. 2008-7003568 Republic of Korea Patent Publication No. 2002-0064489 Republic of Korea Patent Publication No. 2006-7015165

The present invention removes organic contaminants or particles on a glass substrate or a metal film in a process of manufacturing a substrate for a flat panel display, and includes copper wiring, copper alloy wiring, aluminum wiring, or aluminum formed on the substrate for a flat panel display. An object of the present invention is to provide a cleaning liquid composition for a flat panel display device which does not corrode alloy wirings and a method for cleaning the flat panel display device using the same.

In order to achieve the above object, the present invention provides a cleaning liquid composition for a flat panel display device comprising an oxyalkylamine compound, an organic phosphoric acid or a salt compound thereof, a sulfur-containing compound, a water-soluble polar solvent and water represented by the formula (1).

[Chemical Formula]

In Formula 1,

n is 1 to 5,

R ₁ is an alkyl group, acyl group, hydroxyalkyl group, aryl group, alkoxyalkyl group, thiol-containing alkyl group or ether-containing substituent,

R ₂ and R ₃ are each independently hydrogen, an alkyl group, an acyl group, a hydroxyalkyl group, an aryl group, an allyl group, an aminoalkyl group, an alkoxyalkyl group, a hydroxyl group or an amino group,

When R ₂ and R ₃ independently have 1 to 8 carbon atoms, R ₂ and R ₃ together with the nitrogen bonded to R ₂ and R ₃ may form a ring structure.

In addition, the present invention provides a cleaning method of a flat panel display device using the cleaning liquid composition for a flat panel display device.

According to the present invention, the organic contaminants or particles can be removed from the surface of the flat panel display substrate on which the glass or metal film is deposited, and corrosion of the aluminum or aluminum alloy formed on the substrate can be prevented.

In particular, it does not contain an azole anticorrosive, there is no corrosion on metal wiring made of copper or a copper alloy, and the problem that may occur during the addition of a post process or a process caused by the residual anticorrosive on the copper metal surface can be minimized. have.

In addition, the rinsing properties are excellent after use of the cleaning solution compared to the cleaning solution containing a large amount of deionized water, which has a high content of organic compounds.

Hereinafter, the present invention will be described in detail.

The present invention provides a cleaning liquid composition for a flat panel display device comprising an oxyalkylamine compound, an organic phosphoric acid or a salt compound thereof, a sulfur-containing compound, a water-soluble organic solvent, and water represented by the following Chemical Formula 1.

[Formula 1]

In Formula 1, n is 1 to 5, R ₁ is an alkyl group, acyl group, hydroxyalkyl group, aryl group, alkoxyalkyl group, thiol-containing alkyl group or ether-containing substituent, R ₂ and R ₃ are independently hydrogen, Alkyl group, acyl group, hydroxyalkyl group, aryl group, allyl group, aminoalkyl group, alkoxyalkyl group, hydroxyl group or amino group. Furthermore, when R ₂ and R ₃ independently have 1 to 8 carbon atoms, R ₂ and R ₃ together with nitrogen bonded to R ₂ and R ₃ may form a ring structure.

0.01 to 5% by weight of the oxyalkylamine compound represented by Formula 1, 0.001 to 5% by weight of the organophosphoric acid or its salt compound, 0.01 to 10% by weight of sulfur-containing compound, water-soluble based on the total weight of the cleaning liquid composition for a flat panel display device It is preferred that 0.01 to 10% by weight of organic solvent and residual amount of water are included.

The oxyalkylamine compound represented by Chemical Formula 1 may remove particles, organic contaminants, etc. as a basic substance, and may contain an oxygen atom to prevent corrosion of copper when used alone or in combination with other amines. Indicates.

