Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/38—Esters containing sulfur
  • C08F220/382—Esters containing sulfur and containing oxygen, e.g. 2-sulfoethyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/38—Esters containing sulfur
  • C08F220/385—Esters containing sulfur and containing nitrogen
• • 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
  • G03F7/038—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
  • G03F7/20—Exposure; Apparatus therefor

Definitions

• the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, a resist film, a pattern forming method, and an electronic device manufacturing method.
• pattern forming methods include the following methods.
• An actinic ray-sensitive or radiation-sensitive resin film (hereinafter also referred to as a "resist film”) formed using an actinic ray-sensitive or radiation-sensitive resin composition is exposed, and a resist is formed in an area reflecting the exposure pattern. It causes the film to change its solubility in the developer.
• development is performed using a developer (for example, an alkaline aqueous developer or an organic solvent developer) to remove the exposed or non-exposed portions of the resist film to obtain a desired pattern.
• a developer for example, an alkaline aqueous developer or an organic solvent developer
• Patent Document 1 a photoresist polymer containing a repeating unit represented by the following chemical formula; a photoacid generator that generates an acid; A photoresist composition is disclosed in which the content of the generator is 0.1-20 parts by weight and the content of the organic solvent is 300-5000 parts by weight (claims 3 and 6).
• the present inventors have studied the photoresist composition (actinic ray-sensitive or radiation-sensitive resin composition) described in Patent Document 1, and found that, in particular, when obtaining a high-definition pattern, the photoresist composition
• the inventors have found that the pattern obtained after exposure processing using , has many development defects and there is room for improvement.
• the ability to obtain a pattern with few development defects when developed is also referred to as excellent development defect suppression properties.
• an object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition that is excellent in suppressing development defects.
• Another object of the present invention is to provide a resist film, a pattern forming method, and an electronic device manufacturing method related to the actinic ray-sensitive or radiation-sensitive resin composition.
• An actinic ray-sensitive or radiation-sensitive resin composition containing a resin having a repeating unit A represented by formula (A) described later, further comprising a compound represented by any one of the above formulas (1) to (4), wherein the resin further comprises a group that is decomposed by the action of an acid to increase its polarity; and
• the resin further has a repeating unit a having a residue formed by removing one or two hydrogen atoms from the compound represented by any of the formulas (1) to (4), and the repeating unit a content is 10 mol% or more based on all repeating units of the resin, or actinic ray-sensitive or radiation-sensitive resin composition.
• the resin further has a repeating unit a having a residue formed by removing one or two hydrogen atoms from the compound represented by any of the formulas (1) to (4), Actinic ray-sensitive or radiation-sensitive according to [1], wherein the residue contains at least one selected from the group consisting of groups represented by any of formulas (1a) to (4a) described later.
• Resin composition [3] Actinic ray-sensitive or sensitive according to [1] or [2], wherein the compound represented by any of the above formulas (1) to (4) has a substituent having a ⁇ p of more than 0.5 in Hammett's rule A radioactive resin composition.
• [4] further comprising a compound represented by any one of the above formulas (1) to (3), wherein the resin further comprises a group that is decomposed by the action of an acid to increase its polarity; and
• the resin further has a repeating unit a having a residue formed by removing one or two hydrogen atoms from the compound represented by any of the formulas (1) to (3), and the repeating unit a is 10 mol % or more based on the total repeating units of the resin, or the actinic ray-sensitive or radiation-sensitive resin composition according to [1].
• the resin further has the repeating unit a, The actinic ray-sensitive or radiation-sensitive resin according to any one of [1] to [4], wherein the content of the repeating unit a is 40 mol% or more based on the total repeating units of the resin. Composition. [6] The actinic ray-sensitive or radiation-sensitive resin according to any one of [1] to [5], wherein the resin further comprises a repeating unit b having a group that is decomposed by the action of the acid to increase the polarity. Composition.
• the resin further comprises a repeating unit b having a group that is decomposed by the action of the acid to increase its polarity, Any one of [1] to [6], wherein the repeating unit b includes at least one selected from the group consisting of repeating units represented by any of formulas (M1) to (M5) described later.
• Actinic ray-sensitive or radiation-sensitive resin composition according to .
• Light sensitive or radiation sensitive resin composition is a repeating unit b having a group that is decomposed by the action of the acid to increase its polarity, Any one of [1] to [6], wherein the repeating unit b includes at least one selected from the group consisting of repeating units represented by any of formulas (M1) to (M5) described later.
• Actinic ray-sensitive or radiation-sensitive resin composition according to
• [9] [1] A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8]. [10] forming a resist film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8]; exposing the resist film; and developing the exposed resist film using a developer. [11] A method for manufacturing an electronic device, comprising the pattern forming method according to [10].
• the actinic-ray-sensitive or radiation-sensitive resin composition which is excellent in development defect suppression property can be provided.
• the present invention can provide a resist film, a pattern forming method, and an electronic device manufacturing method related to the actinic ray-sensitive or radiation-sensitive resin composition.
• ⁇ is used to mean including the numerical values described before and after it as a lower limit and an upper limit.
• the notation that does not indicate substitution or unsubstituted includes not only a group having no substituent but also a group having a substituent.
• 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).
• Organic group refers to a group containing at least one carbon atom.
• a "substituent” is a monovalent substituent unless otherwise specified.
• the substituents include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; alkoxy groups such as a methoxy group, an ethoxy group and a tert-butoxy group; an aryloxy group such as a phenoxy group and a p-tolyloxy group; alkoxycarbonyl groups such as carbonyl, butoxycarbonyl and phenoxycarbonyl; acyloxy groups such as acetoxy, propionyloxy and benzoyloxy; acetyl, benzoyl, isobutyryl, acryloyl, methacryloyl and methoxalyl acyl group; alkylsulfanyl group such as methylsulfanyl group and tert-butylsulfanyl group; arylsulfany
• substituent K substituent K
• 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: Electron Beam). do.
• Light means actinic rays or radiation.
• exposure means not only exposure by the emission line spectrum of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, X-rays and EUV light, but also particles such as electron beams and ion beams. Including line drawing.
• the bonding direction of the divalent groups described herein is not limited.
• Y when Y is -COO-, Y may be -CO-O- or -O-CO- good too. Further, the above compound may be "X--CO--O--Z" or "X--O--CO--Z.”
• (Meth)acrylate stands for acrylate and methacrylate.
• (Meth)acrylic stands for acrylic and methacrylic.
• the weight average molecular weight (Mw), number average molecular weight (Mn) and dispersity (hereinafter also referred to as "molecular weight distribution”) (Mw/Mn) of the resin were measured using a GPC (Gel Permeation Chromatography) device (HLC-8120GPC manufactured by Tosoh).
• column TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40 ° C.
• flow rate 1.0 mL / min
• detector differential refractive index detection It is defined as a polystyrene conversion value by a device (Refractive Index Detector).
• the resin composition ratio (molar ratio or mass ratio) is measured by 13 C-NMR (nuclear magnetic resonance).
• the acid dissociation constant (pKa) represents the pKa in an aqueous solution.
• pKa The acid dissociation constant
• Software Package 1 Advanced Chemistry Development (ACD/Labs) Software V8.14 for Solaris (1994-2007 ACD/Labs).
• pKa can also be obtained by molecular orbital calculation.
• 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 are not limited to this. .
• DFT density functional theory
• Gaussian16 is an example.
• pKa means a value obtained by calculating a value based on Hammett's substituent constant and a database of known literature values using software package 1, but pKa cannot be calculated by this method. In this case, the values obtained by Gaussian 16 based on DFT (Density Functional Theory) shall be adopted. As described above, pKa means “pKa in aqueous solution", and when pKa in aqueous solution cannot be calculated, “pKa in dimethyl sulfoxide (DMSO) solution” is used.
• DMSO dimethyl sulfoxide
• Solid content means the components that form the resist film and does not include solvent. In addition, as long as it is a component that forms a resist film, it is regarded as a solid content even if its property is liquid.
• the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is a resin having a repeating unit A represented by formula (A) (hereinafter also referred to as “resin A” ), further comprising a compound represented by any one of formulas (1) to (4) (hereinafter also referred to as a “specific compound”), wherein the resin is decomposed by the action of an acid (hereinafter also referred to as “acid-decomposable group”) (rement A), and the resin is a compound represented by any one of formulas (1) to (4) It further has a repeating unit a having a residue formed by removing one or two hydrogen atoms (hereinafter also referred to as a "specific group”), and the content of the repeating unit a is based on the total repeating units of the resin at least one of 10 mol % or more (requirement B).
• the resist composition of the present invention only needs to satisfy Requirement A or Requirement B above, and may satisfy both Requirement A and Requirement B above.
• a resist composition containing resin A which further contains a specific compound, the resin contains the repeating unit a, and the content of the repeating unit a is 10 mol% or more relative to the total repeating units of the resin. and may further have a group that is decomposed by the action of an acid to increase its polarity.
• the present inventors presume as follows.
• a resin having an acid-decomposable group for example, an acid generated from a photoacid generator upon exposure causes the acid-decomposable group to
• the acid-decomposable group in the resin A may be decomposed by acting on the resin possessed, thereby causing a change in polarity in the exposed area.
• the present inventors have found that if the photo-acid generator that has received light is difficult to decompose, the solubility in the developing solution deteriorates during development and tends to remain as defects.
• the specific compound or repeating unit a that can function as a photoacid generator has at least one substituent with ⁇ p greater than 0 in Hammett's rule, so that the intramolecular polarization is easy to grow. Therefore, it is presumed that it is more likely to be decomposed when exposed to light, and further that its solubility in a developer is improved, and its development defect suppressing property is excellent.
• the more excellent development defect suppressing property is also referred to as the more excellent effect of the present invention.
• the resist composition of the present invention will be described in detail below.
• the resist composition may be either a positive resist composition or a negative resist composition. Moreover, it may be either a resist composition for alkali development or a resist composition for organic solvent development.
• the resist composition may be a non-chemically amplified resist composition, or the resist composition may be combined with a mechanism as a chemically amplified resist composition.
• Various components of the resist composition are described in detail below.
• the specific compound is a compound represented by any one of formulas (1) to (4).
• the specific compound is a nonionic compound that decomposes upon irradiation (exposure) with actinic rays or radiation, and can also function as a photoacid generator, which will be described later.
• the specific compound preferably has a substituent with ⁇ p of more than 0.5 in Hammett's rule.
• the specific compound has one or more substituents X, which will be described later.
• a compound represented by any one of formulas (1) to (3) is preferable, and a compound represented by formula (2) is more preferable because the effects of the present invention are more excellent.
• X 11 represents a hydrogen atom or -L 11 -(R 11 )p 11 .
• R 11 to R 13 each independently represent a substituent. At least one of R 11 to R 13 represents a substituent with ⁇ p greater than 0 in Hammett's rule. R 11 and R 13 may combine with each other to form a ring.
• L 11 represents a single bond or a p 11 + monovalent linking group.
• L 12 represents a single bond or a p 12 + monovalent linking group.
• L 13 represents a single bond or a p 13 + monovalent linking group.
• p 11 to p 13 each independently represent an integer of 1 or more. However, p11 represents 1 when L11 represents a single bond, p12 represents 1 when L12 represents a single bond, and p13 represents 1 when L13 represents a single bond.
• X 11 represents a hydrogen atom or -L 11 -(R 11 )p 11 ; X 11 is preferably -L 11 -(R 11 )p 11 .
• L 11 , R 11 and p 11 are as described later.
• R 11 to R 13 each independently represent a substituent. At least one of R 11 to R 13 represents a substituent with ⁇ p greater than 0 in Hammett's rule.
• One to three of R 11 to R 13 preferably represent a substituent X described later, more preferably one or two of R 11 to R 13 represent a substituent X, and R 11 and R 13 It is further preferred that one or two of them represent the substituent X, and it is particularly preferred that one of the R 13 represents the substituent X.
• Two or more R 11 s, two or more R 12 s, and two or more R 13 s may be the same or different.
• the above "at least one of R 11 to R 13 represents a substituent having ⁇ p greater than 0 in Hammett's rule". means that at least one of a plurality of R 11 , a plurality of R 12 and/or a plurality of R 13 represents a substituent X described below.
• R 11 represents a methyl group
• R 12 represents an ethyl group
• One of R 13 may represent a propyl group
• the other of R 13 may represent substituent X
• both R 13 may represent substituent X.
• the compound represented by formula (1) has at least one substituent X.
• the description regarding the said substituent X is the same also in each compound mentioned later.
• the substituent include the groups exemplified for the substituent K described above, more specifically, a hydroxyl group, an amino group and an organic group, preferably an organic group.
• organic groups include hydrocarbon groups. Examples of hydrocarbon groups include alkyl groups (linear or branched), alkenyl groups, cycloalkyl groups and aromatic ring groups, with alkyl groups being preferred.
• the substituent may be a substituent having ⁇ p greater than 0 in Hammett's rule (hereinafter also referred to as "substituent X").
• the substituent X is a group corresponding to an electron-withdrawing group.
• substituent X include a halogen atom, a nitro group (0.78), a thiol group (0.15), an alkyl group having a halogen atom, a cyano group (0.66), an aldehyde group (0.42), Included are groups including carboxy (0.45), acyl, acyloxy, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, sulfamoyl, benzotriazole, sulfo and sulfonyl groups.
• the parenthesized numerical values written together for each group indicate the ⁇ p of each substituent.
• nitro group (0.78) means that the ⁇ p of the nitro group according to Hammet's rule is 0.78.
• substituent X for example, Chem. Rev. , 1991, 91, 165-195, the contents of which are incorporated herein.
• substituent constant ⁇ of Hammet's rule is a numerical value representing the effect of the substituent on the acid dissociation equilibrium constant of the substituted benzoic acid, and is a parameter that indicates the strength of the electron withdrawing and electron donating properties of the substituent. .
• the ⁇ p value of Hammet's rule herein means the substituent constant ⁇ when the substituent is positioned at the para-position of benzoic acid.
• Preferred halogen atoms are Br (0.23), Cl (0.23), F (0.06) and I (0.18).
• the alkyl group having a halogen atom is preferably a brominated alkyl group, a chlorinated alkyl group, a fluorinated alkyl group or an iodinated alkyl group, more preferably a fluorinated alkyl group, and still more preferably a trifluoromethyl group (0.54).
• the acyl group is preferably an acetyl group (0.50), a trifluoroacetyl group (0.80), a propionyl group, a pivaloyl group, a benzoyl group or a 4-methoxybenzoyl group.
• the acyloxy group is preferably an acyloxymethyl group or an acyloxyethyl group.
• Alkoxycarbonyl groups include methoxycarbonyl group (0.45), ethoxycarbonyl group, 2-hydroxyethoxycarbonyl group, 2-(3-trimethoxysilylpropylaminocarbonyloxy)ethoxycarbonyl group, 2-(3-triethoxy A silylpropylaminocarbonyloxy)ethoxycarbonyl group, a 2-ethylhexylcarbonyloxy group, a trifluoromethoxycarbonyl group or a trifluoroethoxycarbonyl group is preferred.
• the aryloxycarbonyl group is preferably a phenoxycarbonyl group or a 4-methoxyphenoxycarbonyl group.
• the carbamoyl group is an unsubstituted carbamoyl group, N,N-dimethylcarbamoyl group, N,N-diethylcarbamoyl group, morpholinocarbamoyl group, N,N-di-n-octylcarbamoyl group or Nn-octylcarbamoyl group. preferable.
• the group containing a sulfonyl group is preferably a methanesulfonyl group (0.72), an ethanesulfonyl group, an octanesulfonyl group or a benzenesulfonyl group.
• the sulfo group is preferably a methanesulfonic acid group (0.36), an ethanesulfonic acid group or an octanesulfonic acid group.
• the sulfamoyl group is preferably an unsubstituted sulfamoyl group (0.60) or an N,N-dimethylsulfamoyl group (0.65).
• the substituent X is a group containing a nitro group, an N,N-dimethylsulfamoyl group, a fluoroalkyl group, a cyano group, an acetyl group, an unsubstituted sulfamoyl group, a trifluoroacetyl group and a sulfonyl group. At least one group selected from the group is preferred.
• the ⁇ p of the substituent X is greater than 0, preferably 0.3 or more, more preferably 0.5 or more, and even more preferably 0.6 or more. Although the upper limit is not particularly limited, it is often 1.0 or less, preferably 0.8 or less.
• the ⁇ p of substituents other than the substituent X is not particularly limited.
• the above substituent may be further substituted with a substituent (which may be either the substituent X or another substituent).
• R 11 and R 13 may combine with each other to form a ring.
• a ring represented by Y 51 in formula (5) described later is preferable.
• L 11 represents a single bond or a p 11 +1 valent linking group.
• L 12 represents a single bond or a p 12 + monovalent linking group.
• L 13 represents a single bond or a p 13 + monovalent linking group.
• L 11 to L 13 are, for example, -CO-, -O-, -S-, -SO-, -SO 2- , -NR N - (R N represents a substituent), hydrocarbon groups (eg, alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups, etc.) and groups in which these groups are combined.
