Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
  • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
  • C07D317/72—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 spiro-condensed with carbocyclic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
  • C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
  • C07D327/06—Six-membered rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
  • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
  • C07D493/10—Spiro-condensed systems
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/22—Esters containing halogen
  • C08F220/24—Esters containing halogen containing perhaloalkyl radicals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
  • C08F220/282—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing two or more oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
  • C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
  • C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
  • C08F220/365—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate containing further carboxylic moieties
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
  • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
  • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor
  • G03F7/2041—Exposure; Apparatus therefor in the presence of a fluid, e.g. immersion; using fluid cooling means

Definitions

• the present invention relates to a radiation-sensitive resin composition and a pattern forming method.
• Photolithography technology that uses resist compositions is used to form fine circuits in semiconductor devices.
• an acid is generated by exposing the film of the resist composition to radiation through a mask pattern, and the acid is used as a catalyst to react with the resin in the exposed area and the unexposed area.
• a resist pattern is formed on a substrate by creating a difference in solubility in an organic solvent-based developer.
• Resist compositions to which a water-repellent compound is added are required to have LWR (Line Width Roughness) performance, water repellency, and development defect suppression, which indicates sensitivity and line width variation of resist patterns, even in the above-mentioned next-generation technology. .
• An object of the present invention is to provide a radiation-sensitive resin composition capable of forming a resist film excellent in sensitivity, LWR performance, water repellency, and development defect suppressing property, and having good storage stability, and a pattern forming method. .
• RK1 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
• L 1 is an alkanediyl group having 1 to 5 carbon atoms.
• R f1 is a fluorinated hydrocarbon group having 2 to 10 carbon atoms and having 5 to 7 fluorine atoms.
• R W is a monovalent organic group having 3 to 40 carbon atoms containing a cyclic structure.
• R fa and R fb are each independently a fluorine atom or a fluorinated hydrocarbon group having 1 to 10 carbon atoms.
• R 11 and R 12 are each independently a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms or a fluorinated hydrocarbon group having 1 to 10 carbon atoms.
• n1 is an integer of 1-4. When n1 is 2 or more, a plurality of Rfa and Rfb are the same or different.
• n2 is an integer of 0-4.
• n2 is 2 or more, a plurality of R 11 and R 12 are the same or different. However, no carbonyl group is interposed between the sulfur atom of the sulfonate ion and the cyclic structure of RW .
• Z + is a monovalent onium cation.
• the radiation-sensitive resin composition it is possible to construct a resist film that has good storage stability, sensitivity, LWR performance, water repellency, and development defect suppression properties.
• the polymer can exhibit high water repellency due to the fluorine atoms contained in the structural unit (I). Further, during the development step, a dissociation reaction occurs in the structural unit (I) in the polymer, and the solubility of the polymer in the developer can be improved, and as a result, the development defect suppressing property can be improved. .
• the relatively bulky structure introduced around the part where the developer dissociation reaction occurs in the structural unit (I) acts as a reaction barrier, and the radiation-sensitive resin composition. Inadvertent dissociation reaction due to moisture or the like during storage can be suppressed. It is presumed that these combined actions can satisfy both the contradictory requirements of storage stability and development defect suppression.
• the generated acid can maintain water repellency. can be appropriately controlled, and as a result, sufficient sensitivity, LWR performance, water repellency, and development defect suppression can be ensured.
• an “organic group” is a group having at least one carbon atom.
• the “hydrocarbon group” includes chain hydrocarbon groups, alicyclic hydrocarbon groups and aromatic hydrocarbon groups unless otherwise specified.
• the “hydrocarbon group” includes both saturated hydrocarbon groups and unsaturated hydrocarbon groups.
• the above-mentioned “chain hydrocarbon group” refers to a hydrocarbon group that does not contain a cyclic structure and is composed only of a chain structure, and includes both a straight chain hydrocarbon group and a branched chain hydrocarbon group.
• alicyclic hydrocarbon group refers to a hydrocarbon group that contains only an alicyclic structure as a ring structure and does not contain an aromatic ring structure, and includes monocyclic alicyclic hydrocarbon groups and polycyclic alicyclic It contains both hydrocarbon groups. However, it does not need to be composed only of an alicyclic structure, and may partially contain a chain structure.
• aromatic hydrocarbon group refers to a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it does not need to be composed only of an aromatic ring structure, and may partially contain a chain structure or an alicyclic structure.
• the present invention provides, in another embodiment, a step of directly or indirectly applying the radiation-sensitive resin composition to a substrate to form a resist film; exposing the resist film; and developing the exposed resist film with a developer.
• the pattern forming method it is possible to form a resist film excellent in sensitivity, LWR performance, water repellency and development defect suppressing property, and since the radiation-sensitive resin composition having good storage stability is used, high A high-quality resist pattern can be efficiently formed.
• the radiation-sensitive resin composition (hereinafter also simply referred to as “composition”) contains a polymer, a radiation-sensitive acid generator, and a solvent.
• the composition contains a resin (hereinafter also referred to as "base resin") that contains a structural unit having an acid-labile group and has a lower mass content of fluorine atoms than the polymer. is preferred.
• the composition preferably further contains an acid diffusion control agent.
• the above composition may contain other optional components as long as they do not impair the effects of the present invention.
• the polymer contains a structural unit (I) represented by formula (1) above and a structural unit different from the structural unit (I) above. Each structural unit will be described below.
• Structural unit (I) Structural unit (I) is represented by the following formula (1).
• RK1 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
• L 1 is an alkanediyl group having 1 to 5 carbon atoms.
• R f1 is a monovalent fluorinated hydrocarbon group having 2 to 10 carbon atoms and having 5 to 7 fluorine atoms.
• R K1 is preferably a hydrogen atom or a methyl group from the viewpoint of copolymerizability of the monomer that gives the structural unit (I).
• the C 1-5 alkanediyl group represented by L 1 includes a group obtained by removing two hydrogen atoms from a chain or branched alkane having the corresponding carbon number.
• the two hydrogen atoms may be removed from the same carbon atom or from different carbon atoms.
• Specific examples include methanediyl group, 1,1-ethanediyl group, 1,2-ethanediyl group, 1,1-dimethyl-1,2-ethanediyl group, 1,1-propanediyl group and 1,2-propanediyl group.
• L 1 is preferably a methanediyl group or an ethanediyl group (1,1-ethanediyl group or 1,2-ethanediyl group).
• the monovalent fluorinated hydrocarbon group having 2 to 10 carbon atoms and having 5 to 7 fluorine atoms represented by R f1 is, for example, 1 of 2 to 10 carbon atoms having 5 to 7 fluorine atoms.
• Examples of the monovalent fluorinated linear hydrocarbon group having 2 to 10 carbon atoms and having 5 to 7 fluorine atoms include a pentafluoroethyl group, a 2,2,3,3,3-pentafluoropropyl group, heptafluoropropyl group, 1,1,1,3,3,3-hexafluoro-2-propyl group, 1,1,1,3,3,3-hexafluoro-2-fluoropropyl group, heptafluoro n- fluorinated alkyl groups such as propyl groups; fluorinated alkenyl groups such as pentafluoropropenyl groups; Examples include fluorinated alkynyl groups such as pentafluorobutynyl groups.
• Examples of the monovalent fluorinated alicyclic hydrocarbon group having 3 to 10 carbon atoms and 5 to 7 fluorine atoms include: pentafluorocyclobutyl group, hexafluorocyclobutyl group, pentaolocyclopentyl group, hexafluorocyclopentyl group, heptafluorocyclopentyl group, pentafluorocyclohexyl group, hexaolocyclohexyl group, pentafluorocyclohexylmethyl group, pentafluoronorbornyl group, fluorinated cycloalkyl groups such as a pentafluoroadamantyl group, a pentafluorobornyl group, and a pentafluoroisobornyl group; Fluorinated cycloalkenyl groups such as a pentafluorocyclopentenyl group and a pentafluorocyclohe
• R f1 is preferably a monovalent fluorinated chain hydrocarbon group having 2 to 8 carbon atoms and having 5 to 7 fluorine atoms, and a monovalent fluorinated chain hydrocarbon group having 2 to 6 carbon atoms and having 5 to 7 fluorine atoms. More preferably a fluorinated chain hydrocarbon group, more preferably a monovalent linear hydrocarbon group having 2 to 4 carbon atoms having 5 to 7 fluorine atoms, and 2 carbon atoms having 5 fluorine atoms A monovalent straight chain hydrocarbon group of ⁇ 4 is even more preferred, and a monovalent straight chain saturated hydrocarbon group of 2 to 4 carbon atoms having 5 fluorine atoms is particularly preferred.
