Classifications

• • 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
  • C08F220/38—Esters containing sulfur
• • 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
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
  • C08F212/30—Sulfur
• • 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
  • G03F7/20—Exposure; Apparatus therefor

Definitions

• Some aspects of the invention relate to polymers used in resist compositions.
• some aspects of the present invention relate to a resist composition containing the polymer, a method for producing a member using the resist composition, a pattern forming method, and a method for forming an inverted pattern.
• KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), ultra-short ultraviolet (EUV, wavelength 13.5 nm) and electron beam.
• Light with a very short wavelength, such as (EB) tends to be used for exposure. Since the lithography technology using these short wavelength lights, especially EUV or electron beam, can be manufactured by single patterning, there is a need for a resist composition that is highly sensitive to EUV, electron beam, or the like. It is expected to increase further in the future.
• the resist composition With the shortening of the wavelength of the exposure light source, the resist composition is required to have improved sensitivity to the exposure light source and lithographic characteristics having high resolution capable of reproducing a pattern of fine dimensions.
• a chemically amplified resist is known as a resist composition that satisfies such a requirement (Patent Document 1).
• Patent Document 1 A chemically amplified resist is known as a resist composition that satisfies such a requirement.
• LWR line edge roughness
• Patent Documents 2 and 3 In order to reduce the LWR of the resist and achieve high resolution, there is a method of reducing the diffusion of acid due to heat by using an acid generator having a large molecular weight and bulky acid anion or an acid anion bonded to a polymer. are known. (Patent Documents 2 and 3)
• Japanese Unexamined Patent Publication No. 9-90637 Japanese Unexamined Patent Publication No. 2011-53622 Japanese Unexamined Patent Publication No. 2010-276910
• Some embodiments of the present invention occur not only by utilizing an acid generated from an acid generator by irradiation with a particle beam or an electromagnetic wave, particularly an electron beam or EUV, but also by irradiation with an electron beam or EUV at the same time as an acid catalytic reaction. It is an object of the present invention to provide a polymer used for a resist composition having excellent characteristics of resolution and pattern performance by significantly suppressing acid diffusion by directly utilizing the reaction. It is an object of some aspects of the present invention to provide a resist composition containing the polymer, a method for producing a member using the resist composition, a pattern forming method, and a method for forming an inverted pattern.
• the present inventors have a unit having a specific onium salt structure having a monovalent organic group having at least one selected from the group consisting of a hydroxyl group and a sulfanyl group as an anion.
• a polymer containing A and a unit B having a specific structure as a polymer of a resist composition, high sensitivity and linewise roughness (LWR) can be suppressed, and some aspects of the present invention have been found.
• LWR linewise roughness
• the resist composition containing the polymer becomes the following when irradiated with a particle beam, an electromagnetic wave, or the like.
• the unit A decomposes and a large polar conversion from ionic to nonionic occurs.
• an acid is generated by the decomposition of the unit A, and the generated acid causes an intramolecular cross-linking reaction between the hydroxyl groups of the unit B and / or between the unit A and the unit B. ..
• the anion having the onium salt structure of the unit A is an anion having an organic group containing a hydroxyl group or a sulfanyl group
• a part of the anion is a hydroxyl group or a sulfanyl group in the anion, the unit B and an acid. It binds by a catalytic reaction and is incorporated into the polymer to become the acid of the polymer anion. Therefore, the resist composition containing the polymer can suppress acid diffusion, has high sensitivity, and can suppress linewise roughness (LWR).
• One aspect of the present invention that solves the above problems has a specific onium salt structure having a monovalent organic group as an anion having at least one selected from the group consisting of a hydroxyl group and a sulfanyl group, and a particle beam.
• it is a polymer containing a unit A that generates an acid by irradiation with an electromagnetic wave and a unit B having a structure that binds by an acid catalytic reaction.
• the unit A is represented by the following formula (1).
• R 1 is a hydrogen atom; a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms; and a linear, branched or cyclic alkenyl group having 1 to 6 carbon atoms; It is one selected from the group consisting of, and at least one hydrogen atom in the above-mentioned alkyl group and alkenyl group in the R 1 may be substituted with a substituent.
• L is a direct bond, a carbonyloxy group, a carbonylamino group, a phenylenediyl group, a naphthalenediyl group, a phenylenediyloxy group, a naphthalenediyloxy group, a phenylenediylcarbonyloxy group, a naphthalenediylcarbonyloxy group, a phenylenediyloxycarbonyl group and One selected from the group consisting of naphthalenediyloxycarbonyl groups, Sp is a direct bond; a linear, branched or cyclic alkylene group having 1 to 6 carbon atoms which may have a substituent; and a linear, branched or cyclic carbon number which may have a substituent.
• M + is a sulfonium ion or an iodonium ion
• X - is a monovalent anion having a monovalent organic group as an anion having at least one selected from the group consisting of a hydroxyl group and a sulfanil group.
• One aspect of the present invention is a resist composition containing the above polymer. Further, one aspect of the present invention includes a resist film forming step of forming a resist film on a substrate using the resist composition, and a photolithography step of exposing the resist film using particle beams or electromagnetic waves. It is a method for manufacturing a member including a pattern forming step of developing an exposed resist film to obtain a photoresist pattern.
• One aspect of the present invention is a resist film forming step of forming a resist film on a substrate using the resist composition, a photolithography step of exposing the resist film using particle beams or electromagnetic waves, and exposure.
• This is a pattern forming method including a pattern forming step of developing a resist film to obtain a photoresist pattern.
• One aspect of the present invention is a resist film forming step of forming a resist film on a substrate using the resist composition, a photolithography step of exposing the resist film using particle beams or electromagnetic waves, and exposure.
• the polymer according to some aspects of the present invention When the polymer according to some aspects of the present invention is used as a resist composition, it is decomposed by irradiation with a particle beam or an electromagnetic wave to change from ionic to nonionic, and at the same time. Generates acid.
• the generated acid causes an intramolecular cross-linking reaction between the hydroxyl groups of the unit B and / or between the unit A and the unit B.
• the generated acid anion has at least one of a hydroxyl group and a sulfanyl group, it reacts with the unit B in the polymer to become an acid of the polymer anion.
• the "particle beam or electromagnetic wave” includes not only electron beam and extreme ultraviolet rays but also ultraviolet rays and the like, but is preferably electron beam or extreme ultraviolet rays.
• "irradiation with particle beams or electromagnetic waves” means irradiating at least a part of the polymer with particle beams or electromagnetic waves.
• a part of the polymer is irradiated with a particle beam or an electromagnetic wave, a specific part of the polymer is excited or ionized, and an active species is generated.
• At least one secondary reaction such as whether a part of the unit is decomposed by the active species, the active species is added to the unit, or hydrogen of the unit is desorbed by the active species. Raise and generate radicals or acids.
• the "active species” refers to radical cations, radicals, electrons and the like.
• Polymer A polymer according to some aspects of the present invention is a polymer containing a unit A that generates an acid having a specific onium salt structure and a unit B having a structure that binds by an acid catalytic reaction.
• an anion and a first radical are generated from the unit A by the reduction of the unit A by irradiating at least a part of the polymer with a particle beam or an electromagnetic wave. Some of the generated anions combine with protons to form acids.
• a cross-linking reaction can occur by catalyzing the acid to ether or thioether by the reaction between the units B and / or between the unit A and the unit B.
• a unit other than the unit B has at least one of a hydroxyl group and a sulfanyl group
• Cross-linking reactions can also occur with at least one of the sulfanyl groups.
• a part of the generated acid anion or the anion of the unit A can be bonded to at least one of the hydroxyl group and the sulfanyl group of the anion by the acid in the unit B to become a polymer acid.
• the first radicals and / or the second radical generated when the unit for generating the radical is contained in the polymer and the first radicals form a bond with each other.
• Intramolecular cross-linking reactions can occur between the units A and / or between the units A and a unit that generates radicals (for example, unit C described later).
• the polymer is excellent in LWR characteristics because acid diffusion can be suppressed by forming a bond between the acid and at least one of the hydroxyl group and sulfanil group of the anion with the unit B.
• the unit A has a specific onium salt structure. Specifically, the onium salt structure undergoes a polarity conversion by irradiating at least a part of the polymer with a particle beam or an electromagnetic wave, and at least one of a hydroxyl group and a sulfanyl group is added to the anion portion of the onium salt. It is preferable to have an organic group containing one. That is, the onium salt structure is not particularly limited as long as it has at least one of a hydroxyl group and a sulfanyl group in the anion portion and generates an acid by reduction of the onium salt. Specifically, for example, the one represented by the following formula (1) can be mentioned.
• "polarity conversion" means that the polarity is directly or indirectly changed from ionic to nonionic by irradiation with a particle beam or an electromagnetic wave.
• M + is a sulfonium ion or an iodonium ion
• X ⁇ is a monovalent anion having an organic group containing at least one selected from the group consisting of a hydroxyl group and a sulfanyl group. ..
• L is not particularly limited as long as it can bond the main chain constituting the polymer to the onium salt structure, but for example, a direct bond, a carbonyloxy group, a carbonylamino group, a phenylenediyl group, a naphthalenediyl group, a phenylenediyloxy group, Any one selected from the group consisting of a naphthalenediyloxy group, a phenylenediylcarbonyloxy group, a naphthalenediylcarbonyloxy group, a phenylenediyloxycarbonyl group and a naphthalenediyloxycarbonyl group can be mentioned.
• L a carbonyloxy group or the like is preferable because it can be easily synthesized.
• Sp is not particularly limited as long as it can be a spacer between the above L and the above onium salt, but is, for example, a direct bond; a linear, branched or cyclic carbon number 1 to 6 which may have a substituent.
• Examples of the linear alkylene group having 1 to 6 carbon atoms of Sp include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group and an n-hexylene group.
• Examples of the branched alkylene group having 1 to 6 carbon atoms of Sp include an isopropylene group, an isobutylene group, a tert-butylene group, an isopentylene group, a tert-pentylene group and a 2-ethylhexylene group.
• Examples of the cyclic alkylene group having 1 to 6 carbon atoms of Sp include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group and a cyclohexylene group. At least one methylene group in Sp may be substituted with a divalent heteroatom-containing group.
