KR20130070061A - Cleaning composition using electronic material - Google Patents

Abstract

PURPOSE: Cleaning solution composition is provided to have excellent removability of organic impurity existed on the surface of the glass substrate or metal film of electronic material and excellent corrosion preventing effect of metal wiring formed on the substrate. CONSTITUTION: Cleaning solution for electronic material comprises 0.001-5 weight% of 'silsesquioxane indicated as follows chemical formula 1: (R1SiO3/2)n', 0.01-10 weight% of organic acid, 0.05-10 weight% of organic amine, and 0.001-1 weight% of anticorrosive agent. In the chemical formula 1, n is an integer of 8-100. R1 is independently hydrogen, alkyl, alkaline, alkyl, allylene or 'alkyl, alkaline, alkyl, alien derivative. The cleaning solution composition also comprises a water-soluble organic solvent and/or deionized water.

Description

Cleaning liquid composition for electronic materials {CLEANING COMPOSITION USING ELECTRONIC MATERIAL}

The present invention relates to a cleaning liquid composition for an electronic material.

Electronic materials used in semiconductor devices, liquid crystal displays such as FPDs, and the like are manufactured through various processes, and as specific examples, are manufactured through processes such as film formation, exposure, and wiring etching. Particles having a particle size of 1 μm or less are attached to the substrate to contaminate the substrate. When the following process treatment is carried out with these contaminants attached, pinholes and pits of the film, disconnection and bridges of the wiring are generated, which greatly reduces the production yield of the product. Therefore, cleaning to remove such contaminants is performed between the respective processes, and various cleaning liquids for this purpose have been introduced.

Korean Patent No. 10-0503231 discloses a cleaning composition for a semiconductor and a TFT-LCD including a specific alkanolamine compound, an organic solvent, a chelate compound, a nonionic surfactant, and water. However, since it contains a chelating compound that causes a color change, the color change of the cleaning agent and precipitation occurs for a long time, there is a problem that the aluminum method is difficult.

Korean Patent Laid-Open Publication No. 2007-0107242 relates to a copper molybdenum cleaner, which is limited in use since there is no anticorrosive effect on aluminum, and has a problem of lowering particle removal power than an alkaline cleaner as a neutral or weakly acidic cleaner.

Republic of Korea Patent No. 10-0503231 Republic of Korea Patent Publication No. 2007-0107242

The present invention is to solve the problems of the prior art as described above, excellent in the ability to remove organic contaminants or particles that contaminate a glass substrate or metal film in the process of manufacturing an electronic material, etc., which is formed on the FPD substrate An object of the present invention is to provide a cleaning liquid composition having excellent corrosion protection against metal wiring such as aluminum and copper.

In order to achieve the above object, the present invention provides a cleaning liquid composition for an electronic material comprising a silsesquioxane, an organic acid, an organic amine and a corrosion inhibitor represented by the following formula (1).

[Formula 1]

_{(R 1 SiO 3/2)} n

In Formula 1, n is an integer of 8 to 100, R ₁ is independently hydrogen, alkyl, alkylene, allyl, allylene or alkyl, alkylene, allyl, allylene derivative having a functional.

The cleaning liquid composition for an electronic material of the present invention is excellent in the ability to remove organic contaminants and particles existing on a glass substrate or metal film surface such as an electronic material, and is formed of a metal such as aluminum, aluminum alloy, copper, or copper alloy formed on the substrate. Excellent corrosion protection against wiring. It also contains a large amount of water, making it easy to handle and environmentally beneficial.

Hereinafter, the present invention will be described in detail.

The present invention provides a cleaning liquid composition for an electronic material comprising a silsesquioxane, an organic acid, an organic amine, and a corrosion inhibitor represented by the following Chemical Formula 1.

[Formula 1]

_{(R 1 SiO 3/2)} n

In Formula 1, n is an integer of 8 to 100, R ₁ is independently hydrogen, alkyl, alkylene, allyl, allylene or alkyl, alkylene, allyl, allylene derivative having a functional.

Also, with respect to the total weight of the cleaning liquid composition for electronic materials, 0.001% to 5% by weight of silsesquioxane, 0.01 to 10% by weight of organic acid, 0.05 to 10% by weight of organic amine, 0.001 to 1% by weight of corrosion inhibitor and residual amount It is preferable to include water.

In addition, it is preferable that the water-soluble organic solvent is further included in the cleaning liquid composition for the electronic material, and the water-soluble organic solvent is preferably contained in an amount of 0.05 to 40% by weight based on the total weight of the cleaning liquid composition.

