Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
  • C07C25/02—Monocyclic aromatic halogenated hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/01—Sulfonic acids
  • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
  • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
  • C07C309/05—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing at least two sulfo groups bound to the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/01—Sulfonic acids
  • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
  • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
  • C07C309/07—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton
  • C07C309/12—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing esterified hydroxy groups bound to the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/01—Sulfonic acids
  • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
  • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
  • C07C309/17—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing carboxyl groups bound to the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/01—Sulfonic acids
  • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
  • C07C309/29—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/01—Sulfonic acids
  • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
  • C07C309/41—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton
  • C07C309/42—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton having the sulfo groups bound to carbon atoms of non-condensed six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
  • C07C311/50—Compounds containing any of the groups, X being a hetero atom, Y being any atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
  • C07C381/12—Sulfonium compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
  • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
  • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
  • C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
  • C07D327/06—Six-membered rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
  • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
  • C07D333/46—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
  • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
  • C07D333/76—Dibenzothiophenes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
  • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
  • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
  • C07D493/12—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains three hetero rings
  • C07D493/16—Peri-condensed systems
• • 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
  • G03F7/039—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 a salt production method, an actinic ray-sensitive or radiation-sensitive resin composition production method, a pattern formation method, and an electronic device production method.
• a method of lithography includes a method of forming a resist film from a photosensitive composition, exposing the obtained film, and then developing it.
• EB Electro Beam
• EUV Extreme Ultraviolet
• the actinic ray- or radiation-sensitive resin composition contains components such as a resin, a compound that generates acid upon exposure to actinic rays or radiation, an acid diffusion controller, and a solvent.
• a salt consisting of an organic cation and an organic anion, which is used as a compound that generates an acid upon exposure to actinic rays or radiation, among the above components.
• some differences between product lots of this salt affect performance variations between product lots of the composition using conventional NMR (nuclear magnetic resonance).
• an object of the present invention is to provide a method for producing a salt that can suppress variations in sensitivity due to differences in product lots of actinic ray-sensitive or radiation-sensitive resin compositions.
• Another object of the present invention is to provide a method for producing the actinic ray-sensitive or radiation-sensitive resin composition, a method for forming a pattern, and a method for producing an electronic device.
• a method for producing a salt (P) of an organic cation and an organic anion comprising the following steps. (1) A step of obtaining a product containing the salt (P) by performing anion exchange on the salt (I) of the organic cation and the halide ion (2) A silver nitrate aqueous solution for the product (3) obtaining the molar ratio X of the salt (I) to the salt (P) by applying a potentiometric titration method using The step [2] of determining whether Furthermore, (4) when the molar ratio X exceeds a predetermined value in the step (3), by applying a measure to improve the purity of the product containing the salt (P), the molar ratio X is reduced to the above
• the method for producing salt (P) according to [1] comprising the step of obtaining a product containing salt (P) having a predetermined value or less.
• the anion exchange in the step (1) is by ion exchange between the salt (I) and the metal salt (M) of the organic anion
• a measure for improving the purity of the product containing the salt (P) in the step (4) is to add the metal salt (M) of the organic anion to the product to perform the anion exchange.
• the concentration Y of the salt (P) based on the total amount of the product containing the salt (P) in which the molar ratio X is the predetermined value or less is determined by high performance liquid chromatography.
• [6] Furthermore, (6) a step of obtaining the concentration Z of the residual acid contained in the product containing the salt (P) by an ultraviolet-visible absorption spectroscopy method, and (7) the concentration Z of the residual acid satisfies a predetermined standard.
• R 201 , R 202 and R 203 each independently represent an organic group.
• Actinic ray-sensitive containing the salt (P) as a compound that generates an acid upon irradiation with actinic rays or radiation including the method for producing the salt (P) according to any one of [1] to [10] Or a method for producing a radiation-sensitive resin composition.
• An actinic ray-sensitive or radiation-sensitive film is formed on a substrate from the actinic ray-sensitive or radiation-sensitive resin composition produced by the method for producing an actinic ray-sensitive or radiation-sensitive resin composition according to [11].
• forming, A pattern forming method comprising the steps of: exposing the actinic ray-sensitive or radiation-sensitive film; and developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer.
• a method for manufacturing an electronic device including the pattern forming method according to [12].
• the manufacturing method of the salt which can suppress the fluctuation
• the manufacturing method of the said actinic-ray-sensitive or radiation-sensitive resin composition, the pattern formation method, and the manufacturing method of an electronic device can be provided.
• the present invention will be described in detail below. The description of the constituent elements described below may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.
• the notation that does not describe substituted or unsubstituted includes groups containing substituents as well as groups that do not have substituents. do.
• an "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
• the term "organic group” as used herein refers to a group containing at least one carbon atom. As a substituent, a monovalent substituent is preferable unless otherwise specified.
• actinic ray or “radiation” means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, and electron beams ( EB means Electron Beam).
• light means actinic rays or radiation.
• exposure means, unless otherwise specified, not only exposure by the emission line spectrum of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV: Extreme ultraviolet), and X-rays, It also includes writing with electron beams and particle beams such as ion beams.
• the term "to” is used to include the numerical values before and after it as lower and upper limits.
• the binding direction of the divalent linking groups indicated is not limited unless otherwise specified.
• Y when Y is -COO-, Y may be -CO-O- or -O-CO- good too.
• the compound may be "X—CO—O—Z” or "X—O—CO—Z.”
• (meth)acrylate refers to acrylate and methacrylate
• (meth)acryl refers to acrylic and methacrylic.
• weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (hereinafter also referred to as "molecular weight distribution") (Mw/Mn) are measured by GPC (Gel Permeation Chromatography) equipment (Tosoh Corporation).
• HLC-8120 GPC manufactured by HLC-8120 GPC by GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 ⁇ L, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40 ° C., flow rate: 1.0 mL / min, detector : Defined as a polystyrene conversion value by a differential refractive index detector (Refractive Index Detector).
• the acid dissociation constant (pKa) represents the pKa in an aqueous solution. is a calculated value.
• Software Package 1 Advanced Chemistry Development (ACD/Labs) Software V8.14 for Solaris (1994-2007 ACD/Labs).
• pKa can also be determined by molecular orbital calculation.
• a specific method there is a method of calculating the H 2 + dissociation free energy in an aqueous solution based on the thermodynamic cycle.
• the H + dissociation free energy can be calculated by, for example, DFT (density functional theory), but various other methods have been reported in literature, etc., and the method is not limited to this. Note that there are a plurality of software that can implement DFT, and Gaussian16 is an example.
• pKa refers to a value obtained by calculating a value based on Hammett's substituent constant and a database of known literature values using Software Package 1, as described above. cannot be calculated, a value obtained by Gaussian 16 based on DFT (density functional theory) shall be adopted.
• pKa refers to "pKa in aqueous solution” as described above, but when pKa in aqueous solution cannot be calculated, “pKa in dimethyl sulfoxide (DMSO) solution” is adopted.
• Solid content means the components forming the actinic ray-sensitive or radiation-sensitive film, and does not include solvent. In addition, as long as it is a component that forms an actinic ray-sensitive or radiation-sensitive film, it is regarded as a solid content even if the property is liquid.
• the method for producing the salt (P) of the present invention is a method for producing the salt (P) of an organic cation and an organic anion, comprising the following steps (1) to (3).
• a step of obtaining a product containing the salt (P) by performing anion exchange on the salt (I) of the organic cation and the halide ion (2)
• a silver nitrate aqueous solution for the product (3) obtaining the molar ratio X of the salt (I) to the salt (P) by applying a potentiometric titration method using The step of determining whether the
• the method for producing the salt (P) includes, first, a step of obtaining a product containing the salt (P) by subjecting the salt (I) of an organic cation and a halide ion to anion exchange.
• the molar ratio X of salt (I) to salt (P) is obtained by applying potentiometric titration using an aqueous solution of silver nitrate. Based on this technique, the purity of the salt (I) in the product is determined, and if necessary, the salt (I) is produced through measures to improve the purity, and the obtained salt (I) is used to make the salt (I) sensitive to actinic radiation.
• the method for producing the salt (P) is a method for producing the salt (P) of an organic cation and an organic anion, including the above steps (1) to (3).
• Step (1) is a step of obtaining a product containing the salt (P) by subjecting the salt (I) of the organic cation and the halide ion to anion exchange.
• a salt (P) is a compound consisting of an organic cation and an organic anion.
• the salt (P) is not particularly limited, but may be a compound (onium salt) represented by “M + X ⁇ ” in the “photoacid generator” described later, or a compound in the “photoacid generator” described later ( At least one selected from the group consisting of I) to (II) can be mentioned.
• the organic cation is not particularly limited, but may be the organic cation M + in the "photoacid generator” described later, preferably the cation represented by the formula (ZaI) described later.
• the organic anion is not particularly limited, but at least one selected from the group consisting of X ⁇ in the “photoacid generator” described below, or compounds (I) to (II) in the “photoacid generator” described below.
• the "anion part" in one can be mentioned.
• the “anion moiety” in compound (I) represents a structure other than cationic site M 1 + and cationic site M 2 + in compound (I).
• the “anion moiety” in compound (II) represents a structure other than the cationic site M 1 + in compound (II).
• a product containing salt (P) can be obtained by subjecting salt (I) of the above organic cation and halide ion to anion exchange.
• Salt (I) is a compound consisting of the above organic cation and halide ion.
• Halide ions include, but are not limited to, chloride ions, bromide ions, and iodide ions.
• Anion exchange can be performed by a conventional method. As a preferred embodiment, each synthesis example described in Examples can be given. Although the method of anion exchange is not particularly limited, it is preferable to carry out the reaction in a two-layer system containing water and a water-immiscible solvent.
• solvents used include halogen solvents such as methylene chloride and chloroform, ester solvents such as ethyl acetate, ketone solvents such as methyl isobutyl ketone, and ether solvents such as cyclopentyl methyl ether and tert-butyl methyl ether. These may be appropriately combined with a water-soluble solvent such as acetone, THF, or methanol.
• Anion exchange is typically by ion exchange between the salt (I) and the metal salt (M) of the organic anion.
• the metal ion in the metal salt (M) of the organic anion is not particularly limited, examples thereof include potassium ion and sodium ion.
• the metal salt of the organic anion may be generated in the reaction system by mixing the proton form of the organic anion with an inorganic salt such as sodium hydrogen carbonate together with the salt (I) and a solvent during the reaction. .
• Step (2) is a step of obtaining the molar ratio X of the salt (I) to the salt (P) by subjecting the product to potentiometric titration using an aqueous solution of silver nitrate.
• An example of a preferred embodiment of a potentiometric titration method using an aqueous silver nitrate solution is described below.
• V1 is the titration volume (ml) of the sample solution
• V2 is the titration volume (ml) of the empty solution
• f is the titer of the titrant (silver nitrate aqueous solution)
• MQ is the molar mass of the halogen atom to be obtained ( g/mol)
• W represents the weight of the product containing salt (P).
• MB (g/mol) represents the molecular weight of salt (P).
• Examples of the titer measurement method include the method described in "JIS K 8001: 2017 Test Reagent Method General Rules Appendix JA.6 Titration Solution-JA.6.4n".
• the above molar ratio X indicates the residual rate (mol%) of salt (I) with respect to 1 mol of salt (P).
• the concentration of the silver nitrate aqueous solution used is not particularly limited, it is preferably 0.01 N (mol/L) or less.
• the amount of the product containing salt (P) used is not particularly limited, but is preferably 50 mg or more.
• the solvent for dissolving the product containing the salt (P) is not particularly limited as long as it is a polar solvent that is water-soluble and does not react with silver nitrate. is preferred.
• the step (3) is a step of determining whether the purity of the salt (P) satisfies a predetermined standard based on the molar ratio X. Based on the molar ratio X, the purity of the salt (P) is determined. If the molar ratio X is high, the purity of the salt (P) will decrease, and if the molar ratio X is low, the purity of the salt (P) will increase. "determining whether or not” is preferably made by "determining whether or not the molar ratio X is equal to or less than a predetermined value".
• the predetermined standard (for example, the predetermined value) can be appropriately set in the method for producing salt (P).
• the salt (I) can function as an acid diffusion control agent, it has a large effect on sensitivity (line width variation), and X is preferably made as small as possible.
