Classifications

• • 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
• • 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
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
  • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
  • G03F7/0295—Photolytic halogen compounds
• • 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
  • C08F220/00—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
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1807—C7-(meth)acrylate, e.g. heptyl (meth)acrylate or benzyl (meth)acrylate
• • 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
  • C08F220/00—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
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
• • 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
  • C08F220/00—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
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/22—Esters containing halogen
  • C08F220/24—Esters containing halogen containing perhaloalkyl radicals
• • 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
  • C08F220/00—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
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
  • C08F220/282—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing two or more oxygen atoms
• • 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
  • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
• • 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
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
• • 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
• • 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
  • G03F7/20—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

Definitions

• the present invention relates to a sensitive light-sensitive or radiation-sensitive resin composition, a pattern forming method, a resist film, and a method for manufacturing an electronic device.
• Patent Document 1 discloses a resist composition containing the following compound.
• a salt containing a sulfonium cation having an aryl group substituted with an acid-degradable group-containing group and having at least three fluorine atoms Includes a resin that decomposes and increases in polarity due to the action of acid.
• the acid-degradable group-containing group contains a group that is decomposed by the action of an acid to increase its polarity.
• the acid-degradable group-containing group is a fluorine atom-free, actinic cheilitis or radiation-sensitive resin composition.
• the process of exposing the resist film and A pattern forming method comprising a step of developing the exposed resist film using a developing solution to form a pattern.
• a sensitive light-sensitive or radiation-sensitive resin composition capable of obtaining a pattern having excellent LWR performance. Further, according to the present invention, it is possible to provide a resist film, a pattern forming method, and a method for manufacturing an electronic device regarding the above-mentioned sensitive light-sensitive or radiation-sensitive resin composition.
• the numerical range represented by using "-" in the present specification means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
• the notation that does not describe substitution or non-substitution includes a group having a substituent as well as a group having no substituent.
• the "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
• the substituent is preferably a monovalent substituent.
• the term "organic group” refers to a group containing at least one carbon atom.
• examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• the bonding direction of the divalent group described in the present specification is not limited unless otherwise specified.
• Y when Y is -COO- in the compound represented by the general formula "XYZ", Y may be -CO-O-, and is -O-CO-. You may. Moreover, the said compound may be "X-CO-O-Z" or "X-O-CO-Z".
• (meth) acrylic is a general term including acrylic and methacryl, and means “at least one of acrylic and methacrylic”.
• (meth) acrylic acid means “at least one of acrylic acid and methacrylic acid”.
• the term “active light” or “radiation” refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X rays, and electron beams (EUV light).
• EUV light Extreme Ultraviolet
• X rays extreme ultraviolet rays
• EUV light extreme ultraviolet rays
• EB Electron Beam
• the term “light” means active light or radiation.
• exposure refers to not only the emission line spectrum of a mercury lamp, exposure to far ultraviolet rays represented by an excimer laser (ArF excimer laser, etc.), X-rays, and exposure to EUV light, etc. It also includes drawing with electron beams and particle beams such as ion beams.
• the weight average molecular weight (Mw), the number average molecular weight (Mn), and the degree of dispersion (hereinafter, also referred to as “molecular weight distribution”) (Mw / Mn) of the resin are referred to as GPC (Gel Permeation Chromatography) apparatus.
• 1 ⁇ is 1 x 10-10 m.
• the acid dissociation constant (pKa) represents pKa in an aqueous solution, and specifically, using the following software package 1, a value based on a database of Hammett's substituent constants and known literature values is used. , It is a value obtained by calculation. All pKa values described herein indicate values calculated using this software package.
• pKa can also be obtained by the molecular orbital calculation method.
• a specific method for this there is a method of calculating H + dissociation free energy in a solvent based on a thermodynamic cycle.
• water is usually used as the solvent, and DMSO (dimethyl sulfoxide) is used when pKa cannot be obtained with water.
• the calculation method of H + dissociation free energy can be calculated by, for example, DFT (density functional theory), but various other methods have been reported in the literature and are not limited thereto.
• DFT density functional theory
• There are a plurality of software capable of performing DFT and examples thereof include Gaussian16.
• pKa in the present specification refers to a value obtained by calculating a value based on a database of Hammett's substituent constants and known literature values using software package 1, and pKa is calculated by this method. If it cannot be calculated, the value obtained by Gaussian 16 based on DFT (Density Functional Theory) shall be adopted.
• DFT Density Functional Theory
• the actinic or radiation-sensitive resin composition of the present invention (hereinafter, also referred to as “resist composition”) will be described.
• the resist composition of the present invention may be a positive type resist composition or a negative type resist composition. Further, it may be a resist composition for alkaline development or a resist composition for organic solvent development.
• the composition of the present invention is typically a chemically amplified resist composition.
• the resist composition of the present invention comprises a salt containing a sulfonium cation having an aryl group substituted with an acid-degradable group-containing group and having at least three fluorine atoms (hereinafter, also referred to as "specific compound”).
• a resin whose polarity is increased by decomposition due to the action of an acid (hereinafter, also simply referred to as "acid-decomposable resin") is included.
• the acid-degradable group-containing group contains a group whose polarity is increased by decomposition by the action of an acid (hereinafter, also simply referred to as "acid-degradable group”), and the acid-degradable group-containing group is fluorine. Does not contain atoms.
• the specific compound is a salt containing a predetermined sulfonium cation and usually acts as a photoacid generator.
• the sulfonium cation has an acid-decomposable group and a predetermined number of fluorine atoms, and such a specific compound has excellent decomposition efficiency at the time of exposure and is compatible with an acid-decomposable resin. Since the compatibility is also excellent, the LWR performance of the formed pattern is good.
• the acid-decomposable groups of the sulfonium cation are decomposed to generate polar groups together with the polar groups generated from the acid-degradable resin, thereby improving the solubility of the exposed part in the alkaline developer and the organic solvent developer. A decrease in the solution is observed, and the LWR tends to improve in both the positive type and the negative type.
• obtaining a pattern having excellent LWR performance is also referred to as excellent effect of the present invention.
• the resist composition of the present invention contains a specific compound.
• the specific compound usually acts as a photoacid generator.
• the photoacid generator is a compound that generates an acid by irradiation (exposure) with active light or radiation (preferably EUV light or ArF).
• the photoacid generator is preferably in the form of a low molecular weight compound.
• the molecular weight is preferably 3000 or less, more preferably 2000 or less, still more preferably 1200 or less.
• the specific compound is preferably a compound that generates an organic acid upon exposure.
• organic acid examples include sulfonic acid (aliphatic sulfonic acid, aromatic sulfonic acid, camphor sulfonic acid, etc.), carboxylic acid (aliphatic carboxylic acid, aromatic carboxylic acid, aralkylcarboxylic acid, etc.), and carbonyl.
• sulfonic acid aliphatic sulfonic acid, aromatic sulfonic acid, camphor sulfonic acid, etc.
• carboxylic acid aliphatic carboxylic acid, aromatic carboxylic acid, aralkylcarboxylic acid, etc.
• carbonyl examples thereof include sulfonylimide acid, bis (alkylsulfonyl) imide acid, and tris (alkylsulfonyl) methidoic acid.
• volume of the acid generated from a specific compound to suppress the diffusion of the non-exposed portion of the acid generated by exposure, from the viewpoint of improving the resolution, 240 ⁇ 3 or more are preferred, 305 ⁇ 3 or higher More preferably, 350 ⁇ 3 or more is further preferable, and 400 ⁇ 3 or more is particularly preferable.
• the volume of the acid generated from the specific compound is preferably 1500 ⁇ 3 or less, 1000 ⁇ 3, more preferably less, 700 ⁇ 3 or less is more preferable. The above volume value is obtained using "WinMOPAC" manufactured by Fujitsu Limited.
• volume value In calculating the volume value, first, the chemical structure of the acid according to each example is input, and then each acid is calculated by molecular mechanics using the MM (Molecular Mechanics) 3 method with this structure as the initial structure. The most stable conformation of each acid can be determined, and then the molecular orbital calculation of these most stable conformations using the PM (Parameterized Model number) 3 method can be performed to calculate the "accessible volume" of each acid.
• MM Molecular Mechanics
• the structure of the acid generated from the specific compound is not particularly limited, but the interaction between the acid generated from the specific compound and the acid-degradable resin described later is in that the diffusion of the acid is suppressed and the resolution is improved. Is preferable.
• the acid generated by the photoacid generator is an organic acid
• the organic acid is a sulfonic acid group, a carboxylic acid group, a carbonylsulfonylimide acid group, a bissulfonylimide acid group, and a trissulfonylmethi. It is preferable to have a polar group in addition to an organic acid group such as a doric acid group.
• Examples of the polar group include an ether group, an ester group, an amide group, an acyl group, a sulfo group, a sulfonyloxy group, a sulfonamide group, a thioether group, a thioester group, a urea group, a carbonate group, a carbamate group, a hydroxyl group, and a mercapto.
• the number of polar groups contained in the generated acid is not particularly limited, and is preferably 1 or more, and more preferably 2 or more. However, the number of polar groups is preferably less than 6 and more preferably less than 4 from the viewpoint of suppressing excessive development.
• the specific compound contains a sulfonium cation having an aryl group substituted with an acid-degradable group-containing group and having at least three fluorine atoms (hereinafter, also simply referred to as “specific cation”).
• the acid-degradable group-containing group contains an acid-degradable group, and the acid-degradable group-containing group does not contain a fluorine atom. That is, the sulfonium cation contained in the specific compound contains an acid-decomposable group containing no fluorine atom and has at least three fluorine atoms.
• the sulfonium cation contained in the specific compound has an aryl group substituted with an acid-degradable group-containing group containing no fluorine atom, and at least three fluorine atoms.
• Preferred sulfonium cations have an aryl group substituted with an acid-degradable group-containing group that does not contain a fluorine atom and an aryl group that has at least 3 fluorine atoms or is substituted with at least 3 fluorine atoms.
• the sulfonium cation may have an aryl group substituted with an acid-degradable group-containing group, and may have a linear or branched alkyl group or a substituent. It may further have an aryl group which may be used.
• the alkyl group may have a cyclic structure.
• the aryl group may be monocyclic or polycyclic. Examples of the substituent contained in the alkyl group and the aryl group include a halogen atom (for example, a fluorine atom and an iodine atom), an alkyl group which may have a halogen atom, a halogen atom and a polar group (for example).
• the above-mentioned substituent is selected from the group consisting of a fluorine atom, an iodine atom, an unsubstituted alkyl group, a fluoroalkyl group, a fluoroalcohol group, and a fluoroalkoxy group because the effect of the present invention is more excellent. At least one is preferable, and at least one selected from the group consisting of a fluorine atom and a fluoroalkyl group is more preferable.
• fluoroalkyl group examples include fluoroalkyl groups that can be contained in the compound represented by the general formula (S-1). The definition of the fluoroalcohol group will be described in detail later.
• a group represented by * -C (Ry) 2 (OH) is preferable.
• Ry represents a fluoroalkyl group.
• the alkyl group, alkoxy group, and fluoroalkyl group preferably have 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 5 carbon atoms.
• the sulfonium cation examples include a triarylsulfonium cation, a diarylalkylsulfonium cation, an aryldialkylsulfonium cation, a diallylcycloalkylsulfonium cation, and an aryldicycloalkylsulfonium cation.
• the triarylsulfonium cation is preferable as the sulfonium cation because the effect of the present invention is more excellent.
• the sulfonium cation contains an aryl group substituted with at least one selected from the group consisting of a fluorine atom and a fluoroalkyl group.
• the sulfonium cation in the specific compound has an aryl group substituted with an acid-degradable group-containing group.
• the aryl group may be monocyclic or polycyclic. Of these, a single ring is preferable.
• the acid-degradable group-containing group includes an acid-degradable group. The acid-degradable group will be described in detail later.
• the number of acid-degradable groups in the acid-degradable-containing group is not particularly limited and may be 1 or more.
• the upper limit is not particularly limited, but in many cases it is 2 or less. Further, the acid-degradable group-containing group does not contain a fluorine atom.
• the acid-degradable group-containing group does not contain a fluorine atom.
• the aryl group substituted with the acid-degradable group-containing group may further have a substituent in addition to the acid-degradable group-containing group. That is, the aromatic hydrocarbon ring in the aryl group may further have a substituent other than the acid-degradable group-containing group.
• the type of the substituent is not particularly limited, and has a halogen atom (for example, a fluorine atom and an iodine atom), an alkyl group which may have a halogen atom, a halogen atom and a polar group (for example, an alcohol group).
• Examples thereof include an alkyl group which may have an alkyl group, an alkoxy group which may have a halogen atom, and an aryl group which may have a halogen atom. That is, the aryl group substituted with the acid-degradable group-containing group may be further substituted with a group containing a halogen atom such as a fluorine atom as a substituent. Further, examples of the above-mentioned substituent include an alkyl group which can be possessed by the above-mentioned sulfonium cation and a substituent possessed by an aryl group.
• the group represented by the general formula (T-1) is preferable.
• the moieties represented by -L T1 -R T1 is, corresponds to the acid-decomposable group-containing group.
• Ar T1 represents an aromatic hydrocarbon ring group which may have a substituent.
• aromatic hydrocarbon ring group represented by Ar T1 include aromatic hydrocarbon ring groups represented by Ar S1 to Ar S3 , which will be described later.
• LT1 represents a single bond or a divalent linking group which may have a substituent containing no fluorine atom.
• the divalent linking group represented by L T1 for example, -O -, - OC -, - CO -, - COO -, - OCO -, - S -, - CS -, - SO -, - SO 2- ,
• a hydrocarbon group which may have a substituent containing no fluorine atom for example, an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, etc.
• a linking group in which a plurality of these are linked for example, an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, etc.
• L T1 unsubstituted hydrocarbon group, or a linking group a plurality of these linked, or, preferably a single bond.
• substituent include a nitro group, a carboxyl group, a hydroxyl group, an amino group, and a cyano group.
• RT1 represents an acid degradable group.
• the acid-degradable group does not contain a fluorine atom.
• An acid-degradable group is a group that is decomposed by the action of an acid to form a polar group.
• the acid-degradable group preferably has a structure in which the polar group is protected by a leaving group that is eliminated by the action of an acid. That is, the salt containing the sulfonium cation of the present invention has a group which is decomposed by the action of an acid to form a polar group.
• the action of the acid increases the polarity, increases the solubility in an alkaline developer, and decreases the solubility in an organic solvent.
• an alkali-soluble group is preferable, and for example, a carboxyl group, a hydroxyl group, a phenolic hydroxyl group, a sulfonic acid group, a phosphoric acid group, a sulfonamide group, a sulfonylimide group, a (alkylsulfonyl) (alkylcarbonyl) methylene group, (Alkylsulfonyl) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group , And acidic groups such as tris (alkylsulfonyl) methylene group.
• the polar group at least one selected from the group consisting of a carboxyl group, a hydroxyl group, a phenolic hydroxyl group, and a sulfonic acid group is preferable, and a carboxyl group, a hydroxyl group, or a phenolic hydroxyl group is more preferable. ..
• Examples of the leaving group that are eliminated by the action of an acid include groups represented by the general formulas (S1) to (S3).
• General formula (S1) -C (Rx S1 ) (Rx S2 ) (Rx S3 )
• General formula (S2): -C ( O) OC (Rx S1 ) (Rx S2 ) (Rx S3 )
• Rx S1 to Rx S3 independently have a linear or branched alkyl group which may have a substituent containing no fluorine atom, or fluorine.
• Rx S1 to Rx S3 are linear or branched alkyl groups which may have a substituent containing no fluorine atom, at least two of Rx S1 to Rx S3 are It is preferably a methyl group or an ethyl group.
• Rx S1 to Rx S3 each independently preferably represent a linear or branched alkyl group which may have a substituent containing no fluorine atom, and Rx S1 to Rx S3 It is more preferable to independently represent a linear alkyl group which may have a substituent containing no fluorine atom. Two of Rx S1 to Rx S3 may be combined to form a monocyclic or polycyclic ring.
• Alkyl groups of Rx S1 to Rx S3 include tert-butyl group, tert-peptyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and the like having 1 to 1 carbon atoms.
• An alkyl group of 10 is preferred.
• Examples of the cycloalkyl group of Rx 1 to Rx 3 include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, and a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group and the like.
• the polycyclic cycloalkyl group of is preferred.
• a cycloalkyl group is preferable as the ring formed by combining two of Rx S1 to Rx S3.
• the cycloalkyl group formed by combining two of Rx S1 to Rx S3 is a cyclopentyl group, a monocyclic cycloalkyl group such as a cyclohexyl group, or a norbornyl group, a tetracyclodecanyl group, or a tetracyclododeca.
• a polycyclic cycloalkyl group such as an nyl group or an adamantyl group is preferable, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
• one of the methylene groups constituting the ring is a heteroatom such as an oxygen atom other than a fluorine atom, or a fluorine atom such as a carbonyl group. It may be substituted with a group having a hetero atom other than.
• Examples of the group represented by the general formula (S1) or (S2) include Rx 1 as a methyl group or an ethyl group, and Rx 2 and Rx 3 may be bonded to each other to form the above-mentioned cycloalkyl group. preferable.
• RS1 to RS3 independently represent a hydrogen atom or a monovalent organic group.
• RS2 to RS3 may be combined with each other to form a ring.
• the monovalent organic group may have a linear or branched alkyl group which may have a substituent which does not contain a fluorine atom, and a cyclo which may have a substituent which does not contain a fluorine atom.
• Alkyl groups can be mentioned. It is also preferable that RS1 is a hydrogen atom.
• the alkyl group and the cycloalkyl group may contain a heteroatom such as an oxygen atom other than the fluorine atom and / or a group having a heteroatom other than the fluorine atom such as a carbonyl group.
• the above-mentioned alkyl group and cycloalkyl group are, for example, groups in which one or more methylene groups have a heteroatom other than a fluorine atom such as an oxygen atom and / or a heteroatom other than a fluorine atom such as a carbonyl group. It may be replaced.
• RS3 may be bonded to each other with another substituent contained in the main chain of the repeating unit to form a ring.
• the group represented by the general formula (a-1) or (a-2) is preferable, and the group represented by the general formula (a-1) is preferable because the effect of the present invention is more excellent. Is more preferable.
• Ra1 represents a linear or branched alkyl group which may have a substituent which does not contain a fluorine atom, or a cycloalkyl group which may have a substituent which does not contain a fluorine atom. ..
• the linear or branched alkyl group which may have a substituent which does not contain a fluorine atom represented by Ra1 is a substituent which does not contain a fluorine atom in that the effect of the present invention is more excellent.
• a branched-chain alkyl group which may be possessed is preferable.
• the alkyl group may be a linear or branched alkyl group having a substituent containing no fluorine atom, or may be an unsubstituted linear or branched alkyl group.
• a hetero atom such as an oxygen atom other than the fluorine atom or an alkyl group containing a hetero atom such as an oxygen atom other than the fluorine atom is preferable.
• an unsubstituted linear or branched alkyl group is preferable as the alkyl group in that the effect of the present invention is more excellent.
• the alkyl group preferably has 1 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and even more preferably 2 to 8 carbon atoms.
• Examples of the alkyl group represented by R a1 include a tert-butyl group, a tert-heptyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a sec-butyl group.
• n-pentyl group isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 2-ethylbutyl group, n-heptyl group, 1-methylhexyl
• examples include a group, an n-octyl group, a 1-methylheptyl group, and a 2-ethylhexyl group.
• the tert-butyl group or the tert-heptyl group is preferable as the alkyl group represented by Ra1 in that the effect of the present invention is more excellent.
• Cycloalkyl group which may have a substituent group containing no fluorine atom represented by R a1 may be a monocyclic or polycyclic. Further, the cycloalkyl group may be a cycloalkyl group having a substituent containing no fluorine atom, or may be an unsubstituted cycloalkyl group. Of these, a cycloalkyl group having a substituent containing no fluorine atom is preferable. As the substituent contained in the cycloalkyl group, for example, an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable. The cycloalkyl group preferably has 4 to 25 carbon atoms, more preferably 4 to 20 carbon atoms, and even more preferably 4 to 15 carbon atoms.
• Examples of the cycloalkyl group represented by R a1 include a cyclopentyl group such as a methylcyclopentyl group or an ethylcyclopentyl group, a cyclohexyl group such as a methylcyclohexyl group or an ethylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group and a norbornyl group.
