TW200919094A - Resin composition for formation of fine pattern, and method for formation of fine pattern - Google Patents

Abstract

Disclosed is a resin composition which enables the smooth shrinkage of a resist pattern by heat treatment and can be removed readily by the treatment with an aqueous alkali solution. Specifically disclosed is a resin composition for forming a fine pattern, which is intended to be used for making a fine resist pattern and comprises a resin, a crosslinking component and an alcohol solvent, wherein the resin has a repeating unit (I) having a side chain represented by the formula (1), a repeating unit (II) having a hydroxy group as a side chain and a repeating unit (III) that is a styrene derivative. (1) wherein R, R' and R'' independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxymethyl group, a trifluoromethyl group, or a phenyl group; A represents a single bond, an oxygen atom, a carbonyl group, a carbonyloxy group, or an oxycarbonyl group; B represents a single bond, or a bivalent organic group having 1 to 20 carbon atoms; Rf represents a linear or branched alkyl group having 1 to 8 carbon atoms in which at least one hydrogen atom is substituted by a fluorine atom.

Description

The present invention relates to a microfabrication technique using a photoresist, and a resin composition for forming a fine pattern formed by shrinking a pattern by heat treatment after patterning and finely. Pattern formation method. More specifically, the present invention relates to a pattern in which the wettability of the photoresist is improved by using an alcohol solvent, and it is possible to easily coat a pattern having a diameter of 60 mm or less without being caught in a bubble, and to form a resin for forming the fine pattern. When the material is not introduced, when the new aqueous coating cup or waste liquid processing equipment is not introduced, the pattern forming composition of the used coating cup or waste liquid processing equipment can be directly used for coating the lower layer film and the photoresist. And the method of forming a fine pattern. [Prior Art] In recent years, along with the progress of miniaturization of semiconductor elements, the lithography process in the manufacturing method has been required to be further miniaturized. In other words, the microlithography process is currently required to be microfabricated at a wavelength of 60 nm or less, and a method of forming a fine pattern using a photoresist material corresponding to short-wavelength irradiation light such as ArF excimer laser light or f2 excimer laser light has been proposed. Review. Since the lithography technique is subject to the exposure wavelength, it is impossible to avoid the boundary caused by the miniaturization, and therefore the feasibility of forming a fine pattern beyond the wavelength limit is investigated. That is, it has been proposed to pattern a photoreceptor for electron beam such as polymethyl methacrylate, apply a positive photoresist on the photoresist pattern, and then heat treatment and the photoresist pattern and A method of providing a reaction layer on the interface of the positive photoresist layer and removing the unreacted portion of the positive photoresist to refine the light pattern of the light-5-200919094 (Patent Document 1): in the lower photoresist pattern a method of forming a reaction layer by thermal crosslinking by an acid generator or an acid with respect to the upper photoresist pattern (Patent Document 2); as the upper photoresist coating liquid, a water-soluble resin is used without using a photosensitive component and a method for producing a semiconductor device by using a water-soluble crosslinking agent or a mixture of such a mixture of a fine pattern forming material dissolved in a water-soluble solvent (Patent Document 3); and a photosensitive layer composed of a chemically amplified photoresist is provided on the substrate, After the image is formed and exposed, a photoresist pattern is formed by development, and a water-soluble resin such as polyvinyl acetate and a water-soluble such as tetrakis (hydroxymethyl) glycol glycoluril are coated on the photoresist pattern. Hydrophilic nitrogen-containing organic compound such as amine And, depending on the case, the coating film forming agent of the fluorine-containing and antimony surfactants is heated, and a water-insoluble reaction layer is formed on the interface between the photoresist pattern and the photoresist pattern miniaturization coating film, followed by pure water. A method of removing an unreacted portion of a coating film for resisting pattern refinement (Patent Document 4). These methods are preferable from the viewpoint of the wavelength limit of the photosensitive photoresist (lower photoresist), and it is possible to easily perform pattern miniaturization of the fine pattern forming material (upper photoresist). However, the unnecessary portion of the bottom portion of the photoresist pattern produces cross-linking of the fine pattern-forming material, resulting in a skirt shape, the perpendicularity of the cross-sectional shape of the fine pattern-forming material becomes poor, or the size of the upper photoresist pattern is due to The problem of causing deviations in the shape of the pattern caused by the heating of the cross-linking and the reverse mixing is still not sufficiently satisfactory. Moreover, these processes have a high thermal dependency with a temperature of 10 nm/° C., and when the substrate is enlarged and the pattern is made fine, it is difficult to keep the temperature in the wafer surface uniform, so that the obtained pattern size control property is lowered. The problem. Further, the fine pattern forming material using the above water-soluble -6 - 200919094 resin has a problem of low resistance to dry etching due to limitation in solubility to water. When the semiconductor device is fabricated, the photoresist pattern is printed on the substrate by dry uranium on the substrate, and a pattern with a low etching resistance is not able to transfer the photoresist pattern on the substrate with high precision. Type problem. In addition, it is proposed that after forming a photoresist pattern on a substrate, applying heat or illuminating radiation to 'flow the photoresist pattern to make the pattern size smaller than the resolution limit' and the so-called heat flow process (Patent Literature 5. Patent Document 6) ° However, it is difficult to control the flow of the photoresist by heat or radiation in this way. Further, as a method for developing the heat flow process, there is proposed a method of forming a photoresist pattern on a substrate, and then providing a water-soluble resin film thereon to control the flow of the photoresist (Patent Document 7). The water-soluble resin such as polyvinyl alcohol used in the method has insufficient solubility and stability over time when water is removed, and has a disadvantage of causing residue. Or a heat-shrinkage pattern of a photoresist pattern formed by a photoresist is used to form a fine pattern, and a coating agent is provided on the photoresist pattern, and the photoresist pattern is heat-shrinked by heat treatment. A method for forming a fine photoresist pattern by using a coating agent for refining a photoresist pattern obtained by water washing, and a method for efficiently forming a fine photoresist pattern (Patent Document 8). However, in this method, the photoresist pattern-forming fine coating agent is In the water system, the coverage of a fine pattern such as a contact hole having a diameter of 1 00 nm or less is insufficient, and since it is a water system, a dedicated coating cup is required at the time of coating, so that the cost is increased, and further, when the conveyance is low. Under -7-200919094, there is a problem of freezing and precipitation. On the other hand, a liquid is known which is formed by forming a polymer which is not dissolved in a solvent during immersion exposure and which maintains a stable film and which is easily dissolved in the film composition of the overlayer film in the alkali developing solution. a polymer for immersing a layer film, which has a repeating unit of -NH-S02-Rf (Rf represents a monovalent organic group of a fluorine-containing atom) in its side chain, and accounts for 30 to 100 mol% of all repeating units and borrows The weight average molecular weight measured by the gel permeation method is 2,000 to 1 Torr, 〇〇〇 (Patent Document 9). However, the reaction between the polymer and the crosslinking agent has not been investigated, and it is still unknown whether it is suitable for the resin composition for forming a fine pattern. Patent Document 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Patent Document 5: Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei. OPERATION OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION [Technical Problem to be Solved by the Invention] The present invention is directed to these problems, and therefore The object of the present invention is to provide a resin composition which can be coated on the photoresist pattern by forming a fine pattern by heat treatment using a light -8*200919094 pattern formed by a photoresist. A resin composition which can be smoothly shrunk by heat treatment and then easily removed by treatment with an aqueous alkali solution, and a fine photoresist pattern forming method for efficiently forming a fine photoresist pattern using the same. The resin composition for forming a fine pattern of the present invention is a resin composition for forming a fine pattern for refining a resist pattern, which is a resin, a cross-linking component of the resin cross-linking, and an alcohol solvent. The repeating unit (I) having a side chain represented by the following formula (1) is contained in the above resin: [Chem. 6]

NH

I 〇=S=0 \

Rt (1) In the formula (1), Rf represents a linear or branched fluorenyl group having 1 to 8 carbon atoms which is substituted with at least one hydrogen atom via a fluorine atom. Further, the repeating unit (I) having a side chain represented by the above formula (1) is derived from a monomer represented by the following formula (2): [Chem. 7]