The amine that can be used in admixture with the oxyalkylamine compound is preferably at least one selected from the group consisting of primary amine, secondary amine, tertiary amine and alkanol amine, but is not limited thereto. Specifically, the primary amine is preferably methylamine, ethylamine and monoisopropylamine, and the secondary amine is preferably diethylamine, diisopropylamine and dibutylamine, and the tertiary amine is trimethylamine, Triethylamine, triisopropylamine, tributylamine and the like are preferred. In addition, alkanol amines are choline, monoethanolamine, diethanolamine, 2-aminoethanol, 2- (ethylamino) ethanol, 2- (methylamino) ethanol, N-methyldiethanolamine, dimethylaminoethanol, diethyl Aminoethanol, nitrilo triethanol, 2- (2-aminoethoxy) ethanol, 1-amino- 2-propanol, triethanolamine, monopropanolamine, dibutanolamine, and the like are preferable.

The oxyalkylamine compound is preferably included in an amount of 0.01 to 5% by weight, and more preferably 0.05 to 2% by weight, based on the total weight of the composition. When the content of the oxyalkylamine compound is less than 0.01% by weight, the activity in the cleaning liquid is lowered to reduce the particle removal effect, and sufficient cleaning effect cannot be achieved, and when it exceeds 2% by weight, copper, copper alloy, aluminum or aluminum There is a problem that the corrosion on the wiring including the alloy is increased.

The oxyalkylamine compound represented by Formula 1 is aminoethoxyethanol, aminopropoxyethanol, aminobutoxyethanol, dimethylaminoethoxyethanethiol, diethylaminoethoxyethanethiol, dipropylaminoethoxyethanethiol, di Butylaminoethoxyethanethiol, dimethylaminoethoxyethanol, diethylaminoethoxyethanol, dipropylaminoethoxyethanol, dibutylaminoethoxyethanol, N- (methoxymethyl) morpholine, N- (ethoxymethyl Morpholine, N- (methoxyethanol) morpholine, N- (ethoxyethanol) morpholine and N- (butoxyethanol) morpholine are preferably one or more selected from the group consisting of amino, more preferably amino It is preferable that it is ethoxy ethanol or dimethylamino ethoxy ethanol.

The organophosphoric acid or its salt compound binds strongly with inorganic ions and disperses the impurity particles so as not to aggregate with each other. According to these properties, the organophosphoric acid or its salt compound is excellent in removing the organic or inorganic contaminants that may occur during the cleaning process. In addition, the organophosphoric acid or a salt compound thereof also serves as a chelate compound for aluminum wiring or aluminum alloy wiring to prevent corrosion of the wiring. In addition, it also serves to adjust the overall pH of the cleaning liquid composition, thereby simultaneously exhibiting metal corrosion prevention and cleaning effects.

The organophosphoric acid compound may be methyldiphosphonic acid, aminotri (methylenephosphonic acid), ethylidenediphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1-hydroxypropylidene-1,1 -Diphosphonic acid, 1-hydroxybutylidene-1,1-diphosphonic acid, ethylaminobis (methylenephosphonic acid), 1,2-propylenediaminetetra (methylenephosphonic acid), dodecylaminobis (methylenephosph) Phonic acid), nitrotris (methylenephosphonic acid), ethylenediaminebis (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), hexenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) and cyclo It is preferably one or more selected from the group consisting of hexanediaminetetra (methylenephosphonic acid). In addition, the salt compound of the organophosphoric acid is preferably a potassium salt or a sodium salt.

The content of the organophosphoric acid or its salt compound is preferably 0.001% to 5% by weight, more preferably 0.01% to 2% by weight based on the total weight of the cleaning liquid composition. When the content is less than 0.001% by weight, it is difficult to expect the cleaning effect and the effect as a chelating compound. When the content is more than 5% by weight, the cleaning and anticorrosive effect does not increase linearly with the content, and copper wiring or The adverse effect of increased corrosion on the copper alloy wiring is generated.

