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
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
• • 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
  • C08F12/00—Homopolymers and 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
  • C08F12/02—Monomers containing only one unsaturated aliphatic radical
• • 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
  • C08F212/22—Oxygen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • 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
• • 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
• • 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
  • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
  • C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
  • C08F32/08—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having two condensed rings
• • 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
  • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
  • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
  • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
  • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/30—Imagewise removal using liquid means
  • G03F7/32—Liquid compositions therefor, e.g. developers
  • G03F7/325—Non-aqueous compositions

Definitions

• the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, an electronic device manufacturing method, a compound, and a resin.
• immersion liquid a liquid with a high refractive index
• Patent Document 1 describes a resin containing a repeating unit derived from p-hydroxystyrene and a repeating unit having an acid-decomposable group as a base component contained in a resist composition.
• the pattern formed on the workpiece has few defects.
• defect means unintended dents, chippings, disconnections in the pattern, patterns not having a desired size, and the like.
• the occurrence of defects could not be sufficiently suppressed.
• the present invention provides an actinic ray- or radiation-sensitive resin composition capable of forming a pattern in which the occurrence of defects is suppressed, and an actinic ray- or radiation-sensitive resin composition formed from the actinic ray- or radiation-sensitive resin composition.
• an actinic ray- or radiation-sensitive resin composition capable of forming a pattern in which the occurrence of defects is suppressed
• an actinic ray- or radiation-sensitive resin composition formed from the actinic ray- or radiation-sensitive resin composition.
• An object of the present invention is to provide a compound and a resin that can be obtained.
• An actinic ray-sensitive or radiation-sensitive resin composition containing a resin (A) containing a repeating unit (a1) having a partial structure in which a phenolic hydroxyl group is protected by a structure represented by the following general formula (1).
• X represents a halogen atom or an electron-withdrawing group.
• R 1 represents a hydroxy group or an organic group.
• k represents an integer of 0 to 3;
• n represents an integer from 0 to (4+2k).
• m represents an integer from 1 to (5+2k).
• * represents the bonding position with the oxygen atom of the phenolic hydroxyl group.
• Y1 represents a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group, or a halogenated alkyl group.
• X represents a halogen atom or an electron-withdrawing group.
• R 1 represents a hydroxy group or an organic group.
• R2 represents a hydroxy group, a halogen atom, or an organic group.
• k represents an integer of 0 to 3;
• n represents an integer from 0 to (4+2k).
• m represents an integer from 1 to (5+2k). However, the relationship 1 ⁇ (n+m) ⁇ (5+2k) is satisfied.
• n represents an integer of 2 or more, multiple R 1s may be the same or different.
• n When m represents an integer of 2 or more, multiple X's may be the same or different.
• l represents an integer of 0 to 2; o2 represents an integer from 0 to (4+2l).
• p2 represents an integer from 1 to (5+2l). However, the relationship 1 ⁇ (o2+p2) ⁇ (5+2l) is satisfied.
• o2 represents an integer of 2 or more, multiple R2 may be the same or different.
• p2 represents an integer of 2 or more, multiple X, R 1 , k, m and n may be the same or different.
• X represents a halogen atom or an electron-withdrawing group.
• R 1 represents a hydroxy group or an organic group.
• R3 represents a hydroxy group, a halogen atom, or an organic group.
• k represents an integer of 0 to 3;
• n represents an integer from 0 to (4+2k).
• m represents an integer from 1 to (5+2k). However, the relationship 1 ⁇ (n+m) ⁇ (5+2k) is satisfied.
• n represents an integer of 2 or more, multiple R 1s may be the same or different.
• m represents an integer of 2 or more, multiple X's may be the same or different.
• o3 represents an integer of 0 to 5;
• p3 represents an integer of 1-6.
• Y4 represents a hydrogen atom, a fluorine atom, or an alkyl group.
• R 41 , R 42 and R 43 each independently represent an organic group. Two of R 41 , R 42 and R 43 may combine with each other to form a ring.
• Y5 represents a hydrogen atom, a fluorine atom, or an alkyl group.
• R 51 , R 52 and R 53 each independently represent an organic group. Two of R 51 , R 52 and R 53 may combine with each other to form a ring.
• Y6 represents a hydrogen atom, a fluorine atom, or an alkyl group.
• R 61 , R 62 and R 63 each independently represent an organic group. Two of R 61 , R 62 and R 63 may combine with each other to form a ring.
• Y1 represents a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group, or a halogenated alkyl group.
• X represents a halogen atom or an electron-withdrawing group.
• R 1 represents a hydroxy group or an organic group.
• R2 represents a hydroxy group, a halogen atom, or an organic group.
• k represents an integer of 0 to 3;
• n represents an integer from 0 to (4+2k).
• m represents an integer from 1 to (5+2k). However, the relationship 1 ⁇ (n+m) ⁇ (5+2k) is satisfied.
• n represents an integer of 2 or more, multiple R 1s may be the same or different.
• n When m represents an integer of 2 or more, multiple X's may be the same or different.
• l represents an integer of 0 to 2; o2 represents an integer from 0 to (4+2l).
• p2 represents an integer from 1 to (5+2l). However, the relationship 1 ⁇ (o2+p2) ⁇ (5+2l) is satisfied.
• o2 represents an integer of 2 or more, multiple R2 may be the same or different.
• p2 represents an integer of 2 or more, multiple X, R 1 , k, m and n may be the same or different.
• X represents a halogen atom or an electron-withdrawing group.
• R 1 represents a hydroxy group or an organic group.
• R3 represents a hydroxy group, a halogen atom, or an organic group.
• k represents an integer of 0 to 3;
• n represents an integer from 0 to (4+2k).
• m represents an integer from 1 to (5+2k). However, the relationship 1 ⁇ (n+m) ⁇ (5+2k) is satisfied.
• n represents an integer of 2 or more, multiple R 1s may be the same or different.
• m represents an integer of 2 or more, multiple X's may be the same or different.
• o3 represents an integer of 0 to 5;
• p3 represents an integer of 1-6.
• Y1 represents a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group, or a halogenated alkyl group.
• X represents a halogen atom or an electron-withdrawing group.
• R 1 represents a hydroxy group or an organic group.
• R2 represents a hydroxy group, a halogen atom, or an organic group.
• k represents an integer of 0 to 3;
• n represents an integer from 0 to (4+2k).
• m represents an integer from 1 to (5+2k). However, the relationship 1 ⁇ (n+m) ⁇ (5+2k) is satisfied.
• n represents an integer of 2 or more, multiple R 1s may be the same or different.
• n When m represents an integer of 2 or more, multiple X's may be the same or different.
• l represents an integer of 0 to 2; o2 represents an integer from 0 to (4+2l).
• p2 represents an integer from 1 to (5+2l). However, the relationship 1 ⁇ (o2+p2) ⁇ (5+2l) is satisfied.
• o2 represents an integer of 2 or more, multiple R2 may be the same or different.
• p2 represents an integer of 2 or more, multiple X, R 1 , k, m and n may be the same or different.
• X represents a halogen atom or an electron-withdrawing group.
• R 1 represents a hydroxy group or an organic group.
• R3 represents a hydroxy group, a halogen atom, or an organic group.
• k represents an integer of 0 to 3;
• n represents an integer from 0 to (4+2k).
• m represents an integer from 1 to (5+2k). However, the relationship 1 ⁇ (n+m) ⁇ (5+2k) is satisfied.
• n represents an integer of 2 or more, multiple R 1s may be the same or different.
• m represents an integer of 2 or more, multiple X's may be the same or different.
• o3 represents an integer of 0 to 5;
• p3 represents an integer of 1-6.
• an actinic ray- or radiation-sensitive resin composition capable of forming a pattern in which the occurrence of defects is suppressed, and an actinic ray- or radiation-sensitive resin composition formed from the actinic ray- or radiation-sensitive resin composition Suitable for use in a light-sensitive or radiation-sensitive resin film, a pattern forming method and an electronic device manufacturing method using the actinic light-sensitive or radiation-sensitive resin composition, and the actinic light-sensitive or radiation-sensitive resin composition It is possible to provide compounds and resins that can be obtained.
• the present invention will be described in detail below. The description of the constituent elements described below may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.
• the notation that does not describe substituted or unsubstituted includes groups containing substituents as well as groups that do not have substituents. do.
• an "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
• the term "organic group” as used herein refers to a group containing at least one carbon atom. As a substituent, a monovalent substituent is preferable unless otherwise specified.
• the type of substituent, the position of the substituent, and the number of substituents when "may have a substituent” are not particularly limited.
• the number of substituents can be, for example, one, two, three, or more.
• substituents include monovalent nonmetallic atomic groups excluding hydrogen atoms, and can be selected from the following substituents T, for example.
• the substituent T includes halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group; an aryloxy group such as a phenoxy group and a p-tolyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group; acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and methoxalyl group, etc.
• halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom
• an alkoxy group such as
• Alkylsulfanyl groups such as a methylsulfanyl group and a tert-butylsulfanyl group; Arylsulfanyl groups such as a phenylsulfanyl group and a p-tolylsulfanyl group; Alkyl groups; Cycloalkyl groups; carboxy group; sulfo group; cyano group; alkylaminocarbonyl group; arylaminocarbonyl group; sulfonamide group; silyl group; A combination of
• actinic ray or “radiation” means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV: Extreme Ultraviolet), X-rays, and electron beams (EB : Electron Beam).
• light means actinic rays or radiation.
• exposure means, unless otherwise specified, not only exposure by the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, and X-rays, but also electron beams and ion beams. It also includes drawing with particle beams such as beams.
• the term "to” is used to include the numerical values before and after it as lower and upper limits.
• the binding direction of the divalent linking groups indicated is not limited unless otherwise specified.
• Y when Y is -COO-, Y may be -CO-O- or -O-CO- good too.
• the compound may be "X—CO—O—Z” or "X—O—CO—Z.”
• (meth)acrylate refers to acrylate and methacrylate
• (meth)acryl refers to acrylic and methacrylic.
• weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (hereinafter also referred to as "molecular weight distribution") (Mw/Mn) are measured by GPC (Gel Permeation Chromatography) equipment (Tosoh Corporation).
• the acid dissociation constant (pKa) represents the pKa in an aqueous solution. is a calculated value.
• Software Package 1 Advanced Chemistry Development (ACD/Labs) Software V8.14 for Solaris (1994-2007 ACD/Labs).
• pKa can also be determined by molecular orbital calculation.
• a specific method there is a method of calculating the H 2 + dissociation free energy in an aqueous solution based on the thermodynamic cycle.
• the H + dissociation free energy can be calculated by, for example, DFT (density functional theory), but various other methods have been reported in literature, etc., and the method is not limited to this. Note that there are a plurality of software that can implement DFT, and Gaussian16 is an example.
• pKa refers to a value obtained by calculating a value based on Hammett's substituent constant and a database of known literature values using Software Package 1, as described above. cannot be calculated, a value obtained by Gaussian 16 based on DFT (density functional theory) shall be adopted.
• pKa refers to "pKa in aqueous solution” as described above, but when pKa in aqueous solution cannot be calculated, “pKa in dimethyl sulfoxide (DMSO) solution” is adopted.
• Solid content means the components forming the actinic ray-sensitive or radiation-sensitive film, and does not include solvent. In addition, as long as it is a component that forms an actinic ray-sensitive or radiation-sensitive film, it is regarded as a solid content even if the property is liquid.
• the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is described below.
• the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is It is an actinic ray-sensitive or radiation-sensitive resin composition containing a resin (A) containing a repeating unit (a1) having a partial structure in which a phenolic hydroxyl group is protected by a structure represented by the following general formula (1).
• X represents a halogen atom or an electron-withdrawing group.
• R 1 represents a hydroxy group or an organic group.
• k represents an integer of 0 to 3;
• n represents an integer from 0 to (4+2k).
• m represents an integer from 1 to (5+2k).
• * represents the bonding position with the oxygen atom of the phenolic hydroxyl group.
• the specific structure of the repeating unit (a1) contained in the resin (A) used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention has a carbonyl group to which an electron-withdrawing group is bonded.
• the group has a high interaction with acid, can appropriately control the diffusion of acid generated in the actinic ray-sensitive or radiation-sensitive film, and can suppress the occurrence of defects resulting from excessive acid diffusion.
• the specific structure has high alkali decomposability. Therefore, for example, in the formation of a pattern using the resist composition of the present invention, when development is performed with an alkaline developer, the specific structure is decomposed and the solubility of the resin (A) in the developer is improved. do. It is presumed that this can also suppress the occurrence of defects caused by resin remaining undissolved in the developer.
• the actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also referred to as "the composition of the present invention") is typically a resist composition, and even if it is a positive resist composition, It may be a negative resist composition.
• the composition of the present invention may be a resist composition for alkali development or a resist composition for organic solvent development.
• the composition of the present invention may be a chemically amplified resist composition or a non-chemically amplified resist composition.
• the composition of the present invention is typically a chemically amplified resist composition.
• the resin (A) contained in the composition of the present invention contains a repeating unit (a1) having a partial structure in which the phenolic hydroxyl group is protected with a structure represented by the following general formula (1).
• X represents a halogen atom or an electron-withdrawing group.
• R 1 represents a hydroxy group or an organic group.
• k represents an integer of 0 to 3;
• n represents an integer from 0 to (4+2k).
• m represents an integer from 1 to (5+2k).
• * represents the bonding position with the oxygen atom of the phenolic hydroxyl group.
• X represents a halogen atom or an electron-withdrawing group.
• a halogen atom represented by X includes a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
• halogenated alkyl groups include alkyl groups having 1 to 12 carbon atoms substituted with halogen atoms, preferably trifluoromethyl group, pentafluoroethyl group and nonafluorobutyl group, more preferably trifluoromethyl group.
• R 1 represents a hydroxy group or an organic group.
• organic groups represented by R 1 include alkyl groups (linear or branched), alkoxy groups (linear or branched), alkenyl groups (linear or branched), cycloalkyl groups (single cyclic or polycyclic), aryl groups (monocyclic or polycyclic), and the like.
• alkyl group examples include alkyl groups having 1 to 15 carbon atoms such as methyl group, ethyl group, n-propyl group and t-butyl group, with methyl group being preferred.
• the alkoxy group includes alkoxy groups having 1 to 15 carbon atoms such as methoxy, ethoxy, n-propyloxy and t-butyloxy, with methoxy being more preferred.
• Alkenyl groups include alkenyl groups having 2 to 15 carbon atoms such as vinyl groups.
• the cycloalkyl group includes cycloalkyl groups having 3 to 20 carbon atoms such as cyclopentyl group and cyclohexyl group.
• aryl group an aryl group having 6 to 15 carbon atoms such as a phenyl group and a naphthyl group is preferable, and a phenyl group is more preferable.
