TWI472874B - Photoresist composition - Google Patents

Description

Photoresist composition Field of invention

The present invention relates to a photoresist composition, and more particularly to a photoresist composition used in the manufacture of a fine circuit pattern, such as a liquid crystal display device circuit or a semiconductor integrated circuit, which is a circuit line. Excellent in uniformity, resolution, development contrast, adhesion, etc., especially in photosensitivity, residual film rate and heat resistance.

Background of the invention

A fine circuit pattern such as a liquid crystal display device circuit or a semiconductor integrated circuit is applied to an insulating film or a conductive metal film formed on a substrate, and the photoresist composition is coated, hardened, exposed, and developed to form a purpose. Shape pattern. After the patterned photoresist film is used as a photomask to etch the metal film or the insulating film, the remaining photoresist film is removed, that is, a fine circuit is formed on the substrate. The photoresist composition for such a liquid crystal display device is classified into a negative type and a positive type in accordance with the change in solubility of the exposed portion.

From the viewpoint of practicability, the characteristics of the important photoresist composition include: the photospeed of the formed photoresist film, heat resistance, development contrast, resolution, adhesion to the substrate, residual film ratio, and circuit line width. Convenience in the use of CD uniformity and human safety.

The so-called photospeed refers to the speed at which the solubility of the photoresist changes by exposure. In order to generate multiple patterns by multiple repetition steps, it is necessary to perform several exposures, especially in a projection exposure technique such as light passing through a series of lenses and filters. It is more important to use a photoresist film that has reduced intensity of light.

In particular, in the case of a thin film transistor liquid crystal display device (hereinafter referred to as TFT-LCD), in order to reduce the exposure time on the production line due to the large area of the substrate which is characteristic of the thin film transistor liquid crystal display device, the photosensitive speed must be required. Improvement. Further, the photospeed is inversely proportional to the residual film ratio, and the faster the photospeed, the tendency of the residual film ratio to decrease.

The development contrast means the ratio of the amount of film loss at the portion exposed by development to the amount of film loss at the portion not exposed. Since the development is usually continued until the exposed substrate coated with the photoresist film has almost completely dissolved and removed the exposed portion of the exposed substrate, the development contrast can be used to measure the film loss at the unexposed portion when the exposed coated portion is completely removed. The amount is simple and decided.

The photoresist film resolution refers to a photoresist film system in which a large number of circuit lines are obtained by spatial division of a photomask used when the photoresist film is exposed, and the majority of the circuit lines are reproduced to appear as a highly sensitive image. ability.

In various industrial applications, particularly in the manufacture of liquid crystal display devices or semiconductor circuits, the photoresist film must have a resolution capable of forming a pattern having a very fine line and a spatial width (1 μm or less).

The above-described resolution is also related to heat resistance, and it is necessary to minimize the deformation of the pattern line width due to the applied heat in the step of performing the pattern shape obtained by the exposure and development steps as a mask.

When the heat resistance of the obtained pattern is low, the pattern flow is increased by the heat in the additional step, and the line width is deformed, so that the resolution is inferior.

Most of the photoresist composition includes a polymer resin, a photosensitive compound, and a solvent for forming a photoresist film. In the prior art, various attempts have been made to improve the photosensitivity, development contrast, resolution, and human body safety of the photoresist composition for a liquid crystal display device circuit.

For example, Patent Document 1 listed below discloses the use of two types of phenol formaldehyde basic soluble resin mixtures and typical photosensitive compounds. Patent Document 2 listed below discloses a configuration in which an organic acid cyclic anhydride is added to a phenol resin and a naphthoquinone diazide (DNQ) sensitizer to increase the photospeed. Patent Document 3 listed below discloses an alkali-soluble resin, an o-quinonediazide photosensitive compound, and a propylene glycol alkyl ether acetate as a solvent for increasing the speed of light and improving human safety. The composition of the photoresist of the ester is composed.

