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
  • G03F7/20—Exposure; Apparatus therefor
  • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
  • G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
• • 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
  • C08F212/06—Hydrocarbons
• • 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
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
  • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
• • 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
  • G03F7/322—Aqueous alkaline compositions
• • 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, and an electronic device manufacturing method.
• a method of lithography includes a method of forming a resist film from a photosensitive composition, exposing the obtained film, and then developing it.
• EB Electro Beam
• EUV Extreme Ultraviolet
• a photosensitive composition containing a resin that improves the contrast of development with a developer by cutting the main chain by exposure and reducing the molecular weight is known, and it is also used as a photosensitive composition corresponding to the above light source. It is
• Patent Document 1 a polymer having a structural unit having a group that decomposes by the action of an acid and becomes alkali-soluble, and a structural unit derived from an acrylate monomer having a halogen atom or a cyano group at the ⁇ -position, and a radiation and an acid generator that generates an acid upon irradiation with a positive radiation-sensitive composition.
• Patent Document 2 discloses a positive radiation-sensitive compound containing a) a compound in which a carboxyl group is protected with an acid-leaving group having three or more aromatic rings and b) an acid generator that generates an acid upon exposure to radiation.
• Compositions are disclosed, specifically described as a), such as a copolymer of trityl ⁇ -chloroacrylate and p-hydroxy- ⁇ -methylstyrene.
• an object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition which is excellent in roughness performance and capable of forming a pattern with good rectangularity.
• Another object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and an electronic device manufacturing method using the actinic ray-sensitive or radiation-sensitive resin composition.
• X represents a halogen atom
• L P represents -COO- or an arylene group
• R Q represents a hydrogen atom or an organic group.
• R represents an alkyl group
• R 1 represents a hydroxyl group, a halogen atom, or an alkyl group.
• p represents an integer of 0 to 5; When p is an integer of 2 to 5, multiple R 1 may be the same or different.
• Y represents a halogen atom, a hydrogen atom, or an alkyl group.
• R Q1 to R Q3 each independently represent an alkyl group, a cycloalkyl group, or an alkenyl group, and two of R Q1 to R Q3 may combine with each other to form a ring.
• the compound that generates an acid upon exposure to actinic rays or radiation includes at least one selected from the group consisting of the following compounds (I) to (II): Actinic ray-sensitive or radiation-sensitive resin composition.
• Structural site Z1 Structural site consisting of an anion site A 1 ⁇ and a cation site M 1 + and forming a first acidic site represented by HA 1 upon irradiation with actinic rays or radiation
• Structural site Z2 Anion site A A structural moiety consisting of 2 ⁇ and a cationic moiety M 2 + and forming a second acidic site represented by HA 2 upon exposure to actinic rays or radiation provided that compound (I) satisfies condition I below.
• Condition I A compound PI obtained by replacing the cation site M 1 + in the structural site Z1 and the cation site M 2 + in the structural site Z2 in the compound (I) with H + in the structural site Z1 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 Z2 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 (II) A compound having two or more of the above structural moieties Z1 and one or more of the following structural moieties Z3, wherein two or more of the first acidic moieties derived from the above structural moieties Z1 are formed by irradiation with actinic rays or radiation. A compound that generates an acid containing the above structural site Z3.
• Structural site Z3 nonionic site capable of neutralizing acid
• Actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the actinic ray-sensitive or radiation-sensitive resin composition contains an acid diffusion inhibitor represented by the following general formula (XN): Or a radiation-sensitive resin composition.
• R XN represents a hydrocarbon group and M X + represents an organic cation.
• [9] forming an actinic ray-sensitive or radiation-sensitive film on a substrate from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [7]; exposing the actinic ray-sensitive or radiation-sensitive film; a step of developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer;
• a pattern forming method comprising: [10] The pattern forming method according to [9], wherein the exposure light source is EUV light. [11] The pattern forming method according to [9] or [10], wherein the developer is an alkaline developer. [12] [9] A method for manufacturing an electronic device, comprising the pattern forming method according to any one of [11].
• an actinic ray- or radiation-sensitive resin composition that is excellent in roughness performance and capable of forming a pattern with good rectangularity, and the actinic ray- or radiation-sensitive resin composition.
• An actinic ray-sensitive or radiation-sensitive film to be used, a pattern forming method, and a method of manufacturing an electronic device can be provided.
• 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.
• 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 light: Extreme Ultraviolet), X-rays, and electron beams ( EB means Electron Beam).
• light means actinic rays or radiation.
• exposure means, unless otherwise specified, not only exposure by the emission line spectrum of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV: Extreme ultraviolet), and X-rays, It also includes writing with electron beams and particle beams such as ion 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).
• HLC-8120 GPC manufactured by HLC-8120 GPC by GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 ⁇ L, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40 ° C., flow rate: 1.0 mL / min, detector : Defined as a polystyrene conversion value by a differential refractive index detector (Refractive Index Detector).
• 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 in detail below.
• the actinic ray-sensitive or radiation-sensitive resin composition is preferably a resist composition, and may be a positive resist composition or a negative resist composition.
• the resist composition may be a resist composition for alkali development or a resist composition for organic solvent development.
• the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably a positive resist composition for alkali development.
• the resist composition may be a chemically amplified resist composition or a non-chemically amplified resist composition.
• the resist composition is typically a chemically amplified resist composition.
• the actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also referred to as "the composition of the present invention") comprises a repeating unit A represented by the following general formula (1) and a general formula (2) and a resin containing repeating unit B represented by general formula (3) and repeating unit C represented by general formula (3), and a compound that generates an acid upon exposure to actinic rays or radiation.
• X represents a halogen atom
• L P represents -COO- or an arylene group
• R Q represents a hydrogen atom or an organic group.
• R represents an alkyl group
• R 1 represents a hydroxyl group, a halogen atom, or an alkyl group.
• p represents an integer of 0 to 5; When p is an integer of 2 to 5, multiple R 1 may be the same or different.
• Y represents a halogen atom, a hydrogen atom, or an alkyl group.
• R Q1 to R Q3 each independently represent an alkyl group, a cycloalkyl group, or an alkenyl group, and two of R Q1 to R Q3 may combine with each other to form a ring.
• composition of the present invention can form a pattern with excellent roughness performance and good rectangularity has not been completely clarified, but the present inventors have made the following I'm guessing.
• the resist pattern forming mechanism including the main chain scission mechanism, exposure causes acid generation and main chain scission of the resin.
• the main chain scission reduces the molecular weight of the resin in the exposed area, thereby increasing the plasticity of the exposed area and promoting the diffusion of the generated acid.
• the resist pattern formation mechanism including the main chain scission mechanism is a deprotection mechanism by the action of acid, that is, in a resin containing a structure in which a polar group is protected by a group (leaving group) that leaves by the action of acid,
• it does not include a mechanism in which the leaving group is deprotected by the action of an acid, and even if it is multiplied with the deprotection mechanism, the leaving group has low reactivity and main chain scission does not occur. Due to the fact that it does not occur sufficiently, the rectangularity of the pattern shape in the depth direction due to insufficient contrast has become a problem.