• Divalent heteroatom-containing groups include -O-, -CO-, -COO-, -OCO-, -O-CO-O-, -NHCO-, -CONH-, -NH-CO-O-, Groups selected from the group consisting of -O-CO-NH-, -NH-, -N ( RSp)-, -N (Ar Sp ) -, -S-, -SO-, -SO 2- , etc. Can be mentioned.
• R Sp include linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms
• Ar Sp include aryl groups having 12 or less carbon atoms such as phenyl groups and naphthyl groups.
• the carbon number of the alkylene group of Sp does not include the carbon number of the substituent that Sp may have.
• the substituent (hereinafter, also referred to as “first substituent”) that Sp may have is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a hydroxy group; a linear or cyclic carbon.
• a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom
• a hydroxy group such as a linear or cyclic carbon.
• alkyl group an aryl group; and a heteroaryl group containing one heteroatom-containing group selected from the group consisting of.
• Examples of the alkyl group containing the alkyl group as the first substituent of Sp and the heteroatom-containing group in the skeleton include an alkyl group in which the alkylene group of Sp is monovalent.
• Examples of the aryl group as the first substituent of Sp are the same as those of Ar Sp .
• Examples of the heteroaryl group as the first substituent of Sp include groups having a skeleton such as furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine and pyrazine.
• the Sp may be a direct bond, but a spacer structure is preferable so that the molecule can move easily from the viewpoint of radical recombination between the units A and the cross-linking reaction between the units B.
• Preferred examples include an alkylene group, an alkyleneoxy group and an alkylenecarbonyloxy group.
• R 1 is selected from the group consisting of a hydrogen atom; a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms; and a linear, branched or cyclic alkenyl group having 1 to 6 carbon atoms; At least one hydrogen atom in the above-mentioned alkyl group and alkenyl group in the R 1 may be substituted with a substituent. Examples of the substituent that R 1 may have include the same as the above-mentioned first substituent.
• Examples of the linear alkyl group having 1 to 6 carbon atoms of R 1 include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group and an n-hexyl group.
• Examples of the branched alkyl group having 1 to 6 carbon atoms of R 1 include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a tert-pentyl group, a 2-ethylexyl group and the like.
• Examples of the cyclic alkyl group having 1 to 6 carbon atoms of R 1 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group.
• the linear, branched or cyclic alkenyl group having 1 to 6 carbon atoms of R 1 at least one of the carbon-carbon single bonds of the linear alkyl group, the branched alkyl group and the cyclic alkyl group shown above is carbon-carbon. Examples include those substituted with double bonds. Further, it may be a fluorinated alkyl group or a fluorinated alkenyl group in which at least one hydrogen atom in the above-mentioned alkyl group and alkenyl group of R 1 is replaced with a fluorine atom. All hydrogen atoms may be substituted with the above-mentioned first substituent. As the alkyl fluoride group, a trifluoromethyl group or the like is preferable.
• the unit A is preferably one in which R 1 is a hydrogen atom or a linear alkyl group and L is a carbonyloxy group, a carbonylamino group or a phenylenediyl group in the above formula (1). Further, as the unit A, L is a carbonyloxy group or a carbonylamino group, Sp is a direct bond, R1 is a methyl group, and the methyl group is carbon among the first substituents.
• a unit having at least one of a number 1 to 4 alkyl group, a halogen atom and an aryl group is preferable from the viewpoint of LWR.
• R 1 having the first substituent is an ethyl group, an isopropyl group, a butyl group, a methyl halide group (fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, etc.), a benzyl group and the like. Can be mentioned.
• M + are sulfonium cations or iodonium cations having a bond that binds to Sp, and specific examples thereof include those represented by the following general formulas (a1) and (a2).
• R 6a is a linear, branched or cyclic alkylene group having 1 to 6 carbon atoms which may have a substituent; a linear, branched or cyclic which may have a substituent.
• Examples of the linear, branched or cyclic alkylene group of R 6a include the same as the above-mentioned Sp alkylene group.
• Examples of the linear, branched or cyclic alkenylene group of R 6a include those similar to the alkenylene group of Sp.
• Examples of the arylene group having 6 to 14 carbon atoms of R 6a include a phenylene group and a naphthylene group.
• the heteroarylene groups of R 6a having 4 to 12 carbon atoms include furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, indole, purine, quinoline, isoquinoline, chromen, thianthene, dibenzothiophene, phenothiazine and phenothiazine. , Xanthene, aclysine, phenothiazine, carbazole and the like, and examples thereof include divalent groups having a skeleton.
• Examples of the alkyl group, alkenyl group, aryl group and heteroaryl group of R 6b include those in which the alkylene group, alkenylene group, arylene group and heteroarylene group of R 6a are monovalent.
• Examples of the substituent of R 6a and R 6b include a substituent similar to the first substituent that Sp may have.
• any two of R 6a and two R 6b are single-bonded directly or from a group consisting of an oxygen atom, a sulfur atom, a divalent nitrogen atom-containing group and a methylene group.
• a ring structure may be formed with the sulfur atom to which they are bonded via any of the selected ones.
• the divalent nitrogen atom-containing group include those containing a nitrogen atom among the divalent heteroatom-containing groups, and specifically, -NHCO-, -CONH-, and -NH-CO-. Examples thereof include O-, -O-CO-NH-, -NH-, -N ( RSp)-and -N (Ar Sp ) -.
• Examples of the sulfonium cation as M + include those having the structure shown below and having a bond that binds to the Sp at any position.
• the compound shown below may have the same substituent as the first substituent in the portion corresponding to the above R 6a and R 6b .
• X - is a monovalent anion having an organic group containing at least one of a hydroxyl group and a sulfanil group.
• the hydroxyl group is derived from any one selected from the group consisting of primary alcohols, secondary alcohols and tertiary alcohols, and the sulfanyl group is selected from the group consisting of primary thiols, secondary thiols and tertiary thiols. It is preferable that it is derived from any of the above. It is more preferable that the hydroxyl group is derived from any one selected from the group consisting of primary alcohols, secondary alcohols, primary thiols and secondary thiols from a steric point of view in binding to the unit B. From the viewpoint of reactivity with the unit B by the acid catalyst, it is preferable that the hydroxyl group is not a phenolic hydroxyl group.
• X - is an alkyl sulphate anion having at least one hydroxyl group and a sulfanyl group; an aryl sulphate anion having at least one hydroxyl group and a sulfanyl group; an alkyl sulfonate anion having at least one hydroxyl group and a sulfanyl group; a hydroxyl group and An arylsulfonate anion having at least one sulfanyl group; an alkylcarboxylate anion having at least one hydroxyl group and a sulfanyl group; an arylcarboxylate anion having at least one hydroxyl group and a sulfanyl group; at least one hydroxyl group and a sulfanyl group.
• It is one selected from the group consisting of a dialkylsulfonylimide anion having; and a trialkylsulfonate methide anion having at least one hydroxyl group and a sulfanyl group; a tetrakisphenylborate anion having at least one hydroxyl group and a sulfanyl group. Is preferable.
• At least one of the hydrogen atoms of the alkyl group and the aryl group in X - may be substituted with a fluorine atom and / or an iodine atom, but the fluorine atom may be substituted from the viewpoint of reactivity in binding to the unit B. And it is preferable that the substitution of the iodine atom is small. More preferably, X - is either an alkyl sulfonate anion having at least one hydroxyl group and a sulfanil group or an aryl sulfonate anion having at least one hydroxyl group and a sulfanil group. At least one of the hydrogen atoms of the alkyl group of the alkyl sulfonate anion and the aryl group of the aryl sulfonate anion may be substituted with a fluorine atom.
• the alkyl sulfate anion having at least one hydroxyl group is preferably 1 to 12 carbon atoms.
• the alkylsulfate anion having at least one sulfanil group preferably has 1 to 12 carbon atoms.
• the alkyl sulfate anion may have a plurality of hydroxyl groups and sulfanil groups.
• the arylsulfate anion having at least one hydroxyl group is preferably 4 to 12 carbon atoms.
• the arylsulfate anion having at least one sulfanil group preferably has 4 to 12 carbon atoms.
• the arylsulfate anion may have a plurality of hydroxyl groups and sulfanil groups.
• the alkyl sulfonate anion having at least one hydroxyl group is preferably 1 to 12 carbon atoms.
• the alkylsulfonate anion having at least one sulfanil group preferably has 1 to 12 carbon atoms.
• the alkylsulfonate anion may have a plurality of hydroxyl groups and sulfanil groups.
• the aryl sulfonate anion having at least one hydroxyl group is preferably 4 to 12 carbon atoms.
• the arylsulfonate anion having at least one sulfanil group preferably has 4 to 12 carbon atoms.
• the arylsulfonate anion may have a plurality of hydroxyl groups and sulfanil groups.
• the alkyl carboxylate anion having at least one hydroxyl group is preferably 2 to 12 carbon atoms.
• the alkylcarboxylate anion having at least one sulfanil group is preferably 2 to 12 carbon atoms.
• the alkylcarboxylate anion may have a plurality of hydroxyl groups and sulfanil groups.
• the arylcarboxylate anion having at least one hydroxyl group is preferably 5 to 12 carbon atoms.
• the arylcarboxylate anion having at least one sulfanil group is preferably 5 to 12 carbon atoms.
• the arylcarboxylate anion may have a plurality of hydroxyl groups and sulfanil groups.
• the dialkylsulfonylimide anion having at least one hydroxyl group is preferably 1 to 12 carbon atoms.
• the dialkylsulfonylimide anion having at least one sulfanil group preferably has 1 to 12 carbon atoms.
• the dialkylsulfonylimide anion may have a plurality of hydroxyl groups and sulfanil groups.
• the trialkylsulfonate methide anion having at least one hydroxyl group is preferably 1 to 12 carbon atoms.
• the trialkylsulfonate methideanion having at least one sulfanil group is preferably 1 to 12 carbon atoms.
• the trialkylsulfonate methide anion may have a plurality of hydroxyl groups and sulfanil groups.
• the tetrakisphenylborate anion having at least one hydroxyl group is preferably 25 to 30 carbon atoms.
• the tetrakisphenylborate anion having at least one sulfanil group preferably has 25 to 30 carbon atoms.
• the tetrakisphenylborate anion may have a plurality of hydroxyl groups and sulfanil groups.
• Examples of the above X- include those shown below.
• L, Sp and X ⁇ are the same as those of L, Sp and X ⁇ of the general formula (1), and R 6a and R 6b are the same as those of the general formula (a1). It is the same as each of R 6a and R 6b .