• the above group may further have a substituent. Examples of the substituent include groups exemplified for the substituent K.
• p 11 to p 13 each independently represent an integer of 1 or more.
• p11 represents 1 when L11 represents a single bond
• p12 represents 1 when L12 represents a single bond
• p13 represents 1 when L13 represents a single bond.
• integers of 1 to 5 are preferable
• integers of 1 to 3 are more preferable
• 1 is even more preferable.
• X 21 represents a hydrogen atom or -L 21 -(R 21 )p 21 .
• X 22 represents a hydrogen atom or -L 22 -(R 22 )p 22 ;
• R 21 to R 24 each independently represent a substituent. At least one of R 21 to R 24 represents a substituent with ⁇ p greater than 0 in Hammett's rule.
• L 21 represents a single bond or a p 21 + monovalent linking group.
• L 22 represents a single bond or a p 22 + monovalent linking group.
• L 23 represents a single bond or a p 23 + monovalent linking group.
• L 24 represents a single bond or a p 24 + monovalent linking group.
• At least two of R 21 , R 22 and R 24 may combine with each other to form a ring.
• p 21 to p 24 each independently represent an integer of 1 or more. provided that if L21 represents a single bond, p21 represents 1 ; if L22 represents a single bond, p22 represents 1 ; if L23 represents a single bond, p23 represents 1 ; p24 represents 1 when L24 represents a single bond.
• n21 represents an integer of 1 or more.
• At least one of X 21 and X 22 preferably represents a hydrogen atom, more preferably both X 21 and X 22 represent a hydrogen atom.
• L 21 , R 21 and p 21 , and L 22 , R 22 and p 22 are as described later.
• R 21 to R 24 examples include substituents represented by R 11 to R 13 in formula (1) above.
• 1 to 4 of R 21 to R 24 preferably represent a substituent X, more preferably 1 or 2 of R 21 to R 24 represent a substituent X, and 1 of R 21 and R 24 It is further preferred that one or two represent substituents X, and it is particularly preferred that one of R 24 represents substituents X.
• a plurality of R 21 may be present, a plurality of R 22 may be present, a plurality of R 23 may be present, and a plurality of R 24 may be the same or different.
• at least two of R 21 , R 22 and R 24 may combine with each other to form a ring.
• R 21 or R 22 and R 24 are preferably bonded to each other to form a ring.
• the ring formed above may be either monocyclic or polycyclic.
• L 21 to L 24 examples include -CO-, -O-, -S- and -SO- , —SO 2 —, —NR N (R N represents a substituent) —, hydrocarbon groups (e.g., alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups, etc.) and combinations thereof. .
• R N represents a substituent
• the above group may further have a substituent.
• substituent examples include groups exemplified for the substituent K.
• Each of p 21 to p 24 is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and still more preferably 1.
• n21 represents an integer of 1 or more. n21 is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, still more preferably 1 or 2, and particularly preferably 1.
• X 31 represents a hydrogen atom or -L 31 -(R 31 )p 31 .
• R 31 and R 32 each independently represent a substituent. At least one of R 31 and R 32 represents a substituent with ⁇ p greater than 0 in Hammett's rule.
• L 31 represents a single bond or a p 31 + monovalent linking group.
• L 32 represents a single bond or a p 32 + monovalent linking group.
• p31 and p32 each independently represent an integer of 1 or more. However, p31 represents 1 when L31 represents a single bond, and p32 represents 1 when L32 represents a single bond.
• Ar 31 represents an aromatic ring group.
• X 31 is preferably -L 31 -(R 31 )p 31 .
• L 31 , R 31 and p 31 are as described later.
• substituents represented by R 31 and R 32 include substituents represented by R 11 to R 13 in formula (1) above.
• one of R 31 and R 32 represents substituent X, more preferably one of R 31 represents substituent X.
• R 31 which may exist in plurality and R 32 which may exist in plurality may be the same or different.
• examples of L 31 include -CO-, -O-, -S-, -SO-, -SO 2 -, -NR N -(R N represents a substituent), hydrocarbon groups (eg, alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups, etc.) and groups in which these groups are combined.
• the above group may further have a substituent.
• substituents include groups exemplified for the substituent K.
• p 31 and p 32 an integer of 1 to 5 is preferable, an integer of 1 to 3 is more preferable, and 1 is even more preferable.
• Ar 31 represents an aromatic ring group.
• the above aromatic ring group may be either monocyclic or polycyclic.
• the number of ring member atoms in the aromatic ring group is preferably 5 to 15.
• the ring member atoms of the aromatic ring group may have one or more (eg, 1 to 5) heteroatoms (eg, oxygen atom, sulfur atom, nitrogen atom, etc.).
• Examples of the aromatic ring constituting the aromatic ring group include aromatic hydrocarbon rings such as benzene ring, naphthalene ring and anthracene ring, and aromatic heterocycles such as thiazole rings such as benzothiazole.
• a hydrocarbon ring is preferred, and a benzene ring is more preferred.
• X 41 represents a hydrogen atom or -L 41 -(R 41 )p 41 .
• X 42 represents a hydrogen atom or -L 42 -(R 42 )p 42 ;
• R 41 to R 43 each independently represent a substituent. At least one of R 41 to R 43 represents a substituent with ⁇ p greater than 0 in Hammett's rule.
• L 41 represents a single bond or a p 41 + monovalent linking group.
• L 42 represents a single bond or a p 42 + monovalent linking group.
• L 43 represents a single bond or a p 43 + monovalent linking group.
• R 41 and R 42 may combine with each other to form a ring.
• p 41 to p 43 each independently represent an integer of 1 or more. However, p41 represents 1 when L41 represents a single bond, p42 represents 1 when L42 represents a single bond, and p43 represents 1 when L43 represents a single bond.
• X 41 represents a hydrogen atom or -L 41 -(R 41 )p 41 .
• X 42 represents a hydrogen atom or -L 42 -(R 42 )p 42 .
• X 41 is preferably -L 41 -(R 41 )p 41 .
• X 42 is preferably -L 42 -(R 42 )p 42 .
• L 41 , R 41 and p 41 , and L 42 , R 42 and p 42 are as described later.
• R 41 to R 43 examples include the substituents represented by R 11 to R 13 in formula (1) above.
• One to three of R 41 to R 43 preferably represent substituent X, and more preferably one or two of R 41 and R 42 represent substituent X.
• a plurality of R 41 may be present, a plurality of R 42 may be present, and a plurality of R 43 may be the same or different.
• L 41 to L 43 are, for example, -CO-, -O-, -S-, -SO-, -SO 2 - .
• the above group may further have a substituent.
• substituents examples include groups exemplified for the substituent K.
• R 41 and R 42 may combine with each other to form a ring.
• the ring formed above may be either monocyclic or polycyclic.
• Each of p 41 to p 43 is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and still more preferably 1.
• a compound represented by Formula (5) is preferable as the compound represented by Formula (1).
• X 51 represents a hydrogen atom or -L 51 -(R 51 )p 51 .
• R51 and R52 each independently represent a substituent. At least one of R 51 and R 52 represents a substituent with ⁇ p greater than 0 in Hammett's rule.
• L 51 represents a single bond or a p 51 + monovalent linking group.
• L 52 represents a single bond or a p 52 + monovalent linking group.
• p51 and p52 each independently represent an integer of 1 or more. However, p51 represents 1 when L51 represents a single bond, and p52 represents 1 when L52 represents a single bond.
• Y 51 represents a ring containing -CO-N-CO-.
• X 51 is preferably -L 51 -(R 51 )p 51 .
• L 51 , R 51 and p 51 are as described later.
• R 51 and R 52 examples include the substituents represented by R 11 to R 13 in formula (1) above.
• one of R 51 and R 52 represents substituent X, more preferably one of R 51 represents substituent X.
• a plurality of R 51 groups and a plurality of R 52 groups may be the same or different.
• L 51 and L 52 are, for example, -CO-, -O-, -S-, -SO-, -SO 2 -, -NR N ( RN represents a substituent)-, hydrocarbon groups (eg, alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups, etc.), and groups in which these groups are combined.
• the above group may further have a substituent.
• the substituent include groups exemplified for the substituent K.
• an integer of 1 to 5 is preferable, an integer of 1 to 3 is more preferable, and 1 is even more preferable.
• Y 51 represents a ring containing -CO-N-CO-.
• the above ring may be either monocyclic or polycyclic.
• the number of ring member atoms in the above ring is preferably 5-20.
• the member atoms of the above ring may have 4 or more (eg, 1 to 5) heteroatoms (eg, oxygen, sulfur, nitrogen, etc.).
• Examples of the ring include an imide ring and a ring obtained by combining an imide ring with a ring selected from the group consisting of an alicyclic ring and an aromatic ring.
• the ring is preferably a polycyclic ring, more preferably a polycyclic ring containing at least one alicyclic ring and an aromatic ring.
• the polycyclic ring may be a condensed ring.
• Imido rings include, for example, maleimide rings, succinimide rings and glutarimide rings.
• Alicyclic rings include monocyclic alicyclic rings such as cycloalkanes and cycloalkenes, and polycyclic alicyclic rings such as bicycloundecane, decahydronaphthalene, norbornene, norbornadiene and adamantane.
• the aromatic ring include aromatic monocycles such as a benzene ring, a naphthalene ring and anthracene ring, and aromatic heterocycles such as a thiazole ring such as benzothiazole.
• a ring or naphthalene ring is more preferred.
• Specific compounds include, for example, the following compounds.
• the content of the specific compound is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, more preferably 5.0% by mass, based on the total solid content of the resist composition. % or more by mass is more preferable.
• the upper limit is preferably 40.0% by mass or less, more preferably 30.0% by mass or less, relative to the total solid content of the resist composition. When two or more are used, the total content is preferably within the range of the preferred content.
• Resin A has a repeating unit A represented by formula (A). Resin A preferably further contains at least one selected from the group consisting of repeating units a and repeating units b. When the resist composition satisfies only requirement A, resin A has an acid-decomposable group (preferably repeating unit b). Further, when the resist composition satisfies only the requirement B, the resin A contains the repeating unit a, and the content of the repeating unit a in the resin A is 10 mol% or more with respect to the total repeating units of the resin A. be.
• R A1 to R A3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkyloxycarbonyl group.
• LA represents a single bond or a divalent linking group.
• Ar A represents an aromatic ring group.
• R A2 and Ar A may combine with each other to form a ring.
• n A represents an integer of 1-5.
• R A1 to R A3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkyloxycarbonyl group.
• the alkyl group may be linear or branched.
• the number of carbon atoms in the alkyl group is preferably 1-6, more preferably 1-3.
• the cycloalkyl group may be either monocyclic or polycyclic.
• the cycloalkyl group preferably has 3 to 15 carbon atoms.
• Halogen atoms include, for example, fluorine, chlorine, bromine and iodine atoms.
• the number of carbon atoms in the alkoxycarbonyl group is preferably 1-10.
• alkyl group portion in the above alkoxycarbonyl group examples include the same groups as the above alkyl groups.
• the alkyl group, the cycloalkyl group and the alkyloxycarbonyl group may further have a substituent.
• substituents include alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxy groups, halogen atoms, alkoxy groups, thioether groups, acyl groups, acyloxy groups, Alkoxycarbonyl groups, cyano groups and nitro groups are included.
• R A1 and R A2 are preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.
• R A3 is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group, and still more preferably a hydrogen atom or a methyl group.
• LA represents a single bond or a divalent linking group.
• the divalent linking group include -CO-, -O-, -COO-, -S-, -SO-, -SO 2 -, and -NR N - (R N represents a substituent. ), hydrocarbon groups (eg, alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups, etc.), and combinations thereof.
• the hydrocarbon group may further have a substituent. Examples of the substituent include groups exemplified for the substituent K.
• L A is preferably a single bond, —COO—, —CONR A — (R A represents a hydrogen atom or an alkyl group), an alkylene group, or a group combining these, and a single bond or —COO— is more preferred.
• Ar A represents an aromatic ring group.
• the above aromatic ring group may be either monocyclic or polycyclic.
• the number of ring member atoms in the aromatic ring group is preferably 5-15, more preferably 6-12.
• the ring member atoms of the aromatic ring group may have one or more (eg, 1 to 5) heteroatoms (eg, oxygen atom, sulfur atom, nitrogen atom, etc.).
• the aromatic ring group includes an aromatic hydrocarbon ring group having 6 to 18 carbon atoms such as a benzene ring group, a methylbenzene ring group, a naphthalene ring group and an anthracene ring group, or a thiophene ring group, a furan ring group, and a pyrrole ring.
• the aromatic ring group may further have a substituent.
• substituent K examples include groups exemplified for the substituent K, preferably an alkyl group or a halogen atom, more preferably a fluorine atom, a chlorine atom, an iodine atom or a bromine atom.
• a divalent arylene group such as a phenylene group optionally having a halogen atom and a naphthylene group optionally having a halogen atom, or a hydrogen atom removed from the divalent arylene group
• a trivalent or tetravalent group formed by removing one or two is preferable, and a phenylene group optionally having a halogen atom, or removing one or two hydrogen atoms from the above divalent phenylene group More preferred is a trivalent or tetravalent group formed by
• R A2 and Ar A may combine with each other to form a ring.
• R A2 and Ar A form a ring R A2 preferably represents a single bond or an alkylene group.
• Examples of the ring formed by combining R A2 and Ar A include polycyclic rings such as acenaphthylene ring and indene ring.
• n A represents an integer of 1-5. n A is preferably an integer of 1 to 3, more preferably an integer of 1 to 2.
• repeating unit A a repeating unit A1 represented by formula (A1) is preferable.
• R A11 represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom or a cyano group.
• RA12 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.
• nA11 represents an integer of 1-5.
• nA12 represents an integer of 0-4.
• n A11 +n A12 represents an integer of 1-5.
• R A11 represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom or a cyano group.
• R A11 has the same meaning as R A3 in the above formula (A), and the preferred embodiments are also the same.
• RA12 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.
• R A12 is preferably a halogen atom, more preferably a fluorine atom, a chlorine atom, an iodine atom or a bromine atom. When multiple R A12 are present, the R A12 may be the same or different.
• nA11 represents an integer of 1-5.
• nA12 represents an integer of 0-4.
• n A11 +n A12 represents an integer of 1-5.
• n A11 is preferably an integer of 1 to 3, more preferably an integer of 1 to 2.
• n A12 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2.
• n A11 +n A12 is preferably an integer of 1 to 3.
• repeating unit A examples include the following repeating units.
• a represents an integer of 1-3.
• the repeating unit A may be used singly or in combination of two or more.
• the content of the repeating unit A is more than 0 mol %, preferably 5 mol % or more, more preferably 10 mol % or more, relative to the total repeating units of the resin A.
• the upper limit is preferably 70 mol % or less, more preferably 65 mol % or less, and even more preferably 60 mol % or less, relative to all repeating units of Resin A.
• Repeating unit a is a repeating unit having a specific group.
• the specific group may be directly bonded to the main chain of repeating unit a, or the specific group may constitute a part of the main chain of repeating unit a.
• the main chain is an ethylene chain
• part of the ethylene chain may be composed of a specific group.
• the repeating unit represented by the formula (ae) derived from the specific compound M-40 is included in the repeating unit a.
• the repeating unit a is a repeating unit having a group that is decomposed by exposure to produce a polar group. When exposed to light, the polarity of the resin A having the repeating unit a increases, so that the solubility in an alkaline developer increases and the solubility in an organic solvent decreases.
• a specific group is a residue formed by removing one or two hydrogen atoms from a specific compound.
• the specific group is decomposed by exposure to actinic rays or radiation to generate a polar group.
• the specific group includes at least one selected from the group consisting of groups represented by any of formulas (1a) to (4a) and groups represented by any of formulas (1b) to (5b) is preferred, and more preferably contains at least one selected from the group consisting of groups represented by any of formulas (1a) to (4a), and represented by any of formulas (1a) to (3a) It is further preferable to contain at least one selected from the group consisting of the group consisting of the group represented by formula (1a) and the group represented by formula (2a). is particularly preferred, and it is most preferred to contain a group represented by formula (2a).
• X 11a represents a hydrogen atom or -L 11a -(R 11a )p 11a .
• R 11a and R 13a each independently represent a substituent. At least one of R 11a and R 13a represents a substituent with ⁇ p greater than 0 in Hammett's rule. R 11a and R 13a may combine with each other to form a ring.
• L 11a represents a single bond or a p 11a + monovalent linking group.
• L 12a represents a single bond or a divalent linking group.
• L 13a represents a single bond or p 13a + monovalent linking group.
• p11a and p13a each independently represent an integer of 1 or more.
• L 11a represents 1 when L 11a represents a single bond
• p 13a represents 1 when L 13a represents a single bond
• * represents a binding position
• X 11a , L 11a , L 13a , R 11a , R 13a , p 11a and p 13a are respectively X 11 , L 11 , L 13 , R 11 , R 13 , p 11 and p 13 in the above formula (1) is synonymous with and preferred embodiments are also the same.
