KR20120029043A - Composition for cleaning flat panel display and cleaning method using the same - Google Patents

Abstract

PURPOSE: A composition for cleaning flat panel display is provided to have excellent removing force of organic pollutants and particles, and to be easy to handle by including a plurality of a large amount of deionized water. CONSTITUTION: A composition for cleaning flat panel display comprises 0.01-20 weight% of fluorine-containing compound, 0.1-40 weight% of water-soluble organic solvent, 0.01-20 weight% of carboxylic acid based copolymer and water on the basis of total weight of the composition. The fluorine-containing compound is selected from hydrofluoric acid, ammonium fluoride, ammonium hydrogen fluoride, tetramethyl ammonium fluoride, tetraethyl ammonium fluoride, fluroboric acid, and fluorobenzen.

Description

COMPOSITION FOR CLEANING FLAT PANEL DISPLAY AND CLEANING METHOD USING THE SAME

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning composition suitable for removing organic contaminants, particles, and polishing debris generated during polishing of a glass substrate in a manufacturing process of a flat panel display substrate, and a cleaning method using the same.

A flat panel display (FPD), which is represented by a liquid crystal display, is manufactured through processes such as film formation, exposure, and etching, and in each manufacturing process, very small particles having a size of 1 μm or less, such as various organic materials and inorganic materials, on the substrate surface. Are attached, causing contamination. Since contamination by these particles lowers the yield of the device, it is necessary to reduce as much as possible before entering the post-process.

Therefore, cleaning to remove contaminants is performed between the steps, and many proposals have been made for cleaning liquids for this purpose.

For example, Korean Patent Laid-Open Publication No. 2007-0117624 discloses a composition for removing a bulk photoresist comprising an organic solvent, an acidifying agent selected from fluorine ions, an inorganic or organic acid, and water, and Korean Patent Laid-Open Publication No. 2009-0012953 The present invention discloses a silicon oxide film etching composition, which is an etching solution for a semiconductor device including an organic solvent, an organic acid having at least one carboxyl group, a fluorine compound, and an inorganic acid, but there are economical and environmental problems due to the use of a large amount of organic solvent. In the case of an organic acid having a carboxyl group, penetration into organic contaminants and a dissolving power are lower than those of a carboxylic acid copolymer.

An object of the present invention is to provide a cleaning composition and a cleaning method suitable for removing organic contaminants or particles on an initial glass substrate and polishing debris generated during polishing of a glass substrate in a manufacturing process of a flat panel display substrate.

The present invention provides a glass substrate cleaning composition comprising a fluorine compound, a water-soluble organic solvent, a carboxylic acid copolymer and water.

Moreover, this invention provides the glass substrate cleaning method using the said glass substrate cleaning composition.

The cleaning composition of the present invention is excellent in removing organic contaminants and particles on the initial glass substrate surface in the manufacturing process of the flat panel display substrate, and is effective in removing polishing residues of the SiO ₂ component generated during polishing of the glass substrate. Deionized water is included for easy handling.

Figure 1a is a photograph showing a before the SiO ₂ particles are removed using the cleaning composition of Example 10, Figure 1b is a photograph showing the after the SiO ₂ particles have been removed by using the cleaning composition of Example 10.
FIG. 2A is a photograph showing the removal of SiO ₂ particles using the cleaning composition of Comparative Example 2, and FIG. 2B is a photograph showing the removal of SiO ₂ particles using the cleaning composition of Comparative Example 2. FIG.

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

The glass substrate cleaning composition of the present invention is characterized by comprising a fluorine compound, a water-soluble organic solvent, a carboxylic acid copolymer and water.

The fluorine-based compound is hydrofluoric acid (HF), ammonium fluoride (NH4F), acidic ammonium fluoride (NH ₄ HF ₂ ), tetramethyl ammonium fluoride ((CH ₃ ) ₄ NF), tetraethyl ammonium fluoride ((CH ₃ CH ₂ ) ₄ NF), it is preferable to use one or more compounds selected from fluoroboric acid, fluorobenzene, and the like, but is not limited thereto.

