KR20160033960A - Cleansing composition for metal film - Google Patents

Abstract

The present invention relates to a detergent composition for a metal film, and more particularly to a detergent composition for removing residues and impurities remaining on a metal film during a flat panel display (FPD) manufacturing process.

Description

TECHNICAL FIELD [0001] The present invention relates to a cleaning composition for a metal film,

The present invention relates to a detergent composition for a metal film, and more particularly, to a detergent composition for removing residues, impurities and contaminants remaining on a metal film after various processes in a flat panel display manufacturing process.

A flat panel display device, such as a semiconductor device, is manufactured through processes such as film formation, exposure, and etching. However, in such a manufacturing process, contamination occurs in which very small particles having a size of 1 mu m or less such as various organic substances and inorganic substances adhere to the substrate surface. When these processings are carried out with these particles attached, pinholes, pits, wirings, and bridges of the film are generated, and the yield of the product is lowered.

Therefore, cleaning for removing contaminants is carried out between respective processes, and a lot of cleaning agents have been also studied for the cleaning.

Korean Patent Publication No. 2004-0035368 discloses a detergent composition for semiconductor and TFT-LCD comprising an alkanolamine, an organic solvent, a chelate compound and water. However, the detergent has insufficient ability to remove organic contaminants and particles, and precipitation problems may occur during long-term use due to polyhydroxybenzene chelate compounds such as catechol or gallic acid. Korean Patent Laid-Open Publication No. 2006-0127098 discloses a cleaning agent for substrates for semiconductor devices including organic acids, organic alkalis, surfactants and water.

However, since the cleaning agent of the above patent is a solution in an acidic range, there is a disadvantage that the residue can remain in the rinsing process and the removing power of the particles is insufficient. In addition, it has a disadvantage that it is not excellent in corrosion resistance against a metal film.

Korea Patent Publication No. 2004-0035368 Korea Patent Publication 2006-0127098

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made to solve the above problems of the prior art, and it is an object of the present invention to provide a detergent composition for a metal film containing an azole compound dimer corrosion inhibitor, It is an object of the present invention to provide a detergent composition for a metal film having a removal ability.

According to the present invention,

(A) at least one member selected from the group consisting of alkali metal hydroxide and alkylammonium hydroxide, (B) a polar solvent capable of dissolving at least 1 part by weight of the hydroxide per 100 parts by weight, and (C) The present invention provides a detergent composition for a metal film, which comprises a compound dimer corrosion inhibitor.

The detergent composition for a metal film of the present invention can prevent corrosion of a metal film during cleaning to prevent metal corrosion, and can easily remove residues and impurities after a process such as etching.

1 is a scanning electron microscope (SEM) photograph showing the corrosion state of the surface of a metal film generated during cleaning,
Fig. 1 (A) shows a state in which no corrosion has occurred after cleaning, Fig. 1 (B) shows a state where a small amount of metal oxide is generated due to slight oxidation, Fig. 1 (C) shows a state where a large amount of metal oxide , And (D) are photographs in which a large amount of metal oxide is etched and then disappears after the generation of a large amount of metal oxide, and the surface is very rough.
2 is a spectrum showing the results of measurement of ¹ H-NMR (proton NMR) of the compound of Formula 3 of the present invention.

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

According to the present invention,

The metal such as the metal film that may be exposed to the cleaning composition in the flat panel display device manufacturing process does not corrode to any unwanted degree and does not corrode any residues such as residues or plasma residue after plasma etching from the substrate or other non- A cleaning agent composition for a metal film is disclosed.

That is, the present invention relates to a detergent composition for a metal film which removes residues and impurities remaining on a substrate after a process such as etching,

(A) at least one hydroxide selected from among alkali metal hydroxide and alkyl ammonium hydroxide, (B) a polar solvent capable of dissolving at least 1 part by weight of the hydroxide per 100 parts by weight, and (C) ) Azole-based compound dimer corrosion inhibitor.

The detergent composition of the present invention has such a composition that it has not only the anticorrosion property against the metal film during cleaning but also the effect of easily removing residues and impurities such as resists, organic insulating films and transparent resins.

Hereinafter, each component will be described in detail.

