TW201643564A - Photoresist developer - Google Patents

Abstract

The photoresist developer according to the present invention comprises a nonionic surfactant having a specific structure and an alkali source, and is capable of maintaining the development of fine patterns and reducing the occurrence of after-image and bubbles caused by the residue of compounds during the development process. This invention relates to a photoresist developer, and more particularly, to a photoresist developer which is capable of improving the workability when developing a negative color photoresist for forming an array of color filters. The disclosed photoresist developing is characterized by comprising a nonionic surfactant represented by the following chemical Formula 1 and an alkali source.

Description

Photoresist developer

The present invention relates to a photoresist developer (photoresist developer), and more particularly to an engineering process for developing a negative photoresist for developing a color filter array or the like. Photoresist developer.

In general, a color filter used for a liquid crystal display unit or the like is manufactured using a negative photoresist, and a method of dyeing a pattern after forming a pattern according to a photosensitive resin composition, and applying a pattern to the formed pattern may be used. a method of forming a voltage by ionizing a composition containing a dispersed pigment; a method of dispersing an ink containing a thermosetting or photocuring composition; or forming a pattern by using a photosensitive composition in which a pigment is dispersed; Wait.

In the above development processing for forming a color filter, an alkaline developing solution such as potassium hydroxide (KOH) or tetramethylammonium hydroxide is usually used, and this developing solution is used during development work. The organic pigment, the inorganic pigment, the photosensitive resin component, and the like for coloring or light-shielding are impregnated, and they are dissolved and dispersed, and the problem of residue due to residual compound and re-adhesion of the undissolved compound should be prevented.

For this purpose, a developing solution containing a large amount of a surfactant is disclosed in the Republic of Korea Publication No. 10-2004-0043620, the Republic of Korea Publication No. 10-2005-0082810, and the publication No. 10-2006-0017870. However, the conventional developer as described above is still adsorbed on the surface of the photoresist and remains, thereby causing problems such as occurrence of liquid crystal alignment problems or image sticking in pixel driving, and in sputtering engineering or the like. , there may be problems such as bubbles, so There is a problem that the developability is lowered.

An object of the present invention is to provide a photoresist developing solution capable of preventing surfactant residues, suppressing generation of bubbles, and improving the formation of fine patterns in a negative photoresist development process.

In order to achieve the above object, a photoresist developing solution comprising a nonionic surfactant represented by the following Chemical Formula 1 and an alkali source is provided.

In the above formula, R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and AO ¹ and AO ² are each independently a vinyl group, an oxypropylene group, or a polyoxyethylene-poly group. One or more selected groups selected from the group consisting of oxypropylene block copolymer-derived groups, Ar represents an aryl group, and m and n are each an integer of 1 to 50.

Further, in the above Chemical Formula 1, R ¹ and R ² may be a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and AO ¹ and AO ² are each independently a vinyl group, an oxypropylene group, or a polyoxyethylene group. One or more selected from the group consisting of a group derived from a polyoxypropylene block copolymer, and Ar represents a substituted or unsubstituted phenylene group, and m and n are each independently an integer of 2 to 20.

According to an embodiment, the above alkali source may include an inorganic basic compound, an organic amine compound, or a mixture thereof.

The inorganic basic compound may be one or more selected from the group consisting of potassium hydroxide, potassium carbonate, potassium hydrogencarbonate, sodium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium citrate and sodium citrate. Things.

In addition, the organic amine compound may be from ethanolamine, diethanolamine, triethanolamine, 1-imidazoleethanol, monoisopropanolamine, 1-aminoisopropanol, 2-amino-1-propanol, N-methylaminoethanol. , 3-amino-1-propanol, 4-amino-1-butanol, 2-(2-aminoethoxy)-1-ethanol (AEE), 2-(2-aminoethylamino)-1- One or more selected from the group consisting of ethanol, tetrahydrofuran, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine.

According to an embodiment of the present invention, the nonionic surfactant represented by the above Chemical Formula 1 may be contained in an amount of from 0.05 to 30% by weight based on the total weight of the composition.