• a cyclopentyl group such as a methylcyclopentyl group or an ethylcyclopentyl group
• a cyclohexyl group such as a methylcyclohexyl group or an ethylcyclohexyl group
• a cycloheptyl group such as a methylcyclohexyl group or an ethylcyclohexyl group
• Examples thereof include an adamantan group such as a group, a tricyclodecanyl group, a tetracyclododecanyl group, a methyl adamantyl group or an ethyl adamantan group.
• an adamantan group such as a group, a tricyclodecanyl group, a tetracyclododecanyl group, a methyl adamantyl group or an ethyl adamantan group.
• at least one selected from the group consisting of a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and an adamantan group is selected as the cycloalkyl group represented by Ra1 in that the effect of the present invention is more excellent.
• a methylcyclopentyl group, an ethylcyclopentyl group, a methylcyclohexyl group, an ethylcyclohexyl group, a methyladamantyl group, or an ethyladamantan group is more preferable.
• R a2 represents a linear or branched alkyl group which may have a substituent which does not contain a fluorine atom, or a cycloalkyl group which may have a substituent which does not contain a fluorine atom. ..
• the linear or branched-chain alkyl group which may have a substituent which does not contain a fluorine atom represented by Ra 2 has a substituent which does not contain a fluorine atom represented by Ra 1 described above. It is synonymous with a linear or branched alkyl group which may be used.
• the cycloalkyl group which may have a substituent which does not contain a fluorine atom represented by Ra 2 may have, for example, the above-mentioned substituent which does not contain a fluorine atom represented by Ra 1. Cycloalkyl groups can be mentioned.
• Ra3 may have a linear or branched alkyl group which may have a substituent which does not contain a hydrogen atom or a fluorine atom, or a cycloalkyl which may have a substituent which does not contain a fluorine atom. Represents a group.
• the linear or branched-chain alkyl group which may have a substituent which does not contain a fluorine atom represented by Ra 3 has a substituent which does not contain a fluorine atom represented by Ra 1 described above. It is synonymous with a linear or branched alkyl group which may be used.
• the cycloalkyl group which may have a substituent which does not contain a fluorine atom represented by Ra 3 may have a substituent which does not contain a fluorine atom represented by Ra 1 described above. Synonymous with group.
• R a2 and R a3 may be combined with each other to form a ring.
• the ring formed by bonding R a2 and R a3 to each other may be a monocyclic ring or a polycyclic ring. Of these, a single ring is preferable.
• Examples of the monocycle formed by bonding R a2 and R a3 to each other include cycloalkanes having 3 to 6 carbon atoms. More specifically, for example, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring can be mentioned.
• a part of the carbon atom in the ring may be replaced by a hetero atom such as an oxygen atom other than the fluorine atom.
• the ring formed by bonding R a2 and R a3 to each other does not have a fluorine atom.
• the sulfonium cation contained in the specific compound has at least three fluorine atoms in a portion other than the acid-degradable group-containing group. That is, the substituents other than the acid-degradable group-containing group contained in the sulfonium cation have a total of 3 or more fluorine atoms, and the acid-degradable group-containing group does not have a fluorine atom.
• the number of fluorine atoms is preferably 6 or more.
• the upper limit of the number of fluorine atoms is not particularly limited, but is preferably 30 or less, more preferably 25 or less, and even more preferably 20 or less.
• the number of fluorine atoms is counted as 3.
• the number of the substituents having a fluorine atom may be one or two or more.
• the sulfonium cation may have a substituent (for example, an unsubstituted alkyl group) other than the above-mentioned acid-degradable group-containing group and substituent having a fluorine atom.
• a substituent for example, an unsubstituted alkyl group
• the sulfonium cation may be used alone or in combination of two or more. Further, two or more sulfonium cations of the same type may be contained.
• the specific compound preferably contains an organic anion.
• the organic anion may be a monovalent anion or a divalent or higher anion.
• the organic anion is preferably an anion having a significantly low ability to cause a nucleophilic reaction, and specific examples thereof include a non-nucleophilic anion.
• non-nucleophilic anions examples include sulfonic acid anions (aliphatic sulfonic acid anions, aromatic sulfonic acid anions, camphor sulfonic acid anions, etc.) and carboxylic acid anions (aliphatic carboxylic acid anions, aromatic carboxylic acid anions, etc.). , And aralkyl carboxylic acid anion, etc.), sulfonylimide anion, bis (alkylsulfonyl) imide anion, and tris (alkylsulfonyl) methide anion.
• the aliphatic moiety in the aliphatic sulfonic acid anion and the aliphatic carboxylic acid anion may be a linear or branched alkyl group or a cycloalkyl group, and may be a linear or linear or cycloalkyl group having 1 to 30 carbon atoms.
• a branched alkyl group or a cycloalkyl group having 3 to 30 carbon atoms is preferable.
• the alkyl group may be, for example, a fluoroalkyl group (may or may not have a substituent other than the fluorine atom. It may be a perfluoroalkyl group).
• the aryl group in the aromatic sulfonic acid anion and the aromatic carboxylic acid anion is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.
• the alkyl group, cycloalkyl group, and aryl group mentioned above may have a substituent.
• the substituent is not particularly limited, but specifically, a halogen atom such as a nitro group, a fluorine atom or a chlorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), and the like.
• An alkyl group (preferably 1 to 10 carbon atoms), a cycloalkyl group (preferably 3 to 15 carbon atoms), an aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), Acrylic group (preferably 2 to 12 carbon atoms), alkoxycarbonyloxy group (preferably 2 to 7 carbon atoms), alkylthio group (preferably 1 to 15 carbon atoms), alkylsulfonyl group (preferably 1 to 15 carbon atoms) , Alkyliminosulfonyl group (preferably 1 to 15 carbon atoms), aryloxysulfonyl group (preferably 6 to 20 carbon atoms) and the like.
• the aralkyl group in the aralkyl carboxylic acid anion is preferably an aralkyl group having 7 to 14 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.
• Examples of the sulfonylimide anion include saccharin anion.
• alkyl group in the bis (alkylsulfonyl) imide anion and the tris (alkylsulfonyl) methide anion an alkyl group having 1 to 5 carbon atoms is preferable.
• substituent of these alkyl groups include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryloxysulfonyl group, and a cycloalkylaryloxysulfonyl group.
• a fluorine atom or an alkyl group substituted with a fluorine atom is preferable.
• the alkyl groups in the bis (alkylsulfonyl) imide anion may be bonded to each other to form a ring structure. This increases the acid strength.
• non-nucleophilic anions e.g., fluorinated phosphorus (e.g., PF 6 -), fluorinated boron (e.g., BF 4 -), and fluorinated antimony (e.g., SbF 6 -) and the like.
• fluorinated phosphorus e.g., PF 6 -
• fluorinated boron e.g., BF 4 -
• fluorinated antimony e.g., SbF 6 -
• non-nucleophilic anion examples include an aliphatic sulfonic acid anion in which at least the ⁇ -position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonic acid anion in which a fluorine atom or a group having a fluorine atom is substituted, and an alkyl group having a fluorine atom.
• a bis (alkylsulfonyl) imide anion substituted with, or a tris (alkylsulfonyl) methide anion in which the alkyl group is substituted with a fluorine atom is preferable.
• perfluoroaliphatic sulfonic acid anion preferably 4 to 8 carbon atoms
• benzenesulfonic acid anion having a fluorine atom is more preferable
• nonafluorobutane sulfonic acid anion, perfluorooctane sulfonic acid anion, and pentafluoro A benzene sulfonic acid anion or a 3,5-bis (trifluoromethyl) benzene sulfonic acid anion is more preferable.
• an anion represented by the following formula (AN1) is also preferable.
• o represents an integer of 1 to 3.
• p represents an integer from 0 to 10.
• q represents an integer from 0 to 10.
• Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
• the number of carbon atoms of this alkyl group is preferably 1 to 10, and more preferably 1 to 4.
• a perfluoroalkyl group is preferable.
• Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably a fluorine atom or CF 3 . In particular, it is more preferable that both Xfs are fluorine atoms.
• R 4 and R 5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. If R 4 and R 5 there are a plurality, R 4 and R 5 may each be the same or different.
• the alkyl group represented by R 4 and R 5 may have a substituent, and has 1 to 4 carbon atoms.
• R 4 and R 5 are preferably hydrogen atoms. Specific examples and preferred embodiments of the alkyl group substituted with at least one fluorine atom are the same as the specific examples and preferred embodiments of Xf in the general formula (AN1).
• L represents a divalent linking group.
• the divalent linking group includes, for example, -O-CO-O-, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO-, -SO 2- , an alkylene group (preferably 1 to 6 carbon atoms), a cycloalkylene group (preferably 3 to 15 carbon atoms), an alkenylene group (preferably 2 to 6 carbon atoms), and a combination thereof.
• Examples include divalent linking groups.
• W represents an organic group containing a cyclic structure.
• a cyclic organic group is preferable.
• the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group.
• the alicyclic group may be monocyclic or polycyclic.
• the monocyclic alicyclic group include a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
• polycyclic alicyclic group examples include a polycyclic cycloalkyl group such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.
• alicyclic groups having a bulky structure having 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group, are preferable.
• the aryl group may be monocyclic or polycyclic.
• Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group.
• the heterocyclic group may be monocyclic or polycyclic.
• the polycycle can suppress the diffusion of acid more. Further, the heterocyclic group may or may not have aromaticity. Examples of the aromatic heterocycle include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring.
• non-aromatic heterocycle examples include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring.
• a heterocycle in the heterocyclic group a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferable.
• the cyclic organic group may have a substituent.
• substituents include an alkyl group (which may be linear or branched, preferably having 1 to 12 carbon atoms) and a cycloalkyl group (single ring, polycyclic, and spiro ring). Any of them may be used, and the number of carbon atoms is preferably 3 to 20), an aryl group (preferably 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group and a sulfonamide. Examples include a group and a sulfonic acid ester group.
• the carbon constituting the cyclic organic group may be carbonyl carbon.
• L, q and W are the same as in the general formula (AN1).
• an anion represented by the following formula (AN2) is also preferable.
• X B1 and X B2 independently represent a monovalent organic group having no hydrogen atom or fluorine atom. It is preferable that X B1 and X B2 are hydrogen atoms. X B3 and X B4 independently represent a hydrogen atom or a monovalent organic group. It is preferable that at least one of X B3 and X B4 is a fluorine atom or a monovalent organic group having a fluorine atom, and both X B3 and X B4 are monovalent organic groups having a fluorine atom or a fluorine atom. Is more preferable. It is even more preferred that both X B3 and X B4 are fluorine-substituted alkyl groups. L, q and W are the same as those in the general formula (AN1).
• an anion represented by the following formula (AN3) is preferable.
• Xa independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
• Xb independently represents an organic group having no hydrogen atom or fluorine atom.
• an anion represented by the following formula (AN4) is also preferable.
• R 1 and R 2 independently represent a substituent or a hydrogen atom that is not an electron-attracting group.
• substituents that are not the electron-attracting group include a hydrocarbon group, a hydroxyl group, an oxy hydrocarbon group, an oxycarbonyl hydrocarbon group, an amino group, a hydrocarbon-substituted amino group, and a hydrocarbon-substituted amide group. ..
• substituents that are not electron-attracting groups -R', -OH, -OR' , -OCOR', -NH 2 , -NR' 2 , -NHR', or -NHCOR are independent of each other. 'Is preferred.
• R' is a monovalent hydrocarbon group.
• Examples of the monovalent hydrocarbon group represented by R'in include an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group; an alkenyl group such as an ethenyl group, a propenyl group and a butenyl group; an ethynyl group.
• Monovalent linear or branched hydrocarbon groups such as alkynyl groups such as propynyl group and butynyl group; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, norbornyl group and adamantyl group; Monovalent alicyclic hydrocarbon groups such as cycloalkenyl groups such as cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, norbornenyl group; phenyl group, trill group, xsilyl group, mesityl group, naphthyl group, methylnaphthyl group, anthryl group , Aryl groups such as methyl anthryl group; monovalent aromatic hydrocarbon groups such as aralkyl groups such as benzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group and anthrylmethyl
• L is a divalent linking group consisting of a combination of one or more linking groups S and an alkylene group which may have one or more substituents, or one or more linking groups.
• Linking group S is, * A -O-CO-O- * B, * A -CO- * B, * A -CO-O- * B, * A -O-CO- * B, * A -O- It is a group selected from the group consisting of * B , * A -S- * B , and * A- SO 2- * B.
• L is one form of "a divalent linking group consisting of a combination of one or more linking groups S and an alkylene group which may have one or more substituents", that is, “one or more”.
• the linking group S is * A- O-CO-O- * B , *.
• a -CO- * B, * A -O -CO- * B, * A -O- * B, * A -S- * B and,, * A -SO 2 - is selected from the group consisting of * B It is preferably a group.
• the alkylene group in "a divalent linking group consisting of a combination of one or more linking groups S and an alkylene group which may have one or more substituents" is an unsubstituted alkylene group.
• the linking group S is, * A -O-CO-O- * B, * A -CO- * B, * A -O-CO- * B, * A -O- * B, * A - It is preferably a group selected from the group consisting of S- * B and * A- SO 2- * B.
• * A represents a represents a bonding position of R 3 side in formula (AN4)
• * B is -SO 3 in the general formula (AN4) - represents a side bonding position.
• a divalent linking group consisting of a combination of one or more linking groups S and an alkylene group which may have one or more substituents
• only one linking group S may be present. There may be more than one. Similarly, only one alkylene group may have a substituent or two or more may be present.
• the plurality of linking groups S may be the same or different from each other.
• the plurality of alkylene groups may be the same or different from each other.
• the linking groups S may be continuously bonded to each other.
• * A -CO- * B, * A -O-CO- * B, and, * A -O- * group selected from the group consisting of B are bonded continuously "* A -O- It is preferable that "CO-O- * B" is not formed. Also, * A -CO- * B and * A -O- * group selected from the group consisting of B are bonded continuously "* A -O-CO- * B" and "* A -CO- It is preferable that none of "O- * B" is formed.
• linking groups S when there are a plurality of linking groups S, the linking groups S when there are a plurality of linking groups S may be the same or different.
• * A -CO- * B, * A -O-CO- * B, and, * A -O- * group selected from the group consisting of B are bonded continuously "* A - It is preferable that "O-CO-O- * B" is not formed.
• * A -CO- * B and * A -O- * group selected from the group consisting of B are bonded continuously "* A -O-CO- * B" and "* A -CO- It is preferable that none of "O- * B" is formed.
• -SO 3 - atom against ⁇ -position is not a carbon atom having a fluorine atom as a substituent.
• the carbon atom does not have to be directly substituted with a fluorine atom, and the carbon atom is a substituent having a fluorine atom (for example, fluoro such as trifluoromethyl group). It may have an alkyl group).
• the atom at the ⁇ -position is an atom in L that directly bonds with ⁇ C (R 1 ) (R 2) ⁇ in the general formula (AN4).
• L preferably has only one linking group S. That is, L is a divalent linking group consisting of a combination of one linking group S and an alkylene group which may have one or more substituents, or a divalent linking consisting of one linking group S. It is preferable to represent a group.
• L is preferably a group represented by the following formula (AN4-2). * A - (CR 2a 2) X -Q- (CR 2b 2) Y - * b (AN4-2)
• * a represents the coupling position with R 3 in the general formula (AN4).
• * B represents the connection position with -C (R 1 ) (R 2 )-in the general formula (AN4).
• X and Y each independently represent an integer of 0 to 10, and an integer of 0 to 3 is preferable.
• R 2a and R 2b independently represent a hydrogen atom or a substituent.
• R 2a and R 2b may each be the same or different, However, when Y is 1 or more, R 2b in CR 2b 2 that directly bonds with ⁇ C (R 1 ) (R 2 ) ⁇ in the general formula (AN4) is other than a fluorine atom.
• Q is, * A -O-CO-O- * B, * A -CO- * B, * A -CO-O- * B, * A -O-CO- * B, * A -O- * B , * A -S- * B , or * A- SO 2- * B.
• R 3 represents an organic group.
• the organic group is not limited as long as it has one or more carbon atoms, and a linear group (for example, a linear alkyl group) may be a branched chain group (for example, a t-butyl group). It may be a branched alkyl group) or may have a cyclic structure.
• the organic group may or may not have a substituent.
• the organic group may or may not have a hetero atom (oxygen atom, sulfur atom, and / or nitrogen atom, etc.).
• R 3 is preferably an organic group having a cyclic structure.
• the cyclic structure may be monocyclic or polycyclic, and may have a substituent.
• the ring in the organic group containing the cyclic structure is preferably directly bonded to L in the general formula (AN4).
• the organic group having the cyclic structure may or may not have, for example, a hetero atom (oxygen atom, sulfur atom, and / or nitrogen atom, etc.). Heteroatoms may be substituted with one or more carbon atoms forming a cyclic structure.
• a hydrocarbon group having a cyclic structure, a lactone ring group, and a sultone ring group are preferable.
• the organic group having a cyclic structure is preferably a hydrocarbon group having a cyclic structure.
• the hydrocarbon group having a cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may have substituents.
• the cycloalkyl group may be a monocyclic ring (cyclohexyl group or the like) or a polycyclic ring (adamantyl group or the like), and the number of carbon atoms is preferably 5 to 12.
• the lactone group and sultone group are represented by, for example, the structures represented by the general formulas (LC1-1) to (LC1-21) described later, and the general formulas (SL1-1) to (SL1-3). In any of the above structures, a group formed by removing one hydrogen atom from the ring-membered atom constituting the lactone structure or the sultone structure is preferable.
• the non-nucleophilic anion may be a benzenesulfonic acid anion, and is preferably a benzenesulfonic acid anion substituted with a branched alkyl group or a cycloalkyl group.
• an aromatic sulfonic acid anion represented by the following formula (AN5) is also preferable.
• Ar represents an aryl group (phenyl group or the like), and may further have a substituent other than the sulfonic acid anion and the ⁇ (DB) group. Further, examples of the substituent which may be possessed include a fluorine atom and a hydroxyl group.
• N represents an integer of 0 or more. As n, 1 to 4 is preferable, 2 to 3 is more preferable, and 3 is further preferable.
• D represents a single bond or a divalent linking group.
• the divalent linking group include an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, a sulfonic acid ester group, an ester group, and a group composed of a combination of two or more of these.
• B represents a hydrocarbon group
• B preferably has an aliphatic hydrocarbon structure.
• B is more preferably an isopropyl group, a cyclohexyl group, and an aryl group (tricyclohexylphenyl group or the like) which may further have a substituent.
• a disulfonamide anion is also preferable.
• Disulfonamide anion for example, N - is an anion represented by (SO 2 -R q) 2.
• R q represents an alkyl group which may have a substituent, a fluoroalkyl group is preferable, and a perfluoroalkyl group is more preferable.
• the two R qs may combine with each other to form a ring.
• the group formed by bonding two R qs to each other is preferably an alkylene group which may have a substituent, preferably a fluoroalkylene group, and even more preferably a perfluoroalkylene group.
• the alkylene group preferably has 2 to 4 carbon atoms.
• examples of the anion include anions represented by the following formulas (d1-1) to (d1-3).
• the specific compound having an anion represented by the following formulas (d1-1) to (d1-3) as an anion can also have a function as an acid diffusion control agent described later.
• R 51 represents a hydrocarbon group (for example, an aryl group such as a phenyl group) which may have a substituent (for example, a hydroxyl group).
• Z 2c represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (however, the carbon atom adjacent to S is not substituted with a fluorine atom).
• the hydrocarbon group in Z 2c may be linear or branched, and may have a cyclic structure.
• the carbon atom in the hydrocarbon group (preferably a carbon atom which is a ring member atom when the hydrocarbon group has a cyclic structure) may be a carbonyl carbon (—CO ⁇ ).
• Examples of the hydrocarbon group include a group having a norbornyl group which may have a substituent.
• the carbon atom forming the norbornyl group may be a carbonyl carbon.
• Z 2c -SO 3 - is preferably different from that from the anion represented by the above formula (AN1) ⁇ (AN5).
• Z 2c is preferably a group other than an aryl group.
• -SO 3 - atoms of ⁇ position and ⁇ -position relative to the atoms other than carbon atoms having a fluorine atom is preferable as the substituent.