Rr (2) In the formula (2), R, R' or R" each independently represents a hydrogen atom, an alkyl group having a carbon number of -9-200919094 1 to 10, a hydroxymethyl group, a trifluoromethyl group or a phenyl group; and A represents a single bond. , an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group; B represents a single bond or a saturated chain hydrocarbon group having a carbon number of 2, a monocyclic hydrocarbon ring group having a carbon number of 3 to 20, or a polycyclic ring having a carbon number of 4 to 20 Rf represents a linear or branched alkyl group having at least one hydrogen atom substituted with a fluorine atom and having a carbon number of 1 to 8. The resin composition for forming a fine pattern of the present invention is characterized by the above resin. And a repeating unit (II) having at least one hydroxyl group selected from the group consisting of a hydroxyl group derived from an alcohol, a phenol, and a carboxylic acid. In particular, it is characterized in that a repeating unit having a hydroxyl group derived from the above phenol has a repeating unit a repeating unit of a guanamine bond. The repeating unit having a guanamine bond is characterized by copolymerizing at least one compound selected from the group consisting of hydroxypropenyl anilide and hydroxymethylpropenyl anilide. The resin composition for pattern formation is characterized in that the above resin contains the following formula 3) The repeating unit (III):

In the formula (3), R1 represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms or a linear or branched alkoxy group having 1 to 8 carbon atoms. A method for forming a fine pattern of the present invention, characterized by comprising: forming a pattern of forming a photoresist pattern on a substrate; and coating a step of forming a resin composition for forming a fine pattern on the photoresist pattern; a step of heat-treating the substrate after the film step; and a step of developing the image with an aqueous alkali solution. -10-200919094 [Effect of the invention] The resin composition for forming a fine pattern of the present invention contains a resin having a side chain represented by the above formula (1), a crosslinking component, and an alcohol solvent in a repeating unit. The coating property of the resist pattern is excellent, and the size controllability of the cured film is excellent. Therefore, regardless of the state of the surface of the substrate, the pattern gap of the photoresist pattern can be made more efficient and more precise, and the wavelength limit can be formed in a state where the pattern defect is small at a good and economical low cost. The pattern. In particular, the resin composition for forming a fine pattern of the present invention has a large shrinkage amount of the resin, a low temperature dependency at the time of shrinkage, and an excellent fine space-pattern formation after shrinkage, and low pitch dependency, so that the process is changed. The pattern forming margin has a wide range of processes. Further, since it has a hydroxyl group derived from a phenol, it is excellent in dry etching resistance. Further, by using the thus formed fine photoresist pattern as a mask for dry etching, a groove pattern and a perforation can be formed with high precision on a semiconductor substrate, and a fine groove pattern and a perforation can be manufactured simply and with high yield. Semiconductor device. [Embodiment] The inventors of the present invention conducted an active investigation on a resin composition which can be smoothly shrunk by a heat treatment and then easily removed by treatment with an aqueous alkali solution, and found to be an alcohol by using a resin which is not water-soluble. The soluble resin-specific resin, the cross-linking component, and the resin composition of the alcohol solvent can efficiently form a fine pattern, and the present invention has been completed based on the findings. -11 - 200919094 <Resin component> The resin constituting the resin composition for forming a fine pattern is a resin containing a repeating unit (I) having a side chain represented by the above formula (1). As the repeating unit (I), any monomer having a polymerizable unsaturated bond and a side chain represented by the formula (1) can be used. As for the monomer for generating the preferred repeating unit (I), there is an example of the formula (2): [Chemical 9] CNII C/R* 'A, , b\nh, οII • S»II ο 'Rf (2) Formula (2) Wherein 'R'R' or R" each independently represents a hydrogen atom, a carbon number of 1 to 10, a transmethyl group, a trifluoromethyl group, or a phenyl group, and A represents a single bond, an oxygen atom, a fluorenyl group, or a hydrazine. An oxy group or an oxo group, B represents a single bond or a divalent organic group having 1 to 20 carbon atoms, and Rf is the same as the formula (!). In the above formula (1) or (2), Rf is at least one hydrogen. A straight-chain or branched fluoroalkyl group having a carbon number of 1 to 8', preferably a carbon number of 4, substituted by a fluorine atom. A fluoroalkyl group having 1 to 8 carbon atoms can be exemplified by difluoromethyl or perfluoromethyl 1,1:1-difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, perfluoroethyl, 1,1,2,2-tetrafluoropropyl, 1 1,2,2,3,3-hexafluoropropyl, perfluoroethylmethyl, 1-(trifluoromethyl)-1,2,2,2-tetrafluoroethyl, perfluoropropyl, -12 - 200919094 1,1,2,2-tetrafluorobutyl, 1,1,2,2,3,3-hexafluorobutyl, 1,1,2,2,3,3,4,4- Octafluorobutyl, perfluorobutyl, 1,1-bis(trifluoro)methyl-2,2,2-trifluoroethyl, 2-(perfluoropropane Ethyl, 1,1,2,2,3,3,4,4-octafluoropentyl, perfluoropentyl, 1,1,2,2,3,3,4,4,5,5 - decafluoropentyl, 1,1-bis(trifluoromethyl)-2,2,3,3,3-pentafluoropropyl, perfluoropentyl, 2-(perfluorobutyl)ethyl, 1 ,1,2,2,3,3,4,4,5,5-decafluorohexyl, 1,1,2,2,3,3,4,4,5,5,6,6-dodecyl fluoride Hexyl, perfluoropentylmethyl, perfluorohexyl, 2-(perfluoropentyl)ethyl, 1,1,2,2,3,3,4,4,5,5,6,6-12 Fluoroheptyl, perfluorohexylmethyl, perfluoroheptyl, 2-(perfluorohexyl)ethyl, 1,1,2,2,3,3,4,4,5,5,6, 6,7 , 7-tetradecyloctyl, perfluoroheptylmethyl, perfluorooctyl ' 2-(perfluoroheptyl)ethyl. Among the above, the larger the carbon number of the fluoroalkyl group, the dissolution of the aqueous alkali solution The lower the degree, the preferred one is perfluoromethyl, perfluoroethyl and perfluoropropyl. In the formula (2), the alkyl group having 1 to 100 carbon atoms of R, R' or R" is exemplified by methyl group and ethyl group. Base, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, fluorenyl. Preferably, R, R" is a hydrogen atom 'R is a hydrogen atom or a methyl group. In the formula (2), a saturated chain hydrocarbon group having 1 to 20 carbon atoms of B is exemplified by a methylene group, an ethyl group, and 1,3. - propyl or 1,2-propanyl propyl, propyl, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethyl, ninth methyl, ten Base, ^--methylene, dodecamethylene, dodecamethylene, tetradecyl, fifteen methylene, hexadecyl, heptamethyl, octamethyl , 19-methylene, 20-methylene, 1-methyl-1,3-propyl, 2-methyl-1,3-propanyl, 2·methyl-1,2-extension Base, 1-methyl-1,4- 13-200919094 butyl, 2-methyl-1,4-butylene, etc. The monocyclic hydrocarbon ring group having a carbon number of 3 to 20 is exemplified as 1,3 - Stretching of a cyclobutyl group such as a cyclobutyl group, a cyclopentyl group such as a 1,3-cyclopentyl group, a cyclohexylene group such as a 1,4-cyclohexylene group, or a stretching of a 1,5-cyclooctyl group or the like Cyclooctyl and the like, a polycyclic hydrocarbon ring group having a carbon number of 4 to 20 is exemplified by 1,4 -norbornyl or 2,5-norbornyl and the like norbornyl, 1,5- Stretching of adamantyl, 2,6-adamantyl, etc. Rare alkyl or the like. Preferred examples of the monomer represented by the formula (2) are 2-(((trifluoromethyl)sulfonyl)amino)ethyl-1-methacrylate, 2-(( ((trifluoromethyl)sulfonyl)amino)ethyl-1-acrylate, and the following