• Examples of L 12a include divalent linking groups that L 12 in the above formula (1) can take.
• the group represented by formula (1a) is preferably a group represented by formula (5a).
• X 51a represents a hydrogen atom or -L 51a -(R 51a )p 51a .
• Each R 51a independently represents a substituent. At least one of R 51a represents a substituent with ⁇ p greater than 0 in Hammett's rule.
• L 51a represents a single bond or a p 51a + monovalent linking group.
• L52a represents a single bond or a divalent linking group.
• p51a represents an integer of 1 or more. However, p51a represents 1 when L51a represents a single bond.
• Y 51a represents a ring containing -CO-N-CO-. * represents a binding position.
• X 51a , L 51a , R 51a , Y 51a and p 51a have the same meanings as X 51 , L 51 , R 51 , Y 51 and p 51 in formula (5) above, and the preferred embodiments are also the same.
• L 52a include divalent linking groups that L 52 in the above formula (5) can take.
• X 21a represents a hydrogen atom or -L 21a -(R 21a )p 21a .
• X 22a represents a hydrogen atom or -L 22a -(R 22a )p 22a .
• R 21a , R 22a and R 24a each independently represent a substituent. At least one of R 21a , R 22a and R 24a represents a substituent with ⁇ p greater than 0 in Hammett's rule.
• L 21a represents a single bond or a p 21a + monovalent linking group.
• L 22a represents a single bond or p 22a + monovalent linking group.
• L23a represents a single bond or a divalent linking group.
• L 24a represents a single bond or a p 24a + monovalent linking group. At least two of R 21a , R 22a and R 24a may combine with each other to form a ring.
• p 21a , p 22a and p 24a each independently represent an integer of 1 or more. However, p21a represents 1 when L21a represents a single bond, p22a represents 1 when L22a represents a single bond, and p24a represents 1 when L24a represents a single bond.
• n21a represents an integer of 1 or more. * represents a binding position.
• X 21a , X 22a , L 21a , L 22a , L 24a , R 21a , R 22a , R 24a , p 21a , p 22a , p 24a and n 21a are respectively X 21 and X 22 in the formula (2) , L 21 , L 22 , L 24 , R 21 , R 22 , R 24 , p 21 , p 22 , p 24 and n 21 , and the preferred embodiments are also the same.
• Examples of L 23a include divalent linking groups that L 23 in the above formula (2) can take.
• X 31a represents a hydrogen atom or -L 31a -(R 31a )p 31a .
• Each R 31a independently represents a substituent. At least one of R 31a represents a substituent with ⁇ p greater than 0 in Hammett's rule.
• L 31a represents a single bond or a p 31a + monovalent linking group.
• L 32a represents a single bond or a divalent linking group.
• p31a represents an integer of 1 or more. However, p 31a represents 1 when L 31a represents a single bond.
• Ar 31a represents an aromatic ring group. * represents a binding position.
• X 31a , L 31a , R 31a , p 31a and Ar 31a have the same meanings as X 31 , L 31 , R 31 , p 31 and Ar 31 in formula (3) above, and the preferred embodiments are also the same.
• L 32a include divalent linking groups that can be taken by L 32 in the above formula (3).
• X 41a represents a hydrogen atom or -L 41a -(R 41a )p 41a .
• X 42a represents a hydrogen atom or -L 42a -(R 42a )p 42a .
• R 41a and R 42a each independently represent a substituent. At least one of R 41a and R 42a represents a substituent with ⁇ p greater than 0 in Hammett's rule.
• L 41a represents a single bond or a p 41a + monovalent linking group.
• L 42a represents a single bond or p 42a + monovalent linking group.
• L 43a represents a single bond or a divalent linking group.
• R 41a and R 42a may combine with each other to form a ring.
• p41a and p42a each independently represent an integer of 1 or more. However, p 41a represents 1 when L 41a represents a single bond, and p 42a represents 1 when L 42a represents a single bond. * represents a binding position.
• X 41a , X 42a , L 41a , L 42a , R 41a , R 42a , p 41a and p 42a are respectively X 41 , X 42 , L 41 , L 42 , R 41 , R 42 in the above formula (4) , p 41 and p 42 , and the preferred embodiments are also the same.
• L 43a includes divalent linking groups that L 43 in the above formula (4) can take.
• X 11b represents a hydrogen atom or -L 11b -(R 11b )p 11b .
• R 11b and R 12b each independently represent a substituent. At least one of R 11b and R 12b represents a substituent with ⁇ p greater than 0 in Hammett's rule.
• L 11b represents a single bond or a p 11b + monovalent linking group.
• L 12b represents a single bond or p 12b + monovalent linking group.
• L 13b represents a single bond or a divalent linking group.
• p11b and p12b each independently represent an integer of 1 or more. However, p 11b represents 1 when L 11b represents a single bond, and p 12b represents 1 when L 12b represents a single bond.
• L 11b , L 11b , L 12b , R 11b , R 12b , p 11b and p 12b are respectively X 11 , L 11 , L 12 , R 11 , R 12 , p 11 and p 12 in the above formula (1) is synonymous with and preferred embodiments are also the same.
• L 13b includes divalent linking groups that L 13 in the above formula (1) can take.
• X 21b represents a hydrogen atom or -L 21b -(R 21b )p 21b .
• X 22b represents a hydrogen atom or -L 22b -(R 22b )p 22b .
• R 21b to R 23b each independently represent a substituent. At least one of R 21b to R 23b represents a substituent with ⁇ p greater than 0 in Hammett's rule.
• L 21b represents a single bond or a p 21b + monovalent linking group.
• L 22b represents a single bond or p 22b + monovalent linking group.
• L 23b represents a single bond or p 23b + monovalent linking group.
• L24b represents a single bond or a divalent linking group.
• R 21b and R 22b may combine with each other to form a ring.
• p 21b to p 23b each independently represent an integer of 1 or more.
• p21b represents 1 when L21b represents a single bond
• p22b represents 1 when L22b represents a single bond
• p23b represents 1 when L23b represents a single bond
• n21b represents an integer of 1 or more.
• * represents a binding position.
• X 21b , X 22b , L 21b to L 23b , R 21b to R 23b , p 21b to p 23b and n 21b are respectively X 21 , X 22 , L 21 to L 23 and R 21 in formula (2) above.
• R 23 , p 21 to p 23 and n 21 and the preferred embodiments are also the same.
• Examples of L 24b include divalent linking groups that L 24 in the above formula (2) can take.
• each R 32b independently represents a substituent. At least one of R 32b represents a substituent with ⁇ p greater than 0 in Hammett's rule.
• L 31b represents a single bond or a divalent linking group.
• L 32b represents a single bond or p 32b + monovalent linking group.
• p32b represents an integer of 1 or more. However, p 32b represents 1 when L 32b represents a single bond.
• Ar 31b represents an aromatic ring group. * represents a binding position.
• R 32b , L 32b , p 32b and Ar 31b have the same meanings as R 32 , L 32 , p 32 and Ar 31 in formula (3) above, and the preferred embodiments are also the same.
• Examples of L 31b include divalent linking groups that L 31 in the above formula (3) can take.
• X 41b represents a hydrogen atom, -L 41b -(R 41b )p 41b or -L 4b -*.
• X 42b represents a hydrogen atom, -L 42b -(R 42b )p 42b or -L 4b -*. Either of X 41b and X 42b represents -L 4b -*.
• L 4b represents a divalent linking group.
• R 41b to R 43b each independently represent a substituent. At least one of R 41b to R 43b represents a substituent with ⁇ p greater than 0 in Hammett's rule.
• L 41b represents a single bond or a p 41b + monovalent linking group.
• L 42b represents a single bond or p 42b + monovalent linking group.
• L 43b represents a single bond or p 43b + monovalent linking group.
• R 41b and R 42b may combine with each other to form a ring.
• Each of p 41b to p 43b independently represents an integer of 1 or more. However, p 41b represents 1 when L 41b represents a single bond, p 42b represents 1 when L 42b represents a single bond, and p 43b represents 1 when L 43b represents a single bond. * represents a binding position.
• X 41b , X 42b , L 41b to L 43b , R 41b to R 43b and p 41b to p 43b are respectively X 41 , X 42 , L 41 to L 43 and R 41 to R 43 in the above formula (4). and p 41 to p 43 , and the preferred embodiments are also the same.
• L 4b includes divalent linking groups that can be taken by L 41 and L 42 in formula (4) above.
• each R 52b independently represents a substituent. At least one of R 52b represents a substituent with ⁇ p greater than 0 in Hbmmet's rule.
• L51b represents a single bond or a divalent linking group.
• L 52b represents a single bond or p 52b + monovalent linking group.
• p52b represents an integer of 1 or more. However, p52b represents 1 when L52b represents a single bond.
• Y 51b represents a ring containing -CO-N-CO-.
• n5b represents an integer of 1 or 2; * represents a binding position.
• R 52b , L 52b , p 52b and Y 51b have the same meanings as R 52 , L 52 , p 52 and Y 51 in formula (5) above, and the preferred embodiments are also the same.
• L 51b include divalent linking groups that can be taken by L 51 in the above formula (5). When multiple L 51b are present, the L 51b may be the same or different.
• repeating unit a a repeating unit represented by formula (a) is preferable.
• R a1 to R a3 each independently represent a hydrogen atom or a substituent.
• L a1 represents a single bond or a divalent linking group.
• T represents a specific group A;
• R a1 to R a3 each independently represent a hydrogen atom or a substituent.
• R a1 to R a3 are each independently preferably a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group, more preferably a hydrogen atom, a halogen atom or an alkyl group, and a hydrogen atom or methyl groups are more preferred.
• L a1 represents a single bond or a divalent linking group.
• the divalent linking group include -CO-, -O-, -S-, -SO-, -SO 2 -, -NR N -, hydrocarbon groups (e.g., alkylene groups, cycloalkylene groups, alkenylene groups and arylene groups) and combinations thereof.
• RN represents a substituent.
• the above hydrocarbon group may further have a substituent, and preferably has a halogen atom (preferably a fluorine atom) as a substituent.
• the above alkylene group may be linear or branched.
• the alkylene group preferably has 1 to 4 carbon atoms.
• the cycloalkylene group may be either monocyclic or polycyclic.
• the cycloalkylene group preferably has 3 to 15 carbon atoms.
• One or more (eg, 1 or 2) —CH 2 — constituting the ring structure of the cycloalkylene group is a hetero atom (eg, —O— and —S—), —SO 2 —, —SO 3- , may be substituted with an alkoxycarbonyl group or a carbonyl group.
• T represents a specific group A;
• the specific group A is a residue formed by removing one hydrogen atom from a specific compound.
• Specific group A includes, for example, monovalent groups among the above specific groups.
• the repeating unit a is more preferably a repeating unit represented by any one of formulas (aa) to (ac).
• R 1a to R 3a each independently represent a hydrogen atom or a substituent.
• L 1a represents a single bond, an alkylene group, —COO—, an aromatic ring group, or a combination thereof.
• Ar represents an aromatic ring group.
• Z represents a group represented by any one of formulas (Z1a) to (Z4a) or a group represented by any one of formulas (Z1b) to (Z4b).
• R 1a to R 3a each independently represent a hydrogen atom or a substituent.
• R 1a to R 3a are each independently preferably a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group, more preferably a hydrogen atom, a halogen atom or an alkyl group, a hydrogen atom or a methyl groups are more preferred.
• L 1a represents a single bond, an alkylene group, —COO—, an aromatic ring group, or a combination thereof.
• the alkylene group may be linear or branched.
• the alkylene group preferably has 1 to 4 carbon atoms.
• the above aromatic ring group may be either monocyclic or polycyclic.
• the number of ring member atoms of the aromatic ring group is preferably 5-15.
• the aromatic ring group may have one or more (eg, 1 to 5) heteroatoms (eg, oxygen, sulfur and/or nitrogen atoms) as ring member atoms.
• a benzene ring group is preferable as the aromatic ring group. Examples of the combined group include -COO-alkylene group and -COO-aromatic ring group-.
• the alkylene group and the aromatic ring group may further have a substituent.
• L 1a is preferably a single bond or an alkylene group, more preferably a single bond.
• Ar represents an aromatic ring group.
• the above aromatic ring group may be either monocyclic or polycyclic.
• the number of ring member atoms of the aromatic ring group is preferably 5-15.
• the ring member atoms of the aromatic ring group may have one or more (eg, 1 to 5) heteroatoms (eg, oxygen atom, sulfur atom, nitrogen atom, etc.).
• the aromatic ring group may further have a substituent. Examples of the above substituent include substituents that R 11 to R 13 in formula (1) can take.
• the aromatic ring group is preferably an arylene group such as a phenylene group and a naphthylene group, more preferably a phenylene group.
• Z represents a group represented by any one of formulas (Z1a) to (Z4a) or a group represented by any one of formulas (Z1b) to (Z4b).
• Z is preferably a group represented by any one of formulas (Z1a) to (Z4a), more preferably a group represented by any one of formulas (Z1a) to (Z3a), and is represented by formula (Z2a). is more preferred.
• the group represented by formula (Z1a) is preferably a group represented by formula (Z5a).
• X 41zb represents a hydrogen atom, -L 41 -(R 41 )p 41 or -*.
• X 42zb represents a hydrogen atom, -L 42 -(R 42 )p 42 or -*.
• Either of X 41zb and X 42zb represents -*.
• * represents a binding position.
• L 41 , R 41 , p 41 , L 42 , R 42 and p 42 are as described above.
• R 1b to R 3b each independently represent a hydrogen atom or a substituent.
• L 1b represents a single bond, an alkylene group, --COO-- or a combination thereof.
• L2b represents a single bond or an alkylene group.
• Z represents a group represented by any one of formulas (Z1a) to (Z4a) or a group represented by any one of formulas (Z1b) to (Z4b).
• R 1b to R 3b each independently represent a hydrogen atom or a substituent.
• R 1b to R 3b are each independently preferably a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group, more preferably a hydrogen atom, a halogen atom or an alkyl group, a hydrogen atom or a methyl groups are more preferred.
• L 1b represents a single bond, an alkylene group, --COO-- or a combination thereof.
• the above alkylene group may be linear or branched.
• the alkylene group preferably has 1 to 4 carbon atoms. Examples of the combined groups include -COO-alkylene groups.
• the alkylene group may further have a substituent. Examples of the above substituent include substituents that R 11 to R 13 in formula (1) can take.
• L1b is preferably a single bond or an alkylene group, more preferably a single bond.
• L2b represents a single bond or an alkylene group.
• alkylene group examples include alkylene groups that can be taken by L a1 in formula (a).
• L 2b is preferably an alkylene group.
• Z represents a group represented by any one of formulas (Z1a) to (Z4a) or a group represented by any one of formulas (Z1b) to (Z4b).
• Z has the same meaning as Z in the above formula (aa), and the preferred embodiments are also the same.
• R 1c to R 3c each independently represent a hydrogen atom or a substituent.
• L 1c represents a single bond, an alkylene group, --COO--, an aromatic ring group, or a combination thereof.
• L2c represents a cycloalkylene group.
• L 3c represents a single bond or a divalent linking group.
• Z represents a group represented by any one of formulas (Z1a) to (Z4a) or a group represented by any one of formulas (Z1b) to (Z4b).
• R 1c to R 3c each independently represent a hydrogen atom or a substituent.
• R 1c to R 3c are each independently preferably a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group, more preferably a hydrogen atom, a halogen atom or an alkyl group, a hydrogen atom or a methyl groups are more preferred.
• L 1c represents a single bond, an alkylene group, --COO--, an aromatic ring group, or a combination thereof.
• L 1c includes L a1 in formula (a).
• L 1c is preferably a single bond, an alkylene group, --COO-- or a combination thereof, more preferably --COO--.
• L2c represents a cycloalkylene group.
• the cycloalkylene group may be either monocyclic or polycyclic.
• the cycloalkylene group preferably has 3 to 15 carbon atoms.
• One or more (eg, 1 or 2) —CH 2 — constituting the ring structure of the cycloalkylene group is a hetero atom (eg, —O— and —S—), —SO 2 —, —SO 3- , may be substituted with an alkoxycarbonyl group or a carbonyl group.
• the cycloalkylene group may further have a substituent. Examples of the above substituent include substituents that R 11 to R 13 in formula (1) can take.
• L 3c represents a single bond or a divalent linking group.
• the divalent linking group include -CO-, -O-, -S-, -SO-, -SO 2 -, -NR N -, hydrocarbon groups (e.g., alkylene groups, cycloalkylene groups, alkenylene groups and arylene groups) and combinations thereof.
• R N represents a substituent (for example, a substituent that the above R 11 to R 13 can take).
• the above hydrocarbon group may further have a substituent, and preferably has a halogen atom (preferably a fluorine atom) as a substituent.
• L 3c is preferably an alkylene group optionally having a fluorine atom or an alkoxycarbonyl group optionally having a fluorine atom.
