KR101341746B1 - Resist stripper composition and a method of stripping resist using the same - Google Patents

Abstract

The present invention is 5-30% by weight of the alkanol amine compound, 50-90% by weight of the glycol ether compound, 0.1-10% by weight of the hydroxy benzene compound, 0.1-10% by weight and 0.1% by weight of the azole compound The present invention relates to a resist stripper composition comprising less than 10% by weight of water and a method for stripping resist using the same.

Resist stripper, alkanol amine, glycol ether, hydroxy benzene, azole

Description

Resist stripper composition and a method of stripping resist using the same

The present invention relates to a resist stripper composition and a method for stripping a resist using the same, and more particularly, to a resist stripper composition and a resist stripper using the same, which can effectively remove a resist pattern and an etching residue without damaging wiring or the like. It is about a method.

Recently, as the demand for high resolution is gradually increased, flat panel display devices continue to make efforts to increase the number of pixels per unit area. This gradually entails a reduction in the wiring width of the thin film transistor, and in order to cope with such miniaturization of the wiring, a dry etching process is introduced.

As a result, the required performance of the stripping solution required for the stripping process, which is a resist removal step, after the metal pattern is completed, is also increasing. In addition, the narrower the wiring width, the more sensitive it is to the influence of corrosion on the wiring, and thus the corrosion inhibiting ability of the wet chemicals used in the process, such as a cleaning liquid and a stripping liquid, is emerging as an important criterion for the application of the process. In particular, as the size of a flat panel display has recently increased, the resistance of the wiring has been improved, and it has become practical to use copper having a lower resistance than aluminum, which is mainly used as the wiring material.

In addition, recently, in order to secure a price competitiveness of the flat panel display device, the demand for price reduction of parts and materials used in the manufacture of the flat panel display device also plays an important role as much as the corrosion inhibiting ability. Therefore, in developing a resist peeling liquid composition, the development of the peeling liquid which can exhibit the same effect, without using a conventional expensive solvent among the essential solvents is calculated | required.

As mentioned above, there are patents suggesting solutions for the removal of resists and etch residues modified by harsh process conditions and corrosion inhibition for metal wiring.

Japanese Patent Laid-Open Nos. 2000-267302 and 10-256210 disclose a stripping solution containing an organic acid, water, and a surfactant, and a stripping solution containing an organic acid and an aqueous cleaner. In the case of the liquid, the peeling force on the precipitate is weak, and if the amount of the organic acid is increased in order to increase the removability of the precipitate, problems such as increased corrosion of the aluminum wiring will occur.

In Korean Patent Laid-Open No. 2001-0024483, as a preferred example, a mixture of N-monoethanolamine, dimethyl sulfoxide, gallic acid and its ester of corrosion inhibitor and residual water can effectively remove the resist at low temperature without redeposition of positive metal ions. It can be disclosed. However, the stripping solution does not have sufficient peeling ability with respect to the resist and dissolving ability with respect to the polymer material constituting the resist, so that the residue of residue is reattached to a semiconductor substrate or a glass substrate, or is applied to heat applied during the peeling process. Due to the large amount of evaporation loss due to the short period of use of the stripper composition.

Korean Patent Laid-Open Publication No. 2003-0022273 discloses that the residue can be effectively removed after etching with a compound containing a fluoride compound, a sulfoxide or sulfone solvent, a basic amine compound and water. However, the stripping solution has a problem in terms of toxicity, workability and wastewater treatment, etc., and has to be used only in the etching process of silicon oxide due to the fluoride compound.

Korean Patent Laid-Open Publication No. 1995-0012144 discloses that an alkali photoresist stripping composition containing a reducing agent can suppress corrosion of metals, but it does not have sufficient sediment removal properties and low corrosion resistance of aluminum wirings in devices having a narrow wiring width. The problem was not solved.

Japanese Patent Laid-Open No. 9-152721 discloses a stripper composition containing an alkanol amine, hydroxy amine, diethylene glycol monoalkyl ether, a sugar compound such as sorbitol, and water as a corrosion inhibitor. However, the above-mentioned stripper composition has disadvantages in that the peeling force on the photoresist film deteriorated and cured by the harsh process and the removal force on the etching residue generated by reacting with the resist and the metallic by-product in the etching process are insufficient. .