The sulfur-containing compound serves as a corrosion inhibitor for inhibiting corrosion of the metal film and a contact angle lowering agent on the surface of the metal film. The sulfur-containing compound is a generic term for a compound containing a mercapto group (-SH), and specific examples thereof include 3-mercaptopropane-1,2-diol (thioglycerol), dithioglycerol, 2-mercaptoethanol, 3-mercapto-1-propanol, 2-mercapto-2-butanol, 2-mercaptophenol, 4-mercaptophenol, acetylmercaptan (thioacetic acid), 2-mercaptoacetic acid (thioglycolic acid), 2 Mercaptobenzoic acid (thiosalicylic acid), mercapto succinic acid, 3-mercaptopropionic acid, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptoimida It is preferably at least one selected from the group consisting of sol, 2-mercapto-5-methylbenzimidazole, 2-mercaptotigotinic acid and 3-mercaptopropyl-trimethoxysilane, more preferably 2-mer Captoethanol, 3-mercapto-1-propanol, 3-mercaptopropane-1,2-diol, 2-mercaptoacetic acid, acetylmercaptan and 2-mercaptobenzoic acid Preferably at least one selected from the group.

The sulfur-containing compound is preferably contained in 0.01 to 10% by weight, more preferably 0.1 to 5% by weight relative to the total weight of the cleaning liquid composition. When the content of the sulfur compound is 0.01 to 10% by weight can effectively inhibit the corrosion of the metal wiring. When the content of the sulfur compound is less than 0.01% by weight, it is difficult to obtain the effect of preventing corrosion of the metal and the contact angle lowering effect due to the addition of the sulfur compound, and when the content exceeds 10% by weight, the anticorrosive effect on the metal wiring is no longer increased. If used in excess of this there is an economic problem.

It is preferable that the water contained in the said cleaning liquid composition is deionized water. By including the deionized water, the rinsing properties after the use of the cleaning solution is superior to the cleaning solution with a high content of the organic compound, the handling is easy, there is an environmentally beneficial effect.

The water-soluble polar solvent is a protic polar solvent and an aprotic polar solvent, these may be used alone or in combination.

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 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 monomethyl ether, polyethylene glycol monoethyl Ether, polyethyleneglycol monopropyl ether, polyethyleneglycol monobutyl ether, propyleneglycol monomethyl ether, dipropyleneglycol monomethyl ether, tripropyleneglycol monomethyl ether and propyleneglycol monomethyl Is at least one selected from the group consisting of Terre acetate is preferred.

The aprotic polar solvent includes 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; 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, and 3-butoxy-N, N-dimethylpropionamide It is preferred that there is at least one.

The water-soluble polar solvent is preferably included in 0.01 to 10% by weight based on the total weight of the cleaning liquid composition, more preferably 0.1 to 5% by weight. When the content of the water-soluble polar solvent is less than 0.01% by weight, the solubility of the cleaning solution composition to the contaminant is insignificant, and when used in excess of 10% by weight, the economical and environmental benefits due to the use of the cleaning solution are low, and the surface of the substrate after the cleaning solution is used. As water-soluble polar solvents remain in the membrane, it is difficult to expect a synergistic effect due to the use of a cleaning liquid.

The present invention provides a cleaning method for a flat panel display device using the cleaning liquid composition for the flat panel display device. The cleaning method of the flat panel display device is preferably a spray method, a spin method, a dipping method, a dipping method using ultrasonic waves, or the like. At this time, the cleaning using the cleaning liquid composition for a flat panel display at a temperature of 20 to 80 ℃ shows the most excellent cleaning effect, more preferably at 20 to 50 ℃. It is also preferable to clean the substrate for 30 seconds to 10 minutes using the cleaning liquid composition of the present invention.

Hereinafter, the present invention will be described in detail by way of examples.

However, the following examples are illustrative of the present invention, and the present invention is not limited to the following examples.

< Example 1>

0.1 wt% of aminoethoxyethanol as oxyalkylamine, 0.1 wt% of thioglycerol as a sulfur-containing compound, 0.5 wt% of diethylene glycol monomethyl ether as a water-soluble polar solvent, and 1-hydroxyethyl as organophosphate 0.05% by weight of den-1,1-diphosphonic acid and the remaining amount of water were mixed and stirred to prepare a cleaning liquid composition.

