KR20100046363A - Photoresist composition - Google Patents

Abstract

PURPOSE: A photoresist composition is provided to improve the resolution, the development contrast, the adhesive force, the photosensitive speed, the remaining rate of a film, and the heat resistance. CONSTITUTION: A photoresist composition contains an alkali-soluble resin, a photo sensitive compound, a colloid phase inorganic material and an organic solvent. 1~50 wt% of colloid phase inorganic material is mixed for the sum of total amounts of the alkali-soluble resin and the photo sensitive compound. 5~50 parts of photo sensitive compound by weight is mixed for the 100 parts of alkali-soluble resin and the colloid phase inorganic material by weight. 10~50wt% of organic solvent is mixed for the total amount of the total composition.

Description

Photoresist composition {PHOTORESIST COMPOSITION}

The present invention relates to a photoresist composition, and more particularly, to a photoresist composition used for manufacturing a fine circuit pattern such as a liquid crystal display circuit or a semiconductor integrated circuit, having excellent uniformity, resolution, development contrast, and adhesion of a circuit line width. In particular, the present invention relates to a composition having excellent photosensitivity, residual film ratio and heat resistance.

A fine circuit pattern, such as a liquid crystal display device circuit or a semiconductor integrated circuit, is coated with a photoresist composition on an insulating film or a conductive metal film formed on a substrate, exposed to light, and developed to form a pattern of a desired shape. The metal film or the insulating film is etched using the patterned photoresist film as a mask, and then the remaining photoresist film is removed to form a fine circuit on the substrate. The photoresist composition for a liquid crystal display device circuit is classified into a negative type and a positive type according to the change in solubility of the exposed portion.

Practically important properties of the photoresist composition include ease of use such as photoresist speed, heat resistance, developed concrete, resolution, adhesion to substrate, residual film ratio, circuit uniformity and human safety of the formed resist film.

The photosensitive speed is the speed at which the solubility of the photoresist changes with exposure, and requires several exposures in order to generate multiple patterns by an iterative process, or intensity, such as projection exposure techniques where light passes through a series of lenses and filters. It is especially important for the photoresist film using the light which was reduced.

In particular, in the case of a thin film transistor liquid crystal display device (hereinafter referred to as TFT-LCD), it is necessary to improve the photosensitive speed in order to reduce the long exposure time in the production line due to the large area of the substrate which is a feature of the thin film transistor liquid crystal display device. . In addition, since the photosensitive speed and the residual film ratio are inversely related, the fast residual film ratio tends to decrease.

The development contrast refers to the ratio of the film loss amount in the exposed part by the development and the film loss amount in the unexposed part. Typically, the exposed substrate coated with the photoresist film is continuously developed until the coating on the exposed portion is almost completely dissolved and removed, so the development contrast is measured by measuring the amount of film loss in the unexposed portion when the exposed coating portion is completely removed. You can simply decide.

Photoresist film resolution refers to the ability of a resist film system to regenerate fine circuit lines into highly sensitive images depending on the spacing of the mask used to expose the resist film.

In various industrial applications, especially in the manufacture of liquid crystal display devices and semiconductor circuits, the photoresist film needs a resolution such that a pattern having a very thin line and a space area (1 μm or less) can be formed.

The resolution is also related to the heat resistance, it is necessary to minimize the deformation of the pattern line width due to the heat applied in the process that proceeds using the pattern of the pattern obtained through the exposure and development process as a mask.

If the heat resistance of the obtained pattern is low, the flow of the pattern may increase due to heat during the further process, and thus the line width may be deformed, thereby causing a decrease in resolution.

Most photoresist compositions include a polymer resin, a photosensitive compound, and a solvent for forming a photoresist film. In the prior art, many attempts have been made to improve the photosensitivity, development contrast, resolution and human stability of photoresist compositions for liquid crystal display circuits.

For example, US Pat. No. 3,666,473 discloses the use of a mixture of two types of phenolformaldehyde alkali soluble resins and typical photosensitive compounds, while US Pat. No. 4,115,128 discloses phenolic resins and naphthos to increase photosensitivity. A composition in which an organic acid cyclic anhydride is added to a quinone diazide photosensitive agent is disclosed, and US Patent No. 4,550,069 discloses an alkali-soluble resin, an o-quinone diazide photosensitive compound, and a solvent to increase the photosensitivity and improve human safety. A photoresist composition using propylene glycol alkyl ether acetate is disclosed.