• the unit A in which M + X ⁇ of the above general formula (1) has an onium salt structure represented by the following general formula (11) or the following formula (12). It is preferable to have.
• the second active energy is lower than the first active energy ray after irradiation with the particle beam or electromagnetic wave (hereinafter, also referred to as “first active energy ray”). It is preferable to expose the lines.
• the second active energy is preferably ultraviolet light, visible light, or the like.
• acetal moiety or thioacetal moiety is also referred to as "(thio) acetal moiety"
• (thio) acetal moiety By using the polymer containing the unit B and the polymer as the polymer of the resist composition and irradiating the resist composition having the polymer with the first active energy ray, the onium salt structure of the unit A is decomposed and acid is generated. ..
• the onium salt structure of the unit A in the composition irradiated with the first active energy ray using this acid as a catalyst has a (thio) acetal moiety
• the structure is changed by the acid to cause the second active energy ray. It is converted into a ketone derivative that has absorption into energy.
• acid is generated with high efficiency and the sensitivity is increased.
• the onium salts of the above general formulas (11) and (12) have a specific structure of the (thio) acetal moiety and the dibenzothiophenium skeleton.
• the decomposition efficiency with respect to the first active energy ray is high, and the absorption is high with respect to the second active energy ray irradiation after the first active energy ray irradiation.
• the onium salt structure of the unit A according to the polymer according to one aspect of the present invention is the onium salt structure represented by the general formulas (11) and (12)
• the unit A is the above-mentioned first item such as ultraviolet rays or visible light.
• the acid generated by the first active energy ray deprotects the (thio) acetal moiety of the onium salt structure and converts it into a ketone derivative without impairing the function of the onium salt structure as a photoacid generator. Will be done. Since the ketone derivative contains a dibenzothiophenium structure having a condensed ring structure, the conjugated length becomes long, so that the absorption wavelength is easily lengthened and the second active energy ray has absorption.
• the ketone derivative is generated in the resist film in the exposed portion irradiated with the first active energy ray, acid is generated in the exposed portion by the first active energy ray by further irradiating the second active energy.
• the amount can be increased.
• the second active energy ray ultraviolet rays having a wavelength of 365 nm or more, visible light, or the like is preferable.
• the second active energy ray is more preferably 420 nm or less.
• the first active energy ray preferably has a higher energy than the second active energy ray, and is not particularly limited as long as an active species such as an acid can be generated from the onium salt of the unit A. PrF excimer laser light, ArF excimer laser light, electron beam, extreme ultraviolet (EUV) and the like are preferably used.
• the above R 14 independently have an alkyl group, a hydroxy group, a mercapto group, an alkoxy group, an aryloxycarbonyl group, a heteroaryloxycarbonyl group, an arylsulfanylcarbonyl group, and a hetero. From arylsulfanylcarbonyl groups, arylsulfanyl groups, heteroarylsulfanyl groups, alkylsulfanyl groups, aryl groups, heteroaryl groups, aryloxy groups, heteroaryloxy groups, (poly) alkyleneoxy groups, alkylamino groups and dialkylamino groups. It is one selected from the group of.
• R 17 and R 18 independently have an alkyl group, a hydroxy group, a mercapto group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, a heteroarylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and a heteroaryloxycarbonyl, respectively.
• the hydrogen atom is a substituent ( Hereinafter, it may be substituted with a "second substituent").
• the alkyl group in R 14 , R 17 and R 18 may be linear, branched or cyclic, and specific examples thereof include the same group as the alkyl group of R e as the second substituent below. Further, the alkyl group portions such as the alkoxy group, the alkylcarbonyl group and the alkoxycarbonyl group in R14 , R17 and R18 are the same as those in R1 . Examples of the aryl group and heteroaryl group in R 14 , R 17 and R 18 include the same as the aryl group and heteroaryl group in R 19 . Examples of the aryl group portion such as the arylcarbonyl group and the aryloxycarbonyl group in R 17 and R 18 are the same as those in R 19 .
• heteroaryl group moiety such as the heteroarylcarbonyl group and the heteroaryloxycarbonyl group in R17 and R18 are the same as those in R1 . It should be noted that R 17 and R 18 are preferably substituents having no heteroaryl group moiety such as the above heteroarylcarbonyl group and heteroaryloxycarbonyl group from the viewpoint of synthesis.
• the onium salt structures represented by the above formulas ( 11) and ( 12 ) have two or more R14, two of R14 may be connected to each other to form a ring structure.
• Examples of the (poly) alkyleneoxy group in R 14 , R 17 and R 18 include polyethylene oxy group and polypropylene oxy group.
• Examples of the halogen atom in R 17 and R 18 include a fluorine atom, a chlorine atom, an iodine atom and the like.
• R 14 , R 17 and R 18 have carbon
• the number of carbon atoms is preferably 1 to 12, and these may have a second substituent.
• the carbon-carbon single bond in the alkyl groups of R 2 , R 3 and R 4 may be replaced with a carbon-carbon double bond.
• the second substituents that R 14 , R 17 and R 18 may have include a hydroxy group, a cyano group, a mercapto group, a carboxy group, an alkyl group (-R e ), an alkoxy group (-OR e ), and the like.
• the R e in the second substituent is preferably an alkyl group having 1 or more carbon atoms. Further, it is more preferable that the number of carbon atoms is 20 or less. Specific examples of the alkyl group having one or more carbon atoms include, for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group and an n-decyl.
• Linear alkyl groups such as groups; branched alkyl groups such as isopropyl group, isobutyl group, tert-butyl group, isopentyl group, tert-pentyl group, 2-ethylexyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl Alicyclic alkyl groups such as groups, adamantan-1-yl groups, adamantan-2-yl groups, norbornan-1-yl groups and norbornan-2-yl groups; one of these hydrogens is a trimethylsilyl group, a triethylsilyl group and Preferred examples thereof include a silyl group substituted alkyl group substituted with a trialkylsilyl group such as a dimethylethylsilyl group; an alkyl group in which at least one of these hydrogen atoms is substituted with a cyano group, a fluoro
• Ar in the second substituent is preferably an aryl group or a heteroaryl group.
• the heteroaryl group is an aryl group containing one or more heteroatoms in the ring structure.
• Specific examples of the above Ar include a phenyl group, a biphenyl group, a terphenyl group, a quaterphenyl group, a naphthyl group, an anthryl group, a phenanthrenyl group, a pentarenyl group, an indenyl group, an indasenyl group, an acenaphthyl group, a fluorenyl group and a heptalenyl group.
• the number of carbon atoms of R 14 , R 17 and R 18 includes the number of carbon atoms of the second substituent and the number of carbon atoms is 1 to 12. Is preferable.
• the onium salt structure according to the polymer according to one aspect of the present invention preferably has at least one R14 . Further, it is preferable that at least one R14 is a hydroxy group or an alkoxy group. Further, R14 is preferably in the ortho-position or the para-position with respect to the binding position of the (thio) acetal site.
• R14 is preferably in the ortho-position or the para-position with respect to the binding position of the (thio) acetal site.
• the onium salt cation structure becomes sterically large by adding a substituent to the cation of the onium salt structure, the hydrophobicity is improved and a dissolution inhibitory effect may occur during development. Therefore, the absorption wavelength of the ketone derivative after the (thio) acetal moiety is deprotected without having a hydrophobic substituent, which tends to have a low affinity for the alkaline developing solution, becomes longer and the second active energy ray is absorbed. It is preferable to have a structure that is large. Further, since the substituent showing basicity deactivates the generated acid and inhibits the decomposition of the acid dissociating group, the configuration in which the substituent showing basicity is introduced is not preferable.
• the onium salt structure cation according to the polymer according to one aspect of the present invention is generated without having a substituent containing an aromatic ring, an alicyclic structure, etc. in R 14 , R 17 and R 18 . It is preferable that it does not have a basic group such as an amino group that reacts with an acid, and it is preferable that the molecular weight of the cation portion of the onium salt structure is 500 or less. It is more preferable that the cation having the onium salt structure according to the polymer according to one aspect of the present invention does not have a basic group such as an amino group in R 17 and R 18 including R 14 .
• R14s When a plurality of R14s are present, it is preferable that at least one of R14s is a hydroxy group or an alkoxy group and is in the ortho-position or the para-position with respect to the binding position of the (thio) acetal moiety.
• the other R 4 When having a plurality of R 14 , if at least one of R 14 is a hydroxy group or an alkoxy group, the other R 4 may not be a hydroxy group or an alkoxy group.
• the substituent is an electron donating group to the aromatic ring to which two or more R 14s are bonded. More preferably, it is preferable to have a hydroxy group or an alkoxy group as R14 at two or more positions at the ortho-position or the para-position with respect to the binding position of the (thio) acetal moiety.
• R 19 is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent; and may have a substituent and may have a linear, branched or cyclic carbon atom number 1 A group consisting of an alkenyl group to 12; an aryl group having 6 to 14 carbon atoms which may have a substituent; and a heteroaryl group having 4 to 12 carbon atoms which may have a substituent; It is one of the more selected.
• linear, branched or cyclic alkyl group having 1 to 12 carbon atoms in R19 are methyl, ethyl, n-propyl, n-butyl, isopropyl, t-butyl and cyclopropyl groups, respectively.
• alkyl group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantan-1-yl group, an adamantan-2-yl group, a norbornan-1-yl group and a norbornan-2-yl group.
• the alkyl group of R 19 may be substituted with a divalent heteroatom-containing group instead of at least one methylene group.
• the divalent heteroatom-containing groups include -O-, -CO-, -COO-, -OCO-, -O-CO-O-, -NHCO-, -CONH-, and -NH-CO-O-. , -O-CO-NH-, -NH-, -N (R e )-, -N (Ar)-, -S-, -SO- and -SO 2- at least one selected from the group. It is a group that contains.
• the sulfur atom (S + ) of the sulfonium group is not directly bonded to the heteroatom-containing group but is bonded to the divalent hydrocarbon group.
• Re and Ar will be described later.
• the alkenyl group of R 19 include those in which at least one carbon-carbon single bond of the above alkyl group is replaced with a carbon-carbon double bond.
• aryl group having 6 to 14 carbon atoms which may have a substituent in R 19 , a monocyclic aromatic hydrocarbon group and at least two monocyclic aromatic hydrocarbons are fused. Examples thereof include fused polycyclic aromatic hydrocarbon groups. These aryl groups may have a substituent.