However, a variety of photoresist compositions have been continuously sought, and the appropriate characteristics of the photoresist composition such as development contrast, resolution, solubility of the polymer resin, adhesion to the substrate, and uniformity of circuit line width are not sacrificed. A characteristic, which is excellent in photospeed, residual film rate, and heat resistance, is a photoresist composition suitable for various industrial steps.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] U.S. Patent No. 3,666,473

[Patent Document 2] U.S. Patent No. 4,115,128

[Patent Document 3] U.S. Patent No. 4,550,069

The present invention takes into consideration the problems of the prior art described above, and aims to provide a novel composition of the photoresist composition, which contains the basic physical properties of the existing photoresist composition, and at the same time, the photospeed and residual film rate of the photoresist film. It has more excellent physical properties in terms of heat resistance.

Other objects of the present invention are to provide a method of fabricating a substrate having a fine circuit pattern by utilizing the photoresist obtained by the foregoing invention.

Another object of the present invention is to provide an electronic component comprising a substrate having a fine circuit pattern obtained by the aforementioned invention.

In order to achieve the above object, the present invention provides a photoresist composition comprising: a) an alkali-soluble resin; b) a photosensitive compound; c) a colloidal inorganic substance; and d) an organic solvent.

The photoresist composition obtained according to the present invention provides a composition excellent in circuit uniformity, resolution, development contrast, adhesion, and chemical resistance by introducing a colloidal inorganic substance, particularly a photosensitive speed, Excellent in residual film ratio and heat resistance. By reducing the long exposure time of the production line due to the decrease in the photospeed, it is expected that the productivity of the circuit can be prevented from being deteriorated by the excellent heat resistance.

Form for implementing the invention

The photoresist composition of the present invention comprises: (a) an alkali-soluble resin; (b) a photosensitive compound; (c) a colloidal inorganic substance; and (d) an organic solvent.

Polymer resins which can be used to produce photoresist compositions are well known in the art. The polymer resin used in the present invention is a polymer copolymer obtained by reacting (a) an alkali-soluble resin-based phenol, an aromatic alcohol such as p-cresol, and an aldehyde, and is preferably a novolak resin.

For example, in terms of phenols, phenol, o-cresol, m-cresol, p-cresol, 2,3-dibenzocresol, 2,5-dibenzocresol, 3,4-diphenyl can be used. Phenol, 3,5-dibenzocresol, 2,3,5-trimethylphenol-benzophenone may be used alone or in combination of two or more.

Further, examples of the aldehyde condensed with the phenol include formaldehyde and tri For formaldehyde, alpha or beta-phenylpropanal, o- or m- or para-hydroxybenzaldehyde.

An acidic catalyst can generally be used in the condensation reaction of phenols with aldehydes.

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

In general, water is often used as a reaction solvent for the synthesis of an alkali-soluble resin. However, in the case of a heterogeneous phase in the initial stage of the reaction, an alcohol such as methanol, ethanol, propanol, butanol or propylene glycol monomethyl ether or tetrahydrofuran may be used. ,two A ketone such as a cyclic ether, methyl ethyl ketone, methyl isobutyl ketone or 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 raw material, and the reaction temperature in the condensation reaction can be adjusted depending on the reactivity of the raw material, and is usually 10 to 200 ° C.

After completion of the condensation reaction, the base material is heated to 130 to 230 ° C in order to remove the residual reaction raw material, the acidic catalyst, the reaction solvent, and the like, and the alkali-soluble resin is obtained by removing under reduced pressure.

In order to improve the performance of the photoresist, the polymer, the medium molecule, the low molecule, and the like in the resin may be appropriately removed, and a resin having a molecular weight suitable for the use may be selected and used.

As the photosensitive compound (b), a diazide compound may be used as appropriate, and for example, trishydroxyphenyl ketone and 2-diazo-1-naphthol-5-sulfonic acid may be esterified by using them alone or in combination. 2,3,4-trihydroxydiphenyl ketone-1,2-naphtholquinonediazide-5-sulfonate produced by the reaction, and tetrahydrodiphenyl ketone and 2-diazo-1 - 2,3,4,4-tetrahydroxydiphenyl ketone-1,2-naphtholquinonediazide-5-sulfonate produced by esterification of naphthol-5-sulfonic acid.