The repeating unit (Z) represented by the formula (1) is a monomer containing 3 to 30 mol%, preferably 8 to 12 mol%, based on the total repeating unit constituting the resin. When the resin shrinks, it is difficult to form a micro-200919094 thin space pattern after shrinking, and if it exceeds 30%, the shrinkage amount of the resin is reduced. The resin which can be used in the present invention preferably contains, in addition to the above repeating unit (I), a repeating unit (Π) containing at least one hydroxyl group selected from the group consisting of hydroxyl groups derived from alcohols, phenols and carboxylic acids in the side chain. The repeating unit (11) is obtained by copolymerizing a monomer having a polymerizable unsaturated bond of the above hydroxyl group in the side chain. The monomer having an alcoholic radical can be exemplified by 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and acrylic acid 4. A hydroxyalkyl (meth)acrylate such as hydroxybutyl ester, 4-hydroxybutyl methacrylate or glycerol monomethacrylate, preferably 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate. These monomers may be used singly or in combination of two or more. The monomer having an alcoholic hydroxyl group is usually from 3 to 40 mol%, preferably from 5 to 30 mol%, based on the total repeating unit constituting the copolymer. /. . The monomer having a phenolic hydroxyl group can be exemplified as p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, α-methyl-p-hydroxystyrene, methyl-m-p-phenylene oxide, --methyl-o--substantially e-sinter, 2-dipropyl phenol, 4-allyl phenol, 2-allyl-6-methyl phenol, 2-allyl-6-methoxy phenol , 4-allyl-2-methoxyphenol, 4-allyl-2,6-dimethoxyphenol, 4-allyloxy-2-hydroxybenzophenone, etc. Preferably, p-hydroxystyrene or α-methyl-p-hydroxystyrene is used. Further, the monomer having a phenolic hydroxyl group is exemplified by a monomer having a guanamine group in the molecule and a monomer represented by the following formula (4): -15- 200919094 mi]

/RJ ch2==c c=o / HN \ R3

R2 and R4 represent a hydrogen atom or a methyl group, R3 represents a linear or valent hydrocarbon group, and R3 may, for example, be a methylene group, an exoethyl group, a propyl group (1, a group, a 1,2-propyl group), and a tetrazene. Methyl, pentamethylene, hexamethylene, octamethylene, hexamethylene, decamethylene, eleven methylene, thirteen methylene, tetradecyl, Hexamethyl hexamethylene, heptamethylidene, octadecylmethyl, 19-methylenemethylene, 1-methyl-1,3-propanyl, 2-methyl-1, 3-propanyl, 1,2-dipropyl, 1-methyl-1,4-butylene, 2-methyl-1,4-butylene, propylene, 2-propylene, etc. a saturated chain hydrocarbon group, a 1,3 -extended ring-like butyl group, a 1,3-cyclopentylene group, a cyclopentyl group, an i,4-extension ring-like hexyl group, a 1,5-cyclooctyl group a monocyclic hydrocarbon ring group having a carbon number of 3 or a cycloalkyl group such as a cyclopentyl group, a 1,4 ·norbornyl group or a norbornyl group such as a norbornyl group, a 1,5-extension A crosslinked cyclic hydrocarbon ring group having 2 to 4 ring carbon atoms such as an adamantyl group such as an adamantyl group or an adamantyl group and having 4 to 3 ring groups. The monomer t-methylpropenyl anilide represented by the formula (4) is preferred. The monomer having a phenolic hydroxyl group represented by the formula (4) is relatively flaky 2- 3-propyl, heptamethyl, phenyl, decene, hexylmethyl-based, cyclopentylenecyclohexyl hydrazine~1 0. 2.5- 2.6- 〇 〇 乂 乂 乂 羟 羟 羟 羟 -16 ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ The monomer derived from the hydroxyl group of an organic acid such as a carboxylic acid may, for example, be acrylic acid, methacrylic acid, crotonic acid, 2-bromodecylethyl (meth)acrylate, or 2-maleyl (meth)acrylate. Ester, 2-hexahydrofurfuryl ethyl (meth)acrylate, ω-carboxy-polycaprolactone monoacrylate, decanoic acid monohydroxyethyl acrylate, acrylic acid dimer, 2-hydroxy-3-benzene a monocarboxylic acid such as oxypropyl acrylate, third butoxy methacrylate or tributyl acrylate; maleic acid, fumaric acid, citraconic acid, methyl fumaric acid, itaconic acid, etc. A (meth)acrylic acid derivative having a carboxyl group such as a carboxylic acid, and these compounds may be used singly or in combination of two or more. Further, a commercially available product of ω-carboxy-polycaprolactone monoacrylate is, for example, ARONIX®- 5 3 00 manufactured by East Asia Synthetic Co., Ltd., and a commercial product of an acrylic acid dimer is, for example, East Asia Synthesis. ARONIX®-5600 manufactured by (Stock): A commercially available product of 2-hydroxy-3-phenoxypropyl acrylate is, for example, ARONIX®-5700 manufactured by Toagosei Co., Ltd. Among these, acrylic acid, methacrylic acid, and 2-hexahydroindenylethyl methacrylate are preferred. The monomer containing a hydroxyl group derived from a carboxylic acid is usually 5 to 60 mol%, preferably 10 to 50 mol%, based on the total repeating unit constituting the copolymer. The monomers having an alcoholic hydroxyl group, a hydroxyl group derived from a carboxylic acid, or a phenolic hydroxyl group are each in the above range with respect to all repeating units constituting the resin. When the constituent unit having a hydroxyl group is too small, the reaction site with the cross-linking component described later is too small, and the pattern shrinkage cannot be caused. Conversely, when the image is excessively displayed, -17-200919094 may cause swelling and may have an embedding pattern. Further, 'a monomer which has a functional group which can be converted into a phenolic hydroxyl group after copolymerization can also be copolymerized' is exemplified by, for example, p-acetoxystyrene, α-methyl-p-acetoxystyrene, p-Benzylmercaptooxystyrene, p-tert-butoxystyrene, p-t-butoxycarbonyloxystyrene, p-t-butyldimethylstannoxystyrene, and the like. When a compound containing such a functional group is used, the obtained resin can be easily converted into a phenolic hydroxyl group by a suitable treatment such as hydrolysis using hydrochloric acid or the like. The monomer before and after the conversion to the phenolic hydroxyl group is usually 5 to 60 mol%, preferably 1 to 50 mol%, based on the total repeating unit constituting the resin. The resin usable in the present invention preferably contains a repeating unit represented by the formula (3) together with the above repeating unit (I) and the repeating unit (II) (ΙΠ 12)

In the formula (3), R1 represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched alkoxy group having a carbon number of 丨8. Preferably, R1 is a third butyl group, an ethoxylated ethoxy group, an ethoxyethoxyethoxy group, and a third butoxy group is preferably a third butoxy group. The monomer which generates the repeating unit (111) is usually 丨〇6 to 〇mol%, preferably 20 to 50 mol%, based on the total repeating unit ' of the constituent resin. . The shrinkage size cannot be increased up to 1 〇mol%, and the dissolution of the developing solution is worse when it exceeds 60% by mole. -18-200919094 The resin constituting the resin composition for forming a fine pattern is preferably a resin containing the above repeating unit (I), repeating unit (II), and repeating unit (III). When the resin of the unit [(I) + (II) + (III)] is repeated, the repeating unit (II) is 37 to 87 mol%. Each repeating unit is obtained by polymerizing the corresponding monomers. Further, the monomer which generates the repeating unit (11) is a monomer having a phenolic hydroxyl group, and is preferably a monomer represented by the formula (4) having a mercapto group in the molecule. Further, the above resin may be copolymerized with other monomers for the purpose of controlling the hydrophilicity and solubility of the resin. The other monomer is a monomer other than the above components. Examples of the other monomer may be aryl (meth)acrylate, dicarboxylic acid diester, a nitrile group-containing polymerizable compound, and a guanamine bond. A polymerizable compound, an ethylene group, an allyl group, a polymerizable compound containing chlorine, a conjugated diene or the like. Specifically, a dicarboxylic acid diester such as diethyl maleate, diethyl fumarate or diethyl itaconate; phenyl (meth)acrylate or benzyl (meth)acrylate can be used. Aryl (meth)acrylate; aromatic vinyl such as vinyl toluene; tert-butyl (meth)acrylate, 4,4,4-trifluoro-3-hydroxy-1-methyl (meth)acrylate - (meth) acrylate such as 3-trifluoromethyl-1-butyl ester; a polymerizable compound containing a nitrile group such as acrylonitrile or methacrylonitrile; acrylamide, methacrylamide or the like a polymerizable compound containing a guanamine bond; a vinyl ester of a fatty acid such as vinyl acetate; a polymerizable compound containing chlorine such as ethylene chloride or vinylidene chloride; 1,3-butadiene, isoprene dioxime, 1 a conjugated diene such as 4-dimethylbutadiene. These compounds may be used singly or in combination of two or more. The above resin may be, for example, a radical polymerization initiator such as hydrogen peroxide, a dialkylperoxy-19-200919094 species, a dicyanoperoxide or an azo compound, and optionally a chain transfer agent. In the presence of a mixture of monomers, in a suitable solvent, it is produced. The solvent used in the above polymerization is exemplified by, for example, an alkane such as n-pentane, n-hexane, n-heptane, n-octane, n-decane or n-decane; cyclohexane, cycloheptane, cyclooctane, decalin , naphthenes such as norbornane; aromatic hydrocarbons such as benzene, toluene, xylene 'ethylbenzene, cumene; chlorobutanes, bromohexanes, dichloroethanes, hexamethylene dibromide Halogenated hydrocarbons such as chlorobenzene: saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, methyl propionate, propylene glycol monomethyl ether acetate; alkyl groups such as γ-butyrolactone Lactones; ethers such as tetrahydrofuran, dimethoxyethanes, diethoxyethanes; alkanones such as 2-butanone, 2-heptanone, and methyl isobutyl ketone; cyclohexanone, etc. Cycloalkanones; alcohols such as 2-propanol, 1-butanol, 4-methyl-2-pentanol, and propylene glycol monomethyl ether. These solvents may be used singly or in combination of two or more. Further, the reaction temperature of the above polymerization is usually 40 to 120 ° C, preferably 50 to 100 t:, the reaction time is usually 1 to 48 hours, preferably 1 to 24 hours, and the resin is preferably in a cylinder purity, not only The content of the dentate and the metal enamel is small, and the residual monomer or oligomer component is preferably below the predetermined enthalpy, for example, by HPLC analysis, 〇·1 mass% or less. According to this, the resin composition for forming a fine pattern of the present invention containing the resin can not only further improve the process stability, the shape of the pattern, etc., but also provide a fine pattern in which the foreign matter and the sensitivity in the liquid do not change over time. A resin composition for forming a type. The purification method of the resin obtained as described above is exemplified by the following method -20-200919094. The method of removing impurities such as metal is exemplified by the method of using a potential filter to adsorb a metal in the I solution; the method of washing the polymer solution with an acidic aqueous solution such as oxalic acid or sulfonic acid to remove the metal into a chelate compound, etc. The method of removing the residual monomer or oligomer component to a predetermined amount or less can be exemplified by a liquid extraction method of removing residual monomer or oligomer component by washing with water or combining a suitable solvent, and extracting and removing only a specific molecular weight or less. Ultrafiltration or the like in a solution state purification method, the polymerization solution is added dropwise to a weak solvent, the resin is solidified in a weak solvent to remove residual monomers by reprecipitation, and the filtered resin slurry is washed with a weak solvent. The method of purifying in a solid state, etc. Further, these methods may be combined. The weight average molecular weight Mw of the resin thus obtained is converted into polystyrene by gel permeation chromatography, usually !~5 〇〇, 〇〇〇, preferably from 1,000 to 50,000, preferably from 1 〇〇〇 to 2 〇, 〇〇 (). If the molecular weight is too large, it may not be removed by the developing solution after the heat curing. If too small after the coated film can not form a sentence of circumstances.