• Examples of monomers that give the structural unit (I) include compounds represented by the following formulas (1-1) to (1-18).
• the lower limit of the content ratio of the structural unit (I) in the total structural units constituting the polymer is preferably 5 mol%, more preferably 10 mol%, 15 mol % is more preferred, and 20 mol % is particularly preferred.
• the upper limit of the content ratio is preferably 95 mol %, more preferably 90 mol %, still more preferably 85 mol %, and particularly preferably 80 mol %.
• a monomer that gives the structural unit (I) can be synthesized by a condensation reaction between an alcohol having a polymerizable group and a fluorine-containing carboxylic acid, as shown in the scheme below.
• Other structures can also be synthesized by changing the structures of alcohols and carboxylic acids.
• the polymer further includes a structural unit (II) represented by the following formula (2) (excluding structures corresponding to the structural unit (I)) as a structural unit different from the structural unit (I). preferably included.
• RK2 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
• L f is a fluorine-substituted or unsubstituted divalent organic group having 1 to 20 carbon atoms.
• L 2 is * -COO- or * -OCO-. * is a bond on the Lf side.
• m is an integer from 0 to 2;
• L f and L 2 are the same or different from each other.
• R f2 is a fluorine-substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms. However, L f and R f2 have a total of 1 or more fluorine atoms.
• R K2 is preferably a hydrogen atom or a methyl group from the viewpoint of copolymerizability of the monomer that gives the structural unit (II).
• L f is a divalent organic group having 1 to 20 carbon atoms, and some or all of the hydrogen atoms may be substituted with fluorine atoms, and may not be substituted with fluorine atoms (may be unsubstituted ).
• the fluorine-substituted or unsubstituted divalent organic group having 1 to 20 carbon atoms represented by L f includes the fluorine-substituted or unsubstituted C 1 to 20 organic group represented by R f2 in the above formula (2). Since a group obtained by removing one hydrogen atom from a monovalent organic group can be suitably employed, R f2 will be explained first.
• R f2 is a monovalent organic group having 1 to 20 carbon atoms, and some or all of the hydrogen atoms may be substituted with fluorine atoms, and may not be substituted with fluorine atoms (may be unsubstituted ).
• the monovalent organic group having 1 to 20 carbon atoms is not particularly limited, and may be a chain structure, a cyclic structure, or a combination thereof. Examples of the chain structure include chain hydrocarbon groups that may be saturated or unsaturated, linear or branched.
• the above cyclic structures include cyclic hydrocarbon groups which may be alicyclic, aromatic or heterocyclic.
• the monovalent organic group includes a substituted or unsubstituted monovalent chain hydrocarbon group having 1 to 20 carbon atoms and a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms. , a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a combination thereof.
• a group in which some or all of the hydrogen atoms contained in a chain structure or cyclic structure are substituted with a substituent group a group in which a heteroatom or a heteroatom-containing group is interposed between carbon-carbon atoms or at the carbon chain end of these groups, etc.
• heteroatom or heteroatom-containing group examples include -CO-, -CS-, -O-, -S-, -SO 2 - or -NR'-, or a combination of two or more thereof. be done.
• R' is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
• Examples of the monovalent chain hydrocarbon group having 1 to 20 carbon atoms include a linear or branched saturated hydrocarbon group having 1 to 20 carbon atoms, or a linear or branched unsaturated hydrocarbon group having 1 to 20 carbon atoms.
• a hydrocarbon group etc. can be mentioned.
• Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a monocyclic or polycyclic saturated hydrocarbon group, a monocyclic or polycyclic unsaturated hydrocarbon group, and the like.
• Preferred monocyclic saturated hydrocarbon groups are cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl groups.
• Preferred polycyclic cycloalkyl groups are bridged alicyclic hydrocarbon groups such as norbornyl, adamantyl, tricyclodecyl and tetracyclododecyl groups.
• Monocyclic unsaturated hydrocarbon groups include monocyclic cycloalkenyl groups such as a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group.
• Polycyclic unsaturated hydrocarbon groups include polycyclic cycloalkenyl groups such as norbornenyl, tricyclodecenyl, and tetracyclododecenyl groups.
• the bridged alicyclic hydrocarbon group is a polycyclic alicyclic hydrocarbon group in which two carbon atoms that are not adjacent to each other among the carbon atoms constituting the alicyclic ring are linked by a bond chain containing one or more carbon atoms.
• a cyclic hydrocarbon group is a polycyclic alicyclic hydrocarbon group in which two carbon atoms that are not adjacent to each other among the carbon atoms constituting the alicyclic ring are linked by a bond chain
• Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group and anthryl group; benzyl group, phenethyl group and naphthylmethyl group; An aralkyl group and the like can be mentioned.
• heterocyclic cyclic hydrocarbon group examples include a group obtained by removing one hydrogen atom from an aromatic heterocyclic structure and a group obtained by removing one hydrogen atom from an alicyclic heterocyclic structure.
• the heterocyclic structure also includes a 5-membered ring aromatic structure having aromaticity by introducing a heteroatom.
• Heteroatoms include oxygen atoms, nitrogen atoms, sulfur atoms, and the like.
• aromatic heterocyclic structures examples include oxygen atom-containing aromatic heterocyclic structures such as furan, pyran, benzofuran, and benzopyran; nitrogen atom-containing aromatic heterocyclic structures such as pyrrole, imidazole, pyridine, pyrimidine, pyrazine, indole, quinoline, isoquinoline, acridine, phenazine, carbazole; sulfur atom-containing aromatic heterocyclic structures such as thiophene; Examples include aromatic heterocyclic structures containing multiple heteroatoms such as thiazole, benzothiazole, thiazine, and oxazine.
• Examples of the alicyclic heterocyclic structures include oxygen atom-containing alicyclic heterocyclic structures such as oxirane, tetrahydrofuran, tetrahydropyran, dioxolane, and dioxane; nitrogen atom-containing alicyclic heterocyclic structures such as aziridine, pyrrolidine, piperidine, piperazine; Sulfur atom-containing alicyclic heterocyclic structures such as thietane, thiolane, and thiane; Examples include alicyclic heterocyclic structures containing multiple heteroatoms such as morpholine, 1,2-oxathiolane, and 1,3-oxathiolane.
• the cyclic structures also include structures containing lactone structures, cyclic carbonate structures, sultone structures and cyclic acetals.
• the fluorine-substituted or unsubstituted divalent organic group having 1 to 20 carbon atoms represented by L f includes the fluorine-substituted or unsubstituted C 1 to 20 organic group represented by R f2 above.
• a group obtained by removing one hydrogen atom from a monovalent organic group can be preferably employed.
• m is preferably 1 or 2, more preferably 1.
• L f and R f2 have a total of 1 or more fluorine atoms.
• the lower limit of the total number of fluorine atoms in L f and R f2 may be two or three.
• the upper limit of the total number may be 10, 8, or 6.
• one or two fluorine atoms or trifluoromethyl groups are preferably bonded to at least one carbon atom adjacent to the carbonyl group in L2 .
• Examples of monomers that give the structural unit (II) include compounds represented by the following formulas (2-1) to (2-45).
• the lower limit of the content of the structural unit (II) in the total structural units constituting the polymer is preferably 1 mol%, more preferably 5 mol%, 8 mol % is more preferred, and 10 mol % is particularly preferred.
• the upper limit of the content ratio is preferably 90 mol %, more preferably 80 mol %, still more preferably 75 mol %, and particularly preferably 70 mol %.
• the polymer preferably further contains a structural unit (III) represented by the following formula (3) as a structural unit different from the structural unit (I).
• R7 is a hydrogen atom, fluorine atom, methyl group or trifluoromethyl group.
• R 8 is a monovalent hydrocarbon group having 1 to 20 carbon atoms.
• R 9 and R 10 are each independently a monovalent chain hydrocarbon group having 1 to 10 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or these groups represents a divalent alicyclic group having 3 to 20 carbon atoms which is combined with the carbon atoms to which they are bonded.
