WO2013089403A1 - Photoresist composition - Google Patents

Abstract

The present invention relates to a photoresist composition, and more particularly, to a photoresist composition for forming a fine pattern for a substrate including a process for forming a halftone on a silicon nitride (SiNx) layer of the substrate. The photoresist composition of the present invention has excellent stability at room temperature, has little discoloration for good permeability, and has good adhesion of the silicon nitride layer so that even when an HMDS process is omitted, there is no possibility of the layer being washed away during the forming process of a fine pattern or of the pattern deteriorating in subsequent processes.

Description

Photoresist composition

The present invention relates to a photoresist composition, and more particularly, to a photoresist composition for forming a micropattern of a substrate including a step of forming a halftone on a silicon nitride film (SiNx) of a substrate, having excellent room temperature stability and discoloration. It is excellent in permeability and excellent in adhesion with silicon nitride film, so there is no risk of loss of pattern during developing process of micronized pattern or collapse of pattern during post-process even if omitting HMDS process and fine using it It relates to a pattern forming method.

In general, a photoresist composition is used to form an insulating film or a protective film in a semiconductor or flat panel display device, and the photoresist composition includes a melamine-based crosslinking agent or a silane-based crosslinking agent to improve adhesion to a substrate.

However, when forming a fine pattern using a photoresist composition containing a melamine-based crosslinking agent or a silane-based crosslinking agent, the adhesive force of the photoresist was deteriorated and the adhesive force had to be secured through a hexamethyldisilazane (HMDS) spraying process. This is because if the HMDS spraying process is not performed, a loss may occur during the development process of the micronized pattern, or a collapse of the pattern may occur during the subsequent process.

Republic of Korea Patent Publication No. 10-2009-39930 to solve the problem 5 to 50% by weight of the organic polymer; 10 to 30% by weight of the photosensitive material; And 3 to 5% by weight of the silane coupling agent containing an isocyanate group at the end and a residual amount of the solvent, and a photoresist composition capable of omitting the HMDS spraying process. However, even in the case of the application, the stability is reduced at room temperature, the color of the formed pattern is changed and the transmittance is decreased, and when the silicon nitride film is to be formed on the silicon nitride film, including a halftone process, a micropattern of 0.1 to 10 um is formed. There was a problem in that the adhesion with the excellent.

The present invention is a photoresist composition for forming a micropattern of a substrate including a process of forming a halftone on a silicon nitride film (SiNx) of a substrate in consideration of the problems of the prior art as described above. HMDS gas bubbles and particle defects can be fundamentally reduced, and the manufacturing cost of the panel can be reduced by reducing the process cost, and the stability at room temperature is excellent, and the permeability is excellent due to the small discoloration, and the adhesion to the silicon nitride film It is an object of the present invention to provide a photoresist composition which is excellent in that there is no fear of occurrence of loss in the development process of the miniaturized pattern or collapse of the pattern in the post-process even if the HMDS process is omitted.

Another object of the present invention is to provide a method for forming a fine pattern including the step of forming a halftone on the silicon nitride film (SiNx) of the substrate using the photoresist.

Another object of the present invention is to provide an electronic device having a fine circuit pattern obtained by the present invention.

The present invention to achieve the above object

(a) i) unsaturated carboxylic acids or anhydrides thereof; ii) epoxy group-containing unsaturated compounds; And iii) 10 to 30% by weight of an acrylic copolymer having a weight average molecular weight of 4000 to 9000 prepared by polymerizing an olefinically unsaturated compound with a monomer;

(b) 0.1-2% by weight of a silane coupling agent containing an isocyanate group (-NCO) in the terminal group;

(c) 1 to 15 weight percent of the photosensitizer; And

(d) Provided is a photoresist composition comprising a residual amount of solvent.

In another aspect, the present invention is a method of forming a fine pattern of a substrate comprising the step of forming a halftone on the silicon nitride film of the substrate using a photoresist composition,

It provides a method for forming a fine pattern of the substrate, characterized in that using the photoresist composition.

The present invention also provides an electronic device comprising a substrate having a fine circuit pattern obtained by the manufacturing method.