However, photosensitivity, residual film rate and heat resistance have not yet been sacrificed without sacrificing any of the desirable properties of the photoresist composition such as development contrast, resolution, solubility of the polymer resin, adhesion to the substrate, and circuit line width uniformity. There is a continuing need for a variety of photoresist compositions suitable for each industrial process.

The present invention is to provide a photoresist composition having a novel composition including the basic physical properties of the conventional photoresist composition and having superior physical properties in terms of photosensitivity, residual film ratio, and heat resistance of the photoresist film. It aims to do it.

Another object of the present invention is to provide a method of manufacturing a substrate having a fine circuit pattern using the photoresist according to the present invention.

It is still another object of the present invention to provide an electronic device including a substrate having a fine circuit pattern obtained by the present invention.

The present invention to achieve the above object

a) alkali soluble resin;

b) photosensitive compounds;

c) colloidal minerals; And

d) organic solvent

It provides a photoresist composition comprising a.

The photoresist composition according to the present invention provides a composition excellent in circuit uniformity (CD uniformity), resolution, development contrast, adhesion and chemical resistance by introducing a colloidal inorganic material, and is particularly excellent in photosensitivity, residual film ratio and heat resistance. . By reducing the photosensitive speed, it is possible to reduce the long exposure time of the production line and to increase productivity by preventing deformation of the circuit line width with excellent heat resistance.

The photoresist composition of the present invention comprises (a) an alkali soluble resin; (b) photosensitive compounds; (c) colloidal minerals; And (d) a photoresist composition comprising an organic solvent.

Polymeric resins that can be used to prepare the photoresist compositions are well known in the art. As the polymer resin used in the present invention, (a) alkali-soluble resin is a polymer polymer synthesized by reacting an aldehyde with an aromatic alcohol such as phenol, meta and / or paracresol, and is preferably a novolak resin.

For example, phenols include phenol, o-cresol, m-cresol, p-cresol, 2,3-kisylenol, 2,5-kisylenol, 3,4-kisylenol, 3,5-kisylenol, 2,3,5 It may be used singly or in combination of two or more thereof by using -trimethylphenol-kisylenol.

Examples of the aldehydes condensed with the above phenols include formaldehyde, trioxane, paraformaldehyde, alpha or beta-phenyl propylaldehyde, o or m or p-hydroxybenzaldehyde, and the like.

In the condensation reaction between phenols and aldehydes, an acidic catalyst may generally be used.

Examples of the acidic catalyst include nitric acid, acetic acid, sulfuric acid, oxalic acid, p-toluenesulfonic acid, and the like.

Generally, water is commonly used as a solvent for synthesizing alkali-soluble resins, but when it becomes a heterogeneous system at the initial stage of reaction, alcohols such as methanol, ethanol, propanol, butanol, and propylene glycol monomethyl ether, cyclic ethers such as tetrahydrofuran and dioxane You may use ketones, such as methyl ethyl ketone, methyl isobutyl ketone, and 2-heptanone.

The reaction solvent is used in an amount of 20 to 10,000 parts by weight based on 100 parts by weight of the reaction raw material, the reaction temperature during the condensation reaction can be controlled by the reactivity of the raw material, but generally 10 to 200 ℃ is preferred.

After completion of the condensation reaction, alkali soluble resin may be obtained by raising the reaction material to 130 to 230 ° C. and removing the same under reduced pressure in order to remove residual reaction raw materials, acidic catalysts, and reaction solvents.

In order to improve the performance of the photoresist, a polymer having a molecular weight suitable for the application may be selected and used by appropriately removing a polymer, a medium molecule, a low molecule, etc. from the resin.

The photosensitive compound (b) may preferably be a diazide compound, for example, 2,3 prepared by esterifying trihydroxy benzophenone and 2-diazo-1-naphthol-5-sulfonic acid. Prepared by esterification of, 4, -trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate with tetrahydroxy benzophenone and 2-diazo-1-naphthol-5-sulfonic acid 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate can be used alone or in combination.

The photosensitive compound may be prepared by reacting a polyhydroxy benzophenone with a diazide compound such as 1,2-naphthoquinone diazide and 2-diazo-1-naphthol-5-sulfonic acid.