Specifically, silsesquioxanes represented by Formula 1 have thermal stability, durability, and corrosion resistance, and are generally used to develop coating fillers and organic-inorganic composite materials, but in the present invention, photoresist By adding to a releasing agent composition, the anticorrosive effect of a metal wiring is excellent.

Preferably, the silsesquioxane is included in an amount of 0.001% by weight to 5% by weight based on the total weight of the detergent composition, and when the content of the silsesquioxane is less than 0.001% by weight, metal anticorrosion deterioration occurs and 5% by weight. If it exceeds%, there is a problem that the coating remains on the metal wiring surface.

In this case, the silsesquioxanes may have various structures such as random type, ladder type, cage type, and partial cage type, and the structure thereof is not particularly limited.

The organic acid of the present invention preferably includes an organophosphate compound or a polycarboxylic acid copolymer as having a contaminant removal and anticorrosive effect.

The organophosphate compound particularly exhibits an excellent effect on removing organic contaminants or particles located on the glass substrate and has a metal corrosion protection effect.

Specifically, the organic acid may be 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 (methylenephosphonic acid), nitrotris (Methylenephosphonic acid), ethylenediaminebis (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), hexenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), cyclohexanediaminetetra (methylene Phosphonic acid), hydroxyphosphonoacetic acid and 2-phosphinic acid butane-1,2,4-tricarboxylic acid.

In addition, the polycarboxylic acid copolymer serves to prevent corrosion of the metal by forming a protective film layer on the surface of the metal to suppress excessive reaction of the metal and alkali ions.

Specifically, the organic acid preferably includes a polycarboxylic acid copolymer represented by the following formula (2).

[Formula 2]

In Chemical Formula 2, R ₂ to R ₄ are each independently hydrogen, a methyl group, an ethyl group, or-(CH ₂ ) _{m 2} COOM ₂ , and M ₁ and M ₂ are each independently hydrogen, an alkali metal, an alkaline earth metal or an ammonium group. M ₁ and m ₂ are each independently an integer of 0 to 2.

In this case, the ammonium group means not only ammonium (NH ₄ ⁺ ), but also one or more of hydrogen atoms bonded to a nitrogen atom includes ammonium substituted with another substituent. For example, the ammonium group includes alkyl ammonium and the like.

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

Specific examples of the polycarboxylic acid copolymer include polyacrylic acid polymer (PAA), polymethyl (meth) acrylic acid copolymer (PMAA), polyacrylic acid maleic acid copolymer (PAMA), and polymethyl acrylate (meth) acrylic acid copolymer ( PAMAA), polymaleic acid copolymer (PMA), polymethyl (meth) acrylic acid maleic acid copolymer (PMAMA), and salts thereof.

Preferably, the organic acid is contained in an amount of 0.01 to 10% by weight based on the total weight of the cleaning liquid composition. When the content of the organic acid is less than 0.01% by weight, corrosion resistance to metal wiring is insufficient, and removal ability to organic contaminants is reduced. When the amount exceeds 10% by weight, the particle cleaning power is lowered due to the pH decrease, and the rinsing power is lowered due to the viscosity increase of the cleaning solution.

The organic amine is preferably represented by the following formula (3) or formula (4).

(3)

[Formula 4]

In Chemical Formula 3 or 4, R ₅ to R ₁₁ are each independently hydrogen; An alkyl group having 1 to 10 carbon atoms unsubstituted or substituted with an amino group; An alkyl group having 1 to 10 carbon atoms substituted with an amino group substituted with an alkyl group having 1 to 4 carbon atoms; Alkenyl groups having 2 to 10 carbon atoms; Hydroxyalkyl groups having 1 to 10 carbon atoms; An alkyl group having 1 to 10 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms unsubstituted or substituted with a carboxyl group or a hydroxy group; An amino group unsubstituted or substituted with an alkyl group having 1 to 4 carbon atoms; A phenyl group unsubstituted or substituted with an alkyl group having 1 to 4 carbon atoms; Or a benzyl group unsubstituted or substituted with an alkyl group having 1 to 4 carbon atoms, and two groups adjacent to each other in R ₅ to R ₁₁ may combine with each other to form a ring. In Formula 4, R ₁₂ is an unsubstituted alkylene group having 1 to 10 carbon atoms.