• Z represents a group represented by any one of formulas (Z1a) to (Z4a) or a group represented by any one of formulas (Z1b) to (Z4b).
• Z has the same meaning as Z in the above formula (aa), and the preferred embodiments are also the same.
• repeating unit a a repeating unit represented by formula (ad) or a repeating unit represented by formula (ae) is also preferable.
• R 1b represents a hydrogen atom or a substituent.
• Y 51d represents a ring containing -CO-N-CO- and one carbon atom.
• R 1d is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group, more preferably a hydrogen atom, a halogen atom or an alkyl group, still more preferably a hydrogen atom or a methyl group.
• Y 51d includes a ring further containing one carbon atom among Y 51 in the above formula (5).
• the number of carbon atoms contained in Y 51d is not particularly limited as long as it is 1, and may be 2 or more.
• Y 51e represents -CO-N-CO- and a ring containing two carbon atoms.
• Y 51e includes a ring further containing two carbon atoms among Y 51 in the above formula (5).
• the number of carbon atoms contained in Y 51e is not particularly limited as long as it is two, and may be three or more.
• repeating unit a examples include repeating units derived from the following monomers.
• the content of the repeating unit a is preferably 1 mol % or more, more preferably 10 mol % or more, still more preferably 30 mol % or more, and particularly preferably 40 mol % or more, based on the total repeating units of the resin A.
• the upper limit is preferably less than 100 mol%, more preferably 90 mol% or less, still more preferably 70 mol% or less, relative to all repeating units.
• the content of the repeating unit a is 10 mol% or more, preferably 30 mol% or more, and 40 mol% with respect to the total repeating units of the resin A. The above is more preferable.
• the upper limit is preferably less than 100 mol%, more preferably 90 mol% or less, still more preferably 70 mol% or less, relative to all repeating units.
• one or more resins A having a repeating unit a content of 40 mol % or more based on the total repeating units be included.
• the content of the repeating unit a is 40 mol% or more of the total repeating units, and the total content of the resin A preferably contains 30 to 100% by mass, preferably 60 to 100% by mass. More preferably, it contains 80 to 100% by mass.
• Resin A may have a repeating unit having an acid group.
• the repeating unit having an acid group is preferably different from the repeating units described above.
• the acid dissociation constant (pKa) of the acid group is preferably 13 or less, more preferably 3-13, even more preferably 5-10.
• the content of acid groups in Resin A is often 0.2 to 6.0 mmol/g, preferably 0.8 to 6.0 mmol/g. , 1.2 to 5.0 mmol/g, more preferably 1.6 to 4.0 mmol/g.
• the acid group is preferably a carboxy group, hydroxyl group, phenolic hydroxyl group, fluorinated alcohol group (preferably hexafluoroisopropanol group), sulfonic acid group, sulfonamide group or isopropanol group.
• fluorinated alcohol group preferably hexafluoroisopropanol group
• sulfonic acid group preferably sulfonamide group or isopropanol group.
• One or more (preferably 1 to 2) fluorine atoms in the hexafluoroisopropanol group may be substituted with groups other than fluorine atoms (eg, alkoxycarbonyl group, etc.).
• Also preferred as an acid group is --C(CF 3 )(OH)--CF 2 -- formed as described above.
• one or more fluorine atoms may be substituted with groups other than fluorine atoms to form a ring containing -C(CF 3 )(OH)-CF 2 -.
• a repeating unit having an acid group may have a fluorine atom or an iodine atom.
• a repeating unit represented by formula (B) is preferable.
• R 3 represents a hydrogen atom or a monovalent organic group optionally having a fluorine atom or an iodine atom.
• a group represented by -L 4 -R 8 is preferred.
• L 4 represents a single bond or -COO-.
• R 8 is an alkyl group optionally having a fluorine atom or an iodine atom, a cycloalkyl group optionally having a fluorine atom or an iodine atom, an aryl group optionally having a fluorine atom or an iodine atom, or It represents a group in which these are combined.
• R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an iodine atom, or an alkyl group optionally having a fluorine atom or an iodine atom.
• L 2 is a single bond, —COO—, —CO—, —O—, or an alkylene group (preferably having 1 to 6 carbon atoms. It may be linear or branched. Further, —CH 2 — is (which may be substituted with a heteroatom) represents a divalent group formed by combining.
• L3 represents an (n+m+1) -valent aromatic ring group or (n+m+1)-valent alicyclic group.
• the aromatic ring group may be either monocyclic or polycyclic. Examples include a benzene ring group and a naphthalene ring group.
• the alicyclic group may be either monocyclic or polycyclic. Examples include cycloalkyl ring groups, norbornene ring groups and adamantane ring groups.
• R6 represents a hydroxyl group or a fluorinated alcohol group.
• a monovalent group represented by formula (3L) is preferred.
• *-L 6X -R 6X (3L) L6X represents a single bond or a divalent linking group.
• divalent linking groups include -CO-, -O-, -SO-, -SO 2 -, and -NR A - (R A represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ), an alkylene group (preferably having 1 to 6 carbon atoms, which may be linear or branched), and a divalent linking group combining a plurality of these.
• the said alkylene group may have a substituent.
• substituents include halogen atoms (preferably fluorine atoms) and hydroxyl groups.
• R 6X represents a hexafluoroisopropanol group.
• L 3 is also preferably an (n+m+1)-valent aromatic ring group.
• R7 represents a halogen atom.
• Halogen atoms include, for example, fluorine, chlorine, bromine and iodine atoms.
• m represents an integer of 1 or more. As m, an integer of 1 to 3 is preferable, and an integer of 1 to 2 is more preferable.
• n represents an integer of 0 or 1 or more. n is preferably an integer of 1-4. (n+m+1) is preferably an integer of 1 to 5.
• repeating units having an acid group include the following repeating units.
• the content of repeating units having an acid group is preferably 5 mol% or more, more preferably 10 mol% or more, relative to the total repeating units of Resin A.
• the upper limit is preferably 70 mol % or less, more preferably 65 mol % or less, and even more preferably 60 mol % or less, relative to all repeating units of Resin A.
• Resin A preferably has an acid-decomposable group.
• the acid-decomposable group does not include the above specific group. Also, the acid-decomposable group does not have a specific group as a part thereof. That is, repeating unit b does not contain repeating unit a.
• “Acid-decomposable group” means a group that is decomposed by the action of an acid to form a polar group.
• the acid-decomposable group preferably has a structure in which the polar group is protected with a leaving group that leaves under the action of an acid. The acid-decomposable group will be described later.
• Resin A having an acid-decomposable group is hereinafter also referred to as an acid-decomposable resin.
• Alkali-soluble groups include, for example, a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphoric acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl) (alkylcarbonyl) methylene group, an (alkylsulfonyl ) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group and tris ( Examples include acidic groups such as alkylsulfonyl)methylene groups, and alcoholic hydroxyl groups.
• the acid-decomposable group preferably has a structure in which the polar group is protected with a leaving group that leaves under the action of an acid.
• the leaving group that leaves by the action of an acid include groups represented by formulas (Y1) to (Y4).
• Formula (Y2): -C( O)OC(Rx 1 )(Rx 2 )(Rx 3 )
• Rx 1 to Rx 3 each independently represent an alkyl group (linear or branched, preferably having 1 to 6 carbon atoms), a cycloalkyl group (monocyclic or polycyclic). ring, preferably 3 to 15 carbon atoms), alkenyl group (linear or branched, preferably 2 to 6 carbon atoms), aryl group (monocyclic or polycyclic, preferably 6 to 15 carbon atoms) or hetero represents an aryl group (monocyclic or polycyclic, preferably having 5 to 15 ring member atoms). Two of Rx 1 to Rx 3 may combine with each other to form a ring. The above ring may be either monocyclic or polycyclic.
• Monocyclic and polycyclic rings include, for example, cycloalkane rings.
• the cycloalkane ring is preferably a monocyclic cycloalkane ring such as cyclopentane ring and cyclohexane ring, or a polycyclic cycloalkane ring such as norbornane ring, tetracyclodecane ring, tetracyclododecane ring and adamantane ring.
• cycloalkane ring for example, one or more (eg, 1 to 3) of the methylene groups constituting the ring are replaced by a heteroatom (—O— or —S—, etc.), —SO 2 —, —SO 3 — , —COO—, a carbonyl group or a vinylidene group.
• one or more (for example, 1 to 2) ethylene groups constituting the cycloalkane ring may be substituted with a vinylene group.
• Rx 1 to Rx 3 are bonded to each other to form a cycloalkane ring, and the cycloalkane ring is the ⁇ carbon relative to the C (carbon) atom in formula (Y1)
• the remaining one of Rx 1 to Rx 3 may be a hydrogen atom.
• R 36 to R 38 each independently represent a hydrogen atom or an organic group.
• the organic group include alkyl groups (linear or branched, preferably having 1 to 6 carbon atoms), cycloalkyl groups (monocyclic or polycyclic, preferably having 3 to 15 carbon atoms), aryl groups (monocyclic or polycyclic (preferably having 6 to 15 carbon atoms), an aralkyl group (preferably having 7 to 18 carbon atoms) or an alkenyl group (linear or branched, preferably having 2 to 6 carbon atoms).
• R 37 and R 38 may combine with each other to form a ring.
• the ring formed above includes, for example, the same monocyclic or polycyclic ring that can be formed by combining two of Rx 1 to Rx 3 .
• Ar represents an aromatic ring group.
• Rn is an alkyl group (linear or branched, preferably 1 to 6 carbon atoms), a cycloalkyl group (monocyclic or polycyclic, preferably 3 to 15 carbon atoms) or an aryl group (monocyclic or polycyclic , preferably 6 to 15 carbon atoms).
• Rn and Ar may combine with each other to form a non-aromatic ring.
• Rn is preferably an aryl group (monocyclic or polycyclic, preferably having 6 to 15 carbon atoms).
• Resin A preferably has a repeating unit having an acid-decomposable group (hereinafter also referred to as "repeating unit b").
• Repeating unit b preferably contains at least one selected from the group consisting of repeating units represented by any of formulas (M1) to (M5), and from the viewpoint of better sensitivity, formula (M4) It is more preferable to include at least one selected from the group consisting of the repeating unit represented by the formula (M5) and the repeating unit represented by formula (M5).
• R m11 to R m13 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
• L m11 represents a single bond or a divalent linking group.
• R m14 to R m16 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. At least two of R m14 to R m16 may combine with each other to form a ring.
• R m11 to R m13 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
• the alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1-6.
• the cycloalkyl group may be either monocyclic or polycyclic.
• the cycloalkyl group preferably has 3 to 15 carbon atoms.
• Halogen atoms include, for example, fluorine, chlorine, bromine and iodine atoms.
• the alkoxycarbonyl group preferably has 1 to 10 carbon atoms.
• R m11 is preferably a hydrogen atom or an alkyl group, more preferably an alkyl group, and even more preferably a methyl group.
• R m12 and R m13 are preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.
• L m11 represents a single bond or a divalent linking group.
• the divalent linking group include -CO-, -O-, -S-, -SO-, -SO 2 -, -NR N - (R N represents a substituent), hydrocarbon groups (eg, alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups, etc.) and groups combining them.
• the above hydrocarbon group may further have a substituent, and preferably has a halogen atom as a substituent.
• L m11 is preferably a single bond or an alkylene group.
• R m14 to R m16 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
• the alkyl group may be linear or branched.
• the number of carbon atoms in the alkyl group is preferably 1-6, more preferably 1-3.
• the cycloalkyl group may be either monocyclic or polycyclic.
• the cycloalkyl group preferably has 3 to 15 carbon atoms.
• the aryl group may be monocyclic or polycyclic.
• the aryl group preferably has 6 to 15 carbon atoms.
• the aralkyl group preferably has 7 to 18 carbon atoms.
• the alkenyl group may be linear or branched.
• the alkenyl group preferably has 2 to 6 carbon atoms.
• the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group and the alkenyl group may further have a substituent, and preferably have a halogen atom (preferably a fluorine atom) as a substituent.
• R m14 to R m16 are preferably an alkyl group or an aryl group, preferably an alkyl group.
• R m21 to R m24 each independently represent a hydrogen atom or an organic group. However, at least one of R m21 and R m22 represents an organic group.
• X m21 represents -CO-, -SO- or -SO 2 -.
• Y m21 represents -O-, -S-, -SO-, -SO 2 - or -NR 34 -.
• R34 represents a hydrogen atom or an organic group.
• L m21 represents a single bond or a divalent linking group.
• R m25 to R m27 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. At least two of R m25 to R m27 may combine with each other to form a ring.
• R m21 to R m24 each independently represent a hydrogen atom or an organic group. However, at least one of R m21 and R m22 represents an organic group. Examples of the organic group include alkyl groups (linear or branched, preferably having 1 to 6 carbon atoms), cycloalkyl groups (monocyclic or polycyclic, preferably having 3 to 15 carbon atoms), aryl groups (monocyclic or polycyclic (preferably having 6 to 15 carbon atoms), an aralkyl group (preferably having 7 to 18 carbon atoms) or an alkenyl group (linear or branched, preferably having 2 to 6 carbon atoms).
• R m21 and R m22 are preferably alkyl groups, more preferably fluorine atom-containing alkyl groups.
• R m23 and R m24 are preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.
• X m21 represents -CO-, -SO- or -SO 2 -.
• X m21 is preferably -CO-.
• Y m21 represents -O-, -S-, -SO-, -SO 2 - or -NR 34 -.
• Y m21 is preferably -O- or -S-, more preferably -O-.
• R34 represents a hydrogen atom or an organic group.
• R 34 is preferably an organic group. Examples of the organic group include organic groups that can be taken by R m21 to R m24 in the formula (M2).
• L m21 represents a single bond or a divalent linking group.
• the divalent linking group include -CO-, -O-, -S-, -SO-, -SO 2 -, -NR N - (R N represents a substituent), hydrocarbon group (for example, an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, etc.) and a group combining them.
• the above hydrocarbon group may further have a substituent, and preferably has a halogen atom as a substituent.
• L m21 is preferably a hydrocarbon group, more preferably an alkylene group.
• R m25 to R m27 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
• the alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1-6.
• the cycloalkyl group may be either monocyclic or polycyclic. The cycloalkyl group preferably has 3 to 15 carbon atoms.
• the aryl group may be monocyclic or polycyclic. The aryl group preferably has 6 to 15 carbon atoms.
• the aralkyl group preferably has 7 to 18 carbon atoms.
• the alkenyl group may be linear or branched.
• the alkenyl group preferably has 2 to 6 carbon atoms.
• the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group and the alkenyl group may further have a substituent, and preferably have a halogen atom (preferably a fluorine atom) as a substituent.
• R m25 to R m27 are preferably alkyl groups or aryl groups. At least two of R m25 to R m27 may combine with each other to form a ring.
• R m31 and R m32 each independently represent a hydrogen atom or an organic group.
• R m33 and R m34 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. At least two of R m31 to R m34 may combine with each other to form a ring.
• Examples of the organic group include organic groups that can be taken by R m21 to R m24 in the formula (M2).
• R m31 and R m32 are preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.
• Examples of R m33 and R m34 include groups that can be taken by R m25 to R m27 in the above formula (M2), preferably a hydrogen atom or an alkyl group. At least two of R m31 to R m34 may combine with each other to form a ring. Among them, R m31 and R m32 , and R m33 and R m34 are preferably bonded to each other to form a ring.
• R m41 to R m43 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
• L m41 represents a single bond or a divalent linking group.
• Arm41 represents an aromatic ring group.
• R m44 to R m46 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. At least two of R m44 to R m46 may combine with each other to form a ring.
• R m41 to R m43 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
• the alkyl group may be linear or branched.
• the number of carbon atoms in the alkyl group is preferably 1-6, more preferably 1-3.
• the cycloalkyl group may be either monocyclic or polycyclic.
• the cycloalkyl group preferably has 3 to 15 carbon atoms.
• Halogen atoms include, for example, fluorine, chlorine, bromine and iodine atoms.
• the alkoxycarbonyl group preferably has 1 to 10 carbon atoms.
• R m41 to R m43 are preferably hydrogen atoms or alkyl groups (preferably methyl groups), more preferably hydrogen atoms.
• L m41 represents a single bond or a divalent linking group.
• L m41 includes groups that can be taken by L m11 in the above formula (M1), and is preferably a single bond.
• Arm41 represents an aromatic ring group.
• the above aromatic ring group may be either monocyclic or polycyclic.
• the number of ring member atoms of the aromatic ring group is preferably 5-15.
• the aromatic ring group may have one or more (eg, 1 to 5) heteroatoms (eg, oxygen, sulfur and/or nitrogen atoms) as ring member atoms.
• the aromatic ring group is preferably a benzene ring group or a naphthalene ring group, more preferably a benzene ring.
• R m44 to R m46 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
• R m44 to R m46 include groups that can be taken by R m25 to R m27 in the above formula (M2).
• R m44 to R m46 are preferably hydrogen atoms or alkyl groups (preferably methyl groups).
• At least two of R m44 to R m46 may combine with each other to form a ring.
