KR101292497B1 - Resist stripper composition and stripping method of resist using the same - Google Patents

Abstract

The present invention relates to a resist stripper composition for a flat panel display such as a liquid crystal display, a plasma display, a flexible display, and the like, to which a fine pattern is applied for high resolution, and a method of peeling a resist using the same. More specifically, as a peeling liquid composition capable of effectively peeling off resists and dry and wet etching residues remaining on a substrate without damaging metal wires or the like formed on the substrate during the process of manufacturing a flat panel display, The present invention relates to a resist stripper composition comprising an alkanol amine compound, a glycol ether compound, and a corrosion inhibitor selected from a gallic acid or a gallic acid ester compound, and a method for removing a resist using the same.

Resist, stripper, flat panel display, alkanol amine compound, glycol ether compound, gallic acid ester compound

Description

RESIST STRIPPER COMPOSITION AND STRIPPING METHOD OF RESIST USING THE SAME

The present invention relates to a resist stripping liquid composition for a flat panel display (FPD), such as a liquid crystal display, a plasma display, a flexible display, and the like, to which a fine pattern is applied for high resolution, and a method of removing the resist using the same. More specifically, non-aqueous resist stripper containing 5-30 wt% of alkanol amine compound, 50-90 wt% of glycol ether compound, and 0.1-10 wt% of corrosion inhibitor selected from gallic acid or gallic acid ester compound, based on the total weight of the composition. The present invention relates to a resist stripper composition further comprising a composition and less than 10% by weight of water based on the total weight of the resist stripper composition, and a method for stripping a resist using the same. It is related with the resist stripping liquid composition which is excellent in the prevention effect, and is applicable to a flat panel display board | substrate manufacturing process.

Flat panel displays (FPDs), which are typically represented by liquid crystal displays, do not require a device scale such as going through an ultra-fine process as high as a semiconductor device. However, as the demand for high resolution is gradually increased, efforts are being made to increase the number of pixels per unit area. This is gradually accompanied by a reduction in the wiring width of the thin film transistor, in order to cope with such a miniaturization of the wiring conditions such as the introduction of a dry etching process is increasingly harsh conditions.

For this reason, the required performance for the stripping liquid required for the stripping process, which is a resist removal step, after the metal pattern is completed, is also increasing. In addition, as the width of the wiring becomes smaller, the influence of corrosion on the wiring becomes more sensitive, and therefore, the ability to suppress corrosion of the wet chemicals used in the process, such as a cleaning liquid and a peeling liquid, has emerged as an important criterion for application to the process.

In addition, in order to secure the price competitiveness of FPD panels, the demand for price reduction of parts and materials to be manufactured in FPD panel has also played an important role in this study as much as peeling force and corrosion inhibiting ability. Therefore, there is a demand for the development of a stripping solution that can achieve the same effect without using an expensive solvent that has been inevitably required in the prior art among the solvents that can not necessarily enter in developing a resist stripping solution composition.

Patents suggesting solutions for the removal of resists and etch residues denatured by such severe process conditions and corrosion inhibition for metal wiring are given.

JP 2000-267302 A and JP 10-256210 A 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 stripping solution, the peeling force on the precipitate is weak, and when 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 are generated.

In Korean Patent Application Laid-Open No. 2001-0024483, as a preferred example, a mixture of N-monoethanolamine, dimethyl sulfoxide, gallic acid, and an ester thereof with a corrosion inhibitor and a residual amount of 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 against the resist, and insufficiently dissolving ability against the polymer material constituting the resist, so that the residue of the resist is reattached to a semiconductor substrate, a glass substrate, or the like due to heat applied during the peeling process. There is a problem in that the evaporation loss amount is short, the short life cycle 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 problems in terms of toxicity, workability and wastewater treatment, etc., and it is difficult to use in a process in which silicon oxide is not etched due to the fluoride compound.

Korean Patent Laid-Open Publication No. 1995-0012144 discloses that an alkaline 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, hydroxyl amine, diethylene glycol monoalkyl ether, sugar compounds such as sorbitol as an anticorrosive and water. 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. .

Accordingly, the present invention provides a resist stripper composition suitable for removing a resist and dry and wet etch residue in a process of manufacturing a substrate for a flat panel display (FPD) to which a fine pattern is applied for high resolution, and a method of removing the resist using the same. The purpose.

Another object of the present invention is to provide a resist stripper composition which does not corrode aluminum or aluminum alloy wirings formed on a flat panel display substrate and a method for stripping resist using the same.

It is still another object of the present invention to provide a low-cost resist stripper composition and a method for stripping resist using the same, which can reduce costs by using a high-cost solvent as a stripper component to reduce the manufacturing cost of a flat panel display substrate.

In order to achieve the above technical problem, the present invention is a non-aqueous resist stripper composition containing no water, 5-30% by weight of an alkanol amine compound, 50-90% by weight of a glycol ether compound, gallic acid or It provides a resist stripper composition comprising 0.1 to 10% by weight of a corrosion inhibitor selected from gallic acid ester compounds.