• X is preferably 0.5 mol % or less, more preferably 0.4 mol % or less, and even more preferably 0.3 mol % or less.
• the method for producing the salt (P) of the present invention further includes (4) measures to improve the purity of the product containing the salt (P) when the molar ratio X exceeds a predetermined value in the step (3). is applied to obtain a product containing a salt (P) in which the molar ratio X is equal to or less than the predetermined value.
• Step (4) when the molar ratio X exceeds a predetermined value in the step (3), by applying a measure to improve the purity of the product containing the salt (P), the molar ratio X is It is a step of obtaining a product containing a salt (P) not more than the predetermined value.
• the step (4) is a step of applying a step of reducing the molar ratio X when the molar ratio X exceeds a predetermined value.
• the predetermined value can be set as appropriate, it is preferably 0.5 mol %, more preferably 0.4 mol %, and even more preferably 0.3 mol %.
• the measure for improving the purity of the product containing the salt (P) in step (4) is purification by removing the salt (I) from the product containing the salt (P). .
• Removal of the salt (I) includes, for example, crystallization of the product.
• Solvents that can be used for crystallization are not particularly limited, but examples include water, alcohol solvents (preferably methanol), nitrile solvents (preferably acetonitrile), ketone solvents (preferably acetone), ester solvents (preferably ethyl acetate), halogen-based solvents (preferably chloroform), ether-based solvents (preferably diisopropyl ether), hydrocarbon-based solvents (preferably hexane), and the like.
• the removal of the salt (I) for example, when the salt (I) has relatively high water solubility, a method of removing the salt (I) by increasing the number of liquid separation operations can be used.
• organic solvents include halogen solvents such as methylene chloride and chloroform, ester solvents such as ethyl acetate, ketone solvents such as methyl isobutyl ketone, and ether solvents such as cyclopentyl methyl ether and tert-butyl methyl ether. , these may be combined with water-soluble solvents such as acetone, THF, methanol, etc. as appropriate.
• the number of liquid separations is preferably 3 or more, more preferably 5 or more.
• various chromatography methods such as silica gel column chromatography, are mentioned as removal of said salt (I).
• the anion exchange in the step (1) is by ion exchange between the salt (I) and the metal salt (M) of the organic anion
• the measure for improving the purity of the product containing the salt (P) in the step (4) is to add the metal salt (M) of the organic anion to the product to perform the anion exchange. be done.
• the amount of the organic anion metal salt (M) to be added can be appropriately set according to the molar ratio X determined in step (3). Since the salt (I) remaining in the product is calculated from the molar ratio X, the amount of the metal salt (M) of the organic anion that reacts with the remaining salt (I) can be appropriately set.
• the anion exchange in the step (1) is by ion exchange between the salt (I) and the metal salt (M) of the organic anion
• Purity improvement measures for the product containing the salt (P) in the step (4) include changing the molar ratio of the salt (I) and the metal salt (M) of the organic anion to the step (1). implementation.
• the molar ratio X of the salt (I) to the salt (P) is obtained by carrying out the step (2) on the product containing the salt (P) obtained based on the above measures for improving the purity. Then, step (3) is performed to determine whether the purity of the salt (P) satisfies a predetermined standard. When the purity of the salt (P) satisfies a predetermined standard (specifically, the molar ratio X is equal to or less than a predetermined value), the reaction is terminated. When the purity of the salt (P) does not satisfy the predetermined standard, the purity improvement measure for the product containing the salt (P) in the step (4) is again carried out in the step (4). A product containing a salt (P) in which the molar ratio X is equal to or less than the predetermined value can be obtained by the step (4). Thus, salt (P) is produced.
• the method for producing the salt (P) of the present invention further comprises (5) the concentration Y of the salt (P) based on the total amount of the product containing the salt (P) in which the molar ratio X is the predetermined value or less. , is preferably determined by high performance liquid chromatography (HPLC).
• Step (5) the concentration Y of the salt (P) based on the total amount of the product containing the salt (P) in which the molar ratio X is the predetermined value or less is determined by high performance liquid chromatography (HPLC). It is a process.
• the salt (P) concentration Y (% by mass) can be obtained by the step (5).
• An example of a preferred embodiment of the method for measuring the concentration Y of the salt (P) by high performance liquid chromatography (HPLC) is described below.
• the internal standard substance is not particularly limited as long as the peaks do not overlap with the cations and anions that make up the salt (P) and there is absorption at the detection wavelength, but it is preferably an aromatic compound. 3,5-trimethoxybenzene etc.), ester group-substituted benzenes (propyl benzoate etc.), alkyl group-substituted benzenes (dibenzyl etc.) and the like.
• the solvent is not particularly limited, and acetonitrile, THF, methanol and the like are preferably used.
• the eluent is not particularly limited, and acetonitrile, THF, methanol and the like are preferably used.
• Ammonium acetate, phosphoric acid/triethylamine, and the like are preferably used as buffers.
• the optimal ratio of the organic solvent to the buffer in the eluent varies depending on the structure of the salt (P) and the type of solvent used. Measurement is preferred.
• the reference lot of salt (P) should be sufficiently free of raw material cations and raw material anions to reduce impurities that affect the cation/anion ratio as much as possible.
• a purification method for sufficiently removing the raw material cations or raw material anions purification by recrystallization, purification by various chromatography methods, and the like are preferable.
• a method of detecting residual halogen by silver nitrate titration is preferred.
• the raw material cation is a salt of an organic anion
• the metal element As a means for confirming that the raw material anion has been completely removed from the reference lot, it is preferable to detect the metal element by means such as ICP-OES or ICP-MS when the raw material anion is a metal salt.
• non-metal salts if there is an element that has only the counter salt between the raw material anion and its counter salt, it can be detected by elemental analysis, but in other cases, the raw material anion is synthesized as a metal salt only in the standard lot. preferably. It is preferable that impurities other than raw material cations and raw material anions and residual solvent are small. Purification methods for reducing impurities include, as mentioned above, purification by recrystallization, purification by various types of chromatography, and the like. It is preferable to confirm that organic impurities are sufficiently removed by HPLC or LCMS measurement.
• a method for reducing the residual solvent there is a method of preparing a solution of a solvent having a low boiling point such as methylene chloride and drying under reduced pressure while heating.
• the residual solvent may be quantified by NMR, gas chromatography, or the like, and used as a reference lot. In this case, the accuracy of the concentration (solid content value) of the reference lot itself is low, but by the method of the present invention, it is possible to manage the lot as a relative value, and in some cases the solid content value may exceed 100%. There is no problem.
• step (5) the salt (P) concentration Y (% by mass) can be obtained.
• the reaction is terminated when the purity of the salt (P) satisfies a predetermined standard (specifically, the molar ratio X is equal to or less than a predetermined value).
• the salt (P) is obtained by such a reaction, and fluctuations in resolution due to differences in production lots of the actinic ray-sensitive or radiation-sensitive resin composition can be suppressed.
• the concentration Y (% by mass) of the salt (P) can be obtained from a viewpoint different from the molar ratio X.
• the concentration Y is based on the product containing the salt (P), and focuses on impurities other than the salt (I) (for example, solvent, etc.). Such a step is preferable because the concentration of the salt (P) can be obtained in more detail, and thus fluctuations in resolution due to differences in product lots of the actinic ray-sensitive or radiation-sensitive resin composition can be further suppressed.
• the product containing salt (P) may or may not be purified.
• a well-known method is mentioned as the purification method.
• the compounding amount of the salt (P) is the expected compounding amount of the salt (P) ⁇ (100/Y).
• the predetermined amount of salt (P) can be added to the resist composition more reliably, and it tends to be possible to further suppress variations in resolution due to differences in product lots, which is preferable.
• the method for producing the salt (P) of the present invention further includes (6) a step of obtaining the residual acid concentration Z contained in the product containing the salt (P) by an ultraviolet-visible absorption spectroscopy method, and (7) ) It is preferable to have a step of determining whether the concentration Z of the residual acid satisfies a predetermined standard.
• the step (6) is a step of obtaining the residual acid concentration Z contained in the product containing the salt (P) by an ultraviolet-visible absorption spectroscopy method.
• the protonated form of the raw material anion may remain, the acid used during liquid separation may remain, or the acid may remain due to the decomposition of the raw material or the salt (P) itself.
• the purity of the salt (P) can be further increased, which is preferable.
• Method for measuring concentration Z An example of a method for measuring the concentration Z by an ultraviolet-visible absorption spectroscopy method is shown below, but the present invention is not limited to this.
• Solution A is prepared by dissolving compound C (hereinafter also referred to as compound C) that develops color with an acid in a solvent.
• a solution B is prepared by dissolving an existing acidic compound D (hereinafter also referred to as compound D) in a solvent.
• Solution D1 is prepared by mixing solution A and solution B and diluting with a solvent.
• the UV-visible absorption spectrum of solution D1 is measured using "UV-1800 (manufactured by Shimadzu Corporation), solvent: acetonitrile" to obtain absorbance Abs D1 at the maximum absorption wavelength of compound C.
• Solutions D2, D3, and D4 are prepared in the same manner by varying the dilution of solution D1.
• the ultraviolet-visible absorption spectra of D2, D3 and D4 obtained are similarly measured to obtain Abs D2 , Abs D3 and Abs D4 .
• a solution E is prepared by diluting only the solution A.
• the ultraviolet-visible absorption spectrum of Solution E is measured to obtain the absorbance Abs E at the maximum absorption wavelength.
• Abs DE1 to Abs DE4 the difference from Abs E is obtained, and the obtained results are defined as Abs DE1 to Abs DE4 , respectively.
• a calibration curve of molar concentration of compound D and absorbance of compound C is prepared.
• the compound C that develops color with an acid is not particularly limited as long as it reacts quantitatively with a trace amount of acid to produce a coloring material having strong absorption at a specific wavelength. manufactured by Aldrich).
• the acidic compound D is not particularly limited as long as it is an acidic compound capable of developing the color of the compound C. Examples thereof include tosylic acid (p-toluenesulfonic acid), methanesulfonic acid, and hydrochloric acid.
• the ultraviolet-visible absorption spectrum of each solution D may be measured a plurality of times, and the average value thereof may be used as Abs D.
• the solvent to be used is not particularly limited as long as it is neutral or basic and has no absorption at the absorption wavelength of the acid color former.
• Preferred solvents include acetonitrile, aprotic polar solvents such as THF, methanol and halogen-based solvents such as methylene chloride.
• a solution A is prepared by dissolving compound C, which develops color with an acid, in a solvent.
• the product Wg containing the salt (P) is weighed out, solution A is added, and solution F diluted with solvent is prepared.
• a solution E is prepared by diluting only the solution A.
• the ultraviolet-visible absorption spectra of solution F and solution E are measured in the same manner as in the preparation of the above calibration curve, and absorbances Abs F and Abs E at the maximum absorption wavelength of compound C are obtained.
• the concentration Z (ppm) in terms of compound D contained in the product containing the salt (P) is calculated.
• Z T ⁇ MT ⁇ LB ⁇ 1000/W (4)
• MT (g/mol) represents the molecular weight of compound D.
• LB represents the total solvent volume of solution F (l).
• the concentration Z of the residual acid contained in the product containing the salt (P) is the concentration in terms of compound D.
• Step (7) is a step of determining whether or not the concentration Z of the residual acid satisfies a predetermined standard.
• the predetermined standard can be appropriately set in the method for producing salt (P).
• Z is preferably 100 ppm or less, more preferably 50 ppm or less.
• Step (8) In the step (7), if the concentration Z of the residual acid exceeds a predetermined value, it is preferable to have a step of (8) implementing measures to reduce the concentration Z of the residual acid.
• a basic compound is appropriately added for purification and extraction.
• a known method can be used for purification and extraction.
• an organic solvent e.g., methylene chloride
• water or water containing a basic compound e.g., ammonia
• the number of times of washing is preferably 3 times or more, more preferably 5 times or more.
• a measure for reducing the concentration Z is to crystallize the product.
• Solvents that can be used for crystallization include, but are not limited to, the same solvents as used in step (4).
• various chromatographic methods such as silica gel column chromatography can be used to reduce the concentration Z described above.
• the salt (P) is preferably a compound that generates an acid upon exposure to actinic rays or radiation for actinic ray-sensitive or radiation-sensitive resin compositions.
• the compound that generates an acid upon exposure to actinic rays or radiation include a photoacid generator (B) and an acid diffusion control agent, which will be described later.