• Z 2c are, -SO 3 - preferably atoms of ⁇ position of the atoms and / or ⁇ position relative to is ring atoms in the cyclic group.
• R 52 represents an organic group (preferably a hydrocarbon group having a fluorine atom)
• Y 3 is a linear, branched, or cyclic alkylene group, arylene group, or , Represents a carbonyl group and Rf represents a hydrocarbon group.
• the organic anion may be used alone or in combination of two or more.
• X ⁇ represents an organic anion.
• the organic anion represented by X ⁇ is synonymous with the above-mentioned organic anion.
• Ar S1 to Ar S3 each independently represent an aromatic hydrocarbon ring group which may have a substituent.
• Examples of the aromatic hydrocarbon ring group represented by Ar S1 to Ar S3 include an aryl group such as a benzene ring group, a naphthalene ring group, and an anthracene ring group. Among them, the aromatic hydrocarbon ring groups are preferably benzene ring groups independently of each other.
• the aromatic hydrocarbon ring groups represented by Ar S1 to Ar S3 may be an aromatic hydrocarbon ring group having a substituent or an unsubstituted aromatic hydrocarbon ring group. Among them, the aromatic hydrocarbon ring group is preferably an aromatic hydrocarbon ring group having a substituent.
• the substituent contained in the aromatic hydrocarbon ring group may include, for example, a halogen atom, a linear or branched alkyl group which may have a halogen atom, and a halogen atom.
• An alkoxy group is mentioned, and more specifically, at least one selected from the group consisting of a fluorine atom, an iodine atom, an alkyl group, a fluoroalkyl group, a fluoroalcohol group, and a fluoroalkoxy group is preferable, and a fluorine atom, And at least one selected from the group consisting of fluoroalkyl groups is more preferred.
• an aromatic hydrocarbon group substituted with at least one selected from the group consisting of a fluorine atom and a fluoroalkyl group is preferable, and the aromatic hydrocarbon group is selected from the group consisting of a fluorine atom and a fluoroalkyl group. More preferably, it contains an aryl group substituted with at least one of the above.
• the number of fluorine atoms of the fluoroalkyl group, fluoroalcohol group, and fluoroalkoxy group may be one or more, and all hydrogen atoms in the alkylene group may be substituted with fluorine atoms.
• Ar S1 to Ar S3 may be bonded to each other to form a ring.
• the alkyl group, alcohol group, and alkoxy group preferably have 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 5 carbon atoms.
• alkyl group examples include a methyl group, a tert-butyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an octyl group, a dodecyl group and a nonadecil group.
• a methyl group or a tert-butyl group is preferable as the alkyl group in that the effect of the present invention is more excellent.
• fluoroalkyl group examples include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nafluorobutyl group, a 2- (perfluorobutyl) ethyl group, and a 3-perfluorobutyl-2-hydroxypropyl group.
• fluoroalkyl group a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, or a nafluorobutyl group is preferable because the effect of the present invention is more excellent.
• fluoroalcohol group examples include -C (CF 3 ) 2 OH, -CF 2 OH, -CH 2 CF 2 OH, -CH 2 CF 2 CF 2 OH, -C (CF 3 ) 2 OH, -CF 2.
• fluoroalcohol group examples include -C (CF 3 ) 2 OH, -CF 2 OH, -CH 2 CF 2 OH, -CH 2 CF 2 CF 2 OH, -C (CF 3 ) 2 OH, -CF 2.
• fluoroalcohol group examples include -C (CF 3 ) 2 OH, -CF 2 OH, -CH 2 CF 2 OH, -CH 2 CF 2 CF 2 OH, -C (CF 3 ) 2 OH, -CF 2.
• fluoroarcoside group examples include a fluoromethoxy group such as a fluoromethoxy group, a difluoromethoxy group and a trifluoromethoxy group; a fluoroethoxy group, a difluoroethoxy group, a trifluoroethoxy group, a tetrafluoroethoxy group and a penta.
• Fluoroethoxy groups such as fluoroethoxy groups; fluoropropoxy groups, difluoropropoxy groups, trifluoropropoxy groups, tetrafluoropropoxy groups, pentafluoropropoxy groups, hexafluoropropoxy groups, heptafluoropropoxy groups, octafluoropropoxy groups and the like.
• Fluoropropoxy groups can be mentioned. Among them, at least one selected from the group consisting of a fluoromethoxy group, a fluoroethoxy group, and a fluoropropoxy group is preferable as the fluoroarcoside group because the effect of the present invention is more excellent, and a trifluoromethoxy group is preferable. Is more preferable.
• At least one of Ar S1 to Ar S3 represents a group represented by the above-mentioned general formula (T-1).
• the aromatic hydrocarbon ring groups represented by Ar 1 to Ar 3 have a total of 3 or more fluorine atoms. Of Ar 1 to Ar 3 , only one may have three or more fluorine atoms and the other may not have a fluorine atom, and all Ar 1 to Ar 3 have one or more fluorine atoms. You may have. That is, the compound represented by the general formula (S-1) has at least three fluorine atoms. The number of fluorine atoms is preferably 6 or more. The upper limit is not particularly limited, but 30 or less is preferable, 25 or less is more preferable, and 20 or less is further preferable.
• the compound represented by the general formula (S-2) is more preferable.
• Ra represents an acid-degradable group-containing group.
• the definition of the acid-degradable group-containing group is as described above, and the group represented by the general formula (S-3) is preferable.
• the definitions of *, LT1 , and RT1 are as described above.
• R b1 , R b2 , and R b3 independently represent a fluorine atom or an organic group having a fluorine atom.
• the organic group having a fluorine atom may have a fluorine atom, for example, a linear or branched alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or a fluorine atom.
• Aryl groups can be mentioned.
• the number of carbon atoms of the alkyl group and the cycloalkyl group is not particularly limited, but the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.
• organic group having a fluorine atom a linear or branched alkyl group having a fluorine atom is preferable, a linear or branched fluoroalkyl group is more preferable, and a linear or branched alkyl group is preferable.
• Perfluoroalkyl groups are even more preferred.
• R c1 , R c2 , and R c3 independently represent organic groups that do not have a fluorine atom, unlike acid-degradable group-containing groups.
• the organic group include an unsubstituted alkyl group, an unsubstituted cycloalkyl group, and an unsubstituted aryl group.
• the number of carbon atoms of the alkyl group and the cycloalkyl group is not particularly limited, but the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.
• b1 represents an integer of 0 to 4
• b2 represents an integer of 0 to 5
• b3 represents an integer of 0 to 5.
• c1 represents an integer of 0 to 4
• c2 represents an integer of 0 to 5
• c3 represents an integer of 0 to 5.
• the sum of b1, b2, and b3 represents an integer of 1 or more.
• the sum of b1 and c1 represents an integer of 0 to 4
• the sum of b2 and c2 represents an integer of 0 to 5
• the sum of b3 and c3 represents an integer of 0 to 5.
• the total number of fluorine atoms in R b1 , the number of fluorine atoms in R b2 , and the number of fluorine atoms in R b3 is 3 or more, more preferably 6 or more.
• the upper limit is not particularly limited, but 30 or less is preferable, 25 or less is more preferable, and 20 or less is further preferable.
• R b1 to R b3 only one may have three or more fluorine atoms and the other may not have a fluorine atom, and all R b1 to R b3 have one or more fluorine atoms. You may have.
• a compound having two or more cation sites and the same number of anion sites as the above-mentioned cation sites, and at least one of the above-mentioned cation sites is a specific cation (hereinafter, also simply referred to as "Compound W").
• a cation site is a structural site containing a positively charged atom or group of atoms.
• at least one of the two or more cation sites is a specific cation.
• it is preferable that all of the two or more cation sites contained in the compound W are specific cations in that the effect of the present invention is more excellent.
• At least one of the two or more cation sites may be a specific cation, and may contain an organic cation other than the specific cation.
• the organic cation other than the specific cation include a sulfonium cation other than the specific cation and an iodonium ion.
• the anionic moiety is a structural moiety containing a negatively charged atom or atomic group, and for example, an anionic functional group that may be present in compound W may be used as the anionic moiety.
• Compound W preferably has an organic anion having the same number of anionic functional groups as the cation moiety of compound W. As described above, compound W has two or more (preferably two to three) cation sites and the same number of anion sites as the above cation sites. That is, compound W has two or more (preferably 2-3) anionic moieties (preferably anionic functional groups).
• anionic functional group for example, -SO 3 - group having as part, -COO - -, and -SO 3 and -COO - groups having as part, -N - - group having as part, and, carbanions (-C - ⁇ ) include groups having as part.
• anion moiety groups represented by the general formulas (B-1) to (B-13) are preferable.
• * represents the bonding position. It is also preferable that * in the general formula (B-12) is a bond position with respect to a group that is neither -CO- nor -SO 2-.
• RX1 represents an organic group.
• RX1 includes an alkyl group (which may be linear or branched, preferably having 1 to 15 carbon atoms), a cycloalkyl group (which may be monocyclic or polycyclic, preferably having 3 to 20 carbon atoms). Alternatively, an aryl group (either monocyclic or polycyclic, preferably 6 to 20 carbon atoms) is preferable.
• RX1 in formula (B-5) in R X1, N - directly attached to atoms and carbon atoms in -CO-, and, -SO 2 - is also preferred not one of sulfur atoms in the.
• the cycloalkyl group in R X1 may be monocyclic or polycyclic.
• Substituents which may have a cycloalkyl group at R X1 represents an alkyl group (a straight-chain or branched-chain. Preferably 1-5 1 carbon atoms) preferably.
• One or more of the carbon atoms are ring member atoms of the cycloalkyl group in R X1 may be replaced by carbonyl carbon atom.
• the number of carbon atoms in the alkyl group in R X1 is preferably 1 to 10, 1 to 5 and more preferable.
• Substituent which may be possessed by the alkyl group in R X1 is a cycloalkyl group, a fluorine atom, or a cyano group.
• the cycloalkyl group as the substituent include the cycloalkyl group described in the case where RX1 is a cycloalkyl group.
• Alkyl group in R X1 is, if they have a fluorine atom as the substituent, the alkyl group may be a perfluoroalkyl group.
• the alkyl group in R X1 is one or more -CH 2 - may be substituted with a carbonyl group.
• Aryl group in R X1 is a benzene ring group.
• Substituent which may be possessed by the aryl group in R X1 is an alkyl group, a fluorine atom, or a cyano group.
• alkyl group as the substituent include the alkyl groups described in the case where RX1 is a cycloalkyl group, and a perfluoroalkyl group is preferable, and a perfluoromethyl group is more preferable.
• RX2 represents a hydrogen atom or a substituent other than a fluorine atom and a perfluoroalkyl group.
• Substituent other than fluorine atom and a perfluoroalkyl group represented by R X2 is an alkyl group other than a perfluoroalkyl group, or a cycloalkyl group are preferable.
• the alkyl groups include alkyl groups other than the perfluoroalkyl group from the alkyl group for R X1. Further, the alkyl group preferably does not have a fluorine atom.
• Examples of the cycloalkyl groups include cycloalkyl groups in R X1. Further, the cycloalkyl group preferably does not have a fluorine atom.
• RXF1 represents a hydrogen atom, a fluorine atom, or a perfluoroalkyl group. However, at least one of the plurality of RXF1s represents a fluorine atom or a perfluoroalkyl group.
• the perfluoroalkyl group represented by RXF1 preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 carbon atoms.
• RXF2 represents a fluorine atom or a perfluoroalkyl group.
• the perfluoroalkyl group represented by RXF2 preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 carbon atoms.
• n represents an integer of 0 to 4.
• Compound W preferably has at least two anionic functional groups (preferably two selected from the general formulas (B-1) to (B-13)).
• the combination of the anionic functional groups of the compound W is not particularly limited.
• compound W has a group represented by the general formula (B-8) or (B-10)
• it may have a group represented by (B-11) to (B-13).
• the compound W is a group represented by the general formula (B-7), it may further have a group represented by the general formula (B-6).
• These compounds W may have further different anionic functional groups.
• a compound W is an anion site, anionic sites A B - (anionic functional groups A B -) preferably has a.
• Anionic part A B - (anionic functional groups A B -) is a group represented by any one of formulas (BX-1) ⁇ (BX -4).
• R B represents an organic group.
• Examples of the organic group for R B has the general formula (B-1) ⁇ (B -5), and examples of the organic group R X1 can be mentioned as well in (B-12).
• the compounds W is as anionic sites, the anionic sites A B - in addition to further anionic sites A A - (anionic functional group A B) - preferably has a - (anionic functional group A A) .
• Anionic part A A - (anionic functional group A A -) is a group represented by any one of formulas (AX-1) ⁇ (AX -2).
• RA represents an organic group.
• RA is preferably an alkyl group.
• the alkyl group may be linear or branched.
• the alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.
• the substituent that the alkyl group may have is preferably a fluorine atom.
• the alkyl group having a fluorine atom as a substituent may or may not be a perfluoroalkyl group.
• AD0 a compound represented by the general formula (AD0) is preferable.
• nk represents an integer of 2 or more.
• the nk is preferably 2 to 10, more preferably 2 to 3.
• the two nks existing in the general formula (AD0) have the same value.
• L 0 represents a nk-valent linking group.
• L 0 represents a single bond or a divalent linking group.
• the divalent organic group include -COO-, -CONH-, -CO-, -O-, an alkylene group (preferably 1 to 6 carbon atoms, which may be linear or branched), and cyclo. Examples thereof include an alkylene group (preferably 3 to 15 carbon atoms), an alkenylene group (preferably 2 to 6 carbon atoms), and a divalent linking group obtained by combining a plurality of these groups.
• One or more of the methylene groups constituting the cycloalkane ring of the cycloalkylene group may be replaced with a carbonyl carbon and / or a hetero atom (oxygen atom or the like).
• These divalent linking groups may further, -S -, - SO -, - SO 2 -, and, -NR N - has the (R N represents a hydrogen atom or a substituent) group is selected from the group consisting of Is also preferable.
• the nk-valent linking group include a single bond and / or each group that the divalent linking group can take, and -CR nk ⁇ , -N ⁇ ,> C ⁇ , a trivalent or higher valent hydrocarbon ring group.
• R nk represents a hydrogen atom or a substituent.
• L 0 is other than a single bond
• the total number of atoms other than hydrogen atoms constituting L 0 is preferably 1 to 100, more preferably 1 to 50.
• a 0 - represents an anionic functional group.
• the anionic functional groups are as described above. More existing A 0 - may each be the same or different.
• a plurality of A 0 - are, for example, "a group represented by the general formula (B-8) or (B-10) and the general formulas (B-1) to (B-7), (B-9). Or, it may have at least a group represented by (B-11) to (B-13), and a group represented by the general formula (B-7) and a group represented by the general formula (B-6). It may have at least a group represented by, and a group represented by any of the general formulas (BX-1) to (BX-4) and the general formulas (AX-1) to (AX-). It may have at least a group represented by any of 2).
• M 0 + represents a cation (specific cation or an organic cation other than the specific cation).
• nk number of M 0 + at least one of the (preferably all) represents a particular cation.
• a plurality of M 0 + may be the same or different from each other.
• the compound W is preferably compound (I), compound (II), or compound (III).
• compounds (I) to (III) will be described.
• Compound (I) is the following compound.
• Compound (I) A compound having one of the following structural sites X and one of the following structural sites Y, and the following first acidic site and the following structure derived from the following structural site X by irradiation with active light or radiation.
• Structural part X Structural part consisting of anion part A 1 ⁇ and cation part M 1 + , and forming the first acidic part represented by HA 1 by irradiation with active light or radiation
• Structural part Y Anion part a 2 - consists of a cationic sites M 2 + and, and, by irradiation with actinic rays or radiation, the represented by HA 2 having a structure different from that of the first acidic site formed by the above structural moiety X structural site to form a second acid sites, provided that at least one of the cationic sites M 1 + and cations sites M 2 + is a specific cation.
• compound (I) satisfies the following condition I.
• Condition I In the compound (I), the compound PI obtained by replacing the cation site M 1 + in the structural site X and the cation site M 2 + in the structural site Y with H + is contained in the structural site X.
• the acid dissociation constant a1 derived from the acidic site represented by HA 1 which is obtained by replacing the above-mentioned cation site M 1 + with H + , and the above-mentioned cation site M 2 + in the above-mentioned structural part Y are replaced with H +.
• the acid dissociation constant a1 and the acid dissociation constant a2 are obtained by the above-mentioned method. More specifically, the acid dissociation constant a1 and the acid dissociation constant a2 of the compound PI refer to the compound PI (the compound PI is a compound having HA 1 and HA 2) when the acid dissociation constant of the compound PI is obtained. .
• the compound PI corresponds to an acid generated by irradiating compound (I) with active light or radiation.
• the difference between the acid dissociation constant a1 and the acid dissociation constant a2 is preferably 0.10 to 20.00, more preferably 0.50 to 17.00, in that the effect of the present invention is more excellent. ..
• the acid dissociation constant a2 is preferably -4.00 to 15.00, more preferably -2.00 to 12.00, in that the effect of the present invention is more excellent.
• the acid dissociation constant a1 is preferably -12.00 to 1.00, more preferably -7.00 to 0.50, in that the effect of the present invention is more excellent.
• the compound (I) is not particularly limited, and examples thereof include a compound represented by the following general formula (Ia).
• M 11 + and M 12 + each independently represents a cation (specific cation or an organic cation other than the specific cation).
• M 11 + and M 12 + of at least one (preferably both) is a specific cation.
• the specific cation is as described above.
• the organic cations other than the specific cations are as described above.
• a 11 - and A 12 - independently represents an anionic functional group.
• a 12 ⁇ represents a structure different from the anionic functional group represented by A 11 ⁇ .
• the anionic functional groups are as described above.
• a 11 - and A 12 - anionic functional group are each independently the general formula (B-1) a group represented by ⁇ (B-13) are preferred.
• a 11 - and A 12 - The combination of the anionic functional group represented by is not particularly limited, for example, A 11 - is a group represented by the general formula (B-8) or (B-10) If, A 12 - Table the anionic functional group represented by the general formula (B-1) ⁇ (B -7), (B-9), or (B-11) ⁇ (B -13) include groups, a 11 - when is a group represented by the general formula (B-7), a 12 - as the anionic functional group represented by the table in the general formula (B-6) The group to be used is mentioned.
• L 1 represents a divalent linking group.
• the divalent linking group represented by L 1 is not particularly limited, and is an -CO-, -NR-, -CO-, -O-, alkylene group (preferably having 1 to 1 to carbon atoms). 6.
• a 5- to 10-membered ring having an N atom, an O atom, an S atom, or a Se atom in the ring structure is preferable, a 5- to 7-membered ring is more preferable, and a 5- to 6-membered ring is further preferable), and a plurality of these. Examples thereof include a divalent linking group in which the above are combined.
• the above R may be a hydrogen atom or a monovalent substituent.
• the monovalent substituent is not particularly limited, but for example, an alkyl group (preferably 1 to 6 carbon atoms) is preferable.
• These divalent linking groups may further include a group selected from the group consisting of -S-, -SO-, and -SO 2-.
• the alkylene group, the cycloalkylene group, the alkaneylene group, and the divalent aliphatic heterocyclic group may be substituted with a substituent.
• the substituent include a halogen atom (preferably a fluorine atom).
• M 1 + and M 2 + each independently represents a cation (specific cation or an organic cation other than the specific cation). At least one (preferably both) of the M 1 + and M 2 + represents a particular cation.
• the specific cation is as described above. The same applies to organic cations other than specific cations.
• L represents a divalent organic group.
• the divalent organic group include -COO-, -CONH-, -CO-, -O-, an alkylene group (preferably 1 to 6 carbon atoms, which may be linear or branched), and a cycloalkylene group.
• the number of carbon atoms is 3 to 15
• an alkenylene group preferably, the number of carbon atoms is 2 to 6
• a divalent linking group in which a plurality of these are combined can be mentioned.
• One or more of the methylene groups constituting the cycloalkane ring of the cycloalkylene group may be replaced with a carbonyl carbon and / or a hetero atom (oxygen atom or the like).
• These divalent linking groups also preferably have a group selected from the group consisting of -S-, -SO-, and -SO 2-.
• L is preferably a group represented by the following general formula (L). * A-LA-LB-LC-LD-LE- * B (L)
• * A represents the connection position with A ⁇ in the general formula (Ib).