Therefore, in order to solve these problems in this field, the development of a new etchant composition is required.

An object of the present invention is suitable for removing residues of resist, residues of dry etching and residues of wet etching in the process of manufacturing a flat panel display device, and does not corrode the wiring including aluminum and the wiring including copper at the same time, The present invention provides a resist stripper composition capable of reducing costs by not using an expensive solvent as a component and a method for stripping a resist using the same.

In order to achieve the above technical problem, the present invention is 5 to 30% by weight of the alkanol amine compound, 50 to 90% by weight of the glycol ether compound, 0.1 to 10% by weight of hydroxy benzene compound, azole compound 0.1 to the total weight of the composition A resist stripper composition is provided comprising at least -10 wt% and at least 0.1 wt% and less than 10 wt% water.

In addition, the present invention provides a method for removing a resist using the resist stripper composition to remove the modified, cured resist residues and etching residues by hot or dry etching.

The resist stripper composition according to the present invention, in the manufacture of a flat panel display device, has excellent removal ability against hardened resist and dry and wet etching residues, and has an anti-corrosion effect on aluminum and aluminum alloy wires and copper and copper alloy wires. Very good Therefore, the present invention can be applied to a manufacturing process of a flat panel display device to which a fine pattern is applied to realize high resolution.

In addition, when the resist stripper composition according to the present invention is used, an equivalent or more effect can be obtained without using other solvents such as a pyrrolidone compound or a sulfoxide compound in addition to the glycol ether, thereby resulting in a resist stripper composition. There is an effect that can be supplied cheaply.

Hereinafter, the present invention will be described in detail.

The alkanol amine compound, which is an alkaline compound used in the resist stripper composition of the present invention, is a water-soluble organic solvent, such as dry etching or wet etching, ashing or ion implant processing, and the like. It penetrates strongly into the polymer matrix of the modified or crosslinked resist under various process conditions and serves to break the attraction force present in or between molecules. Such alkanol amines The action of the compound creates an empty space in the structurally vulnerable portion of the resist remaining in the substrate, thereby transforming the resist into an amorphous polymer gel mass, so that the resist attached to the substrate can be easily removed.

Preferred examples of the alkanol amine compound include monoethanolamine, diethanolamine, 2-aminoethanol, 2- (ethylamino) ethanol, 2- (methylamino) ethanol, N-methyldiethanolamine, dimethylaminoethanol, Diethylaminoethanol, 2- (2-aminoethoxy) ethanol, 1-amino- 2-propanol, triethanolamine, monopropanolamine, monoisopropanolamine, dibutanolamine, and the like, and the like, and these may be used alone or in combination. The above can be mixed and used.

In addition, the alkanol amine compound is preferably contained 5 to 30% by weight based on the total weight of the composition. When included in less than 5% by weight, sufficient cleaning effect cannot be achieved, and when included in excess of 30% by weight, the corrosion rate for the aluminum or aluminum alloy wiring is increased rapidly.

The glycol ether compound used in the resist stripper composition of the present invention is a protic polar solvent, and serves to increase the solubility of the residue after dry etching or wet etching. In addition, due to the high boiling point, the chemical liquid loss due to volatilization can be minimized when the chemical liquid is used.

Preferred examples of the glycol ether compounds include glycol ethers and ester derivatives of glycol ethers, and specific examples thereof 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 monoisopropyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monopropyl ether, ethylene Glycol monophenyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and the like. These may be used alone or in combination of two or more thereof.

The glycol ether compound preferably contains 50 to 90% by weight, more preferably 60 to 80% by weight based on the total weight of the total composition. When the glycol ether compound is included in less than 50% by weight, the ability to dissolve the gelled polymer due to the alkanol amine compound may degrade the peeling performance of the resist, if it exceeds 90% by weight, dry etching residue Removal performance may be degraded.