• the method for producing an actinic ray-sensitive or radiation-sensitive resin composition according to the present invention comprises: A method for producing an actinic ray-sensitive or radiation-sensitive resin composition containing the salt (P) as a compound that generates an acid upon exposure to actinic rays or radiation, including the method for producing the salt (P).
• the actinic ray-sensitive or radiation-sensitive resin composition obtained by the method for producing the composition of the present invention is described below.
• the actinic ray-sensitive or radiation-sensitive resin composition is preferably a resist composition, and may be a positive resist composition or a negative resist composition.
• the resist composition may be a resist composition for alkali development or a resist composition for organic solvent development.
• the resist composition may be a chemically amplified resist composition or a non-chemically amplified resist composition.
• the resist composition is typically a chemically amplified resist composition.
• the actinic ray-sensitive or radiation-sensitive resin composition (hereinafter also referred to as "the composition of the present invention") in the method for producing the actinic ray-sensitive or radiation-sensitive resin composition of the present invention can have Ingredients are detailed.
• the composition of the present invention may contain an acid-decomposable resin (hereinafter also referred to as "resin (A)").
• the resin (A) usually contains a group that is decomposed by the action of an acid to increase its polarity (hereinafter also referred to as "acid-decomposable group”), and preferably contains a repeating unit having an acid-decomposable group.
• an acid-decomposable group typically when an alkaline developer is employed as the developer, a positive pattern is preferably formed and developed. When an organic developer is used as the liquid, a negative pattern is preferably formed.
• a repeating unit having an acid-decomposable group a repeating unit having an acid-decomposable group containing an unsaturated bond is preferable in addition to the repeating unit having an acid-decomposable group described below.
• An acid-decomposable group is a group that is decomposed by the action of an acid to form a polar group.
• the acid-decomposable group preferably has a structure in which the polar group is protected with a group that is released by the action of an acid (leaving group). That is, the resin (A) has a repeating unit having a group that is decomposed by the action of an acid to form a polar group.
• a resin having this repeating unit has an increased polarity under the action of an acid, thereby increasing the solubility in an alkaline developer and decreasing the solubility in an organic solvent.
• the polar group is preferably an alkali-soluble group such as a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphoric acid group, a sulfonamide group, a sulfonylimide group, (alkylsulfonyl)(alkylcarbonyl)methylene group, (alkylsulfonyl)(alkylcarbonyl)imide group, bis(alkylcarbonyl)methylene group, bis(alkylcarbonyl)imide group, bis(alkylsulfonyl)methylene group, bis(alkylsulfonyl)imide group, tris(alkylcarbonyl) Methylene groups, acidic groups such as tris(alkylsulfonyl)methylene groups, and alcoholic hydroxyl groups are included.
• alkali-soluble group such as a carboxyl group, a phenolic
• the polar group is preferably a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group.
• Examples of groups that leave by the action of an acid include groups represented by formulas (Y1) to (Y4).
• Formula (Y1) -C(Rx 1 )(Rx 2 )(Rx 3 )
• Formula (Y3) —C(R 36 )(R 37 )(OR 38 )
• Rx 1 to Rx 3 each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched chain) or an aryl group (monocyclic or polycyclic).
• Rx 1 to Rx 3 are alkyl groups (linear or branched)
• at least two of Rx 1 to Rx 3 are preferably methyl groups.
• Rx 1 to Rx 3 preferably each independently represent a linear or branched alkyl group, and Rx 1 to Rx 3 each independently represent a linear alkyl group. is more preferred.
• Rx 1 to Rx 3 may combine to form a monocyclic or polycyclic ring.
• the alkyl groups of Rx 1 to Rx 3 include alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group. preferable.
• the cycloalkyl groups represented by Rx 1 to Rx 3 include monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. is preferred.
• the aryl group represented by Rx 1 to Rx 3 is preferably an aryl group having 6 to 10 carbon atoms, such as phenyl group, naphthyl group and anthryl group.
• a vinyl group is preferable as the alkenyl group for Rx 1 to Rx 3 .
• the ring formed by combining two of Rx 1 to Rx 3 is preferably a cycloalkyl group.
• the cycloalkyl group formed by combining two of Rx 1 to Rx 3 includes a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, and a tetracyclododeca.
• a polycyclic cycloalkyl group such as a nyl group or an adamantyl group is preferable, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
• one of the methylene groups constituting the ring is a group containing a heteroatom such as an oxygen atom, a heteroatom such as a carbonyl group, or a vinylidene group. may be replaced with In these cycloalkyl groups, one or more ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.
• Rx 1 is a methyl group or an ethyl group
• Rx 2 and Rx 3 combine to form the above-described cycloalkyl group. is preferred.
• composition of the present invention is a resist composition for EUV exposure
• the ring formed by combining two atoms further has a fluorine atom or an iodine atom as a substituent.
• R 36 to R 38 each independently represent a hydrogen atom or a monovalent organic group.
• R 37 and R 38 may combine with each other to form a ring.
• Monovalent organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups. It is also preferred that R 36 is a hydrogen atom.
• the alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a heteroatom such as an oxygen atom and/or a group containing a heteroatom such as a carbonyl group.
• one or more of the methylene groups may be replaced with a heteroatom such as an oxygen atom and/or a group containing a heteroatom such as a carbonyl group.
• R 38 may combine with another substituent of the main chain of the repeating unit to form a ring.
• the group formed by bonding R 38 and another substituent of the main chain of the repeating unit to each other is preferably an alkylene group such as a methylene group.
• monovalent organic groups represented by R 36 to R 38 and R 37 and R 38 are formed by binding to each other.
• the ring also preferably has a fluorine atom or an iodine atom as a substituent.
• L 1 and L 2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining these (e.g., a group combining an alkyl group and an aryl group).
• M represents a single bond or a divalent linking group.
• Q is an alkyl group optionally containing a heteroatom, a cycloalkyl group optionally containing a heteroatom, an aryl group optionally containing a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group combining these (for example, a group combining an alkyl group and a cycloalkyl group).
• one of the methylene groups may be replaced by a heteroatom such as an oxygen atom or a heteroatom-containing group such as a carbonyl group.
• L 1 and L 2 is preferably a hydrogen atom, and the other is preferably an alkyl group, a cycloalkyl group, an aryl group, or a combination of an alkylene group and an aryl group. At least two of Q, M, and L1 may combine to form a ring (preferably a 5- or 6-membered ring).
• L2 is preferably a secondary or tertiary alkyl group, more preferably a tertiary alkyl group.
• Secondary alkyl groups include isopropyl, cyclohexyl, and norbornyl groups, and tertiary alkyl groups include tert-butyl and adamantane groups.
• the Tg (glass transition temperature) and the activation energy are increased, so that the film strength can be ensured and fogging can be suppressed.
• the alkyl group, cycloalkyl group, aryl group, and group combining these represented by L 1 and L 2 are further It is also preferable to have a fluorine atom or an iodine atom as a substituent.
• the alkyl group, cycloalkyl group, aryl group, and aralkyl group preferably contain a heteroatom such as an oxygen atom in addition to the fluorine atom and the iodine atom.
• one of the methylene groups is replaced with a heteroatom such as an oxygen atom, or a group containing a heteroatom such as a carbonyl group.
• the resist composition is a resist composition for EUV exposure
• the alkyl group represented by Q which may contain a heteroatom
• the cycloalkyl group which may contain a heteroatom
• the heteroatom-containing aryl group amino group, ammonium group, mercapto group, cyano group, aldehyde group, and groups in which these are combined
• the heteroatom is selected from the group consisting of a fluorine atom, an iodine atom and an oxygen atom.
• a heteroatom is also preferred.
• Ar represents an aromatic ring group.
• Rn represents an alkyl group, a cycloalkyl group, or an aryl group.
• Rn and Ar may combine with each other to form a non-aromatic ring.
• Ar is preferably an aryl group.
• the aromatic ring group represented by Ar and the alkyl group, cycloalkyl group and aryl group represented by Rn have fluorine as a substituent. It is also preferred to have an atom or an iodine atom.
• the ring member atoms adjacent to the ring member atoms directly bonded to the polar group (or residue thereof) do not have halogen atoms such as fluorine atoms as substituents.
• Groups that can be eliminated by the action of an acid also include a 2-cyclopentenyl group having a substituent (such as an alkyl group) such as a 3-methyl-2-cyclopentenyl group, and a 1,1,4,4 A cyclohexyl group having a substituent (such as an alkyl group) such as a -tetramethylcyclohexyl group may also be used.
• repeating unit having an acid-decomposable group a repeating unit represented by formula (A) is also preferred.
• L 1 represents a divalent linking group optionally having a fluorine atom or an iodine atom
• R 1 is a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group optionally having a fluorine atom or an iodine atom , or represents an aryl group optionally having a fluorine atom or an iodine atom
• R 2 represents a leaving group optionally having a fluorine atom or an iodine atom which is eliminated by the action of an acid.
• at least one of L 1 , R 1 and R 2 has a fluorine atom or an iodine atom.
• the divalent linking group optionally having a fluorine atom or an iodine atom represented by L 1 includes -CO-, -O-, -S-, -SO-, -SO 2 -, fluorine atom or a hydrocarbon group optionally having an iodine atom (eg, an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, etc.), and a linking group in which a plurality of these are linked.
• L 1 is preferably -CO-, an arylene group, or an -arylene group - an alkylene group having a fluorine atom or an iodine atom -, and -CO- or an -arylene group - a fluorine atom or an iodine atom.
• An alkylene group with - is more preferred.
• a phenylene group is preferred as the arylene group.
• Alkylene groups may be linear or branched. Although the number of carbon atoms in the alkylene group is not particularly limited, it is preferably 1-10, more preferably 1-3.
• the total number of fluorine atoms and iodine atoms contained in the alkylene group having fluorine atoms or iodine atoms is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.
• the alkyl group represented by R 1 may be linear or branched. Although the number of carbon atoms in the alkyl group is not particularly limited, it is preferably 1-10, more preferably 1-3. The total number of fluorine atoms and iodine atoms contained in the alkyl group having a fluorine atom or an iodine atom represented by R 1 is not particularly limited, but is preferably 1 or more, more preferably 1 to 5, and 1 to 3. More preferred.
• the alkyl group represented by R 1 may contain a heteroatom such as an oxygen atom other than the halogen atom.
• the leaving group optionally having a fluorine atom or an iodine atom represented by R 2 is represented by the above formulas (Y1) to (Y4) and having a fluorine atom or an iodine atom. groups.
• repeating unit having an acid-decomposable group a repeating unit represented by formula (AI) is also preferred.
• Xa 1 represents a hydrogen atom or an optionally substituted alkyl group.
• T represents a single bond or a divalent linking group.
• Rx 1 to Rx 3 each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl ( monocyclic or polycyclic) group. However, when all of Rx 1 to Rx 3 are alkyl groups (linear or branched), at least two of Rx 1 to Rx 3 are preferably methyl groups. Two of Rx 1 to Rx 3 may combine to form a monocyclic or polycyclic group (such as a monocyclic or polycyclic cycloalkyl group).
• Examples of the optionally substituted alkyl group represented by Xa 1 include a methyl group and a group represented by -CH 2 -R 11 .
• R 11 represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group.
• the monovalent organic group represented by R 11 includes, for example, an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, an acyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group.
• Xa 1 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
• the divalent linking group of T includes an alkylene group, an aromatic ring group, a -COO-Rt- group and a -O-Rt- group.
• Rt represents an alkylene group or a cycloalkylene group.
• T is preferably a single bond or a -COO-Rt- group.
• Rt is preferably an alkylene group having 1 to 5 carbon atoms, a -CH 2 - group, a -(CH 2 ) 2 - group, or a -(CH 2 ) 3 - groups are more preferred.
• the alkyl groups of Rx 1 to Rx 3 include alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group. preferable.
• Cycloalkyl groups of Rx 1 to Rx 3 include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. is preferred.
• the aryl group represented by Rx 1 to Rx 3 is preferably an aryl group having 6 to 10 carbon atoms, such as phenyl group, naphthyl group and anthryl group.
• a vinyl group is preferable as the alkenyl group for Rx 1 to Rx 3 .
• the cycloalkyl group formed by combining two of Rx 1 to Rx 3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group.
• Polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group are also preferred. Among them, monocyclic cycloalkyl groups having 5 to 6 carbon atoms are preferred.
• a cycloalkyl group formed by combining two of Rx 1 to Rx 3 is, for example, a group in which one of the methylene groups constituting the ring contains a heteroatom such as an oxygen atom, a heteroatom such as a carbonyl group, or It may be substituted with a vinylidene group.
• Rx 1 is a methyl group or an ethyl group
• Rx 2 and Rx 3 are preferably combined to form the above-mentioned cycloalkyl group.
• substituents include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group. (2 to 6 carbon atoms).
• the number of carbon atoms in the substituent is preferably 8 or less.
• the repeating unit represented by the formula (AI) includes an acid-decomposable (meth)acrylic acid tertiary alkyl ester-based repeating unit (Xa 1 represents a hydrogen atom or a methyl group, and T represents a single bond. ) is preferred.
• repeating units having an acid-decomposable group are shown below, but are not limited thereto.
• Xa 1 represents H, CH 3 , CF 3 or CH 2 OH
• Rxa and Rxb each independently represent a linear or branched alkyl group having 1 to 5 carbon atoms.
• Resin (A) may have a repeating unit having an acid-decomposable group containing an unsaturated bond as the repeating unit having an acid-decomposable group.
• a repeating unit represented by formula (B) is preferable.
• Xb represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group.
• L represents a single bond or a divalent linking group which may have a substituent.
• Ry 1 to Ry 3 each independently represent a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an alkynyl group, or a monocyclic or polycyclic aryl group . However, at least one of Ry 1 to Ry 3 represents an alkenyl group, an alkynyl group, a monocyclic or polycyclic cycloalkenyl group, or a monocyclic or polycyclic aryl group. Two of Ry 1 to Ry 3 may combine to form a monocyclic or polycyclic ring (a monocyclic or polycyclic cycloalkyl group, cycloalkenyl group, etc.).
• the optionally substituted alkyl group represented by Xb includes, for example, a methyl group and a group represented by —CH 2 —R 11 .
• R 11 represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group, for example, an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group.
• Xb is preferably a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
• the divalent linking group of L includes -Rt- group, -CO- group, -COO-Rt- group, -COO-Rt-CO- group, -Rt-CO- group, and -O-Rt- groups.
• Rt represents an alkylene group, a cycloalkylene group, or an aromatic ring group, preferably an aromatic ring group.
• L is preferably -Rt-, -CO-, -COO-Rt-CO- or -Rt-CO-.
• Rt may have substituents such as halogen atoms, hydroxyl groups, and alkoxy groups.
• the alkyl groups represented by Ry 1 to Ry 3 include alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group. preferable.
• Cycloalkyl groups represented by Ry 1 to Ry 3 include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group and adamantyl group. Polycyclic cycloalkyl groups are preferred.
• the aryl group represented by Ry 1 to Ry 3 is preferably an aryl group having 6 to 10 carbon atoms, such as phenyl group, naphthyl group and anthryl group.
• a vinyl group is preferable as the alkenyl group for Ry 1 to Ry 3 .
• An ethynyl group is preferred as the alkynyl group for Ry 1 to Ry 3 .
• Cycloalkenyl groups represented by Ry 1 to Ry 3 are preferably monocyclic cycloalkyl groups such as cyclopentyl groups and cyclohexyl groups, which partially contain a double bond.
• the cycloalkyl group formed by combining two of Ry 1 to Ry 3 includes a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, and a tetracyclododeca.
• Polycyclic cycloalkyl groups such as a nyl group and an adamantyl group are preferred. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
• a cycloalkyl group formed by combining two of Ry 1 to Ry 3 or a cycloalkenyl group for example, one of the methylene groups constituting the ring is a hetero atom such as an oxygen atom, a carbonyl group, or —SO 2 It may be substituted with a group containing a heteroatom such as a - group and a -SO 3 - group, a vinylidene group, or a combination thereof.
• one or more ethylene groups constituting the cycloalkane ring or cycloalkene ring may be replaced with a vinylene group.
• Ry 1 is a methyl group, an ethyl group, a vinyl group, an allyl group, or an aryl group
• Ry 2 and Ry 3 combine to form the above-mentioned cycloalkyl
• a preferred embodiment forms a group or a cycloalkenyl group.
• substituents include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group. (2 to 6 carbon atoms).
• the number of carbon atoms in the substituent is preferably 8 or less.
• the repeating unit represented by the formula (B) is preferably an acid-decomposable (meth)acrylic acid tertiary ester-based repeating unit (Xb represents a hydrogen atom or a methyl group, and L represents a —CO— group.
• repeating unit represented acid-decomposable hydroxystyrene tertiary alkyl ether-based repeating unit (repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a phenyl group), acid-decomposable styrene carboxylic acid tertiary ester It is a repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a -Rt-CO- group (Rt is an aromatic group)).
• the content of the repeating unit having an acid-decomposable group containing an unsaturated bond is preferably 15 mol% or more, more preferably 20 mol% or more, and 30 mol% or more, based on the total repeating units in the resin (A). is more preferred.
• the upper limit thereof is preferably 80 mol % or less, more preferably 70 mol % or less, and even more preferably 60 mol % or less, based on all repeating units in the resin (A).
• repeating units having an acid-decomposable group containing an unsaturated bond are shown below, but are not limited thereto.
• Xb and L1 represent any of the substituents and linking groups described above
• Ar represents an aromatic group
• R represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, Alkenyl group, hydroxyl group, alkoxy group, acyloxy group, cyano group, nitro group, amino group, halogen atom, ester group (-OCOR''' or -COOR''', R''' is alkyl having 1 to 20 carbon atoms group or fluorinated alkyl group), or a substituent such as a carboxyl group
• R′ is a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an alkynyl group, or , represents a mono
• the content of repeating units having an acid-decomposable group is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, relative to all repeating units in the resin (A).
• the upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol% or less, and particularly 60 mol% or less, relative to all repeating units in the resin (A). preferable.
• the resin (A) may contain at least one repeating unit selected from the group consisting of Group A below and/or at least one repeating unit selected from the group consisting of Group B below. good.
• Group A A group consisting of the following repeating units (20) to (25). (20) a repeating unit having an acid group, which will be described later; A repeating unit (23) having a lactone group, a sultone group, or a carbonate group, and a repeating unit (24) having a photoacid-generating group, which will be described later.
• Repeating unit (25) a repeating unit for reducing the mobility of the main chain
• the represented repeating unit corresponds to (25) the repeating unit for reducing the mobility of the main chain.
• Group B A group consisting of the following repeating units (30) to (32).
• the resin (A) preferably has an acid group, and preferably contains a repeating unit having an acid group, as described later.
• the definition of the acid group will be explained later along with preferred embodiments of repeating units having an acid group.
• the resin (A) may have at least one type of repeating unit selected from the group consisting of the A group.
• the resin (A) has at least one repeating unit selected from the group consisting of Group A above. is preferred.
• Resin (A) may contain at least one of a fluorine atom and an iodine atom.
• the resin (A) preferably contains at least one of a fluorine atom and an iodine atom.
• the resin (A) may have one repeating unit containing both a fluorine atom and an iodine atom, and the resin (A) It may contain two types of a repeating unit containing a fluorine atom and a repeating unit containing an iodine atom.
• Resin (A) may have a repeating unit having an aromatic group.
• the composition of the present invention is used as an actinic ray-sensitive or radiation-sensitive resin composition for EUV exposure, it is also preferred that the resin (A) has a repeating unit having an aromatic group.
• the resin (A) may have at least one type of repeating unit selected from the group consisting of Group B above.
• the resin (A) When the resist composition is used as an actinic ray-sensitive or radiation-sensitive resin composition for ArF, the resin (A) preferably has at least one repeating unit selected from the group consisting of Group B above. When the resist composition is used as an actinic ray-sensitive or radiation-sensitive resin composition for ArF, the resin (A) preferably contains neither fluorine atoms nor silicon atoms. When the composition of the present invention is used as an actinic ray-sensitive or radiation-sensitive resin composition for ArF, the resin (A) preferably has no aromatic group.
• Resin (A) may have a repeating unit having an acid group.
• an acid group having a pKa of 13 or less is preferable.
• the acid dissociation constant of the acid group is preferably 13 or less, more preferably 3-13, even more preferably 5-10.
• the content of the acid group in the resin (A) is not particularly limited, but is often 0.2 to 6.0 mmol/g. Among them, 0.8 to 6.0 mmol/g is preferable, 1.2 to 5.0 mmol/g is more preferable, and 1.6 to 4.0 mmol/g is even more preferable.
• the acid group is preferably, for example, a carboxyl group, a phenolic hydroxyl group, a fluoroalcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group.
• a fluoroalcohol group preferably a hexafluoroisopropanol group
• a sulfonic acid group preferably a sulfonamide group
• an isopropanol group preferably, for example, a carboxyl group, a phenolic hydroxyl group, a fluoroalcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group.
• one or more (preferably 1 to 2) fluorine atoms may be substituted with a group other than a fluor
• the acid group is -C(CF 3 )(OH)-CF 2 - thus formed.
• one or more of the fluorine atoms may be substituted with a group other than a fluorine atom to form a ring containing -C(CF 3 )(OH)-CF 2 -.
• the repeating unit having an acid group is different from the repeating unit having a structure in which the polar group is protected by a group that leaves under the action of an acid, and the repeating unit having a lactone group, a sultone group, or a carbonate group, which will be described later. It is preferably a repeating unit.
• a repeating unit having an acid group may have a fluorine atom or an iodine atom.
• repeating units having an acid group include the following repeating units.
• repeating unit having an acid group a repeating unit represented by the following formula (1) is preferable.
• A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group.
• R represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkyloxycarbonyl group, or an aryloxycarbonyl group; In some cases they may be the same or different. When it has a plurality of R, they may jointly form a ring.
• a hydrogen atom is preferred as R.
• a represents an integer of 1 to 3;
• b represents an integer from 0 to (5-a).
• repeating units having an acid group examples include 1 or 2.
• R represents a hydrogen atom or a methyl group
• a represents 2 or 3.
• the content of repeating units having an acid group is preferably 10 mol% or more, more preferably 15 mol% or more, relative to all repeating units in the resin (A). Moreover, the upper limit thereof is preferably 70 mol % or less, more preferably 65 mol % or less, and still more preferably 60 mol % or less, based on all repeating units in the resin (A).
• the resin (A) has neither an acid-decomposable group nor an acid group, apart from the above-described ⁇ repeating unit having an acid-decomposable group> and ⁇ repeating unit having an acid group>, and contains a fluorine atom and a bromine atom.
• it may have a repeating unit having an iodine atom (hereinafter also referred to as unit X).
• the ⁇ repeating unit having neither an acid-decomposable group nor an acid group and having a fluorine atom, a bromine atom, or an iodine atom> referred to here is a ⁇ repeating unit having a lactone group, a sultone group, or a carbonate group> described later.
• ⁇ repeating unit having a photoacid-generating group> is a ⁇ repeating unit having a lactone group, a sultone group, or a carbonate group> described later.
• a repeating unit represented by formula (C) is preferable.
• L5 represents a single bond or an ester group.
• R9 represents a hydrogen atom or an alkyl group optionally having a fluorine atom or an iodine atom.
• R 10 may have a hydrogen atom, an alkyl group optionally having a fluorine atom or an iodine atom, a cycloalkyl group optionally having a fluorine atom or an iodine atom, a fluorine atom or an iodine atom represents an aryl group or a group combining these;
• repeating units having a fluorine atom or an iodine atom are shown below.
• the content of the unit X is preferably 0 mol% or more, more preferably 5 mol% or more, and still more preferably 10 mol% or more, relative to all repeating units in the resin (A). Moreover, the upper limit thereof is preferably 50 mol % or less, more preferably 45 mol % or less, and still more preferably 40 mol % or less, relative to all repeating units in the resin (A).
• the total content of repeating units containing at least one of a fluorine atom, a bromine atom and an iodine atom is preferably 10 mol% or more with respect to all repeating units of the resin (A). , more preferably 20 mol % or more, still more preferably 30 mol % or more, and particularly preferably 40 mol % or more.
• the upper limit is not particularly limited, it is, for example, 100 mol % or less with respect to all repeating units of the resin (A).