• the resin contained in the composition of the present invention contains a repeating unit A represented by the general formula (1) in which a main chain scission mechanism is expressed by having a halogen atom at the ⁇ -position, and the carboxyl group is highly reactive and a repeating unit C represented by the general formula (3) having an acid-decomposable group protected by a leaving group (group decomposed by the action of an acid to increase polarity).
• the main chain scission mechanism promotes acid diffusion, and the synergistic effect of further promoting diffusion-promoted deprotection due to the presence of a highly reactive leaving group makes it possible to achieve a significant increase in contrast. It is possible to improve not only roughness performance but also shape rectangularity.
• the resin contained in the composition of the present invention contains a repeating unit B represented by general formula (2) having an ⁇ -alkylstyrene structure.
• a repeating unit B represented by general formula (2) having an ⁇ -alkylstyrene structure.
• the composition of the present invention comprises a repeating unit A represented by the general formula (1), a repeating unit B represented by the general formula (2), and a repeating unit C represented by the general formula (3). containing resin (also referred to as resin (A)).
• Resin (A) contains a repeating unit A represented by the following general formula (1). By including the ⁇ -halogen unit represented by the general formula (1) in the resin A, a main chain scission mechanism by exposure is exhibited. Resin (A) is a resin whose main chain is cleaved by exposure.
• X represents a halogen atom
• L P represents -COO- or an arylene group
• R Q represents a hydrogen atom or an organic group.
• the halogen atom represented by X includes a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, preferably a chlorine atom.
• L P represents -COO- or an arylene group.
• the arylene group represented by L P is preferably an arylene group having 6 to 14 carbon atoms, such as a phenylene group, a naphthylene group, and an anthryl group.
• RQ represents a hydrogen atom or an organic group.
• examples of the organic group represented by RQ include a group having a lactone group, a sultone group, or a carbonate group, a group having an acid group, a group having a hydroxyl group, and the like.
• the lactone group or sultone group in the group having a lactone group, a sultone group, or a carbonate group represented by RQ may have a lactone structure or a sultone structure.
• the lactone structure or sultone structure is preferably a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure.
• the lactone group or sultone group is a lactone structure represented by any of the following formulas (LC1-1) to (LC1-21), or any of the following formulas (SL1-1) to (SL1-3).
• a lactone group or a sultone group obtained by extracting one or more hydrogen atoms from the ring member atoms of the sultone structure is preferable.
• 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.
• the acid-decomposable group is as described below.
• a cyclic carbonate group is preferable as the carbonate group.
• the cyclic carbonate group may further have a substituent.
• a group having a lactone group, a sultone group, or a carbonate group represented by R Q is preferably, for example, a group represented by the following formula (AI). -L Q1 -R A1 (AI)
• L Q1 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 represents a divalent linking group combining these.
• L Q1 is preferably a single bond or a linking group represented by -L Q2 -CO 2 -.
• L Q2 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.
• R A1 is a group obtained by extracting one hydrogen atom from a ring member atom of a lactone structure represented by any one of formulas (LC1-1) to (LC1-21), 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), or a cyclic carbonate group.
• any optical isomer may be used.
• one kind of optical isomer may be used alone, or a plurality of optical isomers may be mixed and used.
• its optical purity (ee) is preferably 90 or more, more preferably 95 or more.
• 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 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.
• one or more (preferably 1 to 2) fluorine atoms may be substituted with a group other than a fluorine atom (such as an alkoxycarbonyl group).
• a fluorine atom such as an alkoxycarbonyl group.
• 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 acid group a phenolic hydroxyl group or a fluorinated alcohol group is more preferable.
• the group having an acid group is more preferably an aryl group substituted with a hydroxyl group or a hydrocarbon group substituted with a fluoroalcohol group.
• the hydroxyl-substituted aryl group represented by R Q is preferably a hydroxyl-substituted aryl group having 6 to 14 carbon atoms, and more preferably a group represented by the following formula (A-II).
• R A2 is 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 It represents an aryloxycarbonyl group, and when there are a plurality of groups, they may be the same or different. When it has multiple R A2 , they may be combined with each other to form a ring.
• R A2 is preferably a hydrogen atom.
• a represents an integer of 1 to 3;
• b represents an integer from 0 to (5-a).
• a hydrocarbon group substituted with a fluoroalcohol group, represented by R Q is preferably a group represented by the following formula (A-III). -L Q3 -(R A3 )c (A-III)
• L Q3 represents a (c+1) valent hydrocarbon group.
• R A3 represents a fluorinated alcohol group, and when there are a plurality of groups, they may be the same or different.
• c represents an integer of 1 to 3;
• hydrocarbon group represented by L Q3 for example, in the case of a divalent hydrocarbon group, a linear or branched alkylene group, a monocyclic or polycyclic cycloalkylene group, a monocyclic or polycyclic arylene groups, divalent groups formed by combining these groups, and the like.
• alkylene group an alkylene group having 1 to 4 carbon atoms such as a methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group and isobutylene group is preferable.
• the cycloalkylene group is preferably a cycloalkylene group having 5 to 14 carbon atoms, and a monocyclic cycloalkylene group such as a cyclopentylene group and a cyclohexylene group, or a norbornyl group, a tetracyclodecanyl group, a tetracyclo
• a polycyclic cycloalkylene group obtained by removing one hydrogen atom from a polycyclic cycloalkyl group such as a dodecanyl group and an adamantyl group is preferred.
• the arylene group is preferably an arylene group having 6 to 14 carbon atoms, such as a phenylene group, naphthylene group, and anthryl group.
• the (c+1)-valent hydrocarbon group includes a group obtained by removing (c-1) hydrogen atoms from the above divalent hydrocarbon group.
• RA3 represents a fluorinated alcohol group, preferably a hexafluoroisopropanol group.
• c represents an integer of 1 to 3, preferably 1 or 2.
• the group having a hydroxyl group represented by RQ is preferably a group having an alicyclic hydrocarbon structure substituted with a hydroxyl group.
• the alicyclic hydrocarbon structure is preferably an adamantyl group, a diamantyl group, or a norbornane group.
• the hydroxyl group-containing group represented by R Q is preferably a group represented by the following general formulas (VIIa) to (VIIc).
• R 2c to R 4c each independently represent a hydrogen atom or a hydroxyl group. At least one of R 2c to R 4c represents a hydroxyl group. Preferably, one or two of R 2c to R 4c are hydroxyl groups and the rest are hydrogen atoms. In general formula (VIIa), more preferably two of R 2c to R 4c are hydroxyl groups and the rest are hydrogen atoms.
• repeating unit A represented by formula (1) Specific examples of the repeating unit A represented by formula (1) are listed below, but the present invention is not limited thereto.
• * represents a bond.
• the repeating unit A may be used singly or in combination. From the viewpoint of improving the efficiency of main chain scission, the content of the repeating unit A in the resin (A) is preferably 10 mol% or more based on the total repeating units contained in the resin (A). mol% or more is more preferable.
• the upper limit is preferably 70 mol % or less, more preferably 60 mol % or less.
• the total content of the above repeating unit A and the repeating unit C described later with respect to all repeating units contained in the resin (A) is 60. It is preferably mol % or more, more preferably 65 mol % or more, and even more preferably 70 mol % or more.