The photosensitive compound can be produced by reacting polyhydroxydiphenyl ketone with a diazide compound such as 1,2-naphtholquinone diazide or 2-diazo-1-naphthol-5-sulfonic acid.

The content of the photosensitive compound (b) is preferably from 5 to 50 based on 100 parts by weight of the solid content of the a) alkali-soluble resin and c) the colloidal inorganic substance in order to maintain an appropriate photospeed. When the total content of the photosensitive compound is less than 5 parts by weight, the photospeed may become excessively rapid, but the residual film rate may be seriously deteriorated. If it exceeds 50 parts by weight, the photospeed may be excessively delayed. problem.

(c) The colloidal inorganic substance is on the surface of the inorganic substance, and the reaction medium is obtained by removing water from the reaction of about 1 to 120 parts by weight of the organic decane with respect to 100 parts by weight of the inorganic substance, and adding an organic solvent. Hydrophobized inorganic sol.

Here, the inorganic substance may be at least one selected from the group consisting of cerium oxide, aluminum oxide, titanium oxide, zirconium oxide, tin oxide, zinc oxide, an inorganic substance reactive with organic decane, or an inorganic substance modified by cerium oxide surface.

Further, the organodecane may be represented by R ¹ _0-3 Si(OR ² ) _1-4 , wherein R ¹ may be selected from an alkyl group, a phenyl group, a fluorocarbon alkyl group, an acryl group, and a methyl group. Among the acrylic group, allyl group, vinyl group and epoxy group, the R ² group lower alkyl group may be selected, for example, from an alkyl group having 1 to 4 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group). Among the butyl groups and the like, OR ² may be selected from acetic acid, mercapto or alkoxy groups, and the alkoxy group may be selected, for example, from 1 to 4 carbon atoms.

The hydrophobic organic solvent to be used in the reaction medium is not particularly limited, and may be at least one selected from the group consisting of (d) an organic solvent of the present invention.

The colloidal inorganic substance may have a diameter of about 1 to 100 nm in a spherical shape or a size of about 100 to 1000 nm in a fibrous form.

The colloidal inorganic substance preferably contains from about 1 to 50% by weight based on the total weight of the alkali-soluble resin and the colloidal inorganic solid content.

In the total weight of the solid content of the alkali-soluble resin and the colloidal inorganic substance, if the amount of the colloidal inorganic substance is less than 1% by weight, the speed of the coating film, the residual film ratio, and the heat resistance may be lowered. If it exceeds 50% by weight, There may be problems such as cracking of the coating film and reduction in flatness.

By surface-treating the surface of the colloidal inorganic substance with the organic decane having a reactive group, the particles of the inorganic substance can be stabilized by an organic solvent, and at the same time, chemically bonded at a molecular level excellent in preservability.

The organic solvent (d) is not particularly limited, and may be, for example, selected from the group consisting of methanol, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl acesulfame acetate, ethyl acesulfame acetate, and Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, Propylene glycol methyl ether acetate, propylene glycol acetate, propylene glycol propyl ether, propylene glycol butyl ether, propylene glycol propionate, propylene glycol propionate, propylene glycol propionate, propane propylene glycol butane, toluene, xylene, methyl ethyl ketone, Cyclohexanone, 4-hydroxy 4-methyl 2-pentanone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, 2-hydroxy 2-methylpropionic acid Ester, ethyl 2-hydroxy 2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxypropionic acid Methyl ester, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2 -Hydroxymethyl 3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxy acetic acid Ethyl ester, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, butoxyacetate Ester, ethyl butoxylate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionic acid Propyl ester, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, 2-ethoxypropionic acid Butyl ester, methyl 2-methoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, 3-methoxypropionic acid Methyl ester, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionic acid Ethyl ester, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxypropane Propyl acrylate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate and 3-butoxypropane At least one of ethers such as butyl acrylate.

The solvent is preferably contained in the solid content of the photoresist composition of from about 10 to 50% by weight, more preferably from about 15 to 40% by weight. When the content is less than 10% by weight, not only the thickness of the film may be too thin, but the flatness may be lowered, and if it exceeds about 50% by weight, not only the thickness of the film may be excessively thick, but also the burden on the equipment during coating. .