The content of the fluorine-based compound is preferably 0.01 to 20% by weight, more preferably 0.1 to 10% by weight based on the total weight of the composition.

If the content of the fluorine-based compound is less than 0.01% by weight can not be expected to increase the dissolving power to contaminants due to the glass component of the cleaning composition, when used in excess of 20% by weight of the glass substrate due to excessive glass etching effect due to the use of the cleaning agent The problem arises that the surface smoothness of is changed.

The water-soluble organic solvent is ethylene glycol monobutyl ether (BG), diethylene glycol monoethyl ether (carbitol), diethylene glycol monobutyl ether (BDG), dipropylene glycol monomethyl ether (DPM), dipropylene glycol monoethyl Ether (MFDG), triethylene glycol monobutyl ether (BTG), triethylene glycol monoethyl ether (MTG), propylene glycol monomethyl ether (MFG), N-methylpyrrolidone (NMP), 1,3-dimethyl- 2-imidazolidinone (DMI), dimethylsulfoxide (DMSO), dimethylacetamide (DMAc), dimethylformamide (DMF), tetrahydrofurfuryl alcohol, isophorone, diethyladipate, dimethylglutarate, It is preferable to use at least one compound selected from the group consisting of sulfolane, gamma-butyllactone (GBL) and mixtures thereof.

The content of the water-soluble organic solvent is preferably 0.1 to 40% by weight, more preferably 1 to 30% by weight based on the total weight of the composition.

If the content of the water-soluble organic solvent is less than 0.1% by weight, it is not expected to increase the dissolving power of the cleaning composition to the organic contaminants by the addition of the solvent, if it exceeds 40% by weight economical and environmental benefits due to the use of the cleaning agent Can't expect

The carboxylic acid-based copolymer controls the activity of the fluorine-based compound, not only increases the penetration of the organic compound, but also prevents contaminants from resorbing to the substrate surface. The carboxylic acid-based copolymer preferably includes a structural unit represented by the following formula (1).

[Formula 1]

In Chemical Formula 1, R ₁ to R ₃ may be the same or different, and represent a hydrogen atom, a methyl group, an ethyl group, or (CH ₂ ) m ₂ COOM ₂ , M ₁ and M ₂ may be the same or different, and hydrogen An alkyl ammonium group substituted with an atom, an alkali metal, an alkaline earth metal, an ammonium group, an alkylammonium group or a substituent, m ₁ and m ₂ represent an integer of 0 to 2,

Wherein the alkali metal is Li, Na, K, Rb, Cs or Fr and the alkaline earth metal is Ca, Sr, Ba or Ra.

Examples of the carboxylic acid copolymer include polyacrylic acid polymer (PAA), polymethyl (meth) acrylic acid copolymer (PMAA), polyacrylic acid maleic acid copolymer (PAMA), polymethyl acrylate (meth) acrylic acid copolymer (PAMAA), Polymaleic acid copolymer (PMA), Polymethyl (meth) acrylic acid maleic acid copolymer (PMAMA), these salts, etc. are mentioned.

The carboxylic acid-based copolymer is preferably contained in an amount of 0.01 to 20% by weight based on the total weight of the composition in terms of activity control of the fluorine-based compound, more preferably 0.1 to 10% by weight. .

In addition, organic phosphoric acid or salts thereof may be used as the additional component.

The organophosphate compound has an excellent permeability to contaminants, has an effect on the removal of organic contaminants or particles located on the glass substrate, and has a property to disperse the impurity particles together with the carboxylic acid-based copolymer. In addition, it serves to remove metal contaminants by acting as a complexing agent for metal components.

The organic phosphoric acid or salts thereof are not particularly limited as long as it is a substance used in the art, but 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-propylenediamine Tetra (methylenephosphonic acid), dodecylaminobis (methylenephosphonic acid), nitrotris (methylenephosphonic acid), ethylenediaminebis (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), hexenediaminetetra (methylenephosphonic acid ), Diethylenetriaminepenta (methylenephosphonic acid) and cyclohexanediaminetetra (methylenephosphonic acid) are preferably one or two organic phosphoric acids or salts thereof. Here, the salt of the organophosphoric acid is preferably a potassium salt or a sodium salt.