• the upper limit is preferably 90 mol % or less, more preferably 85 mol % or less.
• Resin A contains a repeating unit B represented by the following general formula (2).
• a repeating unit B represented by the following general formula (2) By containing the ⁇ -alkylstyrene unit represented by the general formula (2) in the resin A, main chain scission due to exposure generated from the ⁇ -halogen unit represented by the general formula (1) is promoted. it is conceivable that.
• R represents an alkyl group
• R 1 represents a hydroxyl group, a halogen atom, or an alkyl group.
• p represents an integer of 0 to 5; When p is an integer of 2 to 5, multiple R 1 may be the same or different.
• R represents an alkyl group.
• the alkyl group represented by R may be linear or branched, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and a methyl group. is more preferred.
• R1 represents a hydroxyl group, a halogen atom, or an alkyl group.
• a halogen atom represented by R 1 includes a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
• the alkyl group represented by R 1 may be linear or branched, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.
• the alkyl group represented by R 1 may have a substituent, and examples of the substituent include halogen atoms, hydroxyl groups, and alkoxy groups.
• R 1 preferably represents a hydroxyl group, a fluorine atom, an iodine atom, or a trifluoromethyl group, and more preferably represents a hydroxyl group from the viewpoint of increasing sensitivity.
• p represents an integer of 0-5.
• p is preferably an integer of 1 to 3, more preferably 1.
• repeating unit B represented by formula (2) Specific examples of the repeating unit B represented by formula (2) are listed below, but the present invention is not limited thereto.
• * represents a bond.
• the repeating unit B may be used singly or in combination.
• the content of the repeating unit B in the resin (A) is preferably 10 mol % or more, more preferably 15 mol % or more, based on the total repeating units contained in the resin (A).
• the upper limit is preferably 50 mol % or less, more preferably 45 mol % or less.
• the resin (A) contains a repeating unit C represented by the following general formula (3) having an acid-decomposable group.
• An acid-decomposable group is a group that is decomposed by the action of an acid to form a polar 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. Further, since the acid-decomposable group contained in the repeating unit C has a highly reactive leaving group, deprotection by the action of acid proceeds further, and a significant increase in contrast becomes possible.
• Y represents a halogen atom, a hydrogen atom, or an alkyl group.
• R Q1 to R Q3 each independently represent an alkyl group, a cycloalkyl group, or an alkenyl group, and two of R Q1 to R Q3 may combine with each other to form a ring.
• Y represents a halogen atom, a hydrogen atom, or an alkyl group.
• the halogen atom represented by Y includes a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, preferably a fluorine atom or a chlorine atom, more preferably a chlorine atom.
• the repeating unit C also acts as a starting point for scission of the main chain by exposure.
• the alkyl group represented by Y may be linear or branched, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and a methyl group. is more preferred.
• Y preferably represents a halogen atom or an alkyl group, more preferably a fluorine atom, a chlorine atom, or a methyl group, and even more preferably a chlorine atom.
• R Q1 to R Q3 each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), or an alkenyl group (linear or branched chain). Two of R Q1 to R Q3 may combine to form a monocyclic or polycyclic ring.
• Alkyl groups represented by R Q1 to R Q3 include 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. is preferred.
• a cycloalkyl group having 5 to 14 carbon atoms is preferable, and a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, and a tetracyclodecanyl group.
• a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, and a tetracyclodecanyl group.
• tetracyclododecanyl groups and polycyclic cycloalkyl groups such as adamantyl groups are preferred.
• the alkenyl group represented by R Q1 to R Q3 is preferably an alkenyl group having 2 to 5 carbon atoms, preferably a vinyl group.
• the ring formed by combining two of R Q1 to R Q3 is preferably a cycloalkyl group.
• the cycloalkyl group formed by combining two of R Q1 to R Q3 includes a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetra
• a polycyclic cycloalkyl group such as a cyclododecanyl 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 It may be substituted with a vinylidene group.
• one or more ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.
• R Q1 to R Q3 for example, it is preferable that R Q1 is a methyl group or an ethyl group, and R Q2 and R Q3 combine to form the above-described cycloalkyl group.
• An alkyl group, a cycloalkyl group, an alkenyl group represented by R Q1 to R Q3 and a ring formed by bonding two of R Q1 to R Q3 may further have a substituent. good.
• the substituents are not particularly limited, and examples thereof include alkyl groups (having 1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (having 1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (having 2 to 4 carbon atoms). 6).
• Alkyl groups and alkoxy groups as additional substituents may be further substituted with other substituents (eg, halogen atoms and hydroxyl groups).
• the number of carbon atoms in the substituent is preferably 8 or less.
• repeating unit C represented by formula (3) Specific examples of the repeating unit C represented by formula (3) are listed below, but the present invention is not limited thereto.
• * represents a bond.
• the repeating unit C may be used singly or in combination.
• the content of the repeating unit C in the resin (A) is preferably 40 mol % or more, more preferably 45 mol %, based on the total repeating units contained in the resin (A) from the viewpoint of increasing the contrast.
• the above is more preferable, and 50 mol % or more is even more preferable.
• the upper limit is preferably 75 mol % or less, more preferably 70 mol % or less.
• the total content of the repeating unit A and the repeating unit C is preferably 60 mol% or more with respect to all repeating units contained in the resin (A). 65 mol % or more is more preferable, and 70 mol % or more is even more preferable.
• the upper limit is preferably 90 mol % or less, more preferably 85 mol % or less.
• the sum of the content of the repeating unit A, the content of the repeating unit B, and the content of the repeating unit C is 75 mol with respect to all repeating units contained in the resin (A). % or more, and more preferably 80 mol % or more.
• the upper limit is preferably 100 mol % or less, more preferably 95 mol % or less.
• the resin (A) may contain other repeating units as repeating units other than the repeating units A to C as long as the effect of the present invention is not impaired.
• 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).
• 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 composition of the present invention 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.
• the resin (A) may have a repeating unit having an acid group in addition to the repeating units A to C described above.
• 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 total content of acid groups in the resin (A) is not particularly limited, but is often 0.2 to 6.0 mmol/g.
• 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.
• one or more (preferably 1 to 2) fluorine atoms may be substituted with a group other than a fluorine atom (such as an alkoxycarbonyl group).
• a fluorine atom such as an alkoxycarbonyl group.
• 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 preferably a repeating unit different from repeating units having a lactone group, a sultone group, or a carbonate group, which will be described later.
• 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, 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 1 or 2.
• R represents a hydrogen atom or a methyl group
• a represents 2 or 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).
• 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 repeating units A and B have an acid group, it is preferable to make the total content including these within the above range.
• the resin (A) has neither an acid-decomposable group nor an acid group, and has a fluorine atom, a bromine atom, or an iodine atom, in addition to the repeating units A to C and the ⁇ repeating unit having an acid group> described above. It may have a repeating unit (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 a photoacid-generating group> is a ⁇ repeating unit having a lactone group, a sultone group, or a carbonate group> described later.
• 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;
• the repeating unit represented by the formula (C) is a repeating unit different from the repeating unit B represented by the above general formula (2).
• 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.
• the repeating units A to C are repeating units containing at least one of a fluorine atom, a bromine atom and an iodine atom, the total content including these is preferably within the above range.
