WO2011125291A1 - ホモアダマンタン誘導体、その製造方法及びフォトレジスト用感光性材料 - Google Patents

ホモアダマンタン誘導体、その製造方法及びフォトレジスト用感光性材料 Download PDF

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WO2011125291A1
WO2011125291A1 PCT/JP2011/001532 JP2011001532W WO2011125291A1 WO 2011125291 A1 WO2011125291 A1 WO 2011125291A1 JP 2011001532 W JP2011001532 W JP 2011001532W WO 2011125291 A1 WO2011125291 A1 WO 2011125291A1
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oxo
oxa
homoadamantan
meth
oxy
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French (fr)
Japanese (ja)
Inventor
田中　慎司
義崇 上野山
大野　英俊
直弥 河野
克樹 伊藤
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Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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Priority to KR1020127025834A priority Critical patent/KR20130034016A/ko
Priority to US13/638,979 priority patent/US20130022914A1/en
Priority to KR1020177021225A priority patent/KR102061400B1/ko
Priority to CN2011800166482A priority patent/CN103097371A/zh
Priority to KR1020187034121A priority patent/KR20180128100A/ko
Publication of WO2011125291A1 publication Critical patent/WO2011125291A1/ja
Anticipated expiration legal-status Critical
Priority to US14/798,990 priority patent/US20150316847A1/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D313/00—Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom
    • C07D313/02—Seven-membered rings
    • C07D313/06—Seven-membered rings condensed with carbocyclic rings or ring systems
    • C07D313/10—Seven-membered rings condensed with carbocyclic rings or ring systems condensed with two six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F224/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/165—Monolayers, e.g. Langmuir-Blodgett
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G03F7/322—Aqueous alkaline compositions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
    • H10P76/20—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials
    • H10P76/204—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials of organic photoresist masks

Definitions

  • the present invention relates to a novel homoadamantane derivative, a (meth) acrylic acid ester, a production method thereof, a (meth) acrylic polymer, a positive photoresist composition, and a resist pattern forming method.
  • a photoacid generator (PAG) is an essential component for causing a photosensitive action (acid decomposition).
  • PAG photoacid generator
  • Patent Documents Patent Documents
  • An object of the present invention is to provide a polymer excellent in roughness reduction, solubility, compatibility, defect reduction, exposure sensitivity, and the like, a monomer (monomer) providing the same, and a precursor thereof (when used as a positive photoresist, Intermediates, modifiers).
  • homoadamantane derivatives represented by the following formula (I).
  • R 1 and R 2 each represent a hydrogen atom or a linear, branched or cyclic hydrocarbon group having 1 to 6 carbon atoms
  • X represents a hydroxyl group or a halogen atom
  • n and m each represent 0 N and m are not simultaneously 0 and n is not 0.
  • n is 2 or more
  • a plurality of R 1 s may be the same or different from each other.
  • R 2 may be the same or different. 2.
  • the homoadamantane derivative according to 1 which is represented by any one of the following formulas (1) to (3): (In the formula, X represents a hydroxyl group or a halogen atom.) 3.
  • n is 2 or more, a plurality of R 1 s may be the same or different, and m is 2 In the above case, the plurality of R 2 may be the same or different from each other.) 6).
  • a positive photoresist composition comprising the (meth) acrylic polymer according to 10.9 and a photoacid generator. 11.
  • a polymer excellent in roughness reduction, solubility, compatibility, defect reduction, exposure sensitivity, and the like a monomer (monomer) providing the polymer, and a precursor thereof ( Intermediates, modifiers).
  • R 1 and R 2 each represent a hydrogen atom or a linear, branched or cyclic hydrocarbon group having 1 to 6 carbon atoms
  • X represents a hydroxyl group or a halogen atom
  • n and m each represent 0 to It is an integer of 3.
  • n and m are not 0 at the same time.
  • the plurality of R 1 may be the same or different
  • the plurality of R 2 may be the same or different.
  • R 1 and R 2 are preferably a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms.
  • alkyl groups include linear groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, hexyl, etc.
  • cyclic structures such as a branched alkyl group, a cyclopentyl ring, a cyclohexyl ring, etc. are mentioned.
  • R 1 and R 2 are particularly preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.
  • X includes a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among them, a hydroxyl group, a chlorine atom, and a bromine atom are preferable.
  • the position of the substituent on the homoadamantane skeleton can take any position number from 1 to 11 except for 4, 5, but is preferably 1 or 2 for ease of synthesis.
  • the homoadamantane derivative of the present invention is preferably represented by any of the following formulas (1) to (3).
  • X represents a hydroxyl group or a halogen atom.
  • X represents a hydroxyl group or a halogen atom.
  • homoadamantane derivative of the present invention represented by the above formula (I) include (5-oxo-4-oxa-5-homoadamantan-1-yl) oxymethanol, 1- (5-oxo-4 -Oxa-5-homoadamantan-1-yl) oxyethanol, 2- (5-oxo-4-oxa-5-homoadamantan-1-yl) oxy-2-oxoethanol, 2- (5-oxo-4) -Oxa-5-homoadamantan-1-yl) oxy-2-oxo-1-methylethanol, 2- (2- (5-oxo-4-oxa-5-homoadamantan-1-yl) oxy-2- Oxoethoxy) -2-oxoethanol, 2- (2- (5-oxo-4-oxa-5-homoadamantan-1-yl) oxy-2-oxo-1-methylethoxy) -2-oxoethane 2- (2- (5-oxo-4-
  • the homoadamantane derivative of the present invention can be produced by various methods, and typical methods include, but are not limited to, methods including the following steps. a. A step of reacting a homoadamantyl alcohol represented by the following formula with a hydrogen halide gas in the presence of an aldehyde to obtain a homoadamantane derivative of the formula (I) which is a halogenated ether: b.
