KR20160034600A - Cleansing composition for metal film - Google Patents

Abstract

The present invention relates to a cleaner composition for a metal film and, more specifically, to a cleaner composition for a metal film, which removes impurities and residue left on a metal film material during a flat panel display manufacturing process. The cleaner composition for a metal film comprises: at least one hydroxide selected from an alkali metal hydroxide and an alkyl ammonium hydroxide; a polar solvent capable of dissolving the hydroxide for at least one part by weight per 100 parts by weight; and a basic corrosion inhibitor, wherein the basic corrosion inhibitor may preferably be a pyridine-containing amine.

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 substrate 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 various organic substances and inorganic substances adhere to the surface of the substrate, resulting in a problem that residues are left. These contaminants are attached or. If the following process is performed in a state in which residues and the like remain, 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

The present invention has been conceived to solve the problems of the prior art, and it is an object of the present invention to provide a detergent composition for a metal film containing a basic corrosion inhibitor without damaging the metal film in the process of removing residues and impurities, And a cleaning agent composition for a metal film which prevents the residue of the corrosion inhibitor from being left in the rinsing process.

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.

The basic corrosion inhibitor may preferably be an amine group-containing pyridine.

The detergent composition for a metal film of the present invention includes a basic corrosion inhibitor to prevent corrosion of metals during cleaning and to provide an effect that no residue remains after rinsing with pure water.

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.

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

According to the present invention,

The metal, such as the metal film, which may be exposed to the cleaning composition in the flat panel display manufacturing process may be removed from the substrate after plasma etching from the substrate without any undesirable degree of elimination and any remaining residues such as residues or other non- And a cleaning agent composition for a metal film which does not leave a residue of a corrosion inhibitor after rinsing.

That is, the present invention relates to a detergent composition for a metal film that prevents corrosion of a metal film after a process such as etching and removes residues and impurities remained on the film,

(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) ) Basic corrosion inhibitor. ≪ / RTI >

The detergent composition of the present invention has such a composition that not only has anticorrosion property against a metal film during cleaning but also easily removes residues and impurities such as a resist, an organic insulating film and transparent resin, It is possible to provide an effect that remains.

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 and 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-methoxyphenylacetamide, 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.

Among the above solvents, water can be preferably used as the protonic polar solvent, and DMSO can be preferably 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 basic corrosion inhibitor is preferably an amine group-containing pyridine. The nitrogen atom in the pyridine in the amine group-containing pyridine is cationized during rinsing with pure water. Therefore, it is excellent in solubility in water and a polar solvent and does not remain on the surface of the metal film. That is, since the corrosion inhibitor which is chelated with the metal film is cationized, the bonding force with the metal film is weakened and the solubility in water and the polar solvent is increased. Therefore, the substrate and the metal film can be easily cleaned .

If the corrosion inhibitor is left on the substrate, the surface of the metal film or the like, the adhesiveness with the layer positioned on the substrate in subsequent steps may be lowered. Therefore, the corrosion inhibitor of the present invention does not leave a residue after rinsing, thereby providing an effect of increasing the precision of a subsequent process.

The corrosion inhibitor is more preferably at least one selected from compounds represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1,

R1 and R2 are each hydrogen, C1-C4 aliphatic hydrocarbon,

R3 may be at least one selected from the group consisting of hydrogen, C1-C4 aliphatic hydrocarbon, hydroxyl group, alkoxy group, carboxylic acid group, amine group and halogen.

Examples of the corrosion inhibitor of Formula 1 include the following Formulas 2 to 8, but the present invention is not limited thereto.

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

These may be used alone or in combination of two or more.