In this case, the organic amine is methylamine, ethylamine, monoisopropylamine, n-butylamine, sec-butylamine, isobutylamine, t-butylamine, pentylamine, dimethylamine, diethylamine, dipropylamine, Diisopropylamine, dibutylamine, diisobutylamine, methylethylamine, methylpropylamine, methylisopropylamine, methylbutylamine, methylisobutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine , Tripentylamine, dimethylethylamine, methyldiethylamine, methyldipropylamine, choline, monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, 2-aminoethanol, 2- (ethylamino) ethanol, 2 -(Methylamino) ethanol, N-methylethanolamine, N-methyldiethanolamine, N, N-dimethylethanolamine, N, N-diethylaminoethanol, 2- (2-aminoethylamino) -1-ethanol , 1-amino- 2-propanol, 2-amino-1-propanol, 3-a No-1-propanol, 4-amino-1-butanol, dibutanolamine, (butoxymethyl) diethylamine, (methoxymethyl) diethylamine, (methoxymethyl) dimethylamine, (butoxymethyl) dimethyl Amine, (isobutoxymethyl) dimethylamine, (methoxymethyl) diethanolamine, (hydroxyethyloxymethyl) diethylamine, methyl (methoxymethyl) aminoethane, methyl (methoxymethyl) aminoethanol, methyl ( Butoxymethyl) aminoethanol, 2- (2-aminoethoxy) ethanol, 1- (2-hydroxyethyl) piperazine, 1- (2-aminoethyl) piperazine, 1- (2-hydroxyethyl) Methylpiperazine, N- (3-aminopropyl) morpholine, 2-methylpiperazine, 1-methylpiperazine, 1-amino-4-methylpiperazine, 1-benzyl piperazine, 1-phenyl piperazine, N , N, N ', N'-tetramethylpropanediamine, N, N, N', N'-tetramethylhexanediamine, N, N, N ', N'-tetraethylmethanediamine and N, N, N' At least one selected from the group consisting of N'-tetramethylethylenediamine More preferably, monoethanolamine, triethanolamine, 1-amino-2-propanol, 2- (2-aminoethoxy) ethanol, N-methylethanolamine, N-methyldiethanolamine, N, N -Dimethylethanol amine, N, N-diethylaminoethanol and 2- (2-aminoethylamino) -1-ethanol are preferably at least one selected from the group consisting of, more preferably N, N, N ', N '-Tetramethylpropanediamine, N, N, N', N'-tetramethylhexanediamine, N, N, N ', N'-tetraethylmethanediamine and N, N, N', N'-tetramethylethylene It is preferably at least one selected from the group consisting of diamines.

The organic amine is preferably 0.05 to 10% by weight, more preferably 0.1 to 5% by weight based on the total weight of the cleaning liquid composition. In addition, the pH of the cleaning liquid composition containing the organic amine is preferably pH 7 to pH 13, more preferably pH 8 to pH 11.

If the content of the organic amine is less than 0.05% by weight, sufficient cleaning effect cannot be achieved. If the content of the organic amine is more than 10% by weight, the pH is increased to increase corrosion of aluminum or aluminum alloy wires. There is a problem to drop.

The corrosion inhibitor serves to suppress the corrosion of the metal wiring, it is preferable that the benzotriazole derivative represented by the formula (5).

[Chemical Formula 5]

In Formula 5, R ₁₃ to R ₁₅ are each independently hydrogen, halogen, alkyl group, cycloalkyl group, allyl group, aryl group, amino group, alkylamino group, nitro group, cyano group, mercapto group, alkyl mercapto group, and hydride. It is a monovalent group which has a carboxyl group, a hydroxyalkyl group, a carboxyl group, a carboxyalkyl group, an acyl group, an alkoxy group, or heterocyclic amino acid as a substituent.

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-benzotriazole-1 -Yl] methyl] imino] bisethanol, 2,2 '-[[[methyl-1 hydrogen-benzotriazol-1-yl] methyl] imino] biscarboxylic acid, 2,2'-[[[methyl- Monohydrogen-benzotriazol-1-yl] methyl] imino] bismethylamine and 2,2 '-[[[amine-1 hydrogen-benzotriazol-1-yl] methyl] imino] bisethanol It is preferably at least one selected from the group.

The corrosion inhibitor is preferably included in 0.0001 to 1.0% by weight, more preferably 0.01 to 0.5% by weight relative to the total weight of the cleaning liquid composition. At this time, when the content of the corrosion inhibitor is less than 0.0001% by weight, there is a problem that the corrosion on the metal wiring occurs, when the content exceeds 1.0% by weight, there is a problem of low economic efficiency.

A water-soluble organic solvent may be further included in the cleaning solution composition including the silsesquioxane, organic acid, organic amine and a corrosion inhibitor. At this time, the water-soluble organic solvent serves as a solvent for dissolving the organic contaminants, and lowers the surface tension of the cleaning liquid to increase the wettability to the glass substrate, thereby improving the cleaning power.

The water-soluble organic solvent is preferably at least one selected from the group consisting of a protic polar solvent and an aprotic polar solvent.