• R m45 and R m47 are preferably bonded to each other to form a ring.
• Arm41 may combine with Rm43 or Rm44 to form a ring.
• R m51 to R m53 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
• L m51 represents a single bond or a divalent linking group.
• R m54 and R m55 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
• R m56 represents an alkyl group, cycloalkyl group, aryl group, aralkyl group or alkenyl group. At least two of R m54 to R m56 may combine with each other to form a ring.
• R m51 to R m53 have the same meanings as R m41 to R m43 in formula (M4) above, and the preferred embodiments are also the same.
• L m51 has the same definition as L m41 in the above formula (M4), and the preferred embodiments are also the same.
• R m54 to R m56 have the same meanings as R m25 to R m27 in formula (M2) above, and the preferred embodiments are also the same. At least two of R m54 to R m56 may combine with each other to form a ring. Among them, R m55 and R m56 are preferably bonded to each other to form a ring.
• the content of the repeating unit b is preferably 1 mol% or more, more preferably 10 mol% or more, and still more preferably 15 mol% or more, relative to the total repeating units of the resin A.
• the upper limit is preferably 80 mol % or less, more preferably 70 mol % or less, and even more preferably 60 mol % or less, relative to all repeating units of Resin A.
• Resin A may have a repeating unit having a lactone group.
• a repeating unit having a lactone group may or may not correspond to the above repeating unit.
• a repeating unit having a lactone group may or may not correspond to the repeating unit a as long as it has a lactone group, and may or may not correspond to the repeating unit having an acid-decomposable group. .
• the lactone group is not particularly limited as long as it has a lactone structure or a sultone structure.
• the lactone structure is preferably a 5- to 7-membered lactone structure, and more preferably the 5- to 7-membered lactone structure is condensed with another ring structure to form a bicyclo structure or a spiro structure.
• Resin A is a repeat having a lactone group formed by removing one or more (for example, 1 or 2) hydrogen atoms from the lactone structure represented by any of formulas (LC1-1) to (LC1-21). It is preferred to have units.
• the lactone group may be directly attached to the main chain.
• the ring member atoms of the lactone group may form part of the resin A backbone.
• the lactone structure may have a substituent (Rb 2 ).
• substituent (Rb 2 ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, carboxy group, a halogen atom, a hydroxyl group, a cyano group, a group containing an acid-decomposable group (the acid-decomposable group itself may be used), and a combination thereof.
• n2 represents an integer from 0 to 4; When n2 is 2 or more, multiple Rb2 may be the same or different, and multiple Rb2 may combine with each other to form a ring.
• ring member atoms of the lactone structure one or more (eg, 1 to 2) methylene groups not adjacent to -COO- or O- may be substituted with heteroatoms such as -O- or -S-. good.
• repeating units having a lactone group examples include repeating units represented by formula (AI).
• Rb 0 represents a hydrogen atom, a halogen atom or an optionally substituted alkyl group having 1 to 4 carbon atoms.
• a hydroxyl group or a halogen atom is preferable as the substituent.
• the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom.
• Rb 0 is preferably a hydrogen atom or a methyl group.
• Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, —COO—, a carbonyl group, a carboxy group, or a group combining these.
• Ab 1 represents a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group. Among them, a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group or a norbornylene group is preferable.
• V represents a group formed by removing one hydrogen atom from a ring member atom of the lactone structure represented by any one of formulas (LC1-1) to (LC1-21).
• repeating unit having a lactone group a repeating unit represented by formula (AII) or a repeating unit represented by (AIII) is preferable.
• each RIII independently represents a hydrogen atom or a substituent.
• RIII is preferably a hydrogen atom.
• ahd 1 represents a group formed by removing one hydrogen atom from each adjacent ring member atom of the lactone structure represented by any one of formulas (LC1-1) to (LC1-21).
• ahd 2 represents a group formed by removing two hydrogen atoms from one ring member atom of the lactone structure represented by any one of formulas (LC1-1) to (LC1-21).
• repeating units having a lactone group include the following repeating units.
• any optical isomer may be used. Moreover, one kind of optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, its optical purity (ee) is preferably 90 or more, more preferably 95 or more. As an upper limit, 100 or less are preferable.
• the content of repeating units having a lactone group is preferably 5 to 99 mol%, more preferably 10 to 80 mol%, still more preferably 15 to 65 mol%, based on the total repeating units of Resin A.
• the total of repeating units having a lactone group corresponding to the repeating unit a and repeating units having a lactone group not corresponding to the repeating unit a may satisfy the above preferable content
• a repeating unit having a lactone group corresponding to repeating unit a may satisfy the above preferred content alone, or a repeating unit having a lactone group not corresponding to repeating unit a may satisfy the above preferred content alone. good too.
• Resin A may have a repeating unit having a sultone group.
• the sultone group is not particularly limited as long as it has a sultone structure.
• the sultone structure is preferably a 5- to 7-membered sultone structure, and more preferably the 5- to 7-membered sultone structure is condensed with another ring structure to form a bicyclo structure or a spiro structure.
• the sultone group may be directly attached to the main chain.
• the ring member atoms of the sultone group may form part of the main chain of Resin A.
• Resin A is a sultone formed by removing one or more hydrogen atoms (for example, 1 to 2) from a ring member atom of a sultone structure represented by any one of formulas (SL1-1) to (SL1-3). It is preferable to have a repeating unit having a group.
• the sultone structure may have a substituent (Rb 2 ).
• the substituent (Rb 2 ) in formulas (SL1-1) to (SL1-3) is the same as the substituent (Rb 2 ) in the lactone structures represented by formulas (LC1-1) to (LC1-21) above. can explain.
• the ring member atoms of the sultone structure one or more methylene groups (eg, 1 to 2) not adjacent to -COO- or -O- are substituted with heteroatoms such as -O- or -S- good too.
• V is a ring member of a sultone structure represented by any one of formulas (SL1-1) to (SL1-3).
• ahd 1 is any of formulas (SL1-1) to (SL1-3)
• ahd 2 is represented by the formula ( SL1-1) to (SL1-3) include repeating units substituted with a group formed by removing two hydrogen atoms from one of the ring member atoms of the sultone structure represented by any one of (SL1-3).
• a cyclic carbonate group is preferred.
• a repeating unit having a cyclic carbonate group a repeating unit represented by formula (A-1) is preferable.
• R A 1 represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group).
• n represents an integer of 0 or more.
• R A 2 represents a substituent. When n is 2 or more, multiple 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, -O-, -COO-, a carbonyl group, a carboxy group, or a group combining these is preferred.
• Z represents a ring containing -O-CO-O-. The above ring may be either monocyclic or polycyclic.
• repeating units having a sultone group or a carbonate group include the following repeating units.
• the content of repeating units having a sultone group or a carbonate group is preferably 1 mol % or more, more preferably 10 mol % or more, relative to the total repeating units of Resin A.
• the upper limit is preferably 85 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol% or less, and particularly preferably 60 mol% or less, relative to all repeating units of Resin A.
• Resin A may have a repeating unit having a fluorine atom or an iodine atom.
• a repeating unit having a fluorine atom or an iodine atom is preferably different from the above repeating unit.
• repeating unit having a fluorine atom or an iodine atom a repeating unit represented by formula (C) is preferable.
• L5 represents a single bond or -COO-.
• 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 It represents an aryl group or a group combining these.
• repeating units having a fluorine atom or an iodine atom include the following repeating units.
• the content of repeating units having a fluorine atom or an iodine atom is preferably 1 mol % or more, more preferably 5 mol % or more, still more preferably 10 mol % or more, relative to the total repeating units of Resin A.
• the upper limit is preferably 50 mol % or less, more preferably 45 mol % or less, and even more preferably 40 mol % or less, relative to all repeating units of Resin A.
• Resin A may have a repeating unit represented by formula (V-1) or a repeating unit represented by formula (V-2).
• the repeating unit represented by formula (V-1) and the repeating unit represented by formula (V-2) are preferably different repeating units from the above repeating units.
• R 6 and R 7 are each independently a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, and a halogen atom.
• —OCOR or —COOR R represents an alkyl group having 1 to 6 carbon atoms or a fluorinated alkyl group
• n3 represents an integer of 0-6.
• n4 represents an integer of 0-4.
• X4 represents a methylene group, an oxygen atom or a sulfur atom.
• the content of the repeating unit represented by the formula (V-1) or the repeating unit represented by the formula (V-2) is preferably 1 to 65 mol%, based on the total repeating units of the resin A, and 5 to 45 mol % is more preferred.
• Resin A may have repeat units to reduce backbone mobility.
• the repeating unit for reducing the mobility of the main chain is preferably a repeating unit different from the above repeating unit.
• 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 above 90°C, more preferably above 100°C, still more preferably above 110°C, and particularly preferably above 125°C. Since an excessively high Tg causes a decrease in the dissolution rate in the developer, the Tg is preferably 400° C. or less, more preferably 350° C. or less.
• the glass transition temperature (Tg) of the polymer such as resin A is calculated by the following method. First, the Tg of a homopolymer consisting only of each repeating unit contained in the polymer (hereinafter also referred to as "Tg of repeating unit”) is calculated by the Bicerano method. Next, the mass ratio (%) of each repeating unit to all repeating units in the polymer is calculated. Next, 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) and others. In addition, calculation of Tg by the Bicerano method can be performed using a polymer property estimation software MDL Polymer (MDL Information Systems, Inc.).
• Methods for reducing the mobility of the main chain of resin A include, for example, 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 has a repeating unit exhibiting a homopolymer Tg of 130° C. or higher. The repeating unit having a homopolymer Tg of 130° C.
• the or higher may be a repeating unit having a homopolymer Tg of 130° C. or higher as calculated by the Bicerano method.
• the homopolymers correspond to repeating units exhibiting Tg of 130° C. or higher.
• RA represents a group having a polycyclic structure.
• R x represents a hydrogen atom, a methyl group or an ethyl group.
• a “group having a polycyclic structure” is a group having multiple ring structures, and the multiple ring structures may or may not be condensed.
• Examples of the repeating unit represented by formula (Aa) include those described in paragraphs [0107] to [0119] of WO 2018/193954.
• the content of the repeating unit represented by formula (Aa) is preferably 1 to 65 mol %, more preferably 5 to 45 mol %, based on the total repeating units of Resin A.
• R b1 to R b4 each independently represent a hydrogen atom or an organic group. At least two or more of R b1 to R b4 represent an organic group. Moreover, when at least one of the organic groups is a group in which a ring structure is directly linked to the main chain in the repeating unit, the type of the other organic group is not particularly limited. Further, when none of the organic groups is a group in which the ring structure is directly linked to the main chain in the repeating unit, at least two of the organic groups have three or more constituent atoms excluding hydrogen atoms. is a substituent. Examples of the repeating unit represented by formula (B) include those described in paragraphs [0113] to [0115] of WO 2018/193954. The content of the repeating unit represented by formula (B) is preferably 1 to 65 mol %, more preferably 5 to 45 mol %, based on the total repeating units of resin A.
• R c1 to R c4 each independently represent a hydrogen atom or an organic group. At least one of R c1 to R c4 represents a group having a hydrogen bonding hydrogen atom within 3 atoms from the main chain carbon. Among them, from the viewpoint of inducing interaction between the main chains of Resin A, it is preferable to have a hydrogen-bonding hydrogen atom within 2 atoms (closer to the main chain side).
• Examples of the repeating unit represented by formula (C) include those described in paragraphs [0119] to [0121] of WO 2018/193954.
• the content of the repeating unit represented by formula (C) is preferably 1 to 65 mol %, more preferably 5 to 45 mol %, based on the total repeating units of Resin A.
• “cylic” represents a group forming a main chain with a cyclic structure.
• the number of atoms constituting the ring is not particularly limited.
• Examples of the repeating unit represented by formula (D) include those described in paragraphs [0126] to [0027] of WO 2018/193954.
• the content of the repeating unit represented by formula (D) is preferably 1 to 65 mol %, more preferably 5 to 45 mol %, relative to the total repeating units of Resin A.
• each Re independently represents a hydrogen atom or an organic group.
• Organic groups include, for example, alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups. The organic group may further have a substituent.
• a "cylic” is a cyclic group containing the main chain carbon atoms. The number of atoms contained in the cyclic group is not particularly limited. Examples of the repeating unit represented by formula (E) include those described in paragraphs [0131] to [0133] of WO 2018/193954.
• the content of the repeating unit represented by formula (E) is preferably 1 to 65 mol %, more preferably 5 to 45 mol %, based on the total repeating units of Resin A.
• Resin A may have a repeating unit having a hydroxyl group or a cyano group. This improves substrate adhesion and/or developer affinity.
• 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 [0153] to [0158] of WO2020/004306.
• the content of repeating units having a hydroxyl group or a cyano group is preferably 1 to 65 mol %, more preferably 5 to 45 mol %, based on the total repeating units of Resin A.
• Resin A may have a repeating unit that has an alicyclic hydrocarbon structure and does not exhibit acid decomposability. This can reduce the elution of low-molecular-weight components from the resist film into the immersion liquid during immersion exposure.
• repeating units include repeating units derived from 1-adamantyl (meth)acrylate, diamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate or cyclohexyl (meth)acrylate.
• the content of repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposability is preferably 1 to 65 mol %, more preferably 5 to 45 mol %, based on the total repeating units in Resin A.
• 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.
• the cyclic structure of R 5 includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group.
• monocyclic hydrocarbon groups include cycloalkyl groups having 3 to 12 carbon atoms (preferably 3 to 7 carbon atoms) and cycloalkenyl groups having 3 to 12 carbon atoms.
• Examples of the definition of each group and the repeating unit in formula (III) include those described in paragraphs [0169] to [0173] of WO2020/004306.
• the content of the repeating unit represented by the formula (III), which has neither a hydroxyl group nor a cyano group, is preferably 1 to 65 mol%, more preferably 5 to 45 mol%, based on the total repeating units of the resin A. more preferred.
• Resin A may have other repeating units in addition to the above repeating units.
• Other repeating units are not particularly limited as long as they are other than the above repeating units.
• Other repeating units include, for example, a group consisting of a repeating unit having an oxathian ring group, a repeating unit having an oxazolone ring group, a repeating unit having a dioxane ring group, a repeating unit having a hydantoin ring group, and a repeating unit having a sulfolane ring group. It may have a repeating unit selected from
• the content of other repeating units is preferably 1 to 65 mol%, more preferably 5 to 45 mol%, relative to the total repeating units of resin A.
• repeating units include, for example, the following repeating units.
• Resin A may have various repeating units for the purpose of adjusting dry etching resistance, standard developer suitability, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, and the like.
• Resin A can be synthesized according to a conventional method (for example, radical polymerization).
• the weight average molecular weight of Resin A is preferably from 1,000 to 200,000, more preferably from 3,000 to 20,000, and still more preferably from 5,000 to 15,000 as a polystyrene equivalent value by GPC method.
• the weight average molecular weight of the resin A is 1,000 to 200,000, the deterioration of heat resistance and dry etching resistance can be further suppressed.
• the degree of dispersion (molecular weight distribution) of Resin A is generally 1 to 5, preferably 1.00 to 3.00, more preferably 1.20 to 3.00, and even more preferably 1.20 to 2.00.
• Resin A may be used alone or in combination of two or more. When two or more are used, the total content is preferably within the range of the preferred content. When two or more kinds of repeating units are used in each repeating unit, the total content of the repeating units in the resin A is preferably within the preferable range of the content of each repeating unit described above.
• the content of resin A is preferably 10.0 to 99.0% by mass, more preferably 20.0 to 98.0% by mass, and 25.0 to 95.0% by mass, based on the total solid content of the resist composition. % by mass is more preferred.
• Photoacid generator In the resist composition, one or more selected from the group consisting of compounds (I) and (II) (hereinafter referred to as "specific photoacid Also referred to as "generating agent”.) may be included. As will be described later, the resist composition may further contain a photoacid generator other than the specific photoacid generator (hereinafter also referred to as “another photoacid generator”). In addition, the resist composition may contain compound (III). In addition, the said compound (1) is not contained in a photo-acid generator. First, the specific photoacid generators (compounds (I) and (II)) will be described below.
• Compound (I) is a compound having one or more structural moieties X shown below and one or more structural moieties Y shown below, wherein the first acidic It is a compound that generates an acid containing a site and a second acidic site described below derived from the structural site Y described below.
• Structural site X Structural site consisting of an anionic site A 1 ⁇ and a cation site M 1 + and forming the first acidic site represented by HA 1 upon exposure to actinic rays or radiation
• Structural site Y anionic site A structural site consisting of A 2 - and a cationic site M 2 + and forming a second acidic site represented by HA 2 upon exposure to actinic rays or radiation, provided that compound (I) satisfies condition I below. Fulfill.
• Condition I A compound PI obtained by replacing the cation site M 1 + in the structural site X and the cation site M 2 + in the structural site Y in the compound (I) with H + in the structural site X and the acid dissociation constant a1 derived from the acidic site represented by HA 1 obtained by replacing the cation site M 1 + with H + , and replacing the cation site M 2 + in the structural site Y with H + It has an acid dissociation constant a2 derived from the acidic site represented by HA2, and the acid dissociation constant a2 is greater than the acid dissociation constant a1.