< Example 2>

In Example 1, except that 0.2% by weight of thioglycerol was carried out in the same manner as in Example 1 to prepare a cleaning liquid composition.

< Example 3>

In Example 2, except that the water-soluble polar solvent is 0.5% by weight of N-methylpyrrolidone was carried out in the same manner as in Example 2 to prepare a cleaning liquid composition.

< Example 4>

In Example 1, except that the amino ethoxy ethanol is 0.5% by weight, thioglycerol is 0.5% by weight, the organophosphoric acid compound is 1-hydroxyethylidene-1,1-diphosphonic acid 0.1% by weight The cleaning solution composition was prepared in the same manner as in Example 1 above.

< Example 5>

In Example 1, the cleaning solution was carried out in the same manner as in Example 1 except that the sulfur-containing compound is 0.1% by weight of 3-mercapto-1-propanol, and 0.05% by weight of the organophosphoric acid compound is aminotri (methylenephosphonic acid) The composition was prepared.

< Example 6>

In Example 2, to prepare a cleaning liquid composition in the same manner as in Example 2 except that the oxyalkylamine is 0.1% by weight of dimethylaminoethoxyethanol, 0.5% by weight of the water-soluble polar solvent triethylene glycol monomethyl ether. It was.

< Example 7>

In Example 6, except that the water-soluble polar solvent is 0.5% by weight of 1,3-dimethyl-2-imidazolidinone was carried out in the same manner as in Example 6 to prepare a cleaning liquid composition.

< Example 8>

In Example 7, the cleaning solution was carried out in the same manner as in Example 7, except that the sulfur-containing compound was 0.2% by weight of 3-mercapto-1-propanol and 0.05% by weight of the organophosphate compound was aminotri (methylenephosphonic acid). The composition was prepared.

< Example 9>

In Example 7, the cleaning liquid composition was prepared in the same manner as in Example 7, except that the oxyalkylamine was 0.5% by weight of dimethylaminoethoxyethanol and the sulfur-containing compound was 0.5% by weight of thioglycerol.

< Example 10>

Example 9, except that the water-soluble polar solvent is 0.5% by weight of diethylene glycol monomethyl ether, the organophosphoric acid compound is 0.12% by weight of 1-hydroxyethylidene-1,1-diphosphonic acid The cleaning solution composition was prepared in the same manner as in Example 9.

< Comparative example 1>

0.4% by weight of tetramethylammonium hydroxide, 0.2% by weight of 3-mercapto-1-propanol, 0.5% by weight of diethylene glycol monomethyl ether, and 1-hydroxyethylidene-1 based on the total weight of the composition 0.05% by weight of 1-diphosphonic acid and the remaining amount of water were mixed and stirred to prepare a cleaning liquid composition.

< Comparative example 2>

In Comparative Example 1, except that the oxyalkylamine is 0.5% by weight of monoethanolamine was carried out in the same manner as in Comparative Example 1 to prepare a cleaning liquid composition.

< Comparative example 3>

In Comparative Example 1, except that the oxyalkylamine is 10.0% by weight of amino ethoxy ethanol was carried out in the same manner as in Comparative Example 1 to prepare a cleaning liquid composition.

< Comparative example 4>

0.2 wt% of thioglycerol as a sulfur-containing compound, 0.5 wt% of triethylene glycol monomethyl ether as a water-soluble polar solvent, and 0.1 wt% of 1-hydroxyethylidene-1,1-diphosphonic acid as an organophosphate compound And the remaining amount of water was mixed and stirred to prepare a cleaning liquid composition.

< Comparative example 5>

0.5 wt% of aminoethoxyethanol as oxyalkylamine, 0.5 wt% of triethylene glycol monomethyl ether as water-soluble polar solvent, and 1-hydroxyethylidene-1,1-diphosphonic acid as organophosphate compound 0.1 wt% and the remaining amount of water were mixed and stirred to prepare a cleaning liquid composition.