  • a homoadamantyl alcohol represented by the following formula is reacted in the presence of an alkyl sulfoxide and an acid anhydride to obtain an alkylthioalkyl ether form, and this is further reacted with a halogenating agent to form a halogenated ether form (I) Obtaining a homoadamantane derivative of c.
  • a step of reacting a homoadamantyl alcohol represented by the following formula with 2-hydroxycarboxylic acid halide, 2-halogenated carboxylic acid halide or 2-halogenated carboxylic acid to obtain a homoadamantane derivative of formula (I) which is an ester d.
  • aldehyde examples include linear or branched aliphatic aldehydes such as formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, and isobutyraldehyde.
  • Examples of the hydrogen halide gas include a single gas such as hydrogen fluoride gas, hydrogen chloride gas, and hydrogen bromide gas, or a mixed gas thereof.
  • alkyl sulfoxide examples include dimethyl sulfoxide, diethyl sulfoxide, di-n-propyl sulfoxide, diisopropyl sulfoxide, di-n-butyl sulfoxide, diisobutyl sulfoxide, di-sec-butyl sulfoxide, di-tert-butyl sulfoxide, diisopentyl sulfoxide.
  • symmetric or asymmetric alkyl sulfoxides such as methyl ethyl sulfoxide and methyl-tert-butyl sulfoxide.
  • acid anhydride examples include acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, pivalic anhydride, benzoic anhydride, chloroacetic anhydride, trifluoroacetic anhydride, etc. And aliphatic or aromatic carboxylic acid anhydrides.
  • halogenating agent examples include sulfur halides such as thionyl chloride, sulfuryl chloride, thionyl bromide, sulfuryl bromide, thionyl chlorobromide, sulfuryl chlorobromide, phosphorus trichloride, phosphorus tribromide, and triiodine.
  • phosphorus halide compounds such as phosphorus trichloride, phosphoric trichloride, phosphoric tribromide, phosphorus pentachloride, and phosphorus pentabromide.
  • 2-hydroxycarboxylic acid examples include aliphatic-2-hydroxycarboxylic acid such as glycolic acid, lactic acid (2-hydroxypropionic acid), 2-hydroxybutanoic acid, and acid anhydrides thereof.
  • the acid examples include 2-halogenated aliphatic carboxylic acids such as 2-chloroacetic acid, 2-bromoacetic acid, 2-chloropionic acid, 2-bromopropionic acid, and acid anhydrides thereof.
  • Examples of 2-hydroxycarboxylic acid halide and 2-halogenated carboxylic acid halide include halides of the above-mentioned 2-hydroxycarboxylic acid and 2-halogenated carboxylic acid.
  • the halogenated ether form in step a can be obtained by reacting homoadamantyl alcohol with hydrogen halide gas in the presence of aldehyde. At this time, the reaction can be performed in the presence or absence of an organic solvent.
  • the substrate concentration in the case of using an organic solvent is not particularly limited as long as it is lower than the saturation solubility of homoadamantyl alcohol, but it is preferable to adjust the substrate concentration to be about 0.1 mol / L to 10 mol / L.
  • a substrate concentration of 0.1 mol / L or more is economically preferable because a necessary amount can be obtained in a normal reactor.
  • a substrate concentration of 10 mol / L or less is preferable because the temperature of the reaction solution can be easily controlled. .
  • Usable organic solvents include hexane, heptane, cyclohexane, ethylcyclohexane, benzene, toluene, xylene and other hydrocarbon solvents, diethyl ether, dibutyl ether, THF (tetrahydrofuran), dioxane, DME (dimethoxyethane) and other ether solvents.
  • the solvent include halogen solvents such as dichloromethane and carbon tetrachloride, and these may be used alone or in combination.
  • it is a halogen type solvent with a high dissolved amount of hydrogen halide gas.
  • the reaction temperature is arbitrary, but if it is too high, the solubility of the hydrogen halide gas may decrease, and if it is too low, the progress of the reaction itself may be delayed.
  • the pressure is arbitrary, but normal pressure is preferable because side reactions need to be controlled under pressurized conditions. If the pressure is too high, a special pressure device is required, which is not economical.
  • the alkylthioalkyl ether of step b can be obtained by reacting homoadamantyl alcohol in the presence of alkyl sulfoxide and an acid anhydride. At this time, the reaction can be carried out in the presence or absence of an organic solvent, but usually the reaction proceeds by using alkylsulfoxide and acid anhydride as a reaction reagent and solvent in a large excess.
  • an organic solvent is separately used, the usable organic solvent and pressure are the same as those in step a, and it is preferable to adjust the substrate concentration to be about 1 mol / L to 10 mol / L.
  • a substrate concentration of 1 mol / L or more is economically preferable because a necessary amount can be obtained in a normal reactor, and a substrate concentration of 10 mol / L or less is preferable because the temperature of the reaction solution can be easily controlled.
  • the reaction temperature is arbitrary, but if it is too high, the selectivity may be lowered due to side reactions, and if it is too low, the progress of the reaction itself may be delayed.