• * B represents the connection position with B ⁇ in the general formula (Ib).
• LA represents ⁇ (C (R LA1 ) (R LA2 )) XA ⁇ .
• the XA represents an integer of 1 or more, preferably 1 to 10, and more preferably 1 to 3.
• R LA1 and R LA2 each independently represent a hydrogen atom or a substituent.
• a fluorine atom or a fluoroalkyl group is preferable, a fluorine atom or a perfluoroalkyl group is more preferable, and a fluorine atom or a perfluoromethyl group is further preferable.
• the R LA1s in which XA are present may be the same or different.
• the R LA2 having XA may be the same or different from each other.
• -(C (R LA1 ) (R LA2 ))- is preferably -CH 2- , -CHF-, -CH (CF 3 )-, or -CF 2- .
• -(C (R LA1 ) (R LA2 ))- which directly binds to A- in the general formula (Ib) is -CH 2- , -CHF-, -CH (CF 3 )-, or -CF. 2 -is preferable.
• Formula (Ib) in A - and a direct bond to - (C (R LA1) ( R LA2)) - other than the - (C (R LA1) ( R LA2)) - are each independently, -CH 2 -, -CHF-, or -CF 2 --is preferable.
• LB represents a single bond, an ester group (-COO-), or a sulfonyl group (-SO 2- ).
• LC represents a single bond, an alkylene group, a cycloalkylene group, or a group composed of a combination thereof (such as "-alkylene group-cycloalkylene group-").
• the alkylene group may be linear or branched.
• the alkylene group preferably has 1 to 5 carbon atoms, more preferably 1 to 2 carbon atoms, and even more preferably 1.
• the cycloalkylene group preferably has 3 to 15 carbon atoms, and more preferably 5 to 10 carbon atoms.
• the cycloalkylene group may be monocyclic or polycyclic. Examples of the cycloalkylene group include a norbornanediyl group and an adamantandiyl group.
• the substituent that the cycloalkylene group may have, an alkyl group (which may be linear or branched, preferably 1 to 5 carbon atoms) is preferable.
• One or more of the methylene groups constituting the cycloalkane ring of the cycloalkylene group may be replaced with a carbonyl carbon and / or a hetero atom (oxygen atom or the like).
• the alkylene group portion is preferably present on the LB side.
• the LC is preferably a single bond or a cycloalkylene group.
• LD represents a single bond, an ether group (-O-), a carbonyl group (-CO-), or an ester group (-COO-).
• LE is a single bond or - (C (R LE1) ( R LE2))
• XE - represents a.
• XE- represents an integer of 1 or more, preferably 1 to 10, and more preferably 1 to 3.
• R LE1 and R LE2 independently represent a hydrogen atom or a substituent. When the number of XEs is 2 or more, the R LE1s having XEs may be the same or different from each other. When the number of XEs is 2 or more, the R LE2s having XEs may be the same or different from each other.
• -(C (R LE1 ) (R LE2 ))- is preferably -CH 2- or -CF 2-.
• L the general formula (L) when LB, LC, and LD are single bonds, it is preferable that LE is also a single bond.
• a - and B - each independently represent an anionic functional group.
• the anionic functional groups are as described above.
• a ⁇ is preferably a group represented by any of the general formulas (AX-1) to (AX-2).
• B ⁇ preferably represents a group represented by any of the general formulas (BX-1) to (BX-4).
• a - and B - are preferably different structures, respectively.
• a ⁇ is a group represented by the general formula (AX-1)
• B ⁇ is a group represented by any of the general formulas (BX-1) to (BX-4).
• a - is a group represented by the general formula (AX-2)
• B - is the general formula (BX-1), general formula (BX-3), and general formula (BX It is preferably a group represented by any of -4).
• M 1 + and M 2 + a compound represented by the HA-L-BH, which are each substituted by a hydrogen atom of the compound represented by, pKa of the group represented by the HA, It is lower than the pKa of the group represented by BH.
• HA-L-BH when obtained an acid dissociation constant for the compound represented by the "HA-L-BH” is - a pKa at which the "A -L-BH""HA and in the pKa of a group represented by "further” a - a pKa of the group represented by "BH a pKa at which the '" - -L-BH "is” a - -L-B.
• "PKa of the group represented by HA” and “pKa of the group represented by BH” are obtained by using "Software Package 1" or "Gaussian 16", respectively.
• the pKa of the group represented by HA corresponds to the acid dissociation constant a1 described above, and the preferred range is also the same.
• the pKa of the group represented by BH corresponds to the acid dissociation constant a2 described above, and the preferred range is also the same.
• the difference between the pKa of the group represented by HB and the pKa of the group represented by HA (“pKa of the group represented by HB”-“pKa of the group represented by HA”) is the acid dissociation constant described above. It corresponds to the difference between a1 and the acid dissociation constant a2, and the preferred range is also the same.
• Compound (II) is the following compound.
• compound (II) satisfies the following condition II.
• Condition II In the compound (II), the compound PII obtained by replacing the cation site M 1 + in the structural site X and the cation site M 2 + in the structural site Y with H + is contained in the structural site X.
• the acid dissociation constant a1 derived from the acidic site represented by HA 1 in which the cation site M 1 + is replaced with H + , and the HA obtained by replacing the cation site M 2 + in the structural site Y with H +. It has an acid dissociation constant a2 derived from the acidic moiety represented by 2, and the acid dissociation constant a2 is larger than the acid dissociation constant a1.
• the acid dissociation constant a1 and the acid dissociation constant a2 are obtained by the above-mentioned method.
• the acid dissociation constant a1 and the acid dissociation constant a2 of the compound PII will be described more specifically.
• compound (II) is, for example, a compound that generates an acid having two first acidic sites derived from the structural site X and one second acidic site derived from the structural site Y.
• Compound PII corresponds to "a compound having two HA 1 and HA 2".
• compound PII is - a pKa of acid dissociation constant a1 when the "one of A 1 and one HA 1 and HA 2 with a compound of", "two a 1 - and HA 2 compound having the "is” two a 1 - and a 2 - pKa when a compound "having a is an acid dissociation constant a2. That is, when the compound PII has a plurality of acid dissociation constants derived from the acidic site represented by HA 1 formed by replacing the cation site M 1 + in the structural site X with H +, the smallest value is acid. It is regarded as the dissociation constant a1.
• compound PII corresponds to an acid generated by irradiating compound (II) with active light rays or radiation.
• compound (II) may have a plurality of the structural sites Y.
• the difference between the acid dissociation constant a1 and the acid dissociation constant a2 is preferably 2.00 or more, and more preferably 3.00 or more, in that the effect of the present invention is more excellent.
• the upper limit of the difference between the acid dissociation constant a1 and the acid dissociation constant a2 is not particularly limited, but is, for example, 15.00 or less.
• the acid dissociation constant a2 is preferably 2.00 or less, more preferably 1.00 or less, in that the effect of the present invention is more excellent.
• the lower limit of the acid dissociation constant a2 is preferably ⁇ 2.00 or higher.
• the acid dissociation constant a1 is preferably 2.00 or less, more preferably 0.50 or less, still more preferably ⁇ 0.10 or less, in that the effect of the present invention is more excellent.
• the lower limit of the acid dissociation constant a1 is preferably -15.00 or higher.
• the compound (II) is not particularly limited, and examples thereof include a compound represented by the following general formula (IIa).
• + M 21 + and M 22 each independently represents a cation (specific cation or an organic cation other than the specific cation). At least one (preferably both) of the M 21 + and M 22 + represents a particular cation.
• a 21 - and A 22 - independently represents an anionic functional group.
• a 22 ⁇ represents a structure different from the anionic functional group represented by A 21 ⁇ .
• L 2 represents a (n1 + n2) valent organic group. n1 represents an integer of 2 or more. n2 represents an integer of 1 or more.
• M 21 +, M 22 +, A 21 -, and, A 22 - is in each above-mentioned general formula (Ia) M 11 +, M 12 +, A 11 -, ⁇ fine a 12 - in the above formula, preferred embodiments are also the same.
• n1 pieces of M 21 + each other, n1 pieces of A 21 + each other, represent each mutually identical groups.
• T 1 represents a trivalent hydrocarbon ring group or a trivalent heterocyclic group
• T 2 is a carbon atom, a tetravalent hydrocarbon ring group, or a tetravalent. Represents the heterocyclic group of.
• the hydrocarbon ring group may be an aromatic hydrocarbon ring group or an aliphatic hydrocarbon ring group.
• the number of carbon atoms contained in the hydrocarbon ring group is preferably 6 to 18, and more preferably 6 to 14.
• the heterocyclic group may be an aromatic heterocyclic group or an aliphatic heterocyclic group.
• the heterocycle is preferably a 5- to 10-membered ring having at least one N atom, an O atom, an S atom, or a Se atom in the ring structure, more preferably a 5- to 7-membered ring, and a 5- to 6-membered ring. Rings are more preferred.
• L 21 and L 22 independently represent a single bond or a divalent linking group, respectively.
• the divalent linking group represented by L 21 and L 22 has the same meaning as the divalent linking group represented by L 1 in the general formula (Ia), and the preferred embodiment is also the same.
• n1 represents an integer of 2 or more.
• the upper limit is not particularly limited, but is, for example, 6 or less, preferably 4 or less, and more preferably 3 or less.
• n2 represents an integer of 1 or more.
• the upper limit is not particularly limited, but is, for example, 3 or less, preferably 2 or less.
• Compound (III) A compound having two or more of the structural site X and the following structural site Z, wherein the first acidic site derived from the structural site X is 2 by irradiation with active light or radiation. one or more and the structural site Z and of generating an acid comprising a compound structural moiety Z: acid organic moieties however possible nonionic neutralize, at least one cationic sites M 1 + is a specific cation.
• the nonionic organic moiety capable of neutralizing the acid in the structural moiety Z is not particularly limited, and is, for example, an organic moiety containing a functional group having a group or an electron capable of electrostatically interacting with a proton. Is preferable.
• a functional group having a group or an electron capable of electrostatically interacting with a proton a functional group having a macrocyclic structure such as a cyclic polyether or a nitrogen atom having an unshared electron pair that does not contribute to ⁇ conjugation is used. Examples thereof include functional groups having.
• the nitrogen atom having an unshared electron pair that does not contribute to ⁇ conjugation is, for example, a nitrogen atom having a partial structure shown in the following formula.
• Substructures of functional groups having groups or electrons that can electrostatically interact with protons include, for example, crown ether structure, aza-crown ether structure, 1-3 amine structure, pyridine structure, imidazole structure, and pyrazine structure. Etc., and among them, the 1st to 3rd grade amine structure is preferable.
• the acid dissociation constant a1 derived from the acidic moiety represented by is preferably 2.0 or less, more preferably 0.5 or less, still more preferably ⁇ 0.1 or less, in that the effect of the present invention is more excellent.
• the lower limit of the acid dissociation constant a1 is preferably -15.0 or higher.
• compound PIII has a plurality of acid dissociation constants derived from the acidic site represented by HA 1 in which the cation site M 1 + in the structural site X is replaced with H +, the smallest value is acid. It is regarded as the dissociation constant a1. That is, when compound (III) is, for example, a compound that generates an acid having two first acidic sites derived from the structural site X and the structural site Z, the compound PIII is "two HA 1". It corresponds to "a compound having.” If asked for the acid dissociation constant of the compound PIII, compound PIII is - pKa when the "one of A 1 and a compound having one HA 1" is an acid dissociation constant a1.
• compound PIII when compound PIII has a plurality of acid dissociation constants derived from the acidic site represented by HA 1 in which the cation site M 1 + in the structural site X is replaced with H +, the smallest value is acid. It is regarded as the dissociation constant a1.
• the compound PIII in which the cation site M 1 + in the structural site X is replaced with H + is, for example, a compound in which the compound (III) is represented by the compound (IIIa) described later. If, HA 31- L 3- N (R 2X ) -L 4- A 31 H corresponds.
• the compound (III) is not particularly limited, and examples thereof include a compound represented by the following general formula (IIIa).
• M 31 + A 31 - corresponds to the structural moiety X.
• Compound (IIIa) produces an acid represented by HA 31- L 3- N (R 2X ) -L 4- A 31 H by irradiation with active light or radiation. That is, "M 31 + A 31 -” forms a first acidic moiety represented by HA 31.
• M 31 + represents a cation (specific cation or an organic cation other than the specific cation). At least one (preferably both) of the M 31 + represents a particular cation.
• a 31 - represents an anionic functional group.
• L 3 and L 4 each independently represent a divalent linking group.
• R 2X represents a monovalent organic group.
• M 31 + and A 31 ⁇ have the same meanings as M 11 + and A 11 ⁇ in the general formula (Ia) described above, respectively, and the preferred embodiments are also the same.
• L 3 and L 4 are synonymous with L 1 in the general formula (Ia) described above, and the preferred embodiments are also the same.
• two M 31 + each other, and two A 31 - each other represent each mutually identical groups.
• the monovalent organic group represented by R 2X is not particularly limited, and for example, -CH 2- is -CO-, -NH-, -O-, -S-,-. SO-, and -SO 2 - may be substituted with one or more combinations selected from the group consisting of an alkyl group (preferably may be 1-10 either linear or branched carbon atoms. ), Cycloalkyl group (preferably 3 to 15 carbon atoms), alkenyl group (preferably 2 to 6 carbon atoms) and the like. Moreover, the said alkylene group, the said cycloalkylene group, and the said alkaneylene group may be substituted with a substituent.
• the composition of the present invention contains a resin (hereinafter, also referred to as "acid-decomposable resin” or “resin (A)”) that is decomposed by the action of an acid to increase its polarity. That is, in the pattern forming method of the present invention, typically, when an alkaline developer is used as the developer, a positive pattern is preferably formed, and when an organic developer is used as the developer, a positive pattern is preferably formed. , A negative pattern is preferably formed.
• the resin (A) usually contains a group that is decomposed by the action of an acid and whose polarity is increased (hereinafter, also referred to as “acid-degradable group”), and preferably contains a repeating unit having an acid-decomposable group.
• An acid-degradable group is a group that is decomposed by the action of an acid to form a polar group.
• the acid-degradable group preferably has a structure in which the polar group is protected by a leaving group that is eliminated by the action of an acid. That is, the resin (A) has a repeating unit having a group which is decomposed by the action of an acid to produce a polar group.
• the polarity of the resin having this repeating unit is increased by the action of the acid, the solubility in the alkaline developer is increased, and the solubility in the organic solvent is decreased.
• an alkali-soluble group is preferable, and for example, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphoric acid group, a sulfonamide group, a sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene.
• alkylsulfonyl alkylcarbonyl imide group
• bis (alkylcarbonyl) methylene group bis (alkylcarbonyl) imide group
• bis (alkylsulfonyl) methylene group bis (alkylsulfonyl) imide group
• tris alkylcarbonyl
• Examples thereof include an acidic group such as a methylene group and a tris (alkylsulfonyl) methylene group, and an alcoholic hydroxyl group.
• a carboxyl group a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group is preferable.
• Examples of the leaving group that are eliminated by the action of an acid include groups represented by the general formulas (Y1) to (Y4).
• General formula (Y1) -C (Rx 1 ) (Rx 2 ) (Rx 3 )
• General formula (Y2): -C ( O) OC (Rx 1 ) (Rx 2 ) (Rx 3 )
• Rx 1 to Rx 3 are independently alkyl groups (linear or branched), cycloalkyl groups (monocyclic or polycyclic), and alkenyl groups (straight). (Orchid or branched chain) or aryl group (monocyclic or polycyclic). When all of Rx 1 to Rx 3 are alkyl groups (linear or branched chain), it is preferable that at least two of Rx 1 to Rx 3 are methyl groups. Among them, Rx 1 to Rx 3 preferably independently represent a linear or branched alkyl group, and Rx 1 to Rx 3 each independently represent a linear alkyl group. Is more preferable.
• Rx 1 to Rx 3 may be combined to form a monocyclic ring or a polycyclic ring.
• alkyl group of Rx 1 to Rx 3 include an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. preferable.
• Examples of the cycloalkyl group of Rx 1 to Rx 3 include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, and a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.
• a polycyclic cycloalkyl group is preferred.
• the aryl group of Rx 1 to Rx 3 is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.
• alkenyl group of Rx 1 to Rx 3 a vinyl group is preferable.
• a cycloalkyl group is preferable as the ring formed by bonding two of Rx 1 to Rx 3.
• the cycloalkyl group formed by combining two of Rx 1 to Rx 3 is a cyclopentyl group, a monocyclic cycloalkyl group such as a cyclohexyl group, or a norbornyl group, a tetracyclodecanyl group, or a tetracyclododeca.
• a polycyclic cycloalkyl group such as an nyl group or an adamantyl group is preferable, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
• the cycloalkyl group formed by combining two of Rx 1 to Rx 3 is, for example, a group in which one of the methylene groups constituting the ring has a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group, or a group having a hetero atom such as a carbonyl group. It may be replaced by a vinylidene group.
• one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.
• the group represented by the general formula (Y1) or (Y2) is, for example, an embodiment in which Rx 1 is a methyl group or an ethyl group, and Rx 2 and Rx 3 are bonded to form the above-mentioned cycloalkyl group. Is preferable.
• R 36 to R 38 each independently represent a hydrogen atom or a monovalent organic group.
• R 37 and R 38 may be combined with each other to form a ring.
• the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group and the like. It is also preferable that R 36 is a hydrogen atom.
• the alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a heteroatom such as an oxygen atom and / or a group having a heteroatom such as a carbonyl group.
• R 38 may be bonded to each other with another substituent contained in the main chain of the repeating unit to form a ring.
• the group formed by bonding R 38 and another substituent of the main chain of the repeating unit to each other is preferably an alkylene group such as a methylene group.
• L 1 and L 2 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group in which these are combined (for example, a group in which an alkyl group and an aryl group are combined).
• .. M represents a single bond or a divalent linking group.
• Q is an alkyl group that may contain a hetero atom, a cycloalkyl group that may contain a hetero atom, an aryl group that may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group, and an aldehyde.
• the alkyl group and the cycloalkyl group for example, one of the methylene groups may be replaced with a heteroatom such as an oxygen atom or a group having a heteroatom such as a carbonyl group.
• one of L 1 and L 2 is a hydrogen atom and the other is an alkyl group, a cycloalkyl group, an aryl group, or a group in which an alkylene group and an aryl group are combined.
• L 2 is preferably a secondary or tertiary alkyl group, and more preferably a tertiary alkyl group.
• the secondary alkyl group include an isopropyl group, a cyclohexyl group and a norbornyl group
• examples of the tertiary alkyl group include a tert-butyl group and an adamantan group.
• Tg glass transition temperature
• activation energy are high, so that in addition to ensuring the film strength, fog can be suppressed.
• Ar represents an aromatic ring group.
• Rn represents an alkyl group, a cycloalkyl group, or an aryl group.
• Rn and Ar may be combined with each other to form a non-aromatic ring.
• Ar is more preferably an aryl group.
• the non-aromatic ring in the non-aromatic ring in the non-aromatic ring, from the viewpoint of excellent acid decomposition property of the repeating unit, it is also preferable that the ring member atom adjacent to the ring member atom directly bonded to the polar group (or its residue) does not have a halogen atom such as a fluorine atom as a substituent.
• Other leaving groups that are eliminated by the action of an acid include a 2-cyclopentenyl group having a substituent (alkyl group, etc.) such as a 3-methyl-2-cyclopentenyl group, and 1,1,4.
• a cyclohexyl group having a substituent (alkyl group, etc.) such as 4-tetramethylcyclohexyl group may be used.
• the repeating unit represented by the general formula (A) is also preferable.
• L 1 represents a divalent linking group which may have a fluorine atom or an iodine atom
• R 1 is an alkyl group which may have a hydrogen atom, a fluorine atom, an iodine atom, a fluorine atom or an iodine atom.
• it represents an aryl group which may have a fluorine atom or an iodine atom
• R 2 represents a desorbing group which is eliminated by the action of an acid and may have a fluorine atom or an iodine atom.
• at least one of L 1 , R 1 , and R 2 has a fluorine atom or an iodine atom.
• L 1 represents a divalent linking group which may have a fluorine atom or an iodine atom.