< Comparative example 6>

0.5 wt% of aminoethoxyethanol with oxyalkylamine, 0.2 wt% of thioglycerol with sulfur-containing compound, 0.5 wt% triethylene glycol monomethyl ether with water-soluble polar solvent, and the remaining water with respect to the total weight of the composition. Was prepared.

Oxyalkylamine Sulfur-containing compound Water soluble polar solvent Organophosphate compounds water Kinds weight% Kinds weight% Kinds weight% Kinds weight% weight% Example 1 AEE 0.1 TGL 0.1 MDG 0.5 HEDP 0.05 99.25 Example 2 AEE 0.1 TGL 0.2 MDG 0.5 HEDP 0.05 99.15 Example 3 AEE 0.1 TGL 0.2 NMP 0.5 HEDP 0.05 99.15 Example 4 AEE 0.5 TGL 0.5 MDG 0.5 HEDP 0.1 98.40 Example 5 AEE 0.1 MPOH 0.1 MDG 0.5 ATMP 0.05 99.25 Example 6 DAEE 0.1 TGL 0.2 MTG 0.5 HEDP 0.05 99.15 Example 7 DAEE 0.1 TGL 0.2 DMI 0.5 HEDP 0.05 99.15 Example 8 DAEE 0.1 MPOH 0.2 DMI 0.5 ATMP 0.05 99.15 Example 9 DAEE 0.5 TGL 0.5 DMI 0.5 HEDP 0.05 98.45 Example 10 DAEE 0.5 TGL 0.5 MDG 0.5 HEDP 0.12 98.38 Comparative Example 1 TMAH 0.4 MPOH 0.2 MDG 0.5 HEDP 0.05 98.85 Comparative Example 2 MEA 0.5 MPOH 0.2 MDG 0.5 HEDP 0.05 98.75 Comparative Example 3 AEE 10 TGL 0.2 MDG 0.5 HEDP 0.05 89.25 Comparative Example 4 - - TGL 0.2 MTG 0.5 HEDP 0.1 99.20 Comparative Example 5 AEE 0.5 - - MTG 0.5 HEDP 0.1 98.90 Comparative Example 6 AEE 0.5 TGL 0.2 MTG 0.5 - - 98.80 AEE: aminoethoxyethanol
DAEE: Dimethylaminoethoxyethanol
TMAH: Tetramethylammonium Hydroxide
MEA: Monoethanolamine
TGL: Thioglycerol
MPOH: 3-mercapto-1-propanol
MDG: Diethylene Glycol Monomethyl Ether
NMP: N-methylpyrrolidone
MTG: Triethylene Glycol Monomethyl Ether
DMI: 1,3-dimethyl-2-imidazolidinone
HEDP: 1-hydroxyethylidene-1,1-diphosphonic acid
ATMP: aminotri (methylenephosphonic acid)

< Experimental Example >

1. Aluminum, copper etching rate evaluation

Glass substrates formed of aluminum having a thickness of 2000 kPa and copper having a thickness of 2500 kPa were immersed for 30 minutes at room temperature (25 ° C) in the cleaning liquid compositions prepared in Examples 1 to 10 and Comparative Examples 1 to 6. The thicknesses of the aluminum and copper films were measured before and after immersion and the dissolution rates of the aluminum and copper films were calculated from the thickness change of the films.

Corrosion evaluation was expressed as excellent (◎) when the dissolution rate was less than 2 kPa / min, good (○) when less than 5 kPa / min, (△) when less than 10 kPa / min and poor (kPa) when 10 kPa / min or more.

2. of organic pollutants Removal power evaluation

In order to evaluate the removal power of organic contaminants, the fingerprint substrate was contaminated with a human fingerprint on a 5 cm x 5 cm glass substrate, and the contaminated substrate was sprayed at room temperature (25 ° C.) for 1 minute using a glass substrate cleaning apparatus. It wash | cleaned with the cleaning liquid composition of 1-10 and Comparative Examples 1-6. After washing for 30 seconds in ultrapure water and dried with nitrogen.