The photoresist composition according to the present invention is a photoresist composition for forming a micropattern of 0.1 to 10 um of a substrate including a process of forming a halftone on a silicon nitride film (SiNx) of a substrate, which is generated by HMDS during the process. It is possible to reduce gas bubbles and particle defects fundamentally, and to reduce the manufacturing cost of the panel by reducing the process cost, and it has excellent room temperature stability, excellent dispersibility due to less discoloration, and excellent adhesion to the silicon nitride film. Therefore, even if the HMDS process is omitted, there is no risk of loss of the pattern during the development of the micronized pattern or collapse of the pattern during the post process.

1 is a result of the adhesion test according to Example 1 of the present invention.

2 is a result of the adhesion experiment according to Comparative Example 2.

The photoresist composition of the present invention

(a) i) unsaturated carboxylic acids or anhydrides thereof; ii) epoxy group-containing unsaturated compounds; And iii) 10 to 30% by weight of an acrylic copolymer having a weight average molecular weight of 4000 to 9000 prepared by polymerizing an olefinically unsaturated compound with a monomer;

(b) 0.1-2% by weight of a silane coupling agent containing an isocyanate group (-NCO) in the terminal group;

(c) 1 to 15 weight percent of the photosensitizer; And

(d) a residual amount of solvent.

In the present invention, the acryl-based copolymer is polymerized in the presence of a solvent and a polymerization initiator using i) unsaturated carboxylic acid or an anhydride thereof, ii) an epoxy group-containing unsaturated compound and iii) an olefinically unsaturated compound as monomers, and then removing unreacted monomers. You can get it.

I) Unsaturated carboxylic acid, unsaturated carboxylic anhydride or mixtures thereof used in the present invention include unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid; Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, metaconic acid and itaconic acid; Or anhydrides of these unsaturated dicarboxylic acids, or the like, may be used alone or in combination of two or more thereof. In particular, the use of methacrylic acid is more preferable in terms of copolymerization reactivity and solubility in an aqueous alkali solution.

The unsaturated carboxylic acid, unsaturated carboxylic anhydride or a mixture thereof is preferably included in an amount of 15 to 30 parts by weight based on the total monomers. When the content is within the above range, the prepared copolymer may secure adhesive strength even in halftones on the silicon nitride film by synergistic action with a silane coupling agent including an isocyaneti group, and have excellent permeability and room temperature stability of the formed pattern.

The epoxy group-containing unsaturated compound of ii) used in the present invention is glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-propyl acrylate, α-n-butyl acrylic acid Glycidyl, acrylic acid-beta -methyl glycidyl, methacrylic acid-beta -methyl glycidyl, acrylic acid-beta -ethylglycidyl, methacrylic acid-beta -ethylglycidyl, acrylic acid -3,4- Epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl Glycidyl ether, m-vinyl benzyl glycidyl ether, or p-vinyl benzyl glycidyl ether, methacrylic acid 3,4-epoxy cyclohexyl, and the like can be used. Can be used.

In particular, the epoxy group-containing unsaturated compound is more preferably used to improve the copolymerization reactivity and the heat resistance of the resulting pattern using glycidyl methacrylate.

The epoxy group-containing unsaturated compound is preferably included in 15 to 30 parts by weight based on the total monomers. When the content is within the above range, the prepared copolymer may secure adhesive strength even in halftones on the silicon nitride film by synergistic action with a silane coupling agent including an isocyaneti group, and have excellent permeability and room temperature stability of the formed pattern.

The olefinically unsaturated compound of iii) used in the present invention is methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, methyl acrylate, iso Propyl acrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl methacrylate, 1-a Monomethyl acrylate, 1-adamantyl methacrylate, dicyclopentanyloxyethyl methacrylate, isobonyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyloxyethyl acrylate, Isobornyl acrylate, 2-hydroxyethyl acrylate, phenyl methacrylate, phenyl acrylate, benzyl acrylate, 2- Hydroxyethyl methacrylate, styrene, σ-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, 1,3-butadiene, isoprene, or 2,3-dimethyl 1,3 -Butadiene etc. can be used, The said compound can be used individually or in mixture of 2 or more types.

In particular, the olefinically unsaturated compound is used by mixing in a weight ratio of styrene 60-80: isobornyl acrylate 5-20: 2-hydroxyethyl acrylate 15-40 is copolymerization reactivity and solubility in an aqueous alkali solution which is a developer. More preferred in terms of aspect.

The olefinically unsaturated compound is preferably included in 40 to 70 parts by weight based on the total total monomers. When the content is within the above range, the prepared copolymer may secure adhesive strength even in halftones on the silicon nitride film by synergistic action with a silane coupling agent including an isocyaneti group, and have excellent permeability and room temperature stability of the formed pattern.

