KR101304622B1 - Cleaning solution - Google Patents

Abstract

This invention provides the cleaning composition which wash | cleans the surface by which aluminum or the alloy containing aluminum is exposed. The cleaning composition of the present invention can be used to clean flat panel display substrates such as semiconductor devices, liquid crystal devices, PDPs, organic light emitting devices, and the like.

Cleaner, Flat Panel Display

Description

Cleaner composition {Cleaning solution}

The present invention relates to a cleaning composition for cleaning a surface on which aluminum or an alloy containing aluminum is exposed. More particularly, the present invention relates to a cleaning composition which is not corrosive to aluminum and an aluminum alloy and is suitable for removing organic inorganic contaminants, particles, and the like, and a cleaning method using the same.

Flat panel display (FPD) devices, which are represented by semiconductor devices or liquid crystal displays, are manufactured through processes such as film formation, exposure, wiring, and etching, and during this process, contaminants and particles such as various organic materials and inorganic materials are generated. Adherence to the substrate surface results in contamination. If such a contaminant is attached and the subsequent process is performed, pinholes or pits of the film, disconnection of wires, bridges, or the like are generated, thereby lowering the yield of the product.

In the cleaning method widely used to clean the current substrate, a quaternary ammonium salt such as tetramethylammonium hydroxide (TMAH) or trimethyl (2-hydroxyethyl) ammonium hydroxide is used at 0.1 to 20% by weight. Although the cleaning method has some effects on the removal of organic and inorganic contaminants and particles, it causes fatal corrosion on the aluminum or aluminum alloy wirings forming the gate electrode and the source / drain electrode formed on the substrate. There are many problems, such as lowering of the overall yield and lowering the reliability of the liquid crystal display device. In order to solve the problems described above, various cleaning compositions have been proposed. For example, Japanese Unexamined Patent Application Publication No. 2002-69495 As a cleaning composition which does not corrode, a cleaning composition containing a reducing agent has been proposed. However, this patent restricts the metal to which the said cleaning composition is applied to Cu, and has no effect with respect to metals, such as aluminum.

The present invention provides a cleaning composition for cleaning an exposed surface of aluminum or an alloy containing aluminum, which is suitable for removing organic contaminants and particles, and which does not corrode aluminum or aluminum alloy wiring. The purpose.

In order to achieve the above object, the present invention has been developed by using an alkaline compound having excellent cleaning power and a reducing agent which suppresses the occurrence of corrosion, and developing a cleaning agent having excellent cleaning power and not corroding aluminum or aluminum alloy wiring.

The present invention is a cleaning composition for cleaning the surface exposed to aluminum or an alloy containing aluminum, comprising an alkaline compound and a reducing agent, the content (wt%) of the reducing agent in the cleaning composition is higher than the content (wt%) of the alkaline compound It is characterized by.

Hereinafter, the present invention will be described in detail.

The alkaline compound in the cleaning composition of the present invention exhibits excellent performance in removing organic-inorganic contaminants and particles, and a reducing agent serves to suppress corrosion of metals.

The ratio A / B of the weight% concentration A of the reducing agent in the cleaning composition to the weight% concentration B of the alkaline compound is preferably 1.1 or more, more preferably 2 or more. This is because corrosion of metal may occur when A / B is less than 1.1.

The detergent composition of the present invention comprises an alkaline compound of 0.05 to 2% by weight, a reducing agent of 0.1 to 5% by weight and the residual amount of water, characterized in that the content of the reducing agent is higher than the content of the alkaline compound.

The content of the alkaline compound is 0.05 to 2% by weight, preferably 0.1 to 1% by weight of the total weight of the detergent composition. This is because if the content of the alkaline compound is less than 0.05% by weight, the cleaning power is significantly lowered, and if it exceeds 2% by weight, the corrosion of the metal is significantly increased. The alkaline compound includes one selected from the group consisting of mono ethanol amine, mono isopropyl amine, hydroxyl amine, ammonia water, tetramethylammonium hydroxide and mixtures thereof, preferably tetramethyl ammonium hydroxide.

The reducing agent serves to prevent corrosion of the metal, the content of the reducing agent is 0.1 to 5% by weight, preferably 1 to 3% by weight of the total weight of the cleaning composition. If the content of the reducing agent is less than 0.1% by weight of the corrosion of the metal occurs, if it exceeds 5% by weight can reduce the cleaning power. Specific examples of reducing agents include thioglycol, thioglycerol, thioglycolic acid, thiodiacetic acid, thioacetic acid, thiodiethanol, and ascorbic acid. , Formic acid, oxalic acid or mixtures thereof, preferably thioglycerol or ascorbic acid are used alone or in combination.