The water-soluble organic solvent is preferably at least one selected from the group consisting of a protic polar solvent and an aprotic polar solvent. Specifically as the proton polar solvent, 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 Monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, with the aprotic polar solvent, N-methyl pyrroli (NMP), N-ethyl pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dipropyl-2-imidazolidinone, γ-butyrolactone, dimethyl sulfoxide (DMSO) , Sulfolane, triethyl phosphate, tributyl phosphate, dimethyl carbonate, ethylene carbonate, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacet Amide, N- (2-hydroxyethyl) acetamide, 3-methoxy-N, N-dimethylpropionamide, 3- (2-ethylhexyloxy) -N, N-dimethylpropionamide and 3-butoxy It is preferably at least one selected from the group consisting of -N, N-dimethylpropionamide.

The increase in the content of the proton polar solvent can improve the removal power of the cleaning agent by water to solve the problem of remaining contaminants on the surface, the aprotic polar solvent can improve the removal of organic contaminants to use the two together More preferred.

When the water-soluble organic solvent is included in the cleaning liquid composition, the water-soluble organic solvent is preferably included in 0.05 to 40% by weight relative to the total weight of the cleaning liquid composition, more preferably 0.5 to 20% by weight. If the content of the water-soluble organic solvent is less than 0.05% by weight can not be expected to increase the dissolving power to the organic contaminants of the cleaning liquid composition, if it exceeds 40% by weight there is a problem that the performance as a cleaning liquid is lowered and the economical efficiency due to the price rise.

In addition, the washing liquid composition may further include deionized water. Deionized water included in the cleaning liquid composition of the present invention improves the activity of the basic compound to increase the cleaning rate of organic contaminants and particles, and the organic contaminants remaining on the substrate during the rinsing process by deionized water mixed with a water-soluble polar solvent and Particles can be removed quickly and completely.

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 >

0.5 wt% of (3- (2-aminoethyl) aminopropyl) methoxyterminated silsesquioxane with silsesquioxane, 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) as organic acid 2.0% by weight, N, N, N ', N'-tetramethylpropanediamine as organic amine, 0.5% by weight, 10.0% by weight N-methylpyrrolidone (NMP) as water-soluble organic solvent, 2,2'- as corrosion inhibitor 0.05 wt% of [[[ethyl-1H-benzotriazol-1-yl] methyl] imino] bisethanol and the remaining amount of water were mixed and stirred to prepare a washing solution.

<Example 2>

In Example 1, 1.0% by weight instead of 0.5% by weight of (3- (2-aminoethyl) aminopropyl) methoxyterminated silsesquioxane, 1-hydroxyethylidene-1,1-dipo A cleaning solution was prepared in the same manner as in Example 1, except that 1.0% by weight instead of 2.0% by weight of spongic acid (HEDP) and 20.0% by weight instead of 10.0% by weight of N-methylpyrrolidone (NMP).

<Example 3>

In Example 1, 1.0% by weight instead of 0.5% by weight of (3- (2-aminoethyl) aminopropyl) methoxyterminated silsesquioxane, N, N, N ', N'-tetramethylpropane Cleaning solution was carried out in the same manner as in Example 1, except that 1.0 wt% of diamine and 10.0 wt% of diethylene glycol monobutyl ether (BDG) instead of 10.0 wt% of N-methylpyrrolidone (NMP) instead of 0.5 wt% of diamine. Was prepared.

<Example 4>

In Example 1, 1.0% by weight instead of 0.5% by weight of (3- (2-aminoethyl) aminopropyl) methoxyterminated silsesquioxane, N, N, N ', N'-tetramethylpropane 0.5% by weight of N, N, N ', N'-tetramethylhexanediamine instead of 0.5% by weight of diamine, 15.0% by weight of diethylene glycol monobutyl ether (BDG) instead of 10.0% by weight of N-methylpyrrolidone (NMP) Except that was carried out in the same manner as in Example 1 to prepare a cleaning liquid.

<Example 5>

2.0 wt% of 1-hydroxyethylidene-1,1-dipo instead of 0.5 wt% of (3- (2-aminoethyl) aminopropyl) methoxyterminated silsesquioxane 1.0% by weight of polyacrylic acid maleic acid copolymer (PAMA) instead of 2.0% by weight of sponic acid (HEDP), N, N, N ', N instead of 0.5% by weight of N, N, N', N'-tetramethylpropanediamine A washing solution was prepared in the same manner as in Example 1 except that 1.0 wt% of '-tetramethylhexanediamine was used.