(A) Hydroxide  compound

The hydroxide compound of the present invention discharges hydroxide ions, and penetrates into residues such as a resist, thereby promoting dissolution of a polymeric resist and the like. Also, it has a cleaning action against organic pollutants and inorganic contaminants, and can prevent the re-adsorption of particles after cleaning, thereby improving the cleaning effect.

The hydroxide compound may be at least one selected from the group consisting of alkali metal hydroxide and alkyl ammonium hydroxide.

Examples of the alkali metal hydroxide include LiOH, NaOH, KOH, RbOH, and CsOH. These alkali metal hydroxides may be used singly or in combination of two or more, but are not limited thereto.

The alkylammonium hydroxide may be, for example, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH) and tetrabutylammonium hydroxide (TBAH) , But is not limited thereto.

The hydroxides of the present invention are preferably contained in an amount of 0.1 to 5% by weight, more preferably 0.3 to 1% by weight, based on the total weight of the detergent composition. If the detergent composition of the present invention contains less than 0.1% by weight of the hydroxide compound, the penetration of the hydroxide ion into the resist polymer is decreased and the dissolution of the resist is lowered. If the concentration exceeds 5% by weight, And there is a problem that the content of water is increased and the solubility of the polymer resin is decreased.

However, the detergent composition of the present invention is preferably the above-mentioned content ratio when it is used as a detergent. However, considering the easiness of transportation and storage, 10 to 30% by weight of the hydroxide compound is included in the total weight of the detergent composition, And it is preferably diluted with the above-mentioned composition at the time of use.

(B) polar solvent

The polar solvent (B) of the present invention penetrates the resist and increases the swelling property, thereby increasing the peeling force of the residue or the like from the substrate surface. It also improves the solubility of the detergent composition of the present invention in water and facilitates the removal of residue and detergent composition in the subsequent water wash step.

The polar solvent is characterized by being capable of dissolving at least 1 part by weight of the hydroxyl compound per 100 parts by weight of the hydroxyl compound. This is necessary in order to suppress the generation of precipitates of the hydroxide compound by aging during manufacture and storage. Further, when the cleaning is carried out under the heating condition in the cleaning step, it is necessary to suppress the generation of the precipitate due to the increase of the concentration of the hydroxide compound due to the volatilization of the solvent.

Examples of the polar solvent include a protonic polar solvent and an aprotic polar solvent, which may be used alone or in combination. Examples of the alkyl alcohols include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, isopropanol, butanol, Pentanol, hexanol, heptanol, octanol and the like,

Examples of glycols 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, 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 monobutyl Alkylene glycol monoalkyl ethers such as ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether and tripropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and tetrahydrofurfuryl Alcohol and the like, all of which are one kinds may be used alone or in combinations of two or more.

Preferable examples of the aprotic polar solvent include pyrrolidone compounds such as N-methylpyrrolidone (NMP) and N-ethylpyrrolidone; Imidazolidinone compounds such as 1,3-dimethyl-2-imidazolidinone and 1,3-dipropyl-2-imidazolidinone; lactone compounds such as? -butyrolactone; Sulfoxide compounds such as dimethylsulfoxide (DMSO), diethylsulfoxide, dipropylsulfoxide, sulfolane and the like; Phosphate compounds such as triethyl phosphate, tributyl phosphate and the like; Carbonate compounds such as dimethyl carbonate, ethylene carbonate, and the like; N, N-dimethylacetamide, N- (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, They may be used singly or in combination of two or more, but the present invention is not limited thereto.

As the polar protic solvent, water may be most preferably used as the polar solvent, and DMSO may preferably be used as the aprotic polar solvent.

The polar solvent of the present invention is preferably contained in an amount of 70 wt% or more based on the total weight of the detergent composition. In consideration of the solubility of the hydroxyl compound, the polar solvent is preferably contained in an amount of 50 wt% .

The aprotic polar solvent is preferably contained in an amount of 0 to 45% by weight, more preferably 10 to 30% by weight based on the total weight of the detergent composition.