The organophosphoric acid or salt thereof is preferably contained in an amount of 0.01 to 20% by weight based on the total weight of the composition, and more preferably in an amount of 0.1 to 10% by weight.

The water is included in the remainder, relative to the total weight of the composition, deionized water is preferred.

The composition for cleaning a glass substrate according to the present invention can be produced by a conventionally known method, and preferably has a purity for a semiconductor process.

The cleaning method to which the glass substrate cleaning composition according to the present invention is applied is not particularly limited, and can be applied to methods such as immersion cleaning, rocking cleaning, ultrasonic cleaning, shower-spray cleaning, puddle cleaning, brush cleaning, stirring cleaning, and the like. In the present invention, an immersion cleaning method or an ultrasonic cleaning method is particularly preferable.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are intended to illustrate the present invention more specifically, but the scope of the present invention is not limited by the following examples.

Example  1 to 15, and Comparative example  1 to 4: Preparation and Cleaning of Cleaning Composition

It mixed and stirred with the component and composition of Table 1, and prepared the cleaning composition.

Fluorine
compound receptivity
Organic solvent Carboxylic acid system
Copolymer Organophosphate or
His salt
water
Kinds weight% Kinds weight% Kinds weight% Kinds weight% Example 1 A-1 1.0 B-1 5 C-1 1.5 - - Balance Example 2 A-1 1.0 B-1 5 C-1 1.0 D-1 1.0 Balance Example 3 A-2 1.0 B-1 5 C-1 1.5 - - Balance Example 4 A-2 1.0 B-2 5 C-2 1.5 - - Balance Example 5 A-2 1.0 B-2 5 C-1 1.0 D-2 1.0 Balance Example 6 A-2 1.0 B-3 5 C-2 1.0 D-2 1.0 Balance Example 7 A-2 1.5 B-1 5 C-3 1.5 D-1 1.5 Balance Example 8 A-2 1.5 B-1 5 C-3 1.5 D-2 1.5 Balance Example 9 A-3 1.0 B-1 5 C-2 1.5 - - Balance Example 10 A-3 1.0 B-2 5 C-2 2.0 - - Balance Example 11 A-3 1.0 B-2 5 C-1 1.0 D-1 1.0 Balance Example 12 A-3 1.0 B-2 5 C-2 1.0 D-2 1.0 Balance Example 13 A-3 2.0 B-1 5 C-2 1.0 D-2 1.0 Balance Example 14 A-3 2.0 B-1 10 C-2 1.0 D-2 1.0 Balance Example 15 A-3 3.0 B-3 5 C-1 0.5 D-2 0.5 Balance Comparative Example 1 A-1 1.0 - - - - - - Balance Comparative Example 2 - - B-2 10 - - - - Balance Comparative Example 3 A-3 1.0 B-2 10 - - - - Balance Comparative Example 4 A-3 1.0 B-2 10 E-1 1.0 - - Balance

A-1: hydrofluoric acid (HF)

A-2: Ammonium fluoride

A-3: Ammonium bifluoride

B-1: diethylene glycol monomethyl ether (MDG)

B-2: triethylene glycol monoethyl ether (MTG)

B-3: N-methylpyrrolidone (NMP)

C-1: polyacrylic acid polymer (PAA)

C-2: polyacrylic acid maleic acid copolymer (PAMA)

C-3: Polymethyl (meth) acrylic acid maleic acid copolymer (PMAMA)

D-1: 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP)

D-2: diethylenetriamine penta (methylenephosphonic acid) sodium salt

E-1: Gluconic Acid

Test Example : Evaluation of Characteristics of Cleaning Composition

1) Evaluation of SiO ₂ Removal

A glass substrate was prepared in a size of 2.5 cm x 2.5 cm for evaluation of SiO ₂ particle removal ability as a glass component, and 5 drops of a solution in which SiO ₂ particles having an average particle size of 0.8 μm were dispersed was added thereto, and baking was performed at 150 ° C. The contaminated glass substrate was then prepared. It was immersed and washed with the cleaning compositions of Examples 1 to 15 and Comparative Examples 1 to 4, and then washed with ultrapure water for 30 seconds and dried with nitrogen.