• R 7 is preferably a hydrogen atom or a methyl group, more preferably a methyl group, from the viewpoint of copolymerizability of the monomer that gives the structural unit (III).
• Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R 8 include a monovalent linear hydrocarbon group having 1 to 10 carbon atoms and a monovalent alicyclic ring having 3 to 20 carbon atoms. and a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms.
• the monovalent chain hydrocarbon group having 1 to 10 carbon atoms represented by R 8 to R 10 the monovalent chain hydrocarbon group having 1 to 20 carbon atoms in R f2 in the above formula (2) Of these, groups having 1 to 10 carbon atoms can be preferably employed.
• Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R 8 to R 10 include carbonized monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms in R f2 of the above formula (2).
• a hydrogen group can be preferably employed.
• the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R 8 is preferably a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms in R f2 of the above formula (2). can be adopted.
• R 8 is preferably a monovalent linear or branched saturated hydrocarbon group having 1 to 10 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms.
• the divalent alicyclic group having 3 to 20 carbon atoms in which the R 9 and R 10 are combined together and formed together with the carbon atoms to which they are bonded is the monocyclic or polycyclic alicyclic hydrocarbon having the above carbon number. is not particularly limited as long as it is a group obtained by removing two hydrogen atoms from the same carbon atoms constituting the carbocyclic ring of .
• Either a monocyclic hydrocarbon group or a polycyclic hydrocarbon group may be used, and the polycyclic hydrocarbon group may be either a bridged alicyclic hydrocarbon group or a condensed alicyclic hydrocarbon group. It may be either a hydrogen group or an unsaturated hydrocarbon group.
• the condensed alicyclic hydrocarbon group is a polycyclic alicyclic hydrocarbon group in which a plurality of alicyclic rings share a side (a bond between two adjacent carbon atoms).
• the saturated hydrocarbon group is preferably a cyclopentanediyl group, a cyclohexanediyl group, a cycloheptanediyl group, a cyclooctanediyl group, or the like
• the unsaturated hydrocarbon group is a cyclopentenediyl group.
• cyclohexenediyl group, cycloheptenediyl group, cyclooctenediyl group, cyclodecenediyl group and the like are preferable.
• the polycyclic alicyclic hydrocarbon group is preferably a bridged alicyclic saturated hydrocarbon group, such as a bicyclo[2.2.1]heptane-2,2-diyl group (norbornane-2,2-diyl group ), bicyclo[2.2.2]octane-2,2-diyl group, tricyclo[3.3.1.1 3,7 ]decane-2,2-diyl group (adamantane-2,2-diyl group) etc. are preferred.
• a bridged alicyclic saturated hydrocarbon group such as a bicyclo[2.2.1]heptane-2,2-diyl group (norbornane-2,2-diyl group ), bicyclo[2.2.2]octane-2,2-diyl group, tricyclo[3.3.1.1 3,7 ]decane-2,2-diyl group (adamantane-2,2-diyl group) etc.
• R 8 is an alkyl group having 1 to 4 carbon atoms or a phenyl group
• R 9 and R 10 are combined with each other and the alicyclic structure composed together with the carbon atom to which they are bonded is polycyclic or monocyclic. is preferably a cycloalkane structure of
• structural unit (III) examples include structural units represented by the following formulas (3-1) to (3-7) (hereinafter also referred to as “structural units (III-1) to (III-7)”). etc.
• R 7 to R 10 have the same meanings as in formula (3) above.
• i and j are each independently an integer of 1 to 4;
• k and l are 0 or 1;
• R8 is preferably a methyl group, an ethyl group, an isopropyl group or a phenyl group.
• R 9 and R 10 are preferably a methyl group or an ethyl group.
• the polymer may contain one or a combination of two or more structural units (III).
• the lower limit of the content ratio of the structural unit (III) in all the structural units constituting the polymer is 5 mol % is preferred, 8 mol % is more preferred, 10 mol % is even more preferred, and 15 mol % is particularly preferred.
• the upper limit of the content ratio is preferably 80 mol %, more preferably 75 mol %, still more preferably 70 mol %, and particularly preferably 65 mol %.
• the polymer contains, as a structural unit different from the structural unit (I), a structural unit (IV) containing at least one selected from the group consisting of a lactone structure, a cyclic carbonate structure and a sultone structure (however, the structural unit (II ) except for structures corresponding to ).
• the polymer can adjust the solubility in the developer, and as a result, the radiation-sensitive resin composition improves lithography performance such as resolution. be able to.
• Structural units (IV) include, for example, structural units represented by the following formulas (T-1) to (T-10).
• R L1 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
• R L2 to R L5 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyano group, a trifluoromethyl group, a methoxy group, a methoxycarbonyl group, a hydroxy group, a hydroxymethyl group, or a dimethylamino group; be.
• R L4 and R L5 may be a divalent alicyclic group having 3 to 8 carbon atoms combined with each other and composed together with the carbon atoms to which they are attached.
• LT is a single bond or a divalent linking group.
• X is an oxygen atom or a methylene group.
• k is an integer from 0 to 3;
• m is an integer of 1-3.
• R 9 and R 10 in the above formula (3) are examples include groups having 3 to 8 carbon atoms among divalent alicyclic groups having 3 to 20 carbon atoms which are composed together with the carbon atoms to which they are bonded.
• One or more hydrogen atoms on this alicyclic group may be replaced with a hydroxy group.
• the divalent linking group represented by L T includes, for example, a divalent linear or branched hydrocarbon group having 1 to 10 carbon atoms, and a divalent alicyclic carbonized group having 4 to 12 carbon atoms.
• a hydrogen group, or a group composed of one or more of these hydrocarbon groups and at least one group selected from -CO-, -O-, -NH- and -S- may be mentioned.
• structural units containing a lactone structure are preferred as structural units (IV), structural units containing a norbornanelactone structure are more preferred, and structural units derived from norbornanelactone-yl (meth)acrylate are even more preferred.
• the lower limit of the content ratio of the structural unit (IV) (the total when there are multiple types of the structural unit (IV)) is based on the total structural units constituting the polymer. , is preferably 5 mol %, more preferably 8 mol %, even more preferably 10 mol %.
• the upper limit of the content ratio is preferably 50 mol%, more preferably 40 mol%, and even more preferably 35 mol%.
• the polymer may contain a structural unit (V) containing a polar group as a structural unit different from the structural unit (I) (provided that the structure corresponding to the structural units (II) and (IV) is except).
• the polymer can adjust the solubility in the developer, and as a result, the lithography performance such as the resolution of the radiation-sensitive resin composition can be improved.
• the polar group include a hydroxy group, a carboxyl group, a cyano group, a nitro group, a sulfonamide group and the like. Among these, a hydroxy group and a carboxy group are preferred, and a hydroxy group is more preferred.
• Examples of structural units (V) include structural units represented by the following formula.
• RA is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
• the lower limit of the content ratio of the structural unit (V) (the total when there are multiple types of structural units (V)) constitutes the polymer. 5 mol% is preferable, 8 mol% is more preferable, and 10 mol% is still more preferable with respect to the total structural units.
• the upper limit of the content ratio is preferably 60 mol%, more preferably 50 mol%, and even more preferably 45 mol%.
• the polymer may contain a structural unit having an alicyclic structure represented by the following formula (6) as a structural unit other than the structural units listed above.
• R 1 ⁇ is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
• R 2 ⁇ is a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms.
• the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R 2 ⁇ includes 3 to 3 carbon atoms represented by R 8 to R 10 in the above formula (3).
• 20 monovalent alicyclic hydrocarbon groups can be preferably employed.
• the lower limit of the content of the structural unit having the alicyclic structure is preferably 5 mol%, and 10 mol, based on the total structural units constituting the polymer. % is more preferred, and 15 mol % is even more preferred.
• the upper limit of the content ratio is preferably 40 mol %, more preferably 30 mol %, and even more preferably 20 mol %.
• the polymer can be synthesized, for example, by subjecting monomers that give each structural unit to a polymerization reaction in an appropriate solvent using a radical polymerization initiator or the like.
• radical polymerization initiator examples include azobisisobutyronitrile (AIBN), 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis(2-cyclopropylpropyl pionitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), azo radical initiators such as dimethyl 2,2'-azobis isobutyrate; benzoyl peroxide, t-butyl hydroperoxide, Peroxide-based radical initiators such as cumene hydroperoxide can be used.