The hydroxy benzene compound used in the resist stripper composition of the present invention forms a complex with aluminum in an alkaline state, adsorbs onto the surface of aluminum to form a protective film, thereby preventing corrosion by hydroxide ions, thereby preventing corrosion on aluminum wiring. Serves to increase.

Preferred examples of the hydroxy benzene compound include catechol, hydroquinone, pyrogarol, gallic acid, methyl gallate, ethyl gallate, n-propyl gallate, isopropyl gallate, n-butyl gallate, and the like. These can be used 1 type or in mixture of 2 or more types.

The hydroxy benzene compound is preferably contained 0.1 to 10% by weight, more preferably 0.5 to 5% by weight based on the total weight of the total composition. When the hydroxy benzene compound is contained in less than 0.1% by weight, the corrosion inhibitory power on the aluminum wiring is not sufficient, when the amount exceeds 10% by weight, the production cost of the peeling solution is increased, which is a problem in productivity.

The azole compound used in the resist stripper composition of the present invention is preferably a triazole compound. The triazole compound forms a chemisorption that a strong bond is formed on the triazole molecule and the metal surface, thereby preventing the penetration of the alkanol amine, which is the cause of metal corrosion, and exhibits a corrosion preventing effect. The triazole compound in particular increases the corrosion inhibitory effect on copper interconnects.

The triazole compound is 1,2,3-triazole, 1,2,4-triazole, 3-amino-1,2,4-triazole, 4-amino-4H-1,2,4-triazole , Benzotriazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 2-methylbenzotriazole, 5-methylbenzotriazole, toryltriazole, benzotriazole-5-carboxylic acid, nitrobenzotria Sol and 2- (2H-benzotriazol-2-yl) -4,6-di- tet-butylphenol, and the like, among others, benzotriazole, 1-hydroxybenzotriazole, 1-methyl Benzotriazole, 2-methylbenzotriazole, 5-methylbenzotriazole, toryltriazole, 1,2,3-triazole, benzotriazole, 5-methylbenzotriazole and mixtures of two or more thereof More preferred.

The azole compound is preferably contained 0.1 to 10% by weight relative to the total weight of the composition. When the azole compound is included in less than 0.1% by weight, the effect of preventing corrosion is lowered, and if it exceeds 10% by weight, bubbles are formed during the cleaning process, making it difficult to proceed with the process, and the problem of removing the photoresist is reduced.

The water used in the resist stripper composition of the present invention is easy to dissolve the water-soluble solid compound added in the preparation of the resist stripper composition of the present invention. In addition, there is an advantage that the price is lowered if a certain amount of water is included in the composition of the present invention.

The water is preferably included in less than 0.1 to 10% by weight relative to the total weight of the composition. When the water is included in less than 0.1% by weight, there is a problem that the ability to remove the photoresist severely deteriorated by the metal by-products generated after the ashing process while the activity of the alkanol amine is reduced. When the water is included in more than 10% by weight, there is a problem that the peeling force to the resist falls. In addition, when the resist stripper composition is used at a high temperature, since water evaporates at a higher rate than other materials of the resist stripper composition, a change in composition is intensified, resulting in problems unsuitable for long-term use. In addition, there is a problem that the corrosiveness to the metal becomes stronger due to excess water.

The resist stripper composition of the present invention may further include a urea compound. The urea compound generates peroxy ions or hydroxy radicals when converted into heat or an alkaline atmosphere in the state of dissociation in water, thereby denatured photoresist. It penetrates and oxidizes or reduces dopant ions penetrated during the dry etching process in the photoresist. The modified photoresist in which the dopant is released can be easily dissolved by a polar organic solvent in the composition. The urea compound may also play a useful role in removing particles generated during the process.

The urea compound is, for example, urea, urea acetate, urea phosphate, thiourea, urea peroxide, hydroxyurea, N-methylurea, 1,1-dimethylurea, 1,3-dimethylurea, N, N-dimethylurea. Monomer compounds such as bovine, tetramethyl urea, ethyl urea, 1,3-diethyl urea, phenyl urea, 1,3-diphenyl urea, allyl urea, ethylene urea and cyclohexyl urea are preferred. More preferred are urea, urea phosphate, thiourea, urea peroxide, hydroxyurea and the like, and even more preferred urea and thiourea.