The component having a solid content in such a range is preferably filtered by a micropore filter of about 0.1 to 1 μm or the like and then applied to a user.

The photoresist composition of the present invention may further contain an additive such as a plasticizer, an adhesion promoter, a speed improving agent, a surfactant, and an antifoaming agent in an amount of 0.01 to 5% by weight, in addition to the above components, as needed.

The present invention provides a method of fabricating a substrate having a fine circuit pattern, the method comprising the step of coating a substrate with a photoresist obtained by the foregoing invention.

The photoresist composition can be applied to the substrate by a usual method including dipping, spin coating, spray coating, or roll coating.

As the substrate, glass, germanium, aluminum, indium tin oxide (ITO), indium zinc oxide (IZO), molybdenum, germanium dioxide, germanium dioxide doped, tantalum nitride, hafnium, copper, poly A material composed of tantalum, ceramic, aluminum/copper mixture or polymerizable resin.

After coating the substrate with the photoresist obtained by the present invention, the solvent can be removed by prebake. At this time, the prebaking step can be completed at about 70 to 110 °C.

The heat treatment is carried out in order to prevent the solid component in the resist composition from being thermally decomposed and evaporating the solvent.

In general, it is preferred to minimize the concentration of the solvent by the pre-bake step.

Thereafter, by using a pattern prepared in advance, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, or the like is irradiated onto the previously formed coating film, and the developing portion is developed to remove unnecessary portions, thereby forming a predetermined pattern.

The developing solution is preferably an aqueous alkaline solution. Specifically, inorganic bases such as sodium hydroxide, potassium hydroxide or sodium carbonate; primary amines such as n-propylamine; diethylamine and n-propylamine can be used. a secondary amine such as a tertiary amine; a tertiary amine such as trimethylamine, methyldiethylamine, diethylamine or triethylamine; an alkanolamine such as dimethylethanolamine, methyldiethanolamine or triethanolamine; or An aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide. In this case, the developer may be used by dissolving the basic compound at a concentration of 0.1 to 10% by weight, or a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added as appropriate.

Further, after developing the developer as described above, it is washed with ultrapure water for 30 to 90 seconds to remove unnecessary portions and dried to form a pattern, and then heat-treated by a hard bake step to make the photoresist film. Adhesion and chemical resistance are improved.

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

The substrate which is developed as described above is treated with an etching solution or a gas plasma to treat the exposed substrate portion. At this time, the unexposed portion of the substrate is protected by the photoresist film.

After the substrate is processed in this manner, the photoresist film is removed by a suitable stripper, whereby a fine circuit pattern can be formed on the substrate.

The photoresist composition obtained according to the present invention can be used for manufacturing a liquid crystal display by having a circuit uniformity (CD uniformity), a resolution, a development contrast, an excellent adhesion, particularly a photospeed, a residual film ratio, and heat resistance. Device or various semiconductor components.

Hereinafter, the examples and comparative examples are presented to understand the present invention. However, the following examples are merely illustrative of the invention, and the scope of the invention is not limited to the following examples.

Example 1 (1-1) Manufacture of alkaline soluble resin

65 g of m-cresol, 43 g of p-cresol, 120 g of 37% formaldehyde aqueous solution, 2 g of oxalic acid, and 25 g of propylene glycol methyl ether (PGMEA) were placed in a four-neck flask which was reflux-cooled, and stirred under a nitrogen atmosphere. The temperature was raised to 100 ° C and allowed to condense for 4 hours.

After the reaction, the temperature was raised to 180 ° C, and the remaining reaction raw materials and the reaction solvent were removed under reduced pressure, and then naturally cooled at room temperature to obtain an alkali-soluble resin.

The molecular weight of the obtained resin was 2,000, and the weight average molecular weight was a polystyrene-equivalent average molecular weight measured by a gel chromatograph (GPC).

(1-2a) Manufacture of photosensitive compounds

2,3,4,4-tetrahydroxydiphenyl ketone 20 g, 1,2-naphthol quinone diazide 5-sulfonate chloride 32 g, two 210 g, stirred and dissolved at room temperature.