The content of the photosensitive compound (b) is preferably 5 to 50 parts by weight based on 100 parts by weight of the total solid content of a) the alkali-soluble resin and c) the colloidal inorganic material in order to maintain an appropriate photosensitive speed. When the total content of the photosensitive compound is less than 5 parts by weight, the photosensitivity may be too fast, leading to a severe reduction of the residual film ratio, and when it exceeds 50 parts by weight, the photoresist may be too slow.

(C) The colloidal inorganic material may be an inorganic sol hydrophobized by removing the water and adding an organic solvent while reacting about 1 to 120 parts by weight of the organosilane with respect to 100 parts by weight of the inorganic material on the surface of the inorganic material.

The inorganic material may be at least one selected from silica, alumina, titania, zirconia, tin oxide, zinc oxide, inorganic material capable of reacting with organic silane, or inorganic material surface-modified with silica.

In addition, the organosilane may be represented by R ¹ _0-3 Si (OR ² ) _1-4 , wherein R ¹ is an alkyl group, a phenyl group, a fluorocarbon group, an acrylic group, a methacryl group, an allyl group, a vinyl group, or an epoxy group. Can be selected, R ² can be selected from lower alkyl groups such as alkyl groups having 1 to 4 carbon atoms (methyl, ethyl, propyl, isopropyl, butyl, etc.), OR ² is selected from acetic acid, oxime group or alkoxy group The alkoxy group may be selected from, for example, 1 to 4 carbon atoms.

The organic solvent that can be used for hydrophobization of the reaction medium is not particularly limited and may be at least one selected from the organic solvent (d) of the present invention.

The colloidal inorganic material may have a diameter of about 1 to 100 nm in spherical shape or may be formed in a size of about 100 to 1000 nm in fiber shape.

The colloidal inorganic material preferably comprises about 1 to 50% by weight of the total weight of the alkali-soluble resin and the colloidal inorganic solids sum.

If the colloidal inorganic material is less than 1% by weight of the total weight of the alkali-soluble resin and the colloidal inorganic solid content, the film's photosensitivity, residual film ratio, and heat resistance may be lowered. It may cause problems such as degradation.

As such, by treating the surface of the colloidal inorganic material with an organosilane having a reactive group, the inorganic particles may be chemically bonded at a molecular level having excellent storage properties while being stabilized in an organic solvent.

The organic solvent (d) is not particularly limited, for example, methanol, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methylethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, propylene glycol methyl ether Acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, propylene glycol methyl ethyl propionate, propylene glycol ethyl ether propionate, propylene glycol Propyl ether propionate, propylene glycol butyl ether propionate, toluene, xylene, methyl ethyl ketone, cyclohexanone, 4-hydroxy 4-methyl 2-pentanone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-hydroxy ethyl propionate, 2-hydroxy 2-methyl methyl propionate, 2-hydroxy 2-methyl ethyl propionate, hydroxy methyl acetate, hydroxy ethyl acetate, hydroxy butyl acetate, methyl lactate, ethyl lactate, propyl lactate , Butyl lactate, 3-hydroxy methyl propionate, 3-hydroxy ethyl propionate, 3-hydroxy propyl propionate, 3-hydroxy butyl propionate, 2-hydroxy 3-methyl butyrate, methyl methoxy acetate, methoxy Ethyl acetate, methoxy propyl acetate, methoxy butyl acetate, ethoxy acetate, ethyl ethoxy acetate, ethoxy propyl acetate, butyl ethoxy acetate, methyl propoxy acetate, ethyl propoxy acetate, propyl propoxy acetate, Butoxy butyl acetate, methyl butoxy acetate, butoxy acetate, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-methoxy Butyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-butoxypropionic acid Propyl, 2-Butoxy Propionate, 3-Methoxypropionate, 3-Methoxypropionate, 3-Methoxypropionate, 3-Methoxypropionate, 3-Ethoxypropionate, 3-Ethoxypropionate Ethyl, 3-Ethoxy Propionate, 3-Ethoxy Propionate, 3-Propoxy Propionate, 3-Propoxy Propionate, 3-Propoxy Propionate, 3-Propyl Propionate, 3-Butoxy Propionate , It may include at least one selected from ethers such as ethyl 3-butoxypropionate, propyl 3-butoxypropionate and butyl 3-butoxypropionate.