Solvents used for solution polymerization of such monomers include alcohols such as methanol, ethanol, benzyl alcohol and hexyl alcohol; Ethylene glycol alkyl ether acetates such as ethylene glycol methyl ether acetate and ethylene glycol ethyl ether acetate; Ethylene glycol monoalkyl ethers such as ethylene glycol alkyl ether propionate such as ethylene glycol methyl ether propionate and ethylene glycol ethyl ether propionate, ethylene glycol methyl ether and ethylene glycol ethyl ether; Diethylene glycol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol propyl ether acetate; Propylene glycol alkyl ether propionates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate and propylene glycol propyl ether propionate; Propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, and propylene glycol butyl ether; Butylene glycol monomethyl ethers such as dipropylene glycol alkyl ethers such as dipropylene glycol dimethyl ether and diporopropylene glycol diethyl ether, butylene glycol monomethyl ether, butylene glycol monoethyl ether; Dibutylene glycol alkyl ethers, such as dibutylene glycol dimethyl ether and dibutylene glycol diethyl ether, tetrahydroxyfuran, toluene, dioxane, etc. can be used individually or in mixture of 2 or more types.

The polymerization initiator used for solution polymerization of such monomers may use a radical polymerization initiator, specifically 2,2-azobisisobutyronitrile, 2,2-azobis (2,4-dimethylvaleronitrile ), 2,2-azobis (4-methoxy 2,4-dimethylvaleronitrile), 1,1-azobis (cyclohexane-1-carbonitrile), or dimethyl 2,2'-azobisisobutyl Rate and the like can be used.

The acrylic copolymer obtained by radical reaction of the above monomers in the presence of a solvent and a polymerization initiator, and removal of unreacted monomers through precipitation, filtration and vacuum drying processes, preferably has a polystyrene reduced weight average molecular weight (Mw) of 4,000 to 9,000. More preferably 5,000 to 7,000. In the above range, it is possible to secure the adhesive force even in the halftone on the silicon nitride film by synergistic action with the silane coupling agent including an isocyaneti group, and the transmittance and room temperature stability of the formed pattern are excellent.

The acrylic copolymer may be included in the photosensitive resin composition of the present invention in 10-30% by weight, in this case excellent in the profile and developability of the pattern, it is possible to ensure the adhesive strength even in the halftone on the silicon nitride film, Excellent permeability and room temperature stability.

In the photosensitive resin composition of this invention, the (b) silane coupling agent containing an isocyanate group (-NCO) in a terminal group is included. The silane coupling agent containing an isocyanate group in the terminal group is diisocyanate ethoxyethyl silane, diisocyanate methoxyethyl silane, diisocyanate ethoxy propyl silane, diisocyanate methoxy propyl silane, 3-isocyanate butyl trimethoxy silane, 3 -Isocyanate oxyethyl ethoxysilane, 3-isocyanate oxyethyl methoxysilane, 3-isocyanate propyl triethoxy silane, 3-isocyanate propyl methoxysilane, 3-isocyanate ethyl triethoxy silane, 3-isocyanate ethyl trimethoxy One or two or more kinds selected from the group consisting of silane and 3-isocyanatebutyltriethoxysilane can be used.

The silane coupling agent containing an isocyanate group in the terminal group may be included in the photosensitive resin composition of the present invention in an amount of 0.1-2% by weight, and when the content thereof is less than 0.1% by weight, the adhesive force may be secured in the halftone pattern portion on the silicon nitride film. If it is more than 2% by weight, room temperature stability is inferior, and the transmittance of the formed pattern is inferior.

In the photosensitive resin composition of the present invention, the (c) photosensitive agent may be a known photosensitive compound, and specific examples thereof include 1,2-quinonediazide 4-sulfonic acid ester, 1,2-quinonediazide 5-sulfonic acid ester, or 1 , 2-quinonediazide 6-sulfonic acid ester and the like can be used.

The photosensitive agent may be included in the photosensitive resin composition of the present invention in an amount of 1-30% by weight, and in this case, the profile and developability of the pattern may be satisfied at the same time.

In addition, the solvent (d) used in the present invention does not generate flatness and coating stains of the organic insulating film, thereby forming a uniform pattern profile.