  • a halogenated alkyl ether is obtained by reacting an alkylthioalkyl ether with a halogenating agent. At this time, it can be carried out in the presence or absence of an organic solvent, but a halogenating agent may be used in a large excess as a reaction reagent and a solvent.
  • a halogenating agent may be used in a large excess as a reaction reagent and a solvent.
  • the substrate concentration, the organic solvent that can be used, and the pressure are the same as in step a.
  • the reaction temperature is arbitrary, but if it is too high, the selectivity may be lowered due to side reactions, and if it is too low, the progress of the reaction itself may be delayed.
  • salt can be generated in the system by allowing a base to act on homoadamantyl alcohol and a reaction reagent, but water generated by azeotropic dehydration reaction is forced out of the system. It is possible to promote the reaction by removing it selectively.
  • the esterification and etherification can be performed in the presence or absence of an organic solvent, but when an organic solvent is used, the substrate concentration is the same as in step a above.
  • organic solvent examples include DMF (N, N-dimethylformamide), DMSO (dimethylsulfoxide), NMP (N-methyl-2-pyrrolidone), HMPA (hexamethyl phosphate) in addition to the solvents exemplified in the above step a.
  • Aprotic polar solvents such as triamide), HMPT (hexamethyl phosphite triamide), carbon disulfide and the like, and these may be used alone or in combination.
  • Examples of the base include sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, silver oxide, sodium phosphate, potassium phosphate, disodium monohydrogen phosphate, dipotassium hydrogen phosphate , Monosodium dihydrogen phosphate, monopotassium dihydrogen phosphate, sodium methoxide, potassium t-butoxide, triethylamine, tributylamine, trioctylamine, pyridine, N, N-dimethylaminopyridine, DBN (1,5-diazabicyclo [4 , 3,0] non-5-ene) and DBU (1,8-diazabicyclo [5,4,0] undec-7-ene) and organic amines are used.
  • a hydrocarbon solvent such as cyclohexane, ethylcyclohexane, toluene, xylene or the like is preferably selected as the solvent.
  • the ratio of the reaction reagent to the homodamantyl alcohol is about 0.01 to 100 times mol, preferably 1 to 1.5 times mol.
  • the addition amount of the base is about 0.1 to 10 times mol, preferably 1 to 1.5 times mol with respect to homoadamantyl alcohol.
  • the reaction temperature may be about ⁇ 200 to 200 ° C., preferably ⁇ 50 to 100 ° C.
  • the reaction pressure is about 0.01 to 10 MPa in absolute pressure, and preferably normal pressure to 1 MPa. When the reaction time is long, the residence time is long, and when the pressure is too high, a special pressure device is required, which is not economical.
  • the reaction product liquid is separated into water and an organic layer, and the product is extracted from the aqueous layer as necessary.
  • the homoadamantane derivative of the present invention is obtained by distilling off the solvent from the reaction solution under reduced pressure. You may refine
  • the purification method can be selected from general purification methods such as distillation, extraction washing, crystallization, activated carbon adsorption, and silica gel column chromatography in consideration of the production scale and the required purity. The method by extraction washing or crystallization is preferable because it can be handled at a low temperature and can process a large amount of sample at a time.
  • the (meth) acrylic acid esters of the present invention are represented by the following formula (II).
  • R 1 and R 2 each represent a hydrogen atom or a linear, branched or cyclic hydrocarbon group having 1 to 6 carbon atoms
  • R 3 represents a hydrogen atom, a methyl group or a trifluoromethyl group.
  • n and m are each an integer of 0 to 3, and n and m are not 0 at the same time.
  • the plurality of R 1 may be the same or different
  • m is 2 or more
  • the plurality of R 2 may be the same or different.
  • R 3 in formula (II) is preferably a hydrogen atom or a methyl group.
  • the (meth) acrylic acid ester of the present invention is preferably represented by any of the following formulas (4) to (6).
  • (meth) acrylic acid ester of the present invention represented by the above formula (II) include (5-oxo-4-oxa-5-homoadamantan-1-yl) oxymethyl methacrylate, 1- (5 -Oxo-4-oxa-5-homoadamantan-1-yl) oxyethyl methacrylate, 2- (5-oxo-4-oxa-5-homoadamantan-1-yl) oxy-2-oxoethyl methacrylate, 2- (5-oxo-4-oxa-5-homoadamantan-1-yl) oxy-2-oxo-1-methylethyl methacrylate, 2- (2- (5-oxo-4-oxa-5-homoadamantane-1) -Yl) oxy-2-oxoethoxy) -2-oxoethyl methacrylate, 2- (2- (5-oxo-4-oxa-5-homoadamantan-1-yl)
  • the (meth) acrylic acid ester of the present invention can be produced by various methods and is not particularly limited, but examples thereof include the following methods.
  • the (meth) acrylic acid ester of formula (II) can be obtained by simply esterifying (also referred to as a (meth) acrylic acid derivative).
  • (meth) acrylic acids examples include halogenated (meth) acrylic acids such as acrylic acid, methacrylic acid, 2-fluoroacrylic acid and 2-trifluoromethylacrylic acid.