<Example 6>

2.0 wt% of 1-hydroxyethylidene-1,1-dipo instead of 0.5 wt% of (3- (2-aminoethyl) aminopropyl) methoxyterminated silsesquioxane 3.0% by weight of polyacrylic acid maleic acid copolymer (PAMA) instead of 2.0% by weight of sponic acid (HEDP), N, N, N ', N instead of 0.5% by weight of N, N, N', N'-tetramethylpropanediamine '-Tetramethylhexanediamine 2.0% by weight, 15.0% by weight instead of 10.0% by weight of N-methylpyrrolidone (NMP), 2,2'-[[[ethyl-1H-benzotriazol-1-yl] methyl] A washing solution was prepared in the same manner as in Example 1, except that 0.1 wt% of imino] bisethanol instead of 0.05 wt%.

&Lt; Example 7 >

2.0 wt% of 1-hydroxyethylidene-1,1-dipo instead of 0.5 wt% of (3- (2-aminoethyl) aminopropyl) methoxyterminated silsesquioxane 1.0% by weight of polyacrylic acid maleic acid copolymer (PAMA) instead of 2.0% by weight of sponic acid (HEDP), N, N, N ', N instead of 0.5% by weight of N, N, N', N'-tetramethylpropanediamine Washing solution was carried out in the same manner as in Example 1 except that 1.0 wt% of '-tetraethylmethanediamine and 10.0 wt% of N-methylpyrrolidone (NMP) instead of 10.0 wt% of diethylene glycol monobutyl ether (BDG). Was prepared.

&Lt; Example 8 >

2.0 wt% of 1-hydroxyethylidene-1,1-dipo instead of 0.5 wt% of (3- (2-aminoethyl) aminopropyl) methoxyterminated silsesquioxane 3.0% by weight of polyacrylic acid maleic acid copolymer (PAMA) instead of 2.0% by weight of sponic acid (HEDP), N, N, N ', N instead of 0.5% by weight of N, N, N', N'-tetramethylpropanediamine 1.0% by weight of '-tetraethylmethanediamine, 15.0% by weight of diethylene glycol monobutyl ether (BDG) instead of 10.0% by weight of N-methylpyrrolidone (NMP), 2,2'-[[[ethyl-1H-benzo Triazol-1-yl] methyl] imino] bisethanol was prepared in the same manner as in Example 1, except that 0.1 wt% was used instead of 0.05 wt%.

&Lt; Example 9 >

1.0% by weight of (3- (2-aminoethyl) aminopropyl) methoxyterminated silsesquioxane as silsesquioxane, 2.0% by weight of polyacrylic acid maleic acid copolymer (PAMA) as organic acid, N as organic amine, N, N ', N'-tetraethylmethanediamine 2.0 wt%, 2,2'-[[[ethyl-1H-benzotriazol-1-yl] methyl] imino] bisethanol and remaining water The mixture was mixed and stirred to prepare a cleaning solution.

&Lt; Comparative Example 1 &

2.0 wt% of 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), 1.0 wt% of N, N, N ', N'-tetramethylhexanediamine, N-methylpyrrolidone (NMP) 10.0 0.05% by weight of 2,2 '-[[[ethyl-1H-benzotriazol-1-yl] methyl] imino] bisethanol and the remaining water were mixed and stirred to prepare a washing solution.

Comparative Example 2

1.0 wt% of (3- (2-aminoethyl) aminopropyl) methoxyterminated silsesquioxane, 0.5 wt% of N, N, N ', N'-tetramethylhexanediamine, N-methylpyrrolidone ( NMP) 15.0 wt%, 2,2 '-[[[ethyl-1H-benzotriazol-1-yl] methyl] imino] bisethanol and 0.05% by weight of the remaining water were mixed and stirred to prepare a washing solution.

&Lt; Comparative Example 3 &

(3- (2-aminoethyl) aminopropyl) methoxyterminated silsesquioxane 2.0 wt%, 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) 2.0 wt%, N, N A washing solution was prepared by mixing and stirring 2.0% by weight of N ', N'-tetramethylhexanediamine, 10.0% by weight of diethylene glycol monobutyl ether (BDG) and the balance of water.