When the organic contaminants were removed (○) and not removed (x), respectively.

3. Air Pollutants Removal power evaluation

A glass substrate containing copper having a thickness of 2500 kPa was left in the air for 24 hours to contaminate various organic materials, inorganic materials, and particles in the air, and 0.5 µl of ultrapure water was dropped on the glass substrate to measure the contact angle before cleaning. Subsequently, the cleaning liquid composition of Examples 1 to 10 and Comparative Examples 1 to 6 was cleaned at room temperature (25 ° C.) for 1 minute using a spray-type glass substrate cleaning device. After washing for 30 seconds in ultrapure water, and dried with nitrogen and drop the 0.5μl of ultrapure water on the glass substrate to measure the contact angle after washing. Good (◎) when the contact angle is reduced by more than 40 °, good (○) when the contact angle is reduced by 30 ° to 40 °, poor (△) when reduced by 20 ° to 30 ° and poor when reduced by less than 20 ° ( X was evaluated.

4. particle Removal power evaluation

The glass substrate was contaminated with a submicron silicon nitride particle solution and spin dried at 3000 rpm for 1 minute. Thereafter, using the cleaning solution compositions prepared in Examples 1, 4, 6, 9 and Comparative Examples 3 to 5, the cleaning of the glass substrate contaminated with silicon nitride particle solution was performed at room temperature (25 ° C.) for 1 minute. . After washing for 30 seconds in ultrapure water and dried with nitrogen. The number of particles before and after washing was measured by a particle size measuring instrument (Topcon, WM-1500) of 0.1 μm or more.

Al etching rate
(Å / min) Cu etching rate
(Å / min) Organic fingerprint Glass substrate contact angle Copper Substrate Contact Angle Example 1 ○ ○ ○ ◎ ◎ Example 2 ○ ◎ ○ ◎ ◎ Example 3 ○ ◎ ○ ◎ ◎ Example 4 ○ ◎ ○ ◎ ◎ Example 5 ○ ○ ○ ◎ ◎ Example 6 ◎ ◎ ○ ◎ ◎ Example 7 ◎ ◎ ○ ◎ ◎ Example 8 ○ ○ ○ ◎ ◎ Example 9 ◎ ◎ ○ ◎ ◎ Example 10 ◎ ◎ ○ ◎ ◎ Comparative Example 1 X X ○ ◎ ◎ Comparative Example 2 X X ○ ◎ ◎ Comparative Example 3 X X ○ ◎ ◎ Comparative Example 4 ○ X X △ ○ Comparative Example 5 X X X △ ○ Comparative Example 6 X △ X △ △

Number of particles before cleaning Number of particles after cleaning Removal rate (%) Example 1 2330 410 82 Example 4 2630 315 88 Example 6 2560 427 83 Example 9 2851 307 89 Comparative Example 3 2510 1620 35 Comparative Example 4 2351 367 84 Comparative Example 5 2621 1743 33

As shown in Table 2, the etching rates of aluminum and copper of the cleaning liquid compositions of Examples 1 to 10 were evaluated as good or better, and showed excellent results in the evaluation of the organic fingerprint and the contact angle. In addition, as shown in Table 3, the particle removal rate of the cleaning liquid compositions prepared in Examples 1, 4, 6 and 9 showed a very good result of 80% or more.

Claims

Cleaning liquid composition for a flat panel display device comprising an oxyalkylamine compound, an organic phosphoric acid or a salt compound thereof, a sulfur compound, a water-soluble polar solvent and water represented by the formula (1).
[Formula 1]

In Chemical Formula 1,
n is 1 to 5,
R ₁ is an alkyl group, acyl group, hydroxyalkyl group, aryl group, alkoxyalkyl group, thiol-containing alkyl group or ether-containing substituent,
R ₂ and R ₃ are each independently hydrogen, an alkyl group, an acyl group, a hydroxyalkyl group, an aryl group, an allyl group, an aminoalkyl group, an alkoxyalkyl group, a hydroxyl group or an amino group,
When R ₂ and R ₃ independently have 1 to 8 carbon atoms, R ₂ and R ₃ together with the nitrogen bonded to R ₂ and R ₃ may form a ring structure.

