KR100485737B1 - Thinner composition for removing resist - Google Patents

Abstract

The present invention relates to a thinner composition for removing an unnecessary portion of a film formed on an edge portion of a resist film coated on a substrate or on a back surface of a substrate in a TFT-LCD device or semiconductor device manufacturing process, wherein the thinner composition comprises a) an inorganic and / or Or 0.1 to 10% by weight of organic alkali; b) 0.1 to 30% by weight of an organic solvent; c) 0.01 to 10% by weight of nonionic surfactant; And d) 50 to 99% by weight of water to provide a thinner composition for resist removal. Here, the thinner composition preferably further comprises 0.01 to 5% by weight of anionic surfactant and / or 0.01 to 1.0% by weight of an antifoaming agent.

Description

Thinner composition for removing resist

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a thinner transistor composition for removing a photosensitive resin film (resist) used in a thin film transistor liquid crystal display (TFT-LCD) or a semiconductor device manufacturing process. A thinner composition for removing an unnecessary film component formed on an edge portion of a resist film coated on a substrate or on a back surface of a substrate in a manufacturing process of an LCD device or a semiconductor device.

In order to form a fine circuit pattern such as a TFT-LCD circuit or a semiconductor integrated circuit, first, the resist composition is uniformly spin-coated or coated on an insulating film or a conductive metal film formed on a substrate such as a glass substrate, and then subjected to an appropriate drying process. The pattern of the desired shape is formed by exposing and developing a resist composition in presence of the mask of a predetermined shape. When manufacturing a TFT-LCD or a semiconductor device by the lithography method as described above, a resist film is essentially formed on a substrate such as glass or silicon wafer, and is formed unnecessarily on the edge of the formed resist film and under the substrate. In order to remove unnecessary films from the substrate, a process of cleaning the substrate with thinner prior to the exposure and development of the resist film is required.

As a thinner for cleaning and removing the resist film on the substrate, the main components include an organic thinner which can be dissolved and removed before the unnecessary resist film is dried, and an alkaline aqueous solution which does not have disadvantages such as toxicity to human body, high flash point and expensive manufacturing cost. It can be divided into an aqueous thinner. In particular, the water-based thinner is chemically stable compared to the conventional organic thinner, so there is no risk of fire, and the toxicity to the human body due to volatilization is remarkably less, and there is an advantage that safety for the operator is guaranteed. In addition, in terms of manufacturing costs, the use of alkali-based water thinners is gradually increasing, rather than organic-based thinners, because it is much more advantageous than expensive organic thinners. Alkali aqueous thinners are classified into inorganic alkali thinners and organic alkali thinners according to the type of alkali used. Inorganic alkali-based thinners may have an inorganic residue after the defective resist film removal operation, causing contamination and corrosion of the process equipment, and has a disadvantage of low resist removal efficiency. Therefore, recently, thinners using only organic alkalis or mixing inorganic and organic alkalis have been used. Organic alkali has almost no foreign matter remaining after volatilization of solvent, and there is little concern about corrosion on equipment, and excellent solubility in resist shows excellent resist removal performance. Inorganic alkalis currently used in alkaline aqueous thinner compositions include potassium hydroxide, sodium hydroxide, sodium phosphate, sodium silicate, sodium carbonate, sodium hydrogen carbonate, and tetramethylammonium hydroxide is widely used as the organic alkali.

Conventional alkali-based thinners for removing unnecessary resist formed at the edges and back of substrates, which are currently applied in TFT-LCD or semiconductor integrated circuit manufacturing processes, are excellent resist removal when the thickness of the coated resist is several micrometers or less. Performance. However, the thickness of the resist coated on the edge of the substrate becomes thicker than 10 μm, or used in the TFT-LCD manufacturing process, such as color resists containing a large amount of pigment, organic black matrix (BM), etc. In the case of a resist including a pigment component having a significantly low solubility in thinner in addition to the component, a large amount of pigment component remains on the substrate even when washed with a conventional alkaline aqueous thinner, and the residual film is not easily removed. In addition, conventional alkali-based thinners may form bubbles during subsequent work processes after dissolving and removing the resist, contaminating the equipment, or corroding the equipment made of stainless steel. In addition, in the case of removing a resist containing a pigment component of remarkably low solubility such as a color resist or an organic BM, the pigment particles of the dissolved resist are unstablely dispersed in the alkali aqueous thinner, so that the pigment particles aggregate and sink, It may cause problems such as clogging the drain pipe of the equipment.