• the resin (A) comprises, apart from the repeating units A to C, 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. may have. 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 of the above formulas (LC1-1) to (LC1-21), or any of the above 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).
• Rb 0 represents a hydrogen 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. 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. Among them, 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.
• one kind of optical isomer may be used alone, or a plurality of optical isomers may be mixed and 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 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 .
• Me represents a methyl group.
• the total content of repeating units having a lactone group, a sultone group, or a carbonate group is preferably 1 mol% or more, and preferably 10 mol, based on the total repeating units of the resin (A). % or more is more preferable.
• 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 repeating unit A is a repeating unit having a lactone group, a sultone group, or a carbonate group
• the total content including this is preferably within the above range.
• the resin (A) is a repeating unit having repeating units A to C and a group that generates an acid upon irradiation with actinic rays or radiation (hereinafter also referred to as a "photoacid-generating group"), in addition to the repeating units A to C and the above repeating units. May have units.
• 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, relative to 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 Tg at each mass ratio is calculated using Fox's formula (described in Materials Letters 62 (2008) 3152, etc.), and these are summed up 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 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) has, apart from the repeating units A to C, a repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group. good too.
• R Q in the general formula (1) is a lactone group, a sultone group, or a carbonate group. and repeating units described in ⁇ Repeating Units Having a Lactone Group, a Sultone Group, or a Carbonate Group>.
• the preferable content is also as described in ⁇ Repeating unit having lactone group, sultone group, or carbonate group>.
• the resin (A) may have a repeating unit having a hydroxyl group or a cyano group apart from the repeating units A to C. 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.
• the resin (A) may have a repeating unit having an alkali-soluble group apart from the repeating units A to C.
• 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.
• the resin (A) may have a repeating unit that has an alicyclic hydrocarbon structure and does not exhibit acid decomposability, apart from the repeating units A to C. 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 have repeating units other than the repeating units described above.
• the resin (A) has repeating units selected from the group consisting of repeating units having an oxathian ring group, repeating units having an oxazolone ring group, repeating units having a dioxane ring group, and repeating units having a hydantoin ring group. You may have Specific examples of repeating units other than the repeating units described above are shown below.
• 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
• the resin (A) in particular, when the composition is used as an actinic ray-sensitive or radiation-sensitive resin composition for ArF, all of the repeating units are repeating units derived from a compound having an ethylenically unsaturated bond. It is preferably composed of
• 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, even 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 resin (A) is preferably 40.0 to 99.9% by mass, more preferably 50.0 to 95.0% by mass, based on the total solid content of the composition. , 60.0 to 90.0 mass % is more preferable.
• the resin (A) may be used singly or in combination.
• the composition of the present invention contains a compound that generates an acid upon exposure to actinic rays or radiation (also referred to as a photoacid generator (B)).
• 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).
• the form of a low-molecular-weight compound and the form incorporated into a part of a polymer for example, the resin (A) described above
• 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) 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
• a hydroxyl group a carboxyl group, an ester group, a sulfinyl group, a sulfonyl group, an alkylthio group, or a phenylthio group.
• 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. It is also preferable to form an acid-decomposable group by any combination of the above substituents.
• 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 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.
• Two of Rx 1 to Rx 3 may combine to form a monocyclic or polycyclic ring.
• 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 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.
• 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 have fluorine as a substituent. It is also preferred to have an atom or an iodine atom.
• 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 each 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), cycloalkyl groups (preferably 3 to 15 carbon atoms), aryl groups (preferably 6 to 14 carbon atoms), alkoxycarbonyl groups (preferably 2 to 7 carbon atoms), acyl groups ( 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 to 15 carbon atoms
• aralkyl group in the aralkylcarboxylate anion an aralkyl group having 7 to 14 carbon atoms is preferable.
• 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 examples 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 preferred.
• 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.
• the substituent is not particularly limited, but a group that is not an electron-withdrawing group is preferred.
• Groups that are not electron-withdrawing groups include, for example, 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 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 also preferably contains at least one selected from the group consisting of compounds (I) to (II). As a preferred embodiment, the photoacid generator is at least one selected from the group consisting of compounds (I) to (II).
• Compound (I) is a compound having one or more structural moieties Z1 below and one or more structural moieties Z2 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 Z2 described below.
• Structural site Z1 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 Z2 anionic site A structural site consisting of A 2 - and a cation site M 2 + and forming a second acidic site represented by HA 2 upon exposure to actinic rays or radiation.
• the compound (I) satisfies Condition I below. .
• Condition I A compound PI obtained by replacing the cation site M 1 + in the structural site Z1 and the cation site M 2 + in the structural site Z2 in the compound (I) with H + in the structural site Z1 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 Z2 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 (I) is, for example, an acid-generating compound having one first acidic site derived from the structural site Z1 and one second acidic site derived from the structural site Z2
• 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 Z1 and one second acidic site derived from the structural site Z2
• compound PI corresponds to "a compound having two HA 1 and one HA 2 ".
• 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 Z1 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 Z1 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 (I) is not particularly limited, but includes, for example, compounds represented by formulas (Ia-1) to (Ia-5) described below.
• the compound represented by formula (Ia-1) generates an acid represented by HA 11 -L 1 -A 12 H upon exposure to actinic rays or radiation.
• M 11 + and M 12 + each independently represent an organic cation.
• a 11 - and A 12 - each independently represent a monovalent anionic functional group.
• L 1 represents a divalent linking group.
• M 11 + and M 12 + may be the same or different.
• a 11 - and A 12 - may be the same or different, but are preferably different from each other.
• the acid dissociation constant a2 derived from the acidic site represented by HA11 is greater than the acid dissociation constant a1 derived from the acidic site represented by HA11 .
• the preferred values of the acid dissociation constant a1 and the acid dissociation constant a2 are as described above.
• the same acid is generated from compound PIa and the compound represented by formula (Ia-1) upon exposure to actinic rays or radiation.
• At least one of M 11 + , M 12 + , A 11 ⁇ , A 12 ⁇ , and L 1 may have an acid-decomposable group as a substituent.
• the organic cations represented by M 11 + and M 12 + include the organic cations represented by M 1 + described above.
• the monovalent anionic functional group represented by A 11 - intends a monovalent group containing the above-described anion site A 1 - .
• the monovalent anionic functional group represented by A 12 - intends a monovalent group containing the above-mentioned anion site A 2 - .
• the monovalent anionic functional groups represented by A 11 - and A 12 - include any of the above formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6). It is preferably a monovalent anionic functional group containing an anion site, selected from the group consisting of formulas (AX-1) to (AX-3) and formulas (BX-1) to (BX-7) is more preferably a monovalent anionic functional group.
• the monovalent anionic functional group represented by A 11 - is, among others, a monovalent anionic functional group represented by any one of formulas (AX-1) to (AX-3). preferable.
• As the monovalent anionic functional group represented by A 12 - monovalent anionic functional groups represented by any one of formulas (BX-1) to (BX-7) are preferred, and A monovalent anionic functional group represented by any one of (BX-1) to (BX-6) is more preferred.
• R A1 and R A2 each independently represent a monovalent organic group. * represents a binding position.