• the repeating unit containing at least one of a fluorine atom, a bromine atom and an iodine atom includes, for example, a repeating unit having a fluorine atom, a bromine atom or an iodine atom and having an acid-decomposable group, a fluorine atom, a bromine repeating units having an acid group, and repeating units having a fluorine atom, a bromine atom, or an iodine atom.
• Resin (A) may have a repeating unit (hereinafter also referred to as “unit Y”) having at least one selected from the group consisting of a lactone group, a sultone group and a carbonate group. It is also preferable that the unit Y does not have a hydroxyl group and an acid group such as a hexafluoropropanol group.
• the lactone group or sultone group may have a lactone structure or sultone structure.
• the lactone structure or sultone structure is preferably a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure.
• the resin (A) has a lactone structure represented by any one of the following formulas (LC1-1) to (LC1-21), or any one of the following formulas (SL1-1) to (SL1-3). It preferably has a repeating unit having a lactone group or a sultone group obtained by removing one or more hydrogen atoms from a ring member atom of a sultone structure, and the lactone group or sultone group may be directly bonded to the main chain.
• ring member atoms of a lactone group or a sultone group may constitute the main chain of resin (A).
• the lactone structure or sultone structure may have a substituent (Rb 2 ).
• Preferred substituents (Rb 2 ) include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 7 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 1 to 8 carbon atoms, and carboxyl groups. , halogen atoms, cyano groups, and acid-labile groups.
• n2 represents an integer of 0-4. When n2 is 2 or more, multiple Rb 2 may be different, and multiple Rb 2 may combine to form a ring.
• Rb 0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferred substituents that the alkyl group of Rb 0 may have include a hydroxyl group and a halogen atom.
• a halogen atom for Rb 0 includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• Rb 0 is preferably a hydrogen atom or a methyl group.
• Ab is a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a combination of these divalent linkages represents a group.
• Ab is preferably a single bond or a linking group represented by -Ab 1 -CO 2 -.
• Ab 1 is a linear or branched alkylene group or a monocyclic or polycyclic cycloalkylene group, preferably a methylene group, ethylene group, cyclohexylene group, adamantylene group or norbornylene group.
• V is a group obtained by removing one hydrogen atom from a ring member atom of a lactone structure represented by any one of formulas (LC1-1) to (LC1-21), or formulas (SL1-1) to (SL1- 3) represents a group obtained by removing one hydrogen atom from a ring member atom of the sultone structure represented by any one of 3).
• any optical isomer may be used.
• one kind of optical isomer may be used alone, or a plurality of optical isomers may be mixed and used.
• its optical purity (ee) is preferably 90 or more, more preferably 95 or more.
• a cyclic carbonate group is preferred.
• a repeating unit having a cyclic carbonate group a repeating unit represented by the following formula (A-1) is preferable.
• R A 1 represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group).
• n represents an integer of 0 or more.
• RA2 represents a substituent. When n is 2 or more, a plurality of R A 2 may be the same or different.
• A represents a single bond or a divalent linking group.
• the divalent linking group includes an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a combination of these.
• a valent linking group is preferred.
• Z represents an atomic group forming a monocyclic or polycyclic ring together with the group represented by -O-CO-O- in the formula.
• Rx represents a hydrogen atom, -CH 3 , -CH 2 OH or -CF 3 .
• the content of the unit Y is preferably 1 mol% or more, more preferably 10 mol% or more, relative to all repeating units in the resin (A).
• the upper limit is preferably 85 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol% or less, and particularly 60 mol% or less, relative to all repeating units in the resin (A). preferable.
• the resin (A) may have, as a repeating unit other than the above, a repeating unit having a group that generates an acid upon exposure to actinic rays or radiation (hereinafter also referred to as a "photoacid-generating group").
• Repeating units having a photoacid-generating group include those described in paragraphs [0109] to [0115] of WO2020/004306.
• Resin (A) may have a repeating unit represented by formula (V-1) or formula (V-2).
• Examples of the repeating unit represented by formula (V-1) or formula (V-2) include those described in paragraphs [0116] to [0119] of WO2020/004306.
• Repeating units for reducing the mobility of the main chain include those described in paragraphs [0120] to [0151] of WO2020/004306.
• the resin (A) may have repeating units having at least one group selected from lactone groups, sultone groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups.
• the repeating unit having a lactone group, a sultone group, or a carbonate group that the resin (A) has include the repeating units described in the above ⁇ Repeating unit having a lactone group, sultone group, or carbonate group>.
• the preferable content is also as described in ⁇ Repeating unit having lactone group, sultone group, or carbonate group>.
• Resin (A) may have a repeating unit having a hydroxyl group or a cyano group. This improves the adhesion to the substrate and the compatibility with the developer.
• a repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group.
• a repeating unit having a hydroxyl group or a cyano group preferably does not have an acid-decomposable group. Examples of repeating units having a hydroxyl group or a cyano group include those described in paragraphs [0081] to [0084] of JP-A-2014-098921.
• Resin (A) may have a repeating unit having an alkali-soluble group.
• the alkali-soluble group includes a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol group substituted with an electron-withdrawing group at the ⁇ -position (e.g., hexafluoroisopropanol group). , is preferably a carboxyl group.
• the resin (A) contains a repeating unit having an alkali-soluble group, the resolution for contact holes is increased. Repeating units having an alkali-soluble group include those described in paragraphs [0085] and [0086] of JP-A-2014-098921.
• Resin (A) may have a repeating unit that has an alicyclic hydrocarbon structure and does not exhibit acid decomposability. Examples of such repeating units include those described in paragraph [0164] of WO2020/004306.
• Resin (A) may have a repeating unit represented by formula (III) that has neither a hydroxyl group nor a cyano group.
• Examples of the repeating unit represented by formula (III) having neither a hydroxyl group nor a cyano group include those described in paragraphs [0165] to [0173] of WO2020/004306.
• the resin (A) may have repeating units other than the repeating units described above.
• the resin (A) has repeating units selected from the group consisting of repeating units having an oxathian ring group, repeating units having an oxazolone ring group, repeating units having a dioxane ring group, and repeating units having a hydantoin ring group. You may have Specific examples of repeating units other than the repeating units described above are shown below.
• the resin (A) may contain various repeating structural units for the purpose of adjusting dry etching resistance, suitability for standard developer, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, and the like. may have
• all of the repeating units are repeating units derived from a compound having an ethylenically unsaturated bond. It is preferably composed of In particular, it is also preferred that all of the repeating units are composed of (meth)acrylate repeating units.
• all of the repeating units are composed of (meth)acrylate repeating units, all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, and all of the repeating units are methacrylates. It is possible to use either one based on repeating units and acrylate repeating units, and it is preferable that the acrylate repeating units be 50 mol % or less of the total repeating units.
• Resin (A) can be synthesized according to a conventional method (for example, radical polymerization).
• the weight average molecular weight of the resin (A) is preferably 30,000 or less, more preferably 1,000 to 30,000, even more preferably 3,000 to 30,000, further preferably 5,000 as a polystyrene equivalent value by GPC method. ⁇ 15,000 is particularly preferred.
• the dispersity (molecular weight distribution) of the resin (A) is preferably 1 to 5, more preferably 1 to 3, still more preferably 1.2 to 3.0, and particularly preferably 1.2 to 2.0. The smaller the degree of dispersion, the better the resolution and resist shape, the smoother the side walls of the resist pattern, and the better the roughness.
• the content of the resin (A) is preferably 40.0 to 99.9% by mass, more preferably 60.0 to 90.0% by mass, based on the total solid content of the composition. .
• the resin (A) may be used singly or in combination.
• the composition of the present invention may contain a compound that generates an acid upon exposure to actinic rays or radiation (hereinafter also referred to as "photoacid generator (B)").
• the photoacid generator (B) may be in the form of a low-molecular-weight compound, or may be in the form of being incorporated into a part of a polymer (for example, a resin (A) described below).
• the form of a low-molecular-weight compound and the form incorporated into a part of a polymer for example, the resin (A) described later
• the molecular weight of the photoacid generator is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less. Although the lower limit is not particularly limited, 100 or more is preferable.
• the photoacid generator (B) is in the form of being incorporated into a part of the polymer, it may be incorporated into a part of the resin (A), or may be incorporated into a resin different from the resin (A). good.
• the photoacid generator (B) is preferably in the form of a low molecular weight compound.
• Examples of the photoacid generator (B) include compounds (onium salts) represented by “M + X ⁇ ”, and compounds that generate an organic acid upon exposure are preferred.
• Examples of the organic acid include sulfonic acid (aliphatic sulfonic acid, aromatic sulfonic acid, camphorsulfonic acid, etc.), carboxylic acid (aliphatic carboxylic acid, aromatic carboxylic acid, aralkylcarboxylic acid, etc.), carbonylsulfonylimide, acids, bis(alkylsulfonyl)imidic acids, and tris(alkylsulfonyl)methide acids.
• M + represents an organic cation.
• the valence of the organic cation may be 1 or 2 or more.
• a cation represented by the formula (ZaI) hereinafter also referred to as “cation (ZaI)
• ZaII a cation represented by the formula (ZaII)
• ZaII a cation represented by the formula (ZaII)
• R 201 , R 202 and R 203 each independently represent an organic group.
• the number of carbon atoms in the organic groups for R 201 , R 202 and R 203 is preferably 1-30, more preferably 1-20.
• Two of R 201 to R 203 may combine to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group.
• Examples of the group formed by combining two of R 201 to R 203 include an alkylene group (eg, a butylene group and a pentylene group) and —CH 2 —CH 2 —O—CH 2 —CH 2 —. mentioned.
• Suitable embodiments of the organic cation in formula (ZaI) include cation (ZaI-1), cation (ZaI-2), cation (ZaI-3b), and cation (ZaI-4b), which will be described later.
• Cation (ZaI-1) is an arylsulfonium cation in which at least one of R 201 to R 203 in formula (ZaI) above is an aryl group. At least one of R 201 to R 203 in formula (ZaI) is preferably an aryl group.
• all of R 201 to R 203 may be aryl groups, or part of R 201 to R 203 may be aryl groups and the rest may be alkyl groups or cycloalkyl groups.
• R 201 to R 203 is an aryl group, and the remaining two of R 201 to R 203 may combine to form a ring structure, in which an oxygen atom, a sulfur atom and an ester group , an amide group, or a carbonyl group.
• the group formed by bonding two of R 201 to R 203 includes, for example, one or more methylene groups substituted with an oxygen atom, a sulfur atom, an ester group, an amide group and/or a carbonyl group. alkylene groups (eg, butylene group, pentylene group, and —CH 2 —CH 2 —O—CH 2 —CH 2 —).
• Arylsulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.
• the aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
• the aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Heterocyclic structures include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene residues.
• the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different.
• the alkyl group or cycloalkyl group optionally possessed by the arylsulfonium cation is a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or 3 to 15 carbon atoms. is preferred, and a methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group or cyclohexyl group is more preferred.
• substituents that the aryl group, alkyl group and cycloalkyl group of R 201 to R 203 may have include an alkyl group (eg, 1 to 15 carbon atoms), a cycloalkyl group (eg, 3 to 3 carbon atoms).
• aryl groups eg, 6 to 14 carbon atoms
• alkoxy groups eg, 1 to 15 carbon atoms
• cycloalkylalkoxy groups eg, 1 to 15 carbon atoms
• halogen atoms eg, fluorine and iodine
• a hydroxyl group a carboxyl group, an ester group, a sulfinyl group, a sulfonyl group, an alkylthio group, or a phenylthio group.
• the substituent may further have a substituent
• the alkyl group preferably has a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group. It is also preferable to form an acid-decomposable group by any combination of the above substituents.
• the acid-decomposable group is intended to be a group that is decomposed by the action of an acid to generate a polar group, and preferably has a structure in which the polar group is protected by a group that is eliminated by the action of an acid.
• the polar group and leaving group are as described above.
• At least one aryl group of R 201 to R 203 in formula (ZaI) preferably has a substituent.
• Cation (ZaI-2) is a cation in which R 201 to R 203 in formula (ZaI) each independently represents an organic group having no aromatic ring.
• Aromatic rings also include aromatic rings containing heteroatoms.
• the number of carbon atoms in the organic group having no aromatic ring as R 201 to R 203 is preferably 1-30, more preferably 1-20.