• R 1 is preferably a hydroxyl group, an alkyl group, an alkoxy group, or an aryl group, more preferably a hydroxyl group, a methyl group, a methoxy group, a phenyl group, or a trifluoromethylphenyl group.
• k represents an integer of 0 to 3, preferably 0 or 1, more preferably 0.
• n represents an integer from 0 to (4+2k).
• m represents an integer from 1 to (5+2k).
• n is preferably an integer of 0 to 2, more preferably 0.
• m is preferably an integer of 1 to 3, more preferably 1 or 2.
• the repeating unit (a1) is preferably a repeating unit derived from a monomer represented by the following general formula (2) or (3).
• the present invention also relates to resins containing repeating units derived from compounds represented by the following general formula (2) or (3) and monomers represented by the following general formula (2) or (3): .
• Y1 represents a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group, or a halogenated alkyl group.
• X represents a halogen atom or an electron-withdrawing group.
• R 1 represents a hydroxy group or an organic group.
• R2 represents a hydroxy group, a halogen atom, or an organic group.
• k represents an integer of 0 to 3;
• n represents an integer from 0 to (4+2k).
• m represents an integer from 1 to (5+2k). However, the relationship 1 ⁇ (n+m) ⁇ (5+2k) is satisfied.
• n represents an integer of 2 or more, multiple R 1s may be the same or different.
• n When m represents an integer of 2 or more, multiple X's may be the same or different.
• l represents an integer of 0 to 2; o2 represents an integer from 0 to (4+2l).
• p2 represents an integer from 1 to (5+2l). However, the relationship 1 ⁇ (o2+p2) ⁇ (5+2l) is satisfied.
• o2 represents an integer of 2 or more, multiple R2 may be the same or different.
• p2 represents an integer of 2 or more, multiple X, R 1 , k, m and n may be the same or different.
• X, R 1 , k, n, and m have the same meanings as X, R 1 , k, n, and m in general formula (1), and preferred examples are also the same.
• Y1 represents a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group, or a halogenated alkyl group.
• a halogen atom represented by Y 1 includes a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
• the alkyl group represented by Y 1 includes linear or branched alkyl groups having 1 to 12 carbon atoms, preferably a methyl group or an ethyl group, more preferably a methyl group.
• Examples of the halogenated alkyl group represented by Y 1 include a group in which the above alkyl group such as a trifluoromethyl group is substituted with a halogen atom.
• Y 1 is preferably a hydrogen atom, a fluorine-substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, or a fluorine atom, more preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a fluorine atom.
• a hydrogen atom or a methyl group is more preferred, and a hydrogen atom is particularly preferred.
• R2 represents a hydroxy group, a halogen atom, or an organic group.
• Halogen atoms represented by R 2 include fluorine, chlorine, bromine and iodine atoms.
• Examples of the organic group represented by R 2 include the organic groups represented by R 1 described above.
• l represents an integer of 0 to 2, preferably 0 or 1.
• o2 represents an integer from 0 to (4+2l).
• p2 represents an integer from 1 to (5+2l).
• o2 is preferably 0 or 1, more preferably 0.
• p2 is 1 or 2.
• the monomer represented by the above general formula (2) is preferably a monomer represented by the following general formula (2-1) or (2-2).
• Y 1 , X, R 1 , R 2 , l, o2, and p2 are Y 1 , X, R 1 , R 2 , l, o2, and p2, and preferred examples are also the same.
• n2 represents an integer of 0-4.
• m2 represents an integer of 1 to 5; However, the relationship 1 ⁇ (n2+m2) ⁇ 5 is satisfied.
• n2 is preferably an integer of 0 to 2, more preferably 0.
• m2 is preferably an integer of 1 to 3, more preferably 1 or 2.
• Y 1 , X, R 1 , R 2 , n2, m2, l, o2 and p2 are Y 1 , X, R 1 and R in general formula (2-1) 2 , n2, m2, l, o2, and p2, and preferred examples are also the same.
• the monomer represented by the above general formula (2-1) or (2-2) is more preferably a monomer represented by the following general formula (2-1A) or (2-2A) .
• Y 1 , X, m2, l, and p2 are synonymous with Y 1 , X, m2, l, and p2 in general formula (2-1), and preferred examples are also It is the same.
• Y 1 , X, m2, l, and p2 are synonymous with Y 1 , X, m2, l, and p2 in general formula (2-2), and preferred examples are also It is the same.
• X represents a halogen atom or an electron-withdrawing group.
• R 1 represents a hydroxy group or an organic group.
• R3 represents a hydroxy group, a halogen atom, or an organic group.
• k represents an integer of 0 to 3;
• n represents an integer from 0 to (4+2k).
• m represents an integer from 1 to (5+2k). However, the relationship 1 ⁇ (n+m) ⁇ (5+2k) is satisfied.
• n represents an integer of 2 or more, multiple R 1s may be the same or different.
• m represents an integer of 2 or more, multiple X's may be the same or different.
• o3 represents an integer of 0 to 5;
• p3 represents an integer of 1-6.
• X, R 1 , k, n, and m have the same meanings as X, R 1 , k, n, and m in general formula (1), and preferred examples are also the same.
• R3 represents a hydroxy group, a halogen atom, or an organic group.
• a halogen atom represented by R3 includes a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
• Examples of the organic group represented by R 3 include the organic groups represented by R 1 described above.
• o3 represents an integer of 0-5.
• p3 represents an integer of 1-6.
• the relationship 1 ⁇ (o3+p3) ⁇ 6 is satisfied.
• o3 is preferably 0 or 1, more preferably 0.
• p3 is preferably 1 or 2, more preferably 1.
• the monomer represented by the above general formula (3) is preferably a monomer represented by the following general formula (3-1).
• X, R 1 , R 3 , o3, and p3 are synonymous with X, R 1 , R 3 , o3, and p3 in general formula (3), and preferred examples are also It is the same.
• n3 represents an integer of 0-4.
• m3 represents an integer of 1 to 5; However, the relationship 1 ⁇ (n3+m3) ⁇ 5 is satisfied.
• n3 is preferably an integer of 0 to 2, more preferably 0.
• m3 is preferably an integer of 1 to 3, more preferably 1 or 2.
• the monomer represented by general formula (3-1) above is more preferably a monomer represented by general formula (3-1A) below.
• X, m3, and p3 have the same meanings as X, m3, and p3 in general formula (3-1), and preferred examples are also the same.
• Specific examples of the monomer corresponding to the repeating unit (a1) are shown below, but are not limited thereto. In the specific examples below, Me represents a methyl group. Specific examples of the monomer represented by the general formula (2) or (3) include those corresponding to the monomers represented by the general formula (2) or (3) in the following specific examples. can be done.
• the content of the repeating unit (a1) is preferably 2 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, relative to all repeating units in the resin (A). Moreover, the upper limit thereof is preferably 80 mol % or less, more preferably 70 mol % or less, and even more preferably 60 mol % or less, based on all repeating units in the resin (A).
• the resin (A) contained in the composition of the present invention contains a group that is decomposed by the action of an acid to increase its polarity (hereinafter also referred to as "acid-decomposable group"), and a repeating unit (a2 ) is preferably included.
• acid-decomposable group a group that is decomposed by the action of an acid to increase its polarity
• a repeating unit (a2 ) is preferably included.
• the resin (A) has an acid-decomposable group
• the pattern forming method of the present specification typically when an alkaline developer is employed as the developer, a positive pattern is preferably formed, and development is performed. When an organic developer is used as the liquid, a negative pattern is preferably formed.
• the repeating unit having an acid-decomposable group a repeating unit having an acid-decomposable group containing an unsaturated bond is preferable in addition to the repeating unit having an acid-decomposable group described below.
• An acid-decomposable group is a group that is decomposed by the action of an acid to form a polar group.
• the acid-decomposable group preferably has a structure in which the polar group is protected with a group that is released by the action of an acid (leaving group). That is, the resin (A) has a repeating unit having a group that is decomposed by the action of an acid to form a polar group.
• a resin having this repeating unit has an increased polarity under the action of an acid, thereby increasing the solubility in an alkaline developer and decreasing the solubility in an organic solvent.
• the polar group is preferably an alkali-soluble group such as a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphoric acid group, a sulfonamide group, a sulfonylimide group, (alkylsulfonyl)(alkylcarbonyl)methylene group, (alkylsulfonyl)(alkylcarbonyl)imide group, bis(alkylcarbonyl)methylene group, bis(alkylcarbonyl)imide group, bis(alkylsulfonyl)methylene group, bis(alkylsulfonyl)imide group, tris(alkylcarbonyl) Methylene groups, acidic groups such as tris(alkylsulfonyl)methylene groups, and alcoholic hydroxyl groups are included.
• alkali-soluble group such as a carboxyl group, a phenolic
• the polar group is preferably a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group.
• Examples of groups that leave by the action of an acid include groups represented by formulas (Y1) to (Y4).
• Formula (Y1) -C(Rx 1 )(Rx 2 )(Rx 3 )
• Formula (Y3) —C(R 36 )(R 37 )(OR 38 )
• Rx 1 to Rx 3 each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched chain) or an aryl group (monocyclic or polycyclic).
• Rx 1 to Rx 3 are alkyl groups (linear or branched)
• at least two of Rx 1 to Rx 3 are preferably methyl groups.
• Rx 1 to Rx 3 preferably each independently represent a linear or branched alkyl group, and Rx 1 to Rx 3 each independently represent a linear alkyl group. is more preferred.
• Rx 1 to Rx 3 may combine to form a monocyclic or polycyclic ring.
• the alkyl groups of Rx 1 to Rx 3 are alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group. preferable.
• the cycloalkyl groups represented by Rx 1 to Rx 3 include monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. is preferred.
• the aryl group represented by Rx 1 to Rx 3 is preferably an aryl group having 6 to 10 carbon atoms, such as phenyl group, naphthyl group and anthryl group.
• a vinyl group is preferable as the alkenyl group for Rx 1 to Rx 3 .
• the ring formed by combining two of Rx 1 to Rx 3 is preferably a cycloalkyl group.
• the cycloalkyl group formed by combining two of Rx 1 to Rx 3 includes a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, and a tetracyclododeca.
• a polycyclic cycloalkyl group such as a nyl group or an adamantyl group is preferable, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
• one of the methylene groups constituting the ring is a group containing a heteroatom such as an oxygen atom, a heteroatom such as a carbonyl group, or a vinylidene group. may be replaced with In these cycloalkyl groups, one or more ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.
• Rx 1 is a methyl group or an ethyl group
• Rx 2 and Rx 3 combine to form the above-described cycloalkyl group. is preferred.
• composition of the present invention is a resist composition for EUV exposure
• the ring formed by combining two atoms further has a fluorine atom or an iodine atom as a substituent.
• R 36 to R 38 each independently represent a hydrogen atom or a monovalent organic group.
• R 37 and R 38 may combine with each other to form a ring.
• Monovalent organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups. It is also preferred that R 36 is a hydrogen atom.
• the alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a heteroatom such as an oxygen atom and/or a group containing a heteroatom such as a carbonyl group.
• one or more of the methylene groups may be replaced with a heteroatom such as an oxygen atom and/or a group containing a heteroatom such as a carbonyl group.
• R 38 may combine with another substituent of the main chain of the repeating unit to form a ring.
• the group formed by bonding R 38 and another substituent of the main chain of the repeating unit to each other is preferably an alkylene group such as a methylene group.
• the resist composition is, for example, a resist composition for EUV exposure
• the monovalent organic groups represented by R 36 to R 38 and the ring formed by combining R 37 and R 38 with each other are Furthermore, it is also preferable to have a fluorine atom or an iodine atom as a substituent.
• L 1 and L 2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining these (e.g., a group combining an alkyl group and an aryl group).
• M represents a single bond or a divalent linking group.
• Q is an alkyl group optionally containing a heteroatom, a cycloalkyl group optionally containing a heteroatom, an aryl group optionally containing a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group combining these (for example, a group combining an alkyl group and a cycloalkyl group).
• one of the methylene groups may be replaced by a heteroatom such as an oxygen atom or a heteroatom-containing group such as a carbonyl group.
• L 1 and L 2 is preferably a hydrogen atom, and the other is preferably an alkyl group, a cycloalkyl group, an aryl group, or a combination of an alkylene group and an aryl group. At least two of Q, M, and L1 may combine to form a ring (preferably a 5- or 6-membered ring).
• L2 is preferably a secondary or tertiary alkyl group, more preferably a tertiary alkyl group.
• Secondary alkyl groups include isopropyl, cyclohexyl, and norbornyl groups, and tertiary alkyl groups include tert-butyl and adamantane groups.
• the Tg (glass transition temperature) and the activation energy are increased, so that the film strength can be ensured and fogging can be suppressed.
• the alkyl group, cycloalkyl group, aryl group, and group combining these represented by L 1 and L 2 are further It is also preferable to have a fluorine atom or an iodine atom as a substituent.
• the alkyl group, cycloalkyl group, aryl group, and aralkyl group preferably contain a heteroatom such as an oxygen atom in addition to the fluorine atom and the iodine atom.
• one of the methylene groups is replaced with a heteroatom such as an oxygen atom, or a group containing a heteroatom such as a carbonyl group.
• composition of the present invention when the composition of the present invention is a resist composition for EUV exposure, an alkyl group optionally containing a heteroatom represented by Q, a cycloalkyl group optionally containing a heteroatom, or a heteroatom is In the aryl group, amino group, ammonium group, mercapto group, cyano group, aldehyde group, and groups in which these groups may be combined, the heteroatom is selected from the group consisting of a fluorine atom, an iodine atom and an oxygen atom. It is also preferred that the heteroatom is
• Ar represents an aromatic ring group.
• Rn represents an alkyl group, a cycloalkyl group, or an aryl group.
• Rn and Ar may combine with each other to form a non-aromatic ring.
• Ar is preferably an aryl group.
• the aromatic ring group represented by Ar and the alkyl group, cycloalkyl group and aryl group represented by Rn are substituents It is also preferable to have a fluorine atom or an iodine atom as.
• the ring member atoms adjacent to the ring member atoms directly bonded to the polar group (or residue thereof) do not have halogen atoms such as fluorine atoms as substituents.
• Groups that can be eliminated by the action of an acid also include a 2-cyclopentenyl group having a substituent (such as an alkyl group) such as a 3-methyl-2-cyclopentenyl group, and a 1,1,4,4 A cyclohexyl group having a substituent (such as an alkyl group) such as a -tetramethylcyclohexyl group may also be used.
• the repeating unit (a2) having an acid-decomposable group is preferably a repeating unit derived from a monomer represented by any one of the following general formulas (4) to (6).
• Y4 represents a hydrogen atom, a fluorine atom, or an alkyl group.