The present invention also provides a resist stripper composition comprising 5 to 30% by weight of an alkanol amine compound, 50 to 90% by weight of a glycol ether compound, and 0.1 to 10% by weight of a corrosion inhibitor selected from gallic acid or gallic acid ester compounds. The present invention provides a resist stripper composition further comprising less than 10% by weight of water, based on the total weight of the resist stripper composition.

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

Hereinafter, the present invention will be described in detail.

Preferable examples of the alkanol amine compound which is an alkaline compound used in the resist stripper composition of the present invention include monoethanolamine, diethanolamine, 2-aminoethanol, 2- (ethylamino) ethanol, and 2- (methylamino) ethanol. , N-methyldiethanolamine, dimethylaminoethanol, diethylaminoethanol, 2- (2-aminoethoxy) ethanol, 1-amino- 2-propanol, triethanolamine, monopropanol amine, dibutanol amine and the like. These may be used alone or in combination of two or more.

In the resist stripper composition of the present invention, the alkanol amine compound is preferably included in an amount of 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 aluminum or aluminum alloy wires is increased drastically.

The glycol ether compound used in the resist stripper composition of the present invention serves to increase the solubility of the residue after dry etching or wet etching. In addition, due to the high boiling point it can minimize the loss of chemicals due to volatilization. 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 mono ethyl ether, ethylene glycol mono isopropyl ether, ethylene glycol mono butyl ether, di Ethylene glycol monomethyl ether, diethylene glycol mono ethyl ether, diethylene glycol mono isopropyl ether, diethylene glycol mono butyl ether, dipropylene glycol mono methyl ether, propylene glycol mono butyl ether, dipropylene glycol mono propyl ether, ethylene glycol Phenyl ether, propylene glycol monomethyl ether acetate and the like. These may be used alone or in combination of two or more.

The content of the glycol ether compound is preferably 50 to 90% by weight, more preferably 60 to 80% by weight based on the total weight of the composition. When the concentration of the glycol ether compound is lower than 50% by weight, the peeling performance of the resist may decrease, while when higher than 90% by weight, the removal performance of the dry etching residue may decrease.

The corrosion inhibitor selected from the gallic acid or the gallic acid ester compound used in the resist stripper composition of the present invention serves to increase the corrosion inhibitive force on the aluminum wiring. Preferred examples of the gallic acid or gallic acid ester compound include gallic acid, methyl gallate, ethyl gallate, n-propyl gallate, isopropyl gallate, n-butyl gallate and the like. These may be used alone or in combination of two or more.

The content of such gallic acid or gallic acid ester compound is preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight, based on the total weight of the composition. If the concentration of the gallic acid or the gallic acid ester compound is lower than 0.1% by weight, the corrosion inhibitory power on the aluminum wiring is not sufficient. If the concentration of the gallic acid or the gallic acid ester compound is higher than 10% by weight, the production price of the stripping solution is increased, which causes a problem in productivity.

In the resist stripper composition of the present invention, the resist removal force does not decrease even if water is not included. In addition, the resist stripper composition of the present invention may further include water, but when water is included, it is preferable to include less than 10% by weight based on the total amount of the resist stripper composition. If the water is higher than 10% by weight, the peeling force on the resist is lowered, which is a problem for long-term use by evaporation under high temperature use conditions. However, as described above, even if the release liquid composition according to the present invention does not contain water, the resist removal ability is not lowered, and the organic component of the release liquid is rinsed off by water-based cleaning during the rinsing process.

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

Denaturation and / or curing resist removal

As a method of removing resist, modified, cured resist and dry, wet etching residue on a flat panel display substrate using the resist stripper composition according to the present invention, a method of depositing a resist-coated object in a liquid, or stripping solution And spraying on the object. In such a case, it is also possible to remove the object more effectively by rotating the object or moving under the blowing off liquid at a constant speed. In this case, a physical treatment such as ultrasonic irradiation, rotation, or contacting the brush rocked from side to side may be used in combination.

 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 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 to remove the modified and / or cured resist and dry etching residue may be too long, and the If the temperature exceeds 100 占 폚, not only the damage of the lower film layer of the resist film is concerned, but also the handling of the stripping solution is difficult. Therefore, the temperature of the resist stripper composition provided on the object is usually in the range of 15 ° C to 100 ° C, more preferably 30 ° C to 70 ° C.

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

In addition, the resist stripper composition according to the present invention can be used for peeling off resists modified and / or cured by etching gas and high temperature, and removing etch residues. 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 the photoresist on the metal film and then drying 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 a patterned photoresist film as a mask, (e) a photoresist pattern after the etching process And peeling the photoresist modified and cured by dry and wet etching from the substrate, wherein the resist stripping method according to the present invention comprises etching the step (e) using the resist stripper composition according to the present invention. Peeling the photoresist pattern and the photoresist modified and cured by dry and wet etching after the process from the substrate .

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. Evaluate resist and etch residue removal performance

The stripper composition of [Table 1] was prepared to confirm the effect of removing the resist and removing the etching residue according to the content and type of alkanolamine compound, glycol ether compound, corrosion inhibitor and water.