At this time, in the following Table 2, the particles were removed or not removed when ◎, mostly removed ○, when not removed, it was represented by x. In addition, the particle removal results according to Example 10, Comparative Example 2 are shown in Figs.

2) Evaluation of Organic Pollutant Removal Capacity-1

In order to evaluate the removal power of organic contaminants, a glass substrate formed of 5 cm x 5 cm is contaminated with a human fingerprint or an organic sign pen, and the contaminated substrate is performed at 40 ° C. for 2 minutes using a spray glass substrate cleaner. It wash | cleaned with the cleaning composition of Examples 1-15 and Comparative Examples 1-4. After washing for 30 seconds in ultrapure water, it was dried over nitrogen.

At this time, when the presence or absence of the removal of organic contaminants in Table 2, ◎, mostly removed ○, when not removed, it is represented by x.

3) Evaluation of Organic Pollutant Removal Capacity-2

In addition, the glass substrate is left in the air for 24 hours to contaminate various organic substances, inorganic substances, particles, etc. in the air, and then, at a temperature of 40 ° C. for 1 minute using a spray-type glass substrate cleaner, Examples 3 to 5 and 9 It wash | cleaned with the cleaning composition of Example 12. Then washed with ultrapure water for 30 seconds and dried with nitrogen. 0.5 µl of ultrapure water drops were dropped on the glass substrate, and the contact angle after washing was measured. The results are shown in Table 2.

4) Evaluation of organic pollutant removal-3

Using the cleaning composition of Example 3, Example 7, Example 10, and Example 12, the glass substrate contaminated with the organic particle solution was performed. That is, the glass substrate was contaminated with an organic particle solution having an average particle size of 0.8 μm, spin dried at 3000 rpm for 1 minute, and then washed with each cleaning liquid at 40 ° C. for 2 minutes using a spray-type glass substrate cleaner. . Then washed with ultrapure water for 30 seconds and dried with nitrogen. The particle number of 0.1 µm or more was measured with a surface particle analyzer (Topcon WM-1500), and the number of particles before and after cleaning was shown in Table 2 below.

SiO ₂ Particle Removal Organic fingerprint abandonment
Signature pen Contact angle Number of particles before cleaning Number of particles after cleaning Removal rate (%) Example 1 ◎ ○ ○ - - - - Example 2 ◎ ○ ○ - - - - Example 3 ◎ ○ ○ 4 1851 484 73.8 Example 4 ◎ ○ ○ 5 - - - Example 5 ◎ ◎ ◎ - - - - Example 6 ◎ ◎ ◎ - - - - Example 7 ◎ ◎ ◎ 1986 454 77.2 Example 8 ◎ ◎ ◎ - - - Example 9 ◎ ○ ○ 7 - - - Example 10 ◎ ○ ○ 8 1899 300 84.2 Example 11 ◎ ◎ ○ 5 - - - Example 12 ◎ ◎ ○ 6 1962 352 82.0 Example 13 ◎ ◎ ○ 5 - - - Example 14 ◎ ◎ ○ 4 - - - Example 15 ◎ ◎ ○ 5 - - - Comparative Example 1 ○ × × - - - - Comparative Example 2 × × △ - - - - Comparative Example 3 ○ × △ - 1798 772 57.0 Comparative Example 4 ○ × △ - 1853 865 53.0

◎: completely removed ○: mostly removed

△: slightly removed ×: not removed

As shown in Table 2, it was confirmed that the cleaning composition according to the present invention has excellent organic contaminants and particle removal power.