• the fluorine atom or a linking group may divalent have a iodine atom, -CO -, - O -, - S -, - SO -, - SO 2 -, have a fluorine atom or an iodine atom Examples thereof include a hydrocarbon group which may be used (for example, an alkylene group, a cycloalkylene group, an alkaneylene group, an arylene group, etc.), a linking group in which a plurality of these groups are linked, and the like.
• the L 1, -CO-, or, - arylene - fluorine atom or an alkylene group having iodine atom - are preferred.
• the arylene group a phenylene group is preferable.
• the alkylene group may be linear or branched.
• the number of carbon atoms of the alkylene group is not particularly limited, but 1 to 10 is preferable, and 1 to 3 is more preferable.
• the total number of fluorine atoms and iodine atoms contained in the alkylene group having a fluorine atom or an iodine atom is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.
• R 1 represents an alkyl group which may have a hydrogen atom, a fluorine atom, an iodine atom, a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom.
• the alkyl group may be linear or branched.
• the number of carbon atoms of the alkyl group is not particularly limited, but 1 to 10 is preferable, and 1 to 3 is more preferable.
• the total number of fluorine atoms and iodine atoms contained in the alkyl group having a fluorine atom or an iodine atom is not particularly limited, but is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3.
• the alkyl group may contain a hetero atom such as an oxygen atom other than the halogen atom.
• R 2 represents a leaving group that is eliminated by the action of an acid and may have a fluorine atom or an iodine atom.
• examples of the leaving group include groups represented by the general formulas (Z1) to (Z4).
• General formula (Z1) -C (Rx 11 ) (Rx 12 ) (Rx 13 )
• General formula (Z2): -C ( O) OC (Rx 11 ) (Rx 12 ) (Rx 13 )
• Rx 11 to Rx 13 are alkyl groups (linear or branched), fluorine atoms or iodine which may independently have a fluorine atom or an iodine atom, respectively.
• a cycloalkyl group (monocyclic or polycyclic) that may have an atom, an alkenyl group (linear or branched) that may have a fluorine atom or an iodine atom, or a fluorine atom or an iodine atom.
• Rx 11 to Rx 13 are alkyl groups (linear or branched chain), it is preferable that at least two of Rx 11 to Rx 13 are methyl groups.
• Rx 11 to Rx 13 are the same as Rx 1 to Rx 3 in (Y1) and (Y2) described above, except that they may have a fluorine atom or an iodine atom, and are an alkyl group or a cycloalkyl group.
• Alkyl group, and aryl group are the same as the definition and preferred range.
• R 136 to R 138 each independently represent a hydrogen atom or a monovalent organic group which may have a fluorine atom or an iodine atom.
• R 137 and R 138 may be combined with each other to form a ring.
• the monovalent organic group which may have a fluorine atom or an iodine atom includes an alkyl group which may have a fluorine atom or an iodine atom, and a cycloalkyl group which may have a fluorine atom or an iodine atom.
• the alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a hetero atom such as an oxygen atom in addition to the fluorine atom and the iodine atom.
• R 138 may be bonded to each other with another substituent contained in the main chain of the repeating unit to form a ring.
• the group formed by bonding R 138 and another substituent of the main chain of the repeating unit to each other is preferably an alkylene group such as a methylene group.
• L 11 and L 12 independently have an alkyl group selected from the group consisting of a hydrogen atom; a fluorine atom, an iodine atom and an oxygen atom; a fluorine atom, an iodine atom and an alkyl group.
• a cycloalkyl group which may have a hetero atom selected from the group consisting of oxygen atoms; an aryl group which may have a hetero atom selected from the group consisting of a fluorine atom, an iodine atom and an oxygen atom; or It represents a group in which these are combined (for example, a group in which an alkyl group and a cycloalkyl group are combined, which may have a hetero atom selected from the group consisting of a fluorine atom, an iodine atom and an oxygen atom).
• M 1 represents a single bond or a divalent linking group.
• Q 1 represents a fluorine atom, an alkyl group which may have a hetero atom selected from the group consisting of iodine atoms and an oxygen atom; Yes fluorine atom, a hetero atom selected from the group consisting of iodine atoms and an oxygen atom May be cycloalkyl group; aryl group selected from the group consisting of fluorine atom, iodine atom and oxygen atom; amino group; ammonium group; mercapto group; cyano group; aldehyde group; or a group combining these (for example).
• Ar 1 represents an aromatic ring group which may have a fluorine atom or an iodine atom.
• Rn 1 may have an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, or an aryl which may have a fluorine atom or an iodine atom.
• Rn 1 and Ar 1 may be combined with each other to form a non-aromatic ring.
• a repeating unit having an acid-decomposable group a repeating unit represented by the general formula (AI) is also preferable.
• Xa 1 represents a hydrogen atom or an alkyl group which may have a substituent.
• T represents a single bond or a divalent linking group.
• Rx 1 to Rx 3 are independently alkyl groups (linear or branched chain), cycloalkyl groups (monocyclic or polycyclic), alkenyl groups (linear or branched chain), or aryl (linear or branched chain). Represents a monocyclic or polycyclic) group. However, when all of Rx 1 to Rx 3 are alkyl groups (linear or branched chain), it is preferable that at least two of Rx 1 to Rx 3 are methyl groups. Two of Rx 1 to Rx 3 may be bonded to form a monocyclic or polycyclic (monocyclic or polycyclic cycloalkyl group, etc.).
• xa 1 Represented by xa 1, as the alkyl group which may have a substituent group, include groups represented by methyl group or -CH 2 -R 11.
• R 11 represents a halogen atom (fluorine atom, etc.), a hydroxyl group, or a monovalent organic group.
• the halogen atom may be substituted, an alkyl group having 5 or less carbon atoms, or a halogen atom may be substituted.
• Examples thereof include an acyl group having 5 or less carbon atoms and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkyl group having 3 or less carbon atoms is preferable, and a methyl group is more preferable.
• Xa 1 a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group is preferable.
• Examples of the divalent linking group of T include an alkylene group, an aromatic ring group, an -COO-Rt- group, an -O-Rt- group and the like.
• Rt represents an alkylene group or a cycloalkylene group.
• T is preferably a single bond or a -COO-Rt- group.
• Rt is preferably an alkylene group having 1 to 5 carbon atoms, and is preferably a -CH 2- group,- (CH 2 ) 2- group, or- (CH 2 ) 3- Groups are more preferred.
• Examples of the alkyl group of Rx 1 to Rx 3 include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. preferable.
• Examples of the cycloalkyl group of Rx 1 to Rx 3 include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.
• the polycyclic cycloalkyl group of is preferred.
• the aryl group of Rx 1 to Rx 3 is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.
• alkenyl group of Rx 1 to Rx 3 a vinyl group is preferable.
• a cyclopentyl group and a monocyclic cycloalkyl group such as a cyclohexyl group are preferable, and in addition, a norbornyl group and a tetracyclodecanyl group are used.
• Tetracyclododecanyl group, and polycyclic cycloalkyl group such as adamantyl group are preferable.
• a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferable.
• the cycloalkyl group formed by combining two of Rx 1 to Rx 3 is, for example, a group in which one of the methylene groups constituting the ring has a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group, or a group having a hetero atom such as a carbonyl group. It may be replaced by a vinylidene group. Further, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.
• Rx 1 is a methyl group or an ethyl group
• Rx 2 and Rx 3 are bonded to form the above-mentioned cycloalkyl group.
• the substituents include, for example, an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group. (2 to 6 carbon atoms) and the like.
• the number of carbon atoms in the substituent is preferably 8 or less.
• the repeating unit represented by the general formula (AI) is preferably an acid-decomposable (meth) acrylic acid tertiary alkyl ester-based repeating unit (Xa 1 represents a hydrogen atom or a methyl group, and T is a single bond. It is a repeating unit that represents.
• the content of the repeating unit having an acid-decomposable group is preferably 15 to 80 mol%, more preferably 20 to 70 mol%, still more preferably 20 to 65 mol%, based on all the repeating units in the resin (A). ..
• Xa 1 represents any of H, F, CH 3 , CF 3 , and CH 2 OH
• Rxa and Rxb represent linear or branched alkyl groups having 1 to 5 carbon atoms, respectively. ..
• the resin (A) may contain a repeating unit other than the repeating unit described above.
• the resin (A) contains at least one repeating unit selected from the group consisting of the following groups A and / or at least one repeating unit selected from the group consisting of the following groups B. May be good.
• Group A A group consisting of the following repeating units (20) to (29).
• Repeating unit (29) The repeating unit B group represented by the formula (E), which will be described later: A group consisting of the following repeating units (30) to (32). (30) A repeating unit having at least one group selected from a lactone group, a sulton group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group, which will be described later. Repetitive unit (32) having and not exhibiting acid decomposition property A repeating unit represented by the general formula (III) having neither a hydroxyl group nor a cyano group, which will be described later.
• the resin (A) may have at least one repeating unit selected from the group consisting of the above group A. preferable.
• the resin (A) preferably contains at least one of a fluorine atom and an iodine atom.
• the resin (A) may have one repeating unit containing both a fluorine atom and an iodine atom, and the resin (A) may have one repeating unit.
• the resin (A) may contain two kinds of a repeating unit having a fluorine atom and a repeating unit containing an iodine atom. Further, when the composition is used as a sensitive light-sensitive or radiation-sensitive resin composition for EUV, it is also preferable that the resin (A) has a repeating unit having an aromatic group.
• the resin (A) may have at least one repeating unit selected from the group consisting of the above group B. preferable.
• the resin (A) does not contain either a fluorine atom or a silicon atom.
• the resin (A) preferably does not have an aromatic group.
• the resin (A) may have a repeating unit having an acid group.
• an acid group having a pKa of 13 or less is preferable.
• the acid group for example, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, an isopropanol group and the like are preferable.
• one or more (preferably one or two) fluorine atoms may be substituted with a group other than the fluorine atom (alkoxycarbonyl group or the like).
• -C (CF 3 ) (OH) -CF 2- thus formed is also preferable as an acid group.
• one or more of the fluorine atoms may be substituted with a group other than the fluorine atom to form a ring containing ⁇ C (CF 3 ) (OH) ⁇ CF 2-.
• the repeating unit having an acid group is a repeating unit having a structure in which a polar group is protected by a leaving group desorbed by the action of the above-mentioned acid, and a repeating unit having a lactone group, a sulton group or a carbonate group described later. It is preferably a repeating unit different from the unit.
• the repeating unit having an acid group may have a fluorine atom or an iodine atom.
• the repeating unit represented by the formula (B) is preferable.
• R 3 represents a hydrogen atom or a monovalent organic group which may have a fluorine atom or an iodine atom.
• the fluorine atom or an organic group may monovalent optionally having iodine atom, a group represented by -L 4 -R 8 are preferred.
• L 4 represents a single bond or an ester group.
• R 8 is an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, and the like. Alternatively, a group combining these can be mentioned.
• R 4 and R 5 each independently represent a hydrogen atom, a fluorine atom, an iodine atom, or an alkyl group which may have a fluorine atom or an iodine atom.
• L 2 represents a single bond or an ester group.
• L 3 represents a (n + m + 1) -valent aromatic hydrocarbon ring group or a (n + m + 1) -valent alicyclic hydrocarbon ring group.
• the aromatic hydrocarbon ring group include a benzene ring group and a naphthalene ring group.
• the alicyclic hydrocarbon ring group may be monocyclic or polycyclic, and examples thereof include cycloalkyl ring groups.
• R 6 represents a hydroxyl group or a fluorinated alcohol group (preferably a hexafluoroisopropanol group).
• L 3 is preferably an aromatic hydrocarbon ring group having a (n + m + 1) valence.
• R 7 represents a halogen atom.
• the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• m represents an integer of 1 or more.
• n represents an integer of 0 or 1 or more.
• n is preferably an integer of 1 to 4.
• (n + m + 1) is preferably an integer of 1 to 5.
• repeating unit having an acid group a repeating unit represented by the following general formula (I) is also preferable.
• R 41 , R 42 and R 43 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
• R 42 may be bonded to Ar 4 to form a ring, in which case R 42 represents a single bond or an alkylene group.
• X 4 represents a single bond, -COO-, or -CONR 64-
• R 64 represents a hydrogen atom or an alkyl group.
• L 4 represents a single bond or an alkylene group.
• Ar 4 represents an (n + 1) -valent aromatic ring group, and represents an (n + 2) -valent aromatic ring group when combined with R 42 to form a ring.
• n represents an integer from 1 to 5.
• the alkyl groups of R 41 , R 42 , and R 43 in the general formula (I) include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, and 2-ethylhexyl.
• Alkyl groups having 20 or less carbon atoms such as groups, octyl groups, and dodecyl groups are preferable, alkyl groups having 8 or less carbon atoms are more preferable, and alkyl groups having 3 or less carbon atoms are further preferable.
• the cycloalkyl groups of R 41 , R 42 , and R 43 in the general formula (I) may be monocyclic or polycyclic. Of these, a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group is preferable.
• Examples of the halogen atoms of R 41 , R 42 , and R 43 in the general formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
• the alkyl group contained in the alkoxycarbonyl group of R 41 , R 42 , and R 43 in the general formula (I) is preferably the same as the alkyl group in R 41 , R 42 , and R 43.
• Preferred substituents in each of the above groups include, for example, an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group and an acyl group. , Achilloxy group, alkoxycarbonyl group, cyano group, and nitro group.
• the substituent preferably has 8 or less carbon atoms.
• Ar 4 represents an (n + 1) -valent aromatic ring group.
• the divalent aromatic ring group when n is 1, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a trilene group, a naphthylene group, and an anthracenylene group, or a thiophene ring, a furan ring, or a pyrrole.
• a divalent aromatic ring group containing a heterocycle such as a ring, a benzothiophene ring, a benzofuran ring, a benzopyrol ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiaziazole ring, and a thiazole ring is preferable.
• the aromatic ring group may have a substituent.
• (n + 1) -valent aromatic ring group when n is an integer of 2 or more, (n-1) arbitrary hydrogen atoms are removed from the above-mentioned specific example of the divalent aromatic ring group. There is a group that is made up of.
• the (n + 1) -valent aromatic ring group may further have a substituent.
• Examples of the substituents that the above-mentioned alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, and (n + 1) -valent aromatic ring group can have include R 41 , R 42 , and R 41 in the general formula (I). , R 43 , an alkoxy group such as an alkyl group, a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, and a butoxy group; an aryl group such as a phenyl group; and the like.
• R 64 represents a hydrogen atom or an alkyl group
• the alkyl group for R 64 in, a methyl group, an ethyl group, a propyl group, an isopropyl group, n- butyl group, sec Examples thereof include alkyl groups having 20 or less carbon atoms such as a butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group, and an alkyl group having 8 or less carbon atoms is preferable.
• X 4 a single bond, -COO-, or -CONH- is preferable, and a single bond or -COO- is more preferable.
• the alkylene group for L 4, a methylene group, an ethylene group, a propylene group, butylene group, hexylene group, and is preferably an alkylene group having 1 to 8 carbon atoms such as octylene group.
• Ar 4 an aromatic ring group having 6 to 18 carbon atoms is preferable, and a benzene ring group, a naphthalene ring group, and a biphenylene ring group are more preferable.
• the repeating unit represented by the general formula (I) preferably has a hydroxystyrene structure. That is, Ar 4 is preferably a benzene ring group.
• the repeating unit represented by the general formula (I) the repeating unit represented by the following general formula (1) is preferable.
• A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group.
• R represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkyloxycarbonyl group or an aryloxycarbonyl group, and there are a plurality of them. In some cases, they may be the same or different. When having a plurality of Rs, they may form a ring jointly with each other.
• a hydrogen atom is preferable as R.
• a represents an integer of 1 to 3.
• b represents an integer from 0 to (5-a).
• a 1 or 2.
• R represents a hydrogen atom or a methyl group
• a represents 2 or 3.
• the content of the repeating unit having an acid group is preferably 10 to 70 mol%, more preferably 10 to 60 mol%, still more preferably 10 to 50 mol%, based on all the repeating units in the resin (A).
• the resin (A) may have a repeating unit having a fluorine atom or an iodine atom in addition to the above-mentioned ⁇ repeating unit having an acid-degradable group> and ⁇ repeating unit having an acid group>.
• the ⁇ repeating unit having a fluorine atom or an iodine atom> referred to here is a ⁇ repeating unit having a lactone group, a sultone group, or a carbonate group>, a ⁇ repeating unit having a photoacid generating group>, etc., which will be described later. It is preferable that the unit is different from other types of repeating units belonging to the group A.
• the repeating unit represented by the formula (C) is preferable.
• L 5 represents a single bond or an ester group.
• R 9 represents an alkyl group which may have a hydrogen atom or a fluorine atom or an iodine atom.
• R 10 may have an alkyl group which may have a hydrogen atom, a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, a fluorine atom or an iodine atom.
• the repeating unit having a fluorine atom or an iodine atom is illustrated below.
• the content of the repeating unit having a fluorine atom or an iodine atom is preferably 0 to 60 mol%, more preferably 5 to 60 mol%, and further preferably 10 to 60 mol% with respect to all the repeating units in the resin (A). preferable.
• the repeating unit having a fluorine atom or an iodine atom does not include ⁇ repeating unit having an acid-degradable group> and ⁇ repeating unit having an acid group>
• the content of the repeating unit having an atom is also intended to be the content of the repeating unit having a fluorine atom or an iodine atom excluding ⁇ repeating unit having an acid-degradable group> and ⁇ repeating unit having an acid group>.
• the total content of the repeating units containing at least one of a fluorine atom and an iodine atom is preferably 1 to 100 mol% with respect to all the repeating units of the resin (A), and is preferably 5 to 100 mol%. 80 mol% is more preferable, and 10 to 60 mol% is further preferable.
• the repeating unit containing at least one of a fluorine atom and an iodine atom includes, for example, a repeating unit having a fluorine atom or an iodine atom and having an acid-degradable group, a fluorine atom or an iodine atom, and Examples thereof include a repeating unit having an acid group and a repeating unit having a fluorine atom or an iodine atom.
• the resin (A) is a repeating unit having at least one selected from the group consisting of a lactone group, a sultone group, and a carbonate group (hereinafter, collectively, a repeating unit having a lactone group, a sultone group, or a carbonate group). It may also have a "unit"). It is also preferable that the repeating unit having a lactone group, a sultone group, or a carbonate group does not have an acid group such as a hexafluoropropanol group.
• the lactone group or sultone group may have a lactone structure or a sultone structure.
• the lactone structure or sultone structure is preferably a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure.
• a 5- to 7-membered ring lactone structure in which another ring structure is fused to form a bicyclo structure or a spiro structure or a 5- to 7-membered ring in the form of a bicyclo structure or a spiro structure.
• a sultone structure in which another ring structure is fused is more preferable.
• the resin (A) has a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-21), or any of the following general formulas (SL1-1) to (SL1-3). It is preferable to have a repeating unit having a lactone group or a sultone group obtained by extracting one or more hydrogen atoms from the ring member atom of the represented sultone structure. Further, a lactone group or a sultone group may be directly bonded to the main chain. For example, a ring-membered atom of a lactone group or a sultone group may form the main chain of the resin (A).
• the lactone structure or sultone structure portion may have a substituent (Rb 2 ).
• Preferred substituents (Rb 2 ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, and a carboxyl group. , Halogen atom, hydroxyl group, cyano group, acid-degradable group and the like.
• n2 represents an integer of 0 to 4. When n2 is 2 or more, Rb 2 existing in plural numbers may be different or may be bonded to form a ring Rb 2 between the plurality of.
• It has a group having a lactone structure represented by any of the general formulas (LC1-1) to (LC1-21) or a sultone structure represented by any of the general formulas (SL1-1) to (SL1-3).
• Examples of the repeating unit include a repeating unit represented by the following general formula (AI).
• Rb 0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferred substituents that the alkyl group of Rb 0 may have include a hydroxyl group and a halogen atom. Examples of the halogen atom of Rb 0 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb 0 is preferably a hydrogen atom or a methyl group.
• Ab is a divalent linking group having a single bond, an alkylene group, a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group obtained by combining these.
• Ab 1 is a linear or branched alkylene group or a monocyclic or polycyclic cycloalkylene group, and a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornene group is preferable.
• V is a group formed by extracting one hydrogen atom from a ring member atom having a lactone structure represented by any of the general formulas (LC1-1) to (LC1-21), or a general formula (SL1-1) to V. It represents a group formed by extracting one hydrogen atom from a ring member atom having a sultone structure represented by any one of (SL1-3).