  • Examples of (meth) acrylic acid halides include acrylic acid fluoride, acrylic acid chloride, acrylic acid bromide, acrylic acid iodide, methacrylic acid fluoride, methacrylic acid chloride, methacrylic acid bromide, methacrylic acid iodide, 2-fluoroacrylic acid fluoride, 2 -Fluoroacrylic acid chloride, 2-fluoroacrylic acid bromide, 2-fluoroacrylic acid iodide, 2-trifluoromethyl acrylic acid fluoride, 2-trifluoromethyl acrylic acid chloride, 2-trifluoromethyl acrylic acid bromide, 2-tri Examples thereof include fluoromethylacrylic acid iodide.
  • (meth) acrylic anhydrides include acrylic anhydride, methacrylic anhydride, 2-fluoroacrylic anhydride, 2-trifluoromethylacrylic anhydride, and the like.
  • Examples of the (meth) acrylic acid 2-hydroxyalkyl include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and the like.
  • Esterification can generate a salt in the system by allowing a base to act on the homoadamantane derivative of formula (I) and the (meth) acrylic acid derivative, but the water generated by the azeotropic dehydration reaction is removed from the system.
  • the reaction can also be promoted by forcibly removing it.
  • Esterification can be carried out in the presence or absence of an organic solvent, but when an organic solvent is used, it is preferable to adjust the substrate concentration to be about 0.1 mol / L to 10 mol / L. .
  • a substrate concentration of 0.1 mol / L or more is economically preferable because a necessary amount can be obtained in a normal reactor, and a substrate concentration of 10 mol / L or less is preferable because the temperature of the reaction solution can be easily controlled.
  • Usable organic solvents include hexane, heptane, cyclohexane, ethylcyclohexane, benzene, toluene, xylene and other hydrocarbon solvents, diethyl ether, dibutyl ether, THF, dioxane, DME and other ether solvents, dichloromethane, carbon tetrachloride.
  • aprotic polar solvents such as DMF, DMSO, NMP, HMPA, HMPT, and carbon disulfide. These may be used alone or in combination of two or more.
  • Bases include sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, silver oxide, sodium phosphate, potassium phosphate, disodium monohydrogen phosphate, dipotassium hydrogen phosphate, Monosodium dihydrogen phosphate, monopotassium dihydrogen phosphate, sodium methoxide, potassium t-butoxide, triethylamine, tributylamine, trioctylamine, pyridine, N, N-dimethylaminopyridine, DBN (1,5-diazabicyclo [4, 3,0] nona-5-ene) and DBU (1,8-diazabicyclo [5,4,0] undec-7-ene) and organic amines are used.
  • the solvent is preferably a hydrocarbon solvent such as cyclohexane, ethylcyclohexane, toluene, xylene.
  • the charging ratio of the reaction reagent to the alicyclic structure-containing alcohol is, for example, about 0.01 to 100 times mol, preferably 1 to 1.5 times mol.
  • the addition amount of the base is, for example, about 0.1 to 10 times mol, desirably 1 to 1.5 times mol, with respect to the alicyclic structure-containing alcohol.
  • the reaction temperature may be about ⁇ 200 to 200 ° C., preferably ⁇ 50 to 100 ° C.
  • the reaction pressure is, for example, about 0.01 to 10 MPa in absolute pressure, and preferably normal pressure to 1 MPa. When the reaction time is long, the residence time is long, and when the pressure is too high, a special pressure device is required, which is not economical.
  • the homoadamantane derivative of the present invention is obtained by distilling off the solvent from the reaction solution under reduced pressure. You may refine
  • the purification method can be selected from general purification methods such as distillation, extraction washing, crystallization, activated carbon adsorption, and silica gel column chromatography in consideration of the production scale and the required purity. The method by extraction washing or crystallization is preferable because it can be handled at a low temperature and can process a large amount of sample at a time.
  • the (meth) acrylic polymer of the present invention is obtained by polymerizing a (meth) acrylic acid ester of the formula (II).
  • the (meth) acrylic polymer of the present invention may be a polymer containing a repeating unit derived from one or more types of (meth) acrylic acid ester of the present invention, and only one (meth) acrylic acid ester is used. It may be a homopolymer, a copolymer using two or more types of (meth) acrylic acid esters, or a copolymer using one or more types of (meth) acrylic acid esters and other polymerizable monomers. It may be a polymer.
  • the (meth) acrylic polymer of the present invention preferably contains 10 to 90 mol%, more preferably 25 to 75 mol% of repeating units derived from the (meth) acrylic acid ester of the formula (II). .
  • the polymerization method is not particularly limited and can be performed by a conventional polymerization method.
  • a known polymerization method such as solution polymerization (boiling point polymerization, polymerization below boiling point), emulsion polymerization, suspension polymerization, bulk polymerization, or the like may be used. It can. The smaller the amount of the high-boiling unreacted monomer remaining in the reaction liquid after polymerization, the better. It is preferable to perform an operation for removing the unreacted monomer as needed during the polymerization or after the completion of the polymerization.
  • a polymerization reaction using a radical polymerization initiator in a solvent is preferable.
  • a peroxide type polymerization initiator, an azo type polymerization initiator, etc. are used.
  • Peroxide polymerization initiators include organic peroxides such as peroxycarbonate, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, and peroxyester (lauroyl peroxide, benzoyl peroxide). Is mentioned.
  • Examples of the azo polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvalero). Nitrile) and azo compounds such as dimethyl 2,2′-azobisisobutyrate.
  • one or more polymerization initiators can be appropriately used depending on the reaction conditions such as the polymerization temperature.
  • Various methods can be adopted as a method for removing the used (meth) acrylic acid ester and other copolymerization monomers from the produced polymer after completion of the polymerization.