The content of the aprotic polar solvent that can be contained in the detergent composition of the present invention can be controlled according to the kind of the object to be cleaned. When the object of the simple object is to be removed, the aprotic polar solvent need not be added. However, when it is intended to remove a polymer such as a photoresist, it is more preferable to use at least 10% by weight of an aprotic polar solvent based on the total weight of the detergent composition to swell the polymer in a crosslinked state and to dissolve the removed polymer have.

However, if the content of the aprotic polar solvent exceeds 45 wt% with respect to the total weight of the detergent composition, the activity of the hydroxide compound is inhibited and the formation of precipitates is liable to occur due to the lowered solubility, .

(C) Corrosion inhibitor

The detergent composition for a metal film of the present invention comprises a corrosion inhibitor (C). The corrosion inhibitor is included in the detergent composition to improve the corrosion inhibiting ability of the metal film including aluminum and / or copper. In particular, it is excellent in solubility in water and polar solvents and does not remain on the surface of the substrate.

The corrosion inhibitor is characterized by being an azole-based compound. The corrosion inhibitor containing an azole-based compound dimer has a chelating effect with the nitrogen atom contained in each azole-based compound to prevent corrosion or damage of the metal by the cleaning composition during the cleaning process can do. The detergent composition of the present invention contains a corrosion inhibitor containing an azole-based compound dimer, thereby increasing the chelating effect with the metal surface and increasing the bonding force.

The reason why the azole-based compound dimer of the present invention exhibits excellent corrosion resistance is described in more detail. The nitrogen atom existing in the molecule of the azole-based compound binds to the surface of the metal and defends the metal surface from attacks such as oxidizing agents. The reaction between the azole compound and the metal surface is a reversible reaction, which results in a dynamic equilibrium of binding and separation. In this case, as the time for bonding of the metal surface and the azole compound increases, the corrosion resistance is improved. When two azole compounds are contained in one molecule, even if one azole compound is separated from the metal surface, The azole-based compound may be bonded to the metal surface. As a result, the azole-based compound can not be far away from the metal surface, so that the part of the azole-based compound that has been separated is again bonded to the metal surface. Thus, it can be explained that the azole compound as the corrosion inhibitor is not separated from the metal surface, so that the corrosion resistance is improved.

The azole-based compound dimer is preferably a benzotriazole dimer.

The benzotriazole dimer may more preferably be a compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

R1 is a C2 to C20 aliphatic hydrocarbon which may be connected to the nitrogen atom of the benzotriazole at one or two times,

R2 may be at least one selected from the group consisting of hydrogen, C1 to C4 aliphatic hydrocarbons, hydroxyl groups and carboxylic acid groups.

That is, the compound of Formula 1 is a tautomers compound represented by the following Formulas 1-1 to 1-3, and each of the compounds of Formulas 1-1 to 1-3, or a mixture thereof .

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In the above Chemical Formulas 1-1 to 1-3, R1 is a C2-C20 aliphatic hydrocarbon,

R2 may be at least one selected from the group consisting of hydrogen, C1 to C4 aliphatic hydrocarbons, hydroxyl groups and carboxylic acid groups.

Examples of the azole-based compound dimer include, but are not limited to, the following formulas (2) to (7), and at least one of them may be selected.

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

The corrosion inhibitor is preferably contained in an amount of 3% by weight or less based on the total weight of the detergent composition for a metal film, more preferably 0.001 to 1% by weight. When included in the above range, it is possible to prevent corrosion in the metal film made of aluminum or aluminum alloy and copper or copper alloy in the cleaning or DI rinse process, and the secondary contamination due to adsorption of the metal film surface and Deterioration of the peeling force can be prevented.

The detergent composition for a metal film of the present invention may further comprise at least one member selected from the group consisting of an oxygen scavenger and a surfactant as further additives (D).

In the present invention, the oxygen scavenger is further included in the detergent composition to help prevent corrosion of the metal. Examples of the scavenger include ethanolamine, but the present invention is not limited thereto. The oxygen scavenger may be included in an amount of 1 wt% or less based on the total weight of the detergent composition.