The crosslinking component used in the present invention is a compound containing a group represented by the following formula (5) (hereinafter referred to as "crosslinking component I"), and has two or more cyclic ethers as a reactive group.丨γ ρ β"

(a mixture of a chemical substance (hereinafter referred to as "cross-linking component II") or "cross-linking component I, B "one + [13] and a parental ingredient II":

(5) In the formula (5), at least one of R5 and R6, R5 and w are a hydrogen atom or the following formula (6) represents a system represented by the following formula (6): -21 - 200919094 [Chem. 14] R7

I -C—O—R9

IR* (6) In the formula (6), R7 and R8 represent a hydrogen atom, a decyl group having 1 to 6 carbon atoms, an alkoxyalkyl group having 1 to 6 carbon atoms, or a bond of R7 and R8 to each other to represent a carbon number of 2 Ring of ~10; R9 represents a hydrogen atom and a carbon number of 1 to 6. The crosslinking component is one in which the resin and/or the crosslinking component act as a crosslinking component (hardening component) which reacts with each other by the action of an acid. The compound (crosslinking component I) represented by the formula (5) is exemplified by a compound having an imino group, a methylol group, a methoxymethyl group or the like as a functional group in the molecule, (poly)methylolated melamine, ( A polynitrogenated compound in which all or a part of the active methylol group such as (poly)methylolated glycol urea, (poly)methylolated benzoguanamine, (poly)methylolated urea or the like is alkylated. The alkyl group may, for example, be a methyl group, an ethyl group, a butyl group or a mixture thereof, or may contain a part of a self-condensed oligomer component. Specifically, it is exemplified by hexamethoxymethylated melamine, hexabutoxymethylated melamine, tetramethoxymethylated glycol urea, tetrabutoxymethylated glycol urea, and the like. Commercially available compounds are CYMEL 300, CYMEL 301, CYMEL 3 03, CYMEL 3 50 'CYMEL 232, CYMEL 23 5, CYMEL 23 6, CYMEL 23 8, CYMEL 266, CYMEL 267, CYMEL 28 5, CYMEL 1123, CYMEL 1123- 10. CYMEL 1170, CYMEL 3 70, CYMEL 771, CYMEL 272, CYMEL 1172, CYMEL 3 2 5, CYMEL 327, CYMEL 703, CYMEL 712, -22- 200919094 CYMEL 254, CYMEL 25 3, CYMEL 212, C YMEL 1128, CYMEL 70 1, CYMEL 202, CYMEL 207 (above is manufactured by CY CYTEC), NICARAK MW-30M, NICARAK MW-30, NICARAK MW-22 'NICARAK MW-24X ' NICARAK MS-21, NICARAK MS-11, NICARAK MS-001, NICARAK MX-002, NICARAK MX-73 0 'NICARAK MX-75 0, NICARAK MX-708, NICARAK MX-706 ' NICARAK MX-042, NICARAK MX-03 5, NICARAK MX-45, NICARAK MX- 410, NICARAK MX-3 02, NICARAK MX-202, NICARAK SM-651, NICARAK SM-65 2. NICARAK SM-653 'NICARAK SM-55 1. NICARAK SM-45 1 > NICARAK SB-401, NICARAK SB- 3 5 5, NICARAK SB-3 03, NICARAK SB-3 0 1 , NICARAK SB-2 5 5 , NICARAK SB-203 , NICARAK SB - 01, NICARAK BX-4 000, NICARAK BX-37, NICARAK BX-55H, NICARAK BL-60 (above is manufactured by Sanwa Chemical Co., Ltd.). Preferably, one of R^R2 in Formula 1 is a hydrogen atom, that is, CYMEL 3 2 5 , CYMEL 3 27, CYMEL 703, CYMEL 712, CYMEL 2 54 which are preferably a cross-linking component containing an imine group. CYMEL 25 3, CYMEL 212, CYMEL 1128, CYMEL 701, CYMEL 202, CYMEL 207. The compound (crosslinking component II) containing two or more cyclic ethers as a reactive group can be exemplified by, for example, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate. , 2-(3,4-Epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, bis(3,4-epoxycyclohexylmethyl) Adipic acid-23- 200919094 ester, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ',4'-Epoxy- 6'-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), ethylene glycol (3,4-epoxy) 3,4-epoxycyclohexylmethyl-3' modified with cyclohexylmethyl)ether, ethyl bis(3,4-epoxycyclohexanecarboxylate), ε-caprolactone modified , 4'-epoxycyclohexane carboxylate, trimethyl caprolactone modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate And α-methyl-δ-valerolactone-modified 3,4-epoxycyclohexylmethyl-3,4'-epoxycyclohexanecarboxylate or the like containing an epoxycyclohexyl group Compound, and bisphenol quinone diglycidyl ether, bisphenol F II Glycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether , hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, three Hydroxymethylpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether; by adding one or two kinds of aliphatic polyvalent alcohols such as ethylene glycol, propylene glycol, glycerin or the like Polyglycidyl ethers of polyether polyols obtained by the above alkylene oxides; diglycidyl esters of aliphatic long-chain dibasic acids; monoglycidyl ethers of aliphatic higher alcohols; phenol, cresol, butylphenol Or a monoglycidic acid of a polyether alcohol obtained by adding an alkylene oxide; a glycidyl ester of a higher fatty acid, 3,7-bis(3-oxetanyl)-5-oxa- Brothel, 3,3'-(1,3-(2-methyl)-propyl-indenyl-bis(oxymethylene)) bis-(3-ethyloxycyclohexane) Alkyl), Shu, 4-bis [(3_ ethyl 3-oxetanyl methoxy) methyl] benzene, 1,2_-bis [(3-ethyl-3-oxo -24-