• the monocyclic aromatic hydrocarbon group include a group having a skeleton such as benzene.
• the fused polycyclic aromatic hydrocarbon group include groups having a skeleton such as indene, naphthalene, azulene, anthracene and phenanthrene.
• the heteroaryl group having 4 to 12 carbon atoms which may have a substituent in R 19 is at least selected from an oxygen atom, a nitrogen atom and a sulfur atom in place of at least one carbon atom of the aryl group. Those containing either of them in the skeleton can be mentioned.
• the heteroaryl group includes a monocyclic aromatic heterocyclic group, and a fused polycyclic aromatic complex in which at least one of the monocyclic aromatic heterocycles is condensed with the aromatic hydrocarbon group, the aliphatic heterocyclic group, or the like. Ring groups and the like can be mentioned. These aromatic heterocyclic groups may have a substituent. Examples of the monocyclic aromatic heterocyclic group include groups having a skeleton such as furan, pyrrole, imidazole, pyran, pyridine, pyrimidine and pyrazine.
• fused polycyclic aromatic heterocyclic group examples include groups having a skeleton such as indole, purine, quinoline, isoquinoline, chromen, phenoxazine, xanthene, acridine, phenazine and carbazole.
• Examples of the substituent (hereinafter, also referred to as “third substituent”) in R 19 include the same as the above-mentioned second substituent.
• the number of carbon atoms of R 19 includes the number of carbon atoms of the third substituent. It is preferably 1 to 20.
• the R 19 and any of the benzene ring to which the R 2 is bonded and the benzene ring to which the R 3 is bonded are directly composed of a single bond or composed of an oxygen atom, a sulfur atom, a nitrogen atom-containing group and a methylene group.
• a ring structure may be formed with the sulfur atom to which they are bonded via any of the groups selected.
• the above-mentioned "nitrogen atom-containing group” includes, for example, a divalent group containing a nitrogen atom such as an aminodiyl group (-NH-), an alkylaminodiyl group (-NR e- ), and an arylaminodiyl group (-NAr-).
• R e and Ar are the same as those of the third substituents R e and Ar.
• an aryl group is preferable from the viewpoint of improving stability.
• the R 19 and any of the benzene ring to which the R 18 is bonded and the benzene ring to which the R 17 is bonded are directly composed of a single bond or composed of an oxygen atom, a sulfur atom, a nitrogen atom-containing group and a methylene group.
• a ring structure may be formed with the sulfur atom to which they are bonded via any of the groups selected.
• R 14 , R 17 and R 18 have a methylene group
• at least one of the methylene groups may be substituted with a divalent heteroatom-containing group.
• Examples of R 14 , R 17 and R 18 in which at least one of the methylene groups may be substituted with a divalent heteroatom-containing group include 2-methoxyethoxy group, 2-ethoxyethoxy group and 2- (2).
• Polyalkyleneoxy groups such as methoxyethoxy) ethoxy group, 2- (2-ethoxyethoxy) ethoxy group, 2-methoxypropoxy group and 3-methoxypropoxy group; 2-methylthioethylthio and 2-ethylthioethylthio groups and the like.
• Polyalkylene thio group; and polyalkylene oxythio group such as 2-methylthioethoxy group and 2-ethoxyethylthio group; and the like.
• some aspects of the invention are not limited to this.
• R 15 and R 16 are linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms, each of which may independently have a substituent; and may have a substituent.
• Heteroaryl groups are preferred, and these are preferably selected from the same options as each of R19 above.
• Examples of the substituents as R 15 and R 16 include the same as the above-mentioned second substituent.
• the R 15 and R 16 may be bonded to each other directly by a single bond or via any one selected from the group consisting of an oxygen atom, a sulfur atom and an alkylene group to form a ring structure. At least one methylene group in R 15 and R 16 may be substituted with a divalent heteroatom-containing group. From the viewpoint of synthesis, it is preferable that R 15 and R 16 are the same.
• L 3 is selected from the group consisting of a direct bond; a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms; an alkenylene group having 2 to 12 carbon atoms; a sulfinyl group, a sulfonyl group and a carbonyl group; Either.
• Y is an oxygen atom or a sulfur atom.
• q is an integer of 0 to 4
• f is an integer of 0 to 3
• g is an integer of 1 to 5
• j is an integer of 0 to 2
• k is an integer of 1 to 4.
• q is used in the general formula (11).
• 0 to 3 or j is 0 to 2
• q is 0 to 3 or j is 0 to 1 in the above general formula (12).
• At least one of the benzene rings in the general formulas (11) and (12) may be a 6-membered heteroaromatic ring having a hetero atom in the ring, and in the general formulas (11) and (12).
• k When the benzene ring bonded to R 14 is the above heteroaromatic ring, k may be 0 to 4.
• two or more R 14s are possessed in the above general formulas (11) and (12), two of the R 14s may be connected to each other to form a ring structure.
• X - is selected from the same options as X - of the general formula (1).
• Examples of the onium salt structure contained in the unit A in the polymer according to some aspects of the present invention include those having the sulfonium cation shown below.
• the wavy line in the sulfonium cation shown below indicates a binding site with Sp in the above formula (1), and when there are a plurality of wavy lines in the same structure, one of them is assumed to bind to the above Sp.
• some aspects of the invention are not limited to this.
• the anion of the unit A is preferably highly hydrophilic from the viewpoint of improving the contrast in the photoresist pattern formation.
• Specific examples thereof include an alkyl sulfate anion, an aryl sulfate anion, an alkyl sulfonate anion, an aryl sulfonate anion, an alkyl carboxylate anion, and an aryl carboxylate anion.
• These anions have at least one hydroxyl group and sulfanil group.
• the polymer according to one aspect of the present invention may have two or more of the above-mentioned units A in the above-mentioned polymer.
• a photoacid generator unit A hereinafter, also referred to as “unit A1”
• the other as a photodisintegrating base unit A (hereinafter, also referred to as “unit A2”).
• the X ⁇ of the photodisintegrating base unit A2 is preferably an alkyl carboxylate anion or an aryl carboxylate anion.
• the photodisintegrating base unit A2 is preferably used in combination with the photoacid generator unit A1. Since the polymer has the effect of reducing the LWR by having the unit A2, it is effective when high resolution is required.
• units having the same M + X - part but different substituents such as R1 and L may be used.
• the onium salt according to the polymer according to some aspects of the present invention preferably has a molar extinction coefficient of 365 nm of less than 1.0 ⁇ 10 5 cm 2 / mol, preferably less than 1.0 ⁇ 10 4 cm 2 / mol. Is more preferable.
• the ketone derivative in which the (thio) acetal moiety of the onium salt according to some aspects of the present invention is deprotected has a molar absorption coefficient of 365 nm of 1.0 ⁇ 105 cm 2 / mol or more. Is preferable, and 1.0 ⁇ 10 6 cm 2 / mol or more is more preferable.
• the 365 nm molar extinction coefficient of the ketone derivative is preferably 5 times or more, more preferably 10 times or more, that is, the 365 nm molar extinction coefficient of the onium salt according to some aspects of the present invention. , 20 times or more is more preferable.
• the onium salt represented by the above formula (11) or (12) may be used.
• the target sulfonium salt structure is a (meth) acrylate monomer that does not contain a (thio) acetal moiety
• the synthesis method shown below can be mentioned.
• a diallyl sulfoxide having an R 6b group and a benzene having a hydroxyl group (R 6a group) are subjected to a Friedel-Crafts reaction using a Bronsted acid to obtain a hydroxyaryl dialyl sulfoxide.
• the desired sulfonium salt is then obtained using a basic catalyst and (meth) acrylic acid chloride.
• the target sulfonium salt structure is a vinyl or isopropenyl monomer containing no (thio) acetal moiety
• the synthesis method shown below can be mentioned.
• a diallyl sulfoxide having an R 6b group and a Glynal reagent (R 6a group) having a vinyl group or an isopropenyl group are optionally reacted with a sulfoxide compound having an R 6b group to form a sulfonium salt structure.
• the desired sulfonium salt structure is obtained by exchanging salts with a salt having an anion.
• the synthetic method shown below can be mentioned.
• the synthetic method shown below can be mentioned.
• Benzene having a hydroxyl group and Bronsted acid were converted to sulfonium by Friedel-Crafts reaction, and then the carbonyl group was acetalized with alcohol ( R15 OH) using an acid catalyst. do.
• the desired sulfonium salt structure is obtained by salt exchange using a salt having a corresponding anion.
• the unit B is not particularly limited as long as it has a structure in which two molecules are bonded by an acid-catalyzed reaction.
• the compound represented by the general formula (I) or (II) is any one of the compounds.
• a unit bonded to the Sp group of the above formula (1) at the position of is preferable.
• the polymer contains at least one of the compounds represented by the following general formula (I) or (II) bonded to the * portion of the following formula (2) at any position of the compound as a unit B.
• the polymer contains the unit B, it is possible to improve the sensitivity to particle beams or electromagnetic waves.
• R1 , L and Sp are the same as the above general formula (1).
• R 2 and R 3 are independently selected from the group consisting of a hydrogen atom; an electron donating group; and an electron withdrawing group; It is preferable that at least one of R 2 and R 3 is the above-mentioned electron donating group because the acid reactivity is improved.
• E is preferably any one selected from the group consisting of a direct bond; an oxygen atom; a sulfur atom; and a methylene group;
• n 1 is an integer of 0 or 1.
• n 4 and n 5 are integers of 1 to 2, respectively.
• n 4 + n 5 is 2 to 4.
• n 4 is 1, n 2 is an integer from 0 to 4.
• n 4 is 2, n 2 is an integer of 0 to 6.
• n 5 is 1, n 3 is an integer from 0 to 4.
• n 5 is 2, n 3 is an integer of 0 to 6.
• R 2 is an electron donating group or an electron attracting group, the two R 2s are single-bonded directly or with an oxygen atom, a sulfur atom, a divalent nitrogen atom-containing group and a group.
• Ring structures may be formed with each other via any of the groups selected from the group consisting of methylene groups.
• n 3 is 2 or more and R 3 is an electron donating group or an electron attracting group
• the two R 3s are single-bonded directly or or with an oxygen atom, a sulfur atom, a divalent nitrogen atom-containing group and a group.
• Ring structures may be formed with each other via any of the groups selected from the group consisting of methylene groups.