Silsesquioxane Organic acid Organic amines Water soluble organic solvent Corrosion inhibitor water Kinds content Kinds content Kinds content Kinds content Kinds content Example 1 a-1 0.5 b-1 2.0 c-1 0.5 d-1 10.0 e-1 0.05 Balance Example 2 a-1 1.0 b-1 1.0 c-1 0.5 d-1 20.0 e-1 0.05 Balance Example 3 a-1 1.0 b-1 2.0 c-1 1.0 d-2 10.0 e-1 0.05 Balance Example 4 a-1 1.0 b-1 2.0 c-2 0.5 d-2 15.0 e-1 0.05 Balance Example 5 a-1 2.0 b-2 1.0 c-2 1.0 d-1 10.0 e-1 0.05 Balance Example 6 a-1 2.0 b-2 3.0 c-2 2.0 d-1 15.0 e-1 0.1 Balance Example 7 a-1 2.0 b-2 1.0 c-3 1.0 d-2 10.0 e-1 0.05 Balance Example 8 a-1 2.0 b-2 3.0 c-3 1.0 d-2 15.0 e-1 0.1 Balance Example 9 a-1 1.0 b-2 2.0 c-3 2.0 - - e-1 0.1 Balance Comparative Example 1 a-1 - b-1 2.0 c-2 1.0 d-1 10.0 e-1 0.05 Balance Comparative Example 2 a-1 1.0 b-1 - c-2 1.0 d-1 15.0 e-1 0.05 Balance Comparative Example 3 a-1 2.0 b-1 2.0 c-2 2.0 d-2 10.0 e-1 - Balance a-1: (3- (2-aminoethyl) aminopropyl) methoxyterminated silsesquioxane
b-1: 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP)
b-2: Polyacrylic acid maleic acid copolymer (PAMA)
c-1: N, N, N ', N'-tetramethylpropanediamine
c-2: N, N, N ', N'-tetramethylhexanediamine
c-3: N, N, N ', N'-tetraethylmethanediamine
d-1: N-methylpyrrolidone (NMP)
d-2: diethylene glycol monobutyl ether (BDG)
e-1: 2,2 '-[[[ethyl-1H-benzotriazol-1-yl] methyl] imino] bisethanol

<Experimental Example 1>

A glass substrate coated with 2000 mm thick and a glass substrate coated with 2500 mm thick were dipped into the cleaning liquids prepared in Examples 1 to 9 and Comparative Examples 1 to 3 for 30 minutes. At this time, the temperature of the cleaning solution is 40 ℃, the thickness of the aluminum and copper film coated on the glass substrate was measured before and after dipping, and each dissolution rate was calculated by measuring the thickness change, and the evaluation thereof is shown in Table 2 below. It was.

Al etching rate (ms / min) Cu etching rate (ms / min) Example 1 ○ ○ Example 2 ○ ○ Example 3 ○ ○ Example 4 ○ ○ Example 5 ◎ ◎ Example 6 ◎ ◎ Example 7 ○ ○ Example 8 ○ ○ Example 9 ○ ○ Comparative Example 1 X △ Comparative Example 2 X ○ Comparative Example 3 ○ X Aluminum and copper corrosion
◎: Excellent (less than 2 ms / minute)
○: Good (less than 5 Å / min)
(Triangle | delta): Inadequate (less than 10 microseconds / minute)
X: Poor (more than 10Å / min)

As shown in Table 2, the cleaning liquids of Examples 1 to 9 are effective in preventing corrosion with an etching rate of less than 5 kW / min for aluminum and copper, but the cleaning liquids of Comparative Examples 1 to 3 are etching for aluminum or copper. It can be seen that the speed is higher than that of the cleaning solutions of Examples 1 to 9, and the effect on preventing corrosion is low.

<Experimental Example 2>

In order to evaluate the removal power of the organic contaminants, the fingerprint substrate was contaminated with a human fingerprint on a glass substrate 5 cm × 5 cm in size, and the contaminated substrate was sprayed at 40 ° C. for 2 minutes using a spray glass substrate cleaning apparatus. It was washed with the washing solution of 6, washed with ultrapure water for 30 seconds and then dried with nitrogen. Thereafter, the presence or absence of organic contaminants was evaluated, and the results are shown in Table 3 below.

Further, in order to evaluate the removal power of the contaminants, the glass substrate formed in 5 cm × 5 cm size was left to stand in the air for 3 days to contaminate, and the contaminated substrate was sprayed at 40 ° C. for 1 minute using a glass substrate cleaning apparatus. The solution was washed with 3 to 6 washes, washed with ultrapure water for 30 seconds, and then dried with nitrogen. Then, the degree of removal of contaminants was evaluated by the amount of contact angle reduction before and after cleaning using a contact angle measuring device, and the results are shown in Table 3 below.

Organic fingerprint Contact angle Example 1 ○ ○ 3 to implementation ○ ○ Example 4 ○ ○ Example 5 ○ ◎ Example 6 ○ ◎ When organic fingerprint is removed (○), when not removed (x)
40 ° or more decrease in contact angle (◎), 40 ~ 30 ° decrease (○), 30 ~ 20 ° decrease (△), less than 20 ° decrease (X)

As shown in Table 3, it can be seen that the cleaning solutions of Examples 1 and 3 to 6 all have the ability to remove organic contaminants, and the contact angle is reduced by 30 ° or more, indicating the ability to remove contaminants.