The urea compound preferably contains 0.1 to 5% by weight based on the total weight of the composition. When the urea compound is included in less than 0.1% by weight, it is difficult to realize the effect caused by the inclusion of the urea compound, when contained in excess of 5% by weight, the solubility of the release agent is lowered depending on the compound used, or the substrate after the peeling treatment There is a possibility of remaining up.

The concentration of the urea compound is the concentration of one compound when the urea compounds are used alone, and the total concentration of the urea compounds when they are used by mixing two or more kinds.

The peeling liquid composition of the present invention may use a surfactant as an additive to improve the uniformity of the peeling. The amount of the additive is not limited, but may be included in 0.001 to 10% by weight, preferably 0.001 to 5% by weight based on the total weight of the total composition.

Moreover, the peeling liquid composition of this invention can add an aprotic polar organic solvent as needed. Examples of aprotic polar organic solvents include pyrrolidone compounds, imidazolidinone compounds, and amide compounds. Specific examples thereof include N-methyl pyrrolidone, N-ethyl pyrrolidone, and 1,3-dimethyl-2. Imidazolidinone, 1,3-dipropyl-2-imidazolidinone, N-methylacetamide, dimethylacetamide (DMAc), dimethylformamide (DMF), N-methyl-N-ethylpropionamide, Diethylacetamide (DEAc), dipropylacetamide (DPAc), N, N-dimethylpropionamide, N, N-dimethylbutylamide, tetramethylenesulfone, γ-butylolactone, dimethylsulfoxide, sulfolane and the like Can be mentioned. It is preferable to use 1 or more types selected from among them.

The aprotic polar organic solvent is preferably included 1 to 30% by weight based on the total weight of the total composition.

Hereinafter, a method of removing the resist, the dry etching residue and the wet etching residue using the resist stripper composition of the present invention will be described in detail.

A method of removing resist, modified resist, cured resist, dry etching residue and wet etching residue on a substrate of a flat panel display device using the resist stripper composition according to the present invention is to deposit an object coated with resist in a liquid. The method or the method of spraying a peeling liquid to the said object is mentioned. In such a case, it is also possible to remove the object more effectively by rotating the object or moving it under a blowing off at a constant speed. In addition, it is possible to use a combination of physical treatments such as ultrasonic irradiation, rotation, or contacting a brush that is rocked from side to side.

After the peeling liquid treatment, the peeling liquid remaining on the object can be removed by a subsequent washing process. In a washing process, it is the same as that of the peeling liquid except having used water or isopropyl alcohol instead of a peeling liquid.

When the temperature of the resist stripper composition of the present invention applied on the object is less than 15 ° C., the time required for removing the modified resist, and / or the cured resist and the dry etching residue may be too long, and the resist When the temperature of the peeling liquid composition exceeds 100 ° C, not only the damage of the lower film layer of the resist film is concerned but also the handling of the peeling liquid is difficult. Therefore, the temperature of the resist stripper composition provided on the object is usually in the range of 15 to 100 ° C, more preferably 30 to 70 ° C.

The resist film of the object is positive and negative g-rays, i-rays, far ultraviolet (DUV) resists, electron beam resists, X-ray resists, ion beam resists, and the like. The resist is a photoresist film composed of a novolac phenol resin and a photoactive compound based on diazonaphthoquinone, and contains a mixture thereof.

In addition, the resist stripper composition according to the present invention can also be used for stripping of the resist modified or cured by the etching gas and high temperature and removing the etching residue.

More specifically, the resist stripping method includes the steps of (a) depositing a conductive metal film on a flat panel display substrate, (b) uniformly applying and then drying the photoresist on the metal film to form a photoresist film, (c) forming a photoresist pattern through a selective exposure and development process using a photomask, (d) etching the conductive metal film using the photoresist pattern as a mask, (e) after the etching process The photoresist pattern and the step of peeling the modified and cured photoresist by dry, wet etching from the substrate, the method of peeling the resist according to the present invention (e) step to the resist stripper composition according to the present invention After the etching process by using a photoresist pattern and dry, wet etching modified and cured photoresist is removed from the substrate The features.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the scope of the present invention is not limited to the following examples and the like.