In addition, the detergent composition according to the present invention may further include a surfactant. The surfactant serves to improve the cleaning speed by lowering the contact angle at which the cleaning composition comes into contact with the surface of the metal. The content of the surfactant is 0.0001 to 1% by weight, preferably 0.01 to 0.5% by weight of the total weight of the detergent composition. If the content of the surfactant is less than 0.0001% by weight it is not possible to improve the cleaning rate, if it exceeds 1% by weight because a large amount of foam is generated.

The surfactant may be used alone or in combination of two or more kinds of anionic surfactants, nonionic surfactants or fluorine-based surfactants, and particularly preferably nonionic surfactants.

Specific examples of the anionic surfactants include carboxylate salts such as higher fatty acid alkali salts (soaps), N-acrylic amino acid salts, alkyl ether carboxylates, and acylated peptide sulfonates; Alkyl sulfonates, alkylbenzenes and alkylamino acid salts; Sulfonate salts such as alkylnaphthalene sulfonate salts, and sulfobacter acid salts; Sulfate ester salts such as sulfated oil, alkyl sulfate, alkyl ether sulfate, alkylaryl ether sulfate and alkylamide sulfate; And phosphate ester salts such as alkyl phosphates, alkyl ether phosphates and alkyl aryl ether phosphates.

The nonionic surfactant is a surfactant which does not have a group dissociated into ions in an aqueous solution, and has a -OH group. Although relatively hydrophilic, the molecule has ester, acid amide, and ether linkages. Specific examples of nonionic surfactants include ether type such as alkyl and alkylaryl polyoxyethylene ethers, alkylaryl formaldehyde condensed polyoxyethylene ethers and block polymers having polyoxypropylene as a lipophilic; Ester ether types such as polyoxyethylene ether of glycerin ester, polyoxyethylene ether of sorbitan ester, and polyoxyethylene ether of sorbitol ester; Ester types such as polyethylene glycol fatty acid esters, glycerin esters, sorbitan esters, propylene glycol esters, sugar esters and alkyl polyglucosides; And nitrogen-containing types such as fatty acid alkanolamides, polyoxyethylene fatty acid amides, polyoxyethylene alkylamines, and amine oxides.

Specific examples of the fluorine-based surfactant include anionics such as perfluoroalkyl carboxylate, perfluoroalkyl sulfonate, perfluoroalkyl sulfate, and perfluoroalkyl phosphate; Cationic systems such as perfluoroalkyl amine salts, and perfluoroalkyl quaternized ammonium salts; Amphoteric ionic systems such as perfluoroalkyl carboxy betaine, and perfluoroalkyl sulfobetaine; And nonionic surfactants such as fluorinated alkyl polyoxyethylene, and perfluoroalcohol polyoxyethylene.

The cleaning method using the cleaning composition according to the present invention is not particularly limited, and an immersion cleaning method, a rocking cleaning method, an ultrasonic cleaning method, a shower spray cleaning method, a puddle cleaning method, a brush cleaning method, or a stirring cleaning method may be used. Cleaning or ultrasonic cleaning is preferred.

 The cleaning method by immersing the substrate in the cleaning composition or by using ultrasonic waves can be performed at room temperature, and thus it is not necessary to clean at a high temperature, thereby saving energy and minimizing corrosion of the metal. Here, room temperature means 10-40 degreeC, Preferably it is 20-30 degreeC, More preferably, it points out about 25 degreeC.

The board | substrate which can use the cleaning composition of this invention is not limited to what is contained in the specific apparatus, As long as it is a film | membrane quality containing the metal used for a semiconductor element or a flat panel display element, it is possible.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited thereto.

Example  1 to 4 and Comparative example  1-3  : Preparation of Cleaning Composition

The cleaning composition was prepared by stirring at a speed of 500 rpm for 1 hour at room temperature using the components and contents shown in Table 1 in a mixing tank equipped with a stirrer.

Experimental Example  : Evaluation of detergency and corrosion

In order to evaluate the detergency and corrosion of the detergent composition according to the present invention, the following experiment was performed.

1. Evaluation of cleaning power

15L of the cleaning composition prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were placed in a spray equipment, and the substrate was contaminated with PSL (Polystylene Latex) for a predetermined time, and then the cleaning product was taken out. Wash with water for minutes. Dry with a spin dryer.

PSL contamination: Dilute PSL to a certain concentration in water, drop a certain amount onto the substrate, leave for 1 minute, and dry with a spin dryer.