• R 41 , R 42 and R 43 each independently represent an organic group. Two of R 41 , R 42 and R 43 may combine with each other to form a ring.
• Y4 represents a hydrogen atom, a fluorine atom, or an alkyl group.
• the alkyl group represented by Y4 may be linear or branched. Although the number of carbon atoms in the alkyl group is not particularly limited, it is preferably 1-10, more preferably 1-3.
• the alkyl group represented by Y 4 may have a substituent, and examples of the substituent include a halogen atom (such as a fluorine atom), a hydroxyl group, and a monovalent organic group.
• Y4 is preferably a hydrogen atom or a methyl group.
• R 41 , R 42 and R 43 each independently represent an organic group.
• Organic groups represented by R 41 , R 42 and R 43 include alkyl groups (linear or branched), cycloalkyl groups (monocyclic or polycyclic) and alkenyl groups (linear or branched). , an aryl group (monocyclic or polycyclic), a heteroaryl group (monocyclic or polycyclic), and the like.
• the alkyl group represented by R 41 , R 42 and R 43 includes 1 to 1 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group. 5 alkyl groups are preferred.
• the cycloalkyl groups represented by R 41 , R 42 and R 43 include monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, norbornyl, tetracyclodecanyl, tetracyclododecanyl, And polycyclic cycloalkyl groups such as adamantyl groups are preferred.
• the aryl group represented by R 41 , R 42 and R 43 is preferably an aryl group having 6 to 10 carbon atoms, such as a phenyl group and a naphthyl group.
• the heteroaryl group represented by R 41 , R 42 and R 43 is preferably a heteroaryl group having 5 to 10 carbon atoms. mentioned.
• a vinyl group is preferable as the alkenyl group represented by R 41 , R 42 and R 43 .
• a cycloalkyl group is preferable as the ring formed by combining two of R 41 , R 42 and R 43 .
• the cycloalkyl group formed by combining two of R 11 , R 12 and R 13 includes a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, norbornyl group, tetracyclodeca
• a polycyclic cycloalkyl group such as a nyl group, a tetracyclododecanyl group or an adamantyl group is preferable, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
• one of the methylene groups constituting the ring contains a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group. may be substituted with a group or a vinylidene group.
• one or more ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.
• the above organic groups represented by R 41 , R 42 and R 43 may further have substituents, and examples of substituents include halogen atoms, hydroxyl groups, and monovalent organic groups.
• substituents include halogen atoms, hydroxyl groups, and monovalent organic groups.
• monovalent organic groups include alkyl groups (having 1 to 4 carbon atoms), alkoxy groups (having 1 to 4 carbon atoms), alkylcarbonyl groups (having 2 to 5 carbon atoms), and alkyl halides such as trifluoromethyl groups. groups (having 1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (having 2 to 6 carbon atoms).
• the number of carbon atoms in the substituent is preferably 8 or less.
• Y5 represents a hydrogen atom, a fluorine atom, or an alkyl group.
• R 51 , R 52 and R 53 each independently represent an organic group. Two of R 51 , R 52 and R 53 may combine with each other to form a ring.
• Y5 represents a hydrogen atom, a fluorine atom, or an alkyl group.
• alkyl group represented by Y 5 include the alkyl group represented by Y 4 , and preferred examples are the same.
• Y5 is preferably a hydrogen atom or a methyl group.
• R 51 , R 52 and R 53 in general formula (5) have the same meanings as R 41 , R 42 and R 43 in general formula (4), and preferred examples are also the same.
• Y6 represents a hydrogen atom, a fluorine atom, or an alkyl group.
• R 61 , R 62 and R 63 each independently represent an organic group. Two of R 61 , R 62 and R 63 may combine with each other to form a ring.
• Y6 represents a hydrogen atom, a fluorine atom, or an alkyl group.
• the alkyl group represented by Y6 includes the alkyl group represented by Y4 , and preferable examples are the same.
• Y6 is preferably a hydrogen atom or a methyl group.
• R 61 , R 62 and R 63 in general formula (6) have the same meanings as R 41 , R 42 and R 43 in general formula (4), and preferred examples are also the same.
• repeating unit having an acid-decomposable group a repeating unit represented by formula (A) is also preferable.
• L 1 represents a divalent linking group optionally having a fluorine atom or an iodine atom
• R 1 is a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group optionally having a fluorine atom or an iodine atom , or represents an aryl group optionally having a fluorine atom or an iodine atom
• R 2 represents a leaving group optionally having a fluorine atom or an iodine atom which is eliminated by the action of an acid.
• at least one of L 1 , R 1 and R 2 has a fluorine atom or an iodine atom.
• the divalent linking group optionally having a fluorine atom or an iodine atom represented by L 1 includes -CO-, -O-, -S-, -SO-, -SO 2 -, fluorine atom or a hydrocarbon group optionally having an iodine atom (eg, an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, etc.), and a linking group in which a plurality of these are linked.
• L 1 is preferably -CO-, an arylene group, or an -arylene group - an alkylene group having a fluorine atom or an iodine atom -, and -CO- or an -arylene group - a fluorine atom or an iodine atom.
• An alkylene group with - is more preferable.
• a phenylene group is preferred as the arylene group.
• Alkylene groups may be linear or branched. Although the number of carbon atoms in the alkylene group is not particularly limited, it is preferably 1-10, more preferably 1-3.
• the total number of fluorine atoms and iodine atoms contained in the alkylene group having fluorine atoms or iodine atoms is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.
• the alkyl group represented by R 1 may be linear or branched. Although the number of carbon atoms in the alkyl group is not particularly limited, it is preferably 1-10, more preferably 1-3. The total number of fluorine atoms and iodine atoms contained in the alkyl group having a fluorine atom or an iodine atom represented by R 1 is not particularly limited, but is preferably 1 or more, more preferably 1 to 5, and 1 to 3. More preferred.
• the alkyl group represented by R 1 may contain a heteroatom such as an oxygen atom other than the halogen atom.
• the leaving group optionally having a fluorine atom or an iodine atom represented by R 2 is represented by the above formulas (Y1) to (Y4) and having a fluorine atom or an iodine atom. groups.
• repeating unit having an acid-decomposable group a repeating unit represented by formula (AI) is also preferred.
• Xa 1 represents a hydrogen atom or an optionally substituted alkyl group.
• T represents a single bond or a divalent linking group.
• Rx 1 to Rx 3 each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl ( monocyclic or polycyclic) group. However, when all of Rx 1 to Rx 3 are alkyl groups (linear or branched), at least two of Rx 1 to Rx 3 are preferably methyl groups. Two of Rx 1 to Rx 3 may combine to form a monocyclic or polycyclic ring (such as a monocyclic or polycyclic cycloalkyl group).
• Examples of the optionally substituted alkyl group represented by Xa 1 include a methyl group and a group represented by -CH 2 -R 11 .
• R 11 represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group.
• Examples of the monovalent organic group represented by R 11 include an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, an acyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group.
• Xa 1 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
• the divalent linking group for T includes an alkylene group, an aromatic ring group, a --COO--Rt-- group, and a --O--Rt-- group.
• Rt represents an alkylene group or a cycloalkylene group.
• T is preferably a single bond or a -COO-Rt- group.
• Rt is preferably an alkylene group having 1 to 5 carbon atoms, a -CH 2 - group, a -(CH 2 ) 2 - group, or a -(CH 2 ) 3 - groups are more preferred.
• the alkyl groups of Rx 1 to Rx 3 include alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group. preferable.
• Cycloalkyl groups of Rx 1 to Rx 3 include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. is preferred.
• the aryl group represented by Rx 1 to Rx 3 is preferably an aryl group having 6 to 10 carbon atoms, such as phenyl group, naphthyl group and anthryl group.
• a vinyl group is preferable as the alkenyl group for Rx 1 to Rx 3 .
• the cycloalkyl group formed by combining two of Rx 1 to Rx 3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group.
• Polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group are also preferred. Among them, monocyclic cycloalkyl groups having 5 to 6 carbon atoms are preferred.
• a cycloalkyl group formed by combining two of Rx 1 to Rx 3 is, for example, a group in which one of the methylene groups constituting the ring contains a heteroatom such as an oxygen atom, a heteroatom such as a carbonyl group, or It may be substituted with a vinylidene group.
• Rx 1 is a methyl group or an ethyl group
• Rx 2 and Rx 3 are preferably combined to form the above-mentioned cycloalkyl group.
• substituents include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group. (2 to 6 carbon atoms).
• the number of carbon atoms in the substituent is preferably 8 or less.
• the repeating unit represented by the formula (AI) includes an acid-decomposable (meth)acrylic acid tertiary alkyl ester-based repeating unit (Xa 1 represents a hydrogen atom or a methyl group, and T represents a single bond. ) is preferred.
• repeating units having an acid-decomposable group are shown below, but are not limited thereto.
• Xa 1 represents H, CH 3 , CF 3 or CH 2 OH
• Rxa and Rxb each independently represent a linear or branched alkyl group having 1 to 5 carbon atoms.
• Resin (A) may have a repeating unit having an acid-decomposable group containing an unsaturated bond as the repeating unit having an acid-decomposable group.
• a repeating unit represented by formula (B) is preferable.
• Xb represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group.
• L represents a single bond or a divalent linking group which may have a substituent.
• Ry 1 to Ry 3 each independently represent a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an alkynyl group, or a monocyclic or polycyclic aryl group . However, at least one of Ry 1 to Ry 3 represents an alkenyl group, an alkynyl group, a monocyclic or polycyclic cycloalkenyl group, or a monocyclic or polycyclic aryl group. Two of Ry 1 to Ry 3 may combine to form a monocyclic or polycyclic ring (a monocyclic or polycyclic cycloalkyl group, cycloalkenyl group, etc.).
• the optionally substituted alkyl group represented by Xb includes, for example, a methyl group and a group represented by —CH 2 —R 11 .
• R 11 represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group, for example, an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group.
• Xb is preferably a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
• the divalent linking group of L includes -Rt- group, -CO- group, -COO-Rt- group, -COO-Rt-CO- group, -Rt-CO- group, and -O-Rt- groups.
• Rt represents an alkylene group, a cycloalkylene group, or an aromatic ring group, preferably an aromatic ring group.
• L is preferably -Rt-, -CO-, -COO-Rt-CO- or -Rt-CO-.
• Rt may have substituents such as halogen atoms, hydroxyl groups, and alkoxy groups.
• the alkyl groups represented by Ry 1 to Ry 3 are alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group. preferable.
• Cycloalkyl groups represented by Ry 1 to Ry 3 include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group and adamantyl group. Polycyclic cycloalkyl groups are preferred.
• the aryl group represented by Ry 1 to Ry 3 is preferably an aryl group having 6 to 10 carbon atoms, such as phenyl group, naphthyl group and anthryl group.
• a vinyl group is preferable as the alkenyl group for Ry 1 to Ry 3 .
• An ethynyl group is preferred as the alkynyl group for Ry 1 to Ry 3 .
• Cycloalkenyl groups represented by Ry 1 to Ry 3 are preferably monocyclic cycloalkyl groups such as cyclopentyl groups and cyclohexyl groups, which partially contain a double bond.
• the cycloalkyl group formed by combining two of Ry 1 to Ry 3 includes a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, and a tetracyclododeca.
• Polycyclic cycloalkyl groups such as a nyl group and an adamantyl group are preferred. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
• a cycloalkyl group formed by combining two of Ry 1 to Ry 3 or a cycloalkenyl group for example, one of the methylene groups constituting the ring is a hetero atom such as an oxygen atom, a carbonyl group, or —SO 2 It may be substituted with a group containing a heteroatom such as a - group and a -SO 3 - group, a vinylidene group, or a combination thereof.
• one or more ethylene groups constituting the cycloalkane ring or cycloalkene ring may be replaced with a vinylene group.
• Ry 1 is a methyl group, an ethyl group, a vinyl group, an allyl group, or an aryl group
• Ry 2 and Ry 3 combine to form the above-mentioned cycloalkyl
• a preferred embodiment forms a group or a cycloalkenyl group.
• substituents include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group. (2 to 6 carbon atoms).
• the number of carbon atoms in the substituent is preferably 8 or less.
• the repeating unit represented by the formula (B) is preferably an acid-decomposable (meth)acrylic acid tertiary ester-based repeating unit (Xb represents a hydrogen atom or a methyl group, and L represents a —CO— group.
• repeating unit represented acid-decomposable hydroxystyrene tertiary alkyl ether-based repeating unit (repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a phenyl group), acid-decomposable styrene carboxylic acid tertiary ester It is a repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a -Rt-CO- group (Rt is an aromatic group)).
• the content of the repeating unit having an acid-decomposable group containing an unsaturated bond is preferably 15 mol% or more, more preferably 20 mol% or more, and 30 mol% or more, based on the total repeating units in the resin (A). is more preferred.
• the upper limit thereof is preferably 80 mol % or less, more preferably 70 mol % or less, and even more preferably 60 mol % or less, based on all repeating units in the resin (A).
• repeating units having an acid-decomposable group containing an unsaturated bond are shown below, but are not limited thereto.
• Xb and L 1 represent any of the substituents and linking groups described above
• Ar represents an aromatic group
• R represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group.
• a monocyclic or polycyclic aryl group is represented, and Q is a heteroatom such as an oxygen atom, a carbonyl group, a heteroatom-containing group such as a —SO 2 — group and a —SO 3 — group, a vinylidene group, or any of these represents a combination, and n, m and l represent integers of 0 or more.
• the content of the repeating unit (a2) having an acid-decomposable group is preferably 15 mol% or more, more preferably 20 mol% or more, and further preferably 30 mol% or more, based on the total repeating units in the resin (A).
• the upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol% or less, and particularly 60 mol% or less, relative to all repeating units in the resin (A). preferable.
• the resin (A) may contain at least one repeating unit selected from the group consisting of Group A below and/or at least one repeating unit selected from the group consisting of Group B below. good.
• Group A A group consisting of the following repeating units (20) to (25).
• a repeating unit having an acid group which will be described later
• (23) a repeating unit having a photoacid-generating group which will be described later
• the repeating units represented by formulas (A) to (E), which will be described later, are (25) reducing the mobility of the main chain corresponds to a repeating unit for Group B: A group consisting of the following repeating units (30) to (32).
• the resin (A) preferably has an acid group, and preferably contains a repeating unit having an acid group, as described later.
• the definition of the acid group will be explained later along with preferred embodiments of repeating units having an acid group.
• the resin (A) may have at least one type of repeating unit selected from the group consisting of the A group.
• the resin (A) has at least one repeating unit selected from the group consisting of Group A above. is preferred.
• Resin (A) may contain at least one of a fluorine atom and an iodine atom.
• the resin (A) preferably contains at least one of a fluorine atom and an iodine atom.