  • a method of washing the acrylic polymer using a poor solvent for the polymer is preferred.
  • the poor solvents for the acrylic polymer those having a low boiling point are preferable, and representative examples thereof include methanol, ethanol, n-hexane, and n-heptane.
  • the (meth) acrylic acid ester of the formula (II) can be obtained from the homoadamantane derivative of the formula (I), and the (meth) acrylic acid ester of the formula (II) is further polymerized ((meta) ) An acrylic polymer can be obtained.
  • the (meth) acrylic polymer of the present invention can be used as a positive photoresist. That is, from a highly reactive homoadamantane derivative of the formula (I), a homoadamantane skeleton can be introduced into a PAG, a low molecular weight positive photoresist or a positive photoresist monomer, and further into a positive photoresist polymer. .
  • the carbon-carbon double bond contained in the (meth) acrylic acid ester of the formula (II) increases the polymerization rate.
  • the polymer of the present invention when it has an acetal bond, it becomes acid-decomposable.
  • a group is bonded to the homoadamantane skeleton through an acetal bond, and this is used for a photoresist, the bond on the side opposite to the homoadamantane side of the oxygen atom is broken by an acid, and the broken group becomes an alkali. It is expected that the roughness will be reduced.
  • the (meth) acrylic polymer of the present invention introduces an adamantane skeleton and a lactone skeleton, which have been introduced from separate monomers, from the same monomer having these simultaneously, so that a (meth) acrylic polymer (photoresist It is considered that the dispersion of these skeletons in the resin) becomes more uniform, leading to a reduction in roughness.
  • the resin composition containing the (meth) acrylic polymer of the present invention has various uses such as circuit forming materials (resist for semiconductor production, printed wiring boards, etc.), image forming materials (printing plate materials, relief images, etc.). In particular, it is preferably used as a resin composition for a photoresist, and more preferably used as a resin composition for a positive photoresist.
  • the positive photoresist composition of the present invention is not particularly limited as long as it contains the (meth) acrylic polymer of the present invention and a photoacid generator, but 100% by mass of the positive photoresist composition of the present invention.
  • those containing 2 to 50% by mass of the (meth) acrylic polymer of the present invention are preferred, and those containing 5 to 15% by mass are more preferred.
  • the positive photoresist composition of the present invention includes quenchers such as organic amines, alkali-soluble resins (for example, novolak resins, phenol resins, imides). Resins, carboxyl group-containing resins, etc.) alkali-soluble components, colorants (for example, dyes), organic solvents (for example, hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, ethers) , Cellosolves, carbitols, glycol ether esters, mixed solvents thereof, and the like) can be added.
  • quenchers such as organic amines, alkali-soluble resins (for example, novolak resins, phenol resins, imides). Resins, carboxyl group-containing resins, etc.) alkali-soluble components, colorants (for example, dyes), organic solvents (for example, hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, ethers) , Cellosolves,
  • Examples of the photoacid generator include conventional compounds that efficiently generate an acid upon exposure.
  • a diazonium salt for example, diphenyliodohexafluorophosphate
  • a sulfonium salt for example, triphenylsulfonium hexafluoroantimony
  • sulfonate esters for example, 1-phenyl-1- (4-methylphenyl) sulfonyloxy-1-benzoylmethane, 1,2,3-tri Sulfonyloxymethylbenzene, 1,3-dinitro-2- (4-phenylsulfonyloxymethyl) benzene, 1-phenyl-1- (4-methylphenylsulfonyloxymethyl) -1-hydroxy-1-benzoy Methane), oxathiazole derivatives, s- triazine derivatives, disulfone derivatives (diphenyl sulfone) imide compound, an oxime sulfonate, a diazonaphthoquinone, and benzoin preparative rate and the like.
  • photoacid generators can be used alone or in combination of
  • the content of the photoacid generator in the positive photoresist composition of the present invention is the strength of the acid generated by light irradiation, the monomer units based on (meth) acrylic acid esters of (meth) acrylic polymers. It can select suitably according to content etc.
  • the content of the photoacid generator is preferably 0.1 to 30 parts by mass, more preferably 1 to 25 parts by mass, and further preferably 2 to 20 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer. is there.
  • the positive photoresist composition of the present invention is prepared by mixing a (meth) acrylic polymer, a photoacid generator and, if necessary, the organic solvent, etc., and, if necessary, separating impurities by a conventional solid separation such as a filter. It can be prepared by removing by means.
  • the positive photoresist composition is applied onto a substrate or substrate, dried, and then exposed to light (or further post-exposure baked) to expose the coating film (resist film) through a predetermined mask. By forming an image pattern and then developing it, a fine pattern can be formed with high accuracy.
  • the present invention also includes a step of forming a resist film on a support using the positive photoresist composition, a step of selectively exposing the resist film, and subjecting the selectively exposed resist film to an alkali development treatment. And a resist pattern forming method including a step of forming a resist pattern.
  • the step of forming a resist film using a positive resist composition can be performed using a conventional coating means such as a spin coater, a dip coater, or a roller coater.
  • the thickness of the resist film is preferably 50 nm to 20 ⁇ m, more preferably 100 nm to 2 ⁇ m.
  • light beams having various wavelengths such as ultraviolet rays and X-rays
  • various wavelengths such as ultraviolet rays and X-rays
  • semiconductor resists usually g-line, i-line, excimer laser (for example, XeCl, KrF, KrCl, ArF). , ArCl, etc.), soft X-rays, etc. are used.