Claims (10)

A glass substrate cleaning composition comprising a fluorine compound, a water-soluble organic solvent, a carboxylic acid copolymer and water. The method according to claim 1, wherein the total weight of the composition, the content of the fluorine-based compound is 0.01 to 20% by weight, the content of the water-soluble organic solvent is 0.1 to 40% by weight, the content of the carboxylic acid-based copolymer is 0.01% by weight To 20% by weight of the glass substrate cleaning composition, characterized in that. The method of claim 1, wherein the fluorine-based compound is hydrofluoric acid (HF), ammonium fluoride (NH4F), acidic ammonium fluoride (NH ₄ HF ₂ ), tetramethyl ammonium fluoride ((CH ₃ ) ₄ NF), tetraethyl ammonium fluoride ((CH ₃ CH ₂ ) ₄ NF), at least one member selected from the group consisting of fluoroboric acid (fluoroboric acid) and fluorobenzene (fluorobenzene) composition for cleaning a glass substrate. The method of claim 1, wherein the water-soluble organic solvent is ethylene glycol monobutyl ether (BG), diethylene glycol monomethyl ether (MDG), diethylene glycol monoethyl ether (carbitol), diethylene glycol monobutyl ether (BDG), di Propylene glycol monomethyl ether (DPM), dipropylene glycol monoethyl ether (MFDG), triethylene glycol monobutyl ether (BTG), triethylene glycol monoethyl ether (MTG), propylene glycol monomethyl ether (MFG), N- Methylpyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone (DMI), dimethylsulfoxide (DMSO), dimethylacetamide (DMAc), dimethylformamide (DMF), tetrahydrofurfuryl alcohol And isophorone, diethyl adipate, dimethyl glutarate, sulfolane, gamma-butyllactone (GBL), and mixtures thereof. The composition according to claim 1, wherein the carboxylic acid copolymer comprises a structural unit represented by the following formula (1).
[Formula 1]

In Chemical Formula 1, R ₁ to R ₃ may be the same or different, and represent a hydrogen atom, a methyl group, an ethyl group, or (CH ₂ ) m ₂ COOM ₂ , M ₁ and M ₂ may be the same or different, and hydrogen An atom, an alkali metal, an alkaline earth metal, an ammonium group, an alkylammonium group or a substituted alkyl ammonium group, m ₁ and m ₂ represent an integer of 0 to 2,
Wherein the alkali metal is Li, Na, K, Rb, Cs or Fr and the alkaline earth metal is Ca, Sr, Ba or Ra. The method of claim 1, wherein the carboxylic acid copolymer is polyacrylic acid polymer (PAA), polymethyl (meth) acrylic acid copolymer (PMAA), polyacrylic acid maleic acid copolymer (PAMA), polymethyl acrylate (meth) acrylic acid copolymer (PAMAA), polymaleic acid copolymer (PMA), polymethyl (meth) acrylic acid maleic acid copolymer (PMAMA), and salts thereof. The composition for cleaning a glass substrate of claim 1, further comprising an organic phosphoric acid or a salt thereof. The composition of claim 7, wherein the organophosphoric acid or a salt thereof is included in an amount of about 0.01 wt% to about 20 wt%, based on the total weight of the composition. The method of claim 7, wherein the organic phosphoric acid or a salt thereof is methyldiphosphonic acid, aminotri (methylenephosphonic acid), ethylidenediphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1-hydrate Oxypropylidene-1,1-diphosphonic acid, 1-hydroxybutylidene-1,1-diphosphonic acid, ethylaminobis (methylenephosphonic acid), 1,2-propylenediaminetetra (methylenephosphonic acid), Dodecylaminobis (methylenephosphonic acid), nitrotris (methylenephosphonic acid), ethylenediaminebis (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), hexenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (Methylene phosphonic acid) and cyclohexanediamine tetra (methylene phosphonic acid) is one or two selected from the group consisting of cleaning composition for a glass substrate. The composition for cleaning a glass substrate according to claim 1, wherein the organic contaminants or particles on the initial glass substrate are removed in the manufacturing process of the flat panel display substrate, and the polishing debris generated when the glass substrate is polished.

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