Further, the above alkali source may contain 0.01 to 30% by weight based on the total weight of the composition.

Since the other photoresist developer of the present invention contains a nonionic surfactant, it is possible to reduce the residual amount of the developer and the amount of bubbles generated on the surface of the photoresist during the development process, and can maintain Simultaneously, the fine pattern damage on the photoresist is minimized.

1 is a photograph showing a pattern obtained by developing a black matrix by the developer according to Example 1; FIG. 2 is a photograph showing a pattern obtained by developing a black matrix by the developer according to Example 2; 3 is a photograph showing a pattern obtained by developing a black matrix by the developer according to Example 4; and FIG. 4 is a photograph showing a pattern obtained by developing a black matrix by the developer according to Comparative Example 1; 5 is a photograph showing a pattern obtained by developing a black matrix by the developer according to Comparative Example 2; and FIG. 6 is a photograph showing a pattern obtained by developing a black matrix by the developer according to Comparative Example 3; FIG. 7 is a photograph showing a pattern obtained by developing a black matrix by the developer according to Comparative Example 4. FIG.

The following is a detailed description of the invention. The terms or words used in the specification and the scope of the claims should not be construed as a general meaning or a meaning in a dictionary, and it should be construed that the inventor defines the concept of the term based on the adjustment in order to explain the invention in the most appropriate manner. A principle conforms to the meaning and concept of the technical idea of the present invention.

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

The present invention provides a photoresist developing solution capable of reducing image sticking caused by a residual liquid on a surface of a substrate and generating bubbles of a developing solution when performing a photoresist developing process, and at the same time, minimizing damage of a fine pattern.

The photoresist developing solution provided by the present invention may contain a nonionic surfactant and an alkali source, and the waste ionizing surfactant may include a compound represented by the following Chemical Formula 1.

In the above Chemical Formula 1, R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; and AO ¹ and AO ² are each independently an oxyethylene group or an oxypropylene group. And one or more selected from the group consisting of polyoxyethylene-polyoxypropylene block copolymers, and Ar represents an aryl group; and m and n are each an integer of from 1 to 50.

In the photoresist development process, the compound of the above Chemical Formula 1 has a weak adhesion to the surface portion of the photoresist to which the pattern must exist, and functions to form a fine pattern of several μm, for example, 0.5 to 10 μm. The formation of fine patterns.

R ¹ and R ² of the compound of the above Chemical Formula 1 may each independently be a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, for example, a hydrogen atom or a carbon number of 1 to 6 Alkyl. The above alkyl group having 1 to 20 carbon atoms may be, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or an isobutyl group. (isobutyl), s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, g. Heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isodonyl , decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl (octadecyl), glycosyl (Korean: ), cyclopentyl, cyclohexyl, cyclohexylmethyl, lauryl group, combinations thereof, and the like.

The above Ar may be an aryl group having 4 to 30 carbon atoms, and specifically, may be a phenylene group, a naphthylenylene group, an anthranylene group, a phenanthrylene group or a aryl group thereof. The combination or the like is not limited thereto, and may preferably be a phenylene group.

The above m and n can produce developability, residual and bubble generation in the photoresist developer The amount or the like may be affected, and may each independently be an integer of 1 to 50, for example, 1 to 30, and more preferably may be an integer of 2 to 20.

The above "substituted" means that at least one hydrogen contained in the compound is a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide group, a cycloalkyl group having 3 to 30 carbon atoms, and the number of carbon atoms is 6 to 30 aryl group, hydroxyl group, alkoxy group having 1 to 10 carbon atoms, carboxylic acid group, aldehyde group, epoxy group Group), a cyano group, a nitro group, an amino group, a sulfonic acid group, and a derivative thereof are substituted for the selected substituent group.