• the resin (A) may have one repeating unit containing both a fluorine atom and an iodine atom, and the resin (A) It may contain two types of a repeating unit containing a fluorine atom and a repeating unit containing an iodine atom.
• Resin (A) may have a repeating unit having an aromatic group.
• the resist composition is used as an actinic ray-sensitive or radiation-sensitive resin composition for EUV exposure, it is also preferred that the resin (A) has a repeating unit having an aromatic group.
• the resin (A) may have at least one type of repeating unit selected from the group consisting of Group B above.
• the resin (A) may have at least one repeating unit selected from the group consisting of Group B above. preferable.
• the resin (A) preferably contains neither fluorine atoms nor silicon atoms.
• Resin (A) may have a repeating unit having an acid group.
• an acid group having a pKa of 13 or less is preferable.
• the acid dissociation constant of the acid group is preferably 13 or less, more preferably 3-13, even more preferably 5-10.
• the content of the acid group in the resin (A) is not particularly limited, but is often 0.2 to 6.0 mmol/g. Among them, 0.8 to 6.0 mmol/g is preferable, 1.2 to 5.0 mmol/g is more preferable, and 1.6 to 4.0 mmol/g is even more preferable.
• the acid group is preferably, for example, a carboxyl group, a phenolic hydroxyl group, a fluoroalcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group.
• a fluoroalcohol group preferably a hexafluoroisopropanol group
• a sulfonic acid group preferably a sulfonamide group
• an isopropanol group preferably, for example, a carboxyl group, a phenolic hydroxyl group, a fluoroalcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group.
• one or more (preferably 1 to 2) fluorine atoms may be substituted with a group other than a fluor
• the acid group is -C(CF 3 )(OH)-CF 2 - thus formed.
• one or more of the fluorine atoms may be substituted with a group other than a fluorine atom to form a ring containing -C(CF 3 )(OH)-CF 2 -.
• the repeating unit having an acid group is different from the repeating unit having a structure in which the polar group is protected by a group that leaves under the action of an acid, and the repeating unit having a lactone group, a sultone group, or a carbonate group, which will be described later. It is preferably a repeating unit.
• a repeating unit having an acid group may have a fluorine atom or an iodine atom.
• repeating units having an acid group include the following repeating units.
• repeating unit having an acid group a repeating unit represented by the following formula (1) is preferable.
• A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group.
• R represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkyloxycarbonyl group, or an aryloxycarbonyl group; In some cases they may be the same or different. When it has a plurality of R, they may jointly form a ring.
• a hydrogen atom is preferred as R.
• a represents an integer of 1 to 3;
• b represents an integer from 0 to (5-a).
• repeating units having an acid group examples include a and a.
• R represents a hydrogen atom or a methyl group
• a represents an integer of 1-3.
• the content of repeating units having an acid group is preferably 10 mol% or more, more preferably 15 mol% or more, relative to all repeating units in the resin (A). Moreover, the upper limit thereof is preferably 70 mol % or less, more preferably 65 mol % or less, and still more preferably 60 mol % or less, based on all repeating units in the resin (A).
• the resin (A) has neither an acid-decomposable group nor an acid group, apart from the above-described ⁇ repeating unit having an acid-decomposable group> and ⁇ repeating unit having an acid group>, and contains a fluorine atom and a bromine atom.
• it may have a repeating unit having an iodine atom (hereinafter also referred to as unit X).
• the ⁇ repeating unit having neither an acid-decomposable group nor an acid group and having a fluorine atom, a bromine atom, or an iodine atom> referred to here is a ⁇ repeating unit having a lactone group, a sultone group, or a carbonate group> described later.
• ⁇ repeating unit having photoacid-generating group> is a ⁇ repeating unit having photoacid-generating group>.
• a repeating unit represented by formula (C) is preferable.
• L5 represents a single bond or an ester group.
• R9 represents a hydrogen atom or an alkyl group optionally having a fluorine atom or an iodine atom.
• R 10 may have a hydrogen atom, an alkyl group optionally having a fluorine atom or an iodine atom, a cycloalkyl group optionally having a fluorine atom or an iodine atom, a fluorine atom or an iodine atom represents an aryl group or a group combining these;
• repeating units having a fluorine atom or an iodine atom are shown below.
• the content of the unit X is preferably 0 mol% or more, more preferably 5 mol% or more, and still more preferably 10 mol% or more, relative to all repeating units in the resin (A). Moreover, the upper limit thereof is preferably 50 mol % or less, more preferably 45 mol % or less, and still more preferably 40 mol % or less, relative to all repeating units in the resin (A).
• the total content of repeating units containing at least one of a fluorine atom, a bromine atom and an iodine atom is preferably 10 mol% or more with respect to all repeating units of the resin (A). , more preferably 20 mol % or more, still more preferably 30 mol % or more, and particularly preferably 40 mol % or more.
• the upper limit is not particularly limited, it is, for example, 100 mol % or less with respect to all repeating units of the resin (A).
• the repeating unit containing at least one of a fluorine atom, a bromine atom and an iodine atom includes, for example, a repeating unit having a fluorine atom, a bromine atom or an iodine atom and having an acid-decomposable group, a fluorine atom, a bromine repeating units having an acid group, and repeating units having a fluorine atom, a bromine atom, or an iodine atom.
• Resin (A) may have a repeating unit (hereinafter also referred to as “unit Y”) having at least one selected from the group consisting of a lactone group, a sultone group and a carbonate group. It is also preferable that the unit Y does not have a hydroxyl group and an acid group such as a hexafluoropropanol group.
• the lactone group or sultone group may have a lactone structure or sultone structure.
• the lactone structure or sultone structure is preferably a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure.
• the resin (A) has a lactone structure represented by any one of the following formulas (LC1-1) to (LC1-21), or any one of the following formulas (SL1-1) to (SL1-3). It preferably has a repeating unit having a lactone group or a sultone group obtained by removing one or more hydrogen atoms from a ring member atom of a sultone structure, and the lactone group or sultone group may be directly bonded to the main chain.
• ring member atoms of a lactone group or a sultone group may constitute the main chain of resin (A).
• the lactone structure or sultone structure may have a substituent (Rb 2 ).
• Preferred substituents (Rb 2 ) include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 7 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 1 to 8 carbon atoms, and carboxyl groups. , halogen atoms, cyano groups, and acid-labile groups.
• n2 represents an integer of 0-4. When n2 is 2 or more, multiple Rb 2 may be different, and multiple Rb 2 may combine to form a ring.
• Rb 0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferred substituents that the alkyl group of Rb 0 may have include a hydroxyl group and a halogen atom.
• a halogen atom for Rb 0 includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• Rb 0 is preferably a hydrogen atom or a methyl group.
• Ab is a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a combination of these divalent linkages represents a group.
• Ab is preferably a single bond or a linking group represented by -Ab 1 -CO 2 -.
• Ab 1 is a linear or branched alkylene group or a monocyclic or polycyclic cycloalkylene group, preferably a methylene group, ethylene group, cyclohexylene group, adamantylene group or norbornylene group.
• V is a group obtained by removing one hydrogen atom from a ring member atom of a lactone structure represented by any one of formulas (LC1-1) to (LC1-21), or formulas (SL1-1) to (SL1- 3) represents a group obtained by removing one hydrogen atom from a ring member atom of the sultone structure represented by any one of 3).
• any optical isomer may be used. Moreover, one optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, its optical purity (ee) is preferably 90 or more, more preferably 95 or more.
• a cyclic carbonate group is preferred.
• a repeating unit having a cyclic carbonate group a repeating unit represented by the following formula (A-1) is preferable.
• R A 1 represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group).
• n represents an integer of 0 or more.
• R A 2 represents a substituent. When n is 2 or more, a plurality of R A 2 may be the same or different.
• A represents a single bond or a divalent linking group.
• the divalent linking group includes an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a combination of these.
• a valent linking group is preferred.
• Z represents an atomic group forming a monocyclic or polycyclic ring together with the group represented by -O-CO-O- in the formula.
• Rx represents a hydrogen atom, -CH 3 , -CH 2 OH or -CF 3 .
• the content of the unit Y is preferably 1 mol% or more, more preferably 10 mol% or more, relative to all repeating units in the resin (A).
• the upper limit is preferably 85 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol% or less, and particularly 60 mol% or less, relative to all repeating units in the resin (A). preferable.
• the resin (A) may have, as a repeating unit other than the above, a repeating unit having a group that generates an acid upon exposure to actinic rays or radiation (hereinafter also referred to as a "photoacid-generating group").
• Repeating units having a photoacid-generating group include repeating units represented by formula (4).
• R41 represents a hydrogen atom or a methyl group.
• L41 represents a single bond or a divalent linking group.
• L42 represents a divalent linking group.
• R40 represents a structural site that is decomposed by exposure to actinic rays or radiation to generate an acid in the side chain. Examples of repeating units having a photoacid-generating group are shown below.
• repeating unit represented by formula (4) includes, for example, repeating units described in paragraphs [0094] to [0105] of JP-A-2014-041327, and International Publication No. 2018/193954. Examples include repeating units described in paragraph [0094].
• the content of the repeating unit having a photoacid-generating group is preferably 1 mol % or more, more preferably 5 mol % or more, relative to all repeating units in the resin (A). Moreover, the upper limit thereof is preferably 40 mol % or less, more preferably 35 mol % or less, and still more preferably 30 mol % or less, based on all repeating units in the resin (A).
• Resin (A) may have a repeating unit represented by the following formula (V-1) or the following formula (V-2).
• Repeating units represented by the following formulas (V-1) and (V-2) below are preferably different repeating units from the repeating units described above.
• R 6 and R 7 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR: R is the number of carbon atoms; 1 to 6 alkyl groups or fluorinated alkyl groups), or a carboxyl group.
• the alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.
• n3 represents an integer of 0-6.
• n4 represents an integer of 0-4.
• X4 is a methylene group, an oxygen atom, or a sulfur atom.
• the repeating units represented by formula (V-1) or (V-2) are exemplified below. Examples of the repeating unit represented by formula (V-1) or (V-2) include repeating units described in paragraph [0100] of WO 2018/193954.
• the resin (A) preferably has a high glass transition temperature (Tg) from the viewpoint of suppressing excessive diffusion of generated acid or pattern collapse during development.
• Tg is preferably greater than 90°C, more preferably greater than 100°C, even more preferably greater than 110°C, and particularly preferably greater than 125°C.
• the Tg is preferably 400° C. or less, more preferably 350° C. or less, from the viewpoint of excellent dissolution rate in the developer.
• Tg of repeating unit is calculated by the following method.
• the Tg of a homopolymer consisting only of each repeating unit contained in the polymer is calculated by the Bicerano method.
• the mass ratio (%) of each repeating unit to all repeating units in the polymer is calculated.
• the Fox formula (described in Materials Letters 62 (2008) 3152, etc.) is used to calculate the Tg at each mass ratio, and these are totaled to obtain the Tg (°C) of the polymer.
• the Bicerano method is described in Prediction of polymer properties, Marcel Dekker Inc, New York (1993). Calculation of Tg by the Bicerano method can be performed using a polymer physical property estimation software MDL Polymer (MDL Information Systems, Inc.).
• Methods for reducing the mobility of the main chain of the resin (A) include the following methods (a) to (e).
• (a) introduction of bulky substituents into the main chain (b) introduction of multiple substituents into the main chain (c) introduction of substituents that induce interaction between the resin (A) into the vicinity of the main chain ( d) Main Chain Formation in Cyclic Structure (e) Linking of Cyclic Structure to Main Chain
• the resin (A) preferably has a repeating unit exhibiting a homopolymer Tg of 130° C. or higher.
• the type of repeating unit exhibiting a homopolymer Tg of 130° C. or higher is not particularly limited as long as it is a repeating unit having a homopolymer Tg of 130° C. or higher as calculated by the Bicerano method.
• the homopolymers correspond to repeating units exhibiting a homopolymer Tg of 130° C. or higher.
• a specific example of means for achieving the above (a) is a method of introducing a repeating unit represented by the formula (A) into the resin (A).
• RA represents a group containing a polycyclic structure.
• R x represents a hydrogen atom, a methyl group, or an ethyl group.
• a group containing a polycyclic structure is a group containing multiple ring structures, and the multiple ring structures may or may not be condensed.
• Specific examples of the repeating unit represented by formula (A) include those described in paragraphs [0107] to [0119] of WO2018/193954.
• a specific example of means for achieving the above (b) is a method of introducing a repeating unit represented by the formula (B) into the resin (A).
• R b1 to R b4 each independently represent a hydrogen atom or an organic group, and at least two or more of R b1 to R b4 represent an organic group.
• the type of other organic group is not particularly limited.
• at least two of the organic groups have three or more constituent atoms excluding hydrogen atoms. is a substituent.
• Specific examples of the repeating unit represented by formula (B) include those described in paragraphs [0113] to [0115] of WO2018/193954.
• a specific example of means for achieving the above (c) is a method of introducing a repeating unit represented by the formula (C) into the resin (A).
• R c1 to R c4 each independently represent a hydrogen atom or an organic group, and at least one of R c1 to R c4 is hydrogen bonding hydrogen within 3 atoms from the main chain carbon It is a group containing atoms. Above all, it is preferable to have a hydrogen-bonding hydrogen atom within 2 atoms (closer to the main chain side) in order to induce interaction between the main chains of the resin (A).
• Specific examples of the repeating unit represented by formula (C) include those described in paragraphs [0119] to [0121] of WO2018/193954.
• a specific example of means for achieving (d) above is a method of introducing a repeating unit represented by the formula (D) into the resin (A).
• Cyclic represents a group forming a main chain with a cyclic structure.
• the number of constituent atoms of the ring is not particularly limited.
• Specific examples of the repeating unit represented by formula (D) include those described in paragraphs [0126] to [0127] of WO2018/193954.
• a specific example of means for achieving (e) above is a method of introducing a repeating unit represented by formula (E) into the resin (A).
• each Re independently represents a hydrogen atom or an organic group.
• organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups, which may have substituents.
• a "Cyclic” is a cyclic group containing carbon atoms in the main chain. The number of atoms contained in the cyclic group is not particularly limited. Specific examples of the repeating unit represented by formula (E) include those described in paragraphs [0131] to [0133] of WO2018/193954.
• the resin (A) may have repeating units having at least one group selected from lactone groups, sultone groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups.
• the repeating unit having a lactone group, a sultone group, or a carbonate group that the resin (A) has include the repeating units described in the above ⁇ Repeating unit having a lactone group, sultone group, or carbonate group>.
• the preferable content is also as described in ⁇ Repeating unit having lactone group, sultone group, or carbonate group>.
• Resin (A) may have a repeating unit having a hydroxyl group or a cyano group. This improves the adhesion to the substrate and the compatibility with the developer.
• a repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group.