In the present invention, the surfactant is further included in the detergent composition to improve the wettability with respect to the surface to be cleaned, thereby improving the cleaning property. Examples thereof include, but are not limited to, tetraethylene glycol dimethyl ether and the like. The surfactant may preferably be present in an amount of up to 1% by weight based on the total weight of the detergent composition.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative 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  And Comparative Example : Preparation of detergent composition

The cleaning agent compositions of Examples 1 to 10 and Comparative Examples 1 to 3 were prepared by mixing the components shown in the following Table 1 according to the determined composition ratios.

(A) Hydroxide
compound (B) polar solvent (C) Corrosion
Inhibitor (D) Other additives Kinds weight% Magnetostrictive
Polar solvent Quantum property
Polar solvent Kinds weight% Kinds weight% Kinds weight% Deionized water Example 1 TMAH 0.4 DMSO 30 Balance Formula 4 0.1 - - Example 2 TMAH 0.4 DMSO 30 Balance Formula 4 0.05 - - Example 3 TMAH 0.4 DMSO 30 Balance Formula 4 0.01 - - Example 4 TMAH 0.4 DMSO 30 Balance Formula 4 0.1 - - Example 5 TMAH 0.4 DMSO 30 Balance Formula 4 0.1 Ethanolamine 0.1 Example 6 TMAH 0.4 DMSO 30 Balance Formula 4 0.1 Tetraethylene glycol
Dimethyl ether 0.5 Example 7 TMAH 0.4 DMSO 30 Balance (2) 0.1 - - Example 8 TMAH 0.4 DMSO 30 Balance Formula 5 0.1 - - Example 9 KOH 0.2 DMSO 30 Balance Formula 4 0.1 - - Example 10 TMAH 0.4 NMP 30 Balance Formula 4 0.1 - - Comparative Example 1 TMAH 0.4 DMSO 30 Balance - - - - Comparative Example 2 TMAH 0.4 DMSO 30 Balance BTA 0.1 - - Comparative Example 3 TMAH 0.4 DMSO 30 Balance ATZ 0.1 - -

week)

(A) Hydroxide  compound

TMAH: tetramethylammonium hydroxide,

KOH: Potassium hydroxide

(B) polar solvent

DMSO: dimethylsulfoxide

NMP: N-methylpyrrolidone

(C) Corrosion inhibitor

[Chemical Formula 2]

[Chemical Formula 4]

[Chemical Formula 5]

BTA: benzotriazole

ATZ: Aminotetrazole

(D) Other additives

Oxygen (O ₂ ) Remover: Ethanolamine

Nonionic surfactant: tetraethylene glycol dimethyl ether

< Experimental Example >

Experimental Example  1: of the detergent composition Residue  And contaminants Cleanliness  evaluation

(One)

The residue and contaminant cleaning properties of the detergent compositions prepared in Examples 1 to 10 and Comparative Examples 1 to 3 were evaluated.

In order to confirm the cleansing property of the cleaning composition for a metal film, a substrate contaminated with silicone oil, Al and SUS (stainless steel) powder on a wafer having a Cu laminate according to a conventional method was immersed in a solution To 10 and Comparative Examples 1 to 3 for 5 minutes. Thereafter, the substrate was cleaned with pure water for 1 minute to remove the cleaning composition remaining on the substrate, and the substrate was completely dried with nitrogen to remove pure water remaining on the substrate after cleaning.

Then, the degree of cleaning of the residue and contaminants was confirmed using a scanning electron microscope (SEM, Hitach S-4700), and the results are shown in Table 2 below.

[Evaluation of cleanliness of residues and contaminants]

◎: 100% removal of residues and contaminants

○: Removal of residues and contaminants more than 80%

△: Removal of less than 80% of residues and contaminants

X: No residues and contaminants were removed.

(2)

Based on the fact that as the pH of the detergent composition increases, cleaning properties such as residues and impurities are improved, 0.4 wt% of TMAH as a hydroxide, 30 wt% of DMSO as a solvent, deionized water balance, 10 and Comparative Examples 1 to 3, respectively. The results are shown in Table 2 below. [Table 2] &lt; tb &gt;&lt; TABLE &gt; Id = Table 2 Columns = 5 &lt; tb &gt;

 [Evaluation of pH change]

○: pH is improved by addition of additives.

?: No change in pH due to addition of additives

×: pH is lowered by addition of additives.