• AIBN and dimethyl 2,2'-azobisisobutyrate are preferred, and AIBN is more preferred.
• These radical initiators can be used individually by 1 type or in mixture of 2 or more types.
• solvents used in the above polymerization reaction include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane; cyclohexane, cycloheptane, cyclooctane, and decalin.
• the reaction temperature in the above polymerization reaction is usually 40°C to 150°C, preferably 50°C to 120°C.
• the reaction time is generally 1 hour to 48 hours, preferably 1 hour to 24 hours.
• the molecular weight of the polymer is not particularly limited, but the lower limit of the polystyrene equivalent weight average molecular weight (Mw) by gel permeation chromatography (GPC) is preferably 2,000, more preferably 4,000, and even more preferably 5,000. , 6,00 are particularly preferred.
• the upper limit of Mw is preferably 20,000, more preferably 12,000, even more preferably 10,000, and particularly preferably 8,000.
• the ratio (Mw/Mn) of Mw to the polystyrene equivalent number average molecular weight (Mn) of the polymer measured by GPC is usually 1 or more and 5 or less, preferably 1 or more and 3 or less, and more preferably 1 or more and 2 or less.
• the lower limit of the content of the polymer is preferably 0.1 parts by mass, more preferably 0.5 parts by mass, even more preferably 1 part by mass, and particularly preferably 2 parts by mass with respect to 100 parts by mass of the base resin described later.
• the upper limit of the content is preferably 40 parts by mass, more preferably 30 parts by mass, still more preferably 20 parts by mass, and particularly preferably 15 parts by mass.
• the base resin is a resin containing a structural unit having an acid-labile group and having a lower mass content of fluorine atoms than the polymer.
• the structural unit having an acid-labile group in the base resin the structural unit (III) contained in the above polymer can be suitably employed (hereinafter also referred to as "structural unit (III)" in the base resin). The same applies to other structural units.).
• the radiation-sensitive resin composition has excellent pattern formability because the base resin has the structural unit (III).
• the lower limit of the content ratio of the structural unit (III) in the total structural units constituting the base resin is preferably 15 mol%, more preferably 25 mol%. , 30 mol % is more preferred, and 35 mol % is particularly preferred.
• the upper limit of the content ratio is preferably 80 mol %, more preferably 75 mol %, still more preferably 70 mol %, and particularly preferably 65 mol %.
• the base resin may contain structural units (IV) and structural units (V) in the polymer in addition to the structural units (III) having an acid-labile group. Furthermore, the base resin may contain a structural unit derived from hydroxystyrene or a structural unit having a phenolic hydroxyl group (hereinafter also referred to as “structural unit (VI)”, described later).
• the lower limit of the content of the structural unit (IV) is preferably 20 mol%, more preferably 30 mol%, more preferably 35 mol%, relative to all structural units constituting the base resin. Mole % is even more preferred.
• the upper limit of the content ratio is preferably 80 mol%, more preferably 70 mol%, and even more preferably 65 mol%.
• the lower limit of the content of the structural unit (V) is preferably 5 mol%, more preferably 8 mol%, based on the total structural units constituting the base resin. , 10 mol % is more preferred.
• the upper limit of the content ratio is preferably 40 mol %, more preferably 30 mol %, and even more preferably 25 mol %.
• Structural unit (VI) is a structural unit derived from hydroxystyrene or a structural unit having a phenolic hydroxyl group. Structural unit (VI) contributes to improvement of etching resistance and improvement of developer solubility difference (dissolution contrast) between exposed and unexposed areas. In particular, it can be suitably applied to pattern formation using exposure to radiation with a wavelength of 50 nm or less, such as electron beams and EUV. In the case of exposure to radiation with a wavelength of 50 nm or less, the base resin preferably has the structural unit (VI), the structural unit (III), and optionally the structural unit (V).
• Structural units derived from hydroxystyrene are represented by, for example, the following formulas (4-1) to (4-2), and structural units having a phenolic hydroxyl group are represented by, for example, the following formulas (4-3) to (4-4 ) etc.
• R 11 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
• the phenolic hydroxyl group is protected by a protective group such as an alkali dissociable group (e.g., an acyl group) during polymerization, and then hydrolyzed to deprotect the structure. It is preferred to obtain units (VI).
• a protective group such as an alkali dissociable group (e.g., an acyl group) during polymerization, and then hydrolyzed to deprotect the structure. It is preferred to obtain units (VI).
• the lower limit of the content of the structural unit (VI) is preferably 10 mol%, more preferably 20 mol%, based on the total structural units constituting the base resin. Moreover, the upper limit of the content ratio is preferably 70 mol %, more preferably 60 mol %.
• the molecular weight of the base resin is not particularly limited, but the lower limit of the polystyrene equivalent weight average molecular weight (Mw) by gel permeation chromatography (GPC) is preferably 1,000, more preferably 2,000, and more preferably 3,000. Preferably, 4,000 is particularly preferred.
• the upper limit of Mw is preferably 20,000, more preferably 15,000, even more preferably 12,000, and particularly preferably 8,000.
• the ratio (Mw/Mn) of Mw to the polystyrene equivalent number average molecular weight (Mn) of the base resin measured by GPC is usually 1 or more and 5 or less, preferably 1 or more and 3 or less, and more preferably 1 or more and 2 or less.
• the base resin can be synthesized by a method similar to the method for synthesizing the polymer described above.
• a radiation-sensitive acid generator is represented by the following formula ( ⁇ ).
• the acid generated by exposure dissociates the acid dissociable group of the structural unit (III) to generate a carboxyl group or the like.
• the radiation-sensitive resin composition contains the radiation-sensitive acid generator, the polarity of the resin in the exposed area increases, and the resin in the exposed area becomes soluble in the developer in the case of alkaline aqueous solution development. On the other hand, in the case of organic solvent development, it becomes sparingly soluble in the developer.
• R W is a monovalent organic group having 3 to 40 carbon atoms containing a cyclic structure.
• R fa and R fb are each independently a fluorine atom or a fluorinated hydrocarbon group having 1 to 10 carbon atoms.
• R 11 and R 12 are each independently a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms or a fluorinated hydrocarbon group having 1 to 10 carbon atoms.
• n1 is an integer of 1-4.
• n1 is 2 or more, a plurality of Rfa and Rfb are the same or different.
• n2 is an integer of 0-4.
• n2 is 2 or more, a plurality of R 11 and R 12 are the same or different.
• no carbonyl group is interposed between the sulfur atom of the sulfonate ion and the cyclic structure of RW .
• Z + is a monovalent onium cation.
• the monovalent organic group having 3 to 40 carbon atoms containing a cyclic structure represented by R W includes the number of carbon atoms in the monovalent organic group having 1 to 20 carbon atoms represented by R f2 in the above formula (2). is extended from 3 to 40, and a group in which a cyclic structure is introduced as an essential structure can be preferably employed. As a result, excellent sensitivity, LWR performance, and development defect suppressing properties can be exhibited during pattern formation.
• the cyclic structure a cyclic structure that can be included in the organic group of R f2 in the above formula (2) can be preferably employed.
• the cyclic structure preferably includes a polycyclic structure, a polycyclic alicyclic hydrocarbon structure having 6 to 15 carbon atoms, or a polycyclic alicyclic hydrocarbon structure having 6 to 15 carbon atoms. More preferably, it contains a combination with a lactone structure or a cyclic acetal structure.
• These structures are preferably included as the minimum basic skeleton of the cyclic structure.
• the number of cyclic structures as the basic skeleton in the organic group may be 1, 2, or 3 or more.
• fluorinated hydrocarbon groups having 1 to 10 carbon atoms represented by R fa , R fb , R 11 and R 12 include trifluoromethyl group, 2,2,2-trifluoroethyl group, and pentafluoroethyl group.
• 2,2,3,3,3-pentafluoropropyl group 1,1,1,3,3,3-hexafluoropropyl group, heptafluoro n-propyl group, heptafluoro i-propyl group, nonafluoro n- butyl group, nonafluoro i-butyl group, nonafluoro t-butyl group, 2,2,3,3,4,4,5,5-octafluoro n-pentyl group, tridecafluoro n-hexyl group, 5,5, fluorinated alkyl groups such as 5-trifluoro-1,1-diethylpentyl group; fluorinated alkenyl groups such as a trifluoroethenyl group and a pentafluoropropenyl group; Examples include fluorinated alkynyl groups such as fluoroethynyl and trifluoropropynyl groups.