MEA: Monoethanol Amine

MIPA: monopropanolamine

TEA: triethanolamine

DBA: Dibutanolamine

BDG: diethylene glycol monobutyl ether

MDG: diethylene glycol monomethyl ether

MTG: triethylene glycol monoethyl ether

BTG: Monobutyl Ether

MFG: propylene glycol monomethyl ether

MG: methylgallate

EG: ethyl gallate

PG: Propylgallate

BG: Butyl Gallate

In order to confirm the peeling effect of the resist stripper composition, wet etching and dry etching after forming a Mo / Al / Mo layer using a thin film sputtering method on a glass substrate according to a conventional method and then forming a photoresist pattern The object to which the metal film was etched by the method is respectively prepared. The peeling liquid composition specified in [Table 1] was kept constant at 60 ° C. using a thermostat, and then the object was deposited for 10 minutes to evaluate the peeling 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 the cleaning. The denaturation, curing resist, and dry etching residue removal performance of the object were confirmed using a scanning electron microscope (SEM, Hitach S-4700), and the results are shown in the following [Table 2].

According to Table 2, in the case of the resist stripping solution of Examples 1 to 13, all of the resist stripping strengths were excellent, and in the case of Comparative Examples 3 and 5, water was added in excess or alkanol. It has been shown that the peel force is weakened due to the exclusion of amines.

2. Evaluation of anticorrosion ability of the stripper composition

In order to evaluate the anti-corrosion ability of the resist stripper composition shown in [Table 1], the substrate used in the above examples was immersed in the composition of [Table 1] at 60 ° C. for 10 minutes to remove the resist, followed by washing and drying. It was. Through this pretreatment, the corrosion protection was evaluated using a substrate with exposed metal wiring. Corrosion evaluation was performed using a scanning electron microscope (SEM, Hitach S-4700) after immersion for 10 minutes in a solution diluted 10-fold, 20-fold, 100-fold diluted solution solution at room temperature, washed and dried. The results are shown in the following [Table 3].

According to [Table 3], all of the resist stripping solutions of Examples 1 to 13 showed excellent corrosion protection against metal wiring, and in Comparative Examples 2 to 3, water was added in excess. Or the excessive addition of alkanol amines showed a weakening of the corrosion protection. In Comparative Example 4, the corrosion protection was hardly shown due to the exclusion of the corrosion inhibitor.

As described above, the resist stripper composition of the present invention is excellent in the ability to remove the cured resist and dry and wet etching residue on the substrate in the manufacture of a substrate for a flat panel display, the aluminum and aluminum alloy wiring formed on the substrate Its excellent anti-corrosion effect makes it applicable to the manufacturing process of flat panel display substrates with fine patterns for high resolution. In addition, by using the composition of the present invention, even if other solvents, such as expensive pyrrolidone compounds and sulfoxide compounds, other than glycol ethers are not used, they can exhibit an effect equal to or higher than that of the stripper using other solvents. There is an excellent effect of supplying a low-cost resist stripper composition.

Claims (6)

A non-aqueous resist stripper composition comprising 5 to 30% by weight of an alkanol amine compound, 50 to 90% by weight of a glycol ether compound, and 0.1 to 10% by weight of a corrosion inhibitor selected from gallic acid or a gallic acid ester compound, based on the total weight of the composition. A resist stripping liquid composition characterized by the above-mentioned. A resist stripper composition comprising 5 to 30% by weight of an alkanol amine compound, 50 to 90% by weight of a glycol ether compound, and 0.1 to 10% by weight of a corrosion inhibitor selected from gallic acid or a gallic acid ester compound, based on the total weight of the composition, wherein the resist stripping composition The resist stripper composition further comprising less than 10% by weight of water based on the total weight of the liquid composition. The method of claim 1 or 2, wherein the alkanol amine compound is monoethanolamine, diethanolamine, 2-aminoethanol, 2- (ethylamino) ethanol, 2- (methylamino) ethanol, N-methyldiethanolamine, dimethyl At least one selected from the group consisting of aminoethanol, diethylaminoethanol, 2- (2-aminoethoxy) ethanol, 1-amino- 2-propanol, triethanolamine, monopropanol amine, and dibutanol amine A resist stripping liquid composition. The method according to claim 1 or 2, wherein the glycol ether compound is ethylene glycol monomethyl ether, ethylene glycol mono ethyl ether, ethylene glycol mono isopropyl ether, ethylene glycol mono butyl ether, diethylene glycol monomethyl ether, diethylene glycol mono ethyl ether , Consisting of diethylene glycol mono isopropyl ether, diethylene glycol mono butyl ether, dipropylene glycol mono methyl ether, propylene glycol mono butyl ether, dipropylene glycol mono propyl ether, ethylene glycol phenyl ether, and propylene glycol monomethyl ether acetate It is at least 1 type selected from the group, The resist stripping liquid composition characterized by the above-mentioned. The gallic acid ester compound according to claim 1 or 2, characterized in that at least one member selected from the group consisting of methyl gallate, ethyl gallate, n-propyl gallate, isopropyl gallate, and n-butyl gallate. Resist stripper composition. The resist stripping method of claim 1 or 2, wherein the resist, the cured resist and the etching residue are removed by high temperature or dry etching.