Experimental Example  2: Metal film  corrosion Preventiveness  evaluation

In order to evaluate the corrosion resistance of the metal film of the detergent compositions prepared in Examples 1 to 10 and Comparative Examples 1 to 3, a glass substrate having a thickness of 2500 Å of copper was formed on a glass substrate by thin film sputtering Prepared. The temperature of the cleaning composition prepared in Examples 1 to 10 and Comparative Examples 1 to 3 was maintained at 40 占 폚, and the glass substrate on which the copper was formed was immersed for 30 minutes to be cleaned. Thereafter, the substrate was rinsed with DIW (deionized water) for 30 seconds, and the detergent composition, DIW, and the like remaining on the substrate were completely removed using nitrogen.

The degree of surface oxidation of the substrate was confirmed using a scanning electron microscope (SEM, Hitachi S-4700), and the results are shown in Table 2 and FIG.

[Evaluation Criteria for Corrosion Resistance]

◎: No corrosion occurred

○: Slight corrosion

△: Severe corrosion

X: etch after corrosion

Cleanliness Corrosion resistance Residues and contaminants
Cleanliness Change in pH Cu Example 1 ◎ ○ ◎ Example 2 ◎ ○ ◎ Example 3 ◎ △ ○ Example 4 ◎ ○ ◎ Example 5 ◎ ○ ◎ Example 6 ◎ ○ ◎ Example 7 ◎ ○ ○ Example 8 ◎ ○ ◎ Example 9 ◎ ○ ○ Example 10 ○ ○ ◎ Comparative Example 1 ◎ △ × Comparative Example 2 ○ × ○ Comparative Example 3 ○ × △

As shown in Table 2, it was confirmed that the cleaning composition of Examples 1 to 10 exhibited a very excellent cleaning effect in the removal of residues. In addition, it was confirmed that corrosion of Cu did not occur even in the evaluation of the corrosion resistance of the metal film, and it was confirmed that it has excellent metal corrosion resistance.

On the other hand, the compositions of Comparative Examples 1 and 3 showed no or low pH increase after addition of the additives, and thus, it was expected that the cleaning properties were low and the cleaning and residue cleaning properties were not excellent. In addition, it has been confirmed that the corrosion prevention evaluation does not prevent the occurrence of severe corrosion of the metal.

Claims (7)

(A) at least one hydroxide selected from among alkali metal hydroxide and alkyl ammonium hydroxide, (B) a polar solvent capable of dissolving at least 1 part by weight per 100 parts by weight of said hydroxide, and (C) ) Azole-based compound dimer corrosion inhibitor.
The method according to claim 1,
0.1 to 5 wt% of a hydroxide based on the total weight of the detergent composition;
At least 70% by weight of a polar solvent; And
And 3% by weight or less of a corrosion inhibitor.
The method according to claim 1,
Wherein the azole-based compound dimer is a benzotriazole dimer.
The method of claim 3,
Wherein the benzotriazole dimer is at least one selected from compounds represented by the following general formula (1).
[Chemical Formula 1]

In Formula 1,
R1 is a C2 to C20 aliphatic hydrocarbon which may be connected to the nitrogen atom of the benzotriazole at one or two times,
R2 may be at least one selected from the group consisting of hydrogen, C1 to C4 aliphatic hydrocarbons, hydroxyl groups and carboxylic acid groups.
The method according to claim 1,
Wherein the alkali metal hydroxide is at least one selected from the group consisting of LiOH, NaOH, KOH, RbOH, and CsOH;
Wherein said alkylammonium hydroxide is selected from the group consisting of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH) and tetrabutylammonium hydroxide (TBAH) By weight or more based on the total weight of the cleaning composition.
The method according to claim 1,
An oxygen scavenger, a surfactant, an oxygen scavenger, and a surfactant.
The method of claim 4,
Wherein the compound of Formula 1 is at least one compound selected from the group consisting of the following Chemical Formulas 1-1 to 1-3.
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In the above Chemical Formulas 1-1 to 1-3, R1 is a C2-C20 aliphatic hydrocarbon,
R2 may be at least one selected from the group consisting of hydrogen, C1 to C4 aliphatic hydrocarbons, hydroxyl groups and carboxylic acid groups.

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