The method according to claim 1, 0.01 to 5% by weight of the oxyalkylamine compound represented by the formula (1), 0.001 to 5% by weight of the organophosphoric acid or its salt compound, 0.01 to 10% by weight sulfur-containing compound, water-soluble polarity A cleaning liquid composition for a flat panel display, characterized in that 0.01 to 10% by weight of a solvent and a residual amount of water are contained.

The oxyalkylamine compound represented by the formula (1) is aminoethoxyethanol, aminopropoxyethanol, aminobutoxyethanol, dimethylaminoethoxyethanethiol, diethylaminoethoxyethanethiol, dipropylamino Methoxyethane thiol, dibutylaminoethoxyethanethiol, dibutylaminoethoxyethanol, dimethylaminoethoxyethanol, diethylaminoethoxyethanol, dipropylaminoethoxyethanol, dibutylaminoethoxyethanol, N- (meth Methoxymethyl) morpholine, N- (ethoxymethyl) morpholine, N- (methoxyethanol) morpholine, N- (ethoxyethanol) morpholine and N- (butoxyethanol) morpholine Cleaning liquid composition for a flat panel display characterized in that at least one.

The method of claim 1, wherein the organophosphate compound is methyldiphosphonic acid, aminotri (methylenephosphonic acid), ethylidenediphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1-hydroxypropyl Lidene-1,1-diphosphonic acid, 1-hydroxybutylidene-1,1-diphosphonic acid, ethylaminobis (methylenephosphonic acid), 1,2-propylenediaminetetra (methylenephosphonic acid), dodecyl Aminobis (methylenephosphonic acid), nitrotris (methylenephosphonic acid), ethylenediaminebis (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), hexenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylene Phosphonic acid) and cyclohexanediaminetetra (methylenephosphonic acid), at least one selected from the group consisting of cleaning liquid composition for a flat panel display device.

The cleaning liquid composition of claim 1, wherein the organophosphate compound is a potassium salt or a sodium salt.

The method according to claim 1, wherein the sulfur-containing compound is 3-mercaptopropane-1,2-diol (thioglycerol), dithioglycerol, 2-mercaptoethanol, 3-mercapto-1-propanol, 2-mercapto-2 Butanol, 2-mercaptophenol, 4-mercaptophenol, acetylmercaptan (thioacetic acid), 2-mercaptoacetic acid (thioglycolic acid), 2-mercaptobenzoic acid (thiosalicylic acid), mercapto succinic acid , 3-mercaptopropionic acid, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptoimidazole, 2-mercapto-5-methylbenzimidazole, 2 A cleaning liquid composition for a flat panel display device, characterized in that at least one selected from the group consisting of mercaptothigotinic acid and 3-mercaptopropyl-trimethoxysilane.

The method of claim 1, wherein the water-soluble 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, 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 monoethyl ether, polyethylene glycol monopropyl ether, polyethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether and propylene Cleaning liquid composition for a flat panel display device, characterized in that at least one selected from the group consisting of glycol monomethyl ether acetate.

The method of claim 1, wherein the water-soluble polar solvent is N-methyl pyrrolidone, N-ethyl pyrrolidone, 1,3-dimethyl- 2-imidazolidinone, 1,3-dipropyl-2-imidazolidinone , γ-butyrolactone, dimethyl sulfoxide, sulfolane, triethyl phosphate, tributyl phosphate, dimethyl carbonate, ethylene carbonato, 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 cleaning liquid composition for a flat panel display device, characterized in that at least one selected from the group consisting of N, N-dimethylpropionamide and 3-butoxy-N, N-dimethylpropionamide.

A flat panel display device cleaning method using the cleaning liquid composition for a flat panel display device of claim 1.