The above oxyalkylene group may, for example, be a vinyl group, an oxypropylene group, a group derived from a polyoxyethylene-polyoxypropylene block copolymer, or a mixture thereof. Specific examples of the above Chemical Formula 1 may include bisphenol, 4,4'-methylenediphenyl, 4,4'-(methane-1,1-diyl)diphenyl or 4, A vinyl group, an oxypropylene group, a polyoxyethylene-polyoxypropylene block copolymer, and a combination thereof are independently added to an oxygen atom such as a 4'-(pentane-3,3-diyl)bisphenol structure.

Specifically, the compound of Chemical Formula 1 may have an ethylene oxide or a propylene oxide attached to the 4,4'-alkane-2,2-diphenol phenol, whereby the oxyalkylene chain A structure that expands to the sides.

The compound of the above Chemical Formula 1 can exert a steric hindrance effect. The steric obstacle effect is caused by the change of energy with the overlapping of the electron cloud of the molecule, and refers to the effect of the influence of the substitution group on the reaction performance of the substance, that is, as the reaction of the compound progresses, the obstacle acts. The compound of the above Chemical Formula 1 has a steric hindrance effect particularly by a compound having a symmetrical structure, and the hydrophobic portion thereof is structurally weakly attached to the photoresist, thereby reducing the adhesion of the developer to the surface of the photoresist and remaining. Problems and problems caused by a large number of bubbles.

When the compound of the above Chemical Formula 1 is contained in a photoresist developer in a small amount, the effect is not sufficient, and in the case where the content is too large, the effect is small with respect to the content, and therefore, the total weight of the composition is For reference, it may comprise from 0.05 to 30% by weight, for example from 0.1 to 20% by weight.

The alkali source contained in the photoresist developing solution provided by the present invention may be an inorganic base compound, an organic amine compound or a mixture thereof, which serves to improve the developability of the photoresist.

The inorganic base compound is not particularly limited as long as it is an inorganic substance which exhibits alkalinity in a solvent. For example, alkali metal ions such as potassium ions, sodium ions, lithium ions, cesium ions, and cesium ions may be included. The inorganic base compound may, for example, be potassium hydroxide, potassium carbonate, potassium hydrogencarbonate, sodium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium citrate, sodium citrate or a mixture thereof.

The organic amine compound acts to make the solvent component easily permeate by acting on a relatively weak portion of the surface of the deformed photoresist. The organic amine compound may be, for example, an alkanolamine, an amino alkanols, or an alkylene amine. Specifically, it may be a monoethanolamine, a diethanolamine, or a diethanolamine. Triethanolamine, imidazolidine ethanol, monoisopropanolamine, amino isopropanol, 2-amino-1-propanol, methyl amino ethanol, 3-amino-1-propanol, 4-amino-1-butanol, 2-(2-aminoethoxy)-1-ethanol (AEE), 2-(2-aminoethylamino)-1- Ethanol, benzyl-piperazine, Tetra-amine hydroperoxide furyl, Diethylenetriamine, Triethylenetetramine, Tetraethylene penta amine and their Mixture, but not limited to these.

According to an embodiment, the inorganic base compound and the organic amine compound may also be mixed. use.

In the case where the content of the above alkali source is low, the pattern developability on the photoresist may be incomplete, and in the case of too much, damage to the fine pattern may be caused. Thus, the alkali source may comprise from 0.01 to 30% by weight, based on the total weight of the composition, for example, may comprise from 0.01 to 20% by weight or from 0.02 to 10% by weight.

The photoresist developer of the present invention is diluted with an appropriate amount of water before use to provide a desired concentrate. In the above case, each component can be present in the developer in an amount within the above-described appropriate range. For example, when the concentrate is diluted to twice, the compound of the chemical formula 1 and each component contained in the photoresist developing solution may be contained in the concentrate in an amount of more than two times the above content. As described above, the above developer composition can be diluted to 1 to 1000 times, for example, 50 to 500 times, and then used.

The photoresist developing solution according to the present invention may contain water, and the above water may generally use deionized water for semiconductor engineering. For example, the water used has a purity of 18 M?/cm or more, and when the total weight of the composition is 100 parts by weight, a photoresist developing solution may be added so that the total content of the other components is 100.