• any optical isomer may be used. Further, one kind of optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, its optical purity (ee) is preferably 90 or more, more preferably 95 or more.
• a cyclic carbonate group is preferable.
• a repeating unit having a cyclic carbonate group a repeating unit represented by the following general formula (A-1) is preferable.
• RA 1 represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group).
• n represents an integer greater than or equal to 0.
• RA 2 represents a substituent. when n is 2 or more, R A 2 existing in plural, may each be the same or different.
• A represents a single bond or a divalent linking group.
• the divalent linking group includes an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a combination thereof.
• the valence group is preferred.
• Z represents an atomic group forming a monocyclic or polycyclic ring with a group represented by —O—CO—O— in the formula.
• the repeating unit having a lactone group, a sultone group, or a carbonate group is illustrated below.
• the content of the repeating unit having a lactone group, a sultone group, or a carbonate group is preferably 1 to 70 mol%, more preferably 5 to 65 mol%, or 5 to 65 mol% with respect to all the repeating units in the resin (A). 60 mol% is more preferred.
• the resin (A) may have a repeating unit having a group that generates an acid by irradiation with active light or radiation (hereinafter, also referred to as “photoacid generating group”) as a repeating unit other than the above.
• the repeating unit having this photoacid-generating group corresponds to a compound that generates an acid by irradiation with active light or radiation described later (hereinafter, also referred to as “photoacid generator”).
• Examples of such a repeating unit include a repeating unit represented by the following general formula (4).
• R 41 represents a hydrogen atom or a methyl group.
• L 41 represents a single bond or a divalent linking group.
• L 42 represents a divalent linking group.
• R 40 represents a structural site that is decomposed by irradiation with active light or radiation to generate an acid in the side chain.
• the repeating unit having a photoacid generating group is illustrated below.
• examples of the repeating unit represented by the general formula (4) include the repeating units described in paragraphs [0094] to [0105] of JP-A-2014-041327.
• the content of the repeating unit having a photoacid generating group is preferably 1 to 40 mol%, more preferably 5 to 35 mol%, and further preferably 5 to 30 mol% with respect to all the repeating units in the resin (A). preferable.
• the resin (A) may have a repeating unit represented by the following general formula (V-1) or the following general formula (V-2).
• the repeating unit represented by the following general formula (V-1) and the following general formula (V-2) is preferably a repeating unit different from the above-mentioned repeating unit.
• R 6 and R 7 independently have a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, and an ester group (-OCOR or -COOR:
• R is the number of carbon atoms. 1 to 6 alkyl groups or fluorinated alkyl groups) or carboxyl groups.
• As the alkyl group a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms is preferable.
• n 3 represents an integer from 0 to 6.
• n 4 represents an integer from 0 to 4.
• X 4 is a methylene group, an oxygen atom, or a sulfur atom.
• the repeating unit represented by the general formula (V-1) or (V-2) is illustrated below.
• the resin (A) preferably has a high glass transition temperature (Tg) from the viewpoint of suppressing excessive diffusion of generated acid or pattern disintegration during development.
• Tg is preferably greater than 90 ° C, more preferably greater than 100 ° C, even more preferably greater than 110 ° C, and particularly preferably greater than 125 ° C. Since excessively high Tg causes a decrease in the dissolution rate in the developing solution, Tg is preferably 400 ° C. or lower, more preferably 350 ° C. or lower.
• the glass transition temperature (Tg) of the polymer such as the resin (A) is calculated by the following method.
• the Tg of a homopolymer composed of only each repeating unit contained in the polymer is calculated by the Bicerano method.
• the calculated Tg is referred to as "repeating unit Tg".
• the mass ratio (%) of each repeating unit to all the repeating units in the polymer is calculated.
• Tg at each mass ratio is calculated using the Fox formula (described in Materials Letters 62 (2008) 3152, etc.), and the sum of them is used as the Tg (° C.) of the polymer.
• the Bicerano method is described in the Precision of policies, Marcel Dekker Inc, New York (1993) and the like. Further, the calculation of Tg by the Bicerano method can be performed using the polymer physical property estimation software MDL Polymer (MDL Information Systems, Inc.).
• the resin (A) preferably has a repeating unit in which the Tg of the homopolymer is 130 ° C. or higher.
• the type of repeating unit having a homopolymer Tg of 130 ° C. or higher is not particularly limited, and any repeating unit having a homopolymer Tg of 130 ° C. or higher calculated by the Bicerano method may be used.
• the homopolymer corresponds to the repeating unit having a Tg of 130 ° C. or higher.
• the formula (A) and RA represent a group having a polycyclic structure.
• R x represents a hydrogen atom, a methyl group, or an ethyl group.
• the group having a polycyclic structure is a group having a plurality of ring structures, and the plurality of ring structures may or may not be condensed.
• Specific examples of the repeating unit represented by the formula (A) include the following repeating units.
• R represents a hydrogen atom, a methyl group, or an ethyl group.
• Ra is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom and an ester group (-OCOR'''.
• the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent.
• the hydrogen atom bonded to the carbon atom in the group represented by Ra may be replaced with a fluorine atom or an iodine atom.
• R'and R'' are independently alkyl group, cycloalkyl group, aryl group, aralkyl group, alkenyl group, hydroxyl group, alkoxy group, asyloxy group, cyano group, nitro group, amino group, halogen atom, respectively.
• R ′′ ′′ is an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group) or a carboxyl group.
• the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent.
• the hydrogen atom bonded to the carbon atom in the group represented by R'and R' may be replaced with a fluorine atom or an iodine atom.
• L represents a single bond or a divalent linking group.
• Examples of the divalent linking group include -COO-, -CO- , -O-, -S-, -SO-, -SO 2- , an alkylene group, a cycloalkylene group, an alkaneylene group, and a plurality of these.
• Examples thereof include a linking group in which is linked.
• m and n each independently represent an integer of 0 or more. The upper limits of m and n are not particularly limited, but are often 2 or less and more often 1 or less.
• R b1 to R b4 independently represent a hydrogen atom or an organic group, and at least two or more of R b1 to R b4 represent an organic group.
• the types of other organic groups are not particularly limited.
• at least two or more organic groups have three or more constituent atoms excluding hydrogen atoms. It is a substituent.
• repeating unit represented by the formula (B) include the following repeating units.
• R independently represents a hydrogen atom or an organic group.
• the organic group include organic groups such as an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group, which may have a substituent.
• R' is independently an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, and an ester group (-OCOR'.
• R'' represents an alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms) or a carboxyl group.
• the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent.
• the hydrogen atom bonded to the carbon atom in the group represented by R' may be replaced with a fluorine atom or an iodine atom.
• m represents an integer of 0 or more. The upper limit of m is not particularly limited, but it is often 2 or less, and more often 1 or less.
• R c1 to R c4 independently represent a hydrogen atom or an organic group, and at least one of R c1 to R c4 is a hydrogen-bonding hydrogen within 3 atoms from the main chain carbon. It is a group having an atom. Among them, in order to induce the interaction between the main chains of the resin (A), it is preferable to have hydrogen-bonding hydrogen atoms within 2 atoms (closer to the main chain).
• repeating unit represented by the formula (C) include the following repeating units.
• R represents an organic group.
• the organic group may have a substituent, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, and an ester group (-OCOR or -COOR:
• R is an alkyl having 1 to 20 carbon atoms. Group or alkyl fluorinated group) and the like.
• R' represents a hydrogen atom or an organic group.
• Examples of the organic group include an organic group such as an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group.
• the hydrogen atom in the organic group may be replaced with a fluorine atom or an iodine atom.
• cyclic represents a group forming a main chain with a cyclic structure.
• the number of constituent atoms of the ring is not particularly limited.
• repeating unit represented by the formula (D) include the following repeating units.
• R is independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, and the like.
• the ester group (-OCOR “or -COOR”: R "is an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group) or a carboxyl group.
• the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. Further, the hydrogen atom bonded to the carbon atom in the group represented by R may be substituted with a fluorine atom or an iodine atom.
• R' is independently an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom and an ester group.
• R is an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group
• the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent.
• the hydrogen atom bonded to the carbon atom in the group represented by R' may be replaced with a fluorine atom or an iodine atom.
• m represents an integer of 0 or more. The upper limit of m is not particularly limited, but it is often 2 or less, and more often 1 or less.
• Re independently represents a hydrogen atom or an organic group.
• the organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group and the like, which may have a substituent.
• Cyclic is a cyclic group containing a carbon atom in the main chain. The number of atoms contained in the cyclic group is not particularly limited.
• repeating unit represented by the formula (E) include the following repeating units.
• R is independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, and a halogen. It represents an atom, an ester group (-OCOR “or -COOR”: R "is an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group), or a carboxyl group.
• the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent.
• the hydrogen atom bonded to the carbon atom in the group represented by R may be substituted with a fluorine atom or an iodine atom.
• R' is independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, and an ester.
• the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent.
• the hydrogen atom bonded to the carbon atom in the group represented by R' may be replaced with a fluorine atom or an iodine atom.
• m represents an integer of 0 or more. The upper limit of m is not particularly limited, but it is often 2 or less, and more often 1 or less.
• the content of the repeating unit represented by the formula (E) is preferably 5 mol% or more, more preferably 10 mol% or more, based on all the repeating units in the resin (A).
• the upper limit is preferably 60 mol% or less, more preferably 55 mol% or less.
• the resin (A) may have a repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group.
• the resin (A) may have a repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group.
• Examples of the repeating unit having a lactone group, a sultone group, or a carbonate group contained in the resin (A) include the repeating unit described in ⁇ Repeating unit having a lactone group, a sultone group, or a carbonate group> described above.
• the preferred content is also as described above in ⁇ Repeating unit having a lactone group, sultone group, or carbonate group>.
• the resin (A) may have a repeating unit having a hydroxyl group or a cyano group. This improves substrate adhesion and developer affinity.
• the repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group.
• the repeating unit having a hydroxyl group or a cyano group preferably has no acid-degradable group. Examples of the repeating unit having a hydroxyl group or a cyano group include repeating units represented by the following general formulas (AIIA) to (AIId).
• R 1c represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
• R 2c to R 4c independently represent a hydrogen atom, a hydroxyl group or a cyano group. However, at least one of R 2c to R 4c represents a hydroxyl group or a cyano group.
• one or two of R 2c to R 4c are hydroxyl groups and the rest are hydrogen atoms. More preferably, two of R 2c to R 4c are hydroxyl groups, and the rest are hydrogen atoms.
• the content of the repeating unit having a hydroxyl group or a cyano group is preferably 5 mol% or more, more preferably 10 mol% or more, based on all the repeating units in the resin (A).
• the upper limit is preferably 60 mol% or less, more preferably 55 mol% or less, still more preferably 50 mol% or less.
• repeating unit having a hydroxyl group or a cyano group are given below, but the present invention is not limited thereto.
• the resin (A) may have a repeating unit having an alkali-soluble group.
• the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol group in which the ⁇ -position is substituted with an electron-attracting group (for example, a hexafluoroisopropanol group).
• a carboxyl group is preferred.
• the repeating unit having an alkali-soluble group includes a repeating unit in which an alkali-soluble group is directly bonded to the main chain of the resin, such as a repeating unit made of acrylic acid and methacrylic acid, or a repeating unit in which the alkali-soluble group is directly bonded to the main chain of the resin via a linking group. Repeat units to which an alkali-soluble group is attached can be mentioned.
• the linking group may have a monocyclic or polycyclic cyclic hydrocarbon structure.
• a repeating unit made of acrylic acid or methacrylic acid is preferable.
• the content of the repeating unit having an alkali-soluble group is preferably 0 mol% or more, more preferably 3 mol% or more, still more preferably 5 mol% or more, based on all the repeating units in the resin (A).
• the upper limit is preferably 20 mol% or less, more preferably 15 mol% or less, still more preferably 10 mol% or less.
• Rx represents H, CH 3 , CH 2 OH, or CF 3 .
• It has at least two selected from a lactone group, a hydroxyl group, a cyano group, and an alkali-soluble group as a repeating unit having at least one group selected from a lactone group, a hydroxyl group, a cyano group, and an alkali-soluble group.
• the repeating unit is preferable, the repeating unit having a cyano group and a lactone group is more preferable, and the repeating unit having a structure in which the cyano group is substituted with the lactone structure represented by the general formula (LC1-4) is further preferable.
• the resin (A) may have an alicyclic hydrocarbon structure and may have a repeating unit that does not exhibit acid decomposition. This makes it possible to reduce the elution of low molecular weight components from the resist film to the immersion liquid during immersion exposure.
• Examples of such a repeating unit include 1-adamantyl (meth) acrylate, diamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, and a repeating unit derived from cyclohexyl (meth) acrylate.
• the resin (A) may have a repeating unit represented by the general formula (III), which has neither a hydroxyl group nor a cyano group.
• R 5 represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxyl group nor a cyano group.
• Ra represents a hydrogen atom, an alkyl group or -CH 2 -O-Ra 2 group.
• Ra 2 represents a hydrogen atom, an alkyl group or an acyl group.
• the cyclic structure of R 5 includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group.
• the monocyclic hydrocarbon group include a cycloalkyl group having 3 to 12 carbon atoms (more preferably 3 to 7 carbon atoms) and a cycloalkenyl group having 3 to 12 carbon atoms.
• Examples of the polycyclic hydrocarbon group include a ring-aggregated hydrocarbon group and a crosslinked ring hydrocarbon group.
• Examples of the crosslinked ring hydrocarbon ring include a bicyclic hydrocarbon ring, a tricyclic hydrocarbon ring, and a tetracyclic hydrocarbon ring.
• the crosslinked hydrocarbon ring also includes a fused ring in which a plurality of 5- to 8-membered cycloalkane rings are condensed.
• Examples of the crosslinked cyclic hydrocarbon group, a norbornyl group, an adamantyl group, a bicyclooctanyl group, or, tricyclo [5,2,1,0 2,6] decanyl group are preferred, norbornyl group or more preferably an adamantyl group.
• the alicyclic hydrocarbon group may have a substituent, and examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group protected by a protecting group, and an amino group protected by a protecting group.
• a halogen atom a bromine atom, a chlorine atom, or a fluorine atom is preferable.
• alkyl group a methyl group, an ethyl group, a butyl group, or a t-butyl group is preferable.
• the alkyl group may further have a substituent, and examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group protected by a protecting group, and an amino group protected by a protecting group.
• Examples of the protecting group include an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, and an aralkyloxycarbonyl group.
• the alkyl group an alkyl group having 1 to 4 carbon atoms is preferable.
• the substituted methyl group a methoxymethyl group, a methoxythiomethyl group, a benzyloxymethyl group, a t-butoxymethyl group, or a 2-methoxyethoxymethyl group is preferable.
• a 1-ethoxyethyl group or a 1-methyl-1-methoxyethyl group is preferable.
• the acyl group an aliphatic acyl group having 1 to 6 carbon atoms such as a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, and a pivaloyl group is preferable.
• an alkoxycarbonyl group an alkoxycarbonyl group having 1 to 4 carbon atoms is preferable.
• the content of the repeating unit represented by the general formula (III), which has neither a hydroxyl group nor a cyano group, is preferably 0 to 40 mol%, preferably 0 to 20 mol%, based on all the repeating units in the resin (A). More preferably mol%.
• Specific examples of the repeating unit represented by the general formula (III) are given below, but the present invention is not limited thereto.
• Ra represents H, CH 3 , CH 2 OH, or CF 3 .
• the resin (A) may have a repeating unit other than the repeating unit described above.
• the resin (A) is a repeating unit selected from the group consisting of a repeating unit having an oxazolone ring group, a repeating unit having an oxazolone ring group, a repeating unit having a dioxane ring group, and a repeating unit having a hydantoin ring group. You may have. Such repeating units are illustrated below.
• the resin (A) contains various repeating structural units for the purpose of adjusting dry etching resistance, standard developer suitability, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, and the like. You may have.
• all the repeating units are composed of (meth) acrylate-based repeating units.
• all of the repeating units are methacrylate-based repeating units
• all of the repeating units are acrylate-based repeating units
• all of the repeating units are either methacrylate-based repeating units or acrylate-based repeating units. It can be used, and it is preferable that the acrylate-based repeating unit is 50 mol% or less of all the repeating units.
• the resin (A) can be synthesized according to a conventional method (for example, radical polymerization).
• the weight average molecular weight of the resin (A) is preferably 1000 to 200,000, more preferably 3,000 to 20,000, and even more preferably 5,000 to 15,000.
• the weight average molecular weight of the resin (A) is preferably 1000 to 200,000, more preferably 3,000 to 20,000, and even more preferably 5,000 to 15,000.
• the dispersity (molecular weight distribution) of the resin (A) is usually 1 to 5, preferably 1 to 3, more preferably 1.20 to 3.00, and even more preferably 1.20 to 2.00.
• the content of the resin (A) is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass, based on the total solid content of the composition.
• the solid content is intended to be a component in the composition excluding the solvent, and any component other than the solvent is regarded as a solid content even if it is a liquid component.
• the resin (A) may be used alone or in combination of two or more.
• the resist composition may contain other photoacid generators that do not correspond to the specific compound (compounds that do not correspond to the specific compound and generate an acid by irradiation with active light or radiation).
• Other photoacid generators are compounds that generate acids upon exposure (preferably exposure to EUV light and / or ArF).
• the other photoacid generator may be in the form of a low molecular weight compound or may be incorporated in a part of the polymer. Further, the form of the low molecular weight compound and the form incorporated in a part of the polymer may be used in combination.
• the molecular weight is preferably 3000 or less, more preferably 2000 or less, still more preferably 1000 or less.
• the other photoacid generator is in the form of being incorporated in a part of the polymer, it may be incorporated in a part of the resin (A) or may be incorporated in a resin different from the resin (A). ..
• the photoacid generator is preferably in the form of a low molecular weight compound.
• Other photoacid generators are not particularly limited, and among them, compounds that generate organic acids are preferable, and examples of the organic acids include organic acids described as organic acids that can generate specific compounds.
• photoacid generators for example, "M + X -" in a compound represented by (onium salts).
• X - "M + X" - represents an organic anion.
• M + X -" X in - is, X described for the general formula (1) in the particular compounds - organic anions represented by the use as well.
• M + X -" in a compound represented by, M + represents an organic cation.
• the organic cations are preferably cations represented by the general formula (ZaI) (cations (ZaI)) or cations represented by the general formula (ZaII) (cations (ZaII)) independently.
• the cation represented by the general formula (ZaI) is different from the specific cation in the specific compound.
• R 201 , R 202 , and R 203 each independently represent an organic group.
• the carbon number of the organic group as R 201 , R 202 , and R 203 is usually 1 to 30, preferably 1 to 20.
• two of R 201 to R 203 may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group.
• the two of the group formed by bonding of the R 201 ⁇ R 203 for example, an alkylene group (e.g., butylene, pentylene), and, -CH 2 -CH 2 -O-CH 2 -CH 2 - Can be mentioned.
• Examples of the cation in the general formula (ZaI) include a cation (ZaI-1) described later.
• the cation (ZaI-1) is an aryl sulfonium cation in which at least one of R 201 to R 203 of the above general formula (ZaI) is an aryl group.
• the aryl sulfonium cation all of R 201 to R 203 may be an aryl group, or a part of R 201 to R 203 may be an aryl group and the rest may be an alkyl group or a cycloalkyl group.
• one of R 201 to R 203 may be an aryl group, and the remaining two of R 201 to R 203 may be bonded to form a ring structure, and an oxygen atom, a sulfur atom, and the like may be formed in the ring.
• It may contain an ester group, an amide group, or a carbonyl group.
• a group formed by bonding two of R 201 to R 203 for example, one or more methylene groups are substituted with an oxygen atom, a sulfur atom, an ester group, an amide group, and / or a carbonyl group.
• an alkylene group e.g., butylene group, pentylene group, or, -CH 2 -CH 2 -O-CH 2 -CH 2 -
• aryl sulfonium cation examples include a triaryl sulfonium cation, a diallyl alkyl sulfonium cation, an aryl dialkyl sulfonium cation, a diallyl cycloalkyl sulfonium cation, and an aryl dicycloalkyl sulfonium cation.
• the aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
• the aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the heterocyclic structure include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, benzothiophene residues and the like.