The solvent is preferably included so that the solid content of the photoresist composition described above is about 10 to 50% by weight, more preferably about 15 to 40% by weight. If the content is less than about 10% by weight, the film thickness may not only be formed too thin, but also the flatness may be lowered. If the content exceeds about 50% by weight, the film may not only be formed too thick, but also may impair the equipment during coating. .

The component having a solid content in this range is preferably used after filtering with a Millipore filter of about 0.1 to 1 ㎛.

The photoresist composition of the present invention may further include additives such as plasticizers, adhesion promoters, speed enhancers, surfactants, and antifoaming agents in the range of 0.01 to 5% by weight, in addition to the above-described components as necessary.

The present invention provides a method of manufacturing a substrate on which a fine circuit pattern is formed, comprising applying the photoresist according to the present invention to a substrate.

The photoresist composition may be applied to the substrate by conventional methods including dipping, spin coating, spraying, roll coating, and the like.

The substrates include glass, silicon, aluminum, indium tin oxide (ITO), indium zinc oxide (IZO), molybdenum, silicon dioxide, doped silicon dioxide, silicon nitride, tantalum, copper, polysilicon, ceramics, aluminum / copper mixtures Or made of a polymerizable resin.

After the photoresist according to the present invention is applied to a substrate, the solvent can be removed by prebake. At this time, the pre-curing step may be performed at about 70 to 110 ℃.

The heat treatment is carried out to evaporate the solvent without pyrolyzing the solid component in the photoresist composition.

In general, it is desirable to minimize the concentration of solvent through precuring processes.

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 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 diethanol amine and triethanol amine; 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 then heat treated again through a hard bake process to improve adhesion and resistance of the photoresist film. Promote chemistry

Such heat treatment is preferably carried out at a temperature below the softening point of the photoresist film, and particularly preferably at a temperature of 90 to 140 ° C.

The developed substrate is treated with a corrosion solution or a gas plasma as described above to treat the exposed substrate, wherein the unexposed portion of the substrate is protected by a photoresist film.

After the substrate is treated in this manner, a fine circuit pattern can be formed on the substrate by removing the photoresist film with an appropriate stripper.

The photoresist composition according to the present invention has excellent CD uniformity, resolution, development contrast, and adhesion of circuit lines, and in particular, it can be used for manufacturing a liquid crystal display device or various semiconductor devices due to its excellent photosensitivity, residual film ratio, and heat resistance. have.

Hereinafter, examples and comparative examples are presented to help understand the present invention. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited to the following examples.

Example 1

(1-1) Preparation of Alkali Soluble Resin

65 g of m-cresol, 43 g of p-cresol, 120 g of 37% aqueous formaldehyde solution, 2 g of oxalic acid, and 25 g of propylene glycol methyl ether acetate (PGMEA) were placed in a reflux-cooled sand dune flask and stirred at a temperature of 100 while stirring under nitrogen atmosphere. It was condensed for 4 hours by rising to ℃.

After the reaction, the reaction mixture was heated up to 180 ° C. to remove the remaining reaction raw material and the reaction solvent, and then cooled to room temperature to obtain an alkali-soluble resin.

The molecular weight of the obtained resin is 2,000 with a weight average molecular weight and this weight average molecular weight is polystyrene conversion average molecular weight measured using GPC.

(1-2a) Preparation of Photosensitive Compound

20 g of 2,3,4,4'-tetrahydroxybenzophenone, 32 g of 1,2-naphthoquinone diazide 5-sulfonic acid chloride and 210 g of dioxane were added to a flask, followed by stirring at room temperature to dissolve.

After sufficiently dissolving, 70 g of a dioxane solution of 20% of triethanolamine was slowly dropped for 30 minutes, and then reacted for 3 hours.

Thereafter, the precipitated triethylamine hydrochloride was filtered off, and the filtrate was slowly dropped into the weak acid aqueous solution to precipitate the reaction product.

The precipitated reaction product was sufficiently washed with ultrapure water, filtered and dried in an oven at 40 ° C. to obtain a photosensitive compound.

The photosensitive compound obtained at this time is called B1.

(1-2b) Preparation of Photosensitive Compound

In the photosensitive compound manufacturing step (1-2a), 20 g of 2,3,4-trihydroxybenzophenone was added to the flask instead of 20 g of 2,3,4,4'-tetrahydroxybenzophenone.