According to an embodiment of the present invention, in addition to the above compounds, one or more of various additives generally used in the art may be included. In the case where the additive as described above is added, the content thereof can be selected in accordance with the purpose of use of each additive or the like. Therefore, in the range which does not impair the effect of the present invention, for example, the content of all the additives is in the range of 10 parts by weight or less based on 100 parts by weight of the photoresist developing solution of the present invention.

According to an embodiment, although the photoresist developing process to which the photoresist developing solution according to the present invention is applied is not particularly limited, for example, a single type such as dipping isostatic or sputtering (spraying) may be employed. Wait. In particular, in the process of developing the photoresist by spraying the developer, the amount of generation of bubbles can be reduced and the developability can be improved.

The present invention can be variously modified and various embodiments can be carried out. The present invention will be described in detail below to enable those skilled in the art to which the present invention belongs. The following examples are intended to exemplify the invention, and the invention is not limited to the following examples, and the invention is to be construed as being limited to all modifications, equivalents and alternatives within the spirit and scope of the invention.

Examples 1 to 8 and Comparative Examples 1 to 4: Fabrication of Photoresist Developer

A photoresist developing solution was prepared by mixing the components and contents described in Table 1 below. The remaining amount of water was added so that the total weight of the composition reached 100 parts by weight.

BPA-16: Add 16 moles of ethylene oxide to 1 mol bisphenol A (SUNFOL BPA-16, SFC)

BPA-18: Add 18 moles of ethylene oxide to 1 mol bisphenol A (SUNFOL BPA-18, SFC)

DPA-14: Add 14 moles of ethylene oxide to 1 molar 4,4'-methylene diphenol (SUNFOL DPA-14, SFC)

BPA-20E2P: Add 20 moles of ethylene oxide and 2 moles of propylene oxide to 1 mole of bisphenol A (SUNFOL BPA-20E2P, SFC)

PCP-8: 8 mol of ethylene oxide in 1 mol of para-cumyl phenol (SUNFOL PCP-8, SFC)

MSP-9: 9 moles of ethylene oxide (SUNFOL MSP-9, SFC) added to mono-styryl phenol

DSP-12: Add 12 moles of ethylene oxide to 1 moles of styrylphenol (SUNFOL DSP-12, SFC)

NPB1200: Add 12 moles of ethylene oxide to 1 naphthol (SUNFOL NPB1200, SFC)

KOH: potassium hydroxide

MEA: ethanolamine (monoethanolamine)

AEE: amino ethoxyethanol

Experimental Example 1) Analysis of surfactant residue content

On a glass substrate (100 mm × 100 mm) used in an alkali-free TFT-LCD, a spin coating film having a thickness of 1.2 to 1.5 μm is used (Red color photoresist, LED1 R, LG Chemical Co., Ltd.) . After the front side exposure (42 mJ/cm ² ), the developing solutions according to the respective examples and comparative examples of the above Table 1 were diluted with water to 100 times. The substrate was treated with an 80% by weight aqueous ethanol solution, and the surface of the color resist was taken out, and the residual amount of the surfactant in the aqueous ethanol solution was measured by liquid chromatography.

Experimental Example 2) Confirmation of the developed photoresist pattern

On a glass substrate (100 mm × 100 mm) used for the alkali-free TFT-LCD, a negative-working photoresist (resin black matrix, TOK5110, TOK Corporation) having a thickness of 1.2 to 1.5 μm was spin-coated, and it was dried at 100 ° C in an oven. 100 seconds pre-bake. Subsequently, after exposure (79 mJ/cm ² ) by a pattern mask, the developing liquids of the respective examples and comparative examples of the above Table 1 were diluted with water to 100 times. After the developer treatment, the mixture was washed with ultrapure water for a certain period of time, rinsed, air-dried with nitrogen, and then hard-bake was performed in an oven at 220 ° C for 20 minutes. The pattern of the photoresist having a width of 1 to 40 μm was observed by an optical microscope to confirm the degree of damage and loss of the pattern.