The solvent may be a known solvent used in the photosensitive resin composition, alcohols such as methanol, ethanol, benzyl alcohol, hexyl alcohol; Ethylene glycol alkyl ether acetates such as ethylene glycol methyl ether acetate and ethylene glycol ethyl ether acetate; Ethylene glycol monoalkyl ethers such as ethylene glycol alkyl ether propionate such as ethylene glycol methyl ether propionate and ethylene glycol ethyl ether propionate, ethylene glycol methyl ether and ethylene glycol ethyl ether; Diethylene glycol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol propyl ether acetate; Propylene glycol alkyl ether propionates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate and propylene glycol propyl ether propionate; Propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, and propylene glycol butyl ether; Butylene glycol monomethyl ethers such as dipropylene glycol alkyl ethers such as dipropylene glycol dimethyl ether and diporopropylene glycol diethyl ether, butylene glycol monomethyl ether, butylene glycol monoethyl ether; Dibutylene glycol alkyl ethers such as dibutylene glycol dimethyl ether and dibutylene glycol diethyl ether.

The solvent is included as the remainder of the entire photosensitive resin composition, and preferably included to be 50 to 90% by weight. When it is in the said range, the coating property and correction stability of the photosensitive resin composition can be improved simultaneously.

The photosensitive resin composition of the present invention comprising the above components may further comprise 0.01 to 10% by weight of a plasticizer, UV stabilizer, radical scavenger, antioxidant, sensitivity enhancer or surfactant as necessary. The plasticizers, UV stabilizers, radical scavengers, antioxidants, sensitivity enhancers or surfactants may be used as well known materials used in the photosensitive resin composition.

It is preferable that the solid content concentration of the photosensitive resin composition of this invention which consists of the above components is 10 to 50 weight%, and the composition which has a solid content of the said range is used after filtering with a Millipore filter of 0.01-0.2 micrometer. good.

In another aspect, the present invention provides a method for forming a micropattern using the photosensitive resin composition and an electric device including the micropattern formed by the method. Preferably, the electric element is a semiconductor or flat panel display having a fine pattern of 0.1 to 10 um, more preferably a fine pattern of 0.1 to 4 um line width.

The method of forming a micropattern according to the present invention is characterized by using the photosensitive resin composition as a photoresist composition for forming a micropattern of a substrate, including forming a halftone on a silicon nitride film (SiNx). Except for using the photosensitive resin composition, a known micropattern forming method may be used.

As a specific example, a method of forming an organic insulating film is as follows.

First, the photosensitive resin composition of this invention is apply | coated to the surface of the board | substrate with which the silicon nitride film was formed by the spray method, the roll coater method, the rotary coating method, etc., and a solvent is removed by prebaking and a coating film is formed. At this time, the prebaking is preferably carried out for 1 to 15 minutes at a temperature of 80-115 ℃.

Then, a predetermined pattern is formed by irradiating visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like on the formed coating film according to a previously prepared pattern, and developing with a developer to remove unnecessary portions.

The developer is preferably an aqueous alkali solution, specifically, inorganic alkalis such as sodium hydroxide, potassium hydroxide and sodium carbonate; Primary amines such as ethylamine and n-propylamine; Secondary amines such as diethylamine and n-propylamine; Tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine and triethylamine; Alcohol amines such as dimethylethanolamine, methyl diethanolamine and triethanolamine; Or an aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide can be used. In this case, the developer is used by dissolving the alkaline compound at a concentration of 0.1-10% by weight, and an appropriate amount of a water-soluble organic solvent such as methanol and ethanol and a surfactant may be added.

In addition, after developing with the developer as described above, it is washed with ultrapure water for 30-90 seconds to remove unnecessary parts and dried to form a pattern, and after irradiating the formed pattern with light such as ultraviolet rays, the pattern is applied to a heating apparatus such as an oven. By heating at a temperature of 150-250 ° C. for 30-90 minutes to obtain a final pattern.