After the addition, the process was performed in the same manner as in the photosensitive compound manufacturing step (1-2a) to obtain a photosensitive compound.

The photosensitive compound obtained at this time is called B2.

(1-3) Preparation of Inorganic Sol

Hydrochloric acid is added to the water-dispersed colloidal mineral Ludox HSA (trade name: Grease) to adjust the pH to 5, and 100 parts by weight of methyltrimethoxysilane, an organic silane diluted in ethyl alcohol, is added to the nanoparticle inorganic surface. The reaction medium was hydrophobized by removing water while reacting the organic silane with propylene glycol methyl ether acetate (PGMEA) as an organic solvent. At this time, the average particle size was measured by a particle size analyzer, the particle size was 30 nm and the solid content was obtained an inorganic sol of 30% by weight.

(2) Preparation of Photoresist Composition

It manufactured so that solid content ratio of alkali-soluble resin obtained by (1-1) and the colloidal inorganic substance obtained by (1-3) might be 90:10.

10 parts by weight of B1 obtained in (1-2a) as a photosensitive compound, 10 parts by weight of B2 obtained in (1-2b) and 2 parts of F171 (Japan Nippon Inks Co., Ltd.) as a silicone-based surfactant based on 100 parts by weight of the solids of the mixture. After adding each part, propylene glycol methyl ether acetate (PGMEA) was added as a solvent to make the total solid content 30% by weight, and then uniformly mixed to prepare a photoresist composition.

The photoresist composition thus prepared was filtered with a 0.45 um Millipore filter to remove impurities. At this time, the photoresist composition had a viscosity of about 15 cps, and when a film was formed, it was about 0.5 to 5.0 um depending on the coating speed. The thickness could be obtained.

Example 2

A photoresist composition was prepared in the same manner as in (2) of Example 1, except that the solid content ratio of the alkali-soluble resin obtained in (1-1) and the colloidal inorganic material obtained in (1-3) was 75:25. Prepared.

The photoresist composition thus prepared was filtered with a 0.45 um Millipore filter to remove impurities. At this time, the photoresist composition had a viscosity of about 15 cps, and when a film was formed, it was about 0.5 to 5.0 um depending on the coating speed. The thickness could be obtained.

Example 3

Photoresist composition as in Example 2 (2) except that the solid content ratio of the alkali-soluble resin obtained in (1-1) and the colloidal inorganic material obtained in (1-3) was 60:40. Was prepared.

The photoresist composition thus prepared was filtered with a 0.45 um Millipore filter to remove impurities. At this time, the photoresist composition had a viscosity of about 15 cps, and when a film was formed, it was about 0.5 to 5.0 um depending on the coating speed. The thickness could be obtained.

Example 4

It manufactured so that solid content ratio of alkali-soluble resin obtained by (1-1) and the colloidal inorganic substance obtained by (1-3) might be 90:10.

To the solids content of the mixture, 20 parts by weight of B1 obtained from (1-2a) as a photosensitive compound and 2 parts by weight of F171 (Japan Nippon Inks) as a silicone surfactant were added, followed by propylene glycol methyl ether acetate (PGMEA) as a solvent. To add a total solid content of 30% by weight and then uniformly mixed to prepare a photoresist composition.

The photoresist composition thus prepared was filtered with a 0.45 um Millipore filter to remove impurities. At this time, the photoresist composition had a viscosity of about 15 cps, and when a film was formed, it was about 0.5 to 5.0 um depending on the coating speed. The thickness could be obtained.

Example 5

A photoresist composition was prepared in the same manner as in Example 4 except that the solid content ratio of the alkali-soluble resin obtained in (1-1) and the colloidal inorganic material obtained in (1-3) was 75:25.

The photoresist composition thus prepared was filtered with a 0.45 um Millipore filter to remove impurities. At this time, the photoresist composition had a viscosity of about 15 cps, and when a film was formed, it was about 0.5 to 5.0 um depending on the coating speed. The thickness could be obtained.

Example 6

A photoresist composition was prepared in the same manner as in Example 4 except that the solid content ratio of the alkali-soluble resin obtained in (1-1) and the colloidal inorganic material obtained in (1-3) was 60:40.