Accordingly, an object of the present invention is particularly useful for the removal of color resists, overcoating liquids, etc., having a film thickness of 10 μm or more on the outer surface of the resist coating film, which are not easily removed by a general aqueous thinner by including a large amount of pigment. It is to provide an alkaline aqueous thinner composition. Another object of the present invention is to provide an alkaline aqueous thinner composition which can suppress corrosion of process equipment and foaming that may occur during process progress. It is another object of the present invention to provide an alkaline aqueous thinner composition capable of stably dispersing the dissolved resist.

In order to achieve the above object, the present invention provides a composition comprising: a) 0.1 to 10% by weight of inorganic and / or organic alkali; b) 0.1 to 30% by weight of an organic solvent; c) 0.01 to 10% by weight of nonionic surfactant; And d) 50 to 99% by weight of water to provide a thinner composition for resist removal. Here, the thinner composition preferably further comprises 0.01 to 5% by weight of anionic surfactant and / or 0.01 to 1.0% by weight of an antifoaming agent. In addition, the nonionic surfactants include polyoxyethyl ether, polyoxypropyl ether, polyoxyethylpropyl ether, polyoxyethylalkylphenyl ether, polyoxypropylalkylphenyl ether, polyoxyethyloxypropylalkylphenyl ether, and their The anionic surfactant is a substance selected from the group consisting of alkyl ether sulfate, alkyl sulfate, alkylbenzene sulfonic acid, alkylbenzene sulfonate, alkyl naphthalene sulfonate and mixtures thereof. Do.

Hereinafter, the present invention will be described in detail.

In the thinner composition for removing a resist of the present invention, the a) inorganic and / or organic alkali components include inorganic alkali components such as potassium hydroxide, sodium hydroxide, sodium phosphate, sodium silicate, sodium carbonate and sodium hydrogen carbonate, and tetramethylammonium. Hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, dimethyldiethylammonium hydroxide, trimethyl (2-hydroxyethyl) ammonium hydroxide Rockside, triethyl (2-hydroxyethyl) ammonium hydroxide, tripropyl (2-hydroxyethyl) ammonium hydroxide, trimethyl (1-hydroxypropyl) ammonium hydroxide, tributyl (2-hydroxy Organic alkali components, such as oxyethyl) ammonium hydroxide, can be used individually or in mixture.

The content of the inorganic and / or organic alkali is preferably 0.1 to 10% by weight, more preferably 0.5 to 5.0% by weight based on the total thinner composition. In particular, the inorganic alkali content is preferably 3.0% by weight or less even when used alone or in combination with an organic alkali. If the content of the inorganic or organic alkali is less than 0.1% by weight, the penetrating power of the thinner composition is insufficient due to insufficient penetrating power, and if it is more than 10% by weight, the penetrating power of the thinner composition is so strong that the resist liquid is present at the resist removal interface. It may build up and remain undeveloped in a later developing step. In addition, when the content of the inorganic alkali is more than 3.0% by weight there is a risk of causing contamination and corrosion on the equipment.