After fully stirring and dissolving, triethanolamine 20% of the two 70 g of the solution was slowly dropped for 30 minutes, and then allowed to react for 3 hours.

Thereafter, the precipitated triethylamine hydrochloride was removed by filtration, and the filtrate was slowly dropped into a weak acid aqueous solution to precipitate a reaction product.

After the reaction product which had been precipitated was sufficiently washed with ultrapure water, it was filtered and dried in an oven at 40 ° C to obtain a photosensitive compound.

The photosensitive compound obtained at this time is referred to as B1.

(1-2b) Manufacture of photosensitive compounds

In the photosensitive compound production step (1-2a), 20 g of 2,3,4-trihydroxydiphenyl ketone was placed in a flask to replace 20 g of 2,3,4,4'-tetrahydroxydiphenyl ketone.

After the introduction, the same procedure as in the above-mentioned photosensitive compound production step (1-2a) is carried out to obtain a photosensitive compound.

The photosensitive compound obtained at this time is referred to as B2.

(1-3) Manufacture of inorganic sol

Ludox HAS, a colloidal inorganic substance that has been dispersed in water (trade name: Guleis ( In a little bit, a little bit of hydrochloric acid is gradually added to adjust the pH to 5, and 100 parts by weight of methyltrimethoxydecane which has been diluted with ethylene glycol is added, and the organic decane is reacted on the surface of the inorganic particles of the nanoparticle. Water was removed and propylene glycol methyl ether acetate (PGMEA) was added as an organic solvent to hydrophobize the reaction medium. At this time, as a result of measuring the average particle size by a particle size analyzer, the particles were 30 nm, and an inorganic sol having a solid content of 30% by weight was obtained.

(2) Manufacture of photoresist composition

The solid content ratio of the alkali-soluble resin obtained in (1-1) and the colloidal inorganic substance obtained in (1-3) was 90:10.

100 parts by weight of the solid content of the mixture, 10 parts by weight of B1 obtained in (1-2a), 10 parts by weight of B2 obtained in (1-2b), and as a photosensitive compound, respectively After 2 parts by weight of F171 (Nippon Ink Co., Ltd.) of the ceria surfactant, a propylene glycol methyl ether (PGMEA) as a solvent was added to make the total solid content 30% by weight, and then uniformly mixed to produce a photoresist composition. Things.

The photoresist composition thus prepared was filtered with a 0.45 μm micropore filter to remove impurities. At this time, the photoresist composition exhibited a viscosity of about 15 cps, and at the time of film formation, about 0.5 was obtained depending on the coating speed. To a thickness of 5.0 μm.

Example 2

The same procedure 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 substance obtained in (1-3) was 75:25. A photoresist composition is produced.

The photoresist composition thus prepared was filtered with a 0.45 μm micropore filter to remove impurities. At this time, the photoresist composition exhibited a viscosity of about 15 cps, and at the time of film formation, about 0.5 was obtained depending on the coating speed. To a thickness of 5.0 μm.

Example 3

The same procedure 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 substance obtained in (1-3) was 60:40. A photoresist composition is produced.

The photoresist composition thus prepared was filtered with a 0.45 μm micropore filter to remove impurities. At this time, the photoresist composition exhibited a viscosity of about 15 cps, and at the time of film formation, about 0.5 was obtained depending on the coating speed. To a thickness of 5.0 μm.

Example 4

The solid content ratio of the alkali-soluble resin obtained in (1-1) and the colloidal inorganic substance obtained in (1-3) was 90:10.

20 parts by weight of B1 obtained by (1-2a) and 2 parts by weight of F171 (Daily Ink Co., Ltd.) as a cerium oxide surfactant as a photosensitive compound were added to the solid content of the mixture. Thereafter, propylene glycol methyl ether acetate (PGMEA) as a solvent was added so that the total solid content was 30% by weight, and then uniformly mixed to produce a photoresist composition.

The photoresist composition thus prepared was filtered with a 0.45 μm micropore filter to remove impurities. At this time, the photoresist composition exhibited a viscosity of about 15 cps, and at the time of film formation, about 0.5 was obtained depending on the coating speed. To a thickness of 5.0 μm.