  • the exposure energy is, for example, about 0.1 to 1000 mJ / cm 2 , preferably about 1 to 100 mJ / cm 2 .
  • the (meth) acrylic polymer contained in the positive resist composition of the present invention preferably has an acetal structure and has an acid-decomposable function.
  • an acid is generated from the photoacid generator by the selective exposure, and the cyclic portion of the structural unit based on the (meth) acrylic ester in the (meth) acrylic polymer is rapidly detached by this acid, Carboxyl groups and hydroxyl groups that contribute to solubilization are generated. Therefore, a predetermined pattern can be formed with high accuracy by performing development using an alkali developer.
  • 5-oxo-4-oxa-5-homoadamantan-1-ol is obtained by the method described in the literature (J. Org. Chem., 48, 1099-1101 (1983)) using 2-adamantanone as a raw material.
  • Oxo-1-adamantanol was synthesized and further synthesized by reaction with formic acid consisting of formic acid and hydrogen peroxide.
  • 5-Oxo-4-oxa-5-homoadamantan-2-ol is obtained from 2-adamantanone as a starting material by the method described in the literature (J. Am. Chem. Soc., 108, 15, 4484 (1986)).
  • Bicyclo [3.3.1] non-6-ene-3-carboxylic acid was synthesized and further synthesized by reaction with formic acid consisting of formic acid and hydrogen peroxide.
  • Example 1 Synthesis of homoadamantane derivative: (5-oxo-4-oxa-5-homoadamantan-1-yl) oxymethyl chloride Into a 1 L flask was added 54.7 g of 5-oxo-4-oxa-5-homoadamantan-1-ol. (300 mmol), 400 mL (5.6 mol) of dimethyl sulfoxide (DMSO) and 200 mL (2.1 mol) of acetic anhydride were added, and the mixture was stirred for 3 days, followed by gas chromatographic analysis. As a result, 5-oxo-4-oxa-5- It was confirmed that homoadamantan-1-ol was completely converted to a methylthiomethyl ether form.
  • DMSO dimethyl sulfoxide
  • Example 4 Synthesis of homodamantane derivative: 2- (5-oxo-4-oxa-5-homoadamantan-2-yl) oxy-2-oxoethyl chloride
  • Example 3 5-oxo-4-oxa-5-homoadamantane
  • the target 2- (5- 37.0 g (143 mmol, isolated yield 71.5%, GC purity 98.0%) of oxo-4-oxa-5-homoadamantan-2-yl) oxy-2-oxoethyl chloride was isolated.
  • Each data of GC-MS, 1 H-NMR and 13 C-NMR is shown below.
  • Example 5 Synthesis of homodamantane derivative: 2- (5-oxo-4-oxa-5-homoadamantan-1-yl) oxy-2-oxoethyl chloride 5-oxo-4-oxa-5-homoadamantane-1 in a 1 L flask -36.4 g (200 mmol) of all, 1.9 g (10 mmol) of paratoluenesulfonic acid monohydrate and 28.3 g (300 mmol) of chloroacetic acid were added and dissolved in 500 mL of toluene. The temperature was raised until toluene was boiled, and then stirring was continued for 8 hours. Then, 100 mL of water was added to stop the reaction.
  • Example 6 Synthesis of homodamantane derivative: 2- (5-oxo-4-oxa-5-homoadamantan-2-yl) oxy-2-oxoethyl chloride
  • 5-oxo-4-oxa-5-homoadamantane As a result of conducting in the same manner as in Example 5 except that 5-oxo-4-oxa-5-homoadamantan-2-ol was used instead of -1-ol, the target 2- (5-oxo-4- 49.1 g (190 mmol, isolated yield 94.9%, GC purity 98.0%) of oxa-5-homoadamantan-2-yl) oxy-2-oxoethyl chloride was isolated. Each data of GC-MS, 1 H-NMR and 13 C-NMR is shown below.
  • Example 8 Synthesis of homodamantane derivative: 2- (2- (5-oxo-4-oxa-5-homoadamantan-2-yl) oxy-2-oxoethoxy) -2-oxoethanol
  • 2- (5-oxo-4-oxa-5) synthesized in Example 4 instead of the synthesized 2- (5-oxo-4-oxa-5-homoadamantan-1-yl) oxy-2-oxoethyl chloride
  • the target 2- (2- (5-oxo-4-oxa) -5-Homoadamantan-2-yl) oxy-2-oxoethoxy) -2-oxoethanol 11.3 g (37.9 mmol, isolated yield 75.8%, GC purity 99.0%) was isolated. It was.
  • Example 9 Synthesis of homodamantane derivative: 2- (5-oxo-4-oxa-5-homoadamantan-1-yl) oxymethoxy-2-oxoethyl chloride synthesized in Example 1 in a 100 mL flask (5-oxo-4- 11.5 g (50 mmol) of oxa-5-homoadamantan-1-yl) oxymethyl chloride was added and dissolved by adding 50 mL of tetrahydrofuran, and stirring was started by adding 9.1 mL (65 mmol) of triethylamine.