• a repeating unit having a hydroxyl group or a cyano group preferably does not have an acid-decomposable group. Examples of repeating units having a hydroxyl group or a cyano group include those described in paragraphs [0081] to [0084] of JP-A-2014-098921.
• Resin (A) may have a repeating unit having an alkali-soluble group.
• the alkali-soluble group includes a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol group substituted with an electron-withdrawing group at the ⁇ -position (e.g., hexafluoroisopropanol group). , is preferably a carboxyl group.
• the resin (A) contains a repeating unit having an alkali-soluble group, the resolution for contact holes is increased. Repeating units having an alkali-soluble group include those described in paragraphs [0085] and [0086] of JP-A-2014-098921.
• Resin (A) may have a repeating unit that has an alicyclic hydrocarbon structure and does not exhibit acid decomposability. This can reduce the elution of low-molecular-weight components from the resist film into the immersion liquid during immersion exposure.
• Repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposability include, for example, 1-adamantyl (meth)acrylate, diamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, or cyclohexyl (meth) Examples include repeating units derived from acrylates.
• Resin (A) may have a repeating unit represented by formula (III) that has neither a hydroxyl group nor a cyano group.
• R5 represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxyl group nor a cyano group.
• Ra represents a hydrogen atom, an alkyl group or a --CH 2 --O--Ra 2 group.
• Ra2 represents a hydrogen atom, an alkyl group or an acyl group. Examples of the repeating unit represented by formula (III) having neither a hydroxyl group nor a cyano group include those described in paragraphs [0087] to [0094] of JP-A-2014-098921.
• the resin (A) may contain various repeating structural units for the purpose of adjusting dry etching resistance, suitability for standard developer, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, and the like. may have
• Resin (A) can be synthesized according to a conventional method (for example, radical polymerization).
• the weight average molecular weight of the resin (A) is preferably 30,000 or less, more preferably 1,000 to 30,000, still more preferably 3,000 to 30,000, further preferably 5,000 as a polystyrene equivalent value by GPC method. ⁇ 15,000 is particularly preferred.
• the dispersity (molecular weight distribution) of the resin (A) is preferably 1 to 5, more preferably 1 to 3, still more preferably 1.2 to 3.0, and particularly preferably 1.2 to 2.0. The smaller the degree of dispersion, the better the resolution and resist shape, the smoother the side walls of the resist pattern, and the better the roughness.
• the content of the resin (A) is preferably 40.0 to 99.9% by mass, more preferably 50.0 to 90.0% by mass, based on the total solid content of the composition. .
• the resin (A) may be used singly or in combination.
• the composition of the present invention may further contain a resin different from resin (A).
• a resin different from resin (A) the content thereof is preferably 0.01 to 20.0% by mass, more preferably 0.1 to 15.0% by mass, based on the total solid content of the composition. 0% by mass is more preferred.
• the resin different from the resin (A) is not particularly limited as long as it does not contain the repeating unit (a1) having a partial structure in which the phenolic hydroxyl group is protected by the structure represented by the general formula (1). , for example, a hydrophobic resin described later.
• composition of the present invention preferably further contains a photoacid generator and a solvent.
• a photoacid generator and a solvent.
• Components other than the resin (A) are described below.
• the composition of the present invention preferably contains a compound that generates an acid upon exposure to actinic rays or radiation (also referred to as a photoacid generator or photoacid generator (B)).
• a photoacid generator is a compound that generates an acid upon exposure (preferably exposure to EUV light).
• the photoacid generator (B) may be in the form of a low-molecular-weight compound, or may be in the form of being incorporated into a part of a polymer (for example, resin (A) described above). Moreover, the form of a low-molecular-weight compound and the form of being incorporated into a part of a polymer (for example, the resin (A) described above) may be used in combination.
• the photoacid generator (B) is in the form of a low-molecular-weight compound
• the molecular weight of the photoacid generator is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less. Although the lower limit is not particularly limited, 100 or more is preferable.
• the photoacid generator (B) When the photoacid generator (B) is in the form of being incorporated into a part of the polymer, it may be incorporated into a part of the resin (A), or may be incorporated into a resin different from the resin (A). good.
• the photoacid generator (B) is preferably in the form of a low molecular weight compound.
• Examples of the photoacid generator (B) include compounds (onium salts) represented by “M + X ⁇ ”, and compounds that generate an organic acid upon exposure are preferred.
• Examples of the organic acid include sulfonic acid (aliphatic sulfonic acid, aromatic sulfonic acid, camphorsulfonic acid, etc.), carboxylic acid (aliphatic carboxylic acid, aromatic carboxylic acid, aralkylcarboxylic acid, etc.), carbonylsulfonylimide, acids, bis(alkylsulfonyl)imidic acids, and tris(alkylsulfonyl)methide acids.
• M + represents an organic cation.
• the valence of the organic cation may be 1 or 2 or more.
• a cation represented by the formula (ZaI) hereinafter also referred to as “cation (ZaI)
• ZaII a cation represented by the formula (ZaII)
• ZaII a cation represented by the formula (ZaII)
• R 201 , R 202 and R 203 each independently represent an organic group.
• the number of carbon atoms in the organic groups for R 201 , R 202 and R 203 is preferably 1-30, more preferably 1-20.
• Two of R 201 to R 203 may combine to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group.
• Examples of the group formed by combining two of R 201 to R 203 include an alkylene group (eg, a butylene group and a pentylene group) and —CH 2 —CH 2 —O—CH 2 —CH 2 —. mentioned.
• Suitable embodiments of the organic cation in formula (ZaI) include cation (ZaI-1), cation (ZaI-2), cation (ZaI-3b), and cation (ZaI-4b), which will be described later.
• Cation (ZaI-1) is an arylsulfonium cation in which at least one of R 201 to R 203 in formula (ZaI) above is an aryl group.
• R 201 to R 203 may be aryl groups, or part of R 201 to R 203 may be aryl groups and the rest may be alkyl groups or cycloalkyl groups.
• R 201 to R 203 is an aryl group, and the remaining two of R 201 to R 203 may combine to form a ring structure, in which an oxygen atom, a sulfur atom and an ester group , an amide group, or a carbonyl group.
• the group formed by bonding two of R 201 to R 203 includes, for example, one or more methylene groups substituted with an oxygen atom, a sulfur atom, an ester group, an amide group and/or a carbonyl group. alkylene groups (eg, butylene group, pentylene group, and —CH 2 —CH 2 —O—CH 2 —CH 2 —).
• Arylsulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.
• the aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
• the aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Heterocyclic structures include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene residues.
• the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different.
• the alkyl group or cycloalkyl group optionally possessed by the arylsulfonium cation is a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or 3 to 15 carbon atoms. is preferred, and a methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group or cyclohexyl group is more preferred.
• substituents that the aryl group, alkyl group and cycloalkyl group of R 201 to R 203 may have include an alkyl group (eg, 1 to 15 carbon atoms), a cycloalkyl group (eg, 3 to 3 carbon atoms).
• aryl groups eg, 6 to 14 carbon atoms
• alkoxy groups eg, 1 to 15 carbon atoms
• cycloalkylalkoxy groups eg, 1 to 15 carbon atoms
• halogen atoms eg, fluorine and iodine
• the substituent may further have a substituent
• the alkyl group preferably has a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group.
• the acid-decomposable group is intended to be a group that is decomposed by the action of an acid to generate a polar group, and preferably has a structure in which the polar group is protected by a group that is eliminated by the action of an acid.
• the polar group and leaving group are as described above.
• Cation (ZaI-2) is a cation in which R 201 to R 203 in formula (ZaI) each independently represents an organic group having no aromatic ring.
• Aromatic rings also include aromatic rings containing heteroatoms.
• the number of carbon atoms in the organic group having no aromatic ring as R 201 to R 203 is preferably 1-30, more preferably 1-20.
• R 201 to R 203 are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, and a linear or branched 2-oxoalkyl group, 2-oxocycloalkyl group, or An alkoxycarbonylmethyl group is more preferred, and a linear or branched 2-oxoalkyl group is even more preferred.
• the alkyl groups and cycloalkyl groups of R 201 to R 203 are, for example, linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, , butyl group, and pentyl group), and cycloalkyl groups having 3 to 10 carbon atoms (eg, cyclopentyl group, cyclohexyl group, and norbornyl group).
• R 201 to R 203 may be further substituted with a halogen atom, an alkoxy group (eg, 1-5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group. It is also preferred that the substituents of R 201 to R 203 each independently form an acid-decomposable group by any combination of substituents.
• the cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).
• R 1c to R 5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkyl represents a carbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group, or an arylthio group; R 6c and R 7c each independently represent a hydrogen atom, an alkyl group (eg, t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group.
• R 6c and R 7c each independently represent a hydrogen atom, an alkyl group (eg, t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an ary
• R x and R y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group. It is also preferred that the substituents of R 1c to R 7c , R x and R y independently form an acid-decomposable group by any combination of substituents.
• R 1c to R 5c , R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y may combine with each other to form a ring.
• the rings may each independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
• Examples of the ring include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic hetero rings, and polycyclic condensed rings in which two or more of these rings are combined.
• the ring includes a 3- to 10-membered ring, preferably a 4- to 8-membered ring, more preferably a 5- or 6-membered ring.
• Examples of groups formed by bonding two or more of R 1c to R 5c , R 6c and R 7c , and R x and R y include alkylene groups such as a butylene group and a pentylene group. A methylene group in this alkylene group may be substituted with a heteroatom such as an oxygen atom.
• the group formed by combining R 5c and R 6c and R 5c and R x is preferably a single bond or an alkylene group.
• Alkylene groups include methylene and ethylene groups.
• R 1c to R 5c , R 6c , R 7c , R x , R y , and two or more of R 1c to R 5c , R 5c and R 6c , R 6c and R 7c , R 5c and R x , and the ring formed by combining each other with R x and R y may have a substituent.
• the cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).
• R 13 is a hydrogen atom, a halogen atom (e.g., fluorine atom, iodine atom, etc.), a hydroxyl group, an alkyl group, a halogenated alkyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a group containing a cycloalkyl group (cycloalkyl may be the group itself, or may be a group partially containing a cycloalkyl group). These groups may have a substituent.
• a halogen atom e.g., fluorine atom, iodine atom, etc.
• R 14 is a hydroxyl group, a halogen atom (e.g., fluorine atom, iodine atom, etc.), an alkyl group, a halogenated alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl represents a group containing a group (either a cycloalkyl group itself or a group partially containing a cycloalkyl group). These groups may have a substituent. When two or more R 14 are present, each independently represents the above group such as a hydroxyl group.
• a halogen atom e.g., fluorine atom, iodine atom, etc.
• Each R 15 independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. Two R 15 may be joined together to form a ring. When two R 15 are combined to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom. In one aspect, two R 15 are alkylene groups, preferably joined together to form a ring structure. The ring formed by combining the alkyl group, the cycloalkyl group, the naphthyl group, and the two R 15 groups may have a substituent.
• the alkyl groups of R 13 , R 14 and R 15 may be linear or branched.
• the number of carbon atoms in the alkyl group is preferably 1-10.
• the alkyl group is preferably a methyl group, an ethyl group, an n-butyl group, a t-butyl group, or the like. It is also preferred that each of the substituents of R 13 to R 15 , R x and R y independently forms an acid-decomposable group by any combination of substituents.
• R 204 and R 205 each independently represent an aryl group, an alkyl group or a cycloalkyl group.
• the aryl group for R 204 and R 205 is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
• the aryl group for R 204 and R 205 may be an aryl group having a heterocyclic ring having an oxygen atom, a nitrogen atom, a sulfur atom, or the like.
• Skeletons of heterocyclic aryl groups include, for example, pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
• the alkyl group and cycloalkyl group for R 204 and R 205 include a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, or pentyl group), or a cycloalkyl group having 3 to 10 carbon atoms (eg, cyclopentyl group, cyclohexyl group, or norbornyl group).
• the aryl group, alkyl group and cycloalkyl group of R 204 and R 205 may each independently have a substituent.
• substituents that the aryl group, alkyl group and cycloalkyl group of R 204 and R 205 may have include an alkyl group (eg, 1 to 15 carbon atoms) and a cycloalkyl group (eg, 3 to 15), aryl groups (eg, 6 to 15 carbon atoms), alkoxy groups (eg, 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups. It is also preferred that the substituents of R 204 and R 205 each independently form an acid-decomposable group by any combination of substituents.
• X ⁇ represents an organic anion.
• the organic anion is not particularly limited, and includes organic anions having a valence of 1, 2 or more.
• an anion having a significantly low ability to cause a nucleophilic reaction is preferred, and a non-nucleophilic anion is more preferred.
• non-nucleophilic anions examples include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, and aralkyl carboxylic acid anions), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methide anions.
• sulfonate anions aliphatic sulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc.
• carboxylate anions aliphatic carboxylate anions, aromatic carboxylate anions, and aralkyl carboxylic acid anions
• sulfonylimide anions bis(alkylsulfonyl)imide anions
• the aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be a linear or branched alkyl group or a cycloalkyl group, and may be a straight chain having 1 to 30 carbon atoms. Alternatively, a branched alkyl group or a cycloalkyl group having 3 to 30 carbon atoms is preferred.
• the alkyl group may be, for example, a fluoroalkyl group (which may have a substituent other than a fluorine atom, or may be a perfluoroalkyl group).
• the aryl group in the aromatic sulfonate anion and the aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group.
• the alkyl group, cycloalkyl group, and aryl group listed above may have a substituent.
• the substituents are not particularly limited, but examples include nitro groups, halogen atoms such as fluorine atoms and chlorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), alkyl groups ( preferably 1 to 10 carbon atoms), a cycloalkyl group (preferably 3 to 15 carbon atoms), an aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group ( preferably 2 to 12 carbon atoms), alkoxycarbonyloxy group (preferably 2 to 7 carbon atoms), alkylthio group (preferably 1 to 15 carbon atoms), alkylsulfonyl group (preferably 1 to 15 carbon atoms), alkylimino A sulfonyl group (preferably having 1
• aralkyl group in the aralkylcarboxylate anion an aralkyl group having 7 to 14 carbon atoms is preferred.
• Aralkyl groups having 7 to 14 carbon atoms include, for example, benzyl, phenethyl, naphthylmethyl, naphthylethyl and naphthylbutyl groups.
• Sulfonylimide anions include, for example, saccharin anions.
• alkyl group in the bis(alkylsulfonyl)imide anion and the tris(alkylsulfonyl)methide anion an alkyl group having 1 to 5 carbon atoms is preferable.
• substituents of these alkyl groups include halogen atoms, halogen-substituted alkyl groups, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryloxysulfonyl groups.
• a fluorine atom or an alkyl group substituted with a fluorine atom is preferred.