• the aryl sulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different.
• the alkyl group or cycloalkyl group that the arylsulfonium cation has as needed is a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a branched alkyl group having 3 carbon atoms.
• a cycloalkyl group of up to 15 is preferable, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group. ..
• the aryl group, alkyl group, and substituent that the cycloalkyl group of R 201 to R 203 may have are independently an alkyl group (for example, 1 to 15 carbon atoms) and a cycloalkyl group (for example, carbon number of carbon atoms). 3 to 15), aryl group (for example, 6 to 14 carbon atoms), alkoxy group (for example, 1 to 15 carbon atoms), cycloalkyl alkoxy group (for example, 1 to 15 carbon atoms), halogen atom, hydroxyl group, or phenylthio group. preferable.
• the substituent may further have a substituent if possible.
• the alkyl group may have a halogen atom as a substituent and may be an alkyl halide group such as a trifluoromethyl group. good.
• photoacid generators examples include the following compounds.
• the content thereof is not particularly limited, but the effect of the present invention is more excellent, and the content is 0.5% by mass or more based on the total solid content of the composition. Is preferable, 1% by mass or more is more preferable, and 2% by mass or more is further preferable.
• the content is preferably 40% by mass or less, more preferably 35% by mass or less, and further preferably 30% by mass or less.
• the photoacid generator may be used alone or in combination of two or more.
• the resist composition may contain a solvent.
• Solvents consist of (M1) propylene glycol monoalkyl ether carboxylate, and (M2) propylene glycol monoalkyl ether, lactic acid ester, acetate ester, alkoxypropionic acid ester, chain ketone, cyclic ketone, lactone, and alkylene carbonate. It preferably contains at least one selected from the group.
• the solvent may further contain components other than the components (M1) and (M2).
• the present inventors have found that when such a solvent and the above-mentioned resin are used in combination, the coatability of the composition is improved and a pattern having a small number of development defects can be formed. The reason is not always clear, but since these solvents have a good balance of solubility, boiling point and viscosity of the above-mentioned resins, uneven film thickness of the composition film and generation of precipitates in spin coating can be suppressed. The present inventors believe that this is due to.
• the component (M1) is preferably at least one selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA: propylene glycol monomethyl ether acetate), propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether acetate, preferably propylene glycol.
• PGMEA propylene glycol monomethyl ether acetate
• PGMEA Monomethyl ether acetate
• the component (M2) is preferably the following solvent.
• propylene glycol monoalkyl ether propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether (PGEE) are preferable.
• the lactate ester is preferably ethyl lactate, butyl lactate, or propyl lactate.
• the acetic acid ester is preferably methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl acetate, ethyl acetate, butyl acetate, propyl acetate, or 3-methoxybutyl acetate.
• alkoxypropionate ester is preferably methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP).
• Chain ketones are 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone.
• Acetoneacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthyl ketone, or methyl amyl ketone is preferred.
• the cyclic ketone is preferably methylcyclohexanone, isophorone, cyclopentanone, or cyclohexanone.
• the lactone is preferably ⁇ -butyrolactone.
• the alkylene carbonate is preferably propylene carbonate.
• the component (M2) is more preferably propylene glycol monomethyl ether (PGME), ethyl lactate, ethyl 3-ethoxypropionate, methyl amyl ketone, cyclohexanone, butyl acetate, pentyl acetate, ⁇ -butyrolactone, or propylene carbonate.
• PGME propylene glycol monomethyl ether
• ethyl lactate ethyl 3-ethoxypropionate
• methyl amyl ketone cyclohexanone
• butyl acetate pentyl acetate
• ⁇ -butyrolactone propylene carbonate
• an ester solvent having 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12 and even more preferably 7 to 10) and having a heteroatom number of 2 or less.
• ester solvent having 7 or more carbon atoms and 2 or less heteroatomic atoms examples include amyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, butyl propionate, and iso.
• Examples thereof include isobutyl butyrate, heptyl propionate, butyl butanoate and the like, and isoamyl acetate is preferable.
• the component (M2) is preferably a solvent having a flash point (hereinafter, also referred to as “fp”) of 37 ° C. or higher.
• Such components (M2) include propylene glycol monomethyl ether (fp: 47 ° C.), ethyl lactate (fp: 53 ° C.), ethyl 3-ethoxypropionate (fp: 49 ° C.), and methylamyl ketone (fp: 42 ° C.).
• Cyclohexanone (fp: 44 ° C), pentyl acetate (fp: 45 ° C), methyl 2-hydroxyisobutyrate (fp: 45 ° C), ⁇ -butyrolactone (fp: 101 ° C), or propylene carbonate (fp: 132 ° C).
• °C is preferable.
• propylene glycol monoethyl ether, ethyl lactate, pentyl acetate, or cyclohexanone is more preferable, and propylene glycol monoethyl ether or ethyl lactate is even more preferable.
• the "flash point” means a value described in the reagent catalog of Tokyo Chemical Industry Co., Ltd. or Sigma-Aldrich Co., Ltd.
• the solvent preferably contains the component (M1). It is more preferable that the solvent is substantially composed of only the component (M1) or is a mixed solvent of the component (M1) and other components. In the latter case, the solvent more preferably contains both the component (M1) and the component (M2).
• the mass ratio (M1 / M2) of the component (M1) to the component (M2) is preferably "100/0" to "0/10", more preferably “100/0” to "15/85", and ""100/0" to “40/60” are more preferable, and "100/0" to "60/40” are particularly preferable. That is, when the solvent contains both the component (M1) and the component (M2), the mass ratio of the component (M1) to the component (M2) is preferably 15/85 or more, more preferably 40/60 or more. 60/40 or more is more preferable. By adopting such a configuration, the number of development defects can be further reduced.
• the mass ratio of the component (M1) to the component (M2) is, for example, 99/1 or less.
• the solvent may further contain components other than the components (M1) and (M2).
• the content of the components other than the components (M1) and (M2) is preferably 5 to 30% by mass with respect to the total amount of the solvent.
• the content of the solvent in the resist composition is preferably set so that the solid content concentration is 0.5 to 30% by mass, and more preferably 1 to 20% by mass. This way The coatability of the resist composition can be further improved.
• the solid content means all components other than the solvent.
• the resist composition may further contain an acid diffusion control agent.
• the acid diffusion control agent acts as a quencher for trapping the acid generated from the photoacid generator, and plays a role of controlling the acid diffusion phenomenon in the resist film.
• the acid diffusion control agent may be, for example, a basic compound.
• the basic compound is preferably a compound having a structure represented by the following general formulas (A) to (E).
• R 200 , R 201 and R 202 may be the same or different, and may be the same or different, and may be a hydrogen atom, an alkyl group (preferably 1 to 20 carbon atoms), or a cycloalkyl group (preferably 1 to 20 carbon atoms). Represents an aryl group (preferably 6 to 20 carbon atoms), and R 201 and R 202 may be bonded to each other to form a ring.
• the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms.
• R 203 , R 204 , R 205 and R 206 may be the same or different and represent an alkyl group having 1 to 20 carbon atoms. It is more preferable that the alkyl groups in the general formula (A) and the general formula (E) are unsubstituted.
• guanidine aminopyrrolidin, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholin (alkyl group portion may be linear or branched chain, partly replaced with ether group and / or ester group.
• the total number of all amino acids other than the hydrogen atom in the alkyl group portion is preferably 1 to 17), or piperazine or the like is preferred.
• Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, and benzimidazole.
• Compounds having a diazabicyclo structure include, for example, 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] nona-5-ene, and 1,8-diazabicyclo [ 5,4,0] Undeca-7-en and the like.
• Examples of the compound having an onium hydroxide structure include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, and sulfonium hydroxide having a 2-oxoalkyl group.
• triphenylsulfonium hydroxide tris (t-butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxydo.
• Examples of the compound having an onium carboxylate structure include those in which the anion portion of the compound having an onium hydroxide structure is carboxylated, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkyl carboxylate. Can be mentioned.
• Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine.
• Examples of the aniline compound include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline and the like.
• Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, tris (methoxyethoxyethyl) amine, and "(HO-C 2 H 4- OC 2 H 4). ) 2 N (-C 3 H 6 -O-CH 3 ) "and the like.
• Examples of the aniline derivative having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline and the like.
• Preferred examples of the basic compound include an amine compound having a phenoxy group and an ammonium salt compound having a phenoxy group.
• amine compound for example, primary, secondary and tertiary amine compounds can be used, and an amine compound in which at least one alkyl group is bonded to a nitrogen atom is preferable.
• the amine compound is more preferably a tertiary amine compound.
• the amine compound has a cycloalkyl group (preferably 3 to 20 carbon atoms) or an aryl group (preferably 3 to 20 carbon atoms) in addition to the alkyl group as long as at least one alkyl group (preferably 1 to 20 carbon atoms) is bonded to the nitrogen atom.
• the amine compound preferably has an oxyalkylene group.
• the number of oxyalkylene groups is preferably 1 or more in the molecule, more preferably 3 to 9, and even more preferably 4 to 6.
• an oxyethylene group (-CH 2 CH 2 O-) or an oxypropylene group (-CH (CH 3 ) CH 2 O- or CH 2 CH 2 CH 2 O-) is preferable, and oxyethylene. Groups are more preferred.
• ammonium salt compound examples include primary, secondary, tertiary and quaternary ammonium salt compounds, and an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom is preferable.
• the ammonium salt compound has a cycloalkyl group (preferably 3 to 20 carbon atoms) or an aryl group in addition to the alkyl group as long as at least one alkyl group (preferably 1 to 20 carbon atoms) is bonded to the nitrogen atom. (Preferably 6 to 12 carbon atoms) may be bonded to the nitrogen atom.
• the ammonium salt compound preferably has an oxyalkylene group.
• the number of oxyalkylene groups is preferably 1 or more in the molecule, more preferably 3 to 9, and even more preferably 4 to 6.
• an oxyethylene group (-CH 2 CH 2 O-) or an oxypropylene group (-CH (CH 3 ) CH 2 O- or -CH 2 CH 2 CH 2 O-) is preferable.
• Oxyethylene groups are more preferred.
• the anion of the ammonium salt compound include a halogen atom, a sulfonate, a borate, and a phosphate, and among them, a halogen atom or a sulfonate is preferable.
• the halogen atom is preferably a chlorine atom, a bromine atom, or an iodine atom.
• the sulfonate is preferably an organic sulfonate having 1 to 20 carbon atoms.
• Examples of the organic sulfonate include an alkyl sulfonate having 1 to 20 carbon atoms and an aryl sulfonate.
• the alkyl group of the alkyl sulfonate may have a substituent, and examples of the substituent include a fluorine atom, a chlorine atom, a bromine atom, an alkoxy group, an acyl group, an aromatic ring group and the like.
• alkyl sulphonate examples include methane sulphonate, ethane sulphonate, butane sulphonate, hexane sulphonate, octane sulphonate, benzyl sulphonate, trifluoromethane sulphonate, pentafluoroethane sulphonate, and nonafluorobutane sulphonate.
• aryl group of the aryl sulfonate examples include a benzene ring group, a naphthalene ring group, and an anthracene ring group.
• the substituents that the benzene ring group, the naphthalene ring group, and the anthracene ring group can have are a linear or branched alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms. preferable.
• Examples of the linear or branched alkyl group and cycloalkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, i-butyl group and t-butyl group. Examples thereof include an n-hexyl group and a cyclohexyl group.
• substituents include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a nitro group, an acyl group, an acyloxy group and the like.
• the amine compound having a phenoxy group and the ammonium salt compound having a phenoxy group are those having a phenoxy group at the terminal opposite to the nitrogen atom of the alkyl group of the amine compound or the ammonium salt compound.
• the substituent of the phenoxy group include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and Examples thereof include an aryloxy group.
• the substituent of the substituent may be any of 2 to 6 positions.
• the number of substituents may be any of 1 to 5.
• oxyalkylene group between the phenoxy group and the nitrogen atom.
• the number of oxyalkylene groups is preferably 1 or more in the molecule, more preferably 3 to 9, and even more preferably 4 to 6.
• an oxyethylene group (-CH 2 CH 2 O-) or an oxypropylene group (-CH (CH 3 ) CH 2 O- or -CH 2 CH 2 CH 2 O-) is preferable, and oxy Ethylene groups are more preferred.
• a primary or secondary amine having a phenoxy group and a haloalkyl ether are heated and reacted, and then a strong base (for example, sodium hydroxide, potassium hydroxide, and tetraalkylammonium hydroxide) is added to the reaction system.
• a strong base for example, sodium hydroxide, potassium hydroxide, and tetraalkylammonium hydroxide
• Etc. is added, and the reaction product is further extracted with an organic solvent (for example, ethyl acetate, chloroform, etc.).
• the resist composition has a proton-accepting functional group as an acid diffusion control agent, and is decomposed by irradiation with active light or radiation to reduce or eliminate the proton accepting property, or is acidic from the proton accepting property. It may contain a compound (hereinafter, also referred to as “compound (PA)”) that generates a compound changed to.
• compound (PA) also referred to as “compound (PA)”
• the proton-accepting functional group is a group capable of electrostatically interacting with a proton or a functional group having an electron, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or a functional group having a macrocyclic structure. It means a functional group having a nitrogen atom having an unshared electron pair that does not contribute to ⁇ -conjugation.
• the nitrogen atom having an unshared electron pair that does not contribute to ⁇ conjugation is, for example, a nitrogen atom having a partial structure shown in the following general formula.
• Preferred partial structures of the proton acceptor functional group include, for example, a crown ether structure, an aza-crown ether structure, a primary to tertiary amine structure, a pyridine structure, an imidazole structure, a pyrazine structure and the like.
• the compound (PA) is decomposed by irradiation with active light or radiation to reduce or eliminate the proton acceptor property, or generate a compound in which the proton acceptor property is changed to acidic.
• the decrease or disappearance of the proton acceptor property or the change from the proton acceptor property to the acidity is a change in the proton acceptor property due to the addition of a proton to the proton acceptor property functional group.
• Examples of the compound (PA) include those described in paragraphs [0421] to [0428] of JP-A-2014-413328 and paragraphs [0108]-[0116] of JP-A-2014-134686. Incorporated and these contents are incorporated herein.
• a low molecular weight compound having a nitrogen atom and a group desorbed by the action of an acid can also be used as an acid diffusion control agent.
• the low molecular weight compound is preferably an amine derivative having a group eliminated by the action of an acid on a nitrogen atom.
• the group eliminated by the action of the acid is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminol ether group, and a carbamate group or a hemiaminol ether group is more preferable. preferable.
• the molecular weight of the low molecular weight compound is preferably 100 to 1000, more preferably 100 to 700, and even more preferably 100 to 500.
• the low molecular weight compound may have a carbamate group having a protecting group on the nitrogen atom.
• the content of the acid diffusion control agent is preferably 0.001 to 15% by mass, preferably 0.01 to 8% by mass, based on the total solid content of the resist composition. More preferred.
• the acid diffusion control agent may be used alone or in combination of two or more.
• the resist composition is represented by a specific compound having an anion represented by any of the formulas (d1-1) to (d1-3) and / or any of the formulas (d1-1) to (d1-3).
• d1 photoacid generators When other photoacid generators having an anions (hereinafter, collectively referred to as "d1 photoacid generators") are contained, the d1 photoacid generators also play a role as an acid diffusion control agent. Can also be given.
• the resist composition contains a d1 photoacid generator
• the resist composition does not substantially contain an acid diffusion control agent.
• the fact that the acid diffusion control agent is not substantially contained means that the content of the acid diffusion control agent is 5% by mass or less with respect to the total content of the d1 photoacid generator.
• the total content thereof is preferably 1 to 30% by mass, more preferably 3 to 20% by mass.
• the molar ratio is preferably 2.0 or more from the viewpoint of sensitivity and resolution, and the molar ratio is preferably 300 or less from the viewpoint of suppressing a decrease in resolution due to the thickening of the resist pattern over time from exposure to heat treatment.
• the photoacid generator / acid diffusion control agent (molar ratio) is more preferably 2.0 to 200, and even more preferably 2.0 to 150.
• Examples of the acid diffusion control agent include the compounds described in paragraphs [0140] to [0144] of JP2013-011833 (amine compounds, amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, etc.). Can also be mentioned.
• the resist composition may contain a hydrophobic resin different from the resin (A) in addition to the resin (A).
• Hydrophobic resins are preferably designed to be unevenly distributed on the surface of the resist film, but unlike surfactants, they do not necessarily have to have hydrophilic groups in the molecule and are a uniform mixture of polar and non-polar substances. It does not have to contribute to.
• the effects of adding the hydrophobic resin include controlling the static and dynamic contact angles of the resist film surface with respect to water, and suppressing outgas.
• Hydrophobic resin from the viewpoint of uneven distribution in the film surface layer, "fluorine atom”, “silicon atom”, and has any one or more "CH 3 partial structure contained in the side chain portion of the resin” It is preferable to have two or more kinds. Further, the hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be contained in the main chain of the resin or may be substituted in the side chain.
• the fluorine atoms and / or silicon atoms in the hydrophobic resin may be contained in the main chain of the resin and may be contained in the side chain. You may.
• the partial structure having a fluorine atom is preferably an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom.
• the alkyl group having a fluorine atom (preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. Further, it may have a substituent other than a fluorine atom.
• the cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than the fluorine atom.
• the aryl group having a fluorine atom include those in which at least one hydrogen atom of an aryl group such as a phenyl group and a naphthyl group is substituted with a fluorine atom, and further have a substituent other than the fluorine atom. May be.
• Examples of the repeating unit having a fluorine atom or a silicon atom include the repeating unit exemplified in paragraph [0519] of US2012 / 0251948A1.
• the hydrophobic resin may preferably contain a CH 3 partial structure side chain moiety.
• CH 3 partial structure contained in the side chain portion in the hydrophobic resin an ethyl group, and is intended to include CH 3 partial structure a propyl group has.
• the methyl group directly bonded to the main chain of the hydrophobic resin (for example, the ⁇ -methyl group of the repeating unit having a methacrylic acid structure) contributes to the uneven distribution of the surface of the hydrophobic resin due to the influence of the main chain. small Therefore, not included in the CH 3 partial structures in the present invention.
• the hydrophobic resin may have a repeating unit having an acid-degradable group.
• the resins described in JP2011-24801A, JP2010-175859, and JP2012-032544 can also be preferably used.
• a preferable example of the monomer corresponding to the repeating unit constituting the hydrophobic resin is shown below.
• the content of the hydrophobic resin is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, based on the total solid content of the resist composition. ..
• the resist composition may contain a surfactant.
• a surfactant When a surfactant is included, a pattern having better adhesion and fewer development defects can be formed.
• the surfactant is preferably a fluorine-based and / or silicon-based surfactant. Fluorine-based and / or silicon-based surfactants include, for example, the surfactants described in paragraph [0276] of US Patent Application Publication No. 2008/0248425.
• Ftop EF301 or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Florard FC430, 431, and 4430 (manufactured by Sumitomo 3M Co., Ltd.); Megafuck F171, F173, F176, F189, F113, F110, F177, F120, and R08 (manufactured by DIC Co., Ltd.); Surflon S-382, SC101, 102, 103, 104, 105 or 106 (manufactured by Asahi Glass Co., Ltd.); Troysol S-366 (manufactured by Troy Chemical Co., Ltd.) ); GF-300 or GF-150 (manufactured by Toa Synthetic Chemical Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.); EF801, EF802 or EF601 (manufactured by Gemco Co., Ltd.); PF636, PF
• the surfactant is a fluoroaliphatic compound produced by a telomerization method (also referred to as a telomer method) or an oligomerization method (also referred to as an oligomer method). May be synthesized using. Specifically, a polymer having a fluoroaliphatic group derived from this fluoroaliphatic compound may be used as a surfactant. This fluoroaliphatic compound can be synthesized, for example, by the method described in JP-A-2002-090991. In addition, surfactants other than the fluorine-based and / or silicon-based surfactants described in paragraph [0280] of US Patent Application Publication No. 2008/0248425 may be used.
• surfactants may be used alone or in combination of two or more.
• the content of the surfactant is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass, based on the total solid content of the composition.
• the resist composition includes a dissolution inhibitory compound, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility in a developing solution (for example, a phenol compound having a molecular weight of 1000 or less, or a carboxylic acid. It may further contain a group-containing alicyclic or aliphatic compound).