  • Example 10 Synthesis of homoadamantane derivative: 2- (5-oxo-4-oxa-5-homoadamantan-2-yl) oxymethoxy-2-oxoethyl chloride
  • Example 9 the compound (5-oxo- (5-oxo-4-oxa-5-homoadamantan-2-yl) oxymethyl chloride synthesized in Example 2 was used instead of 4-oxa-5-homoadamantan-1-yl) oxymethyl chloride
  • 12.3 g of the target 2- (5-oxo-4-oxa-5-homoadamantan-2-yl) oxymethoxy-2-oxoethyl chloride represented by the following formula ( 43 mmol, isolated yield 85.0%, GC purity 95.8%).
  • Each data of GC-MS, 1 H-NMR and 13 C-NMR is shown below.
  • Example 11 Synthesis of (meth) acrylic acid ester: (5-oxo-4-oxa-5-homoadamantan-1-yl) oxymethyl methacrylate
  • 4.7 g (55 mmol) of methacrylic acid was used instead of chloroacetic acid
  • 13.5 g (48 mmol, isolated yield) of the target (5-oxo-4-oxa-5-homoadamantan-1-yl) oxymethyl methacrylate of the following formula 96.3% rate, GC purity 97.8%) was isolated.
  • Each data of GC-MS, 1 H-NMR and 13 C-NMR is shown below.
  • Example 12 Synthesis of (meth) acrylic acid ester: (5-oxo-4-oxa-5-homoadamantan-2-yl) oxymethyl methacrylate
  • Example 11 (5-oxo-4-oxa-) synthesized in Example 1 Example except that (5-oxo-4-oxa-5-homoadamantan-2-yl) oxymethyl chloride synthesized in Example 2 was used instead of 5-homoadamantan-1-yl) oxymethyl chloride
  • GC purity 98.2% Each data of GC-MS, 1 H-NMR and 13 C-NMR is shown below.
  • Example 14 Synthesis of (meth) acrylic acid ester: 2- (5-oxo-4-oxa-5-homoadamantan-2-yl) oxy-2-oxoethyl methacrylate
  • the target 2- (5-oxo-4-oxa-5-homoadamantane-2- Yl) oxy-2-oxoethyl methacrylate (7.8 g, 25.3 mmol, isolated yield 84.3%, GC purity 96.9%) was isolated.
  • Example 15 Synthesis of (meth) acrylic acid ester: 2- (2- (5-oxo-4-oxa-5-homoadamantan-1-yl) oxy-2-oxoethoxy) -2-oxoethyl methacrylate
  • 2- instead of 2- (5-oxo-4-oxa-5-homoadamantan-1-yl) oxy-2-oxoethyl chloride synthesized in Example 3, 2- (2- (5- (5- As a result of carrying out in the same manner as in Example 13 except that oxo-4-oxa-5-homoadamantan-1-yl) oxy-2-oxoethoxy) -2-oxoethanol was used.
  • Example 16 Synthesis of (meth) acrylic acid ester: 2- (2- (5-oxo-4-oxa-5-homoadamantan-2-yl) oxy-2-oxoethoxy) -2-oxoethyl methacrylate
  • 2- instead of 2- (5-oxo-4-oxa-5-homoadamantan-1-yl) oxy-2-oxoethyl chloride synthesized in Example 3, 2- (2- (5- (5- (5- The same procedure as in Example 13 was conducted except that oxo-4-oxa-5-homoadamantan-2-yl) oxy-2-oxoethoxy) -2-oxoethanol was used.
  • Example 17 Synthesis of (meth) acrylic acid ester: 2- (5-oxo-4-oxa-5-homoadamantan-1-yl) oxymethoxy-2-oxoethyl methacrylate
  • 2- 2- (5-oxo-4-oxa-5-homoadamantane-1-synthesized in Example 9 instead of (5-oxo-4-oxa-5-homoadamantan-1-yl) oxy-2-oxoethyl chloride
  • the target 2- (5-oxo-4-oxa-5-homoadamantane- 1-yl) oxymethoxy-2-oxoethyl methacrylate 7.2 g (21.3 mmol, isolated yield 70.9%, GC purity 95.3%) was isolated.
  • Example 18 Synthesis of (meth) acrylic acid ester: 2- (5-oxo-4-oxa-5-homoadamantan-2-yl) oxymethoxy-2-oxoethyl methacrylate
  • 2- 2- (5-Oxo-4-oxa-5-homoadamantane-) synthesized in Example 10 instead of (5-oxo-4-oxa-5-homoadamantan-1-yl) oxy-2-oxoethyl chloride
  • the target 2- (5-oxo-4-oxa-5-homoadamantane- 7.6 g (22.5 mmol, isolated yield 74.9%, GC purity 95.0%) of 2-yl) oxymethoxy-2-oxoethyl methacrylate was isolated.
  • Examples 27-34 Preparation of Positive Resist Composition 5 parts by weight of triphenylsulfonium nonafluorobutanesulfonate was added as a photoacid generator to 100 parts by weight of each of the copolymers P1 to P8 obtained in Examples 19 to 26. 90 parts by mass of propylene glycol monomethyl ether acetate was dissolved in 10 parts by mass of the resin composition to prepare resist compositions R1 to R8. The prepared resist compositions R1 to R8 were applied onto a silicon wafer and baked at 110 ° C. for 60 seconds to form a resist film. The wafer thus obtained was open-exposed with light having a wavelength of 248 nm at an exposure amount of 100 mJ / cm 2 .
  • the film was heated at 110 ° C. for 60 seconds, and then developed with an aqueous tetramethylammonium hydroxide solution (2.38% by mass) for 60 seconds.
  • Table 2 shows whether or not the resist film decreased at this time. A circle indicates that the resist film is completely removed.