• the hydrocarbon group having 1 to 10 carbon atoms represented by R 11 and R 12 includes 1 carbon atom among the monovalent hydrocarbon groups having 1 to 20 carbon atoms represented by R 8 in the above formula (3). Groups corresponding to ⁇ 10 can be suitably employed.
• n1 is preferably an integer of 1-3, more preferably 1 or 2.
• n2 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and even more preferably 0 or 1.
• no carbonyl group is interposed between the sulfur atom of the sulfonate ion and the cyclic structure of RW above.
• RW includes a plurality of cyclic structures, consideration is given from the sulfur atom side to the first cyclic structure (however, atoms forming a cyclic structure are not included). Therefore, a carbonyl group may be present in the terminal structure after the first ring structure from the sulfur atom side in the above RW .
• anion portion of the radiation-sensitive acid generator represented by the formula ( ⁇ ) is not particularly limited, for example, structures represented by the following formulas ( ⁇ -1-1) to ( ⁇ -1-19), etc. mentioned.
• the monovalent onium cation represented by Z + includes, for example, S, I, O, N, P, Cl, Br, F, As, Se, Sn, Sb, Te, Onium cations containing elements such as Bi can be mentioned.
• Onium cations include, for example, sulfonium cations, tetrahydrothiophenium cations, iodonium cations, phosphonium cations, diazonium cations, pyridinium cations, and ammonium cations. Among them, a sulfonium cation or an iodonium cation is preferred. Sulfonium cations or iodonium cations are preferably represented by the following formulas (X-1) to (X-6).
• R a1 , R a2 and R a3 each independently represent a substituted or unsubstituted C 1-12 linear or branched alkyl group, alkoxy group or alkoxycarbonyl oxy group, substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 12 carbon atoms, substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, hydroxy group, halogen atom, —OSO 2 —R P , —SO 2 —R Q or —S—R T , or represents a ring structure composed of two or more of these groups combined together.
• the ring structure may contain a heteroatom such as O or S between the carbon-carbon bonds forming the skeleton.
• R P , R Q and R T are each independently a substituted or unsubstituted linear or branched C 1-12 alkyl group, a substituted or unsubstituted C 5-25 alicyclic It is a hydrocarbon group or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms.
• k1, k2 and k3 are each independently an integer from 0 to 5; When R a1 to R a3 and R P , R Q and R T are each plural, R a1 to R a3 and R P , R Q and R T may be the same or different.
• R b1 is a substituted or unsubstituted linear or branched alkyl group or alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted acyl group having 2 to 8 carbon atoms. , or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 8 carbon atoms, or a hydroxy group.
• nk is 0 or 1; When nk is 0, k4 is an integer of 0-4, and when nk is 1, k4 is an integer of 0-7.
• R b1 When there are a plurality of R b1 , the plurality of R b1 may be the same or different, and the plurality of R b1 may represent a ring structure formed by being combined with each other.
• R b2 is a substituted or unsubstituted C 1-7 linear or branched alkyl group or a substituted or unsubstituted C 6 or 7 aromatic hydrocarbon group.
• LC is a single bond or a divalent linking group.
• k5 is an integer from 0 to 4;
• the plurality of Rb2 's may be the same or different, and the plurality of Rb2 's may represent a ring structure formed by being combined with each other.
• q is an integer from 0 to 3;
• the ring structure containing S + may contain a heteroatom such as O or S between the carbon-carbon bonds forming the skeleton.
• R c1 , R c2 and R c3 are each independently a substituted or unsubstituted C 1-12 linear or branched alkyl group.
• R g1 is a substituted or unsubstituted linear or branched alkyl group or alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted acyl group having 2 to 8 carbon atoms. , or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 8 carbon atoms, or a hydroxy group.
• nk is 0 or 1; When nk2 is 0, k10 is an integer of 0-4, and when nk2 is 1, k10 is an integer of 0-7.
• R g1 When there are a plurality of R g1 , the plurality of R g1 may be the same or different, and the plurality of R g1 may represent a ring structure formed by being combined with each other.
• R g2 and R g3 are each independently a substituted or unsubstituted C 1-12 linear or branched alkyl group, an alkoxy group or an alkoxycarbonyloxy group, a substituted or unsubstituted C 3 -12 monocyclic or polycyclic cycloalkyl groups, substituted or unsubstituted C6-12 aromatic hydrocarbon groups, hydroxy groups, halogen atoms, or these groups combined together Represents a ring structure.
• k11 and k12 are each independently an integer of 0-4. When each of R g2 and R g3 is plural, the plural R g2 and R g3 may be the same or different.
• R d1 and R d2 are each independently a substituted or unsubstituted C 1-12 linear or branched alkyl group, alkoxy group or alkoxycarbonyl group, substituted or an unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, a nitro group, or two or more of these groups combined with each other Represents the ring structure that is composed.
• k6 and k7 are each independently an integer from 0 to 5; When each of R d1 and R d2 is plural, the plural R d1 and R d2 may be the same or different.
• R e1 and R e2 are each independently a halogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted is an aromatic hydrocarbon group having 6 to 12 carbon atoms.
• k8 and k9 are each independently an integer of 0-4.
• onium cation examples include, but are not limited to, the structures of the following formulas (i-2-1) to (i-2-44).
• radiation-sensitive acid generators include structures in which the above anion moieties and the above onium cations are arbitrarily combined.
• Specific examples of the radiation-sensitive acid generator include, but are not limited to, structures represented by the following formulas ( ⁇ -1) to ( ⁇ -19).
• the lower limit of the content ratio of the radiation-sensitive acid generator in the total weight of the components other than the solvent in the radiation-sensitive resin composition is 0.1. % by mass is preferred, 1% by mass is more preferred, 2% by mass is even more preferred, and 4% by mass is particularly preferred.
• the upper limit of the content ratio is preferably 40% by mass, more preferably 25% by mass, still more preferably 20% by mass, and particularly preferably 15% by mass.
• the composition contains an acid diffusion control agent.
• the acid diffusion control agent controls the diffusion phenomenon in the resist film of the acid generated from the radiation-sensitive acid generator upon exposure, and has the effect of suppressing unfavorable chemical reactions in the non-exposed regions.
• the storage stability of the resulting radiation-sensitive resin composition is improved.
• the resolution of the resist pattern is further improved, and the line width change of the resist pattern due to the fluctuation of the holding time from exposure to development can be suppressed, and a radiation-sensitive resin composition excellent in process stability is obtained. be done.
• nitrogen-containing compound (I) a compound represented by the following formula (7)
• nitrogen-containing compounds (II) a compound having two nitrogen atoms in the same molecule
• nitrogen-containing compounds (III) compounds having three nitrogen atoms
• amide group-containing compounds urea compounds, nitrogen-containing heterocyclic compounds, and the like.
• R 22 , R 23 and R 24 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or It is a substituted or unsubstituted aralkyl group.
• nitrogen-containing compound (I) examples include monoalkylamines such as n-hexylamine; dialkylamines such as di-n-butylamine; trialkylamines such as triethylamine; and aromatic amines such as aniline. be done.
• nitrogen-containing compound (II) examples include ethylenediamine and N,N,N',N'-tetramethylethylenediamine.
• nitrogen-containing compound (III) examples include polyamine compounds such as polyethyleneimine and polyallylamine; polymers such as dimethylaminoethylacrylamide.
• amide group-containing compounds include formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone and the like. be done.
• Urea compounds include, for example, urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, and tributylthiourea.
• nitrogen-containing heterocyclic compounds examples include pyridines such as pyridine and 2-methylpyridine; morpholines such as N-propylmorpholine and N-(undecylcarbonyloxyethyl)morpholine; pyrazines and pyrazoles.
• a compound having an acid dissociable group can also be used as the nitrogen-containing organic compound.
• Nitrogen-containing organic compounds having such an acid-labile group include, for example, Nt-butoxycarbonylpiperidine, Nt-butoxycarbonylimidazole, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2 -Phenylbenzimidazole, N-(t-butoxycarbonyl)di-n-octylamine, N-(t-butoxycarbonyl)diethanolamine, N-(t-butoxycarbonyl)dicyclohexylamine, N-(t-butoxycarbonyl)diphenylamine , Nt-butoxycarbonyl-4-hydroxypiperidine, Nt-amyloxycarbonyl-4-hydroxypiperidine and the like.