• Examples of the divalent nitrogen atom-containing group for forming the ring structure in the above formula (I) include the same divalent nitrogen atom-containing groups in the above formula (a1).
• R 4 is independently selected from the group consisting of a hydrogen atom; an electron-donating group; and an electron-withdrawing group. It is preferable to use at least one of R 4 as the electron donating group because the acid reactivity is improved.
• R 5 is any one selected from the group consisting of a hydrogen atom; an alkyl group which may have a substituent; and an alkenyl group which may have a substituent; and at least one of the above R 5 .
• the methylene group may be substituted with a divalent heteroatom-containing group. Further, R 5 may form a ring structure together with a benzene ring to which the hydroxymethylene group having R 5 is bonded.
• Examples of the alkyl group of R 5 include a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms. Specifically, the same alkyl group as R 6b can be raised. Examples of the substituent of R 5 include the same as the above-mentioned first substituent of the above-mentioned Sp.
• n 6 is an integer from 0 to 7 and n 7 is 1 or 2.
• n 7 is 1, n 6 is an integer of 0 to 5.
• n 7 is 2, n 6 is an integer from 0 to 7.
• Ring structures may be formed with each other via any of the groups selected from the group consisting of methylene groups.
• Examples of the divalent nitrogen atom-containing group for forming the ring structure in the above formula (II) include those similar to the divalent nitrogen atom-containing group in the above formula (a1).
• At least one of the alkyl group (-R 13 ) and the carbon-carbon single bond of the alkyl group (-R 13 ) is replaced with a carbon-carbon double bond.
• the R 13 is preferably an alkyl group having 1 or more carbon atoms.
• Specific examples of the alkyl group having 1 or more carbon atoms include, for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group and an n-decyl group.
• Linear alkyl groups such as isopropyl group, isobutyl group, tert-butyl group, isopentyl group, tert-pentyl group, 2-ethylexyl group and other branched alkyl groups; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group.
• Alicyclic alkyl groups such as adamantan-1-yl group, adamantan-2-yl group, norbornan-1-yl group and norbornan-2-yl group; one of these hydrogens is trimethylsilyl group, triethylsilyl group and dimethyl.
• Alkyl groups in which at least one is substituted with a cyano group, a fluoro group or the like; and the like are preferably mentioned.
• the R 13 preferably has 4 or less carbon atoms.
• Examples of the compound represented by the above general formula (I) or (II) include those specifically represented below.
• any of the compounds represented by the above general formula (I) or (II) is placed in the * portion of the above formula (2) at any position of the compound. It is an embodiment contained in the polymer as the bound unit B. In that case, any of R 2 , R 3 and R 4 is preferable as the position to be coupled to the * portion of the above formula (2).
• the unit B is preferably one in which R 1 is a hydrogen atom or a linear alkyl group in the above formula (2), and is an L carbonyloxy group, a carbonylamino group or a phenylenediyl group. Further, as the unit B, L is a carbonyloxy group or a carbonylamino group, Sp is a direct bond, R1 is a methyl group, and the methyl group is carbon among the first substituents.
• a unit having at least one of a number 1 to 4 alkyl groups, a halogen atom and an aryl group is preferable from the viewpoint of LWR.
• R 1 having the first substituent is an ethyl group, an isopropyl group, a butyl group, a methyl halide group (fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, etc.), a benzyl group and the like.
• the polymer according to one aspect of the present invention may have two or more of the above-mentioned units B in the above-mentioned polymer.
• the unit C is a unit having a radical generation structure containing at least one multiple bond selected from the group consisting of a multiple bond of a carbon atom and a carbon atom and a multiple bond of a carbon atom and a hetero atom, and is a unit of a polymer.
• a radical generation structure containing at least one multiple bond selected from the group consisting of a multiple bond of a carbon atom and a carbon atom and a multiple bond of a carbon atom and a hetero atom, and is a unit of a polymer.
• An intramolecular cross-linking reaction may occur between the unit A and the unit C by irradiating with a particle beam, an electromagnetic wave, or the like.
• the multiple bond in the unit C is not particularly limited as long as it generates a radical cation under the influence of a particle beam or an electromagnetic wave and the radical cation is decomposed into a second radical and a cation, but it is contained in a benzene-based aromatic. However, it is preferably at least one of the bonds shown below.
• the benzene-based aromatics include not only benzene but also aromatics having a benzene skeleton such as naphthalene and azulene. "Not a multiple bond contained in a benzene-based aromatic" means that it is not a multiple bond possessed by these aromatics.
• radical generation structure containing the multiple bonds include units having any one selected from the group consisting of an alkylphenone skeleton, an acyloxime skeleton, and a benzyl ketal. If it has these skeletons, it may have an arbitrary substituent, and the unit having an alkylphenone skeleton includes an ⁇ -aminoacetophenone skeleton and the like. More specifically, those represented by at least one of the following general formulas (4) are preferably mentioned.
• R1 , L and Sp similar to those of the general formula (1) L and Sp can be mentioned.
• Each of R 7 is independently a hydrogen atom; a hydroxy group; -R a (R a is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent); -OR a ; and a group in which at least one of the carbon-carbon single bonds in the Ra is substituted with a carbon-carbon double bond; and -R b (R b is the number of carbon atoms which may have a substituent ) .
• R 3s form a ring structure either directly in a single bond or via one selected from the group consisting of oxygen atoms, sulfur atoms, divalent nitrogen atom-containing groups and methylene groups. May be.
• R a include the same as the alkyl group of R 13a .
• R b include the same as the aryl group of R 13b .
• R a and R b may have include the same substituents as those of Sp.
• three of R 7 are not hydrogen atoms.
• at least one of the three R 7s is OH.
• the two R 8s are selected directly by a single bond or from the group consisting of an oxygen atom, a sulfur atom, a divalent nitrogen atom-containing group and a methylene group.
• a ring structure may be formed via either of them.
• n 2 is an integer of 1 to 3
• m 1 is an integer of 0 to 4 when m 2 is 1
• m 1 is an integer of 0 to 6 when m 2 is 2
• m 2 is an integer of 3.
• m 1 is an integer from 0 to 8.
• R 1 is a hydrogen atom or a linear alkyl group
• L is a carbonyloxy group, a carbonylamino group or a phenylenediyl group.
• L is a carbonyloxy group or a carbonylamino group
• Sp is a direct bond
• R1 is a methyl group
• the methyl group has the number of carbon atoms among the first substituents.
• a unit having at least one of 1 to 4 alkyl groups, a halogen atom and an aryl group is preferable from the viewpoint of LWR.
• R 1 having the first substituent is an ethyl group, an isopropyl group, a butyl group, a methyl halide group (fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, etc.), a benzyl group and the like. Can be mentioned.
• the polymer according to one aspect of the present invention may have two or more of the above-mentioned units C in the above-mentioned polymer.
• the polymer in one embodiment of the present invention preferably further contains a unit having an aryloxy group (hereinafter, also referred to as "unit D").
• unit D a unit in which the phenol structure is bonded to the * portion of the above formula (2) at any position of the structure is preferable.
• the unit D is not particularly limited as long as it can improve the generation efficiency of the acid generated by the unit A, and specific examples thereof include the units shown below.
• each of R 11 is independently selected from the group consisting of a hydrogen atom and an alkyl group.
• the alkyl group as R 11 may have a substituent.
• the alkyl group include a methyl group, an ethyl group, an isopropyl group, an n-isopropyl group, a sec-butyl group, a tert-butyl group, an n-butyl group, a pentyl group and the like in a linear or branched manner having 1 to 5 carbon atoms.
• Alkyl group in the form can be mentioned.
• Examples of the substituent that the alkyl group may have include a hydroxy group, a sulfonyloxy group, an alkylcarbonyloxy group, an alkyloxycarbonyl group, a cyano group, a methoxy group, an ethoxy group and the like.
• Examples of the substituent that R 11 may have include the same as the above-mentioned first substituent that the above-mentioned Sp has.
• the two R 11s that are not hydrogen atoms are single-bonded directly or directly or with an oxygen atom, a sulfur atom, a divalent nitrogen atom-containing group and a divalent nitrogen atom-containing group.
• a ring structure may be formed via any of the groups selected from the group consisting of methylene groups. n 8 is 4.
• the unit D include those composed of a monomer such as 4-hydroxyphenyl (meth) acrylate.
• the polymer contains the unit D, it is possible to improve the acid generation efficiency.
• R 1 is a hydrogen atom or a linear alkyl group
• L is a carbonyloxy group or a phenylenediyl group.
• L is a carbonyloxy group or a carbonylamino group
• Sp is a direct bond
• R1 is a methyl group
• the methyl group has the number of carbon atoms among the first substituents.
• a unit having at least one of 1 to 4 alkyl groups, a halogen atom and an aryl group is preferable from the viewpoint of LWR.
• R 1 having the first substituent is an ethyl group, an isopropyl group, a butyl group, a methyl halide group (fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, etc.), a benzyl group and the like.
• the polymer according to one aspect of the present invention may have two or more of the above-mentioned units D in the above-mentioned polymer.
• the polymer in one embodiment of the present invention is an organometallic compound-containing unit E having a metal atom selected from the group consisting of Sn, Sb, Ge, Bi and Te in addition to the above units A to D (hereinafter, “unit”). It is also preferable to further contain (also referred to as "E").
• the metal atom contained in the unit E is not particularly limited as long as it has high absorption to EUV or an electron beam, and may be an atom of the 10th to 16th groups of the periodic table other than the metal atom. good.
• the unit E is a unit in which an alkyl and aryl tin, an alkyl and aryl antimony, an alkyl and an aryl Germanic, or an alkyl and an aryl bismucin structure are bonded to the * portion of the above formula (2) at any position of the structure. Is preferable.
• Unit E has high secondary electron generation efficiency due to EUV irradiation, and can increase the decomposition efficiency of unit A and unit B.
• the unit E is not particularly limited as long as it contains the metal atom having high EUV absorption, and specific examples thereof include the units shown below.
• each of R 12a is independently selected from the group consisting of a hydrogen atom and an alkyl group.
• the alkyl group as R 12a may have a substituent.
• the alkyl group include a methyl group, an ethyl group, an isopropyl group, an n-isopropyl group, a sec-butyl group, a tert-butyl group, an n-butyl group, a pentyl group and the like in a linear or branched manner having 1 to 5 carbon atoms.