• R 201 to R 203 are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, and a linear or branched 2-oxoalkyl group, 2-oxocycloalkyl group, or An alkoxycarbonylmethyl group is more preferred, and a linear or branched 2-oxoalkyl group is even more preferred.
• the alkyl groups and cycloalkyl groups of R 201 to R 203 are, for example, linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, , butyl group, and pentyl group), and cycloalkyl groups having 3 to 10 carbon atoms (eg, cyclopentyl group, cyclohexyl group, and norbornyl group).
• R 201 to R 203 may be further substituted with a halogen atom, an alkoxy group (eg, 1-5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group. It is also preferred that the substituents of R 201 to R 203 each independently form an acid-decomposable group by any combination of substituents.
• the cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).
• R 1c to R 5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkyl represents a carbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group, or an arylthio group; R 6c and R 7c each independently represent a hydrogen atom, an alkyl group (eg, t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group.
• R 6c and R 7c each independently represent a hydrogen atom, an alkyl group (eg, t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an ary
• R x and R y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group. It is also preferred that the substituents of R 1c to R 7c , R x and R y each independently form an acid-decomposable group by any combination of substituents.
• R 1c to R 5c , R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y may combine with each other to form a ring.
• the rings may each independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
• Examples of the ring include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic hetero rings, and polycyclic condensed rings in which two or more of these rings are combined.
• the ring includes a 3- to 10-membered ring, preferably a 4- to 8-membered ring, more preferably a 5- or 6-membered ring.
• Examples of groups formed by bonding two or more of R 1c to R 5c , R 6c and R 7c , and R x and R y include alkylene groups such as a butylene group and a pentylene group. A methylene group in this alkylene group may be substituted with a heteroatom such as an oxygen atom.
• the group formed by combining R 5c and R 6c and R 5c and R x is preferably a single bond or an alkylene group.
• Alkylene groups include methylene and ethylene groups.
• R 1c to R 5c , R 6c , R 7c , R x , R y , and two or more of R 1c to R 5c , R 5c and R 6c , R 6c and R 7c , R 5c and R x , and the ring formed by combining each other with R x and R y may have a substituent.
• the cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).
• R 13 is a hydrogen atom, a halogen atom (e.g., fluorine atom, iodine atom, etc.), a hydroxyl group, an alkyl group, a halogenated alkyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a group containing a cycloalkyl group (cycloalkyl may be the group itself, or may be a group partially containing a cycloalkyl group). These groups may have a substituent.
• a halogen atom e.g., fluorine atom, iodine atom, etc.
• R 14 is a hydroxyl group, a halogen atom (e.g., fluorine atom, iodine atom, etc.), an alkyl group, a halogenated alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl represents a group containing a group (either a cycloalkyl group itself or a group partially containing a cycloalkyl group). These groups may have a substituent. When two or more R 14 are present, each independently represents the above group such as a hydroxyl group.
• a halogen atom e.g., fluorine atom, iodine atom, etc.
• Each R 15 independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. Two R 15 may be joined together to form a ring. When two R 15 are combined to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom. In one aspect, two R 15 are alkylene groups, preferably joined together to form a ring structure. The ring formed by combining the alkyl group, the cycloalkyl group, the naphthyl group, and the two R 15 groups may have a substituent.
• the alkyl groups of R 13 , R 14 and R 15 may be linear or branched.
• the number of carbon atoms in the alkyl group is preferably 1-10.
• the alkyl group is preferably a methyl group, an ethyl group, an n-butyl group, a t-butyl group, or the like. It is also preferred that each of the substituents of R 13 to R 15 , R x and R y independently forms an acid-decomposable group by any combination of substituents.
• R 204 and R 205 each independently represent an aryl group, an alkyl group or a cycloalkyl group.
• the aryl group for R 204 and R 205 is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
• the aryl group for R 204 and R 205 may be an aryl group having a heterocyclic ring having an oxygen atom, a nitrogen atom, a sulfur atom, or the like.
• Skeletons of heterocyclic aryl groups include, for example, pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
• the alkyl group and cycloalkyl group for R 204 and R 205 include a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, or pentyl group), or a cycloalkyl group having 3 to 10 carbon atoms (eg, cyclopentyl group, cyclohexyl group, or norbornyl group).
• the aryl group, alkyl group and cycloalkyl group of R 204 and R 205 may each independently have a substituent.
• substituents that the aryl group, alkyl group and cycloalkyl group of R 204 and R 205 may have include an alkyl group (eg, 1 to 15 carbon atoms) and a cycloalkyl group (eg, 3 to 15), aryl groups (eg, 6 to 15 carbon atoms), alkoxy groups (eg, 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups. It is also preferred that the substituents of R 204 and R 205 each independently form an acid-decomposable group by any combination of substituents.
• X ⁇ represents an organic anion.
• the organic anion is not particularly limited, and includes organic anions having a valence of 1, 2 or more.
• an anion having a significantly low ability to cause a nucleophilic reaction is preferred, and a non-nucleophilic anion is more preferred.
• non-nucleophilic anions examples include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, and aralkyl carboxylic acid anions), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methide anions.
• sulfonate anions aliphatic sulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc.
• carboxylate anions aliphatic carboxylate anions, aromatic carboxylate anions, and aralkyl carboxylic acid anions
• sulfonylimide anions bis(alkylsulfonyl)imide anions
• the aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be a linear or branched alkyl group or a cycloalkyl group, and may be a straight chain having 1 to 30 carbon atoms. Alternatively, a branched alkyl group or a cycloalkyl group having 3 to 30 carbon atoms is preferred.
• the alkyl group may be, for example, a fluoroalkyl group (which may have a substituent other than a fluorine atom, or may be a perfluoroalkyl group).
• the aryl group in the aromatic sulfonate anion and the aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group.
• the alkyl group, cycloalkyl group, and aryl group listed above may have a substituent.
• the substituents are not particularly limited, but examples include nitro groups, halogen atoms such as fluorine atoms and chlorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), alkyl groups (preferably 1 to 10 carbon atoms), cycloalkyl groups (preferably 3 to 15 carbon atoms), aryl groups (preferably 6 to 14 carbon atoms), alkoxycarbonyl groups (preferably 2 to 7 carbon atoms), acyl groups ( preferably 2 to 12 carbon atoms), alkoxycarbonyloxy group (preferably 2 to 7 carbon atoms), alkylthio group (preferably 1 to 15 carbon atoms), alkylsulfonyl group (preferably 1 to 15 carbon atoms), alkylimino A sulfonyl group (preferably having 1 to 15 carbon atoms
• aralkyl group in the aralkylcarboxylate anion an aralkyl group having 7 to 14 carbon atoms is preferred.
• Aralkyl groups having 7 to 14 carbon atoms include, for example, benzyl, phenethyl, naphthylmethyl, naphthylethyl and naphthylbutyl groups.
• Sulfonylimide anions include, for example, saccharin anions.
• alkyl group in the bis(alkylsulfonyl)imide anion and the tris(alkylsulfonyl)methide anion an alkyl group having 1 to 5 carbon atoms is preferable.
• substituents of these alkyl groups include halogen atoms, halogen-substituted alkyl groups, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryloxysulfonyl groups.
• a fluorine atom or an alkyl group substituted with a fluorine atom is preferred.
• the alkyl groups in the bis(alkylsulfonyl)imide anion may combine with each other to form a ring structure. This increases the acid strength.
• non-nucleophilic anions include, for example, phosphorous fluorides (eg, PF 6 ⁇ ), boron fluorides (eg, BF 4 ⁇ ), and antimony fluorides (eg, SbF 6 ⁇ ).
• non-nucleophilic anions include aliphatic sulfonate anions in which at least the ⁇ -position of sulfonic acid is substituted with fluorine atoms, aromatic sulfonate anions in which fluorine atoms or groups having fluorine atoms are substituted, and alkyl groups in which fluorine atoms are present.
• a bis(alkylsulfonyl)imide anion substituted with or a tris(alkylsulfonyl)methide anion in which an alkyl group is substituted with a fluorine atom is preferable.
• perfluoroaliphatic sulfonate anions preferably having 4 to 8 carbon atoms
• benzenesulfonate anions having a fluorine atom are more preferable, nonafluorobutanesulfonate anions, perfluorooctanesulfonate anions, pentafluoro A benzenesulfonate anion or a 3,5-bis(trifluoromethyl)benzenesulfonate anion is more preferred.
• an anion represented by the following formula (AN1) is also preferable.
• R 1 and R 2 each independently represent a hydrogen atom or a substituent.
• the substituent is not particularly limited, but a group that is not an electron-withdrawing group is preferred.
• Groups that are not electron-withdrawing groups include, for example, hydrocarbon groups, hydroxyl groups, oxyhydrocarbon groups, oxycarbonyl hydrocarbon groups, amino groups, hydrocarbon-substituted amino groups, and hydrocarbon-substituted amide groups.
• Groups that are not electron-withdrawing groups are preferably -R', -OH, -OR', -OCOR', -NH 2 , -NR' 2 , -NHR' or -NHCOR' each independently.
• R' is a monovalent hydrocarbon group.
• Examples of the monovalent hydrocarbon group represented by R' include alkyl groups such as methyl, ethyl, propyl, and butyl; alkenyl groups such as ethenyl, propenyl, and butenyl; ethynyl monovalent linear or branched hydrocarbon groups such as alkynyl groups such as groups, propynyl groups, and butynyl groups; cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, cyclohexyl groups, norbornyl groups, and adamantyl groups Cycloalkyl group; monovalent alicyclic hydrocarbon group such as cycloalkenyl group such as cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, and norbornenyl group; phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, methyl aryl groups such as
• L represents a divalent linking group.
• divalent linking groups include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO 2 -, alkylene groups ( preferably 1 to 6 carbon atoms), a cycloalkylene group (preferably 3 to 15 carbon atoms), an alkenylene group (preferably 2 to 6 carbon atoms), and a divalent linking group combining a plurality of these.
• the divalent linking group includes -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -SO 2 -, and -O-CO-O-alkylene group- , -COO-alkylene group-, or -CONH-alkylene group- is preferred, and -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, -SO 2 - , or -COO-alkylene group- is more preferred.
• a group represented by the following formula (AN1-1) is preferable. * a - (CR 2a 2 ) X - Q- (CR 2b 2 ) Y - * b (AN1-1)
• * a represents the bonding position with R3 in formula (AN1).
• * b represents the bonding position with -C(R 1 )(R 2 )- in formula (AN1).
• X and Y each independently represent an integer of 0-10, preferably an integer of 0-3.
• R 2a and R 2b each independently represent a hydrogen atom or a substituent. When multiple R 2a and R 2b are present, the multiple R 2a and R 2b may be the same or different. However, when Y is 1 or more, R 2b in CR 2b 2 directly bonded to —C(R 1 )(R 2 )— in formula (AN1) is other than a fluorine atom.
• Q is * A -O-CO-O-* B , * A -CO-* B , * A -CO-O-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B or * A - SO2- * B .
• R3 represents an organic group.
• the organic group is not particularly limited as long as it has 1 or more carbon atoms. branched chain alkyl group) or a cyclic group.
• the organic group may or may not have a substituent.
• the organic group may or may not have a heteroatom (oxygen atom, sulfur atom, and/or nitrogen atom, etc.).
• R 3 is preferably an organic group having a cyclic structure.
• the cyclic structure may be monocyclic or polycyclic, and may have a substituent.
• the ring in the organic group containing a cyclic structure is preferably directly bonded to L in formula (AN1).
• the organic group having a cyclic structure may or may not have a heteroatom (oxygen atom, sulfur atom, and/or nitrogen atom, etc.), for example. Heteroatoms may replace one or more of the carbon atoms that form the ring structure.
• the organic group having a cyclic structure is preferably, for example, a hydrocarbon group having a cyclic structure, a lactone ring group, or a sultone ring group.
• the organic group having a cyclic structure is preferably a hydrocarbon group having a cyclic structure.
• the above hydrocarbon group having a cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may have a substituent.
• the cycloalkyl group may be monocyclic (such as cyclohexyl group) or polycyclic (such as adamantyl group), and preferably has 5 to 12 carbon atoms.
• Examples of the lactone group and sultone group include structures represented by the above formulas (LC1-1) to (LC1-21) and structures represented by formulas (SL1-1) to (SL1-3). , preferably a group obtained by removing one hydrogen atom from a ring member atom constituting a lactone structure or a sultone structure.