• an onium salt compound that generates an acid with a higher pKa than the acid generated from the radiation-sensitive acid generator by irradiation with radiation (hereinafter also referred to as a "radiation-sensitive weak acid generator” for convenience). ) can also be suitably used.
• the acid generated by the radiation-sensitive weak acid generator is a weak acid that does not induce dissociation of the acid-dissociable groups in the resin under conditions that dissociate the acid-dissociable groups.
• "dissociation" of an acid-dissociable group means dissociation upon post-exposure baking at 110°C for 60 seconds.
• radiation-sensitive weak acid generators examples include sulfonium salt compounds represented by the following formula (8-1) and iodonium salt compounds represented by the following formula (8-2).
• J + is a sulfonium cation and U + is an iodonium cation.
• Sulfonium cations represented by J + include sulfonium cations represented by the above formulas (X-1) to (X-4), among which sulfonium cations containing a fluorine-substituted aromatic ring structure are preferred.
• the iodonium cation represented by U + includes iodonium cations represented by the above formulas (X-5) to (X-6), among which iodonium cations containing a fluorine-substituted aromatic ring structure are preferred.
• E - and Q - are each independently anions represented by R ⁇ -O - , R ⁇ -COO - and -N - -.
• R ⁇ is an alkyl group, an aryl group or an aralkyl group.
• a hydrogen atom of an alkyl group represented by R ⁇ or a hydrogen atom of an aromatic ring of an aryl group or an aralkyl group is a halogen atom, a hydroxy group, a nitro group, or a halogen atom-substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. Alternatively, it may be substituted with an alkoxy group having 1 to 12 carbon atoms.
• Examples of the acid diffusion control agent include compounds represented by the following formula.
• the acid diffusion controller may be used alone or in combination of two or more.
• the lower limit of the content of the acid diffusion control agent (total when multiple acid diffusion control agents are present) is 1 mass per 100 parts by mass of the base resin. part is preferred, 3 parts by mass is more preferred, and 5 parts by mass is even more preferred.
• the upper limit of the content of the acid diffusion control agent is preferably 20 parts by mass, more preferably 15 parts by mass, and even more preferably 10 parts by mass with respect to 100 parts by mass of the base resin, from the viewpoint of ensuring transparency to radiation. .
• the radiation-sensitive resin composition contains a solvent.
• the solvent is not particularly limited as long as it is capable of dissolving or dispersing at least the polymer together with the base resin and the radiation-sensitive acid generator that are preferably contained, other additives that are optionally contained, and the like.
• solvents examples include alcohol-based solvents, ether-based solvents, ketone-based solvents, amide-based solvents, ester-based solvents, and hydrocarbon-based solvents.
• alcohol solvents include Carbon such as iso-propanol, 4-methyl-2-pentanol, 3-methoxybutanol, n-hexanol, 2-ethylhexanol, furfuryl alcohol, cyclohexanol, 3,3,5-trimethylcyclohexanol, diacetone alcohol Monoalcoholic solvents of numbers 1 to 18; C2-C18 poly(ethylene glycol) such as ethylene glycol, 1,2-propylene glycol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol and tripropylene glycol. a alcohol-based solvent; A polyhydric alcohol partial ether solvent obtained by etherifying a part of the hydroxy groups of the above polyhydric alcohol solvent may be used.
• ether solvents examples include Dialkyl ether solvents such as diethyl ether, dipropyl ether, dibutyl ether; Cyclic ether solvents such as tetrahydrofuran and tetrahydropyran; Aromatic ring-containing ether solvents such as diphenyl ether and anisole (methylphenyl ether); Examples thereof include polyhydric alcohol ether solvents obtained by etherifying the hydroxy groups of the above polyhydric alcohol solvents.
• ketone solvents include linear ketone solvents such as acetone, butanone, and methyl-iso-butyl ketone: Cyclic ketone solvents such as cyclopentanone, cyclohexanone, and methylcyclohexanone: 2,4-pentanedione, acetonylacetone, acetophenone and the like.
• amide solvents include cyclic amide solvents such as N,N'-dimethylimidazolidinone and N-methylpyrrolidone; Chain amide solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and the like.
• ester solvents include monocarboxylic acid ester solvents such as n-butyl acetate and ethyl lactate; Polyhydric alcohol partial ether acetate solvents such as diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate; Lactone solvents such as ⁇ -butyrolactone and valerolactone; Carbonate solvents such as diethyl carbonate, ethylene carbonate, propylene carbonate; Polyvalent carboxylic acid diester solvents such as propylene glycol diacetate, methoxytriglycol acetate, diethyl oxalate, ethyl acetoacetate, ethyl lactate and diethyl phthalate can be used.
• monocarboxylic acid ester solvents such as n-butyl acetate and ethyl lactate
• hydrocarbon solvents examples include aliphatic hydrocarbon solvents such as n-hexane, cyclohexane, and methylcyclohexane; Aromatic hydrocarbon solvents such as benzene, toluene, di-iso-propylbenzene, n-amylnaphthalene and the like are included.
• ester-based solvents ether-based solvents, and ketone-based solvents are preferred, and polyhydric alcohol partial ether acetate-based solvents, polyhydric alcohol ether-based solvents, polyvalent carboxylic acid diester-based solvents, cyclic ketone-based solvents, and lactone-based solvents.
• Solvents are more preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, cyclohexanone, and ⁇ -butyrolactone are even more preferred.
• the radiation-sensitive resin composition may contain one or more solvents.
• the radiation-sensitive resin composition may contain other optional components in addition to the components described above.
• the other optional components include a cross-linking agent, an uneven distribution promoter, a surfactant, an alicyclic skeleton-containing compound, a sensitizer, and the like. These other optional components may be used alone or in combination of two or more.
• the radiation-sensitive resin composition can be prepared, for example, by mixing a second resin, a radiation-sensitive acid generator, an acid diffusion control agent and a solvent in a predetermined ratio together with a polymer, if necessary. After mixing, the radiation-sensitive resin composition is preferably filtered through a filter having a pore size of about 0.05 ⁇ m to 0.2 ⁇ m.
• the solid content concentration of the radiation-sensitive resin composition is usually 0.1% by mass to 50% by mass, preferably 0.5% by mass to 30% by mass, more preferably 1% by mass to 20% by mass.
• a pattern forming method comprises: A step (1) of directly or indirectly applying the radiation-sensitive resin composition to a substrate to form a resist film (hereinafter also referred to as a “resist film forming step”); Step (2) of exposing the resist film (hereinafter also referred to as “exposure step”); and a step (3) of developing the exposed resist film (hereinafter also referred to as “development step”).
• the resist pattern forming method it is possible to form a resist film having excellent sensitivity, LWR performance, water repellency, and development defect suppressing property. A high-quality resist pattern can be efficiently formed. Each step will be described below.
• a resist film is formed from the radiation-sensitive resin composition.
• the substrate on which the resist film is formed include conventionally known substrates such as silicon wafers, silicon dioxide, and aluminum-coated wafers. Further, for example, an organic or inorganic antireflection film disclosed in JP-B-6-12452, JP-A-59-93448, etc. may be formed on the substrate. Examples of coating methods include spin coating, casting coating, and roll coating. After coating, if necessary, prebaking (PB) may be performed in order to volatilize the solvent in the coating film.
• the PB temperature is usually 60°C to 150°C, preferably 80°C to 130°C.
• the PB time is usually 5 to 600 seconds, preferably 10 to 300 seconds.
• the thickness of the resist film to be formed is preferably 10 nm to 1,000 nm, more preferably 10 nm to 500 nm.
• the receding contact angle of the resist film after prebaking is preferably 70° or more, more preferably 72° or more, and even more preferably 74° or more.
• the method for measuring the receding contact angle is described in Examples.
• an immersion protective film that is insoluble in the immersion liquid may be provided on the resist film formed above in order to avoid direct contact between the immersion liquid and the resist film.
• a solvent peelable protective film that is peeled off with a solvent before the development process see, for example, JP-A-2006-227632
• a developer peelable protective film that is peeled off at the same time as development in the development process may be used.