Experimental Example 3) Confirmation of bubble generation amount of development treatment liquid

The developer according to each of the examples and the comparative examples of the above Table 1 was diluted with water to 100 times, and the amount of generation of bubbles was analyzed. In a 100 mL glass bottle, 10 mL of the diluted developing solution according to the examples and the comparative examples were placed, and the volume of the bubbles was confirmed after shaking for 10 seconds.

The analysis results of the above Experimental Examples 1 to 3 are shown in Table 2 below and Figs. 1 to 7. 1 to 3 are photographs taken after development of the black matrix resin by the developing solutions according to Examples 1, 2 and 4, and Figs. 4 to 7 show the use of the developing solutions according to Comparative Examples 1 to 4 for the black matrix resin. Photo taken after development.

As apparent from the above, according to Examples 1 to 8, the residual amount of the surfactant remaining on the photoresist was at least 3 times smaller than the residual amount shown in Comparative Examples 1 to 4.

In addition, there is at least a difference of 2 to 7 times between the embodiment and the comparative example for the minimum amplitude of the fine pattern after development of the photoresist, and it can be confirmed from FIGS. 1 to 7 that the case of the comparative example is compared with the embodiment. More damage.

Further, in the amount of bubble generation, the developing solutions of Comparative Examples 1 to 4 were also about twice as large as those of the developing solutions of Examples 1 to 8.

From the above results, it was confirmed that the photoresist developing solution provided by the present invention can maintain the developability while keeping the surfactant less in the light which is crosslinked by the light energy while performing the photoresist developing process. The surface of the glue is engraved, and damage to the fine pattern is minimized, bubble generation is reduced, and engineering is improved.

The detailed description of the specific portions of the present invention as described above is intended to be a preferred embodiment of the present invention, and the scope of the present invention is not limited to the specific embodiments described above.

Claims (8)

A photoresist developing solution comprising the nonionic surfactant and the alkali source represented by the following Chemical Formula 1: In the above formula, R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and AO ¹ and AO ² are each independently a vinyl group, an oxypropylene group and a polyoxyethylene-poly group. One or more groups selected from the group consisting of oxypropylene block copolymer-derived groups, Ar represents an aryl group, and m and n are each independently an integer of from 1 to 50. The photoresist developer according to claim 1, wherein R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and AO ¹ and AO ² are each independently One or more groups selected from the group consisting of a vinyl group, an oxypropylene group, and a group derived from a polyoxyethylene-polyoxypropylene block copolymer, and Ar represents a substituted or unsubstituted phenylene group, m and n are each independently an integer of 2 to 20. The photoresist developer according to claim 1, wherein the alkali source comprises an inorganic basic compound, an organic amine compound or a mixture thereof. The photoresist developer according to claim 3, wherein the inorganic basic compound is potassium hydroxide, potassium carbonate, potassium hydrogencarbonate, sodium hydroxide, sodium carbonate, sodium hydrogencarbonate or citric acid. One or more compounds selected from potassium and sodium citrate. The photoresist developer solution of claim 3, wherein The organic amine compound is from ethanolamine, diethanolamine, triethanolamine, 1-imidazoleethanol, monoisopropanolamine, 1-aminoisopropanol, 2-amino-1-propanol, N-methylaminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, 2-(2-aminoethoxy)-1-ethanol (AEE), 2-(2-aminoethylamino)-1-ethanol And one or more selected from the group consisting of tetrahydrofuran, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine. The photoresist developer according to claim 1, wherein the content of the nonionic surfactant represented by the above Chemical Formula 1 is 0.05 to 30% by weight based on the total weight of the composition. The photoresist developer according to claim 1, wherein the alkali source is contained in an amount of from 0.01 to 30% by weight based on the total mass of the composition. The photoresist developer according to claim 1, wherein the photoresist developer is used in a negative photoresist development process.