• the non-nucleophilic anion may be a benzenesulfonate anion, preferably a benzenesulfonate anion substituted with a branched alkyl group or cycloalkyl group.
• an anion represented by the following formula (AN2) is also preferable.
• o represents an integer of 1-3.
• p represents an integer from 0 to 10;
• q represents an integer from 0 to 10;
• Xf represents a hydrogen atom, a fluorine atom, an alkyl group substituted with at least one fluorine atom, or an organic group having no fluorine atom.
• the number of carbon atoms in this alkyl group is preferably 1-10, more preferably 1-4.
• a perfluoroalkyl group is preferred as the alkyl group substituted with at least one fluorine atom.
• Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF 3 , and even more preferably both Xf are fluorine atoms.
• R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When multiple R 4 and R 5 are present, each of R 4 and R 5 may be the same or different.
• the alkyl groups represented by R 4 and R 5 preferably have 1 to 4 carbon atoms. The above alkyl group may have a substituent. Hydrogen atoms are preferred as R 4 and R 5 .
• L represents a divalent linking group.
• the definition of L is synonymous with L in formula (AN1).
• W represents an organic group containing a cyclic structure.
• a cyclic organic group is preferable.
• Cyclic organic groups include, for example, alicyclic groups, aryl groups, and heterocyclic groups.
• the alicyclic group may be monocyclic or polycyclic.
• Monocyclic alicyclic groups include, for example, monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
• the polycyclic alicyclic group includes, for example, a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and a polycyclic cycloalkyl group such as an adamantyl group.
• alicyclic groups having a bulky structure with 7 or more carbon atoms such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups, are preferred.
• Aryl groups may be monocyclic or polycyclic. Examples of the aryl group include phenyl group, naphthyl group, phenanthryl group, and anthryl group.
• a heterocyclic group may be monocyclic or polycyclic. Especially, when it is a polycyclic heterocyclic group, diffusion of acid can be further suppressed.
• a heterocyclic group may or may not have an aromatic character. Heterocyclic rings having aromaticity include, for example, furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, and pyridine ring.
• Non-aromatic heterocycles include, for example, a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring.
• the heterocyclic ring in the heterocyclic group is preferably a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring.
• the cyclic organic group may have a substituent.
• substituents include alkyl groups (either linear or branched, preferably having 1 to 12 carbon atoms), cycloalkyl groups (monocyclic, polycyclic, and spirocyclic). any group, preferably having 3 to 20 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), hydroxyl group, alkoxy group, ester group, amide group, urethane group, ureido group, thioether group, sulfonamide and sulfonate ester groups.
• carbonyl carbon may be sufficient as carbon (carbon which contributes to ring formation) which comprises a cyclic
• Examples of anions represented by formula (AN2) include SO 3 ⁇ —CF 2 —CH 2 —OCO-(L) q′ —W, SO 3 ⁇ —CF 2 —CHF—CH 2 —OCO-(L) q ' -W, SO 3 - -CF 2 -COO-(L) q' -W, SO 3 - -CF 2 -CF 2 -CH 2 -CH 2 -(L) q -W, or SO 3 - - CF 2 —CH(CF 3 )—OCO—(L) q′ —W is preferred.
• L, q and W are the same as in formula (AN2).
• q' represents an integer from 0 to 10;
• an aromatic sulfonate anion represented by the following formula (AN3) is also preferable.
• Ar represents an aryl group (such as a phenyl group) and may further have a substituent other than the sulfonate anion and -(D-B) group.
• Substituents which may be further included include, for example, a fluorine atom and a hydroxyl group.
• n represents an integer of 0 or more. n is preferably 1 to 4, more preferably 2 to 3, and still more preferably 3.
• D represents a single bond or a divalent linking group.
• Divalent linking groups include ether groups, thioether groups, carbonyl groups, sulfoxide groups, sulfone groups, sulfonate ester groups, ester groups, and groups consisting of combinations of two or more thereof.
• B represents a hydrocarbon group.
• B is preferably an aliphatic hydrocarbon group, more preferably an isopropyl group, a cyclohexyl group, or an optionally substituted aryl group (such as a tricyclohexylphenyl group).
• Disulfonamide anions are also preferred as non-nucleophilic anions.
• a disulfonamide anion is, for example, an anion represented by N ⁇ (SO 2 —R q ) 2 .
• R q represents an optionally substituted alkyl group, preferably a fluoroalkyl group, more preferably a perfluoroalkyl group.
• Two R q may combine with each other to form a ring.
• the group formed by bonding two R q together is preferably an optionally substituted alkylene group, preferably a fluoroalkylene group, more preferably a perfluoroalkylene group.
• the alkylene group preferably has 2 to 4 carbon atoms.
• Non-nucleophilic anions also include anions represented by the following formulas (d1-1) to (d1-4).
• R 51 represents a hydrocarbon group (eg, an aryl group such as a phenyl group) optionally having a substituent (eg, hydroxyl group).
• Z 2c represents an optionally substituted hydrocarbon group having 1 to 30 carbon atoms (provided that the carbon atom adjacent to S is not substituted with a fluorine atom).
• the above hydrocarbon group for Z 2c may be linear or branched, and may have a cyclic structure.
• the carbon atom in the hydrocarbon group (preferably the carbon atom that is a ring member atom when the hydrocarbon group has a cyclic structure) may be carbonyl carbon (--CO-).
• Examples of the hydrocarbon group include a group having an optionally substituted norbornyl group.
• a carbon atom forming the norbornyl group may be a carbonyl carbon.
• Z 2c —SO 3 ⁇ in formula (d1-2) is preferably different from the anions represented by formulas (AN1) to (AN3) above.
• Z 2c is preferably other than an aryl group.
• the ⁇ -position and ⁇ -position atoms with respect to —SO 3 — in Z 2c are preferably atoms other than carbon atoms having a fluorine atom as a substituent.
• the ⁇ -position atom and/or the ⁇ -position atom with respect to —SO 3 — is preferably a ring member atom in a cyclic group.
• R 52 represents an organic group (preferably a hydrocarbon group having a fluorine atom)
• Y 3 represents a linear, branched or cyclic alkylene group, an arylene group, or represents a carbonyl group
• Rf represents a hydrocarbon group
• R 53 and R 54 each independently represent an organic group (preferably a hydrocarbon group having a fluorine atom). R 53 and R 54 may combine with each other to form a ring.
• the organic anions may be used singly or in combination of two or more.
• the photoacid generator is also preferably at least one selected from the group consisting of compounds (I) to (II).
• Compound (I) is a compound having one or more structural moieties X shown below and one or more structural moieties Y shown below, wherein the first acidic It is a compound that generates an acid containing a site and a second acidic site described below derived from the structural site Y described below.
• Structural site X Structural site consisting of an anionic site A 1 ⁇ and a cation site M 1 + and forming a first acidic site represented by HA 1 upon exposure to actinic rays or radiation
• Structural site Y anionic site A structural site consisting of A 2 - and a cation site M 2 + and forming a second acidic site represented by HA 2 upon exposure to actinic rays or radiation.
• the compound (I) satisfies Condition I below. .
• Condition I A compound PI obtained by replacing the cation site M 1 + in the structural site 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.
• compound PI corresponds to "a compound having HA 1 and HA 2 ".
• the acid dissociation constant a1 and the acid dissociation constant a2 of compound PI are defined as "a compound having A 1 - and HA 2 " when the acid dissociation constant of compound PI is determined. is the acid dissociation constant a1, and the pKa when the "compound having A 1 - and HA 2 " becomes the "compound having A 1 - and A 2 - " is the acid dissociation constant a2 be.
• compound (I) is, for example, an acid-generating compound having two first acidic sites derived from the structural site X and one second acidic site derived from the structural site Y
• compound PI corresponds to "a compound having two HA 1 and one HA 2 ".
• the acid dissociation constant of compound PI is obtained, the acid dissociation constant when compound PI becomes "a compound having one A 1 - , one HA 1 and one HA 2 " and "one A 1 - and one HA 1 and one HA 2 ” becomes a “compound having two A 1 - and one HA 2 ” corresponds to the acid dissociation constant a1 described above. .
• the acid dissociation constant when "a compound having two A 1 - and one HA 2 -" becomes "a compound having two A 1 - and A 2 - " corresponds to the acid dissociation constant a2. That is, in the case of the compound PI, when it has a plurality of acid dissociation constants derived from the acidic site represented by HA 1 obtained by replacing the cation site M 1 + in the structural site X with H + , a plurality of acid dissociation constants The value of the acid dissociation constant a2 is larger than the largest value of a1.
• the acid dissociation constant when the compound PI becomes "a compound having one A 1 - , one HA 1 and one HA 2 " is aa, and "one A 1 - and one HA 1 and 1
• the relationship between aa and ab satisfies aa ⁇ ab, where ab is the acid dissociation constant when a compound having two HA2 's becomes a compound having two A1- and one HA2 . .
• the acid dissociation constant a1 and the acid dissociation constant a2 are determined by the method for measuring the acid dissociation constant described above.
• the above compound PI corresponds to an acid generated when compound (I) is irradiated with actinic rays or radiation.
• the structural moieties X may be the same or different.
• Two or more of A 1 ⁇ and two or more of M 1 + may be the same or different.
• a 1 - and A 2 - , and M 1 + and M 2 + may be the same or different, but A 1 - and A 2 - are preferably different.
• the difference (absolute value) between the acid dissociation constant a1 (the maximum value when there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is preferably 0.1 or more, and preferably 0.5 or more. More preferably, 1.0 or more is even more preferable.
• the upper limit of the difference (absolute value) between the acid dissociation constant a1 (the maximum value if there are a plurality of acid dissociation constants a1) and the acid dissociation constant a2 is not particularly limited, but is, for example, 16 or less.
• the acid dissociation constant a2 is preferably 20 or less, more preferably 15 or less.
• the lower limit of the acid dissociation constant a2 is preferably -4.0 or more.
• the acid dissociation constant a1 is preferably 2.0 or less, more preferably 0 or less.
• the lower limit of the acid dissociation constant a1 is preferably ⁇ 20.0 or more.
• the anion site A 1 - and the anion site A 2 - are structural sites containing negatively charged atoms or atomic groups, for example, formulas (AA-1) to (AA-3) and formula (BB -1) to (BB-6).
• the anion site A 1 - is preferably one capable of forming an acidic site with a small acid dissociation constant, and more preferably one of the formulas (AA-1) to (AA-3). AA-1) and (AA-3) are more preferred.
• the anion site A 2 - is preferably one capable of forming an acidic site with a larger acid dissociation constant than the anion site A 1 - , and is any of the formulas (BB-1) to (BB-6).
• RA represents a monovalent organic group.
• the monovalent organic group represented by RA is not particularly limited, examples thereof include a cyano group, a trifluoromethyl group and a methanesulfonyl group.
• the cation site M 1 + and the cation site M 2 + are structural sites containing positively charged atoms or atomic groups, such as monovalent organic cations.
• Examples of organic cations include organic cations represented by M + described above.
• compound (I) is not particularly limited, but includes, for example, compounds represented by formulas (Ia-1) to (Ia-5) described later.
• the compound represented by formula (Ia-1) generates an acid represented by HA 11 -L 1 -A 12 H upon exposure to actinic rays or radiation.
• M 11 + and M 12 + each independently represent an organic cation.
• a 11 - and A 12 - each independently represent a monovalent anionic functional group.
• L 1 represents a divalent linking group.
• M 11 + and M 12 + may be the same or different.
• a 11 - and A 12 - may be the same or different, but are preferably different from each other.
• the acid dissociation constant a2 derived from the acidic site represented by HA11 is greater than the acid dissociation constant a1 derived from the acidic site represented by HA11 .
• the preferred values of the acid dissociation constant a1 and the acid dissociation constant a2 are as described above.
• the same acid is generated from compound PIa and the compound represented by formula (Ia-1) upon exposure to actinic rays or radiation.
• At least one of M 11 + , M 12 + , A 11 ⁇ , A 12 ⁇ , and L 1 may have an acid-decomposable group as a substituent.
• the organic cations represented by M 11 + and M 12 + include the organic cations represented by M 1 + described above.
• the monovalent anionic functional group represented by A 11 - intends a monovalent group containing the above-described anion site A 1 - .
• the monovalent anionic functional group represented by A 12 - intends a monovalent group containing the above-mentioned anion site A 2 - .