The method of forming a micropattern using the photosensitive resin composition of the present invention can omit the HMDS spraying process when forming the micropattern of 0.1 to 10 um, thereby reducing HMDS gas bubbles and particle defects caused by the HMDS process. It is possible to reduce the manufacturing cost of the panel by reducing the process cost, and it has excellent room temperature stability, excellent dispersibility due to less discoloration, and excellent adhesion to silicon nitride film. There is no fear of loss in the developing process or collapse of the pattern in the later process.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

EXAMPLE

Example 1

(Acrylic copolymer production)

10 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile), 200 parts by weight of propylene glycol monomethyl ether acetate, 20 parts by weight of methacrylic acid, and methacrylic acid in a flask equipped with a cooling tube and a stirrer 25 parts by weight of cydyl, 40 parts by weight of styrene, 5 parts by weight of 2-hydroxyethyl acrylate, and 10 parts by weight of isobornyl acrylate were added, followed by nitrogen replacement, followed by gentle stirring. The reaction solution was heated to 55 ° C. to prepare a polymer solution containing an acrylic copolymer while maintaining this temperature for 24 hours.

Solid content concentration of the polymer solution containing the said acrylic copolymer was 50 weight%, and the weight average molecular weight of the polymer was 5,000. At this time, the weight average molecular weight is the polystyrene reduced average molecular weight measured using GPC.

(1,2-quinonediazide compound preparation)

1 mole of 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and 1,2-naphthoquinonediazide-5-sulfonic acid [ Chloride] condensation reaction of 2 moles to give 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol 1,2-naphthoquinonediazide -5-sulfonic acid ester was prepared.

 (Photosensitive resin composition production)

100 parts by weight of the polymer solution containing the acrylic copolymer prepared above and the prepared 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] 25 parts by weight of bisphenol 1,2-naphthoquinonediazide-5-sulfonic acid ester and 5 parts by weight of a silane coupling agent containing an isocyanate group at the terminal were mixed. Further, diethylene glycol dimethyl ether was added to dissolve so that the solid content concentration of the mixture was 30 wt% by weight, and filtered through a 0.05 μm millipore filter to prepare a photosensitive resin composition. In the present embodiment, the content of the silane coupling agent was 1.875 wt% final.

Example 2

A photosensitive resin composition was prepared in the same manner as in Example 1, except that 1 part by weight of the silane coupling agent containing an isocyanate group was used in the preparation of the photosensitive resin composition of Example 1. In this embodiment, the content of the silane coupling agent was 0.375% by weight.

Comparative Example 1

Except for using a melamine-based crosslinking agent in place of the silane coupling agent containing an isocyanate group in the terminal of the photosensitive resin composition of Example 1 was prepared in the same manner as in Example 1 to prepare a photosensitive resin composition.

Comparative Example 2

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the final content of the silane coupling agent containing an isocyanate group in the terminal of the photosensitive resin composition of Example 1 was 0.05% by weight.

Comparative Example 3

A photosensitive resin composition was prepared in the same manner as in Example 1 except that the final content of the silane coupling agent containing an isocyanate group in the terminal of the photosensitive resin composition of Example 1 was 4% by weight.

The adhesive force, permeability, and room temperature stability with the silicon nitride film were evaluated using the photosensitive resin composition of the said Example 1-2 and the comparative example 1-3.

a) Adhesion-After applying the photosensitive resin composition solution prepared in Example 1-2 and Comparative Example 1-2 without applying the HMDS solution on the glass substrate on which SiNx is deposited 500-3000 kPa, 90 The film was formed by prebaking on a hot plate at −100 ° C. for 50-180 seconds. The thickness of the coated film was 0.2-4 um, and the obtained film was 5 ~ 5 uv in intensity of 10 mW / cm ² at 365 nm using a mask with 1-5 um Line & Space and Contact Hole & Dot pattern. Irradiation was made for 20 seconds. Thereafter, the solution was developed with an aqueous tetramethyl ammonium hydroxide solution at 19-27 ° C. for 50 seconds to 180 seconds, and then washed with ultrapure water for 1 minute. As a result, as shown in Figure 1 in the case of Example 1 was not lost at all in the 2 um pattern, and in the case of Example 2 also showed a result similar to Example 1, although not shown in the figure.

On the contrary, in Comparative Example 1, loss occurred severely in a 4 um pattern, and in Comparative Example 2, some patterns were lost as shown in FIG. 2.

b) Permeability: After applying the photosensitive resin composition solution prepared in Example 2 and Comparative Examples 1 and 3 on the Bare Glass substrate, the film was formed by prebaking on a hot plate at 90-100 ° C. for 50-180 seconds. . The thickness of the coated film was 3 μm, and the entire bare glass coated with the film was irradiated with ultraviolet light having a strength of 10 mW / cm ² at 365 nm for 0 to 50 seconds without using a mask. Then, after curing for 1 hour at 220 ℃ in a convection oven, the transmittance was measured at 400nm using a Uv Visible Meter.