Example 5

A photoresist was produced 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 substance obtained in (1-3) was 75:25. Composition.

The photoresist composition thus prepared was filtered with a 0.45 μm micropore filter to remove impurities. At this time, the photoresist composition exhibited a viscosity of about 15 cps, and at the time of film formation, about 0.5 was obtained depending on the coating speed. To a thickness of 5.0 μm.

Example 6

A photoresist was produced 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 substance obtained in (1-3) was 60:40. Composition.

The photoresist composition thus prepared was filtered with a 0.45 μm micropore filter to remove impurities. At this time, the photoresist composition exhibited a viscosity of about 15 cps, and at the time of film formation, about 0.5 was obtained depending on the coating speed. To a thickness of 5.0 μm.

Example 7

The solid content ratio of the alkali-soluble resin obtained in (1-1) and the colloidal inorganic substance obtained in (1-3) was 90:10.

20 parts by weight of B2 obtained by (1-2b) and 2 parts by weight of F171 (Daily Ink Co., Ltd.) as a cerium oxide surfactant as a photosensitive compound are added to the solid content of the mixture. Thereafter, propylene glycol methyl ether acetate (PGMEA) as a solvent was added so that the total solid content was 30% by weight, and then uniformly mixed to produce a photoresist composition.

The photoresist composition thus prepared was filtered with a 0.45 μm micropore filter to remove impurities. At this time, the photoresist composition exhibited a viscosity of about 15 cps, and at the time of film formation, about 0.5 was obtained depending on the coating speed. To a thickness of 5.0 μm.

Example 8

A photoresist was produced 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 substance obtained in (1-3) was 75:25. Composition.

The photoresist composition thus prepared was filtered with a 0.45 μm micropore filter to remove impurities. At this time, the photoresist composition exhibited a viscosity of about 15 cps, and at the time of film formation, about 0.5 was obtained depending on the coating speed. To a thickness of 5.0 μm.

Example 9

A photoresist was produced 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 substance obtained in (1-3) was 60:40. Composition.

Comparative example 1

100 parts by weight of the alkali-soluble resin obtained by (1-1), 10 parts by weight of B1 obtained as (1 to 2a), and B2 obtained by (1-2b) as a photosensitive compound. 10 parts by weight and 2 parts by weight of F171 (Dainippon Ink Co., Ltd.) as a ceria surfactant, and propylene glycol methyl ether (PGMEA) as a solvent was added so that the total solid content was 30% by weight, and then The photoresist composition was produced by uniform mixing.

The photoresist composition thus prepared was filtered with a 0.45 μm micropore filter to remove impurities. At this time, the photoresist composition exhibited a viscosity of about 15 cps, and at the time of film formation, about 0.5 was obtained depending on the coating speed. To a thickness of 5.0 μm.

Comparative example 2

100 parts by weight of the alkali-soluble resin obtained in (1-1), 20 parts by weight of B1 obtained as (1 to 2a), and F171 (as a cerium oxide surfactant) as a photosensitive compound. To Japan Mobile Co., Ltd., 2 parts by weight, and propylene glycol methyl ether acetate (PGMEA) as a solvent were added so that the total solid content was 30% by weight, and then uniformly mixed to produce a photoresist composition.

The photoresist composition thus prepared was filtered with a 0.45 μm micropore filter to remove impurities. At this time, the photoresist composition exhibited a viscosity of about 15 cps, and at the time of film formation, about 0.5 was obtained depending on the coating speed. To a thickness of 5.0 μm.

Comparative example 3

100 parts by weight of the alkali-soluble resin obtained by the above (1-1), 20 parts by weight of the B2 obtained as the photosensitive compound (1-2b), and F171 (as the cerium oxide surfactant) To Japan Mobile Co., Ltd., 2 parts by weight, and propylene glycol methyl ether acetate (PGMEA) as a solvent were added so that the total solid content was 30% by weight, and then uniformly mixed to produce a photoresist composition.

The photoresist composition thus prepared was filtered with a 0.45 μm micropore filter to remove impurities. At this time, the photoresist composition exhibited a viscosity of about 15 cps, and at the time of film formation, about 0.5 was obtained depending on the coating speed. To a thickness of 5.0 μm.