B) As an organic solvent component, Alkanolamine, such as monoethanolamine, diethanolamine, and triethanolamine, Alkylamine, such as monoethylamine, diethylamine, and triethylamine, Ethylene glycol amine, Propylene glycol amine, Butylene Alkaline organic amine solvents such as glycol amine, diethylene glycol amine and dipropylene glycol amine; Ethylene glycol alkyl ether (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, etc.), propylene glycol alkyl ether, butylene glycol alkyl ether, diethylene glycol alkyl ether (diethylene glycol monomethyl ether, di Ethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, etc.), dipropylene glycol alkyl ether (dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, etc.), dibutylene glycol alkyl ether Alcohol ethers including alcohol ethers such as alkylene glycol phenyl ethers (ethylene glycol phenyl ether, propylene glycol phenyl ether, butylene glycol phenyl ether, diethylene glycol phenyl ether, dipropylene glycol phenyl ether and the like) and acetate derivatives thereof Organic solvents; N-alkylpyrrolidone (N-methylpyrrolidone, N-ethylpyrrolidone, N-propylpyrrolidone, etc.), N-hydroxyalkylpyrrolidone (N-hydroxymethylpyrrolidone, N- Nitrogen-containing organic solvents such as hydroxyethylpyrrolidone and the like; Sulfur-containing organic solvents, such as dialkylsulfuroxide, such as dimethyl sulfoxide (DMSO), and sulfolane, etc. can be used individually or in mixture.

In the alkaline organic amine solvent, the alkyl group of the alkanolamine and the alkylamine is preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. In addition, the alkyl group may be a branched alkyl group having one, two or three branches. The alkyl group of the alcohol ether (acetate) organic solvent and the nitrogen-containing organic solvent is preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. In addition, the alkyl group of the sulfur-containing organic solvent is preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.

The content of the organic solvent is preferably 0.1 to 30% by weight, more preferably 1.0 to 20% by weight based on the total thinner composition. If the content of the organic solvent is less than 0.1% by weight, the removal force on the resist film is lowered, and if the content of the organic solvent exceeds 30% by weight, the solubility in water is reduced or the waste solution is not easily processed.

In the resist composition for removing a resist of the present invention, c) as the nonionic surfactant, polyoxyethyl ether, polyoxypropyl ether, polyoxyethylpropyl ether, polyoxyethylalkylphenyl ether, polyoxypropylalkylphenyl ether , Polyoxyethyloxypropylalkylphenyl ether and the like can be used alone or in combination, and two or more kinds thereof can be used in combination. In the surfactant, the alkyl group preferably has 1 to 15 carbon atoms, and the polyoxyethyl ether and polyoxypropyl ether preferably have a monomer repeating group of 1 to 30. The surfactant has a property of being well mixed and dissolved in water and an organic solvent, the content of the surfactant is preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight. When the content of the nonionic surfactant is less than 0.01% by weight, the wettability of the thinner composition to the resist film is lowered, so that the resist remaining film remains on the substrate after the treatment, and thus the resist removal ability is lowered. In addition, the viscosity of the thinner composition increases, which may leave a part of the thinner composition as impurities after treatment, and the wettability of the thinner composition becomes too large, resulting in the build-up of resist on the resist removal interface, and in a later development process. It may remain without developing.

In the thinner composition of the present invention, as the anionic surfactant that can be used if necessary, alkyl ether sulfate, alkyl sulfate, alkylbenzene sulfonic acid, alkyl benzene sulfonate, alkyl naphthalene sulfonate, and the like are used alone or in combination. The alkyl group has 1 to 15 carbon atoms. Such anionic surfactants not only increase the solubility of the organic solvent and water, but also improve the dispersion stability of resists, color resist pigments, and other resist additives dissolved in the thinner composition. The content of the anionic surfactant is preferably 0.01 to 5% by weight, and if the content of the surfactant is less than 0.01% by weight, the mixing of the organic amine, the organic solvent and water is not smooth, and the dispersion of the dissolved resist component Degradation of the stability may cause a precipitate, and when the content exceeds 5% by weight, there is a disadvantage in that the resist removing ability of the thinner composition is reduced.

In the present invention, as the antifoaming agent used as necessary, LDC-220A of Dow Corning Corporation, Safinol 82, Safinol 104, BYK Chemi Corporation BYK-019, BYK-024, etc. It may be used alone or in combination, the content of the defoaming agent is preferably 0.01 to 1.0% by weight. If the content of the antifoaming agent is less than 0.01% by weight, the foaming of the thinner composition is excessive, there is a fear of equipment contamination during the process, if the content exceeds 1.0% by weight has a disadvantage that the resist removal force of the thinner composition.