• the exposure step which is the next step, is performed with radiation having a wavelength of 50 nm or less, the structural unit (III) and the structural unit (VI) as the base resin in the composition, and if necessary, the structural unit (V). It is preferable to use a resin having
• the resist film formed in the resist film forming step (step (1) above) is coated through a photomask (in some cases, through an immersion medium such as water). , emit radiation and expose. Radiation used for exposure depends on the line width of the desired pattern. A charged particle beam and the like can be mentioned. Among these, far ultraviolet rays, electron beams, and EUV are preferred, and ArF excimer laser light (wavelength 193 nm), KrF excimer laser light (wavelength 248 nm), electron beams, and EUV are more preferred. The following electron beams and EUV are more preferable.
• the immersion liquid used When exposure is performed by immersion exposure, examples of the immersion liquid used include water and fluorine-based inert liquids.
• the immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has a temperature coefficient of refractive index as small as possible so as to minimize distortion of the optical image projected onto the film.
• excimer laser light wavelength: 193 nm
• water it is preferable to use water from the viewpoints of availability and ease of handling in addition to the above viewpoints.
• an additive that reduces the surface tension of water and increases surface activity may be added in a small proportion. This additive preferably does not dissolve the resist film on the wafer and has negligible effect on the optical coating on the bottom surface of the lens. Distilled water is preferred as the water used.
• a post-exposure bake is performed to accelerate the dissociation of the acid-dissociable groups of the resin or the like by the acid generated from the radiation-sensitive acid generator upon exposure in the exposed portions of the resist film.
• This PEB causes a difference in solubility in a developer between the exposed area and the unexposed area.
• the PEB temperature is usually 50°C to 180°C, preferably 80°C to 130°C.
• the PEB time is usually 5 to 600 seconds, preferably 10 to 300 seconds.
• step (3) above the resist film exposed in the exposure step (step (2) above) is developed. Thereby, a predetermined resist pattern can be formed. After development, it is common to wash with a rinsing liquid such as water or alcohol and dry.
• a rinsing liquid such as water or alcohol
• TMAH tetramethylammonium hydroxide
• a TMAH aqueous solution is preferable, and a 2.38% by mass TMAH aqueous solution is more preferable.
• organic solvents such as hydrocarbon solvents, ether solvents, ester solvents, ketone solvents, alcohol solvents, or solvents containing organic solvents can be used.
• the organic solvent include one or more of the solvents listed above as the solvent for the radiation-sensitive resin composition.
• ether-based solvents, ester-based solvents, and ketone-based solvents are preferred.
• the ether solvent a glycol ether solvent is preferable, and ethylene glycol monomethyl ether and propylene glycol monomethyl ether are more preferable.
• ester solvent an acetate solvent is preferable, and n-butyl acetate and amyl acetate are more preferable.
• ketone-based solvent a chain ketone is preferred, and 2-heptanone is more preferred.
• the content of the organic solvent in the developer is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly preferably 99% by mass or more.
• Components other than the organic solvent in the developer include, for example, water and silicon oil.
• the developer may be either an alkaline developer or an organic solvent developer, but it is preferable that the developer contains an alkaline aqueous solution and the resulting pattern is a positive pattern.
• Examples of the developing method include a method of immersing the substrate in a tank filled with a developer for a certain period of time (dip method), and a method of developing by standing still for a certain period of time while the developer is heaped up on the surface of the substrate by surface tension (puddle method).
• dip method a method of immersing the substrate in a tank filled with a developer for a certain period of time
• puddle method a method of developing by standing still for a certain period of time while the developer is heaped up on the surface of the substrate by surface tension
• method a method of spraying the developer onto the substrate surface
• spray method a method of continuously discharging the developer while scanning the developer discharge nozzle at a constant speed onto the substrate rotating at a constant speed
• Mw and Mn Weight average molecular weight (Mw) and number average molecular weight (Mn)
• Mw and Mn of the polymer are determined by gel permeation chromatography (GPC) using Tosoh Corporation GPC columns (2 "G2000HXL”, 1 "G3000HXL”, and 1 "G4000HXL”). was measured under the conditions of Further, the degree of dispersion (Mw/Mn) was calculated from the measurement results of Mw and Mn.
• Elution solvent Tetrahydrofuran Flow rate: 1.0 mL/min Sample concentration: 1.0% by mass
• Sample injection volume 100 ⁇ L
• 13 C-NMR analysis 13 C-NMR analysis of the polymer and base resin was performed using a nuclear magnetic resonance spectrometer (“JNM-Delta400” manufactured by JEOL Ltd.).
• the polymerization solution was cooled with water to 30° C. or lower.
• the cooled polymerization solution was poured into methanol (2,000 parts by mass), and the precipitated white powder was separated by filtration.
• the filtered white powder was washed twice with methanol, filtered, and dried at 50° C. for 24 hours to obtain a white powdery base resin (A-1) (yield: 72%).
• the base resin (A-1) had an Mw of 6,000 and an Mw/Mn of 1.53.
• the content ratio of each structural unit derived from (M-1), (M-2) and (M-10) is 34.2 mol% and 19.9 mol%, respectively. and 45.9 mol%.
• the polymerization solution was cooled with water to 30° C. or lower.
• the cooled polymerization solution was poured into hexane (2,000 parts by mass), and the precipitated white powder was separated by filtration.
• the filtered white powder was washed twice with hexane, filtered, and dissolved in 1-methoxy-2-propanol (300 parts by mass).
• methanol 500 parts by mass
• triethylamine 50 parts by mass
• ultrapure water 10 parts by mass
• the base resin (A-12) had an Mw of 6,100 and an Mw/Mn of 1.49.
• the content ratios of structural units derived from (M-1) and (M-18) were 49.2 mol % and 50.8 mol %, respectively.
• B-1 to B-8 compounds represented by the following formulas (B-1) to (B-8)
• b-1 to b-6 represented by the following formulas (b-1) to (b-6) compound
• [[C] acid diffusion inhibitor] C-1 to C-7 compounds represented by the following formulas (C-1) to (C-7)
• Example 1 [A] 100 parts by mass of (A-1) as a base resin, [B] 10.0 parts by mass of (B-1) as a radiation-sensitive acid generator, [C] as an acid diffusion controller (C- 1) 7.0 parts by mass, [E] 5.0 parts by mass (E-1) as a polymer (solid content), and [D] as a solvent (D-1) / (D-2) / ( A radiation-sensitive resin composition (J-1) was prepared by mixing 3,230 parts by mass of the mixed solvent of D-3) and filtering through a membrane filter with a pore size of 0.2 ⁇ m.
• a resist film with an average thickness of 90 nm was formed.
• the film was exposed through a 55 nm line-and-space mask pattern under the following conditions.
• PEB post-exposure bake
• the resist film is alkali-developed using a 2.38% by mass aqueous TMAH solution as an alkali developer, washed with water after development, and dried to form a positive resist pattern (55 nm line and space pattern). formed.
• the exposure dose for forming a 55 nm line-and-space pattern is defined as the optimum exposure dose, and the optimum exposure dose is defined as sensitivity (mJ/cm 2 ). did.
• the sensitivity was evaluated as "good” when it was 35 mJ/cm 2 or less, and as “bad” when it exceeded 35 mJ/cm 2 .
• LWR performance A resist pattern was formed by adjusting the mask size so as to form a 55 nm line-and-space pattern by irradiating with the optimum exposure amount determined in the above sensitivity evaluation. The formed resist pattern was observed from above the pattern using the scanning electron microscope. Line width variation was measured at a total of 500 points, a 3 sigma value was obtained from the distribution of the measured values, and this 3 sigma value was defined as LWR (nm). LWR indicates that the smaller the value, the smaller the roughness of the line and the better. The LWR performance was evaluated as "good” when less than or equal to 3.0 nm, and as “poor” when greater than 3.0 nm.
• Water was discharged from the DSA-10 needle to form 25 ⁇ L water droplets on the resist film, and then the water droplets were sucked by the needle at a rate of 10 ⁇ L/min for 90 seconds, and the contact angle was measured every second (90 times in total). .
• the average value of the contact angles at a total of 20 points was calculated from the time when the contact angles became stable, and this was taken as the receding contact angle (°) after PB.
• the receding contact angle after PB was evaluated as "good” when it was 70° or more, and as "bad” when it was less than 70°.
• Rate of change in receding contact angle (%) ⁇ ( ⁇ 0 - ⁇ 1 )/ ⁇ 0 ⁇ ⁇ 100 ( ⁇ 0 is the receding contact angle before storage, and ⁇ 1 is the receding contact angle after one month of storage.)