• the compound (I) is, for example, a compound that generates an acid having one first acidic site derived from the structural site X and one second acidic site derived from the structural site Y.
• compound PI corresponds to "a compound having HA 1 and HA 2 ".
• the acid dissociation constant a1 and the acid dissociation constant a2 of the compound PI are such that when the acid dissociation constant of the compound PI is determined, the compound PI has "A 1 - and HA 2 is the acid dissociation constant a1, and the pKa when the above "compound having A 1 - and HA 2 " becomes "the compound having A 1 - and A 2 - " is the acid dissociation constant. constant a2.
• the compound (I) is, for example, a compound that generates an acid having two first acidic sites derived from the structural site X and one second acidic site derived from the structural site Y.
• the 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- , one HA 1 and one HA 2 " is converted into a "compound having two A 1- and one HA 2 " corresponds to the above-mentioned acid dissociation constant a1. do.
• 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 such a compound PI, if it has a plurality of acid dissociation constants derived from the acidic site represented by HA 1 obtained by replacing the cation site M 1 + in the structural site X with H + , a plurality of The value of the acid dissociation constant a2 is larger than the largest value among the acid dissociation constants a1 of .
• 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 acid dissociation constants described above.
• the above compound PI corresponds to an acid generated when compound (I) is irradiated with actinic rays or radiation.
• the structural moieties X may be the same or different.
• Two or more of the A 1 - groups and two or more of the M 1 + groups 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 ⁇ may be the same or different.
• Each A 2 - is preferably different.
• the difference (a2-a1) between the acid dissociation constant a1 (when there are multiple acid dissociation constants a1, the maximum value) and the acid dissociation constant a2 is preferably 0.1 or more, more preferably 0.5 or more, and still more preferably 1.0 or more.
• the upper limit of the difference (a2-a1) 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 preferably 16.0 or less.
• the acid dissociation constant a2 is preferably 20.0 or less, more preferably 15.0 or less, from the viewpoint that the LWR performance of the formed pattern is more excellent.
• the lower limit -4.0 or more is preferable.
• the acid dissociation constant a1 is preferably 2.0 or less, more preferably 0 or less, from the viewpoint that the LWR performance of the formed pattern is more excellent.
• the lower limit is preferably -20.0 or more.
• Anion site A 1 - and anion site A 2 - are structural sites containing negatively charged atoms or atomic groups, and are represented, for example, by formulas (AA-1) to (AA-3) shown below. and structural moieties selected from the group consisting of groups represented by formulas (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 any of the groups represented by formulas (AA-1) to (AA-3).
• the anion site A 2 - is preferably one capable of forming an acidic site having a larger acid dissociation constant than the anion site A 1 - . Either is more preferred.
• RA represents a monovalent organic group.
• the monovalent organic group represented by RA includes a cyano group, a trifluoromethyl group, a methanesulfonyl group, and the like.
• the cation site M 1 + and the cation site M 2 + are structural sites containing positively charged atoms or atomic groups, and examples thereof include monovalent organic cations.
• Examples of organic cations include those similar to organic cations represented by M 11 + and M 12 + in formula (Ia-1) described later.
• compound (I) include, for example, compounds represented by formulas (Ia-1) to (Ia-5) described below. First, the compound represented by Formula (Ia-1) will be described below.
• the compounds represented by formula (Ia-1) are as follows.
• Compound (Ia-1) generates an acid from a compound 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.
• a 12 H The acid dissociation constant a2 derived from the acidic site represented 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. Further, the compound PIa and the acid generated from the compound represented by the formula (Ia-1) upon exposure to actinic rays or radiation are the same. 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 monovalent anionic functional group represented by A 11 - means a monovalent group containing the anion site A 1 - .
• the monovalent anionic functional group represented by A 12 - means a monovalent group containing the anion site A 2 - .
• the monovalent anionic functional groups represented by A 11 - and A 12 - are represented by the above formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6).
• AX-1) to (AX-3) It is preferably a monovalent anionic functional group containing any anion site represented by the formulas (AX-1) to (AX-3) and the formulas (BX-1) to (BX It is more preferably a monovalent anionic functional group selected from the group consisting of monovalent anionic functional groups containing an anionic moiety represented by -7).
• a 11 - As the monovalent anionic functional group represented by A 11 - , any one of the monovalent anionic functional groups represented by formulas (AX-1) to (AX-3) is preferable.
• the monovalent anionic functional group represented by A 12 - is preferably any of the monovalent anionic functional groups represented by formulas (BX-1) to (BX-7), and the formula ( Any one of the monovalent anionic functional groups represented by 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 includes, for example, 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 1 to 6 carbon atoms) or a cyano group, and a fluorine atom, an iodine atom, or a perfluoroalkyl group. Fluoroalkyl 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, and 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. When the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group.
• the carbon atom directly bonded to -CO- indicated in the formula in the alkyl group is in the case of formulas (BX-2) and (BX-3), the carbon atom directly bonded to —SO 2 — specified in the formula in the alkyl group is applicable, and in formula (BX-6) In some cases, this corresponds to the carbon atom directly bonded to the N 2 - specified in the formula 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 of the alkyl group may be substituted with 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 e.g., preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.
• an alkoxycarbonyl group e.g., 2 to 10 carbon atoms are preferably having 2 to 6 carbon atoms
• a fluorine atom, an iodine atom, a perfluoroalkyl group, an alkyl group, an alkoxy group or an alkoxycarbonyl group preferably 1 to 6 carbon atoms.
• an alkoxy group e.g., preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.
• an alkoxycarbonyl group e.g., 2 to 10 carbon atoms are preferably having 2 to 6 carbon atoms
• the divalent linking group represented by L 1 includes -CO-, -NR-, -CO-, -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 carbon atoms ⁇ 6), a divalent aliphatic heterocyclic group (preferably a 5- to 10-membered ring having at least one nitrogen atom, oxygen atom, sulfur 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 (a 5- to 10-membered ring having at least one nitrogen atom, oxygen atom, sulfur atom or Se atom in the ring structure is preferred, 5- A 7-membered ring is more preferred
• an alkyl group preferably having 1 to 6 carbon atoms
• the alkylene group, the cycloalkylene group, the alkenylene group, the divalent aliphatic heterocyclic group, the divalent aromatic heterocyclic group and the divalent aromatic ring group have a substituent.
• Substituents include, for example, halogen atoms (preferably fluorine atoms).
• a divalent linking group represented by formula (L1) is preferable.
• L 111 represents a single bond or a divalent linking group.
• the divalent linking group represented by L 111 includes, for example, —CO—, —NH—, —O—, —SO—, —SO 2 —, an optionally substituted alkylene group (preferably is more preferably 1 to 6 carbon atoms.It may be either linear or branched), a cycloalkylene group optionally having a substituent (preferably 3 to 15 carbon atoms), a substituent aryl (preferably having 6 to 10 carbon atoms) and a divalent linking group combining a plurality of these.
• Substituents include, for example, 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 the alkyl group is preferably 1-10, more preferably 1-4.
• a perfluoroalkyl group is preferable as the alkyl group substituted with at least one fluorine atom.
• Each Xf2 independently represents a hydrogen atom, a fluorine atom, or an alkyl group optionally having a fluorine atom as a substituent.
• the number of carbon atoms in the alkyl group is preferably 1-10, more preferably 1-4.
• Xf 2 is preferably 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 , and both Xf 1 and Xf 2 are fluorine atoms.
• * represents a binding position.
• organic cations represented by M 11 + and M 12 + are described in detail in (Ia-1).
• the organic cations represented by M 11 + and M 12 + are each independently an organic cation represented by formula (ZaI) (cation (ZaI)) or an organic cation represented by formula (ZaII) (cation (ZaII )) is preferred.
• R 201 , R 202 and R 203 each independently represent an organic group.
• the number of carbon atoms in the organic group as R 201 , R 202 and R 203 is generally 1-30, 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, —COO—, 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 —. be done.
• Preferred embodiments of the organic cation in formula (ZaI) include cation (ZaI-1), cation (ZaI-2), and organic cations represented by formula (ZaI-3b) (cation (ZaI-3b) ) and an organic cation represented by the formula (ZaI-4b) (cation (ZaI-4b)).
• 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 may be 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, -COO-, an amide group or a carbonyl group may be included.
• 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, —COO—, an amide group and/or a carbonyl group. alkylene group (eg, butylene group, pentylene group or —CH 2 —CH 2 —O—CH 2 —CH 2 —).
• Arylsulfonium cations include, for example, 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 a branched alkyl group having 3 to 15 carbon atoms.
• a cycloalkyl group is preferred, and a methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, cyclohexyl group and the like are more preferred.
• the substituents that the aryl group, alkyl group and cycloalkyl group of R 201 to R 203 may have are each independently an alkyl group (eg, 1 to 15 carbon atoms), a cycloalkyl group (eg, 3 to 3 carbon atoms).
• aryl group eg, 6 to 14 carbon atoms
• alkoxy group eg, 1 to 15 carbon atoms
• cycloalkylalkoxy group eg, 1 to 15 carbon atoms
• halogen atom eg, fluorine, iodine
• hydroxyl group carboxy -COO-, sulfinyl, sulfonyl, alkylthio or phenylthio groups are preferred.
• the above substituents may further have a substituent if possible.
• the above alkyl group may have a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group. preferable.
• the above substituents form an acid-decomposable group by any combination.
• the acid-decomposable group is intended to be a group that is decomposed by the action of an acid to generate an acid group, and preferably has a structure in which the acid group is protected by a leaving group that is eliminated by the action of an acid.
• the above acid group and leaving group are as described above.
• Cation (ZaI-2) is a cation in which R 201 to R 203 in formula (ZaI) each independently represents an organic group having no aromatic ring.
• the aromatic ring includes an aromatic ring containing a hetero atom.
• the organic group having no aromatic ring as R 201 to R 203 generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
• 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 alkoxycarbonylmethyl groups are more preferred, and linear or branched 2-oxoalkyl groups are even more preferred.
• alkyl groups and cycloalkyl groups represented by R 201 to R 203 include linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (eg, methyl, ethyl, propyl 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.
• Cation (ZaI-3b) is a cation represented by 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 (such as a t-butyl group), a cycloalkyl group, a halogen atom, a cyano group or a aryl group.
• R x and R y each independently represent an alkyl group, cycloalkyl group, 2-oxoalkyl group, 2-oxocycloalkyl group, alkoxycarbonylalkyl group, allyl group or vinyl group. It is also preferred that the substituents of R 1c to R 7c , R x and R y independently form an acid-decomposable group by any combination of substituents.
• R 1c to R 5c , R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y may be bonded to 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.
• 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 butylene and pentylene. A methylene group in this alkylene group may be substituted with a heteroatom such as an oxygen atom.
• the group formed by combining R5c and R6c and R5c and Rx is preferably a single bond or an alkylene group.
• Alkylene groups include, for example, 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 R x and R y with each other may have a substituent.
• Cation (ZaI-4b) is a cation represented by formula (ZaI-4b).
• a halogen atom e.g., fluorine atom, iodine atom, etc.
• R 13 is a hydrogen atom, a halogen atom (e.g., fluorine atom, iodine atom, etc.), a hydroxyl group, an alkyl group, a halogenated al
• 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 group (may be a cycloalkyl group itself or a group partially containing a cycloalkyl group). These groups may have a substituent. When there are a plurality of R 14 , 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 combine with each other 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 for 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 more preferably methyl group, ethyl group, n-butyl group or t-butyl group. It is also preferred that the substituents of R 13 to R 15 , R x and R y each independently form 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 of R 204 and R 205 are linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl 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), a cycloalkyl group (eg, 3 to 15 carbon atoms), ), 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.
• 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 - mean monovalent groups containing the anion site A 1 - .
• the monovalent anionic functional groups represented by A 21a - and A 21b - include, for example, monovalent anionic functional groups selected from the group consisting of the above formulas (AX-1) to (AX-3) is mentioned.
• a 22 - represents a divalent anionic functional group.
• the divalent anionic functional group represented by A 22 - means a divalent group containing the 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 + have the same meanings as M 1 + above, and the preferred embodiments are also the same.
• L21 and L22 each independently represent a divalent organic group.
• the acidic site represented by A 22 H is greater than the acid dissociation constant a1-1 derived from A 21a H and the acid dissociation constant a1-2 derived from the acidic site represented by A 21b H.
• the acid dissociation constant a1-1 and the acid dissociation constant a1-2 correspond to the above acid dissociation constant a1.
• a 21a - and A 21b - may be the same or different.
• M 21a + , M 21b + and M 22 + may be the same or different.
• At least one of M 21a + , M 21b + , M 22 + , A 21a ⁇ , A 21b ⁇ , L 21 and L 22 may have an acid-decomposable group as a substituent.
• 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) above, and the preferred embodiments are also the same.
• the monovalent anionic functional group represented by A 32 - means a monovalent group containing the anion site A 2 - .
• Examples of the monovalent anionic functional group represented by A 32 - include monovalent anionic functional groups selected from the group consisting of the above formulas (BX-1) to (BX-7).
• a 31b - represents a divalent anionic functional group.
• the divalent anionic functional group represented by A 31b - means a divalent group containing the anion site A 1 - .
• 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.
• M 31a + , M 31b + , and M 32 + organic cations are synonymous with M 1 + above, and preferred embodiments are also the same.
• L 31 and L 32 each independently represent a divalent organic group.
• the acidic site represented by A 32 H is greater 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.
• 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) above.
• the definition of the monovalent anionic functional group represented by A 42 - is the same as A 32 - in formula (Ia-3) above, and the preferred embodiments are also the same.
• M 41a + , M 41b + and M 42 + each independently represent an organic cation.
• L41 represents a trivalent organic group.
• the acidic site represented by A 42 H is greater than the acid dissociation constant a1-5 derived from the acidic site represented by A 41a H and the acid dissociation constant a1-6 derived from the acidic site represented by A 41b H.
• the acid dissociation constant a1-5 and the acid dissociation constant a1-6 correspond to the above acid dissociation constant a1.
• a 41a ⁇ , A 41b ⁇ and A 42 ⁇ may be the same or different.
• 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.
• 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) include -CO- and -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 has 3 to 15 carbon atoms), an alkenylene group (preferably 2 to 6 carbon atoms), a divalent aliphatic heterocyclic group (at least one nitrogen atom, oxygen atom, sulfur atom or Se atom in the ring structure 5 ⁇ 10-membered ring is preferred, 5- to 7-membered ring is more preferred, and 5- to 6-membered ring is even more preferred.), divalent aromatic heterocyclic group (at least one nitrogen atom, oxygen atom, sulfur atom or Se atom in the ring structure is preferably a 5- to 10-membered ring, more preferably a
• the above R includes a hydrogen atom or a monovalent organic group.
• a monovalent organic group for example, an alkyl group (preferably having 1 to 6 carbon atoms) is preferred.
• the alkylene group, the cycloalkylene group, the alkenylene group, the divalent aliphatic heterocyclic group, the divalent aromatic heterocyclic group and the divalent aromatic ring group may have a substituent. good.
• Substituents include, for example, halogen atoms (preferably fluorine atoms).
• divalent organic groups represented by L 21 and L 22 in formula (Ia-2) and L 31 and L 32 in formula (Ia-3) include those represented by formula (L2) It is also preferred that it is a divalent organic group.
• 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 preferable 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 . More preferably, both Xf are fluorine atoms.
• LA represents a single bond or a divalent linking group.
• the divalent linking group represented by L A include -CO-, -O-, -SO-, -SO 2 -, alkylene groups (preferably having 1 to 6 carbon atoms, linear and branched ), a cycloalkylene group (preferably having 3 to 15 carbon atoms), a divalent aromatic ring group (preferably a 6- to 10-membered ring, more preferably a 6-membered ring.) and a plurality of these A combined divalent linking group is included.
• the alkylene group, the cycloalkylene group and the divalent aromatic 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.
• the substituent is an alkyl group (preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), an alkoxy group (preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms) or alkoxycarbonyl. Groups (having preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms) are preferred.
• L 21 and L 22 in formula (Ia-2) represent a divalent organic group represented by formula (L2)
• the bond (*) on the L A side in formula (L2) is represented by formula ( It preferably binds to A 21 - and A 21b - in Ia-2).
• L 31 and L 32 in formula (Ia-3) represent a divalent organic group represented by formula (L2)
• the bond (*) on the L A side in formula (L2) is Bonding with A 31a - and A 32 - in formula (Ia-3) is preferred.
• Examples of trivalent organic groups represented by L 41 in formula (Ia-4) include trivalent organic groups represented by formula (L3).
• LB represents a trivalent hydrocarbon ring group or a trivalent heterocyclic group. * represents a binding position.
• the hydrocarbon ring group may be either an aromatic ring group or an aliphatic hydrocarbon ring group.