• the monovalent organic group represented by R A1 is not particularly limited, and examples thereof include a cyano group, a trifluoromethyl group and a methanesulfonyl group.
• the monovalent organic group represented by RA2 is preferably a linear, branched or cyclic alkyl group or aryl group.
• the number of carbon atoms in the alkyl group is preferably 1-15, more preferably 1-10, even more preferably 1-6.
• the above alkyl group may have a substituent.
• the substituent is preferably a fluorine atom or a cyano group, more preferably a fluorine atom.
• the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group.
• the aryl group is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
• the aryl group may have a substituent.
• the substituent is preferably a fluorine atom, an iodine atom, a perfluoroalkyl group (eg, preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms), or a cyano group, a fluorine atom, an iodine atom, or , perfluoroalkyl groups are more preferred.
• R 2 B represents a monovalent organic group.
• * represents a binding position.
• the monovalent organic group represented by RB is preferably a linear, branched or cyclic alkyl group or aryl group.
• the number of carbon atoms in the alkyl group is preferably 1-15, more preferably 1-10, even more preferably 1-6.
• the above alkyl group may have a substituent. Although the substituent is not particularly limited, the substituent is preferably a fluorine atom or a cyano group, more preferably a fluorine atom. When the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group.
• the carbon atom serving as the bonding position in the alkyl group has a substituent, it is also preferably a substituent other than a fluorine atom or a cyano group.
• the carbon atom to be the bonding position in the alkyl group is, for example, in the case of formulas (BX-1) and (BX-4), the carbon directly bonded to -CO- indicated in the formula in the alkyl group In the case of formulas (BX-2) and (BX-3), the carbon atom directly bonded to —SO 2 — indicated in the formula in the alkyl group corresponds to the formula (BX-6)
• the carbon atom in the alkyl group that is directly bonded to the N 2 - specified in the formula is applicable.
• a carbon atom of the alkyl group may be substituted with a carbonyl carbon.
• the aryl group is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
• the aryl group may have a substituent.
• substituents include a fluorine atom, an iodine atom, a perfluoroalkyl group (eg, preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), a cyano group, an alkyl group (eg, 1 to 10 carbon atoms).
• an alkoxy group eg, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.
• an alkoxycarbonyl group eg, 2 to 10 carbon atoms are preferred, and those having 2 to 6 carbon atoms are more preferred.
• the divalent linking group represented by L 1 is not particularly limited, and includes -CO-, -NR-, -O-, -S-, -SO-, -SO 2 - , an alkylene group (preferably having 1 to 6 carbon atoms, which may be linear or branched), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), divalent of an aliphatic heterocyclic group (preferably a 5- to 10-membered ring having at least one N atom, O atom, S atom, or Se atom in the ring structure, more preferably a 5- to 7-membered ring, a 5- to 6-membered ring is more preferable), a divalent aromatic heterocyclic group (preferably a 5- to 10-membered ring having at least one N atom, O atom, S atom, or Se atom in the ring structure, and a 5- to 7-membered
• the monovalent organic group is not particularly limited, for example, an alkyl group (preferably having 1 to 6 carbon atoms) is preferable.
• the alkylene group, the cycloalkylene group, the alkenylene group, the divalent aliphatic heterocyclic group, the divalent aromatic heterocyclic group, and the divalent aromatic hydrocarbon ring group have a substituent.
• Substituents include, for example, halogen atoms (preferably fluorine atoms).
• the divalent linking group represented by L1 is preferably a divalent linking group represented by formula (L1).
• L 111 represents a single bond or a divalent linking group.
• the divalent linking group represented by L 111 is not particularly limited, and may be, for example, —CO—, —NH—, —O—, —SO—, —SO 2 —, or have a substituent.
• Alkylene group preferably having 1 to 6 carbon atoms, which may be linear or branched
• optionally substituted cycloalkylene group preferably having 3 to 15 carbon atoms
• substituted An aryl group preferably having 6 to 10 carbon atoms
• a divalent linking group combining a plurality of these groups may be mentioned.
• the substituent is not particularly limited, and examples thereof include halogen atoms.
• Each Xf 1 independently represents a fluorine atom or an alkyl group substituted with at least one 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.
• Each Xf2 independently represents a hydrogen atom, an alkyl group optionally having a fluorine atom as a substituent, or a fluorine atom.
• the number of carbon atoms in this alkyl group is preferably 1-10, more preferably 1-4.
• Xf2 preferably represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, more preferably a fluorine atom or a perfluoroalkyl group.
• Xf 1 and Xf 2 are each independently preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF 3 .
• both Xf 1 and Xf 2 are more preferably fluorine atoms.
• * represents a binding position.
• a 21a - and A 21b - each independently represent a monovalent anionic functional group.
• the monovalent anionic functional groups represented by A 21a - and A 21b - are meant to be monovalent groups containing the above-described anionic site A 1 - .
• the monovalent anionic functional groups represented by A 21a - and A 21b - are not particularly limited.
• Anionic functional groups are included.
• a 22 - represents a divalent anionic functional group.
• the divalent anionic functional group represented by A 22 - intends a divalent linking group containing the above-mentioned anion site A 2 - .
• Examples of the divalent anionic functional group represented by A 22 - include divalent anionic functional groups represented by formulas (BX-8) to (BX-11) shown below.
• M 21a + , M 21b + , and M 22 + each independently represent an organic cation.
• the organic cations represented by M 21a + , M 21b + , and M 22 + are synonymous with M 11 + above, and the preferred embodiments are also the same.
• L21 and L22 each independently represent a divalent organic group.
• a 31a - and A 32 - each independently represent a monovalent anionic functional group.
• the definition of the monovalent anionic functional group represented by A 31a - is synonymous with A 21a - and A 21b - in formula (Ia-2) described above, and the preferred embodiments are also the same.
• the monovalent anionic functional group represented by A 32 - intends a monovalent group containing the above-mentioned anion site A 2 - .
• the monovalent anionic functional group represented by A 32 - is not particularly limited, and is, for example, a monovalent anionic functional group selected from the group consisting of the above formulas (BX-1) to (BX-7). is mentioned.
• a 31b - represents a divalent anionic functional group.
• the divalent anionic functional group represented by A 31b - intends a divalent linking group containing the anionic site A 1 - described above.
• Examples of the divalent anionic functional group represented by A 31b - include a divalent anionic functional group represented by formula (AX-4) shown below.
• M 31a + , M 31b + , and M 32 + each independently represent a monovalent organic cation.
• the organic cations represented by M 31a + , M 31b + , and M 32 + are synonymous with M 11 + above, and the preferred embodiments are also the same.
• L 31 and L 32 each independently represent a divalent organic group.
• the derived acid dissociation constant a2 is larger than the acid dissociation constant a1-3 derived from the acidic site represented by A 31a H and the acid dissociation constant a1-4 derived from the acidic site represented by A 31b H.
• the acid dissociation constant a1-3 and the acid dissociation constant a1-4 correspond to the acid dissociation constant a1 described above.
• a 31a - and A 32 - may be the same or different.
• M 31a + , M 31b + , and M 32 + may be the same or different. At least one of M 31a + , M 31b + , M 32 + , A 31a ⁇ , A 32 ⁇ , L 31 and L 32 may have an acid-decomposable group as a substituent.