• the alkyl groups in the bis(alkylsulfonyl)imide anion may combine with each other to form a ring structure. This increases the acid strength.
• non-nucleophilic anions include, for example, phosphorous fluorides (eg, PF 6 ⁇ ), boron fluorides (eg, BF 4 ⁇ ), and antimony fluorides (eg, SbF 6 ⁇ ).
• non-nucleophilic anions include aliphatic sulfonate anions in which at least the ⁇ -position of sulfonic acid is substituted with fluorine atoms, aromatic sulfonate anions in which fluorine atoms or groups having fluorine atoms are substituted, and alkyl groups in which fluorine atoms are present.
• a bis(alkylsulfonyl)imide anion substituted with or a tris(alkylsulfonyl)methide anion in which an alkyl group is substituted with a fluorine atom is preferable.
• perfluoroaliphatic sulfonate anions preferably having 4 to 8 carbon atoms
• benzenesulfonate anions having a fluorine atom are more preferable, nonafluorobutanesulfonate anions, perfluorooctanesulfonate anions, pentafluoro A benzenesulfonate anion or a 3,5-bis(trifluoromethyl)benzenesulfonate anion is more preferred.
• an anion represented by the following formula (AN1) is also preferable.
• R 1 and R 2 each independently represent a hydrogen atom or a substituent.
• substituent is not particularly limited, a group that is not an electron-withdrawing group is preferred.
• groups that are not electron-withdrawing groups include hydrocarbon groups, hydroxyl groups, oxyhydrocarbon groups, oxycarbonyl hydrocarbon groups, amino groups, hydrocarbon-substituted amino groups, and hydrocarbon-substituted amide groups.
• Groups that are not electron-withdrawing groups are preferably -R', -OH, -OR', -OCOR', -NH 2 , -NR' 2 , -NHR' or -NHCOR' each independently.
• R' is a monovalent hydrocarbon group.
• Examples of the monovalent hydrocarbon group represented by R' include alkyl groups such as methyl, ethyl, propyl, and butyl; alkenyl groups such as ethenyl, propenyl, and butenyl; ethynyl monovalent linear or branched hydrocarbon groups such as alkynyl groups such as groups, propynyl groups, and butynyl groups; cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, cyclohexyl groups, norbornyl groups, and adamantyl groups Cycloalkyl group; monovalent alicyclic hydrocarbon group such as cycloalkenyl group such as cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, and norbornenyl group; phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, methyl aryl groups such as
• L represents a divalent linking group.
• divalent linking groups include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO 2 -, alkylene groups ( preferably 1 to 6 carbon atoms), a cycloalkylene group (preferably 3 to 15 carbon atoms), an alkenylene group (preferably 2 to 6 carbon atoms), and a divalent linking group combining a plurality of these.
• the divalent linking group includes -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -SO 2 -, and -O-CO-O-alkylene group- , -COO-alkylene group-, or -CONH-alkylene group- is preferred, and -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, -SO 2 - , or -COO-alkylene group- is more preferable.
• a group represented by the following formula (AN1-1) is preferable. * a - (CR 2a 2 ) X - Q- (CR 2b 2 ) Y - * b (AN1-1)
• * a represents the bonding position with R3 in formula (AN1).
• * b represents the bonding position with -C(R 1 )(R 2 )- in formula (AN1).
• X and Y each independently represent an integer of 0-10, preferably an integer of 0-3.
• R 2a and R 2b each independently represent a hydrogen atom or a substituent. When multiple R 2a and R 2b are present, the multiple R 2a and R 2b may be the same or different. However, when Y is 1 or more, R 2b in CR 2b 2 directly bonded to —C(R 1 )(R 2 )— in formula (AN1) is other than a fluorine atom.
• Q is * A -O-CO-O-* B , * A -CO-* B , * A -CO-O-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B or * A - SO2- * B .
• R3 represents an organic group.
• the organic group is not particularly limited as long as it has 1 or more carbon atoms. branched chain alkyl group) or a cyclic group.
• the organic group may or may not have a substituent.
• the organic group may or may not have a heteroatom (oxygen atom, sulfur atom, and/or nitrogen atom, etc.).
• R 3 is preferably an organic group having a cyclic structure.
• the cyclic structure may be monocyclic or polycyclic, and may have a substituent.
• the ring in the organic group containing a cyclic structure is preferably directly bonded to L in formula (AN1).
• the organic group having a cyclic structure may or may not have a heteroatom (oxygen atom, sulfur atom, and/or nitrogen atom, etc.), for example. Heteroatoms may replace one or more of the carbon atoms that form the ring structure.
• the organic group having a cyclic structure is preferably, for example, a hydrocarbon group having a cyclic structure, a lactone ring group, or a sultone ring group.
• the organic group having a cyclic structure is preferably a hydrocarbon group having a cyclic structure.
• the above hydrocarbon group having a cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may have a substituent.
• the cycloalkyl group may be monocyclic (such as cyclohexyl group) or polycyclic (such as adamantyl group), and preferably has 5 to 12 carbon atoms.
• Examples of the lactone group and sultone group include structures represented by the above formulas (LC1-1) to (LC1-21) and structures represented by formulas (SL1-1) to (SL1-3). , preferably a group obtained by removing one hydrogen atom from a ring member atom constituting a lactone structure or a sultone structure.
• the non-nucleophilic anion may be a benzenesulfonate anion, preferably a benzenesulfonate anion substituted with a branched alkyl group or cycloalkyl group.
• an anion represented by the following formula (AN2) is also preferable.
• o represents an integer of 1-3.
• p represents an integer from 0 to 10;
• q represents an integer from 0 to 10;
• Xf represents a hydrogen atom, a fluorine atom, an alkyl group substituted with at least one fluorine atom, or an organic group having no fluorine atom.
• the number of carbon atoms in this alkyl group is preferably 1-10, more preferably 1-4.
• a perfluoroalkyl group is preferred as the alkyl group substituted with at least one fluorine atom.
• Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF 3 , and even more preferably both Xf are fluorine atoms.
• R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When multiple R 4 and R 5 are present, each of R 4 and R 5 may be the same or different.
• the alkyl groups represented by R 4 and R 5 preferably have 1 to 4 carbon atoms. The above alkyl group may have a substituent. Hydrogen atoms are preferred as R 4 and R 5 .
• L represents a divalent linking group.
• the definition of L is synonymous with L in formula (AN1).
• W represents an organic group, preferably an organic group containing a cyclic structure.
• a cyclic organic group is preferable.
• Cyclic organic groups include, for example, alicyclic groups, aryl groups, and heterocyclic groups.
• the alicyclic group may be monocyclic or polycyclic.
• Monocyclic alicyclic groups include, for example, monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
• the polycyclic alicyclic group includes, for example, a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and a polycyclic cycloalkyl group such as an adamantyl group.
• alicyclic groups having a bulky structure with 7 or more carbon atoms such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups, are preferred.
• Aryl groups may be monocyclic or polycyclic. Examples of the aryl group include phenyl group, naphthyl group, phenanthryl group, and anthryl group.
• a heterocyclic group may be monocyclic or polycyclic. Especially, when it is a polycyclic heterocyclic group, diffusion of acid can be further suppressed.
• a heterocyclic group may or may not have an aromatic character. Heterocyclic rings having aromaticity include, for example, furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, and pyridine ring.
• Non-aromatic heterocycles include, for example, a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring.
• the heterocyclic ring in the heterocyclic group is preferably a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring.
• the cyclic organic group may have a substituent.
• substituents include alkyl groups (either linear or branched, preferably having 1 to 12 carbon atoms), cycloalkyl groups (monocyclic, polycyclic, and spirocyclic). any group, preferably having 3 to 20 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), hydroxyl group, alkoxy group, ester group, amide group, urethane group, ureido group, thioether group, sulfonamide and sulfonate ester groups.
• carbonyl carbon may be sufficient as carbon (carbon which contributes to ring formation) which comprises a cyclic
• Examples of anions represented by formula (AN2) include SO 3 ⁇ —CF 2 —CH 2 —OCO-(L) q′ —W, SO 3 ⁇ —CF 2 —CHF—CH 2 —OCO-(L) q ' -W, SO 3 - -CF 2 -COO-(L) q' -W, SO 3 - -CF 2 -CF 2 -CH 2 -CH 2 -(L) q -W, or SO 3 - - CF 2 —CH(CF 3 )—OCO—(L) q′ —W is preferred.
• L, q and W are the same as in formula (AN2).
• q' represents an integer from 0 to 10;
• an aromatic sulfonate anion represented by the following formula (AN3) is also preferable.
• Ar represents an aryl group (such as a phenyl group) and may further have a substituent other than the sulfonate anion and -(D-B) group.
• Substituents which may be further included include, for example, a fluorine atom and a hydroxyl group.
• n represents an integer of 0 or more. n is preferably 1 to 4, more preferably 2 to 3, and still more preferably 3.
• D represents a single bond or a divalent linking group.
• Divalent linking groups include ether groups, thioether groups, carbonyl groups, sulfoxide groups, sulfone groups, sulfonate ester groups, ester groups, and groups consisting of combinations of two or more thereof.
• B represents a hydrocarbon group.
• B is preferably an aliphatic hydrocarbon group, more preferably an isopropyl group, a cyclohexyl group, or an optionally substituted aryl group (such as a tricyclohexylphenyl group).
• Disulfonamide anions are also preferred as non-nucleophilic anions.
• a disulfonamide anion is, for example, an anion represented by N ⁇ (SO 2 —R q ) 2 .
• R q represents an optionally substituted alkyl group, preferably a fluoroalkyl group, more preferably a perfluoroalkyl group.
• Two R q may combine with each other to form a ring.
• the group formed by bonding two R q together is preferably an optionally substituted alkylene group, preferably a fluoroalkylene group, more preferably a perfluoroalkylene group.
• the alkylene group preferably has 2 to 4 carbon atoms.
• Non-nucleophilic anions also include anions represented by the following formulas (d1-1) to (d1-4).
• R 51 represents a hydrocarbon group (eg, an aryl group such as a phenyl group) optionally having a substituent (eg, hydroxyl group).
• Z 2c represents an optionally substituted hydrocarbon group having 1 to 30 carbon atoms (provided that the carbon atom adjacent to S is not substituted with a fluorine atom).
• the above hydrocarbon group for Z 2c may be linear or branched, and may have a cyclic structure.
• the carbon atom in the hydrocarbon group (preferably the carbon atom that is a ring member atom when the hydrocarbon group has a cyclic structure) may be carbonyl carbon (--CO-).
• Examples of the hydrocarbon group include a group having an optionally substituted norbornyl group.
• a carbon atom forming the norbornyl group may be a carbonyl carbon.
• Z 2c —SO 3 ⁇ in formula (d1-2) is preferably different from the anions represented by formulas (AN1) to (AN3) above.
• Z 2c is preferably other than an aryl group.
• the ⁇ -position and ⁇ -position atoms with respect to —SO 3 — in Z 2c are preferably atoms other than carbon atoms having a fluorine atom as a substituent.
• the ⁇ -position atom and/or the ⁇ -position atom with respect to —SO 3 — is preferably a ring member atom in a cyclic group.
• R 52 represents an organic group (preferably a hydrocarbon group having a fluorine atom)
• Y 3 represents a linear, branched or cyclic alkylene group, an arylene group, or represents a carbonyl group
• Rf represents a hydrocarbon group
• R 53 and R 54 each independently represent an organic group (preferably a hydrocarbon group having a fluorine atom). R 53 and R 54 may combine with each other to form a ring.
• the organic anions may be used singly or in combination of two or more.
• the photoacid generator is also preferably at least one selected from the group consisting of compounds (I) to (II).
• Compound (I) is a compound having one or more structural moieties X shown below and one or more structural moieties Y shown below, wherein the first acidic It is a compound that generates an acid containing a site and a second acidic site described below derived from the structural site Y described below.
• Structural site X Structural site consisting of an anionic site A 1 ⁇ and a cation site M 1 + and forming a first acidic site represented by HA 1 upon exposure to actinic rays or radiation
• Structural site Y anionic site A structural site consisting of A 2 - and a cationic site M 2 + and forming a second acidic site represented by HA 2 upon exposure to actinic rays or radiation.
• the compound (I) satisfies the following condition I. .
• Condition I A compound PI obtained by replacing the cation site M 1 + in the structural site X and the cation site M 2 + in the structural site Y in the compound (I) with H + in the structural site X and an acid dissociation constant a1 derived from the acidic site represented by HA 1 obtained by replacing the cation site M 1 + with H + , and replacing the cation site M 2 + in the structural site Y with H + It has an acid dissociation constant a2 derived from the acidic site represented by HA2 , and the acid dissociation constant a2 is greater than the acid dissociation constant a1.
• compound PI corresponds to "a compound having HA 1 and HA 2 ".
• the acid dissociation constant a1 and the acid dissociation constant a2 of compound PI are defined as "a compound having A 1 - and HA 2 " when the acid dissociation constant of compound PI is determined. is the acid dissociation constant a1, and the pKa when the "compound having A 1 - and HA 2 " becomes the "compound having A 1 - and A 2 - " is the acid dissociation constant a2 be.
• compound (I) is, for example, an acid-generating compound having two first acidic sites derived from the structural site X and one second acidic site derived from the structural site Y
• compound PI corresponds to "a compound having two HA 1 and one HA 2 ".
• the acid dissociation constant of compound PI is obtained, the acid dissociation constant when compound PI becomes "a compound having one A 1 - , one HA 1 and one HA 2 " and "one A 1 - and one HA 1 and one HA 2 ” becomes a “compound having two A 1 - and one HA 2 ” corresponds to the acid dissociation constant a1 described above. .
• the acid dissociation constant when "a compound having two A 1 - and one HA 2 - " becomes "a compound having two A 1 - and A 2 - " corresponds to the acid dissociation constant a2. That is, in the case of the compound PI, when it has a plurality of acid dissociation constants derived from the acidic site represented by HA 1 obtained by replacing the cation site M 1 + in the structural site X with H + , a plurality of acid dissociation constants The value of the acid dissociation constant a2 is larger than the largest value of a1.
• the acid dissociation constant when the compound PI becomes "a compound having one A 1 - , one HA 1 and one HA 2 " is aa, and "one A 1 - and one HA 1 and 1
• the relationship between aa and ab satisfies aa ⁇ ab, where ab is the acid dissociation constant when a compound having two HA2 's becomes a compound having two A1- and one HA2 . .
• the acid dissociation constant a1 and the acid dissociation constant a2 are determined by the method for measuring the acid dissociation constant described above.
• the above compound PI corresponds to an acid generated when compound (I) is irradiated with actinic rays or radiation.
• the structural moieties X may be the same or different.
• Two or more of A 1 ⁇ and two or more of M 1 + may be the same or different.