• Alkyl group in the form can be mentioned.
• alkyl group may have examples include a hydroxy group, a sulfonyloxy group, an alkylcarbonyloxy group, an alkyloxycarbonyl group, a cyano group, a methoxy group, an ethoxy group and the like.
• R 12a when two or more R 12a are not hydrogen atoms, the two R 12a in which the R 12a is not a hydrogen atom are single-bonded directly or directly, or an oxygen atom, a sulfur atom, a divalent nitrogen atom-containing group and a divalent nitrogen atom-containing group.
• a ring structure may be formed via any of the groups selected from the group consisting of methylene groups.
• the two R 12bs form a ring structure either directly in a single bond or via one selected from the group consisting of oxygen atoms, sulfur atoms, divalent nitrogen atom-containing groups and methylene groups. You may. n 9 is an integer from 0 to 4.
• R 12b is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms which may have a substituent; a linear, branched or cyclic alkyl group which may have a substituent.
• Examples of the linear, branched or cyclic alkyl group of R 12b include the same as the above-mentioned alkyl group of R 2b .
• Examples of the linear, branched or cyclic alkenyl group of R 12b include the same group as the alkenyl group of R 2b .
• Examples of the aryl group having 6 to 14 carbon atoms of R 12b include those similar to the aryl group of R 2b .
• Examples of the heteroaryl group having 4 to 12 carbon atoms of R 12b include the same as the heteroaryl group of R 2b .
• Two or more R 12a form a ring structure either directly in a single bond or via one selected from the group consisting of oxygen atoms, sulfur atoms, divalent nitrogen atom-containing groups and methylene groups. May be good. Further, any two of the three R 12bs may be bonded to each other to form a ring structure together with the metal atoms to which they are bonded.
• Examples of the substituent that R 12a and R 12b may have include the same as the above-mentioned first substituent having the above-mentioned Sp.
• the polymer contains the unit E, it is possible to improve the efficiency
• R 1 is a hydrogen atom or a linear alkyl group
• L is a carbonyloxy group or a phenylenediyl group.
• L is a carbonyloxy group or a carbonylamino group
• Sp is a direct bond
• R1 is a methyl group
• the methyl group has the number of carbon atoms among the first substituents.
• a unit having at least one of 1 to 4 alkyl groups, a halogen atom and an aryl group is preferable from the viewpoint of LWR.
• R 1 having the first substituent is an ethyl group, an isopropyl group, a butyl group, a methyl halide group (fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, etc.), a benzyl group and the like. Can be mentioned.
• the polymer according to one aspect of the present invention may have two or more of the above-mentioned units E in the above-mentioned polymer.
• the polymer in one embodiment of the present invention preferably further has a unit F represented by the following formula (7) having a halogen atom.
• R 1 , L and Sp are preferably selected from the same options as R 1 , L and Sp in the general formula (2), respectively.
• R h is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent; and may have a substituent and may have a linear, branched or cyclic carbon number of 1 to 12 carbon atoms.
• alkenyleneoxy groups Selected from the group consisting of 12 alkenyleneoxy groups; an aryl group having 6 to 14 carbon atoms which may have a substituent; and a heteroaryl group having 4 to 12 carbon atoms which may have a substituent; And some or all of the hydrogen atoms substituted with carbon atoms are substituted with fluorine atoms or iodine atoms.
• alkyl group, alkenyl group, alkyleneoxy group alkylene group, alkenyleneoxy group alkenylene group, aryl group and heteroaryl group of Rh are the same as those of Sp. Further, examples of these substituents are the same as those of Sp substituents.
• unit F examples include units obtained from the monomers shown below.
• the unit F is preferably one in which R 1 is a hydrogen atom or a linear alkyl group in the above formula (7), and is an L carbonyloxy group, a carbonylamino group or a phenylenediyl group. Further, as the unit F, L is a carbonyloxy group or a carbonylamino group, Sp is a direct bond, R1 is a methyl group, and the methyl group has the number of carbon atoms among the first substituents.
• a unit having at least one of 1 to 4 alkyl groups, a halogen atom and an aryl group is preferable from the viewpoint of LWR.
• R 1 having the first substituent is an ethyl group, an isopropyl group, a butyl group, a methyl halide group (fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, etc.), a benzyl group and the like. Can be mentioned.
• the polymer according to one aspect of the present invention may have two or more of the above-mentioned units F in the above-mentioned polymer.
• the polymer in one embodiment of the present invention may have a unit usually used as a resist composition as long as the effects of the present invention are not impaired.
• a unit having a skeleton containing an ether group, a lactone skeleton, an ester group, a hydroxy group, an epoxy group, a glycidyl group, an oxetanyl group, etc. in the * portion of the above formula (2) (hereinafter, also referred to as “unit G”) can be mentioned.
• a unit having a skeleton having an alcoholic hydroxy group in the * portion of the above formula (2) (hereinafter, also referred to as “unit H”) can be mentioned.
• the unit H is different from the above units A to G. It is preferable that the unit H is contained in the polymer because the ratio of the intramolecular cross-linking reaction tends to increase.
• a unit having a skeleton containing an epoxy group, a glycidyl group, an oxetanyl group, or the like is preferable because cationic polymerization may occur when the acid generated from the unit A is a strong acid.
• the polymer in one embodiment of the present invention may have a unit I represented by the following general formula (8).
• Unit I is a unit different from the above units A to H.
• the polymer in one embodiment of the present invention has a unit I, the polymer main chain can be easily cleaved by the action of a radical generated by irradiation with a particle beam or an electromagnetic wave, and the polymer chain at the exposure boundary can be shortened. It has the effect of reducing the LWR.
• each substituent is preferably as follows.
• R 10 is any one selected from the group consisting of a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms; and a linear, branched or cyclic alkenyl group having 1 to 6 carbon atoms; At least one hydrogen atom in the alkyl group and the alkenyl group in R 10 may be substituted with a substituent, L 10 is a direct bond and R c has the first substituent.
• the alkyl group having 1 to 6 carbon atoms and the alkenyl group having 1 to 6 carbon atoms of R 10 are selected from the same options as the alkyl group having 1 to 6 carbon atoms and the alkenyl group having 1 to 6 carbon atoms of R1. .. Alternatively, R 10 is a methyl group, the methyl group has at least one of the above-mentioned first substituents, an alkyl group having 1 to 4 carbon atoms, a halogen atom and an aryl group, and L is carbonyloxy.
• a group or a carbonylamino group wherein R c is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a hydrogen atom or the first substituent.
• L is a carbonyloxy group or a carbonylamino group
• R c is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms
• R 10 is a methyl group, and the methyl.
• the group has at least one of an alkyl group having 1 to 4 carbon atoms, a halogen atom and an aryl group among the above-mentioned first substituents.
• R 10 having the first substituent are an ethyl group, an isopropyl group, a butyl group, a methyl halide group (fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, etc.), a benzyl group and the like.
• the unit I is a unit different from the units A to H.
• the unit I is, for example, ⁇ -methylstyrene derivative, 2-ethylacrylic acid and its ester derivative, 2-benzylacrylic acid and its ester derivative, 2-propylacrylic acid and its ester derivative, 2-isopropylacrylic acid and its ester derivative.
• Examples thereof include units derived from monomers such as methylacrylic acid and its ester derivatives, 2-iodomethylacrylic acid and its ester derivatives.
• Specific examples of the unit I include those derived from the monomers shown below.
• the polymer in one embodiment of the present invention may have a unit J represented by the following general formula (9).
• R 1 , L and Sp are selected from the same options as those of the general formula (2) R 1 , L and Sp, respectively.
• R d is a linear, branched or cyclic alkylsilyl group having 1 to 12 carbon atoms which may have a substituent; and may have a substituent and may have a linear, branched or cyclic carbon number 1 to 12; 12 alkyloxysilyl groups; linear, branched or cyclic alkenylsilyl groups having 1-12 carbon atoms which may have substituents; linear, branched or cyclic carbons which may have substituents.
• the unit J is selected from the alkenyloxysilyl group of the number 1-12; It may contain a siloxane bond in which hydrogen or carbon to be bonded is replaced with oxygen by substituting a part of carbon atom with a silicon atom and an oxygen atom.
• the unit J can enhance the etching resistance of oxygen plasma by containing silicon. Further, when the polymer has a silane structure as the unit J, water is generated by the reaction of the unit B in the presence of an acid catalyst, and the water hydrolyzes the unit J to silanol to form a siloxane bond for cross-linking. This is preferable because it has the effect of improving sensitivity and substrate adhesion.
• the unit J is different from the units A to I.
• Unit J is, for example, 4-trimethylsilylstyrene, 4-trimethoxysilylstyrene, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 8-methacryloxyoctyl.
• the resist composition according to one aspect of the present invention is characterized in that an intramolecular cross-linking reaction occurs by irradiation with a particle beam or an electromagnetic wave. Therefore, a unit K having an onium salt structure other than the unit A may be included. Examples of the unit K include those in which the anion X ⁇ in the unit A becomes the following Y ⁇ .
• Y ⁇ is a monovalent anion having an organic group containing neither a hydroxyl group nor a sulfanil group.
• Y ⁇ includes alkyl sulfate anion, aryl sulfate anion, alkyl sulfonate anion, aryl sulfonate anion, alkyl carboxylate anion, aryl carboxylate anion, tetrafluoroborate anion, hexafluorophosphonate anion, dialkyl sulfonylimide anion, and trialkyl. It is preferably one selected from the group consisting of a sulfonate methide anion, a tetrakisphenylborate anion and a hexafluoroantimonate anion.
• any one selected from the group consisting of a monovalent metal oxonium anion and a hydrofluoric acid anion containing the monovalent metal oxonium anion can be mentioned.
• at least one of the hydrogen atoms of the alkyl group and the aryl group in Y may be substituted with a fluorine atom, or may have the first substituent (excluding the hydroxyl group).
• the number of carbon atoms of Y ⁇ is preferably 1 to 6 including the substituents.
• the metal oxonium anion include NiO 2- and SbO 3- .
• the monovalent to divalent metal cation may be an ordinary one, and examples thereof include Na +, Sn 2+ , Ni 2+ and the like.
• a unit having an acid dissociation group as another unit is used as the polymer in the present invention. It is preferable not to include it as a unit of. The reason is that when a unit having an acid dissociation group as another unit is included as a unit of the polymer in the present invention, the polymer becomes more soluble in a water-soluble developer due to the action of the acid generated by the decomposition of the unit K. This is because there is a tendency.