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 oxygen scavenger include, but are not limited to, ethanolamine. 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 be included in an amount of 1 wt% or less 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 7 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) 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 (3) 0.2 - - Example 2 TMAH 0.4 DMSO 30 Balance (3) 0.05 - - Example 3 TMAH 0.4 DMSO 30 Balance (3) 0.01 - - Example 4 TMAH 0.4 DMSO 30 Balance Formula 4 0.2 - - Example 5 TMAH 0.4 DMSO 30 Balance Formula 5 0.2 Example 6 TEAH 0.5 DMSO 30 Balance (3) 0.2 Ethanolamine 0.3 Example 7 TMAH 0.4 DMSO 30 Balance Formula 9 0.2 Tetraethylene glycol
Dimethyl ether 0.5 Comparative Example 1 TMAH 0.4 DMSO 30 Balance - - - - Comparative Example 2 TMAH 0.4 DMSO 30 Balance BTA 0.2 - - Comparative Example 3 TMAH 0.4 DMSO 30 Balance ATZ 0.2 - -

week)

(B) polar solvent

DMSO: dimethylsulfoxide

(C) Corrosion inhibitor

[Chemical Formula 9]

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 7 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 stacked layer according to a conventional method was immersed in the solution of Example 1 To 7 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, The pH change of the detergent composition prepared with 0.1 wt% of the same type of corrosion inhibitor as in each of Examples 1 to 7 and Comparative Examples 1 to 3 was measured and the results are shown in Table 2 below.

 [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 7 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 7 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

Experimental Example  3: Contact angle  evaluation

The contact angle evaluation test was carried out to evaluate the change of the contact angle according to the residual corrosion inhibitor of the cleaning composition prepared in Examples 1 to 7 and Comparative Examples 1 to 3. [

A glass substrate having a thickness of 2500 Å of copper was prepared on a glass substrate by a thin film sputtering method according to a conventional method. The substrate was allowed to stand in the air for 24 hours and contaminated with various organic substances, minerals, particles and the like in the air, and then sprayed with a cleaning agent composition of Examples 1 to 7 and Comparative Examples 1 to 3 at 40 ° C for 2 minutes using a spray- Respectively. After washing, it was washed with ultrapure water for 30 seconds and then dried with nitrogen. 0.5 [micro] l of ultrapure water droplets were dropped on the substrate to measure the contact angle after cleaning, and the results are shown in Table 2 below.

[Contact Angle Evaluation Standard]

○: The contact angle is lower than that of the copper surface before cleaning. (Reduction in contact angle due to increase in roughness of copper surface due to cleaning)

X: The contact angle is higher than that of the copper surface before cleaning. (Increase in contact angle due to surface residue of the corrosion inhibitor)

Cleanliness Corrosion resistance Contact angle evaluation Residues and contaminants
Cleanliness Change in pH Cu Example 1 ◎ ○ ○ ○ Example 2 ◎ ○ ○ ○ Example 3 ◎ ○ ○ ○ Example 4 ◎ ○ ○ ○ Example 5 ◎ ○ ○ ○ Example 6 ◎ ○ ○ ○ Example 7 ◎ ○ ○ ○ 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 7 exhibited a very excellent cleaning effect in the removal of residues. In addition, it was confirmed that corrosion does not occur in the evaluation of the corrosion resistance of the metal film, and it has excellent metal corrosion preventive property. In addition, in the contact angle evaluation, it was confirmed that the contact angle with respect to the surface of the copper before cleaning was lowered, so that no corrosion inhibitor remained.

On the other hand, the compositions of Comparative Examples 1 to 3 showed no or low pH increase after the addition of the additives, and thus, it was presumed that the cleaning properties were low, and the results of the evaluation of the residue cleaning were not excellent. In addition, the evaluation of the corrosion inhibition did not prevent the occurrence of serious corrosion, and it was confirmed that the corrosion inhibitor remained on the surface of the metal because the contact angle with respect to the copper surface before cleaning was increased.

Claims (6)

(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) ) &Lt; / RTI &gt; basic detergent composition.
The method according to claim 1,
Wherein the basic corrosion inhibitor is an amine group-containing pyridine.
The method of claim 2,
Wherein the amine group-containing pyridine is represented by the following general formula (1).
[Chemical Formula 1]

In Formula 1,
R1 and R2 are each hydrogen or a C1-C4 aliphatic hydrocarbon,
R3 may be at least one selected from the group consisting of hydrogen, C1-C4 aliphatic hydrocarbon, hydroxyl group, alkoxy group, carboxylic acid group, amine group and halogen.
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 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.

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