By measuring the transmittance, it is determined that it is Bad when it is 90% or less at 400 nm, Normal when it is 93% or more, and Good when it is 95% or more.

Table 1 Example 2 Comparative Example 1 Comparative Example 3 Transmittance 96% 88% 89%

As shown in Table 1, in the case of the embodiment of the present invention it was confirmed that the markedly improved transmittance compared to Comparative Examples 1 and 3.

c) Room temperature storage: The storage stability of the photosensitive resin composition of Example 1 and Comparative Examples 1, 2, and 3 left at room temperature for 120 hours, and then evaluated the adhesive strength to confirm the stability of the material. The adhesive strength evaluation method used the same method as the method used in said a). The results were as shown in Table 2 below.

TABLE 2 Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Room temperature stability No loss even in 2um pattern 4um pattern loss 4um pattern loss 4um pattern loss

As shown in Table 2, the loss did not occur even in the 2 um pattern in the Example, it was confirmed that the loss occurs in the 4 um pattern in Comparative Examples 1 to 3.

As shown above, the photosensitive resin composition of the embodiment according to the present invention has excellent adhesion to a silicon nitride film and thus forms a fine pattern of 0.1 to 10 um of a substrate including a process of forming a halftone on a silicon nitride film (SiNx). As a photoresist composition for processing, HMDS gas bubbles and particle defects generated by HMDS can be reduced at the time of process, and the manufacturing cost of the panel can be reduced by reducing the process cost. It is less and excellent in permeability.

The photoresist composition according to the present invention is a photoresist composition for forming a micropattern of 0.1 to 10 um of a substrate including a process of forming a halftone on a silicon nitride film (SiNx) of a substrate, which is generated by HMDS during the process. It is possible to reduce gas bubbles and particle defects fundamentally, and to reduce the manufacturing cost of the panel by reducing the process cost, and it has excellent room temperature stability, excellent dispersibility due to less discoloration, and excellent adhesion to the silicon nitride film. Therefore, even if the HMDS process is omitted, there is no risk of loss of the pattern during the development of the micronized pattern or collapse of the pattern during the post process.

Claims (11)

(a) i) unsaturated carboxylic acids or anhydrides thereof; ii) epoxy group-containing unsaturated compounds; And iii) 10 to 30% by weight of an acrylic copolymer having a weight average molecular weight of 4000 to 9000 prepared by polymerizing an olefinically unsaturated compound; (b) 0.1-2% by weight of a silane coupling agent containing an isocyanate group (-NCO) in the terminal group; (c) 1 to 15 weight percent of the photosensitizer; And (d) A photoresist composition comprising a residual amount of solvent. The method of claim 1, The acrylic copolymer is i) unsaturated carboxylic acid or anhydride 15 to 30 parts by weight as a monomer; ii) 15 to 30 parts by weight of an epoxy group-containing unsaturated compound; And iii) polymerization using 40 to 70 parts by weight of an olefinically unsaturated compound. The method of claim 1, I) unsaturated carboxylic acid is methacrylic acid, characterized in that the photoresist composition. The method of claim 1, The epoxy group containing unsaturated compound of said ii) is glycidyl methacrylate, The photoresist composition characterized by the above-mentioned. The method of claim 1, Said iii) olefinically unsaturated compound is a mixture of styrene, 2-hydroxyethyl methacrylate, and isobornyl acrylate, The photoresist composition characterized by the above-mentioned. The method of claim 1, The photoresist composition, characterized in that the weight average molecular weight of the acrylic copolymer is 5000 to 7000. The method of claim 1, The photoresist composition further comprises 0.01 to 10% by weight of a plasticizer, UV stabilizer, radical scavenger, antioxidant, sensitivity enhancer or surfactant. In the method of forming a fine pattern of a substrate comprising the step of forming a halftone on the silicon nitride film of the substrate using a photoresist composition, The method of forming a micropattern of a substrate, wherein the photoresist composition is a photoresist composition according to any one of claims 1 to 7. A substrate having a micropattern formed by the method of claim 8. The method of claim 9, The line width of the fine pattern is a substrate having a fine pattern, characterized in that having a 0.1 to 4um. An electronic device comprising the substrate of claim 9.

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