• a 41a ⁇ , A 41b ⁇ , and A 42 ⁇ each independently represent a monovalent anionic functional group.
• the definitions of the monovalent anionic functional groups represented by A 41a - and A 41b - are the same as those of A 21a - and A 21b - in formula (Ia-2) described above.
• the definition of the monovalent anionic functional group represented by A 42 - is the same as A 32 - in formula (Ia-3) described above, and the preferred embodiments are also the same.
• M 41a + , M 41b + , and M 42 + each independently represent an organic cation.
• the organic cations represented by M 41a + , M 41b + , and M 42 + are synonymous with M 11 + above, and the preferred embodiments are also the same.
• L41 represents a trivalent organic group.
• M 41a + , M 41b + , and M 42 + may be the same or different. At least one of M 41a + , M 41b + , M 42 + , A 41a ⁇ , A 41b ⁇ , A 42 ⁇ , and L 41 may have an acid-decomposable group as a substituent.
• the divalent organic groups represented by L 21 and L 22 in formula (Ia-2) and L 31 and L 32 in formula (Ia-3) are not particularly limited, for example, —CO— , —NR—, —O—, —S—, —SO—, —SO 2 —, an alkylene group (preferably having 1 to 6 carbon atoms, which may be linear or branched), a cycloalkylene group (preferably 3 to 15 carbon atoms), alkenylene groups (preferably 2 to 6 carbon atoms), divalent aliphatic heterocyclic groups (at least one N atom, O atom, S atom, or Se atom in the ring structure 5 A to 10-membered ring is preferred, a 5- to 7-membered ring is more preferred, and a 5- to 6-membered ring is even more preferred.), a divalent aromatic heterocyclic group (at least one N atom, O atom, S atom, or Se A 5- to 10-membered ring having an atom in the
• R in -NR- is a hydrogen atom or a monovalent organic group.
• the monovalent organic group is not particularly limited, for example, an alkyl group (preferably having 1 to 6 carbon atoms) is preferable.
• the alkylene group, the cycloalkylene group, the alkenylene group, the divalent aliphatic heterocyclic group, the divalent aromatic heterocyclic group, and the divalent aromatic hydrocarbon ring group have a substituent.
• Substituents include, for example, halogen atoms (preferably fluorine atoms).
• Examples of divalent organic groups represented by L 21 and L 22 in formula (Ia-2) and L 31 and L 32 in formula (Ia-3) are represented by the following formula (L2): It is also preferred that it is a divalent organic group that
• q represents an integer of 1-3. * represents a binding position.
• Each Xf independently represents a fluorine atom or an alkyl group substituted with at least one 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 C 1-4 perfluoroalkyl group, more preferably a fluorine atom or CF 3 . In particular, it is more preferable that both Xf are fluorine atoms.
• LA represents a single bond or a divalent linking group.
• the divalent linking group represented by L A is not particularly limited, and examples thereof include -CO-, -O-, -SO-, -SO 2 -, alkylene groups (preferably having 1 to 6 carbon atoms, straight-chain may be in the form of a branched chain), a cycloalkylene group (preferably having 3 to 15 carbon atoms), a divalent aromatic hydrocarbon ring group (preferably a 6- to 10-membered ring, more preferably a 6-membered ring), and Divalent linking groups in which a plurality of these are combined are included.
• the alkylene group, the cycloalkylene group, and the divalent aromatic hydrocarbon ring group may have a substituent. Substituents include, for example, halogen atoms (preferably fluorine atoms).
• Examples of the divalent organic group represented by formula (L2) include *-CF 2 -*, *-CF 2 -CF 2 -*, *-CF 2 -CF 2 -CF 2 -*, *- Ph-O- SO2 - CF2- *, *-Ph-O- SO2 - CF2 - CF2- *, *-Ph-O- SO2 - CF2 - CF2 - CF2- *, and , *—Ph—OCO—CF 2 —*.
• Ph is an optionally substituted phenylene group, preferably a 1,4-phenylene group.
• an alkyl group eg, preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms
• an alkoxy group eg, preferably having 1 to 10 carbon atoms, 1 to 1 carbon atoms, 6 is more preferable
• an alkoxycarbonyl group eg, preferably having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms.
• a 51a ⁇ , A 51b ⁇ , and A 51c ⁇ each independently represent a monovalent anionic functional group.
• the monovalent anionic functional groups represented by A 51a ⁇ , A 51b ⁇ , and A 51c ⁇ are intended to be monovalent groups containing the above-described anion site A 1 ⁇ .
• the monovalent anionic functional groups represented by A 51a ⁇ , A 51b ⁇ , and A 51c ⁇ are not particularly limited, but are, for example, the group consisting of the above formulas (AX-1) to (AX-3) A selected monovalent anionic functional group can be mentioned.
• a 52a - and A 52b - represent divalent anionic functional groups.
• the divalent anionic functional groups represented by A 52a - and A 52b - are intended to be divalent linking groups containing the above-mentioned anion site A 2 - .
• the divalent anionic functional group represented by A 22 - includes, for example, divalent anionic functional groups selected from the group consisting of the above formulas (BX-8) to (BX-11).
• M 51a + , M 51b + , M 51c + , M 52a + , and M 52b + each independently represent an organic cation.
• the organic cations represented by M 51a + , M 51b + , M 51c + , M 52a + , and M 52b + are synonymous with M 11 + described above, and the preferred embodiments are also the same.
• L51 and L53 each independently represent a divalent organic group.
• the divalent organic groups represented by L 51 and L 53 have the same meanings as L 21 and L 22 in formula (Ia-2) above, and the preferred embodiments are also the same.
• L52 represents a trivalent organic group.
• the trivalent organic group represented by L 52 has the same definition as L 41 in formula (Ia-4) above, and the preferred embodiments are also the same.
• the acid dissociation constants a1-1 to a1-3 correspond to the acid dissociation constant a1 described above, and the acid dissociation constants a2-1 and a2-2 correspond to the acid dissociation constant a2 described above.
• a 51a ⁇ , A 51b ⁇ , and A 51c ⁇ may be the same or different.
• a 52a - and A 52b - may be the same or different.
• M 51a + , M 51b + , M 51c + , M 52a + , and M 52b + may be the same or different.
• M 51b + , M 51c + , M 52a + , M 52b + , A 51a ⁇ , A 51b ⁇ , A 51c ⁇ , L 51 , L 52 and L 53 is an acid-decomposable group as a substituent may have
• Compound (II) is a compound having two or more structural moieties Z1 and one or more structural moieties Z3 described below, wherein the first acidic It is a compound that generates an acid containing two or more moieties and the above structural moiety Z3.
• Structural site Z3 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 Z1 and the structural site Z3, 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 Z1 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 acid-neutralizable nonionic site in structural site Z3 is not particularly limited, and is, for example, a site that includes a group that can electrostatically interact with protons or a functional group that has 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 compound (II) is not particularly limited, but includes, for example, compounds represented by the following formulas (IIa-1) and (IIa-2).
• a 61a - and A 61b - have the same meanings as A 11 - in formula (Ia-1) above, and preferred embodiments are also the same.
• M 61a + and M 61b + have the same meanings as M 11 + in formula (Ia-1) described above, and the preferred embodiments are also the same.