• a line-and-space pattern with a line width of 55 nm was formed by exposing the resist film with the optimum exposure dose, and a wafer for defect inspection was obtained.
• the number of defects on this defect inspection wafer was measured using a defect inspection apparatus (KLA-Tencor "KLA2810"). Defects with a diameter of 50 ⁇ m or less were determined to be derived from the resist film, and the number of defects was calculated. The number of defects after development was evaluated as "good” when the number of defects determined to be derived from the resist film was 50 or less, and as "bad” when the number exceeded 50.
• the radiation-sensitive resin compositions of Examples had sensitivity, LWR performance, receding contact angle after PB, and storage stability when used for ArF exposure. , the number of development defects was good, but in the comparative example, each characteristic was inferior to that in the example. Therefore, when the radiation-sensitive resin composition of the example is used for ArF exposure, a resist pattern with high sensitivity and good LWR performance, water repellency, storage stability, and defect resistance can be formed.
• Example 64 [Preparation of positive radiation-sensitive resin composition for extreme ultraviolet (EUV) exposure] [Example 64] [A] 100 parts by mass of (A-12) as a resin, [B] 20.0 parts by mass of (B-3) as a radiation-sensitive acid generator, [C] (C-5 as an acid diffusion control agent ) 12.0 parts by mass, [E] 3.0 parts by mass (E-1) as a polymer (solid content), and [D] a mixed solvent of (D-1) / (D-4) as a solvent A radiation-sensitive resin composition (J-64) was prepared by mixing 6,110 parts by mass and filtering through a membrane filter with a pore size of 0.2 ⁇ m.
• EUV extreme ultraviolet
• a spin coater (“CLEAN TRACK ACT12" available from Tokyo Electron Co., Ltd.) was used to apply a composition for forming a lower antireflection film ("ARC66" available from Bulwer Science).
• a lower antireflection film having an average thickness of 105 nm was formed by heating at 205° C. for 60 seconds.
• the positive radiation-sensitive resin composition for EUV exposure prepared above was applied onto this lower antireflection film using the above spin coater, and PB was performed at 130° C. for 60 seconds. Then, by cooling at 23° C. for 30 seconds, a resist film with an average thickness of 55 nm was formed.
• the exposure dose for forming a 32 nm line-and-space pattern is defined as the optimum exposure dose, and this optimum exposure dose is defined as sensitivity (mJ/cm 2 ). did. The sensitivity was evaluated as "good” when it was 30 mJ/cm 2 or less, and as “bad” when it exceeded 30 mJ/cm 2 .
• LWR performance A resist pattern was formed by adjusting the mask size so as to form a 32 nm line-and-space pattern by irradiating with the optimum exposure amount determined by the evaluation of sensitivity. The formed resist pattern was observed from above the pattern using the scanning electron microscope. Line width variation was measured at a total of 500 points, a 3 sigma value was obtained from the distribution of the measured values, and this 3 sigma value was defined as LWR (nm). LWR indicates that the smaller the value, the smaller the roughness of the line and the better. The LWR performance was evaluated as "good” when less than or equal to 3.0 nm, and as “poor” when greater than 3.0 nm.
• Water was discharged from the DSA-10 needle to form 25 ⁇ L water droplets on the resist film, and then the water droplets were sucked by the needle at a rate of 10 ⁇ L/min for 90 seconds, and the contact angle was measured every second (90 times in total). .
• the average value of the contact angles at a total of 20 points was calculated from the time when the contact angles became stable, and this was taken as the receding contact angle (°) after PB.
• the receding contact angle after PB was evaluated as "good” when it was 70° or more, and as "bad” when it was less than 70°.
• Rate of change in receding contact angle (%) ⁇ ( ⁇ 0 - ⁇ 1 )/ ⁇ 0 ⁇ ⁇ 100 ( ⁇ 0 is the receding contact angle before storage, and ⁇ 1 is the receding contact angle after one month of storage.)
• a line-and-space pattern with a line width of 32 nm was formed by exposing the resist film with the optimum exposure dose, and a wafer for defect inspection was obtained.
• the number of defects on this defect inspection wafer was measured using a defect inspection apparatus (KLA-Tencor "KLA2810"). Defects with a diameter of 50 ⁇ m or less were determined to be derived from the resist film, and the number of defects was calculated. The number of defects after development was evaluated as "good” when the number of defects determined to be derived from the resist film was 50 or less, and as "bad” when the number exceeded 50.
• the radiation-sensitive resin compositions of Examples exhibited good sensitivity, LWR performance, receding contact angle after PB, storage stability, and the number of development defects when used for EUV exposure.
• each characteristic was inferior to those in Examples. Therefore, when the radiation-sensitive resin composition of the example is used for EUV exposure, a resist pattern with high sensitivity and good LWR performance, water repellency, storage stability, and defect resistance can be formed.
• Example 75 [A] 100 parts by mass of (A-10) as a base resin, [B] 10.0 parts by mass of (B-3) as a radiation-sensitive acid generator, [C] (C- 4) 8.0 parts by mass, [E] 5.0 parts by mass (E-32) as a polymer (solid content), and [D] as a solvent (D-1) / (D-2) / ( D-3) mixed solvent 3,230 parts by mass (mass ratio 2240 parts / 960 parts / 30 parts) was mixed and filtered through a membrane filter with a pore size of 0.2 ⁇ m to obtain a radiation-sensitive resin composition (J- 75) was prepared.
• a spin coater (“CLEAN TRACK ACT 12" from Tokyo Electron Co., Ltd.) was used to apply a composition for forming a lower anti-reflection film ("ARC66" from Bulwer Science).
• a lower antireflection film having an average thickness of 100 nm was formed by heating at 205° C. for 60 seconds.
• the negative type radiation-sensitive resin composition for ArF exposure (J-75) prepared above was applied onto this lower antireflection film using the above spin coater, and PB (pre-baking) was performed at 100° C. for 60 seconds. Then, by cooling at 23° C. for 30 seconds, a resist film with an average thickness of 90 nm was formed.
• PEB post-exposure bake
• the resist pattern using the negative radiation-sensitive resin composition for ArF exposure and the resist film before ArF exposure are evaluated in the same manner as the evaluation of the resist pattern using the positive radiation-sensitive resin composition for ArF exposure. did.
• the radiation-sensitive resin composition of Example 75 formed a negative resist pattern by ArF exposure, the receding contact angle after PB, the number of defects after development, and the storage stability were high with high sensitivity. It was good.
• Example 76 [A] 100 parts by mass of (A-14) as a base resin, [B] 20.0 parts by mass of (B-2) as a radiation-sensitive acid generator, [C] as an acid diffusion controller (C- 5) 12.0 parts by mass, [E] 5.0 parts by mass (E-32) as a polymer (solid content), and [D] a mixture of (D-1) / (D-4) as a solvent
• a radiation-sensitive resin composition (J-76) was prepared by mixing 6,110 parts by mass of a solvent (mass ratio of 4280 parts/1830 parts) and filtering through a membrane filter with a pore size of 0.2 ⁇ m.
• a spin coater (“CLEAN TRACK ACT 12" from Tokyo Electron Co., Ltd.) was used to apply a composition for forming a lower anti-reflection film ("ARC66" from Bulwer Science).
• a lower antireflection film having an average thickness of 105 nm was formed by heating at 205° C. for 60 seconds.
• the negative type radiation-sensitive resin composition for EUV exposure (J-76) prepared above was applied onto this lower antireflection film using the above spin coater, and PB was performed at 130° C. for 60 seconds. Then, by cooling at 23° C. for 30 seconds, a resist film with an average thickness of 55 nm was formed.
• the resist pattern using the negative radiation-sensitive resin composition for EUV exposure was evaluated in the same manner as the resist pattern using the negative radiation-sensitive resin composition for ArF exposure. As a result, even when the radiation-sensitive resin composition of Example 76 formed a negative resist pattern by EUV exposure, the receding contact angle after PB, the number of defects after development, and the storage stability were high with high sensitivity. It was good.
• the radiation-sensitive resin composition and the pattern forming method of the present invention it is possible to form a resist pattern having good sensitivity to exposure light, excellent LWR performance, water repellency, and storage stability, and few development defects. . Therefore, these materials can be suitably used in the processing of semiconductor devices, which are expected to further miniaturize in the future.

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