• the number of carbon atoms contained in the hydrocarbon ring group is preferably 6-18, more preferably 6-14.
• the heterocyclic group may be either an aromatic ring group or an aliphatic hydrocarbon ring group.
• the heterocyclic ring is preferably a 5- to 10-membered ring having at least one nitrogen atom, oxygen atom, sulfur atom or Se atom in the ring structure, more preferably a 5- to 7-membered ring, and further a 5- to 6-membered ring.
• LB is preferably a trivalent hydrocarbon ring group, more preferably a benzene ring group or an adamantane ring group.
• the benzene ring group or adamantane ring group may have a substituent.
• Substituents include, for example, halogen atoms (preferably fluorine atoms).
• L B1 to L B3 each independently represent a single bond or a divalent linking group.
• divalent linking groups represented by L B1 to L B3 include —CO—, —NR—, —O—, —S—, —SO—, —SO 2 —, alkylene groups (preferably carbon Number 1 to 6, which may be linear or branched.), cycloalkylene group (preferably having 3 to 15 carbon atoms), alkenylene group (preferably having 2 to 6 carbon atoms), divalent Aliphatic heterocyclic group (5- to 10-membered ring having at least one nitrogen atom, oxygen atom, sulfur atom or Se atom in the ring structure is preferred, 5- to 7-membered ring is more preferred, 5- to 6-membered ring is further is preferred), a divalent aromatic heterocyclic group (preferably a 5- to 10-membered ring having at least one nitrogen atom, oxygen atom, sulfur atom or Se atom in the ring structure, more preferably a 5- to
• the above R includes a hydrogen atom or a monovalent organic group.
• a monovalent organic group for example, an alkyl group (preferably having 1 to 6 carbon atoms) is preferred.
• the alkylene group, the cycloalkylene group, the alkenylene group, the divalent aliphatic heterocyclic group, the divalent aromatic heterocyclic group and the divalent aromatic ring group may have a substituent. good.
• Substituents include, for example, halogen atoms (preferably fluorine atoms).
• divalent linking groups represented by L B1 to L B3 —CO—, —NR—, —O—, —S—, —SO—, —SO 2 —, even if having a substituent A good alkylene group or a divalent linking group combining these is preferred.
• divalent linking groups represented by L B1 to L B3 a divalent linking group represented by formula (L3-1) is more preferable.
• L B11 represents a single bond or a divalent linking group.
• the divalent linking group represented by L B11 includes, for example, —CO—, —O—, —SO—, —SO 2 —, an optionally substituted alkylene group (preferably a to 6, which may be linear or branched), and divalent linking groups combining these.
• Substituents include, for example, halogen atoms.
• r represents an integer of 1 to 3;
• Xf has the same definition as Xf in formula (L2) above, and the preferred embodiments are also the same.
• * represents a binding position.
• Examples of divalent linking groups represented by L B1 to L B3 include *-O-*, *-O-SO 2 -CF 2 -*, *-O-SO 2 -CF 2 -CF 2 - *, *--O--SO 2 --CF 2 --CF 2 --CF 2 --* and *--COO--CH 2 --CH 2 --*.
• L 41 in formula (Ia-4) contains a divalent organic group represented by formula (L3-1), and the divalent organic group represented by formula (L3-1) and A 42 ⁇ is bound, the bond (*) on the carbon atom side shown in formula (L3-1) preferably binds to A 42 — in formula (Ia-4).
• 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 - mean monovalent groups containing the anion site A 1 - .
• Examples of the monovalent anionic functional groups represented by A 51a - , A 51b - and A 51c - include monovalent anions selected from the group consisting of the above formulas (AX-1) to (AX-3) functional groups.
• a 52a - and A 52b - represent divalent anionic functional groups.
• the divalent anionic functional groups represented by A 52a - and A 52b - mean divalent groups containing the anion site A 2 - .
• Examples of the divalent anionic functional group represented by A 22 - include divalent anionic functional groups selected from the group consisting of the above formulas (BX-8) to (BX-11). be done.
• 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 + have the same meanings as M 1 + above, and 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 meaning as L 41 in formula (Ia-4) above, and the preferred embodiments are also the same.
• a The acid dissociation constant a2-1 derived from the acidic site represented by 52a H and the acid dissociation constant a2-2 derived from the acidic site represented by A 52b H are the acid dissociation constant a1-1 derived from A 51a H. , A 51b H and the acid dissociation constant a1-3 derived from the acidic site represented by A 51c H.
• the acid dissociation constants a1-1 to a1-3 correspond to the acid dissociation constant a1
• the acid dissociation constants a2-1 and a2-2 correspond to the acid dissociation constant a2.
• 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.
• At least one of 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 substituent. You may have a group.
• Compound (II) is a compound having two or more of the above structural moieties X and one or more of the following structural moieties Z, wherein the first acidic It is a compound that generates an acid containing two or more sites and the structural site Z described above.
• Structural site Z nonionic site capable of neutralizing acid
• the preferred range of the acid dissociation constant a1 derived from the acidic site represented by is the same as the acid dissociation constant a1 in the above compound PI.
• the compound (II) is a compound that generates an acid having two of the first acidic sites derived from the structural site X and the structural site Z
• the compound PII is "two HA 1 It corresponds to "a compound having When determining the acid dissociation constant of this compound PII, 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 1 and corresponds to the acid dissociation constant a1.
• the acid dissociation constant a1 is obtained by the method for measuring the acid dissociation constant described above.
• the above compound PII corresponds to an acid generated when compound (II) is irradiated with actinic rays or radiation.
• the two or more structural sites X may be the same or different.
• Two or more of A 1 ⁇ and two or more of M 1 + may be the same or different.
• the acid-neutralizable nonionic site in the structural site Z is preferably a site containing a group capable of electrostatically interacting with protons or a functional group having electrons.
• groups that can electrostatically interact with protons or functional groups that have electrons include functional groups that have a macrocyclic structure such as cyclic polyethers, or nitrogen atoms that have a lone pair of electrons that do not contribute to ⁇ conjugation.
• a functional group having 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 formula.
• Examples of partial structures of functional groups having electrons or groups capable of electrostatically interacting with protons include crown ether structures, azacrown ether structures, primary to tertiary amine structures, pyridine structures, imidazole structures and pyrazine structures. A primary to tertiary amine structure is preferred.
• Examples of compound (II) include compounds represented by formulas (IIa-1) and (IIa-2).
• a 61a - and A 61b - have the same meanings as A 11 - in the above formula (Ia-1), and preferred embodiments are also the same.
• M 61a + and M 61b + have the same meanings as M 11 + in formula (Ia-1) above, and the preferred embodiments are also the same.
• L 61 and L 62 have the same meanings as L 1 in formula (Ia-1), and preferred embodiments are also the same.
• R 2X represents a monovalent organic group.
• —CH 2 — is selected from the group consisting of —CO—, —NH—, —O—, —S—, —SO— and —SO 2 —.
• Alkyl groups preferably having 1 to 10 carbon atoms, which may be linear or branched
• cycloalkyl groups optionally substituted by one or a combination of two or more selected (preferably having 3 to 15 carbon atoms) or an alkenyl group (preferably having 2 to 6 carbon atoms).
• the alkylene group, the cycloalkylene group, and the alkenylene group may have a substituent.
• Substituents include, for example, halogen atoms (preferably fluorine atoms).
• the acid derived from the acidic site represented by A 61a H The dissociation constant a1-7 and the acid dissociation constant a1-8 derived from the acidic site represented by A 61b H correspond to the above acid dissociation constant a1.
• the compound PIIa-1 obtained by replacing the cation sites M 61a + and M 61b + in the structural site X in the structural site X in 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 the above formula (Ia-1), and preferred embodiments are also the same.
• M 71a + , M 71b + , and M 71c + each have the same meaning as M 11 + in formula (Ia-1) above, and preferred embodiments are also the same.
• L 71 , L 72 and L 73 each have the same meaning as L 1 in formula (Ia-1) above, and preferred embodiments are also the same.
• the acidic represented by A 71a H The acid dissociation constant a1-9 derived from the site, 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 above acid dissociation constant a1.
• the compound PIIa-2 obtained by replacing the cation sites M 71a + , M 71b + , and M 71c + in the structural site X in the compound (IIa-1) 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.
• At least one of 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.
• organic cations and other moieties that the specific photoacid generator may have are shown below.
• the organic cations are, for example, M 11 + , M 12 + , M 21a + , M 21b + , M 22 + , M 31a + in the compounds represented by formulas (Ia-1) to (Ia-5).
• the other moieties include, for example, M 11 + , M 12 + , M 21a + , M 21b + , M 22 + , M 22 + , M 12 + , M 21a + , M 21b + , M 31a + , M 31b + , M 32 + , M 41a + , M 41b + , M 42 + can be used as moieties other than M 51a + , M 51b + , M 51c + , M 52a + and M 52b + .
• An appropriate combination of the organic cations shown below and other moieties can be used as the specific photoacid generator.
• the molecular weight of the specific photoacid generator is preferably from 100 to 10,000, more preferably from 100 to 2,500, even more preferably from 100 to 1,500.
• the content of the specific photoacid generator (total content of compounds (I) and (II)) is preferably 10% by mass or more, preferably 15% by mass or more, and 20% by mass, based on the total solid content of the resist composition. % by mass or more is more preferable, and 40% by mass or more is even more preferable.
• the upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less, relative to the total solid content of the resist composition.
• the specific photoacid generator may be used singly or in combination of two or more. When two or more are used, the total content is preferably within the range of the preferred content.
• Compound (III) is a compound (onium salt) represented by “M + X ⁇ ”, and is preferably a compound that generates an organic acid upon exposure.
• organic acid include sulfonic acid (aliphatic sulfonic acid such as fluoroaliphatic sulfonic acid, aromatic sulfonic acid and camphorsulfonic acid), bis(alkylsulfonyl)imidic acid and tris(alkylsulfonyl)methide acid. be done.
• M + represents an organic cation.
• the organic cation is preferably an organic cation represented by formula (ZaI) (cation (ZaI)) or an organic cation represented by formula (ZaII) (cation (ZaII)).
• ZaI organic cation represented by formula (ZaI)
• ZaII organic cation represented by formula (ZaII)
• X ⁇ represents an organic anion.
• a non-nucleophilic anion an anion having a remarkably low ability to cause a nucleophilic reaction
• non-nucleophilic anions examples include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc.), sulfonylimide anions, bis(alkylsulfonyl)imide anions and tris(alkylsulfonyl) methide anion.
• the aliphatic moiety in the aliphatic sulfonate anion may be an alkyl group or a cycloalkyl group, and may be a linear or branched alkyl group having 1 to 30 carbon atoms or a cycloalkyl group having 3 to 30 carbon atoms. Alkyl groups are preferred.
• the alkyl group may be, for example, a fluoroalkyl group (which may or may not have a substituent other than a fluorine atom; it 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.
• substituents include a nitro group, a halogen atom such as a fluorine atom and a chlorine atom, a carboxy group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), an alkyl group (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 12 carbon atoms), acyl groups (preferably 2 to 12 carbon atoms), alkoxycarbonyloxy groups (preferably 2 to 18 carbon atoms), alkylthio groups (preferably 1 to 15 carbon atoms), alkylsulfonyl groups (preferably 1 to 15 carbon atoms), alkyliminosulfonyl groups (preferably having 1 to 15 carbon atoms
• 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, and fluorine atoms.
• an alkyl group substituted with a fluorine atom is preferred.
• the alkyl groups in the bis(alkylsulfonyl)imide anion may be bonded to each other to form a ring structure. This increases the acid strength.
• non-nucleophilic anions 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 the alkyl group is substituted with a fluorine atom is preferred.
• an anion represented by formula (AN1) 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 fluorine atom or an alkyl group substituted with at least one fluorine atom.
• the number of carbon atoms in the alkyl group is preferably 1-10, more preferably 1-4.
• a perfluoroalkyl group is preferable 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 number of carbon atoms in the alkyl group represented by R 4 and R 5 is preferably 1-4.
• the above alkyl group may have a substituent.
• Hydrogen atoms are preferred as R 4 and R 5 .
• Specific examples and preferred aspects of the alkyl group substituted with at least one fluorine atom are the same as the specific examples and preferred aspects of Xf in formula (AN1).
• 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), cycloalkylene groups (preferably 3 to 15 carbon atoms), alkenylene groups (preferably 2 to 6 carbon atoms), and divalent linking groups combining 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 preferred.
• 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.
• polycyclic alicyclic groups include polycyclic cycloalkyl groups such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl and adamantyl groups. Among them, 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.
• 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. Moreover, the heterocyclic group may or may not have aromaticity. 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, tetrahydropyran, lactone, sultone and decahydroisoquinoline rings.
• 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). preferably having 3 to 20 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and A sulfonic acid ester group is mentioned.
• carbonyl carbon may be sufficient as carbon (carbon which contributes to ring formation) which comprises a cyclic
• Examples of anions represented by formula (AN1) 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 (AN1).
• q' represents an integer from 0 to 10;
• an anion represented by the following formula (AN2) is also preferable.
• X B1 and X B2 each independently represent a hydrogen atom or a monovalent organic group having no fluorine atom.
• X B1 and X B2 are preferably hydrogen atoms.
• X B3 and X B4 each independently represent a hydrogen atom or a monovalent organic group.
• At least one of X B3 and X B4 is preferably a fluorine atom or a monovalent organic group having a fluorine atom, and both of X B3 and X B4 are a fluorine atom or a monovalent organic group having a fluorine atom is more preferred. More preferably, both X B3 and X B4 are fluorine-substituted alkyl groups.
• L, q and W are the same as in formula (AN1).
• an anion represented by formula (AN3) is preferable.
• each Xa independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
• Each Xb independently represents a hydrogen atom or an organic group having no fluorine atom.
• an anion represented by formula (AN4) is also preferred.
• R 1 and R 2 each independently represent a substituent that is not an electron-withdrawing group or a hydrogen atom.
• substituents that are not electron-withdrawing groups include hydrocarbon groups, hydroxyl groups, oxyhydrocarbon groups, oxycarbonyl hydrocarbon groups, amino groups, hydrocarbon-substituted amino groups, and hydrocarbon-substituted amide groups. be done.
• substituents that are not electron-withdrawing groups independently include -R', -OH, -OR', -OCOR', -NH 2 , -NR' 2 , -NHR', or -NHCOR ' is preferred.
• 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 propynyl and butynyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl and adamantyl; Monovalent alicyclic hydrocarbon groups such as cycloalkenyl groups such as cyclopropenyl group, cyclobutenyl group, cyclopentenyl group and norbornenyl group; phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, methylnaphthyl group, anthryl group and aryl
• L is a divalent linking group consisting of a combination of one or more linking groups S and an alkylene group optionally having one or more substituents, or one or more links represents a divalent linking group consisting of group S;
• the linking group S is * A -O-CO-O-* B , * A -CO-* B , * A -CO-O-* B , * A -O-CO-* B , * A -O- A group selected from the group consisting of * B , * A -S-* B and * A - SO2-* B .
• L is one form of "a divalent linking group consisting of a combination of one or more linking groups S and an alkylene group optionally having one or more substituents", "one or more and a divalent linking group consisting of a combination of the linking group S and one or more unsubstituted alkylene groups", the linking group S is * A -O-CO-O-* B , * selected from the group consisting of A -CO-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B , and * A - SO2-* B It is preferably a group.
• the alkylene groups in the "divalent linking group consisting of a combination of one or more linking groups S and an alkylene group optionally having one or more substituents" are all unsubstituted alkylene groups.
• the linking group S is * A -O-CO-O-* B , * A -CO-* B , * A -O-CO-* B , * A -O-* B , * A- It is preferably a group selected from the group consisting of S-* B and * A - SO2-* B .
• * A represents the bonding position on the R 3 side in formula (AN4)
• * B represents the bonding position on the —SO 3 — side in formula (AN4).
• a divalent linking group consisting of a combination of one or more linking groups S and an alkylene group optionally having one or more substituents
• only one linking group S may be present; There may be more than one.
• the optionally substituted alkylene group may be present singly, or may be present two or more times.
• the linking groups S present in plurality may be the same or different.
• the alkylene groups present in plurality may be the same or different.
• the connecting groups S may be continuously bonded to each other.
• groups selected from the group consisting of * A -CO-* B , * A -O-CO-* B , and * A -O-* B are continuously bonded to form "* A -O- It is preferred that no CO—O—* B ” is formed.
• groups selected from the group consisting of * A -CO-* B and * A -O-* B are continuously bonded to form "* A -O-CO-* B " and "* A -CO- It is preferred that none of O-* B '' is formed.
• linking groups S are present in a divalent linking group consisting of one or more linking groups S, only one linking group S may be present, or two or more linking groups S may be present. When multiple linking groups S are present, the linking groups S may be the same or different. In this case, groups selected from the group consisting of * A -CO-* B , * A -O-CO-* B , and * A -O-* B are continuously bonded to form "* A -O —CO—O—* B ” is preferably not formed.