  • any composition containing the (meth) acrylic polymer of the present invention functions as a positive photoresist composition.
  • the (meth) acrylic acid ester of the present invention has a high polymerization rate.
  • the resin composition containing the (meth) acrylic polymer of the present invention can be used for circuit forming materials (resist for semiconductor production, printed wiring boards, etc.), image forming materials (printing plate materials, relief images, etc.), etc. It can be used as a positive photoresist resin composition.

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JP6864994B2 (ja) 2015-06-26 2021-04-28 住友化学株式会社 レジスト組成物
JP6670694B2 (ja) * 2015-07-14 2020-03-25 住友化学株式会社 レジスト組成物及びレジストパターン製造方法
JP6960308B2 (ja) * 2016-12-01 2021-11-05 住友化学株式会社 レジスト組成物及びレジストパターンの製造方法
US11414373B2 (en) 2017-01-20 2022-08-16 Evonik Operations Gmbh Glycerol (meth)acrylate carboxylic ester having a long shelf life
JP7040280B2 (ja) * 2017-06-13 2022-03-23 住友化学株式会社 化合物、樹脂、レジスト組成物及びレジストパターンの製造方法
JP6780602B2 (ja) 2017-07-31 2020-11-04 信越化学工業株式会社 レジスト組成物及びパターン形成方法
EP3611155A1 (en) 2018-08-16 2020-02-19 Evonik Operations GmbH Preparation of (meth)acrylic acid esters

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000122294A (ja) * 1998-08-10 2000-04-28 Toshiba Corp 感光性組成物及びパタ―ン形成方法
JP2003005375A (ja) * 2001-06-21 2003-01-08 Fuji Photo Film Co Ltd ポジ型レジスト組成物
WO2005108343A1 (ja) * 2004-05-10 2005-11-17 Idemitsu Kosan Co., Ltd. アダマンタン誘導体、その製造方法及びフォトレジスト用感光材料
WO2005111097A1 (ja) * 2004-05-18 2005-11-24 Idemitsu Kosan Co., Ltd. アダマンタン誘導体、その製造方法及びフォトレジスト用感光材料
JP2009223300A (ja) * 2008-02-22 2009-10-01 Tokyo Ohka Kogyo Co Ltd ポジ型レジスト組成物、レジストパターン形成方法および高分子化合物
JP2009280538A (ja) * 2008-05-23 2009-12-03 Idemitsu Kosan Co Ltd 脂環構造含有化合物、（メタ）アクリル酸エステル類、（メタ）アクリル系重合体並びにそれを含むポジ型レジスト組成物

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1179750B1 (en) * 2000-08-08 2012-07-25 FUJIFILM Corporation Positive photosensitive composition and method for producing a precision integrated circuit element using the same
WO2005085301A1 (ja) * 2004-03-08 2005-09-15 Mitsubishi Rayon Co., Ltd. レジスト用重合体、レジスト組成物、およびパターン製造方法、並びにレジスト用重合体用原料化合物
US20050282985A1 (en) * 2004-06-17 2005-12-22 Hiroshi Koyama Fluorine-atom-containing polymerizable unsaturated-monomer, fluorine-atom-containing polymeric compound and photoresist resin composition
TWI400571B (zh) * 2006-03-14 2013-07-01 Fujifilm Corp 正型光阻組成物及使用它之圖案形成方法
EP1975705B1 (en) * 2007-03-28 2016-04-27 FUJIFILM Corporation Positive resist composition and pattern-forming method
JP4671065B2 (ja) * 2008-09-05 2011-04-13 信越化学工業株式会社 ダブルパターン形成方法
JP5629454B2 (ja) * 2008-12-12 2014-11-19 富士フイルム株式会社 重合性化合物、ラクトン含有化合物、ラクトン含有化合物の製造方法、及び、該重合性化合物を重合させた高分子化合物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000122294A (ja) * 1998-08-10 2000-04-28 Toshiba Corp 感光性組成物及びパタ―ン形成方法
JP2003005375A (ja) * 2001-06-21 2003-01-08 Fuji Photo Film Co Ltd ポジ型レジスト組成物
WO2005108343A1 (ja) * 2004-05-10 2005-11-17 Idemitsu Kosan Co., Ltd. アダマンタン誘導体、その製造方法及びフォトレジスト用感光材料
WO2005111097A1 (ja) * 2004-05-18 2005-11-24 Idemitsu Kosan Co., Ltd. アダマンタン誘導体、その製造方法及びフォトレジスト用感光材料
JP2009223300A (ja) * 2008-02-22 2009-10-01 Tokyo Ohka Kogyo Co Ltd ポジ型レジスト組成物、レジストパターン形成方法および高分子化合物
JP2009280538A (ja) * 2008-05-23 2009-12-03 Idemitsu Kosan Co Ltd 脂環構造含有化合物、（メタ）アクリル酸エステル類、（メタ）アクリル系重合体並びにそれを含むポジ型レジスト組成物

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013257537A (ja) * 2012-05-14 2013-12-26 Sumitomo Chemical Co Ltd レジスト組成物及びレジストパターンの製造方法
JP2013257539A (ja) * 2012-05-15 2013-12-26 Sumitomo Chemical Co Ltd レジスト組成物及びレジストパターンの製造方法
JP2014142424A (ja) * 2013-01-22 2014-08-07 Tokyo Ohka Kogyo Co Ltd レジストパターン形成方法

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