200919094 Heterocyclic butylmethoxy)methyl]ethane, I,3-bis[(3-ethylbutylmethoxy)methyl]propane, ethylene glycol bis(3-ethylmethyl)ether, dicyclopentane Alkenyl bis(3-ethyloxocarbamic acid, diethyl bis(3-ethyl-3-oxetanylmethyl) alcohol bis(3-ethyl-3-oxycarbonylmethyl)ether, three Ring ketone methyl (3-ethyl-3-oxetanylmethyl)-, tri- and 3-ethyl-3-oxazetyl butyl ether, 1,4 bis (3 ethyl butyl methoxy) Butane, 1,6-bis(3-ethyl_3_oxacyclo) hexanol, pentaerythritol dream (3-ethyl-3-oxetanyl and pentaerythritol oxime (3-ethyl-) 3-oxetanylmethyl) acid, 3-ethyl-3-oxetanylmethyl ether, dipentaerythritol 3-oxetanylmethyl)ether, dipentaerythritol (3-ethlylmethyl)ether, Dipentaerythritol bismuth (3-ethyl-3-octyl) ether, caprolactone modified dipentaerythritol tert (3-ethyl-3-methyl) ether, caprolactone modified dipentaerythritol (3_B Butylmethyl)ether, bis(trimethylol)propane oxime (3_ethylbutylmethyl) ether, ethylene oxide (ΕΟ) Bisphenol-3-oxetanylmethyl)ether, propylene oxide (ρ〇) bis(3-ethyl-3-oxetanylmethyl)ether, Ε0 battle A double (3-ethyl- 3-oxetanylmethyl)ether, p〇Xun A bis(3-ethyl-3-oxetanylmethyl)ether, EO modified (3-ethyl-3-oxetanylmethyl)ether, etc. In the molecule, an oxetane compound of an oxetane ring.

Commercially available compounds can be exemplified by ARON OXETANE -3-oxo-3-oxequile! butylmethyl)ether, tetraethylenedioxanediyldiimidopropane ginyl (yl-3-oxo oxime) Butylmethoxy!-yl)ether, quaternary: ethylene glycol bis(L-(3-ethyl-yl-3-oxocyclo)cyclopentylmethyl-oxetanyl-3-oxocyclyl-3- Oxaphthalene bis (3-ethyl modified bisphenol: hydrogenated bisphenol: hydrogenated bisphenol: bisphenol F: more than two OXT-101, -25- 200919094

ARON OXETANE OXT-121, ARON OXETANE is manufactured by East Asia Synthetic Co., Ltd., oxtp, oxbp, and manufactured by Ube Industries Co., Ltd.). Among these, as the crosslinking component Π, it is preferably 1,6 _ glyceryl ether or dipentaerythritol (3-ethyl-3-oxetan, OXTP, OXBP, manufactured by Ube Industries Co., Ltd. The crosslinking component may be used singly or in combination of two or more. The blending component of the present invention is used in an amount of from 1 to 1 part by weight, preferably from 5 to 70 parts by weight, per part by weight of the tree. If the hardening is insufficient, there is a problem that the 100 parts by weight of the pattern cannot be excessively hardened and the pattern is embedded. Further, the total amount of the resin and the crosslinking component is 0.1 to the total resin composition of the post-solvent. 30% by weight '$% by weight. The total weight % of the resin having a hydroxyl group and the cross-linking component is too thin to be caused by the pattern etching portion, and the viscosity is too high and fine when it exceeds 30% by weight. The pattern may not be used in the alcohol solvent which can be used in the present invention, and any solvent can be used as long as it can sufficiently dissolve the tree and is applied to the photoresist film. The monovalent alcohol having 1 to 8 carbon atoms is preferably 1-propanol, isopropanol or Alcohol, 2-butanol, tert-butyl, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1.yl-2-butanol, ;-hexanol , 2-hexanol, 3-hexanol, 2-methyl OXT-221 ( OXIPA (--hexanediol dimethyl methyl) ether OXIPA. The weight of the upper blush 1000 is not a problem, more than The alcohol content is 1~20 if it is not reached. 1 The problem of the film is buried and the cross-linking is formed into a photoresist film. The examples are alcohol, 1-pentanol-butanol, 3-methyl- 1-pentanol, 2 - -26- 200919094 methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-pentanol, 3-methyl-2-pentanol, 3-methyl Base-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 1-heptanol, 2-heptanol, 2-methyl-2-heptanol, 2-A It is preferred to use 1-butanol, 2-butanol or 4-methyl-2-pentanol, and these alcohol solvents may be used singly or in combination of two or more. The solvent may be contained in an amount of 1% by weight or less to preferably 1% by weight or less based on the total amount of the solvent. When the amount is more than 10% by weight, the solubility of the resin is lowered. More preferably, it is an anhydrous alcohol solvent containing no water. type The resin composition for forming can be mixed with other solvents in order to adjust the coating property when applied to the photoresist film. The other solvent is a uranium resist film which is not impregnated, and has a resin composition for forming a fine_type. The role of cloth.

Other solvents are listed as cyclic ethers such as tetrachloromethane and dioxane; ethylene glycol monomethyl ether, ethylene glycol monoethyl _, ethylene glycol dimethyl ether, and ethyl alcohol monoethyl ether , Ethyl alcohol monomethyl _, 2: ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol single Methyl ether, methyl ether, propylene glycol monoethyl ether, etc. An alkyl ether acetate of a polyvalent alcohol such as an acid ester; an aromatic hydrocarbon such as toluene or xylene; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4 hydroxy group 4 Ketones such as 2-methyl-2-pentanone and diacetone alcohol; ethyl acetate, butyl acetate, ethyl octahydroxypropionate, ethyl 2-hydroxypropionate, hydroxy-2-methylpropane Ethyl acetate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxyl_3_methyl-27- 200919094 methyl butyrate, methyl 3-methoxypropionate, 3-methoxypropionic acid Ethyl ester, ethyl 3-ethoxypropionate, 3-ethoxyl An ester such as methyl propionate, ethyl acetate or butyl acetate, or water. Among these, 'cyclic ethers, alkyl ethers of polyvalent alcohols, alkyl ether acetates of polyvalent alcohols, ketones, esters, and water are preferred. In the above, the blending ratio of the other solvent is 30% by weight or less based on the total solvent, preferably 20% by weight or less. When the amount is more than 30% by weight, there is a problem that the photoresist film is immersed in the resin composition and the resin composition for forming a fine pattern is mixed with each other, and the photoresist pattern is buried. Further, when water is mixed, it is 10% by weight or less. The resin composition for forming a fine pattern of the present invention may be formulated with an interface active agent to improve coatability, defoaming property, advection property and the like. As the surfactant, for example, B Μ - 1 0 0 0, B Μ -1 1 0 0 (above BM Chem), MEGAFACK F142D, MEGAFACK F172 ' MEGAFACK F1 7 3 ; MEGAFACK FI 83 (above is Japan) Ink Chemical Industry (manufacturing), FLUORAD FC-135, FLUORAD FC-170C, FLUORAD FC-430, FLUORAD FC-431 (above Sumitomo 3M (manufacturing)), SURFLON S-112, SURFLON S-113, SURFLON S-131, SURFLON S-141, SURFLON S-145 (above manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (The above is Toray Dow Corning) A fluorine-based surfactant sold under the trade name of (manufacturing). The amount of the surfactant to be added is preferably 5% by weight or less based on 100 parts by weight of the resin having a hydroxyl group. -28- 200919094 The fine resin pattern-forming resin composition is used to form a fine pattern by the following method: (1) The pattern of the photoresist pattern is formed by a conventionally known method such as spin coating at 8 吋 or 1 2 吋. An anti-reflection film (organic film or inorganic mold) is formed on the sand wafer substrate. Next, the photoresist is applied by a conventionally known method such as spin coating, and prebaking (PB) is carried out, for example, at about 80 ° C to 140 ° C for about 60 to 120 seconds. Subsequently, it is exposed by ultraviolet rays such as g-line or i-line, KrF excimer laser light, ArF excimer laser light, X-ray 'electron beam, etc., and is exposed to light after exposure at, for example, 80 ° C to 140 ° C. After baking (PEB), the photoresist pattern is formed by visualization. (2) Formation of fine pattern The resin composition for forming a fine pattern of the present invention is applied to a substrate on which the resist pattern is formed by a conventionally known method such as spin coating. Sometimes, the solvent is volatilized by spin coating to form a coating film. In addition, if necessary, for example, a coating film of a resin composition for forming a fine pattern is formed by prebaking (P B ) about 60 to 120 seconds, for example, at about 80 ° C to 110 ° C. Next, the substrate after coating the photoresist pattern with the resin composition for forming a fine pattern is subjected to heat treatment. After the heat treatment, the acid from the photoresist diffuses from the interface with the photoresist to the resin composition layer for forming a fine pattern to cause a crosslinking reaction of the resin composition for forming a fine pattern. The crosslinking reaction state from the photoresist interface is determined depending on the material of the resin composition for forming a fine pattern, the photoresist to be used, the baking treatment temperature, and the baking treatment time. The heat treatment temperature and the heat treatment time are usually about 90 to 120 seconds at a temperature of about 90 ° C to 160 ° C for -29-200919094. Then, the coating film of the resin composition for forming a fine pattern is subjected to development processing (for example, '60 to 120 seconds) with an aqueous alkali solution such as tetramethylammonium hydroxide (TMAH) or the like to form a micrograph of uncrosslinked. The coating film of the resin composition for forming a type is dissolved and removed. Finally, the water is washed, and the perforation pattern, the elliptical pattern, and the groove pattern can be made fine. EXAMPLES Hereinafter, the present invention will be described by way of examples, but the invention is not limited to the examples. A synthetic example of the resin used in the examples and the like will be described below. Synthesis Example 1 [Chemical 15]