• groups selected from the group consisting of * A -CO-* B and * A -O-* B are continuously bonded to form "* A -O-CO-* B " and "* A -CO- It is preferred that none of O-* B '' is formed.
• the ⁇ -position atom with respect to —SO 3 — in L is not a carbon atom having a fluorine atom as a substituent.
• the carbon atom may not be directly substituted with a fluorine atom, and the carbon atom may be a substituent having a fluorine atom (for example, a fluorine atom such as a trifluoromethyl group). alkyl group).
• the ⁇ -position atom is, in other words, an atom in L directly bonded to —C(R 1 )(R 2 )— in formula (AN4).
• L preferably has only one linking group S. That is, L is a divalent linking group consisting of a combination of one linking group S and an alkylene group optionally having one or more substituents, or a divalent linking group consisting of one linking group S preferably represents a group.
• L is preferably, for example, a group represented by formula (AN4-2). * a - (CR 2a 2 ) X - Q- (CR 2b 2 ) Y - * b (AN4-2)
• * a represents the bonding position with R3 in formula ( AN4).
• * b represents the bonding position with —C(R 1 )(R 2 )— in formula (AN4).
• 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 (AN4) is other than a fluorine atom.
• Q is * A -O-CO-O-* B , * A -CO-* B , * A -CO-O-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B or * A - SO2-* B .
• Q is * A -O-CO- O-* B , * A -CO-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B , or * A - SO2-* B show.
• * A represents the bonding position on the R 3 side in formula (AN4)
• * B represents the bonding position on the —SO 3 — side in formula (AN4).
• R 3 represents an organic group.
• the above organic group is not limited as long as it has 1 or more carbon atoms. It may be a 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 heteroatoms (oxygen, sulfur and/or nitrogen atoms, 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 (AN4).
• 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.
• lactone group and sultone group for example, any of the structures represented by the above formulas (LC1-1) to (LC1-21) and the structures represented by the above formulas (SL1-1) to (SL1-3) In (1) above, a group having one hydrogen atom from the ring member atoms constituting the lactone structure or sultone structure is preferred.
• the non-nucleophilic anion may be a benzenesulfonate anion, preferably a benzenesulfonate anion substituted with a branched alkyl group or cycloalkyl group.
• an aromatic sulfonate anion represented by formula (AN5) is also preferred.
• 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.
• the divalent linking group includes -O-, thioether group, carbonyl group, sulfoxide group, sulfone group, sulfonic acid -COO-, -COO- and a group consisting of a combination of two or more thereof.
• B represents a hydrocarbon group
• B preferably has an aliphatic hydrocarbon structure.
• B is 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 Rq 's 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.
• Compound (III) 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. Moreover, the form of a low-molecular-weight compound and the form incorporated into a part of a polymer may be used in combination.
• the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less. As a lower limit, 100 or more is preferable.
• the compound (III) 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 into a resin different from the resin A.
• Compound (III) is preferably in the form of a low molecular weight compound.
• the resist composition contains compound (III), its content is preferably 0.5% by mass or more, more preferably 1% by mass or more, relative to the total solid content of the resist composition.
• the upper limit is preferably 40% by mass or less, more preferably 30% by mass or less, relative to the total solid content of the resist composition.
• Other photoacid generators may be used singly or in combination of two or more. When two or more are used, the total content is preferably within the range of the preferred content.
• the resist composition may contain an acid diffusion control agent.
• the acid diffusion control agent traps the acid generated from the photoacid generator or the like during exposure, and acts as a quencher that suppresses the reaction of the acid-decomposable resin in the unexposed area due to excess generated acid.
• the type of acid diffusion controller is not particularly limited, and examples include basic compounds (CA), low-molecular-weight compounds (CB) having nitrogen atoms and groups that leave under the action of acids, and actinic rays or radiation. and a compound (CC) whose ability to control acid diffusion decreases or disappears upon irradiation.
• an onium salt compound (CD) which becomes a relatively weak acid with respect to the photoacid generator
• a basic compound (CE) whose basicity is reduced or lost by irradiation with actinic rays or radiation.
• specific examples of the basic compound (CA) include those described in paragraphs [0132] to [0136] of International Publication No. 2020/066824, and basicity is obtained by irradiation with actinic rays or radiation.
• Specific examples of the basic compound that decreases or disappears include those described in paragraphs [0137] to [0155] of WO 2020/066824, have a nitrogen atom, and Specific examples of the low-molecular compound (CB) having a leaving group include those described in paragraphs [0156] to [0163] of WO2020/066824, and onium having a nitrogen atom in the cation moiety. Specific examples of salt compounds (CE) include those described in paragraph [0164] of WO2020/066824. Further, specific examples of the onium salt compound (CD), which is a relatively weak acid with respect to the photoacid generator, include those described in paragraphs [0305] to [0314] of International Publication No. 2020/158337. .
• 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 content of the acid diffusion control agent (the total when multiple types are present) is 0.1 to 15.0 with respect to the total solid content of the resist composition. % by mass is preferable, and 1.0 to 15.0% by mass is more preferable.
• the acid diffusion controller may be used singly or in combination of two or more.
• the resist composition may further contain a hydrophobic resin different from resin A.
• the hydrophobic resin is 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 fluorine atoms, silicon atoms, and CH3 partial structures contained in the side chain portion of the resin, and two or more. It is more preferred to have Moreover, the hydrophobic resin preferably has a hydrocarbon group having 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. % is more preferred.
• the resist composition may contain a surfactant.
• a surfactant is contained, the adhesion is better and a pattern with fewer development defects can be formed.
• the surfactant is preferably a fluorine-based and/or silicon-based surfactant.
• silicon-based surfactants and/or fluorine-based surfactants having 7 or less carbon atoms may be used. Fluorinated and/or silicon-based surfactants include surfactants disclosed in paragraphs [0218] and [0219] of WO2018/019395.
• One type of surfactant 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, and 0.0005 to 1.0% by mass, based on the total solid content of the resist composition. %, more preferably 0.1 to 1.0% by mass.
• the resist composition preferably contains a solvent.
• Solvents are (M1) propylene glycol monoalkyl ether carboxylates, and (M2) the group consisting of propylene glycol monoalkyl ethers, lactate esters, acetate esters, alkoxypropionate esters, linear ketones, cyclic ketones, lactones and alkylene carbonates. It is preferred to include at least one selected from The solvent may further contain components other than components (M1) and (M2).
• 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 resist composition 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 resist composition can be further improved.
• the resist composition contains a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and/or a compound that promotes solubility in a developer (for example, a phenol compound having a molecular weight of 1000 or less, or a carboxyl group alicyclic or aliphatic compounds containing) may further be included.
• a dissolution inhibiting compound for example, a phenol compound having a molecular weight of 1000 or less, or a carboxyl group alicyclic or aliphatic compounds containing
• the resist composition may further contain a dissolution inhibiting compound.
• dissolution inhibiting compound as used herein means a compound having a molecular weight of 3000 or less, which is decomposed by the action of an acid to reduce its solubility in an organic developer.
• the resist composition of the present invention is suitably used as a photosensitive composition for EUV light.
• 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, "photon shot noise", in which the number of photons stochastically varies, has a great influence, 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, 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 a resin A, a photoacid generator, an acid diffusion controller, and a solvent
• the resin A, the photoacid generator, and the acid diffusion controller correspond to the solid content.
• the total atoms of the total solid content correspond to the sum of all atoms derived from the resin A, 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 resin A, hydrogen atoms derived from the photoacid generator, and derived from the acid diffusion control agent with respect to the total of all atoms derived from the photoacid generator and all atoms derived from the acid diffusion control agent represents the total molar ratio of the hydrogen atoms of
• 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. .
• the procedure of the pattern forming method using the resist composition preferably includes the following steps.
• Step 1 A step of forming a resist film on a substrate using a resist composition
• Step 2 A step of exposing the resist film
• Step 3 A step of developing the exposed resist film using a developer
• Step 1 is a step of forming a resist film on a substrate using a resist composition.
• the definition of the resist composition is as described above.
• a method of forming a resist film on a substrate using a resist composition includes, for example, a method of coating the substrate with the resist composition. Before coating, it is preferable to filter the resist composition as necessary.
• the pore size of the filter is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, and even more preferably 0.03 ⁇ m or less. The lower limit is often 0.01 ⁇ m or more.
• the filter is preferably made of polytetrafluoroethylene, polyethylene or nylon.
• the resist composition can be applied onto substrates such as those used in the manufacture of integrated circuit devices (eg, silicon and silicon dioxide coatings) by a suitable coating method such as 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.
• various underlying films for example, an inorganic film, an organic film, an antireflection film, etc. may be formed under the resist film.
• Heating can be carried out by means provided in a normal exposure machine and/or 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 resist film is preferably 10 to 120 nm from the point of being able to form fine patterns with higher precision.
• the film thickness of the resist film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm.
• a topcoat composition may be used to form a topcoat on the upper layer of the resist film. It is preferable that the topcoat composition does not mix with the resist film and can be uniformly coated on the upper layer of the resist film.
• the topcoat is not particularly limited, and a conventionally known topcoat can be formed by a conventionally known method. can be formed. For example, it is preferable to form a topcoat containing a basic compound as described in JP-A-2013-61648 on the resist film.
• Basic compounds that the topcoat may contain include, for example, 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 a step of exposing the resist film.
• the exposure method include a method of irradiating the formed resist film with actinic rays or radiation through a predetermined mask.
• Actinic rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays and electron beams.
• Far ultraviolet light is preferred as the wavelength of actinic rays or radiation.
• the wavelength of far-ultraviolet light is preferably 250 nm or less, more preferably 220 nm or less, and still more preferably 1 to 200 nm.
• Specific examples include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser ( 157 nm), EUV light (13 nm), X-rays and electron beams.
• 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 post-exposure bake (PEB).
• PEB post-exposure bake
• Step 3 is a step of developing the exposed resist film using a developer to form a pattern.
• the developer may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an "organic developer").
• Examples of the development 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 standing still for a certain period of time by raising the developer on the surface of the substrate by surface tension (paddle method). ), a method of spraying the developer onto the surface of the substrate (spray method), and a method of continuously ejecting the developer onto the substrate rotating at a constant speed while scanning the developer ejection nozzle at a constant speed (dynamic dispensing method). mentioned. 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 As the alkaline developer.
• alkaline aqueous solutions include, for example, aqueous alkaline solutions containing quaternary ammonium salts typified by tetramethylammonium hydroxide, inorganic alkalis, primary amines, secondary amines, tertiary amines, alcohol amines or cyclic amines. .
• 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 0.1 to 20 mass %.
• the pH of the alkaline developer is usually 10.0 to 15.0.
• the content of water in the alkaline developer is preferably 51 to 99.95% by mass.
• 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. preferable.
• 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, relative to the total mass of the developer, and should be substantially free of water.
• the content of the organic solvent in the organic developer is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and 95 to 100% by mass, based on the total mass of the developer. % by weight is particularly preferred.
• 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 liquid preferably contains at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents.
• 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) can be mentioned.
• the pattern forming method of the present invention may include a heating step (Post Bake) after the rinsing step. This step removes the developer and rinse liquid remaining between the patterns and inside the patterns. 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 2 minutes).
• 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 the substrate) to form the pattern on the substrate.
• the method of 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 to form a pattern on the substrate.
• a method of forming is preferred. Dry etching is preferably oxygen plasma etching.
• Various materials used in the resist composition and the pattern forming method of the present invention are free of impurities such as metals. preferably not included.
• the content of impurities contained in these materials is preferably 1 mass ppm or less, more preferably 10 mass ppb or less, and 100 mass ppt (parts per trillion) or less with respect to the total solid content of the resist composition or various materials. More preferably, 10 mass ppt or less is particularly preferable, and 1 mass ppt or less is most preferable. As a lower limit, 0 mass ppt or more is preferable.
• 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. is mentioned.
• a method of reducing impurities such as metals contained in various materials for example, a method of selecting a raw material with a low metal content as a raw material constituting various materials, a method of filtering the raw materials constituting various materials 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 In order to reduce impurities such as metals contained in the above various materials, 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. As a lower limit, 0 mass ppt or more is preferable.
• Conductive compounds are added to organic treatment liquids such as rinsing liquids to prevent damage to chemical piping and various parts (filters, O-rings, tubes, etc.) due to electrostatic charging and subsequent electrostatic discharge.
• Conductive compounds include, for example, methanol.
• the amount to be added 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. As a lower limit, 0 mass % or more is preferable.
• the chemical pipe for example, SUS (stainless steel) or various pipes coated with antistatic polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can be used.
• filters and O-rings antistatic treated polyethylene, polypropylene or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can also be used.
• the present invention also relates to an electronic device manufacturing method including the pattern forming method and an electronic device manufactured by this manufacturing method.
• the electronic device of the present invention is suitably mounted in electric/electronic equipment (household appliances, OA (Office Automation), media-related equipment, optical equipment, communication equipment, etc.).
• the resins (A-1 to A-42 (corresponding to resin A), a-1) used in the preparation of the resist composition are shown below.
• the "molar ratio” column shows the content (mol%) of each repeating unit with respect to all repeating units.
• the “Mw” column indicates the weight average molecular weight.
• the “Mw/Mn” column indicates the dispersity. Mn indicates number average molecular weight.
• M-31 to M-65 correspond to specific compounds.
• Photoacid generator The structures of the photoacid generators (B-1 to B-16 (corresponding to specific compounds), b-1 to b-10) used in the preparation of the resist composition are shown below.
• composition ratio mass ratio, corresponding from left to right
• weight average molecular weight Mw
• degree of dispersion Mw/Mn
• Mn number average molecular weight
• W-1 Megafac R08 (manufactured by DIC, fluorine- and silicon-based surfactant)
• W-2 Megafac F176 (manufactured by DIC, fluorine-based surfactant)
• W-3 Troisol S-366 (manufactured by Troy Chemical Co., fluorine-based surfactant)
• W-4 PF656 (manufactured by OMNOVA, fluorine-based surfactant)
• TMAH tetramethylammonium hydroxide
• the number of development defects is less than 0.5/cm 2
• B The number of development defects is 0.5/cm 2 or more and less than 1.0/cm 2
• C The number of development defects is 1.0 /cm 2 or more and less than 5.0/cm 2
• D The number of development defects is 5.0/cm 2 or more
• ⁇ Sensitivity> The line width of the line-and-space pattern formed while changing the exposure amount (electron beam irradiation amount) was measured, and the exposure amount when the line width was 50 nm was obtained, and this was taken as the sensitivity (Eop, ⁇ C/cm 2 ). did. The smaller the sensitivity value, the better the sensitivity.
• resin A further contains a compound represented by formula (2), and resin A further has a group that is decomposed by the action of an acid to increase the polarity, and resin A is a hydrogen atom from the compound represented by formula (2) Further has a repeating unit a having a residue formed by removing one or two of, and at least one of the content of the repeating unit a is 10 mol% or more with respect to the total repeating units of the resin It was confirmed that the sensitivity was more excellent when these conditions were satisfied (comparison between Example 5a and Example 2a, comparison between Example 8a and Example 7a, etc.).
• the resin A further contains a repeating unit b having a group that is decomposed by the action of an acid to increase the polarity (Examples 13a, 16a, 39a and Examples 9a, 10a, 22a, 23a, etc.).
• Resin A further includes a repeating unit b having a group that decomposes under the action of an acid to increase polarity, and the repeating unit b is a group consisting of repeating units represented by any one of formulas (M1) to (M5). It was confirmed that the sensitivity is better when at least one selected from is included (comparison of Examples 5a, 8a, 11a and Examples 13a, 16a, 39a, etc.).
• the repeating unit b contains at least one selected from the group consisting of repeating units represented by the formula (M4) and repeating units represented by the formula (M5), the sensitivity is better ( Examples 12a, 14a, 15a and Examples 5a, 8a, 11a, etc.).
• resin A further contains a compound represented by formula (2), and resin A further has a group that is decomposed by the action of an acid to increase the polarity, and resin A is a hydrogen atom from the compound represented by formula (2) Further has a repeating unit a having a residue formed by removing one or two of, and at least one of the content of the repeating unit a is 10 mol% or more with respect to the total repeating units of the resin It was confirmed that the sensitivity was better when the conditions were satisfied (comparison between Examples 9b and 10b and Examples 34b and 35b, etc.).
• the resin A further contains a repeating unit b having a group that is decomposed by the action of an acid to increase the polarity (Example 16b and Examples 9b, 10b, 22b, and 23b). comparison, etc.).
• Resin A further includes a repeating unit b having a group that decomposes under the action of an acid to increase polarity, and the repeating unit b is a group consisting of repeating units represented by any one of formulas (M1) to (M5). It was confirmed that the sensitivity is better when at least one selected from is included (comparison between Examples 19b and 20b and Example 16b, etc.).
• the repeating unit b contains at least one selected from the group consisting of repeating units represented by the formula (M4) and repeating units represented by the formula (M5), the sensitivity is better ( Examples 12b, 15b, 21b and Examples 19b, 20b, etc.).

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