The photoresist composition thus prepared was filtered with a 0.45 um Millipore filter to remove impurities. At this time, the photoresist composition had a viscosity of about 15 cps. The thickness could be obtained.

Example 7

It manufactured so that solid content ratio of alkali-soluble resin obtained by (1-1) and the colloidal inorganic substance obtained by (1-3) might be 90:10.

To the solids content of the mixture, 20 parts by weight of B2 obtained from (1-2b) as a photosensitive compound and 2 parts by weight of F171 (Japan Nippon Ink Co., Ltd.) were added as a silicone-based surfactant, followed by propylene glycol methyl ether acetate (PGMEA) as a solvent. To add a total solids content of 30% by weight and then uniformly mixed to prepare a photoresist composition.

The photoresist composition thus prepared was filtered with a 0.45 um Millipore filter to remove impurities. At this time, the photoresist composition had a viscosity of about 15 cps, and when a film was formed, it was about 0.5 to 5.0 um depending on the coating speed. The thickness could be obtained.

Example 8

A photoresist composition was prepared in the same manner as in Example 7, except that the solid content ratio of the alkali-soluble resin obtained in (1-1) and the colloidal inorganic material obtained in (1-3) was 75:25.

The photoresist composition thus prepared was filtered with a 0.45 um Millipore filter to remove impurities. At this time, the photoresist composition had a viscosity of about 15 cps, and when a film was formed, it was about 0.5 to 5.0 um depending on the coating speed. The thickness could be obtained.

Example 9

A photoresist composition was prepared in the same manner as in Example 7, except that the solid content ratio of the alkali-soluble resin obtained in (1-1) and the colloidal inorganic material obtained in (1-3) was 60:40.

The photoresist composition thus prepared was filtered with a 0.45 um Millipore filter to remove impurities. At this time, the photoresist composition had a viscosity of about 15 cps, and when a film was formed, it was about 0.5 to 5.0 um depending on the coating speed. The thickness could be obtained.

Comparative Example 1

100 parts by weight of the alkali-soluble resin solid obtained in (1-1), 10 parts by weight of B1 obtained in (1-2a) as the photosensitive compound, 10 parts by weight of B2 obtained in (1-2b), and F171 (large in the silicone-based surfactant). 2 parts by weight of Nippon Ink Co., Ltd. were added, and propylene glycol methyl ether acetate (PGMEA) was added as a solvent so that the total solid content was 30% by weight, and then uniformly mixed to prepare a photoresist composition.

The photoresist composition thus prepared was filtered with a 0.45 um Millipore filter to remove impurities. At this time, the photoresist composition had a viscosity of about 15 cps, and when a film was formed, it was about 0.5 to 5.0 um depending on the coating speed. The thickness could be obtained.

Comparative Example 2

 100 parts by weight of the alkali-soluble resin solid content obtained in (1-1), 20 parts by weight of B1 obtained from (1-2a) as the photosensitive compound, and 2 parts by weight of F171 (Japan Nippon Ink Co., Ltd.) as a silicone surfactant, and propylene as a solvent. Glycol methyl ether acetate (PGMEA) was added so that the total solid content was 30% by weight, and then uniformly mixed to prepare a photoresist composition.

The photoresist composition thus prepared was filtered with a 0.45 um Millipore filter to remove impurities. At this time, the photoresist composition had a viscosity of about 15 cps, and when a film was formed, it was about 0.5 to 5.0 um depending on the coating speed. The thickness could be obtained.

Comparative Example 3

100 parts by weight of the alkali-soluble resin solid content obtained in (1-1), 20 parts by weight of B2 obtained in (1-2b) as the photosensitive compound, and 2 parts by weight of F171 (Japan Nippon Ink) as a silicone surfactant, and propylene as a solvent. Glycol methyl ether acetate (PGMEA) was added so that the total solid content was 30% by weight, and then uniformly mixed to prepare a photoresist composition.

The photoresist composition thus prepared was filtered with a 0.45 um Millipore filter to remove impurities. At this time, the photoresist composition had a viscosity of about 15 cps. The thickness could be obtained.

After evaluating the physical properties of the photoresist compositions prepared in Examples 1 to 9 and Comparative Examples 1 to 3 in the following manner, the results are shown in Table 1 below.