• the unit K may be used as a photodisintegrating base (also referred to as "unit K2" when the unit K is used as a photodisintegrating base).
• the anion of the unit K2 is preferably any of Y ⁇ selected from the group consisting of alkyl carboxylate anions and aryl carboxylate anions. These are monovalent anions having an organic group containing neither a hydroxyl group nor a sulfanyl group, and at least one of the hydrogen atoms of the alkyl group of the alkyl carboxylate anion and the aryl group of the aryl carboxylate anion. May be substituted with a fluorine atom. Since the polymer has the effect of reducing the LWR by having the unit K2, it is effective when high resolution is required.
• the polymer according to one aspect of the present invention may have two or more of the above units K in the above polymer.
• the unit A is preferably 1 and the unit B is preferably 0.2 to 5, and the unit C is 0 to 3, respectively.
• the unit D is 0 to 2
• the unit E is preferably 0 to 2
• the unit F is preferably 0 to 2
• the unit G is 0 to 2.
• the unit H is preferably 0 to 2
• the unit I is preferably 0 to 0.5
• the unit J is preferably 0 to 4
• the unit K is 0. It is preferably ⁇ 2.
• the polymer contains at least one of the unit A1 and the unit A2 and the unit K2 as a photodisintegrating base, the total of the unit A2 and the unit K2 is 0 in terms of the molar ratio with respect to the unit A1.
• the polymer according to one aspect of the present invention can be obtained by using the monomer components constituting each of the above units as a raw material and polymerizing them by a usual method so as to have the above-mentioned compounding ratio. Further, a polymer containing a unit having an onium salt structure (referred to as “precursor polymer”) is first synthesized, and in the precursor polymer, the anion portion of the onium salt structure is salt-exchanged to have a desired anion. It may be a polymer containing unit A.
• the molecular weight of the polymer in one embodiment of the present invention is not particularly limited.
• the resist composition according to one aspect of the present invention is characterized by containing the above polymer.
• components such as a polysubstituted alcohol compound, an organometallic compound and an organometallic complex may be optionally contained.
• the blending amount of the polymer in the resist composition is preferably 70 to 100% by mass in total of the solid content.
• the resist composition of one aspect of the present invention may be configured to contain only the above polymer, but in addition to the above polymer, other components such as ethylene glycol, triethylene glycol, erythritol, arabitol, 1, Compounds having two or more hydroxyl groups in the molecule, such as 4-benzenedimethanol and 2,3,5,6-tetrafluoro-1,4-benzenedimethanol, may be further contained.
• other components such as ethylene glycol, triethylene glycol, erythritol, arabitol, 1, Compounds having two or more hydroxyl groups in the molecule, such as 4-benzenedimethanol and 2,3,5,6-tetrafluoro-1,4-benzenedimethanol, may be further contained.
• the resist composition according to one aspect of the present invention preferably further contains either an organometallic compound or an organometallic complex.
• the metals include Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, I, Xe, Hf, Ta, W.
• the unit A and the unit B are sensitized by being at least one selected from the group consisting of Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Po, At, Rn and Ra. It is preferable because it can be done.
• organometallic compound examples include tetraaryl tin, tetraalkyl tin, and bis (alkylphosphine) platinum.
• organic metal complex examples include hafnium acrylate (IV), zirconium acrylate (IV), bismuth acrylate (III), bismuth acetate (III), tin oxalate (II) and the like.
• the blending amount of the organometallic compound and the organometallic complex in the resist composition is preferably 0 to 0.5 molar equivalent with respect to the unit A.
• the resist composition according to one aspect of the present invention may contain other components as long as the effects of the present invention are not impaired.
• the components that can be blended include known additives such as a fluorine-containing water-repellent polymer, an acid diffusion control agent, an organic carboxylic acid, a surfactant, a filler, a pigment, an antistatic agent, a flame retardant, and a light stabilizer. At least one selected from antioxidants, ion-replenishing agents, organic solvents and the like may be added.
• the fluorine-containing water-repellent polymer include those usually used in an immersion exposure process, and a polymer having a higher fluorine atom content is preferable.
• the fluorine-containing water-repellent polymer can be unevenly distributed on the surface of the resist film due to the water repellency of the fluorine-containing water-repellent polymer. ..
• the acid diffusion control agent has the effect of controlling the diffusion phenomenon of the acid generated from the photoacid generator in the resist film and controlling the unfavorable chemical reaction in the non-exposed region. Therefore, the storage stability of the obtained resist composition is further improved, the resolution as a resist is further improved, and the line width change of the resist pattern due to the fluctuation of the leaving time from the exposure to the development process can be suppressed. , A resist composition having excellent process stability can be obtained.
• the acid diffusion control agent examples include a compound having one nitrogen atom in the same molecule, a compound having two nitrogen atoms, a compound having three nitrogen atoms, an amide group-containing compound, a urea compound, and a nitrogen-containing heterocyclic compound. Be done.
• the acid diffusion control agent may be used as a monomer constituting the unit of the polymer and may be contained in the polymer.
• a photodisintegrating base that is exposed to light and generates a weak acid by exposure can also be used.
• the photodisintegrating base include onium salt compounds and iodonium salt compounds that are decomposed by exposure and lose their acid diffusion controllability.
• Japanese Patent Application Laid-Open No. 3577743 Japanese Patent Application Laid-Open No. 2001-215689, Japanese Patent Application Laid-Open No. 2001-166476, Japanese Patent Application Laid-Open No. 2008-102383, Japanese Patent Application Laid-Open No. 2010-243773, JP-A-2011-37835 and Japanese Patent Laid-Open No. Examples thereof include the compounds described in Kai 2012-173505 and the like.
• the content of the acid diffusion control agent is preferably 0.01 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and 1 to 10 parts by mass with respect to 100 parts by mass of the polymer component. It is more preferable to have.
• the surfactant is preferably used to improve the coatability. Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters. Agents, fluorosurfactants, organosiloxane polymers and the like.
• the content of the surfactant is preferably 0.0001 to 12 parts by mass, more preferably 0.0005 to 1% by mass with respect to 100 parts by mass of the polymer component.
• organic solvent examples include ethylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether.
• the method for preparing a resist composition according to one aspect of the present invention is not particularly limited, and the resist composition is prepared by a known method such as mixing, dissolving or kneading the above polymer and other optional components. be able to.
• the polymer can be synthesized by appropriately polymerizing the monomers constituting the units A and B, and if necessary, the monomers constituting the other units by a usual method.
• the method for producing a polymer according to the present invention is not limited to this.
• the resist composition component is preferably dissolved in the above organic solvent and dissolved in a solid content concentration of 1 to 40% by mass. It is more preferably 1 to 30% by mass, still more preferably 3 to 20% by mass.
• the above film thickness can be achieved by setting the solid content concentration in such a range.
• composition of one aspect of the present invention is obtained by mixing each component of the above composition, and the mixing method is not particularly limited.
• One aspect of the present invention is a resist film forming step of forming a resist film on a substrate using the resist composition, and a pattern of the resist film using a particle beam or an electromagnetic wave. It is a method for manufacturing a member including a photolithography step of exposing to the surface and a pattern forming step of developing an exposed resist film to obtain a photoresist pattern. Examples of the member include a device, a mask, and the like.
• Examples of the particle beam or electromagnetic wave used for exposure in the photolithography process include electron beam and EUV, respectively.
• the amount of light irradiation varies depending on the type and blending ratio of each component in the photocurable composition, the film thickness of the coating film, and the like, but is preferably 1 J / cm 2 or less or 1000 ⁇ C / cm 2 or less.
• the resist composition is contained as a sensitizing unit (unit C) in the polymer, or when it is contained as a sensitizing compound, it is also preferable to perform a second exposure with ultraviolet rays or the like after irradiation with particle beams or electromagnetic waves.
• one aspect of the present invention is the manufacture of a device including, in the photolithography step, a step of irradiating a second active energy ray having a lower energy than the particle beam or the electromagnetic wave after exposure to the particle beam or the electromagnetic wave. The method.
• the first active energy ray and the second active energy ray are not particularly limited as long as the onium salt according to the polymer according to some aspects of the present invention does not have significant absorption in the second active energy ray. It is preferable that the wavelength of the first active energy ray is shorter than that of the second active energy ray, or the energy of the photon or particle beam is high. Each active energy ray is illustrated below, but the wavelength is not limited to this as long as the wavelength of the first active energy ray is shorter than that of the second active energy ray or the energy of the photon or particle beam is high.
• the first active energy ray is not particularly limited as long as it can generate an active species such as an acid in the resist film after irradiation with the resist film, and is, for example, KrF excimer laser light, ArF excimer laser light, electron beam or extreme. Ultraviolet light (EUV) and the like are preferably mentioned.
• the acid generated in the resist film after irradiation with the first active energy ray deprotects the (thio) acetal moiety of the onium salt according to the polymer according to some aspects of the present invention.
• Any light may be used as long as it can activate the produced ketone derivative to generate an active species such as an acid.
• it means KrF excimer laser light, UV, visible light, etc., and it is particularly preferable to use light in the range of 365 nm (i line) to 436 nm (g line) among UV light.
• the method for manufacturing a device preferably includes a step of irradiating the first active energy and a step of irradiating the second active energy ray with a heating wire or a laser. ..
• a heating wire or a laser e.g., a laser.
• the step of heating can be carried out on a hot plate or the like, and in the method of manufacturing the device, the step of prebaking corresponds to the step.
• the coating film obtained by applying the composition for an inversion pattern so as to cover at least the recesses of the photoresist pattern is etched to expose the surface of the photoresist pattern. It is preferable to further include a step of allowing the resist to be formed and a step of removing the resist film on the surface portion of the exposed resist pattern to obtain an inverted pattern.
• a known composition for an inversion pattern can be used, and examples thereof include a composition containing a siloxane polymer described in International Publication WO2015 / 025665.
• one aspect of the present invention is a resist film forming step of forming a resist film on a substrate using the resist composition.
• a photolithography process that exposes the resist film using particle beams or electromagnetic waves, It is a method for forming an inverted pattern including a pattern forming step of developing an exposed resist film to obtain a photoresist pattern.
• one aspect of the present invention is a resist film forming step of forming a resist film on a substrate using the resist composition.