• the resist composition may further contain a dissolution inhibitory compound.
• a dissolution inhibitory compound is a compound having a molecular weight of 3000 or less, which is decomposed by the action of an acid to reduce its solubility in an organic developer.
• Step 1 Using a resist composition to form a resist film on a substrate
• Step 2 Step of exposing the resist film
• Step 3 Develop the exposed resist film with a developing solution to form a pattern Steps The procedure of each of the above steps will be described in detail below.
• Step 1 is a step of forming a resist film on the substrate using the resist composition.
• the definition of the resist composition is as described above.
• Examples of the method of forming a resist film on a substrate using a resist composition include a method of applying a resist composition on a substrate. It is preferable to filter the resist composition as necessary before coating.
• the pore size of the filter is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, and even more preferably 0.03 ⁇ m or less.
• the filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.
• the resist composition can be applied onto a substrate (eg, silicon, silicon dioxide coating) such as that used in the manufacture of integrated circuit elements by an appropriate coating method such as a spinner or coater.
• the coating method is preferably spin coating using a spinner.
• the rotation speed at the time of spin coating using a spinner is preferably 1000 to 3000 rpm.
• the substrate may be dried to form a resist film. If necessary, various undercoat films (inorganic film, organic film, antireflection film) may be formed under the resist film.
• drying method examples include a method of heating and drying.
• the heating can be carried out by a means provided in a normal exposure machine and / or a developing machine, and may be carried out by using a hot plate or the like.
• the heating temperature is preferably 80 to 150 ° C, more preferably 80 to 140 ° C, and even more preferably 80 to 130 ° C.
• the heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, still more preferably 60 to 600 seconds.
• the film thickness of the resist film is not particularly limited, but 10 to 65 nm is preferable, and 15 to 50 nm is more preferable, from the viewpoint of being able to form a fine pattern with higher accuracy.
• a top coat may be formed on the upper layer of the resist film by using the top coat composition. It is preferable that the topcoat composition is not mixed with the resist film and can be uniformly applied to the upper layer of the resist film.
• the topcoat composition contains, for example, a resin, an additive, and a solvent.
• the resin the same resin as the above-mentioned hydrophobic resin can be used.
• the content of the resin is preferably 50 to 99.9% by mass, more preferably 60 to 99.7% by mass, based on the total solid content of the topcoat composition.
• the additive the above-mentioned acid diffusion control agent and d1 photoacid generator can be used.
• a compound having a radical trap group such as a compound having an N-oxyl-free radical group can also be used.
• examples of such a compound include [4- (benzoyloxy) -2,2,6,6-tetramethylpiperidinooxy] radicals.
• the content of the additive is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, based on the total solid content of the topcoat composition.
• the solvent preferably does not dissolve the resist film, for example, an alcohol solvent (4-methyl-2-pentanol, etc.), an ether solvent (diisoamyl ether, etc.), an ester solvent, a fluorine solvent, and a solvent. Examples thereof include hydrocarbon solvents (n-decane and the like).
• the content of the solvent in the topcoat composition is preferably set so that the solid content concentration is 0.5 to 30% by mass, and more preferably 1 to 20% by mass.
• the top coat composition may contain a surfactant in addition to the above-mentioned additives, and as the above-mentioned surfactant, a surfactant which may be contained in the composition of the present invention can be used.
• the content of the surfactant is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass, based on the total solid content of the topcoat composition.
• the top coat is not particularly limited, and a conventionally known top coat can be formed by a conventionally known method. Can form a top coat.
• a top coat containing a basic compound as described in JP2013-061648 on the resist film.
• the basic compound that can be contained in the top coat include basic compounds that may be contained in the resist composition.
• the top coat also preferably contains a compound containing at least one group or bond selected from the group consisting of ether bonds, thioether bonds, hydroxyl groups, thiol groups, carbonyl bonds, and ester bonds.
• Step 2 is a step of exposing the resist film.
• Examples of the exposure method include a method of irradiating the formed resist film with EUV light through a predetermined mask.
• the heating temperature is preferably 80 to 150 ° C, more preferably 80 to 140 ° C, and even more preferably 80 to 130 ° C.
• the heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds.
• the heating can be carried out by means provided in a normal exposure machine and / or a developing machine, and may be carried out by using a hot plate or the like. This process is also called post-exposure baking.
• Step 3 is a step of developing the exposed resist film using a developing solution to form a pattern.
• the developer may be an alkaline developer or a developer containing an organic solvent (hereinafter, also referred to as "organic developer").
• Examples of the developing method include a method of immersing the substrate in a tank filled with a developing solution for a certain period of time (dip method), and a method of raising the developing solution on the surface of the substrate by surface tension and allowing it to stand for a certain period of time for development (paddle). Method), a method of spraying the developer on the surface of the substrate (spray method), and a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic discharge). Law). Further, after the step of performing the development, a step of stopping the development may be carried out while substituting with another solvent.
• the development time is not particularly limited as long as the resin in the unexposed portion is sufficiently dissolved, and is preferably 10 to 300 seconds, more preferably 20 to 120 seconds.
• the temperature of the developing solution is preferably 0 to 50 ° C, more preferably 15 to 35 ° C.
• alkaline aqueous solution containing alkali is not particularly limited, and for example, a quaternary ammonium salt typified by tetramethylammonium hydroxide, an inorganic alkali, a primary amine, a secondary amine, a tertiary amine, an alcohol amine, a cyclic amine, or the like can be used.
• Examples include alkaline aqueous solutions containing.
• the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt typified by tetramethylammonium hydroxide (TMAH).
• TMAH tetramethylammonium hydroxide
• An appropriate amount of alcohols, surfactants and the like may be added to the alkaline developer.
• the alkali concentration of the alkaline developer is usually 0.1 to 20% by mass.
• the pH of the alkaline developer is usually 10.0 to 15.0.
• the organic developer is a developer containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, an ether solvent, and a hydrocarbon solvent. Is preferable.
• ketone solvent examples include 1-octanone, 2-octanone, 1-nonanonone, 2-nonanonone, acetone, 2-heptanone (methylamylketone), 4-heptanone, 1-hexanone, 2-hexanone, and diisobutylketone.
• Examples thereof include cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.
• ester solvent examples include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and the like.
• the alcohol solvent for example, the solvents disclosed in paragraphs [0715] to [0718] of US Patent Application Publication No. 2016/0070167A1 can be used. ..
• a plurality of the above solvents may be mixed, or may be mixed with a solvent other than the above or water.
• the water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, further preferably less than 10% by mass, and particularly preferably substantially free of water.
• the content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, and 90% by mass or more and 100% by mass or less, based on the total amount of the developing solution. The following is more preferable, and 95% by mass or more and 100% by mass or less is particularly preferable.
• the pattern forming method preferably includes a step of washing with a rinsing liquid after the step 3.
• Examples of the rinsing solution used in the rinsing step after the step of developing with an alkaline developer include pure water. An appropriate amount of surfactant may be added to pure water. An appropriate amount of surfactant may be added to the rinse solution.
• the rinse solution used in the rinse step after the development step using the organic developer is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used.
• a rinsing solution a rinsing solution containing at least one organic solvent selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and an ether solvent is used. Is preferable.
• the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the amide solvent, and the ether solvent include those similar to those described in the developing solution containing an organic solvent.
• the method of the rinsing process is not particularly limited, for example, a method of continuously discharging the rinsing liquid onto a substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinsing liquid for a certain period of time. Examples thereof include a method (dip method) and a method of spraying a rinse liquid on the surface of the substrate (spray method).
• the pattern forming method of the present invention may include a heating step (Post Bake) after the rinsing step. In this step, the developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed by baking. In addition, this step has the effect of smoothing the resist pattern and improving the surface roughness of the pattern.
• the heating step after the rinsing step is usually performed at 40 to 250 ° C. (preferably 90 to 200 ° C.) for 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).
• the substrate may be etched using the formed pattern as a mask. That is, the pattern formed in step 3 may be used as a mask to process the substrate (or the underlayer film and the substrate) to form the pattern on the substrate.
• the processing method of the substrate (or the underlayer film and the substrate) is not particularly limited, but the substrate (or the underlayer film and the substrate) is dry-etched using the pattern formed in step 3 as a mask to obtain the substrate.
• the method of forming the pattern is preferable.
• the dry etching may be one-step etching or multi-step etching. When the etching is an etching consisting of a plurality of stages, the etching of each stage may be the same process or different processes.
• etching any known method can be used for etching, and various conditions and the like are appropriately determined according to the type and application of the substrate.
• the Bulletin of the International Society of Optical Engineering (Proc. Of SPIE) Vol. Etching can be performed according to 6924, 692420 (2008), Japanese Patent Application Laid-Open No. 2009-267112, and the like. It is also possible to follow the method described in "Chapter 4 Etching" of "Semiconductor Process Textbook 4th Edition 2007 Published Publisher: SEMI Japan". Of these, oxygen plasma etching is preferable for dry etching.
• the resist composition and various materials used in the pattern forming method of the present invention are made of metal or the like. It is preferable that it does not contain impurities.
• the content of impurities contained in these materials is preferably 1 mass ppm or less, more preferably 10 mass ppt or less, further preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less.
• examples of the metal impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, etc. W, Zn and the like can be mentioned.
• Examples of the method for removing impurities such as metals from various materials include filtration using a filter.
• the filter pore size is preferably less than 100 nm, more preferably 10 nm or less, and even more preferably 5 nm or less.
• the filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.
• the filter may be composed of a composite material in which the above filter material and an ion exchange medium are combined.
• a filter that has been previously washed with an organic solvent may be used.
• Filter In the filtration step, a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different pore diameters and / or materials may be used in combination.
• various materials may be filtered a plurality of times, and the step of filtering the various materials a plurality of times may be a circulation filtration step.
• the step of filtering the various materials a plurality of times may be a circulation filtration step.
• a polyethylene filter having a pore diameter of 50 nm, a nylon filter having a pore diameter of 10 nm, and a polyethylene filter having a pore diameter of 3 nm in a permutation and perform circulation filtration 10 times or more.
• the inside of the resist composition manufacturing apparatus is preferably gas-replaced with an inert gas such as nitrogen. This makes it possible to suppress the dissolution of an active gas such as oxygen in the resist composition.
• the resist composition is filtered through a filter and then filled in a clean container.
• the resist composition filled in the container is preferably stored in a refrigerator. As a result, performance deterioration over time is suppressed.
• the shorter the time from the completion of filling the composition into the container to the start of refrigerated storage is preferably, generally within 24 hours, preferably within 16 hours, more preferably within 12 hours, and 10 Within hours is even more preferred.
• the storage temperature is preferably 0 to 15 ° C, more preferably 0 to 10 ° C, and even more preferably 0 to 5 ° C.
• a method of reducing impurities such as metals contained in various materials for example, a method of selecting a raw material having a low metal content as a raw material constituting various materials, and filter filtration of the raw materials constituting various materials are performed. Examples thereof include a method of performing the distillation and a method of performing distillation under conditions in which contamination is suppressed as much as possible by lining the inside of the apparatus with Teflon (registered trademark).
• impurities may be removed by an adsorbent, or filter filtration and an adsorbent may be used in combination.
• a known adsorbent can be used, and for example, an inorganic adsorbent such as silica gel and zeolite, and an organic adsorbent such as activated carbon can be used.
• an inorganic adsorbent such as silica gel and zeolite
• an organic adsorbent such as activated carbon
• Conductive compounds are added to organic treatment liquids such as rinse liquids to prevent damage to chemical liquid piping and various parts (filters, O-rings, tubes, etc.) due to static electricity charging and subsequent electrostatic discharge. You may.
• the conductive compound is not particularly limited, and examples thereof include methanol.
• the amount to be added is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, in terms of maintaining preferable development characteristics or rinsing characteristics.
• antistatic treated polyethylene, polypropylene, or fluororesin polytetrafluoroethylene, perfluoroalkoxy resin, etc.
• a method for improving the surface roughness of the pattern may be applied to the pattern formed by the method of the present invention.
• Examples of the method for improving the surface roughness of the pattern include a method of treating the pattern with a plasma of a hydrogen-containing gas disclosed in International Publication No. 2014/002808.
• Japanese Patent Application Laid-Open No. 2004-235468, US Patent Application Publication No. 2010/0020297, Japanese Patent Application Laid-Open No. 2008-083384, and Proc. Of SPIE Vol. 8328 83280N-1 "EUV Resist Curing Technology for LWR Redox And Etch Sensitivity Enhancement" can be mentioned.
• the aspect ratio obtained by dividing the pattern height by the line width is preferably 2.5 or less, more preferably 2.1 or less, still more preferably 1.7 or less. ..
• the pattern to be formed is a trench pattern or a contact hole pattern
• the aspect ratio obtained by dividing the pattern height by the trench width or the hole diameter is preferably 4.0 or less, preferably 3.5. The following is more preferable, and 3.0 or less is further preferable.
• the pattern forming method of the present invention can also be used for guide pattern forming in DSA (Directed Self-Assembly) (see, for example, ACS Nano Vol. 4 No. 8 Page 4815-4823).
• DSA Directed Self-Assembly
• the pattern formed by the above method can be used as, for example, the core material (core) of the spacer process disclosed in Japanese Patent Application Laid-Open No. 3-270227 and Japanese Patent Application Laid-Open No. 2013-164509.
• the present invention also relates to a method for manufacturing an electronic device including the above-mentioned pattern forming method, and an electronic device manufactured by this manufacturing method.
• the electronic device of the present invention is suitably mounted on an electrical and electronic device (home appliance, OA (Office Automation), media-related device, optical device, communication device, etc.).
• X-1-A (30.0 g) was added to a mixture of phosphorus pentoxide (6.8 g) and methanesulfonic acid (90.8 g). The obtained mixture was cooled to 10 ° C., 2,6-dimethylphenol (11.9 g) was added, and the mixture was stirred at 20 ° C. for 30 minutes. The obtained mixture was heated to 50 ° C. and stirred for another 3 hours, and then water (300 mL) was added dropwise at 20 ° C. or lower. Extraction was performed with methylene chloride (300 mL), the organic layer was washed with water (300 mL), and the solvent was distilled off. The concentrate was crystallized from ethyl acetate (300 mL) and filtered to give X-1-B (35 g) (yield 73%).
• the comparative compounds Z-1 to Z-3 are shown below.
• the photoacid generator is shown below.
• the table below shows the molar ratio of repeating units based on each monomer, the weight average molecular weight (Mw) of each resin, and the degree of dispersion (Mw / Mn) in the hydrophobic resin used in the composition.
• composition of each resist composition is shown below.
• top coat composition when a resist film was prepared using the resist composition, a top coat prepared on the resist film was further prepared as desired.
• the components used in the topcoat composition used to form the topcoat and the manufacturing procedure are shown below.
• ⁇ Resin> The mole fraction of the repeating unit based on each monomer, the weight average molecular weight (Mw) of each resin, and the dispersity (Mw / Mn) of the resin used in the topcoat composition are shown in the table below.
• Mw weight average molecular weight
• Mn dispersity
• topcoat compositions TC-1 to TC-3 Each component was dissolved in a solvent to prepare a solution so as to satisfy the formulations shown in the table below and to have a solid content concentration of 3.8% by mass. Then, the obtained solution was filtered through a polyethylene filter having a pore size of 0.1 ⁇ m to prepare topcoat compositions TC-1 to TC-3.
• FT-1 4-Methyl-2-pentanol (MIBC)
• MIBC 4-Methyl-2-pentanol
• FT-2 n-decane
• FT-3 diisoamyl ether
• the underlayer film forming composition AL412 (manufactured by Brewer Science) was applied onto a silicon wafer and baked at 205 ° C. for 60 seconds to form a base film having a film thickness of 20 nm.
• the resist composition shown in Table 6 was applied thereto and baked at 100 ° C. for 60 seconds to form a resist film having a film thickness of 30 nm.
• an EUV exposure apparatus Micro Exposure Tool, NA0.3, Quadruple, outer sigma 0.68, inner sigma 0.36, manufactured by Exitech
• pattern irradiation was performed on the silicon wafer having the obtained resist film. rice field.
• the resist film after exposure was baked at 90 ° C. for 60 seconds, developed with n-butyl acetate for 30 seconds, and spin-dried to obtain a negative pattern.
• the LWR (nm) is 4.6 nm or less, preferably 4.2 nm or less, more preferably 3.9 nm or less, still more preferably 3.7 nm or less.
• the resist composition of the present invention can form a pattern having excellent LWR performance when a pattern is obtained by EUV exposure and organic solvent development. From the comparison of Examples 1-1 to 1-45, when the sulfonium cation has an acid-degradable group represented by the general formula (a-1) or (a-2), the effect of the present invention may be more excellent. confirmed. Further, from the same comparison, it was confirmed that the effect of the present invention is further excellent when the sulfonium cation has an acid-decomposable group represented by the general formula (a-1).
• the underlayer film forming composition AL412 (manufactured by Brewer Science) was applied onto a silicon wafer and baked at 205 ° C. for 60 seconds to form a base film having a film thickness of 20 nm.
• the resist composition shown in Table 7 was applied thereto and baked at 100 ° C. for 60 seconds to form a resist film having a film thickness of 30 nm.
• an EUV exposure apparatus Micro Exposure Tool, NA0.3, Quadruple, outer sigma 0.68, inner sigma 0.36, manufactured by Exitech
• pattern irradiation was performed on the silicon wafer having the obtained resist film. rice field.
• the resist film after exposure was baked at 90 ° C. for 60 seconds, developed with an aqueous solution of tetramethylammonium hydroxide (2.38% by mass) for 30 seconds, and then rinsed with pure water for 30 seconds. Then, this was spin-dried to obtain a positive pattern.
• the obtained pattern was evaluated by the same method as in which the LWR of the pattern was evaluated by ⁇ EUV exposure, organic solvent development>.
• the organic antireflection film forming composition ARC29SR (manufactured by Brewer Science) was applied onto a silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a film thickness of 98 nm.
• the resist composition shown in Table 8 was applied thereto and baked at 100 ° C. for 60 seconds to form a resist film (active light-sensitive or radiation-sensitive film) having a film thickness of 90 nm.
• a topcoat film was formed on the upper layer of the resist film (the types of topcoat compositions used are shown in Table 8). The film thickness of the top coat film was 100 nm in each case.
• the line width is 45 nm 1: Exposure was performed through a 6% halftone mask with a 1-line and space pattern. Ultrapure water was used as the immersion liquid. The exposed resist film was baked at 90 ° C. for 60 seconds, developed with n-butyl acetate for 30 seconds, and then rinsed with 4-methyl-2-pentanol for 30 seconds. Then, this was spin-dried to obtain a negative pattern.
• a length-measuring scanning electron microscope (SEM Co., Ltd.) was used for a 45 nm (1: 1) line-and-space pattern resolved at the optimum exposure amount when resolving a line pattern with an average line width of 45 nm. It was observed from the upper part of the pattern using Hitachi, Ltd. S-9380II)). The line width of the pattern was observed at arbitrary points (100 points), and the measurement variation was evaluated by 3 ⁇ to obtain an LWR. The smaller the LWR value, the better the LWR performance.
• the LWR (nm) is 3.8 nm or less, preferably 3.2 nm or less, more preferably 2.9 nm or less, further preferably 2.7 nm or less, and 2.5 nm. The following are particularly preferred.
• the organic antireflection film forming composition ARC29SR (manufactured by Brewer Science) was applied onto a silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a film thickness of 98 nm.
• the resist composition shown in Table 9 was applied thereto and baked at 100 ° C. for 60 seconds to form a resist film having a film thickness of 90 nm. note that.
• a topcoat film was formed on the upper layer of the resist film (the types of topcoat compositions used are shown in Table 9). The film thickness of the top coat film was 100 nm in each case.
• the line width is 45 nm 1: Exposure was performed through a 6% halftone mask with a 1-line and space pattern. Ultrapure water was used as the immersion liquid. The resist film after exposure was baked at 90 ° C. for 60 seconds, developed with an aqueous solution of tetramethylammonium hydroxide (2.38% by mass) for 30 seconds, and then rinsed with pure water for 30 seconds. Then, this was spin-dried to obtain a positive pattern.
• the obtained pattern was evaluated by the same method as in which the LWR of the pattern was evaluated by ⁇ ArF immersion exposure, organic solvent development>.

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