• a 1 - and A 2 - , and M 1 + and M 2 + may be the same or different, but A 1 - and A 2 - are preferably different.
• the difference (absolute value) between the acid dissociation constant a1 (the maximum value when there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is preferably 0.1 or more, and preferably 0.5 or more. More preferably, 1.0 or more is even more preferable.
• the upper limit of the difference (absolute value) between the acid dissociation constant a1 (the maximum value if there are a plurality of acid dissociation constants a1) and the acid dissociation constant a2 is not particularly limited, but is, for example, 16 or less.
• the acid dissociation constant a2 is preferably 20 or less, more preferably 15 or less.
• the lower limit of the acid dissociation constant a2 is preferably -4.0 or more.
• the acid dissociation constant a1 is preferably 2.0 or less, more preferably 0 or less.
• the lower limit of the acid dissociation constant a1 is preferably ⁇ 20.0 or more.
• the anion site A 1 - and the anion site A 2 - are structural sites containing negatively charged atoms or atomic groups, for example, formulas (AA-1) to (AA-3) and formula (BB -1) to (BB-6).
• the anion site A 1 - is preferably one capable of forming an acidic site with a small acid dissociation constant, and more preferably one of the formulas (AA-1) to (AA-3). AA-1) and (AA-3) are more preferred.
• the anion site A 2 - is preferably one capable of forming an acidic site with a larger acid dissociation constant than the anion site A 1 - , and is any of the formulas (BB-1) to (BB-6).
• RA represents a monovalent organic group.
• the monovalent organic group represented by RA is not particularly limited, examples thereof include a cyano group, a trifluoromethyl group and a methanesulfonyl group.
• the cation site M 1 + and the cation site M 2 + are structural sites containing positively charged atoms or atomic groups, such as monovalent organic cations.
• Examples of organic cations include organic cations represented by M + described above.
• Compound (II) is a compound having two or more of the above structural moieties X and one or more of the following structural moieties Z, wherein the first acidic It is a compound that generates an acid containing two or more sites and the structural site Z described above.
• Structural site Z nonionic site capable of neutralizing acid
• the preferred range of the acid dissociation constant a1 derived from the acidic site represented by is the same as the acid dissociation constant a1 in the above compound PI.
• the compound (II) is a compound that generates an acid having two of the first acidic sites derived from the structural site X and the structural site Z
• the compound PII is "two HA 1 It corresponds to "a compound having When the acid dissociation constant of this compound PII is determined, the acid dissociation constant when the compound PII is "a compound having one A 1 - and one HA 1 " and "one A 1 - and one HA
• the acid dissociation constant when the "compound having 1 " becomes "the compound having two A 1 - " corresponds to the acid dissociation constant a1.
• the acid dissociation constant a1 is obtained by the method for measuring the acid dissociation constant described above.
• the above compound PII corresponds to an acid generated when compound (II) is irradiated with actinic rays or radiation.
• the two or more structural sites X may be the same or different.
• Two or more of A 1 ⁇ and two or more of M 1 + may be the same or different.
• the nonionic site capable of neutralizing the acid in the structural site Z is not particularly limited.
• a site containing a group capable of electrostatically interacting with protons or a functional group having electrons is preferred.
• a group capable of electrostatically interacting with protons or a functional group having electrons is a functional group having a macrocyclic structure such as a cyclic polyether, or a lone pair of electrons that does not contribute to ⁇ conjugation.
• a functional group having a nitrogen atom is included.
• a nitrogen atom having a lone pair of electrons that does not contribute to ⁇ -conjugation is, for example, a nitrogen atom having a partial structure represented by the following formula.
• Partial structures of functional groups having electrons or groups capable of electrostatically interacting with protons include, for example, a crown ether structure, an azacrown ether structure, a primary to tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure. Among them, primary to tertiary amine structures are preferred.
• the content is not particularly limited, but since the cross-sectional shape of the formed pattern becomes more rectangular, the total solid content of the composition is , is preferably 0.5% by mass or more, more preferably 1.0% by mass or more.
• the content is preferably 50.0% by mass or less, more preferably 30.0% by mass or less, and even more preferably 25.0% by mass or less, relative to the total solid content of the composition.
• the photoacid generator (B) may be used alone or in combination of two or more.
• the composition of the present invention may contain an acid diffusion control agent.
• the acid diffusion control agent traps the acid generated from the photoacid generator or the like during exposure, and acts as a quencher that suppresses the reaction of the acid-decomposable resin in the unexposed area due to excess generated acid.
• the type of acid diffusion controller is not particularly limited, and examples include basic compounds (CA), low-molecular-weight compounds (CB) having nitrogen atoms and groups that leave under the action of acids, and actinic rays or radiation. and a compound (CC) whose ability to control acid diffusion decreases or disappears upon irradiation.
• a basic compound (CA) include, for example, those described in paragraphs [0132] to [0136] of WO2020/066824, and the basicity is reduced or reduced by exposure to actinic rays or radiation.
• Specific examples of the disappearing basic compound (CE) include those described in paragraphs [0137] to [0155] of WO 2020/066824, and paragraph [0164] of WO 2020/066824.
• CB low-molecular compound having a nitrogen atom and a group that leaves under the action of an acid
• CD onium salt compound
• paragraphs [0627] to [0664] of US Patent Application Publication No. 2016/0070167A1 paragraphs [0095] to [0187] of US Patent Application Publication No. 2015/0004544A1
• paragraphs [0237190A1 and paragraphs [0259] to [0328] of US Patent Application Publication No. 2016/0274458A1 can be suitably used as acid diffusion control agents.
• the content of the acid diffusion control agent (the total if there are more than one) is 0.1 to 15.0% relative to the total solid content of the composition. 0% by mass is preferred, and 1.0 to 15.0% by mass is more preferred.
• one type of acid diffusion control agent may be used alone, or two or more types may be used in combination.
• the composition of the invention may further comprise a hydrophobic resin different from resin (A).
• Hydrophobic resins are preferably designed to be unevenly distributed on the surface of the resist film. may not contribute to
• the effects of adding a hydrophobic resin include control of the static and dynamic contact angles of the resist film surface with respect to water, and suppression of outgassing.
• the hydrophobic resin preferably has one or more of a fluorine atom, a silicon atom, and a CH3 partial structure contained in the side chain portion of the resin. It is more preferable to have The hydrophobic resin preferably has a hydrocarbon group with 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted on the side chain. Hydrophobic resins include compounds described in paragraphs [0275] to [0279] of WO2020/004306.
• the content of the hydrophobic resin is preferably 0.01 to 20.0% by mass, and 0.1 to 15.0% by mass, based on the total solid content of the composition. % by mass is more preferred.
• the composition of the invention may contain a surfactant.
• a surfactant When a surfactant is contained, it is possible to form a pattern with excellent adhesion and fewer development defects.
• the surfactant is preferably a fluorine-based and/or silicon-based surfactant.
• Fluorinated and/or silicon-based surfactants include surfactants disclosed in paragraphs [0218] and [0219] of WO2018/193954.
• One type of these surfactants may be used alone, or two or more types may be used.
• the content of the surfactant is preferably 0.0001 to 2.0% by mass, preferably 0.0005 to 1.0%, based on the total solid content of the composition. % by mass is more preferred, and 0.1 to 1.0% by mass is even more preferred.
• the composition of the invention preferably contains a solvent.
• Solvent consists of (M1) propylene glycol monoalkyl ether carboxylate and (M2) propylene glycol monoalkyl ether, lactate, acetate, alkoxypropionate, linear ketone, cyclic ketone, lactone, and alkylene carbonate. It is preferable to include at least one selected from the group.
• the solvent may further contain components other than components (M1) and (M2).
• a combination of the above-described solvent and the above-described resin is preferable from the viewpoint of improving the coatability of the composition of the present invention and reducing the number of pattern development defects. Since the solvent described above has a good balance of solubility, boiling point, and viscosity of the resin described above, it is possible to suppress unevenness in the thickness of the resist film and generation of deposits during spin coating. Details of component (M1) and component (M2) are described in paragraphs [0218] to [0226] of WO2020/004306, the contents of which are incorporated herein.
• the content of components other than components (M1) and (M2) is preferably 5 to 30% by mass relative to the total amount of the solvent.
• the content of the solvent in the composition of the present invention is preferably determined so that the solid content concentration is 0.5 to 30% by mass, more preferably 1 to 20% by mass. By doing so, the coatability of the composition of the present invention can be further improved.
• the solid content means all components other than the solvent, and as described above, it means the components that form the actinic ray-sensitive or radiation-sensitive film.
• the solid content concentration is the mass percentage of the mass of other components excluding the solvent relative to the total mass of the composition of the present invention. "Total solid content” refers to the total mass of components excluding the solvent from the total composition of the composition of the present invention.
• the “solid content” is a component excluding the solvent, and may be solid or liquid at 25° C., for example.
• the composition of the present invention contains a dissolution-inhibiting compound, a dye, a plasticizer, a photosensitizer, a light-absorbing agent, and/or a compound that promotes solubility in a developer (for example, a phenolic compound having a molecular weight of 1000 or less, or An alicyclic or aliphatic compound containing a carboxyl group) may further be included.
• a dissolution-inhibiting compound for example, a phenolic compound having a molecular weight of 1000 or less, or An alicyclic or aliphatic compound containing a carboxyl group
• the “dissolution-inhibiting compound” is a compound with a molecular weight of 3000 or less, which is decomposed by the action of an acid to reduce its solubility in an organic developer.
• the resist composition of the present specification is suitably used as a photosensitive composition for EB exposure and a photosensitive composition for EUV exposure.
• EUV light has a wavelength of 13.5 nm, which is shorter than ArF (wavelength 193 nm) light and the like, so the number of incident photons is smaller when exposed with the same sensitivity. Therefore, the influence of "photon shot noise", in which the number of photons stochastically varies, is large, leading to deterioration of LER and bridge defects.
• photon shot noise there is a method of increasing the number of incident photons by increasing the amount of exposure, but this is a trade-off with the demand for higher sensitivity.
• Step 1 A step of forming an actinic ray-sensitive or radiation-sensitive film on a substrate using an actinic ray-sensitive or radiation-sensitive resin composition
• Step 2 A step of exposing the actinic ray-sensitive or radiation-sensitive film 3: Step of developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer
• Step 1 actinic ray-sensitive or radiation-sensitive film forming step
• Step 1 is a step of forming an actinic ray-sensitive or radiation-sensitive film on a substrate using an actinic ray-sensitive or radiation-sensitive resin composition.
• a method for forming an actinic ray-sensitive or radiation-sensitive film (preferably a resist film) on a substrate from the actinic ray-sensitive or radiation-sensitive resin composition includes, for example, coating the composition of the present invention on the substrate. method.
• the pore size of the filter is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, and even more preferably 0.03 ⁇ m or less.
• Filters are preferably made of polytetrafluoroethylene, polyethylene, or nylon.
• compositions of the present invention can be applied onto substrates such as those used in the manufacture of integrated circuit devices (eg, silicon, silicon dioxide coatings) by any suitable coating method such as a spinner or coater.
• the coating method is preferably spin coating using a spinner.
• the rotation speed for spin coating using a spinner is preferably 1000 to 3000 rpm.
• the substrate may be dried to form an actinic ray-sensitive or radiation-sensitive film. If necessary, various undercoat films (inorganic film, organic film, antireflection film) may be formed under the actinic ray-sensitive or radiation-sensitive film.
• Heating can be carried out by a means provided in a normal exposure machine and/or a developing machine, and may be carried out using a hot plate or the like.
• the heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, even more preferably 80 to 130°C.
• the heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, even more preferably 60 to 600 seconds.
• the film thickness of the actinic ray-sensitive or radiation-sensitive film is not particularly limited, it is preferably 10 to 120 nm from the viewpoint of forming finer patterns with higher precision.
• the film thickness of the actinic ray-sensitive or radiation-sensitive film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm.
• the thickness of the actinic ray-sensitive or radiation-sensitive film is more preferably 10 to 120 nm, still more preferably 15 to 90 nm.
• a topcoat composition may be used to form a topcoat on the upper layer of the actinic ray-sensitive or radiation-sensitive film.
• the topcoat composition does not mix with the actinic ray-sensitive or radiation-sensitive film and can be uniformly applied over the actinic ray- or radiation-sensitive film.
• the topcoat is not particularly limited, and a conventionally known topcoat can be formed by a conventionally known method. can be formed.
• Specific examples of basic compounds that the topcoat may contain include basic compounds that the resist composition may contain.
• the topcoat also preferably contains a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond.
• Step 2 is the step of exposing the actinic ray-sensitive or radiation-sensitive film.
• the exposure method include a method of irradiating the formed actinic ray-sensitive or radiation-sensitive film with actinic rays or radiation through a predetermined mask.
• Actinic rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, preferably 250 nm or less, more preferably 220 nm or less, 1 to 200 nm Particularly preferred are wavelengths of deep UV light, specifically KrF excimer lasers (248 nm), ArF excimer lasers (193 nm), F2 excimer lasers (157 nm), EUV (13.5 nm), X-rays, and electron beams.
• baking is preferably performed before development. Baking accelerates the reaction in the exposed area, resulting in better sensitivity and pattern shape.
• the heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, even more preferably 80 to 130°C.
• the heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, even more preferably 30 to 120 seconds. Heating can be carried out by a means provided in a normal exposing machine and/or developing machine, and may be carried out using a hot plate or the like. This step is also called a post-exposure bake.
• Step 3 is a step of developing the exposed actinic ray-sensitive or radiation-sensitive film using a developer to form a pattern.
• the developer may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer).
• 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 the developer on the surface of the substrate for a certain period of time by raising the developer by surface tension (puddle method). method), a method of spraying the developer onto the substrate surface (spray method), and 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 (dynamic dispensing method). ). Further, after the step of developing, a step of stopping development may be performed while replacing the solvent with another solvent.
• the development time is not particularly limited as long as the resin in the unexposed area is sufficiently dissolved, and is preferably 10 to 300 seconds, more preferably 20 to 120 seconds.
• the temperature of the developer is preferably 0 to 50°C, more preferably 15 to 35°C.
• alkaline aqueous solution containing alkali is not particularly limited, for example, quaternary ammonium salts represented by tetramethylammonium hydroxide, inorganic alkalis, primary amines, secondary amines, tertiary amines, alcohol amines, or cyclic amines. and an alkaline aqueous solution containing Among them, the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt represented by tetramethylammonium hydroxide (TMAH). Suitable amounts of alcohols, surfactants and the like may be added to the alkaline developer.
• the alkali concentration of the alkali developer is usually preferably 0.1 to 20% by mass.
• the pH of the alkaline developer is preferably 10.0 to 15.0.
• the organic developer is a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. Preferably.
• a plurality of the above solvents may be mixed, or may be mixed with a solvent other than the above or water.