• a photolithography process that exposes the resist film using particle beams or electromagnetic waves,
• a pattern forming step of developing an exposed resist film to obtain a photoresist pattern
• a step of applying the composition for inversion pattern so as to cover at least the recesses of the photoresist pattern and etching the coating film obtained to expose the surface of the photoresist pattern.
• It is a method of forming an inversion pattern including the step of removing the resist film of the exposed resist pattern surface portion to obtain an inversion pattern.
• a usual method for forming an inversion pattern may be used.
• the substrate is an inorganic substrate such as Si, SiO 2 , SiN, SiON, TiN, WSi and BPSG (Boron Phosphorus Silicon Glass); for example, SOG (Spin on Glass) or the like to which an organic antireflection film is applied is applied.
• an inorganic substrate such as Si, SiO 2 , SiN, SiON, TiN, WSi and BPSG (Boron Phosphorus Silicon Glass); for example, SOG (Spin on Glass) or the like to which an organic antireflection film is applied is applied.
• SOG Spin on Glass
• a system-based inorganic substrate or the like is a method for manufacturing a device, it is preferably mentioned.
• an inorganic substrate such as Cr, CrO, CrON, MoSi 2 and SiO 2 is preferably raised, and the inorganic substrate has an EUV absorbing layer such as TaO. Is more preferable.
• the substrate for manufacturing the mask may have the same configuration as the substrate used for a
• a transmissive mask it is preferable that it is transparent to the transmitted light of the target, and in the case of a reflective mask, it is preferable. It is preferable to have a high reflectance with respect to the target light (electromagnetic wave such as EUV).
• An ordinary developer can be used for development in the pattern forming step, and examples of the developer include an alkaline developer, a neutral developer, and an organic solvent developer. Further, as a developer other than the above, a water-soluble developer containing a water-soluble organic solvent is also preferably used.
• the water-soluble organic solvent include organic compounds having 1 or more carbon atoms to be mixed with water at an arbitrary ratio, and examples thereof include methanol, ethanol, isopropyl alcohol, diacetone alcohol, ethylene glycol, ethylene glycol monomethyl ether, and propylene glycol.
• Propylene glycol monomethyl ether triethylene glycol, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, diglyme, triglime, acetonitrile, acetone, N, N-dimethylformamide, dimethylsulfoxide, formic acid, acetic acid, propionic acid, etc. Specifically, it can be mentioned.
• the water-soluble developer may be an aqueous solution by containing one or more kinds of water-soluble organic solvents, and a water-insoluble organic solvent may be further mixed.
• the water-insoluble organic solvent include alcohols that are immiscible with water, ethers that are immiscible with water, nitriles that are immiscible with water, ketones that are immiscible with water, esters such as ethyl acetate that are immiscible with water, and the like.
• examples thereof include organic halogen compounds such as methylene chloride.
• the substrate is not particularly limited and a known substrate can be used.
• a metal substrate such as silicon, silicon nitride, titanium, tantalum, palladium, copper, chromium, aluminum; a glass substrate; and the like can be mentioned.
• the active energy rays used for exposure in the photolithography step used to obtain an interlayer insulating film for creating an LSI include UV, KrF excimer laser light, ArF excimer laser light, electron beams, or Extreme ultraviolet (EUV) and the like are preferably mentioned.
• EUV Extreme ultraviolet
• the irradiation amount of the first active energy ray varies depending on the type and blending ratio of each component in the photocurable composition, the film thickness of the coating film, etc., but is 1 J / cm 2 or less or 1000 ⁇ C / cm 2 or less. Is preferable.
• the film thickness of the resist film formed by the resist composition is preferably 10 to 200 nm.
• the resist composition is applied onto a substrate by an appropriate coating method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, etc., and is applied at 60 to 150 ° C. for 1 to 20 minutes, preferably 80 to 80 to. Prebake at 120 ° C. for 1-10 minutes to form a thin film.
• the film thickness of this coating film is 5 to 200 nm, preferably 10 to 100 nm.
• the polymer of some embodiments of the present invention is not limited thereto.
• the polymer 3 was subjected to the same operation as in Synthesis Example 48 above except that 3- [N, N-bis (2-hydroxyethyl) amino] -2-hydroxypropanesulfonic acid was used instead of 2-hydroxysulfonic acid. To obtain 1.6 g.
• the developer was prepared as follows. (1) A film coated with a resist composition sample 1 to 7 in which each of the above polymers 1, 4 to 6 and 8 and comparative polymers 1 and 2 is dissolved so as to have a film thickness of 100 nm by a spin coating method. Prepare. (2) Prepare an aqueous acetonitrile solution having an acetonitrile concentration of 0 to 80% by mass. (3) Each film obtained in (1) above is impregnated with each aqueous acetonitrile solution, and the minimum concentration of acetonitrile in the aqueous acetonitrile solution in which the composition applied to the film is completely dissolved is determined within 30 seconds. (4) The acetonitrile aqueous solution obtained in (3) above is used as a developing solution for each resist composition sample.
• the resist composition sample 1 is spin-coated on a silicon wafer. This is prebaked on a hot plate at 110 ° C. for 1 minute to obtain a substrate on which a coating film having a thickness of 30 nm is formed.
• An electron beam drawing apparatus (Elionix ELS-F100T) is used to draw a 50 nm line pattern with a 160 nm pitch on the coating film of the substrate with an electron beam of 125 keV.
• the substrate after electron beam irradiation is subjected to Post Exposure Bake (PEB) on a hot plate at 90 ° C. for 1 minute.
• PEB Post Exposure Bake
• the developer is developed for 1 minute with a developer for patterning in which the acetonitrile concentration of the above developer optimized for each polymer is increased by 5% by mass, and then rinsed with pure water to obtain a line pattern of 50 nm.
• the irradiation amount at this time is set to E max [ ⁇ C / cm 2 ], and the sensitivity by electron beam irradiation is obtained.
• the obtained 50 nm line pattern is observed using a scanning electron microscope (SEM) (S-5500 manufactured by Hitachi High-Tech Co., Ltd.) to measure LWR.
• SEM scanning electron microscope
• Table 2 shows the results obtained as relative sensitivity and relative LWR by comparing the sensitivity of each resist composition sample 2 to 7 with the LWR using the sensitivity of the resist composition sample 1 (Comparative Example 1) and the LWR as reference values. show.
• Examples 3 and 4 have the same cationic structure as Comparative Example 2, but the sensitivity can be further increased by 15% or more as compared with Comparative Example 2.
• the sensitivity of Comparative Example 2 is higher than that of Comparative Example 1, but the LWR is 20% larger than that of Comparative Example 1.
• Examples 3 and 4 use a polymer having a hydroxyl group in the anion of the unit A, the sensitivity is better than that of Comparative Example 1, and the LWR can be reduced by 30% or more.
• Example 5 From the results of Example 5, it is possible to improve the sensitivity and lower the LWR as compared with the standard example, as in the case of the anion having a hydroxyl group of the anion having a thiol.
• the developer was prepared as follows. (1) Using resist composition samples 8 to 15 in which each of the above polymers 4, 14 to 20 is dissolved, a film coated with the composition so as to have a film thickness of 100 nm is prepared by a spin coating method. (2) Prepare an aqueous acetonitrile solution having an acetonitrile concentration of 0 to 80% by mass. (3) Each film obtained in (1) above is impregnated with each aqueous acetonitrile solution, and the minimum concentration of acetonitrile in the aqueous acetonitrile solution in which the composition applied to the film is completely dissolved is determined within 30 seconds. (4) The acetonitrile aqueous solution obtained in (3) above is used as a developing solution for each resist composition sample.
• the resist composition sample 8 is spin-coated on a silicon wafer. This is prebaked on a hot plate at 110 ° C. for 1 minute to obtain a substrate on which a coating film having a thickness of 30 nm is formed.
• An electron beam drawing apparatus (Elionix ELS-F100T) is used to draw a 50 nm line pattern with a 160 nm pitch on the coating film of the substrate with an electron beam of 125 keV.
• the substrate after electron beam irradiation is subjected to Post Exposure Bake (PEB) on a hot plate at 90 ° C. for 1 minute.
• PEB Post Exposure Bake
• the entire surface was irradiated with an exposure amount of 1000 mJ / cm 2 by a 395 nm UV-LED.
• the developer is developed for 1 minute with a developer for patterning in which the acetonitrile concentration of the above developer optimized for each polymer is increased by 5% by mass, and then rinsed with pure water to obtain a line pattern of 50 nm.
• the irradiation amount at this time is set to E max [ ⁇ C / cm 2 ], and the sensitivity by electron beam irradiation is obtained.
• the obtained 50 nm line pattern is observed using a scanning electron microscope (SEM) (S-5500 manufactured by Hitachi High-Tech Co., Ltd.) to measure LWR.
• SEM scanning electron microscope
• Table 4 shows the relative sensitivity and the results obtained as the relative LWR by comparing the sensitivity of each resist composition sample 9 to 16 with the LWR using the sensitivity of the resist composition sample 8 and the LWR as reference values.
• Examples 6 and Examples 7 to 10 having the same composition ratios of units A, B, and E were compared.
• the hydroxyl groups of the anions of the compounds A7 to A10 contained in Examples 7 to 10 are acids generated by electron beam irradiation and are bonded to the unit B by an acid catalytic reaction.
• the units B are also bonded to each other by an acid catalytic reaction.
• the acetal moiety of the onium salt in the unit A is hydrolyzed to become a ketone derivative by the water generated by the acid-catalyzed reaction, so that the wavelength of light absorption is lengthened and the polymer is changed to have UV absorption of 395 nm. .. Therefore, the sensitivity of Examples 7 to 10 is improved even if the composition is the same as that of Example 6 by further generating acid by UV full exposure after EB irradiation.
• Example 8 Comparing Example 8 and Example 14, the addition of the unit K suppresses the action of the acid generated from the unit A, so that the sensitivity is lowered, but the suppression of the acid diffusion tends to reduce the LWR. It turns out that there is. This is effective when high resolution is required.
• a polymer having high absorption efficiency of particle beams such as EUV or electromagnetic waves and excellent characteristics of sensitivity, resolution and pattern performance and a resist composition containing the polymer.

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• 2021
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  • 2021-08-19 KR KR1020237009448A patent/KR20230052959A/ko active Pending
  • 2021-08-19 WO PCT/JP2021/030330 patent/WO2022039212A1/ja not_active Ceased

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