2. Corrosion assessment

100 ml of the cleaning composition prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were placed in a beaker having a capacity of 250 ml, respectively, and the substrate having the aluminum single layer formed thereon was immersed for 30 minutes for cleaning. The washings were taken out, washed with water, dried with nitrogen gas to remove the water on the surface of the washings, and dried, and the degree of corrosion was observed by visual observation and a four-point probe.

The results of detergency and corrosiveness (marked with X when the etching rate for the aluminum film exceeds 1 μs / min) are shown in Table 1.

[Table 1]

Alkaline compounds
TMAH
(weight%) reducing agent Nonionic
Surfactants
(weight%) water
(weight%) Cleaning power causticity TGL
(weight%) Ascorbic acid
(weight%) Example 1 0.5 2 - Balance 77% ○
(Etching Speed≤1Å / min) Example 2 0.5 One One - Balance 75% ○
(Etching Speed≤1Å / min) Example 3 One - 2 - Balance 82% ○
(Etching Speed≤1Å / min) Example 4 0.5 2 - 0.05 Balance 85% ○
(Etching Speed≤1Å / min) Comparative Example 1 0.5 - - - Balance 66% 〉
(Completely removed) Comparative Example 2 - One - - Balance 45% ○
(Etching Speed≤1Å / min) Comparative Example 3 0.5 0.1 - - Balance 75% 〉
(Translucent)

* TMAH: Tetramethylammonium Hydroxide

* TGL: Thioglycerol

As shown in Table 1, the cleaning composition according to the present invention was confirmed that not only excellent cleaning power, but also no corrosiveness. In addition, the cleaning power was better when the surfactant is further included.

On the other hand, the cleaning composition prepared in Comparative Example 1 and Comparative Example 3 is excellent in the cleaning effect on the metal but can not be used as a corrosion of the metal layer, the cleaning composition prepared in Comparative Example 2 has good corrosion resistance to the metal but the cleaning power It is low and cannot be used as a cleaning composition.

As a result, it can be seen that using the cleaning composition according to the present invention, it is easy to clean the contaminants on the substrate without corrosion of the metal.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning composition for cleaning a surface on which aluminum or an alloy containing aluminum is exposed.

In particular, the cleaning agent according to the present invention can not only cause metal corrosion but also can remove contaminants on the substrate well. In a process where no metal is used, TMAH alone can be used as a cleaning agent, and TMAH at this time has excellent cleaning power. However, if there is a metal layer, the corrosion is severe and cannot be used. Therefore, the cleaning agent according to the present invention has a capability equal to or higher than that of the conventionally used cleaning power, and since the corrosion of the metal does not occur, it can be used even in a substrate having a metal layer. Therefore, the cleaning composition of the present invention may be a substrate containing a metal used in a flat panel display device such as a semiconductor device, a liquid crystal display device, a PDP, an organic light emitting device.

Claims (9)

A cleaning composition for cleaning surfaces exposed to aluminum or an alloy containing aluminum, comprising a reducing agent and an alkaline compound, wherein the weight percent of the reducing agent is higher than the weight percent of the alkaline compound, The reducing agent is included in 0.1 to 5% by weight of the total weight of the detergent composition, thioglycol (Thioglycol), thioglycerol (thioglycerol), Thioglycolic acid, Thiodiacetic acid, thioacetic acid ), Thiodiethanol, ascorbic acid, oxalic acid, and mixtures thereof. The cleaning composition according to claim 1, wherein the ratio A / B of the weight% concentration A of the reducing agent and the weight% concentration B of the alkaline compound in the cleaning composition is 1.1 or more. The method according to claim 1, wherein the alkaline compound is contained in 0.05 to 2% by weight of the total weight of the cleaning composition, the group consisting of mono ethanol amine, mono isopropyl amine, hydroxyl amine, ammonia water, tetramethylammonium hydroxide and mixtures thereof The cleaning composition, characterized in that selected from. delete The cleaning composition of claim 1, further comprising a surfactant in the cleaning composition. The detergent composition of claim 5, wherein the amount of the surfactant comprises 0.0001 to 1 wt% of the total weight of the detergent composition. The cleaning composition according to claim 6, wherein the surfactant is used alone or in combination of two or more anionic surfactants, nonionic surfactants or fluorine-based surfactants. The cleaning composition according to claim 7, wherein the surfactant is a nonionic surfactant. A method for cleaning a semiconductor device or a substrate for manufacturing a flat panel display device using the cleaning composition according to any one of claims 1 to 3 and 5 to 8.