Example  1 to 7 and Comparative Example  1 to 6: Resist Peeling liquid  Preparation of the composition

An alkanol amine compound, a glycol ether compound, a hydroxy benzene compound, an azole compound and urea were mixed in a composition ratio with respect to the total weight of the total composition specified in [Table 1] to prepare a resist stripper.

MEA: Monoethanolamine

MIPA: Monoisopropanolamine

DBA: Dibutanolamine

BDG: diethylene glycol monobutyl ether

MDG: Diethylene Glycol Monomethyl Ether

MTG: triethylene glycol monomethyl ether

BTA: Benzotriazole

NBTA: nitrobenzotriazole

Test Example  One: Resist  And Etching Residue  Removal performance evaluation

According to a conventional method, a Mo / Al / Mo layer was formed on a glass substrate using a sputtering method, and then a photoresist pattern was formed. Then, objects to which the metal film was etched by wet etching and dry etching were prepared, respectively. The peeling liquid compositions prepared in Examples 1 to 7 and Comparative Examples 1 to 6 were kept at a constant temperature at 60 ° C. using a thermostat, and then the objects were deposited for 10 minutes to evaluate the peel force. Thereafter, washing was performed with pure water for 1 minute to remove the stripping solution remaining on the substrate, and the substrate was completely dried using nitrogen to remove the pure water remaining on the substrate after cleaning. Denatured resist, cured resist and dry etch residue removal performance of the object were confirmed using a scanning electron microscope (SEM, Hitach S-4700), the results are shown in Table 2 below.

Note) [Peeling performance] ◎: Excellent, ○: Good, △: Normal, X: Poor

According to Table 2, Examples 1 to 7 were found to be excellent in the peeling force of the resist in the case of the resist stripping solution, in the case of Comparative Example 1 and Comparative Example 5 is excess water or excluded alkanol amine As a result, the peeling force was weakened.

Test Example 2 : Peeling liquid  Evaluation of the anticorrosion ability of the composition

In order to evaluate the anti-corrosion ability of the resist stripper compositions of Examples 1 to 7 and Comparative Examples 1 to 6, the corrosion resistance was evaluated using a substrate exposed with copper wiring and Mo / Al / Mo wiring. Corrosion evaluation for aluminum was immersed in the stripper composition stock solution at 60 ° C. for 30 minutes, and corrosion evaluation for copper was immersed for 10 minutes, washed, dried, and evaluated using a scanning electron microscope (SEM, Hitach S-4700). The results are shown in the following [Table 3].

Note) Corrosion evaluation: ◎: Very good, ○: Good, △: Normal, X: Poor

According to Table 3, all of the resist stripping solutions according to Examples 1 to 7 and Comparative Example 5 were excellent in the corrosion protection against the metal wiring, Comparative Example 1, Comparative Example 2 and Comparative Example 6 In the case of the excess of water or the addition of the alkanol amine in excess of the corrosion protection against aluminum and copper was found to be weak. In addition, in Comparative Example 3, since the corrosion inhibitor for aluminum was excluded, almost no corrosion protection against aluminum was observed. In addition, in Comparative Example 4, since the corrosion inhibitor for copper was excluded, almost no corrosion protection against copper was observed.

Test Example 3 : Peeling liquid  Of the composition particle  Removal and Reattachment Assessment

The substrate used for resist stripping evaluation was exposed to air for 24 hours, and then immersed in the composition for 10 minutes, and then washed and dried, and evaluated using a scanning electron microscope (SEM, Hitach S-4700). 4].

Note) [Particle removal force] ◎: Very good, ○: Good, △: Normal, X: Poor

Referring to Table 4, in the case of Comparative Example 5 was shown that the particle removal force is poor, while the other Examples and Comparative Examples are generally good. In particular, it can be seen that Example 6, Example 7, Comparative Example 6, which includes the element is very excellent particle removal force.