17.21 g of p-cyanomethyl propyl anilide (ml), 8.56 g of p-t-butoxy styrene (m 2 ), 4.23 g of 2 (((trifluoromethyl) sulfonate) Mercapto)amino)ethyl-1-methacrylate (m-3), and 2.3 g of azobisisobutyronitrile are dissolved in 90 g of isopropanol (-30 - 200919094 IPA), and The polymerization was carried out under reflux conditions (82 ° C) for 6 hours. The reaction vessel was cooled with running water, poured into methanol of 9000 g with stirring. After reprecipitation, it was suction filtered. The reprecipitation operation (pour into IP A - suction filtration) was repeated 4 times and then vacuum dried at 5 Torr. As a result, 26 g of a repeating unit derived from p-hydroxyphenylmethacryl oxime anilide/repeating unit derived from p-t-butoxy styrene/derived from 2_((difluoromethyl)) was obtained. A repeating unit of mercapto)amino)ethyl-1-methyl acrylate = 70/20/10 (mole ratio) copolymer (yield 87% by weight). This copolymer is referred to as Resin P-1. The Mw and Μη of the resin (p -1 ) and each of the polymers obtained in the following synthesis examples were determined by using a GPC column (2 G2000HXL, 1 G3000HXL, 1 G4000HXL) manufactured by TOSOH Co., Ltd. The measurement was carried out by gel permeation chromatography (GPC) at a flow rate of 1. 〇ml/min, dissolved solvent tetrahydrofuran, column temperature 4 (TC analysis conditions using monodisperse polystyrene as a standard. Mw of -1 was 5,800, Mw/Mn 1 · 6. Synthesis Example 2 Using the same starting materials as in Synthesis Example 1, a repeat derived from p-hydroxyphenylmethacryl oxime was obtained as in Synthesis Example 1. Unit / repeating unit derived from tert-butoxystyrene / repeating unit derived from 2-(((trifluoromethyl)sulfonyl)amino)ethyl-1-methacrylate = 6 0 / 3 5/5 (Wear ratio), copolymer of Mw 5,200, Mw/Mn 1.5. The copolymer is referred to as Resin P-2. -31 - 200919094 Synthesis Example 3 The same starting materials as in Synthesis Example 1 were used. The weight of the repeating unit derived from p-hydroxyphenylmethacryl oxime anilide/derived from the third butoxy styrene was obtained in the same manner as in Synthesis Example 1. Unit / repeating unit derived from 2-(((trifluoromethyl)sulfonyl)amino)ethyl-1-methacrylate = 60/30/10 (mole ratio), Mw 5,200, Mw/ a copolymer of Mn 1.5. The copolymer is referred to as Resin P-3. Synthesis Example 4 [Chem. 16]

CHj=C

CH,

(m-i)

(m-2)

OH will be 8.14 g of p-hydroxymethylpropenyl anilide (m-1), 35.86 g of p-t-butoxystyrene (m-2), 8.91 g of azobisisobutyronitrile, 4.81 g 2 4-Diphenyl-4-methyl-1-pentane was dissolved in 3 60 g of methanol, and polymerization was carried out under reflux conditions (631) for 8 hours. The polymerization solution was reprecipitated and purified in methanol/water and reprecipitated in isopropanol/heptane to obtain a repeating unit derived from p-hydroxymethylpropenanilide of Mw 8,500, Mw/Mn 2.08. / Copolymer derived from a repeating unit of p-t-butoxystyrene = 7 0 / 30 (mole ratio). This copolymer is referred to as Resin -32-200919094 P-4. Example 1 to Example 5, Comparative Example 1 and Comparative Example 2 The resin component, the crosslinking component, the alcohol solvent and other additives were added in the ratio shown in Table 1, and after stirring for 3 hours, filtration using a pore size 〇·〇3μιη The resin composition for forming a fine pattern is obtained. The crosslinking component and the alcohol solvent used in each of the examples and the comparative examples are shown under & Cross-linking component cl: NICARAK ΜΧ-7 5 0 (manufactured by Nippon Carbon Chemical Co., Ltd., commercial C-2: pentaerythritol tetraacrylate C-3: oxime alcohol solvent S-ι: 1-butanol S-2: 4-methyl- 2-pentanol synthesis example 5 -33- 200919094 [Chem. 17]

1 7.6 2 g of p-hydroxymethylpropenanilide (m-Ι), 10-22 g of p-t-butoxystyrene (m-2), 2.16 g, as starting material

2-(((Trifluoromethyl)sulfonyl)amino)ethyl-1-methacrylate (m_3), and 2.18 g of azobisisobutyronitrile were dissolved in 90 g of isopropanol (IPA) And the polymerization reaction was carried out under reflux conditions (82. (:) for 6 hours. After the reaction vessel was cooled by running water, 60 g of ethyl acetate, 42 g of IPA, 42 g of methanol was added to the polymerization solution and homogenized therein. 18 g of water was added and allowed to stand for 1 hour. The viscous polymer deposited on the lower layer was recovered and vacuum dried at a temperature of 5 ° C. As a result, 26 g (yield 87 wt%) of a copolymer was obtained. The Mw and ΜN of the resin P-5D resin Re-5 and the respective polymers obtained in the following synthesis examples were measured using a GPC column manufactured by TOSOH Co., Ltd. (G2000HXL 2, G3000HXL 1, G4000HXL 1 Root), measured by gel permeation chromatography (GPC) at a flow rate of 1 · 0 ml / min, dissolved solvent tetrahydrofuran, column temperature 40 t: under the conditions of monodisperse polystyrene as a standard. As a result, the mw of the resin P_5 is 5,8 00, -34- 200919094