• L 61 and L 62 have the same definitions as L 1 in formula (Ia-1) above, and the preferred embodiments are also the same.
• R 2X represents a monovalent organic group.
• the monovalent organic group represented by R 2X is not particularly limited, and may be an alkyl group (preferably having 1 to 10 carbon atoms, which may be linear or branched), a cycloalkyl group (preferably having 3 to 15), or an alkenyl group (preferably having 2 to 6 carbon atoms).
• —CH 2 — contained in the alkyl group, cycloalkyl group and alkenyl group in the monovalent organic group represented by R 2X is —CO—, —NH—, —O—, —S—, and —SO— , and —SO 2 — may be substituted with one or a combination of two or more.
• the alkylene group, the cycloalkylene group, and the alkenylene group may have a substituent. Examples of substituents include, but are not particularly limited to, halogen atoms (preferably fluorine atoms).
• the acid dissociation constant a1-8 derived from the acidic site represented by a1-7 and A 61b H corresponds to the acid dissociation constant a1 described above.
• the compound PIIa-1 obtained by replacing the cation sites M 61a + and M 61b + in the structural site Z1 of the compound (IIa-1) with H + is HA 61a -L 61 -N(R 2X ) -L 62 -A 61b H.
• compound PIIa-1 is the same as the acid generated from the compound represented by formula (IIa-1) upon exposure to actinic rays or radiation.
• At least one of M 61a + , M 61b + , A 61a ⁇ , A 61b ⁇ , L 61 , L 62 and R 2X may have an acid-decomposable group as a substituent.
• a 71a ⁇ , A 71b ⁇ , and A 71c ⁇ have the same meanings as A 11 ⁇ in formula (Ia-1) above, and preferred embodiments are also the same.
• M 71a + , M 71b + , and M 71c + have the same meanings as M 11 + in formula (Ia-1) above, and the preferred embodiments are also the same.
• L 71 , L 72 , and L 73 have the same meanings as L 1 in formula (Ia-1) above, and preferred embodiments are also the same.
• the acid dissociation constant a1-9 derived from, the acid dissociation constant a1-10 derived from the acidic site represented by A 71b H, and the acid dissociation constant a1-11 derived from the acidic site represented by A 71c H are It corresponds to the acid dissociation constant a1 described above.
• a compound PIIa-2 obtained by replacing the cation sites M 71a + , M 71b + , and M 71c + in the structural site Z1 of the compound (IIa-1) with H + is HA 71a -L 71 -N(L 73 -A 71c H) -L 72 -A 71b H.
• compound PIIa-2 is the same as the acid generated from the compound represented by formula (IIa-2) upon exposure to actinic rays or radiation.
• M 71a + , M 71b + , M 71c + , A 71a ⁇ , A 71b ⁇ , A 71c ⁇ , L 71 , L 72 and L 73 has an acid-decomposable group as a substituent; may
• the content of the photo-acid generator (B) contained in the composition of the present invention is not particularly limited. 0.5% by mass or more is preferable, and 1.0% by mass or more is more preferable.
• the content is preferably 60.0% by mass or less, more preferably 50.0% by mass or less, and even more preferably 40.0% 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 control agent is not particularly limited, and examples include basic compounds (DA), low-molecular-weight compounds (DB) having nitrogen atoms and groups that leave under the action of acids, and actinic rays or radiation. and a compound (DC) whose ability to control acid diffusion decreases or disappears upon irradiation.
• an onium salt compound (DD) which becomes a relatively weak acid with respect to the photoacid generator, and a basic compound (DE), whose basicity decreases or disappears upon exposure to actinic rays or radiation.
• Specific examples of the basic compound (DA) include, for example, those described in paragraphs [0132] to [0136] of WO2020/066824, and the basicity is reduced or Specific examples of the disappearing basic compound (DE) include those described in paragraphs [0137] to [0155] of WO 2020/066824, have a nitrogen atom, and are eliminated by the action of an acid.
• low-molecular-weight compounds having a group include those described in paragraphs [0156] to [0163] of WO 2020/066824, and basicity is obtained by irradiation with actinic rays or radiation.
• Specific examples of the basic compound (DE) that decreases or disappears include those described in paragraph [0164] of WO2020/066824.
• Specific examples of the onium salt compound (DD), which is a relatively weak acid relative to the photoacid generator, include those described in paragraphs [0305] to [0314] of WO2020/158337. .
• 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 composition of the present invention contains an acid diffusion control agent
• the composition of the present invention has the following general formula (XN) from the viewpoint of easiness of capturing the acid generated in the exposed area in the unexposed area. It is preferable to contain an acid diffusion control agent represented by.
• R XN represents a hydrocarbon group and M X + represents an organic cation.
• the hydrocarbon group for R 1 XN is not particularly limited, but examples thereof include hydrocarbon groups having 1 to 30 carbon atoms.
• the hydrocarbon group may have a hetero atom, a halogen atom (eg, fluorine atom, bromine atom, iodine atom, etc.) and the like.
• the hydrocarbon group includes, for example, an alkyl group, a cycloalkyl group, or an aryl group.
• the alkyl group may be linear or branched, preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms.
• the cycloalkyl group may be monocyclic or polycyclic, preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 3 to 10 carbon atoms. At least one methylene group as a ring member constituting the cycloalkyl group may be replaced with an oxygen atom or a carbonyl group.
• the aryl group may be monocyclic or polycyclic, preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms.
• the above alkyl group, cycloalkyl group and aryl group may further have a substituent.
• substituents include, but are not limited to, hydroxy groups, alkyl groups (preferably having 1 to 6 carbon atoms), halogen atoms (eg, fluorine atoms, bromine atoms, iodine atoms, etc.), arylcarbonyloxy groups, and alkylcarbonyl groups.
• An amino group etc. can be mentioned.
• Each of the above groups may have a plurality of substituents.
• the alkyl group, arylcarbonyloxy group, and alkylcarbonylamino group as additional substituents may further have a substituent.
• the content of the acid diffusion control agent (the total when multiple types are present) is 0.1 to 15% relative to the total solid content of the resist composition. 0% by mass is preferred, and 1.0 to 15.0% by mass is more preferred. In the composition of the present invention, 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, more preferably 0.1 to 15.0% by mass, based on the total solid content of the resist composition. 0% 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, more preferably 0.0005 to 1.0% by mass, based on the total solid content of the resist composition. 0% by mass is more preferable, and 0.1 to 1.0% by mass is even more preferable.
• 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 resist composition and reducing the number of development defects in the pattern. 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 the components other than the solvent, and as described above, 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 the 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 specification is suitably used as 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 effect 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.
• the EUV light and electron beam absorption efficiency of the resist film formed from the resist composition increases, which is effective in reducing photon shot noise.
• the A value represents the absorption efficiency of the EUV light and the electron beam relative to the mass ratio of the resist film.
• A ([H] x 0.04 + [C] x 1.0 + [N] x 2.1 + [O] x 3.6 + [F] x 5.6 + [S] x 1.5 + [I] ⁇ 39.5) / ([H] ⁇ 1 + [C] ⁇ 12 + [N] ⁇ 14 + [O] ⁇ 16 + [F] ⁇ 19 + [S] ⁇ 32 + [I] ⁇ 127)
• the A value is preferably 0.120 or more.