1 is a photograph taken with a scanning electron microscope (SEM) of a Mo / Al / Mo substrate treated by the method of Test Example 2 using the stripping solution of Example 1 of the present invention, Figure 2 is a comparison of the present invention It is the photograph which took the Mo / Al / Mo board | substrate processed by the method of Test Example 2 using the peeling liquid of Example 2 with the scanning electron microscope (SEM).

Referring to FIG. 1, it can be seen that Mo / Al / Mo has a relatively constant profile. Referring to FIG. 2, it can be seen that galvanic phenomenon occurs and Al of Mo / Al / Mo is excessively corroded.

3 is a photograph taken with a scanning electron microscope (SEM) of a Cu substrate treated by the method of Test Example 2 using the stripping solution of Example 1 of the present invention, Figure 4 is a stripping solution of Comparative Example 2 of the present invention It is the photograph which photographed the Cu board | substrate processed by the method of the test example 2 using the scanning electron microscope (SEM).

Referring to FIG. 3, the surface of the copper substrate is smoothly formed, while referring to FIG. 4, it can be seen that the surface of the copper substrate is corroded and rough.

1 is a photograph taken with a scanning electron microscope (SEM) of a Mo / Al / Mo substrate treated by the method of Test Example 2 using a peeling solution of Example 1 of the present invention.

2 is a photograph taken with a scanning electron microscope (SEM) of a Mo / Al / Mo substrate treated by the method of Test Example 2 using a peeling solution of Comparative Example 2 of the present invention.

3 is a photograph taken with a scanning electron microscope (SEM) of a copper substrate treated by the method of Test Example 2 using the stripper of Example 1 of the present invention.

4 is a photograph taken with a scanning electron microscope (SEM) of a copper substrate treated by the method of Test Example 2 using the stripper of Comparative Example 2 of the present invention.

Claims (8)

5-30% by weight of alkanol amine compound, 50-90% by weight of glycol ether compound, 0.1-10% by weight of hydroxy benzene compound, 0.1-10% by weight of azole compound and at least 0.1% by weight and 10% by weight of the total composition A resist stripper composition comprising less than% water. The method according to claim 1, The alkanol amine compound is monoethanolamine, diethanolamine, 2-aminoethanol, 2- (ethylamino) ethanol, 2- (methylamino) ethanol, N-methyldiethanolamine, dimethylaminoethanol, diethylaminoethanol , 2- (2-aminoethoxy) ethanol, 1-amino- 2-propanol, triethanolamine, monopropanolamine, monoisopropanolamine and dibutanolamine, characterized in that one or two or more selected from the group consisting of Resist stripper composition. The method according to claim 1, The glycol ether compound 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, diethylene glycol monoisopropyl With ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monopropyl ether, ethylene glycol monophenyl ether, triethylene glycol monoethyl ether and propylene glycol monomethyl ether acetate It is 1 type (s) or 2 or more types chosen from the group which consisted of, The resist stripping liquid composition characterized by the above-mentioned. The method according to claim 1, The hydroxy benzene compound is one selected from the group consisting of catechol, hydroquinone, pyrogarol, gallic acid, methyl gallate, ethyl gallate, n-propyl gallate, isopropyl gallate and n-butyl gallate or 2 or more types of resist stripper composition. The method according to claim 1, The azole compound is 1,2,3-triazole, 1,2,4-triazole, 3-amino-1,2,4-triazole, 4-amino-4H-1,2,4-triazole , Benzotriazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 2-methylbenzotriazole, 5-methylbenzotriazole, toryltriazole, benzotriazole-5-carboxylic acid, nitrobenzotria 1 or 2 or more types selected from the group consisting of sol and 2- (2H-benzotriazol-2-yl) -4,6-di-tet-butylphenol. The method according to claim 1, The resist stripper composition further comprises 0.1 wt% to 5 wt% of the urea compound, based on the total weight of the total composition. The method according to claim 1, The resist stripper composition further comprises 1% to 30% by weight of an aprotic polar organic solvent based on the total weight of the total composition. A method for stripping a resist, comprising using the resist stripper composition according to any one of claims 1 to 7 to remove the modified, cured resist and the etching residue by high temperature or dry etching.

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