Mw/Mn 1.5. Further, the analysis results of the composition by l3C-NMR were as follows. Since the peak derived from the monomer (m-2) is 0.704 at 78 ppm, and the peak derived from the monomers (m-1) and (m-2) is 1.627 at 150 to 155 ppm, the fraction derived from (m_2) is subtracted. The peak derived from (m-1) is 〇·923. Since the peaks derived from (m-3) and (m-1) are 1.000 at 170 to 180 nm, the subtraction is derived from (m · 1 ). The peak derived from (m -3 ) after the integral is 0.07 7, so the composition of the resin P-5 is a repeating unit derived from p-hydroxymethylpropenanilide/derived from p-tert-butoxy The repeating unit (mol ratio) of the repeating unit of styrene/2_(((trifluoromethyl)sulfonyl)amino)ethyl-1-methacrylate was 4.2/41.3/4.5. Synthesis Example 6 Using the same starting materials as in Synthesis Example 5, 20.07 g of p-hydroxymethylpropenanilide (m-oxime), 5.70 g of p-t-butoxystyrene (m-2), 4 23 g of 2-(((trifluoromethyl)sulfonyl)amino)ethyl-1-methacrylate (m-3) ' and 2.13 g of azobisisobutyronitrile dissolved in 90 g of isopropyl The polymerization was carried out for 6 hours in an alcohol (IPA) under reflux conditions (82 t). After the reaction vessel was cooled with flowing water, 60 g of ethyl acetate, 42 g of IPA, and 42 g of methanol were added to the polymerization solution and homogenized, and 180 g of water was added thereto and allowed to stand for 1 hour. The viscous polymer settled to the lower layer was recovered and vacuum dried at a temperature of 50 °C. As a result, 22.5 g (yield 75 wt%) of a copolymer was obtained. This copolymer is referred to as resin p _ 6 . The resin P -6 ' was subjected to the same measurement as in Synthesis Example 5, and the repeating unit derived from p-hydroxymethylpropenanilide/weight derived from p-t-butoxystyrene-35-200919094 Repeating unit derived from 2-(((trifluoromethyl)sulfonyl)amino)ethyl-j _ methacrylate = 64.8/2 6.0/9.2 (mole ratio), Mw 5,200, Mw/Mn 1.5 〇 Synthesis Example 7 Using the same starting materials as in Synthesis Example 5, 1 7 · 2 1 g of p-methylmethacryl anilide (m-oxime), 8.56 g of p-t-butoxy group Phenylethylene (m-2), 4.23 g of 2-(((trifluoromethyl)sulfonyl)amino)ethyl-1 methacrylate (m-3), and 2.13 g of azobis The nitrile was dissolved in 90 g of isopropyl alcohol (IP A ), and polymerization was carried out under reflux conditions (82 ° C) for 6 hours. After the reaction vessel was cooled with flowing water, 60 g of ethyl acetate, 42 g of IPA, and 42 g of methanol were added to the polymerization solution and homogenized, and 180 g of water was added thereto and allowed to stand for 1 hour. The viscous polymer settled to the lower layer was recovered and vacuum dried at a temperature of 50 °C. As a result, 21.5 g (yield 72% by weight) of a copolymer was obtained. This copolymer is referred to as Resin P-7. The resin P-7 was subjected to the same measurement as in Synthesis Example 5, and the repeating unit derived from p-hydroxymethylpropenanilide/repeating unit derived from p-t-butoxystyrene was derived from 2-( Repeating unit of ((trifluoromethyl)sulfonyl)amino)ethyl- methacrylate = 5 5.4/34.8/9.8 (mole ratio), Mw 5, 2 0 0, M w/Mn 1 · 5 〇Synthesis Example 8 -36- 200919094 [Chem. 18]

62.13 g of p-hydroxymethylpropenanilide (^丨), 37 & gram of p-t-butoxyphenethyl bromide (m-2), 10.21 g of azobisisobutyrate dissolved in 300 g of different The polymerization was carried out for 6 hours in propanol (IPA) under reflux conditions (8 μc). After the reaction vessel was cooled by flowing water, the polymerization solution was added with 200 g of ethyl acetate, 140 g of yttrium, 140 g of methanol, and homogenized, and 600 g of water was added thereto and allowed to stand for 1 hour. The viscous polymer settled to the lower layer was recovered and vacuum dried at a temperature of 5 °C. Obtaining Mw 8,5 00 'Mw/Mn 2.08 from repeating units of p-hydroxymethylpropenyl hydrazine, repeating unit derived from p-t-butoxy styrene = 55.4/44_6 (mole Ratio) copolymer. This copolymer is referred to as Resin P-8. Example 6 to Example 10, Comparative Example 3, and Comparative Example 4 A resin component, a crosslinking component, an alcohol solvent, and other additives were added at a ratio shown in Table 3, and after stirring for 3 hours, an aperture 〇. 〇3 μιη was used. The filter was filtered to obtain a resin composition for forming a fine pattern. The crosslinking component and the alcohol solvent used in each of the examples and the comparative examples are shown below. -37- 200919094 Cross-linking component Cl : NICARAK MX-750 (manufactured by Nippon Carbonization Co., Ltd.) C-2: dipentaerythritol tert-(3-ethyl-3-oxetanylmethyl alcohol solvent S -1 : 1 - butanol S-2: 4-methyl-2-pentanol A substrate for evaluation in which a photoresist pattern was attached in order to evaluate the obtained resin composition for forming a fine pattern. CLEAN TRACK ACT8 (Tokyo Electronics Co., Ltd.) Transfer coating on a 8 吋 wafer with a film thickness of 77 nm (PB20 5 °C, 60 lower anti-reflection film ARC29A (BULEWAR SCIENCE, after the formation of a coating film, JSR ArF AR1 244J (JSR AG, aliphatic) AR1 244J of the sensitive radiation linear resin composition is coated on the same CLEAN TRACK ACT8 by a PB (1 3 0X:, 90 seconds), cooled (23 ° C, 30 seconds) 210 nm coating film And with an ArF projection exposure apparatus S 3 06C (strand)), NA: 0.78, σ: 0.85, 2/3 Ann optical strip exposure (exposure amount 3 OmJ/cm2), and on the same CLEAN ACT 8 heating plate, After p EB ( 1 3 Ot:, 90 seconds), cooling (3 sec), the LD nozzle of the developing cup was used as an aqueous solution of 2.38 wt%. Manufacturing stirred developing liquid developer (60 seconds), to an ultrapure, product) ether following manner by spin seconds) of) Limited miniaturized. The cloth was deposited by a film thickness (Nikon piece was subjected to TRACK 2 3, TM AH water-washing strip-38-200919094, followed by shaking at 4000 rpm for 15 seconds and spin-drying to obtain a substrate for evaluation. The substrate obtained in this step was evaluated. Using the substrate A, a plurality of evaluation substrates A prepared under the same conditions were prepared. The obtained evaluation substrate was a scanning electron microscope (S-9380 manufactured by Hitachi Instruments Co., Ltd.), and an 80 nm diameter perforation pattern was observed for the pattern. Type, 100 nm interval mask pattern (through hole +3 Onm / 1 1 〇 nm via hole / 70 nm spacing on the mask), measuring the aperture diameter of the photoresist pattern. Evaluation with the light pattern In the examples described in Tables 1 and 3, the resin composition for forming a fine pattern was evaluated by the following method. The evaluation results are shown in Tables 2 and 4. (1) The shrinkage size and the baking temperature dependence were evaluated. On the substrate A for evaluation, a resin composition for forming a fine pattern described in Tables 1 and 3 having a film thickness of 15 onm was applied by spin coating on a CLEAN TRACK ACT8, and then the pattern and the pattern of the pattern were made. The pattern formation is reacted with a resin composition, as shown in Table 1 and The shrinkage evaluation conditions described in 3 were baked. Subsequently, after cooling with the same CLEAN TRACK ACT8 on a 23 ° C cooling plate for 30 seconds, the LD nozzle was used as a developing cup, and a 2.38% by weight TMAH aqueous solution was used as a developing solution. Stirring development (60 seconds), washing with ultrapure water' followed by shaking at 400 rpm for 15 seconds and spin-drying. The substrate obtained in this step was used as the evaluation substrate B. The pattern size shrinkage measurement was performed by scanning electrons. Microscope (S-93 8 0 manufactured by Hitachi Instruments Co., Ltd.), for this pattern, observe the 60 nm diameter perforation pattern and the 120 nm interval reticle pattern (through hole + 3 Onm / 1 1 Onm diameter on the mask) Through hole / 70 nm interval) 'Measure the aperture diameter of the photoresist pattern. -39- 200919094 Shrinkage size (nm) = φ 1 · φ2 φ 1 : Evaluation of the substrate Α photoresist pattern through hole diameter (nm) φ 2 : For the evaluation of the substrate B, the photoresist pattern-through hole diameter (nm) is judged as shrinkage, and when the shrinkage size is 20 nm or more, it is marked as "〇", when the shrinkage or pattern is not confirmed, or the shrinkage size is not When it reaches 20 nm, it is called "X". (2) Confirmation evaluation evaluation base of insoluble matter B is a scanning electron microscope (S-48 00 manufactured by Hitachi Instruments Co., Ltd.), and a 60 nm diameter perforation pattern and a 120 nm interval reticle pattern are observed for the pattern cross section (through hole + 30 nm/mask) Ll 〇 nm diameter via hole / 70 nm interval), when there is no insoluble matter at the bottom of the opening, it is marked as "〇", and when insoluble matter is observed, it is marked as "X". (3) Shape evaluation after pattern shrinkage evaluation substrate A And the substrate B for evaluation, a scanning electron microscope (S - 4 80 0 manufactured by Hitachi Instruments Co., Ltd.), and a 60 nm diameter perforation pattern is observed for the pattern profile existing at the same position in the pattern, L2 〇nm interval reticle pattern (through hole + 30nm / mask on the 11 〇 nm diameter through hole / 70nm interval). The cross-sectional shape is shown in Fig. 1 and Fig. 2. If the angle of the side wall 2a of the perforation pattern 2 relative to the substrate 于 is less than 3 degrees below the angle of the pattern before contraction (Fig. i(l)) and the angle after the pattern is contracted (Fig. i(l5)) (see 1), and when the photoresist film thickness t of the evaluation substrate A (Fig. 2(a)) is 1 〇〇, only the portion from the substrate through which the photoresist film thickness t-t' is 80 is The deteriorated portion t was observed in the pattern on the evaluation substrate b, which was regarded as good (Fig. 2(b)), and the others were marked as defective (see Fig. 2). -40- 200919094 [Table i] Resin cross-linking agent solvent shrinkage evaluation Baking conditions Type of blending amount (g) Type of blending amount (g) Type of blending amount (g) Temperature (〇c) Time (sec) Example 1 P- 1 10.0 C-1 4.2 S-1 270 150 90 Example 2 P-2 10.0 C-1 4.2 S-1 270 150 90 Example 3 P-3 10.0 C-1 4.2 S-1 270 150 90 Example 4 P -2 10.0 C-3 4.2 S-162/108 150 90 2/S- 1 Example 5 P-2 10.0 C-2 4.2 S-162/108 150 90 2/S- 1 Comparative Example 1 P-4 10.0 C -1 4.2 S-1 270 150 90 Comparative Example 2 P-4 10.0 C-1 4.2 S-2 270 150 90 [Table 2] Observation of shrinkage P-value insoluble matter Shape evaluation Shrinkage (nm) Judgment Example 1 21 〇〇 Good Example 2 24 〇〇 Good Example 3 22 〇〇 Good Example 4 23 〇〇 Good Example 5 22 〇〇 Good Comparative Example 1 16 X 〇 Good Comparative Example 2 Unable to measure XX Bad -41 - 200919094 [Table 3] Resin cross-linking agent solvent shrinkage evaluation Baking condition type blending amount (g) Kinding amount (g) Kinding amount (g) Temperature ΓΟ Time (seconds) Example 6 P-5 10.0 C-1 4.2 S-1 270 150 90 Example 7 P-6 10.0 C-1 4.2 S-1 270 150 90 Example 8 P-7 10.0 C-1 4.2 S-1 270 150 90 Example 9 P-6 10.0 C-1 4.2 S-2 270 150 90 Example 10 P-6 10.0 C-2 4.2 S-2 270 150 90 Comparative Example 3 P-8 10.0 C-1 4.2 S-1 270 150 90 Comparative Example 4 P-8 10.0 C- 1 4.2 S-2 270 150 90 [Table 4] Evaluation of shrinkage Evaluation of the presence or absence of insoluble matter Size shrinkage (nm) Judging Example 6 21 〇〇 Good Example 7 24 〇〇 Good Example 8 22 〇〇 Good example 9 23 〇〇Good Example 10 22 〇〇Good Comparative Example 3 16 X 〇Good Comparative Example 4 Unable to measure XX defective-42 - 200919094 Industrial Applicability The resin composition for forming a fine pattern of the present invention can be effective and high Accurately refine the pattern gap of the resist pattern, and form a pattern that exceeds the wavelength limit in a good and economical manner. It can be used very well in the future and is increasingly represented in the future. Microfabrication field. [Simple description of the drawing] Fig. 1 is a sectional shape of a perforated pattern. Figure 2 is a cross-sectional view of a perforated pattern. [Main component symbol description] 1 : Substrate 2 : Perforated pattern -43-