• the upper limit is not particularly limited, but if the A value is too large, the EUV light and electron beam transmittance of the resist film will decrease, the optical image profile in the resist film will deteriorate, and as a result, it will be difficult to obtain a good pattern shape. Therefore, 0.240 or less is preferable, and 0.220 or less is more preferable.
• [H] represents the molar ratio of hydrogen atoms derived from the total solid content to the total atoms of the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition
• [C] represents the molar ratio of carbon atoms derived from the total solid content to the total atoms of the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition
• [N] is the actinic ray-sensitive or radiation-sensitive resin
• [O] is the total atoms of the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition
• [F] represents the molar ratio of fluorine atoms derived from the total solid content to the total atoms of the total solid content in the actinic ray-sensitive or radiation-sensitive resin
• [S] represents the molar ratio of sulfur atoms derived from the total solid content to the total atoms of the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition
• [I] is the actinic ray-sensitive represents the molar ratio of iodine atoms derived from the total solid content to the total atoms of the total solid content in the curable or radiation-sensitive resin composition.
• the resist composition contains an acid-decomposable resin, a photoacid generator, an acid diffusion controller, and a solvent
• the acid-decomposable resin, the photoacid generator, and the acid diffusion controller correspond to the solid content. do.
• the total atoms of the total solid content correspond to the sum of all atoms derived from the resin, all atoms derived from the photoacid generator, and all atoms derived from the acid diffusion control agent.
• [H] represents the molar ratio of hydrogen atoms derived from the total solid content to the total atoms of the total solid content.
• hydrogen atoms derived from the acid-decomposable resin, hydrogen atoms derived from the photoacid generator, and the acid with respect to the sum of all atoms derived from the photoacid generator and all atoms derived from the acid diffusion control agent It represents the total molar ratio of hydrogen atoms derived from the diffusion control agent.
• the A value can be calculated by calculating the contained atomic ratio when the structure and content of the constituent components of the total solid content in the resist composition are known. Further, even if the constituent components are unknown, the constituent atomic number ratio can be calculated by analytical methods such as elemental analysis for the resist film obtained by evaporating the solvent component of the resist composition. .
• Step 1 Step of forming an actinic ray-sensitive or radiation-sensitive film on a substrate with an actinic ray-sensitive or radiation-sensitive resin composition
• Step 2 Step of exposing the actinic ray-sensitive or radiation-sensitive film
• Step 3 Step of Developing the Exposed Actinic Ray-Sensitive or Radiation-Sensitive Film Using a Developer Below, the procedures of each of the above steps will be described in detail.
• Step 1 is a step of forming an actinic ray-sensitive or radiation-sensitive film (preferably a resist film) on a substrate using an actinic ray-sensitive or radiation-sensitive resin composition.
• the actinic ray-sensitive or radiation-sensitive resin composition is applied onto 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.
• the actinic ray-sensitive or radiation-sensitive resin composition can be applied onto a substrate (eg, silicon, silicon dioxide coating) used in the manufacture of integrated circuit elements by a 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 a resist film. If necessary, various base films (inorganic film, organic film, antireflection film) may be formed under the resist 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 actinic rays or radiation through the formed actinic ray-sensitive or radiation-sensitive film.
• 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 wavelengths of far-ultraviolet light, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), EUV light (13.5 nm), X-rays, and electron beams. , EUV light is most preferred.
• baking is preferably performed before development. Baking accelerates the reaction of 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), and is more preferably an alkaline 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 to be 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.).
• Table 1 shows the type and content (content ratio (mol % ratio)) of the repeating unit, weight average molecular weight (Mw), and degree of dispersion (Mw/Mn) of the resin (A) used.
• the weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) of Resin (A) were measured by GPC (solvent: tetrahydrofuran (THF)).
• the resin composition ratio (mol% ratio) was measured by 13 C-NMR (nuclear magnetic resonance).
• Photoacid generator (B) The structure of the photoacid generator (B) used is shown below.
• ⁇ Hydrophobic resin (E)> The composition ratio (mol% ratio; corresponding from left to right), weight average molecular weight (Mw), and degree of dispersion (Mw/Mn) of each repeating unit in the hydrophobic resin used are shown below.
• the weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) of the hydrophobic resin were measured by GPC (solvent: tetrahydrofuran (THF)). Also, the resin composition ratio (mol% ratio) was measured by 13 C-NMR (nuclear magnetic resonance).
• each repeating unit shown in Table 2 The structural formula of each repeating unit shown in Table 2 is shown below. Each repeating unit is shown as the structural formula of the corresponding raw material monomer.
• 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)
• H-4 Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd., silicone surfactant)
• F Propylene glycol monomethyl ether acetate
• F-2 Propylene glycol monomethyl ether
• F-3 Propylene glycol monoethyl ether
• F-5 cyclopentanone
• 6 2-heptanone
• F-7 ethyl lactate
• F-8 ⁇ -butyrolactone
• F-9 propylene carbonate
• F-10 diacetone alcohol
• the content (% by mass) of each component other than the solvent means the content ratio with respect to the total solid content.
• Table 3 below shows the content ratio (% by mass) of the solvent used with respect to the total solvent.
• a pattern obtained for a silicon wafer having a resist film obtained using an EUV exposure apparatus (Exitech, Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36)
• 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.
• An underlayer film forming composition AL412 manufactured by Brewer Science was applied onto a silicon wafer and baked at 205° C. for 60 seconds to form an underlayer film having a thickness of 20 nm.
• the resist compositions of Examples 40 to 47 and Comparative Example 4 shown in the table were applied thereon and baked at 100° C. for 60 seconds to form a resist film having a thickness of 35 nm.
• an EUV exposure apparatus Exitech, Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36
• Pattern irradiation was performed so that the average line width was 20 nm.
• a mask having a line size of 20 nm and a line:space ratio of 1:1 was used as the reticle.
• 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.
• Roughness performance was evaluated by line width roughness (LWR) performance.
• the sensitivity (Eop) was defined as the irradiation energy for resolving a 1:1 line-and-space pattern with an average line width of 20 nm.
• the line width was measured, the standard deviation was obtained, and 3 ⁇ (nm) was calculated.
• Table 3 shows the evaluation results obtained.
• the pattern obtained by the pattern forming method using the resist composition of the present invention has excellent roughness performance and a pattern shape with good rectangularity.
• the resin (A) in Comparative Example 1 which does not have the repeating unit A, Comparative Example 2 which does not have the repeating unit B, and Comparative Examples 3 and 4 which do not have the repeating unit C, roughness The results were inferior to those of the examples in both performance and rectangularity. For this reason, in order to obtain a pattern shape having excellent roughness performance and good rectangularity, it is important that the resin (A) contains all repeating units A, B and C without missing any one. I know there is.
• an actinic ray- or radiation-sensitive resin composition that is excellent in roughness performance and capable of forming a pattern with good rectangularity, and the actinic ray- or radiation-sensitive resin composition.
• An actinic ray-sensitive or radiation-sensitive film to be used, a pattern forming method, and a method of manufacturing an electronic device can be provided.

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