<Experimental Example 3>

A 5 cm x 5 cm sized glass substrate on which aluminum and copper patterns were formed, respectively, was washed with the cleaning liquids of Examples 1, 3 and 6 at 40 ° C. for 2 minutes using a spray-type glass substrate cleaning device, and then washed with ultrapure water for 30 seconds. After drying with nitrogen.

The degree of corrosion occurrence in the aluminum and copper patterns after cleaning and the degree of oxide film removal of the copper film were evaluated and shown in Table 4. At this time, the oxide film removal degree of the copper film was confirmed through XPS (x-ray photoelectron spectroscopy).

Aluminum pattern corrosion Copper pattern corrosion Copper oxide removal ability Example 1 ○ △ ○ Example 3 ○ ○ ○ Example 4 ○ ○ ○ Example 5 ○ ○ ○ Example 6 ○ ○ ○ Aluminum and copper pattern corrosion: no corrosion (○), slight corrosion (△), large amount of corrosion (X)
Copper oxide removal ability: Remove all (○), remove partial (△), not remove (X)

As shown in Table 4, the cleaning liquids of Examples 1 and 3 to 6 of the present invention are excellent in corrosion protection against aluminum and copper patterns and effective in removing copper oxide films.

Claims (14)

Cleaning liquid composition for an electronic material comprising a silsesquioxane, an organic acid, an organic amine, and a corrosion inhibitor represented by the following Chemical Formula 1.
[Formula 1]
_{(R 1 SiO 3/2)} n
In Formula 1, n is an integer of 8 to 100, R ₁ is independently hydrogen, alkyl, alkylene, allyl, allylene or alkyl, alkylene, allyl, allylene derivative having a functional. The cleaning liquid composition for an electronic material according to claim 1, wherein the cleaning liquid composition further comprises a water-soluble organic solvent. The cleaning liquid composition for an electronic material according to claim 1 or 2, further comprising deionized water in the cleaning liquid composition. The method according to claim 1, wherein the total weight of the cleaning liquid composition, 0.001% to 5% by weight of silsesquioxane, 0.01 to 10% by weight of organic acid, 0.05 to 10% by weight of organic amine, 0.001 to 1% by weight of corrosion inhibitor and residual amount Cleaning liquid composition for an electronic material containing water. The cleaning liquid composition of claim 4, further comprising 0.05 to 40% by weight of a water-soluble organic solvent based on the total weight of the cleaning liquid composition. The method according to claim 1, wherein the organic acid is aminotri (methylene phosphonic acid), ethylidene diphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1-hydroxypropylidene-1,1-dipo Sonic 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 (methylenephosphonic acid), cyclohexanediamine The cleaning liquid composition for an electronic material, characterized in that at least one selected from the group consisting of tetra (methylenephosphonic acid), hydroxyphosphonoacetic acid and 2-phosphinic acid butane-1,2,4-tricarboxylic acid. The cleaning liquid composition according to claim 1, wherein the organic acid comprises a polycarboxylic acid copolymer represented by the following Chemical Formula 2.
(2)

In Chemical Formula 2, R ₂ to R ₄ are each independently hydrogen, a methyl group, an ethyl group, or-(CH ₂ ) _{m 2} COOM ₂ , and M ₁ and M ₂ are each independently hydrogen, an alkali metal, an alkaline earth metal or an ammonium group. M ₁ and m ₂ are each independently an integer of 0 to 2. The method of claim 7, wherein the polycarboxylic acid copolymer is a polyacrylic acid polymer (PAA), polymethyl (meth) acrylic acid copolymer (PMAA), polymaleic acid maleic acid copolymer (PAMA), polymethyl acrylate (meth) acrylic acid air A cleaning liquid composition for an electronic material, characterized in that at least one selected from the group consisting of copolymer (PAMAA), polymaleic acid copolymer (PMA), polymethyl (meth) acrylic acid maleic acid copolymer (PMAMA), and salts thereof. The method of claim 1, wherein the organic amine is a cleaning liquid composition for an electronic material, characterized in that represented by the formula (3) or (4).
(3)

[Chemical Formula 4]