Claims (1)

200919094 X. Patent Application No. 1 _ a resin composition for forming a fine pattern for refining a photoresist pattern, which comprises a resin, a crosslinking component crosslinked with the resin, and an alcohol solvent, which is characterized by The resin contains a repeating unit having a side chain represented by β (" ([1] ΝΗ I o=s=o \ Rf (1) (in the formula (1), Rf represents at least one hydrogen atom via a fluorine atom) A resin composition for forming a fine pattern of the first aspect of the invention, wherein the side chain of the formula (1) is repeated The unit (I) is derived from a monomer represented by the following formula (2): [Chemical 2] c=c B NH o=s=o Rf (2) (In the formula (2), R, R, or R" independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxymethyl group, a trifluoromethyl group or a phenyl group. 'A is not a single bond, an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group; B represents a single bond or a monocyclic hydrocarbon group having a carbon number of -44 - 200919094 1 to 2 0, a saturated chain hydrocarbon group of 3 to 20 carbon atoms; a polycyclic hydrocarbon ring group having a carbon number of 4 to 2; Rf represents a linear or branched alkyl group having 1 to 8 carbon atoms substituted with at least one hydrogen atom via a fluorine atom. A resin composition for forming a fine pattern of two items, wherein the repeating unit (I) is from 3 to 30 mol% with respect to all repeating units constituting the resin. 4. The fine pattern formation as in the first item of the patent application A resin composition in which Rf in the above formula (1) is selected from the group consisting of a perfluoromethyl group, a perfluoroethyl group, and a perfluoropropyl group. 5. For forming a fine pattern of the first aspect of the patent application a resin composition in which Rf in the above formula (1) is a perfluoromethyl group. 6. A resin composition for forming a fine pattern according to item 2 of the patent application, The above monomer is 2-(((trifluoromethyl)sulfonyl)amino)ethyl-1-methacrylate. 7 · Resin composition for forming a fine pattern according to item 1 of the patent application The resin having a weight average molecular weight of 1,000 to 20,000. The resin composition for forming a fine pattern according to the first aspect of the invention, wherein the alcohol solvent is a monovalent alcohol having 1 to 8 carbon atoms. The resin composition for forming a fine pattern according to the first aspect of the invention, wherein the crosslinking component is a compound selected from the group consisting of a group represented by the following formula (5) and containing two or more cyclic ethers as a reactive group. At least one compound of the compound: -45- 200919094 [Chemical 3] \r* (5) (In the formula (5), R5 and R6 represent a hydrogen atom or the following formula (6), and at least one of R5 and R6 is represented by the following formula (6): [Chemical 4] R7 I - C - Ο —R» I R8 (6 ) (In the formula (6), R7 and R8 represent a hydrogen atom, a carbon number of 1 to 6 or an alkoxyalkyl group having 1 to 6 carbon atoms, or R7 and R8 are linked to each other. A ring having a carbon number of 2 to 10; R9 represents a hydrogen atom and an alkyl group having 1 to 6 carbon atoms. 10. The resin composition for forming a fine pattern according to the first aspect of the invention, wherein the amount of the crosslinking component is 5 to 70 parts by weight based on 100 parts by weight of the resin. 11. The resin composition for forming a fine pattern according to the first aspect of the invention, wherein the total amount of the resin and the crosslinking component is 0.1 to 30% by weight based on the total of the resin composition. 12. The resin composition for forming a fine pattern according to the first aspect of the invention, wherein the resin further contains a repeating unit having at least one hydroxyl group selected from a hydroxyl group derived from an alcohol, a phenol, and a carboxylic acid in a side chain ( 11) The resin composition for forming a fine pattern according to Item 12 of the patent application, wherein the repeating unit having a hydroxyl group derived from a phenol is a repeating unit having a guanamine bond in the repeating unit. -46 - 200919094 14. The resin composition for forming a fine pattern according to Item 13 of the patent application, wherein the repeating unit having a guanamine bond in the repeating unit is selected from the group consisting of hydroxypropenyl anilide and hydroxymethyl group A compound obtained by polymerizing at least one compound of propenyl anilide. 15. The resin composition for forming a fine pattern according to the first aspect of the invention, wherein the resin contains a repeating unit (III) represented by the following formula (3): [Chemical 5] (In the formula (3), R1 represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms or a linear or branched alkoxy group having 1 to 8 carbon atoms). In the above formula (3), R1 is a group selected from the group consisting of a third butyl group and a third butylene group, in the resin composition for forming a fine pattern of the fifteenth aspect of the invention. The resin composition for forming a fine pattern of the first aspect of the invention, wherein R1 is a third butoxy group in the above formula (3). The resin composition for forming a fine pattern of the fifteenth aspect of the patent application, wherein the repeating unit (III) is obtained by polymerizing a third butoxystyrene. A method for forming a fine pattern, comprising the step of forming a pattern of a photoresist pattern formed on a substrate; and coating the resin composition for forming a fine pattern of the first application of the patent pattern on the photoresist pattern a step of subjecting the substrate after the film-removing step to a heat treatment; and a step of developing the image with an aqueous alkali solution of -47 to 200919094. -48 -