In the chemical thinner composition for removing a resist of the present invention, it is preferable to use pure water filtered through an ion exchange resin as d) water, which is an essential component, and more preferably, ultrapure water having a specific resistance of 18 megohm (Ω) or more. Do. The content of the water is preferably 50 to 99% by weight with respect to the entire thinner composition, and if the content of the water is less than 50% by weight, there is a problem in waste liquid treatment, etc., and when the content exceeds 99% by weight, the resist removal ability is lowered.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to the following Examples. In the following examples, unless stated otherwise, percentages and mixing ratios are by weight.

EXAMPLE

Specimen Preparation: Color Resist composition (used by FujiFilm Arch, trade name: CR-9110L, CG-9130L, CB) which is commonly used for LCD glass on which chromium black matrix is deposited. -9110L, CR-8131L, CG-8130L, CB-8140L)) were spin-coated, and applied to a final film thickness of 1.0-2.0 μm, followed by vacuum drying (0.5 torr) for 30 seconds in a chamber. .

Preparation of thinner composition: The thinner compositions of Examples 1 to 8 and Comparative Examples 1 to 4 were prepared by adjusting the amounts of inorganic and / or organic alkalis, organic solvents, surfactants, antifoaming agents, and water as shown in Table 1 below.

(a) inorganic and / or organic alkalis (b) organic solvent (c) (d) (e) (e) water Example KOH Na ₂ CO ₃ TMAH DEGA TEA TEOA DMSO PPOH DPGME AS POEO LDC water One 0.1 3.0 1.0 5.0 1.0 1.0 0.5 0.1 88.3 2 0.1 2.0 1.0 5.0 5.0 1.0 0.5 0 85.4 3 0.5 3.0 1.0 10.0 1.0 0.5 0 84.0 4 0.5 2.0 1.0 5.0 5.0 1.0 0 0.1 85.4 5 1.0 3.0 1.0 1.0 10.0 1.0 0 0.1 82.9 6 1.0 2.0 1.0 5.0 5.0 1.0 0 0 85.0 7 2.0 0.1 1.0 10.0 1.0 1.0 0.5 0.1 84.3 8 3.0 1.0 10.0 5.0 10.0 1.0 0.5 0.1 69.4 Comparative example NaOH TMAH n-BA PGME PGMEA DPGME water One 5.0 5.0 5.0 85.0 2 0.3 5.0 5.0 89.7 3 3.0 5.0 5.0 87.0 4 3.0 10.0 87.0

In Table 1, KOH is potassium hydroxide, Na ₂ CO ₃ is sodium carbonate, TMAH is tetramethylammonium hydroxide, NaOH is sodium hydroxide, DEGA is diethylene glycol amine, TEA is triethylamine, TEOA is triethanolamine, DMSO Is dimethyl sulfoxide, PPOH is propylene glycol phenyl ether, DPGME is dipropylene glycol monomethyl ether, n-BA is n-butyl acetate, PGME is propylene glycol monomethyl ether, PGMEA is propylene glycol monomethyl ether acetate, AS is alkyl Sulfate, POEO is polyoxyethyloctylphenyl ether, and LDC is LDC-220A, respectively.

After dipping the glass substrate coated with the resist on the thinner composition of the examples and the comparative example for 2 seconds, and then washed with DI water, the state of the substrate was visually and optical electron microscope (LEICA, Model: FTM-200). Defective film removal state of the outer surface and back surface of the substrate, dispersion stability of the removed resist to the thinner composition, and foaming of the thinner composition were judged as good or bad, and the results are shown in Table 2.

Resist Removal Force Observation Visual observation Optical electron microscope observation Dispersion stability Bubble generation Example 1 Good Good Good Good Example 2 Good Good Good Bad Example 3 Good Good Bad Bad Example 4 Good Good Bad Good Example 5 Good Good Good Good Example 6 Good Good Bad Bad Example 7 Good Good Good Good Example 8 Good Good Good Good Comparative Example 1 Bad Bad Bad Bad Comparative Example 2 Bad Bad Bad Bad Comparative Example 3 Good Bad Bad Bad Comparative Example 4 Good Bad Bad Bad

As can be seen from Table 2, in the case where the resist is applied to the thinner composition according to the embodiment of the present invention, the defective film removal state, dispersion stability, and foaming items by visual and optical electron microscopic observation are performed. Although all of these were good, it can be seen that they are not good when washed with the thinner composition of the comparative example.