1) Photospeed and Remaining Rate

Initial film thickness = loss thickness + residual film thickness

Residual Film Ratio (%) = (Residual Film Thickness / Initial Film Thickness)

The photosensitivity was determined by measuring the energy that the film completely melted under a certain developing condition according to the exposure energy. After precuring at 110 ° C., after exposure and development, the residual film rate was measured. The thickness difference of was measured.

2) heat resistance

After applying the photoresist compositions prepared in Examples 1 to 9 and Comparative Examples 1 to 3 using a spin coater on a glass substrate, the film formed by precuring on a hot plate for about 90 seconds at about 110 ℃ with a differential scanning calorimeter The glass transition temperature was measured.

3) resolution

After coating the photoresist compositions prepared in Examples 1 to 9 and Comparative Examples 1 to 3 using a spin coater on the glass substrate, the film formed by precuring on a hot plate at about 110 ° C. for about 90 seconds was subjected to ultraviolet exposure and development. After a certain pattern was obtained through the process, the resolution of the pattern was measured through a scanning electron microscope.

4) adhesion

On the glass substrate coated with ITO, the photoresist film prepared by the photoresist compositions prepared in Examples 1 to 9 and Comparative Examples 1 to 3 was hot at 130 ° C. after obtaining a desired pattern (fine wire width) in precuring and developing processes. After the heat treatment for about 90 seconds in the plate was treated with a corrosion solution to remove the ITO of the exposed area by measuring the length of corrosion of the ITO not exposed to the corrosion solution was tested for adhesion.

TABLE 1

Photospeed (mJ / cm ² ) Residual rate (%) Heat resistance (℃) Resolution (um) Adhesion (um) Example 1 19.5 95 111 2.5 0.98 Example 2 15.9 95 120 2.5 1.09 Example 3 11.8 97 124 2.5 1.00 Example 4 24.8 95 112 2.3 1.10 Example 5 22.4 96 119 2.4 1.12 Example 6 17.0 98 126 2.4 1.16 Example 7 12.7 93 110 3.0 1.12 Example 8 11.5 95 114 2.9 1.11 Example 9 10.1 95 122 3.0 1.15 Comparative Example 1 22.3 91 106 2.5 1.08 Comparative Example 2 29.0 93 107 2.4 1.12 Comparative Example 3 14.5 89 104 3.0 1.14

Through Table 1, Examples 1 to 9 in the photoresist composition prepared according to the embodiment of the present invention is excellent in the photosensitivity rate, residual film rate, heat resistance, and resolution and adhesive strength compared to Comparative Examples 1 to 3 It can confirm that a favorable characteristic is shown.

Claims (9)

a) alkali soluble resin; b) photosensitive compounds; c) colloidal minerals; d) organic solvent Photoresist composition comprising a. The method of claim 1, The colloidal inorganic material is 1 to 50% by weight of the total weight of the solid content of the alkali-soluble resin and the colloidal inorganic material, The photosensitive compound is contained 5 to 50 parts by weight based on 100 parts by weight of the solids of the alkali-soluble resin and the colloidal inorganic material, The organic solvent is a photoresist composition comprising a solid content of 10 to 50% by weight. The method of claim 1, Alkali-soluble resin is a high molecular polymer synthesized by reacting an aromatic alcohol with an aldehyde compound. The method of claim 1, The colloidal inorganic material is selected from those in which the inorganic material is surface treated with an organosilane. The method of claim 4, wherein Colloidal inorganic material is a spherical photoresist composition, characterized in that having a diameter of 1 to 100 nm or a fiber size of 100 to 1000 nm. The method of claim 4, wherein The organosilane may be represented by R ¹ _0-3 Si (OR ² ) _1-4 , wherein R ¹ is an alkyl group, phenyl, fluorocarbon alkyl group, acrylic group, methacryl group, allyl group, vinyl group, and epoxy group. And R ² is selected from lower alkyl group, and OR ² is selected from acetic acid, oxime group or alkoxy group. The method of claim 1, The inorganic material constituting the colloidal inorganic material is at least one selected from silica, alumina, titania, zirconia, tin oxide, zinc oxide, inorganic material capable of reacting with organosilane, or inorganic material surface-modified with silica. A method of manufacturing a substrate having a pattern using a photoresist, the method comprising: applying a photoresist composition according to any one of claims 1 to 7 to a substrate. An electronic device comprising a substrate having a pattern formed by the method of claim 8.