In Chemical Formulas 3 and 4, R ₅ to R ₁₁ are each independently hydrogen; An alkyl group having 1 to 10 carbon atoms unsubstituted or substituted with an amino group; An alkyl group having 1 to 10 carbon atoms substituted with an amino group substituted with an alkyl group having 1 to 4 carbon atoms; Alkenyl groups having 2 to 10 carbon atoms; Hydroxyalkyl groups having 1 to 10 carbon atoms; An alkyl group having 1 to 10 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms unsubstituted or substituted with a carboxyl group or a hydroxy group; An amino group unsubstituted or substituted with an alkyl group having 1 to 4 carbon atoms; A phenyl group unsubstituted or substituted with an alkyl group having 1 to 4 carbon atoms; Or a benzyl group unsubstituted or substituted with an alkyl group having 1 to 4 carbon atoms, two groups adjacent to each other in R ₅ to R ₁₁ may combine with each other to form a ring, and in Formula 4, R ₁₂ may be unsubstituted C 1. To alkyl group of 10. The method of claim 1, wherein the organic amine is methylamine, ethylamine, monoisopropylamine, n-butylamine, sec-butylamine, isobutylamine, t-butylamine, pentylamine, dimethylamine, diethylamine, di Propylamine, diisopropylamine, dibutylamine, diisobutylamine, methylethylamine, methylpropylamine, methylisopropylamine, methylbutylamine, methylisobutylamine, trimethylamine, triethylamine, tripropylamine, Tributylamine, tripentylamine, dimethylethylamine, methyldiethylamine, methyldipropylamine, choline, monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, 2-aminoethanol, 2- (ethylamino) Ethanol, 2- (methylamino) ethanol, N-methylethanolamine, N-methyldiethanolamine, N, N-dimethylethanolamine, N, N-diethylaminoethanol, 2- (2-aminoethylamino)- 1-ethanol, 1-amino-2-propanol, 2-amino-1- Ropanol, 3-amino-1-propanol, 4-amino-1-butanol, dibutanolamine, (butoxymethyl) diethylamine, (methoxymethyl) diethylamine, (methoxymethyl) dimethylamine, ( Butoxymethyl) dimethylamine, (isobutoxymethyl) dimethylamine, (methoxymethyl) diethanolamine, (hydroxyethyloxymethyl) diethylamine, methyl (methoxymethyl) aminoethane, methyl (methoxymethyl) Aminoethanol, methyl (butoxymethyl) aminoethanol, 2- (2-aminoethoxy) ethanol, 1- (2-hydroxyethyl) piperazine, 1- (2-aminoethyl) piperazine, 1- (2 -Hydroxyethyl) methylpiperazine, N- (3-aminopropyl) morpholine, 2-methylpiperazine, 1-methylpiperazine, 1-amino-4-methylpiperazine, 1-benzyl piperazine, 1- Phenyl piperazine, N, N, N ', N'-tetramethylpropanediamine, N, N, N', N'-tetramethylhexanediamine, N, N, N ', N'-tetraethylmethanediamine and N , N, N ', N'-tetramethylethylenediamine selected from the group consisting of Cleaning liquid composition for an electronic material, characterized in that more than one. The cleaning liquid composition of claim 2, wherein the water-soluble organic solvent is at least one selected from the group consisting of a protic polar solvent and an aprotic polar solvent. The method of claim 2, wherein the water-soluble organic 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 monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, N-methyl pyrrolidone (NMP), N-ethyl pyrrolidone, 1,3-dimethyl- 2-imidazolidinone, 1,3-dipropyl-2-imidazolidinone, γ-butyrolactone, dimethyl sulfoxide (DMSO), sulfolane, triethyl phosphate, tributyl phosphate , Dimethyl carbonate, ethylene carbonate, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N- (2-hydroxyethyl) Group consisting of acetamide, 3-methoxy-N, N-dimethylpropionamide, 3- (2-ethylhexyloxy) -N, N-dimethylpropionamide and 3-butoxy-N, N-dimethylpropionamide Cleaning liquid composition for an electronic material, characterized in that at least one selected from. The method of claim 1, wherein the corrosion inhibitor is a cleaning liquid composition for an electronic material, characterized in that the benzotriazole derivative represented by the formula (5).
[Chemical Formula 5]

In Formula 5, R ₁₃ to R ₁₅ are each independently hydrogen, halogen, alkyl group, cycloalkyl group, allyl group, aryl group, amino group, alkylamino group, nitro group, cyano group, mercapto group, alkyl mercapto group, and hydride. It is a monovalent group which has a carboxyl group, a hydroxyalkyl group, a carboxyl group, a carboxyalkyl group, an acyl group, an alkoxy group, or heterocyclic amino acid as a substituent. The method according to claim 1, wherein the corrosion inhibitor 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-benzo Triazol-1-yl] methyl] imino] bismethylamine and 2,2 '-[[[amine-1 hydrogen-benzotriazol-1-yl] methyl] imino] bisethanol Cleaning liquid composition for an electronic material, characterized in that at least one.