• the water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and particularly preferably substantially free of water.
• the content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, and 90% by mass or more and 100% by mass with respect to the total amount of the developer. The following are more preferable, and 95% by mass or more and 100% by mass or less are particularly preferable.
• the pattern forming method preferably includes a step of washing with a rinse after step 3.
• Pure water is an example of the rinse solution used in the rinse step after the step of developing with an alkaline developer.
• An appropriate amount of surfactant may be added to pure water.
• An appropriate amount of surfactant may be added to the rinse solution.
• the rinse solution used in the rinse step after the development step using the organic developer is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used.
• the rinse solution should contain at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. is preferred.
• the method of the rinsing step is not particularly limited. For example, a method of continuously discharging the rinsing liquid onto the substrate rotating at a constant speed (rotation coating method), or a method of immersing the substrate in a tank filled with the rinsing liquid for a certain period of time. a method (dip method) and a method of spraying a rinse liquid onto the substrate surface (spray method).
• the pattern forming method may include a heating step (Post Bake) after the rinsing step. In this step, the developing solution and the rinse solution remaining between the patterns and inside the patterns due to baking are removed. In addition, this process smoothes the resist pattern, and has the effect of improving the roughness of the surface of the pattern.
• the heating step after the rinsing step is usually carried out at 40 to 250° C. (preferably 90 to 200° C.) for 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).
• the substrate may be etched using the formed pattern as a mask. That is, the pattern formed in step 3 may be used as a mask to process the substrate (or the underlying film and substrate) to form a pattern on the substrate.
• the method for processing the substrate (or the underlying film and the substrate) is not particularly limited, but the substrate (or the underlying film and the substrate) is dry-etched using the pattern formed in step 3 as a mask.
• a method of forming a pattern is preferred. Dry etching is preferably oxygen plasma etching.
• composition of the present specification and various materials used in the pattern forming method of the present specification are It is preferable not to contain impurities such as metals.
• the content of impurities contained in these materials is preferably 1 mass ppm or less, more preferably 10 mass ppb or less, still more preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less.
• the lower limit is not particularly limited, and is preferably 0 mass ppt or more.
• examples of metal impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn.
• Methods for reducing impurities such as metals contained in various materials include, for example, a method of selecting raw materials with a low metal content as raw materials constituting various materials, and a method of filtering raw materials constituting various materials with a filter. and a method of performing distillation under conditions in which contamination is suppressed as much as possible by, for example, lining the inside of the apparatus with Teflon (registered trademark).
• impurities may be removed with an adsorbent, or filter filtration and adsorbent may be used in combination.
• adsorbent known adsorbents can be used.
• inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.
• metal impurities such as metals contained in the various materials described above, it is necessary to prevent metal impurities from entering during the manufacturing process. Whether the metal impurities are sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of the metal component contained in the cleaning liquid used for cleaning the manufacturing equipment.
• the content of the metal component contained in the cleaning liquid after use is preferably 100 mass ppt (parts per trillion) or less, more preferably 10 mass ppt or less, and even more preferably 1 mass ppt or less.
• the lower limit is not particularly limited, and is preferably 0 mass ppt or more.
• Organic processing liquids such as rinsing liquids should contain conductive compounds to prevent damage to chemical piping and various parts (filters, O-rings, tubes, etc.) due to electrostatic charging and subsequent electrostatic discharge.
• the conductive compound is not particularly limited, and examples thereof include methanol.
• the amount added is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, from the viewpoint of maintaining preferable developing properties or rinsing properties.
• the lower limit is not particularly limited, and is preferably 0.01% by mass or more.
• chemical liquid pipe for example, SUS (stainless steel), antistatic treated polyethylene, polypropylene, or various pipes coated with fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can be used.
• Antistatic treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can also be used for filters and O-rings.
• the present specification also relates to an electronic device manufacturing method, including the pattern forming method described above, and an electronic device manufactured by this manufacturing method.
• a preferred embodiment of the electronic device of the present specification includes a mode in which it is installed in electric/electronic equipment (household appliances, OA (Office Automation), media-related equipment, optical equipment, communication equipment, etc.).
• the method for producing the compound represented by the general formula (2) is not particularly limited, but for example, a solution containing a raw material monomer having a phenolic hydroxyl group before being protected by the structure represented by the general formula (1) can be obtained by adding a compound represented by the following general formula (1a) in the presence of a basic compound and reacting the two.
• X, R 1 , k, n and m in general formula (1a) are synonymous with X, R 1 , k, n and m in general formula (1).
• Examples of basic compounds include 4-dimethylaminopyridine and triethylamine.
• the reaction time is not particularly limited, preferably 1 to 12 hours. Moreover, the reaction temperature is preferably 0 to 80°C.
• the method for producing the compound represented by the general formula (3) is not particularly limited. By reacting both, an acenaphthene compound having a partial structure in which the phenolic hydroxyl group is protected by the structure represented by the general formula (1) is obtained, and a 1,2-dihalogenated acenaphthylene compound is obtained by a halogenation reaction. After that, it can be converted to an acenaphthylene compound by dehalogenation.
• Basic compounds include 4-dimethylaminopyridine and triethylamine.
• the reaction time of the acenaphthene compound and the compound represented by general formula (1a) is not particularly limited, and is preferably 1 to 12 hours. Moreover, the reaction temperature is preferably 0 to 80°C.
• Halogenating agents in the halogenation reaction include N-bromosuccinimide, bromine, N-iodosuccinimide, iodine, N-chlorosuccinimide, chlorine and the like.
• the reaction time for the halogenation reaction is not particularly limited, and is preferably 1 to 12 hours. Moreover, the reaction temperature is preferably 0 to 130°C.
• Examples of the dehalogenating agent in the dehalogenation include potassium iodide and Zn (zinc).
• the reaction time of the dehalogenation reaction is not particularly limited, and is preferably 1 to 12 hours. Moreover, the reaction temperature is preferably 0 to 130°C.
• the present invention also relates to resins containing repeating units derived from the monomers represented by formula (2) or (3) above. Preferred aspects of each substituent of the monomer represented by general formula (2) or (3) and examples of preferred compounds are as described above.
• Other repeating units in the resin containing a repeating unit derived from a monomer represented by general formula (2) or (3) include repeating units other than the repeating unit (a1) described in the resin (A) section above. and preferred examples are also the same.
• the method for producing the resin containing repeating units derived from the monomer represented by formula (2) or (3) is not particularly limited, and known production methods can be used.
• the production (synthesis) method includes, for example, a radical polymerization method.
• the radical polymerization method includes a batch polymerization method in which a monomer species, an initiator, etc. are dissolved in a solvent and then polymerized by heating, and a solution of a monomer species and an initiator in a heated solvent over 1 to 10 hours.
• a dropping polymerization method, which is added dropwise, is exemplified, and the dropping polymerization method is preferred.
• the monomer species a monomer represented by general formula (2) or (3) is essential, and if necessary, a monomer represented by any one of the above general formulas (4) to (6), etc. may be used.
• reaction solvents include ethers such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate; dimethylformamide and dimethylacetamide.
• amides such as; propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone and the like;
• the polymerization reaction is preferably carried out under an inert gas atmosphere such as nitrogen and/or argon.
• an inert gas atmosphere such as nitrogen and/or argon.
• commercially available radical initiators azo initiators, peroxides, etc.
• an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is more preferable.
• Specific examples of polymerization initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, and dimethyl 2,2'-azobis(2-methylpropionate).
• a polymerization initiator is added additionally or dividedly, and after the reaction is completed, the resin is recovered.
• the concentration of the reactants is preferably 5-50% by mass, more preferably 10-30% by mass.
• the reaction temperature is not particularly limited, and is generally preferably 10 to 150°C, more preferably 30 to 120°C, even more preferably 60 to 100°C.
• Purification methods include liquid extraction to remove residual monomers and/or oligomers by washing with water and/or a combination of appropriate solvents; solution such as ultrafiltration to extract and remove compounds with a specific molecular weight or less.
• a reprecipitation method in which a solution containing a resin precursor is dropped into a poor solvent to solidify the resin precursor in the poor solvent to remove residual monomers, etc.; Ordinary methods such as a purification method in a solid state such as washing with a solvent can be used.
• M-80-b (10.0 g) and N-bromosuccinimide (NBS) (11.7 g) were dissolved in ethyl acetate (AcOEt) (80.0 g). After the mixture was stirred at 80° C. for 2 hours, it was diluted with ethyl acetate (200 mL) and washed with saturated aqueous sodium hydrogencarbonate solution (150 mL) and distilled water (150 mL). By evaporating the solvent from the organic layer, M-80-c (17.4 g) was obtained (yield 99%).
• M-81-b (10.0 g) and N-bromosuccinimide (NBS) (11.7 g) were dissolved in ethyl acetate (AcOEt) (80.0 g). After the mixture was stirred at 80° C. for 2 hours, it was diluted with ethyl acetate (200 mL) and washed with saturated aqueous sodium hydrogencarbonate solution (150 mL) and distilled water (150 mL). By evaporating the solvent from the organic layer, M-81-c (14.6 g) was obtained (yield 99%).
• compositional ratio (mol% ratio; corresponding from left to right) of each repeating unit measured by 13 C-NMR (nuclear magnetic resonance) was 34/8/58. Further, the weight average molecular weight (Mw) was 6400 and the degree of dispersion (Mw/Mn) was 1.61. The weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) were measured by GPC (carrier: tetrahydrofuran (THF)) (in terms of polystyrene).
• GPC carrier: tetrahydrofuran (THF)
• the obtained A-1-2-a solution was reprecipitated with a large amount of heptane/ethyl acetate mixed solution, filtered, and the obtained solid was dried in vacuo to obtain 85 g of resin A-1-2-a. Ta.
• compositional ratio (mol% ratio; corresponding from left to right) of each repeating unit measured by 13 C-NMR was 40/13/47. Also, the weight average molecular weight (Mw) was 7100, and the degree of dispersion (Mw/Mn) was 1.61.
• the resulting A-1-3-a solution was reprecipitated with a large amount of heptane/ethyl acetate mixed solution, filtered, and the obtained solid was vacuum-dried to obtain 80 g of resin A-1-3-a. Ta.
• compositional ratio (mol% ratio; corresponding from left to right) of each repeating unit measured by 13 C-NMR was 22/12/66. Also, the weight average molecular weight (Mw) was 6900, and the degree of dispersion (Mw/Mn) was 1.59.
• the obtained A-1-4-a solution was reprecipitated with a large amount of heptane/ethyl acetate mixed solution, filtered, and the obtained solid was vacuum-dried to obtain 90 g of resin A-1-4-a. Ta.
• compositional ratio (mol% ratio; corresponding from left to right) of each repeating unit measured by 13 C-NMR was 38/9/53. Also, the weight average molecular weight (Mw) was 6500 and the degree of dispersion (Mw/Mn) was 1.54.
• Resin (A) [Various Components of Actinic Ray-Sensitive or Radiation-Sensitive Resin Composition] ⁇ Resin (A)>
• the resins (A) (resins A-1 to A-67, A-1R to A-2R) shown in Table 3 are shown below. Resins A-1 to A-67 and A-1R to A-2R were synthesized according to the synthesis method of resin A-1-1-a (Synthesis Example 4) described above.
• Table 1 shows the compositional ratio (mol% ratio; corresponding from left to right), weight average molecular weight (Mw), and dispersity (Mw/Mn) of each repeating unit shown later.
• the weight-average molecular weight (Mw) and dispersion degree (Mw/Mn) of resins A-1 to A-67 and A-1R to A-2R were measured by GPC (carrier: tetrahydrofuran (THF)) (polystyrene equivalent is).
• the resin composition ratio (mol% ratio) was measured by 13 C-NMR (nuclear magnetic resonance).
• Photoacid generator (B) The structures of the photoacid generators (B) (compounds B-1 to B-39) shown in Table 3 are shown below.
• Resins I-1 to I-8 shown in Table 3 are shown below.
• Resins I-1 to I-8 were synthesized according to the synthesis method of resin A-1-1-a described above (Synthesis Example 4).
• Table 2 shows the composition ratio (mol% ratio; corresponding from left to right), weight average molecular weight (Mw), and dispersity (Mw/Mn) of each repeating unit shown later.
• the weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) of the resins I-1 to I-8 were measured by GPC (carrier: tetrahydrofuran (THF)) (in terms of polystyrene).
• the resin composition ratio (mol% ratio) was measured by 13 C-NMR (nuclear magnetic resonance).
• H-1 Megafac F176 (manufactured by DIC Corporation, fluorine-based surfactant)
• H-2 Megafac R08 (manufactured by DIC Corporation, fluorine- and silicon-based surfactant)
• H-3 PF656 (manufactured by OMNOVA, fluorine-based surfactant)
• a pattern obtained for a silicon wafer having a resist film obtained using an EUV exposure apparatus (Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36, manufactured by Exitech)
• the pattern irradiation was carried out so that the average line width of was 20 nm.
• As the reticle a mask having a line size of 20 nm and a line:space ratio of 1:1 was used.
• the exposed resist film was baked at 90° C. for 60 seconds, developed with n-butyl acetate for 30 seconds, and spin-dried to obtain a negative pattern.
• the resist composition of the present invention has excellent defect performance (defect suppressing property) when a pattern is formed by organic solvent development.
• Examples 2-1 to 2-67, Comparative Examples 2-1 to 2-2> [EUV exposure, alkaline aqueous solution development]
• An underlayer film forming composition AL412 (manufactured by Brewer Science) was applied onto a silicon wafer with a diameter of 12 inches and baked at 205° C. for 60 seconds to form an underlayer film with a thickness of 20 nm.
• a resist composition shown in Table 3 was applied thereon and baked at 100° C. for 60 seconds to form a resist film having a thickness of 30 nm.
• a pattern obtained for a silicon wafer having a resist film obtained using an EUV exposure apparatus (Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36, manufactured by Exitech) The pattern irradiation was carried out so that the average line width of was 20 nm.
• As the reticle a mask having a line size of 20 nm and a line:space ratio of 1:1 was used.
• the exposed resist film was baked at 90° C. for 60 seconds, developed with a tetramethylammonium hydroxide aqueous solution (2.38 mass %) for 30 seconds, and then rinsed with pure water for 30 seconds. After that, it was spin-dried to obtain a positive pattern. Using the obtained positive pattern, defect suppression was evaluated in the same manner as described above.
• the resist composition of the present invention is excellent in defect performance (defect suppressing property) even when a pattern is formed by alkali development.

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• 2023
  • 2023-01-16 KR KR1020247027656A patent/KR102946530B1/ko active Active
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  • 2023-01-19 TW TW112102729A patent/TW202334752A/zh unknown
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  • 2024-08-19 US US18/808,397 patent/US20240419071A1/en active Pending

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