The physical properties of the photoresist compositions produced in the above-described Examples 1 to 9 and Comparative Examples 1 to 3 were evaluated by the following methods, and the results are shown in Table 1 below.

1) Photospeed and residual film rate

Initial film thickness = loss thickness + residual film thickness

Residual film rate (%) = (thickness of residual film / initial film thickness)

The photospeed is determined by measuring the energy of the film under the fixed development conditions, and the film is pre-baked at 110 ° C. After exposure and development, the residual film rate is measured, and the measurement can be performed before and after development. The thickness is poor.

2) Heat resistance

The photoresist compositions prepared in the foregoing Examples 1 to 9 and Comparative Examples 1 to 3 were coated on a glass substrate using a spin coater, and then prebaked on a hot plate at about 110 ° C for 90 seconds to form a film. The glass transition temperature was measured by a differential scanning calorimeter.

3) Resolution

The photoresist compositions prepared in the foregoing Examples 1 to 9 and Comparative Examples 1 to 3 were coated on a glass substrate using a spin coater, and then prebaked on a hot plate at about 110 ° C for 90 seconds to form a film. After obtaining a fixed pattern by ultraviolet exposure and development steps, the resolution of the pattern was measured by a scanning electron microscope.

4) Adhesion

On the glass substrate coated with ITO, the photoresist film produced by the photoresist compositions manufactured in the above Examples 1 to 9 and Comparative Examples 1 to 3 was subjected to a prebaking and developing step to obtain a desired pattern (fine After the line width), heat treatment was performed on the hot plate at about 130 ° C for about 90 seconds, and then treated with an etching solution to remove the exposed portion of ITO, and the etching solution was measured to etch the length of the unexposed ITO to test the adhesion.

It can be confirmed from the above Table 1 that the photoresist compositions produced in the examples of the present invention, that is, Examples 1 to 9, are excellent in photosensitivity, residual film ratio, and heat resistance as compared with Comparative Examples 1 to 3. It exhibits good resolution and good adhesion.

Claims (8)

A photoresist composition comprising: a) an alkali-soluble resin; b) a photosensitive compound; c) a colloidal inorganic substance; and d) an organic solvent; wherein the colloidal inorganic substance is selected from the group consisting of organic decane Surface treatment. The photoresist composition according to claim 1, wherein the colloidal inorganic substance is 1 to 50% by weight based on the total weight of the solid content of the alkali-soluble resin and the colloidal inorganic substance; and the photosensitive compound is relatively It is contained in an amount of 5 to 50 parts by weight based on 100 parts by weight of the total solid content of the alkali-soluble resin and the colloidal inorganic substance; and the organic solvent is contained in an amount of about 10 to 50% by weight. The photoresist composition according to claim 1, wherein the alkali-soluble resin is a polymer synthesized by reacting an aromatic alcohol with an aldehyde compound. The photoresist composition according to claim 1, wherein the colloidal inorganic substance has a spherical shape and has a diameter of about 1 to 100 nm, or a fibrous shape of about 100 to 1000 nm. The photoresist composition of claim 1, wherein the organodecane is represented by R ¹ _0-3 Si(OR ² ) _1-4 , wherein R ¹ is selected from the group consisting of alkyl, phenyl, and fluorine. Among the fluorocarbon alkyl, acryl-based, methacrylic, allyl, vinyl and epoxy groups, R ² is selected from lower alkyl, and OR ² is selected from acetic acid, sulfhydryl or Alkoxy. The photoresist composition of claim 1, wherein the inorganic substance constituting the colloidal inorganic substance is selected from the group consisting of ceria, alumina, titania, zirconia, tin oxide, zinc oxide, and inorganic substances reactive with organic decane. Or at least one of the inorganic substances modified by the surface of cerium oxide. A method for producing a substrate, wherein the substrate is formed with a pattern using a photoresist, and the method of manufacturing comprises the step of coating a substrate with a photoresist composition obtained according to any one of claims 1 to 6. . An electronic component comprising a substrate formed with a pattern manufactured by the manufacturing method of claim 7 of the patent application.