As described above, the thinner composition according to the present invention is organic such as inorganic alkalis such as potassium hydroxide, sodium hydroxide, sodium phosphate, sodium silicate, sodium carbonate, sodium hydrogen carbonate, tetramethylammonium hydroxide and the like. It solves the problem of incomplete detergency for resists of organic solvent mixtures such as alkali and n-butyl acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, and contains a large amount of pigment. It has excellent solubility that does not leave cosmetic anatomy even for color resist and overcoating solution.

Claims (12)

0.1 to 10 weight percent of inorganic and / or organic alkali; 0.1-30 wt% of an organic solvent; 0.01 to 10% by weight of nonionic surfactant; Antifoaming agent 0.01-1.0 wt%; And Thinner composition for removing a resist, characterized in that it comprises 50 to 99% by weight of water. The thinner composition according to claim 1, wherein the thinner composition further comprises 0.01 to 5% by weight of anionic surfactant. delete The method of claim 1, wherein the inorganic alkali component is selected from the group consisting of potassium hydroxide, sodium hydroxide, sodium phosphate, sodium silicate, sodium carbonate, sodium hydrogen carbonate and mixtures thereof, wherein the organic alkali component is tetramethylammonium hydride Lockside, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, dimethyldiethylammonium hydroxide, trimethyl (2-hydroxyethyl) ammonium hydroxide Said, triethyl (2-hydroxyethyl) ammonium hydroxide, tripropyl (2-hydroxyethyl) ammonium hydroxide, trimethyl (1-hydroxypropyl) ammonium hydroxide, tributyl (2-hydroxy Being selected from the group consisting of ethyl) ammonium hydroxide and mixtures thereof Thinner composition for removing a resist, characterized in that. The method of claim 1, wherein the organic solvent is monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, triethylamine, ethylene glycol amine, propylene glycol amine, butylene glycol amine, diethylene glycol amine And a thinner composition for removing a resist, comprising an organic amine solvent selected from the group consisting of dipropylene glycol amine and mixtures thereof. The method of claim 1, wherein the organic solvent is ethylene glycol alkyl ether, propylene glycol alkyl ether, butylene glycol alkyl ether, diethylene glycol alkyl ether, dipropylene glycol alkyl ether, dibutylene glycol alkyl ether, alkylene glycol phenyl ether And an alcohol ether organic solvent selected from the group consisting of acetate derivatives thereof and mixtures thereof. The thinner for removing resists according to claim 1, wherein the organic solvent comprises a nitrogen-containing organic solvent selected from the group consisting of N-alkylpyrrolidone, N-hydroxyalkylpyrrolidone and mixtures thereof. Composition. The thinner composition of claim 1, wherein the organic solvent comprises a sulfur-containing organic solvent selected from the group consisting of dialkylsulfuroxide, sulfolane, and mixtures thereof. The method of claim 1, wherein the nonionic surfactant is polyoxyethyl ether, polyoxypropyl ether, polyoxyethylpropyl ether, polyoxyethylalkylphenyl ether, polyoxypropylalkylphenyl ether, polyoxyethyloxypropylalkylphenyl Thinner composition for removing a resist, characterized in that the material selected from the group consisting of ethers and mixtures thereof. The thinner composition for removing a resist according to claim 9, wherein the alkyl group of the nonionic surfactant has 1 to 15 carbon atoms, and the polyoxyethyl ether and polyoxypropyl ether have a monomer repeating group of 1 to 30. 3. The resist removal of claim 2, wherein the anionic surfactant is a substance selected from the group consisting of alkyl ether sulfate, alkyl sulfate, alkyl benzene sulfonic acid, alkyl benzene sulfonate, alkyl naphthalene sulfonate and mixtures thereof. Thinner composition for. The thinner composition for removing a resist according to claim 11, wherein the alkyl group of the anionic surfactant has 1 to 15 carbon atoms.