• the monovalent anionic functional groups represented by A 11 - and A 12 - include any of the above formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6). It is preferably a monovalent anionic functional group containing an anion site, selected from the group consisting of formulas (AX-1) to (AX-3) and formulas (BX-1) to (BX-7) is more preferably a monovalent anionic functional group.
• the monovalent anionic functional group represented by A 11 - is, among others, a monovalent anionic functional group represented by any one of formulas (AX-1) to (AX-3). preferable.
• As the monovalent anionic functional group represented by A 12 - monovalent anionic functional groups represented by any one of formulas (BX-1) to (BX-7) are preferred, and A monovalent anionic functional group represented by any one of (BX-1) to (BX-6) is more preferable.
• R A1 and R A2 each independently represent a monovalent organic group. * represents a binding position.
• the monovalent organic group represented by R A1 is not particularly limited, and examples thereof include a cyano group, a trifluoromethyl group and a methanesulfonyl group.
• the monovalent organic group represented by RA2 is preferably a linear, branched or cyclic alkyl group or aryl group.
• the number of carbon atoms in the alkyl group is preferably 1-15, more preferably 1-10, even more preferably 1-6.
• the above alkyl group may have a substituent.
• the substituent is preferably a fluorine atom or a cyano group, more preferably a fluorine atom.
• the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group.
• the aryl group is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
• the aryl group may have a substituent.
• the substituent is preferably a fluorine atom, an iodine atom, a perfluoroalkyl group (eg, preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms), or a cyano group, a fluorine atom, an iodine atom, or , perfluoroalkyl groups are more preferred.
• R 2 B represents a monovalent organic group.
• * represents a binding position.
• the monovalent organic group represented by RB is preferably a linear, branched or cyclic alkyl group or aryl group.
• the number of carbon atoms in the alkyl group is preferably 1-15, more preferably 1-10, even more preferably 1-6.
• the above alkyl group may have a substituent. Although the substituent is not particularly limited, the substituent is preferably a fluorine atom or a cyano group, more preferably a fluorine atom. When the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group.
• the carbon atom serving as the bonding position in the alkyl group has a substituent, it is also preferably a substituent other than a fluorine atom or a cyano group.
• the carbon atom to be the bonding position in the alkyl group is, for example, in the case of formulas (BX-1) and (BX-4), the carbon directly bonded to -CO- indicated in the formula in the alkyl group In the case of formulas (BX-2) and (BX-3), the carbon atom directly bonded to —SO 2 — indicated in the formula in the alkyl group corresponds to the formula (BX-6)
• the carbon atom in the alkyl group that is directly bonded to the N 2 - specified in the formula is applicable.
• a carbon atom of the alkyl group may be substituted with a carbonyl carbon.
• the aryl group is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
• the aryl group may have a substituent.
• substituents include a fluorine atom, an iodine atom, a perfluoroalkyl group (eg, preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), a cyano group, an alkyl group (eg, 1 to 10 carbon atoms).
• an alkoxy group eg, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.
• an alkoxycarbonyl group eg, 2 to 10 carbon atoms are preferred, and those having 2 to 6 carbon atoms are more preferred.
• the divalent linking group represented by L 1 is not particularly limited, and includes -CO-, -NR-, -O-, -S-, -SO-, -SO 2 - , an alkylene group (preferably having 1 to 6 carbon atoms, which may be linear or branched), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), divalent of an aliphatic heterocyclic group (preferably a 5- to 10-membered ring having at least one N atom, O atom, S atom, or Se atom in the ring structure, more preferably a 5- to 7-membered ring, a 5- to 6-membered ring is more preferable), a divalent aromatic heterocyclic group (preferably a 5- to 10-membered ring having at least one N atom, O atom, S atom, or Se atom in the ring structure, and a 5- to 7-membered
• the monovalent organic group is not particularly limited, for example, an alkyl group (preferably having 1 to 6 carbon atoms) is preferable.
• the alkylene group, the cycloalkylene group, the alkenylene group, the divalent aliphatic heterocyclic group, the divalent aromatic heterocyclic group, and the divalent aromatic hydrocarbon ring group have a substituent.
• Substituents include, for example, halogen atoms (preferably fluorine atoms).
• the divalent linking group represented by L1 is preferably a divalent linking group represented by formula (L1).
• L 111 represents a single bond or a divalent linking group.
• the divalent linking group represented by L 111 is not particularly limited, and may be, for example, —CO—, —NH—, —O—, —SO—, —SO 2 —, or have a substituent.
• Alkylene group preferably having 1 to 6 carbon atoms, which may be linear or branched
• optionally substituted cycloalkylene group preferably having 3 to 15 carbon atoms
• substituted An aryl group preferably having 6 to 10 carbon atoms
• a divalent linking group combining a plurality of these groups may be mentioned.
• the substituent is not particularly limited, and examples thereof include halogen atoms.
• Each Xf 1 independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
• the number of carbon atoms in this alkyl group is preferably 1-10, more preferably 1-4.
• a perfluoroalkyl group is preferred as the alkyl group substituted with at least one fluorine atom.
• Each Xf2 independently represents a hydrogen atom, an alkyl group optionally having a fluorine atom as a substituent, or a fluorine atom.
• the number of carbon atoms in this alkyl group is preferably 1-10, more preferably 1-4.
• Xf2 preferably represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, more preferably a fluorine atom or a perfluoroalkyl group.
• Xf 1 and Xf 2 are each independently preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF 3 .
• both Xf 1 and Xf 2 are more preferably fluorine atoms.
• * represents a binding position.
• a 21a - and A 21b - each independently represent a monovalent anionic functional group.
• the monovalent anionic functional groups represented by A 21a - and A 21b - are meant to be monovalent groups containing the above-described anionic site A 1 - .
• the monovalent anionic functional groups represented by A 21a - and A 21b - are not particularly limited.
• Anionic functional groups are included.
• a 22 - represents a divalent anionic functional group.
• the divalent anionic functional group represented by A 22 - intends a divalent linking group containing the above-mentioned anion site A 2 - .
• Examples of the divalent anionic functional group represented by A 22 - include divalent anionic functional groups represented by formulas (BX-8) to (BX-11) shown below.
• M 21a + , M 21b + , and M 22 + each independently represent an organic cation.
• the organic cations represented by M 21a + , M 21b + , and M 22 + are synonymous with M 11 + above, and the preferred embodiments are also the same.
• L21 and L22 each independently represent a divalent organic group.
• a 31a - and A 32 - each independently represent a monovalent anionic functional group.
• the definition of the monovalent anionic functional group represented by A 31a - is synonymous with A 21a - and A 21b - in formula (Ia-2) described above, and the preferred embodiments are also the same.
• the monovalent anionic functional group represented by A 32 - intends a monovalent group containing the above-mentioned anion site A 2 - .
• the monovalent anionic functional group represented by A 32 - is not particularly limited, and is, for example, a monovalent anionic functional group selected from the group consisting of the above formulas (BX-1) to (BX-7). is mentioned.
• a 31b - represents a divalent anionic functional group.
• the divalent anionic functional group represented by A 31b - intends a divalent linking group containing the anionic site A 1 - described above.
• Examples of the divalent anionic functional group represented by A 31b - include a divalent anionic functional group represented by formula (AX-4) shown below.
• M 31a + , M 31b + , and M 32 + each independently represent a monovalent organic cation.
• the organic cations represented by M 31a + , M 31b + , and M 32 + are synonymous with M 11 + above, and the preferred embodiments are also the same.
• L 31 and L 32 each independently represent a divalent organic group.
• the derived acid dissociation constant a2 is larger than the acid dissociation constant a1-3 derived from the acidic site represented by A 31a H and the acid dissociation constant a1-4 derived from the acidic site represented by A 31b H.
• the acid dissociation constant a1-3 and the acid dissociation constant a1-4 correspond to the acid dissociation constant a1 described above.
• a 31a - and A 32 - may be the same or different.
• M 31a + , M 31b + , and M 32 + may be the same or different. At least one of M 31a + , M 31b + , M 32 + , A 31a ⁇ , A 32 ⁇ , L 31 and L 32 may have an acid-decomposable group as a substituent.
• a 41a ⁇ , A 41b ⁇ , and A 42 ⁇ each independently represent a monovalent anionic functional group.
• the definitions of the monovalent anionic functional groups represented by A 41a - and A 41b - are the same as those of A 21a - and A 21b - in formula (Ia-2) described above.
• the definition of the monovalent anionic functional group represented by A 42 - is the same as A 32 - in formula (Ia-3) described above, and the preferred embodiments are also the same.
• M 41a + , M 41b + , and M 42 + each independently represent an organic cation.
• the organic cations represented by M 41a + , M 41b + , and M 42 + are synonymous with M 11 + above, and the preferred embodiments are also the same.
• L41 represents a trivalent organic group.
• M 41a + , M 41b + , and M 42 + may be the same or different. At least one of M 41a + , M 41b + , M 42 + , A 41a ⁇ , A 41b ⁇ , A 42 ⁇ , and L 41 may have an acid-decomposable group as a substituent.
• the divalent organic groups represented by L 21 and L 22 in formula (Ia-2) and L 31 and L 32 in formula (Ia-3) are not particularly limited, for example, —CO— , —NR—, —O—, —S—, —SO—, —SO 2 —, an alkylene group (preferably having 1 to 6 carbon atoms, which may be linear or branched), a cycloalkylene group (preferably 3 to 15 carbon atoms), alkenylene groups (preferably 2 to 6 carbon atoms), divalent aliphatic heterocyclic groups (at least one N atom, O atom, S atom, or Se atom in the ring structure 5 A to 10-membered ring is preferred, a 5- to 7-membered ring is more preferred, and a 5- to 6-membered ring is even more preferred.), a divalent aromatic heterocyclic group (at least one N atom, O atom, S atom, or Se A 5- to 10-membered ring having an atom in the
• R in -NR- is a hydrogen atom or a monovalent organic group.
• the monovalent organic group is not particularly limited, for example, an alkyl group (preferably having 1 to 6 carbon atoms) is preferable.
• the alkylene group, the cycloalkylene group, the alkenylene group, the divalent aliphatic heterocyclic group, the divalent aromatic heterocyclic group, and the divalent aromatic hydrocarbon ring group have a substituent.
• Substituents include, for example, halogen atoms (preferably fluorine atoms).
• Examples of divalent organic groups represented by L 21 and L 22 in formula (Ia-2) and L 31 and L 32 in formula (Ia-3) are represented by the following formula (L2): It is also preferred that it is a divalent organic group that
• q represents an integer of 1-3. * represents a binding position.
• Each Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
• the number of carbon atoms in this alkyl group is preferably 1-10, more preferably 1-4.
• a perfluoroalkyl group is preferred as the alkyl group substituted with at least one fluorine atom.
• Xf is preferably a fluorine atom or a C 1-4 perfluoroalkyl group, more preferably a fluorine atom or CF 3 . In particular, it is more preferable that both Xf are fluorine atoms.
• LA represents a single bond or a divalent linking group.
• the divalent linking group represented by L A is not particularly limited, and examples thereof include -CO-, -O-, -SO-, -SO 2 -, alkylene groups (preferably having 1 to 6 carbon atoms, straight-chain may be in the form of a branched chain), a cycloalkylene group (preferably having 3 to 15 carbon atoms), a divalent aromatic hydrocarbon ring group (preferably a 6- to 10-membered ring, more preferably a 6-membered ring), and Divalent linking groups in which a plurality of these are combined are included.
• the alkylene group, the cycloalkylene group, and the divalent aromatic hydrocarbon ring group may have a substituent. Substituents include, for example, halogen atoms (preferably fluorine atoms).
• Examples of the divalent organic group represented by formula (L2) include *-CF 2 -*, *-CF 2 -CF 2 -*, *-CF 2 -CF 2 -CF 2 -*, *- Ph-O- SO2 - CF2- *, *-Ph-O- SO2 - CF2 - CF2- *, *-Ph-O- SO2 - CF2 - CF2 - CF2- *, and , *—Ph—OCO—CF 2 —*.
• Ph is an optionally substituted phenylene group, preferably a 1,4-phenylene group.
• an alkyl group eg, preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms
• an alkoxy group eg, preferably having 1 to 10 carbon atoms, 1 to 1 carbon atoms, 6 is more preferable
• an alkoxycarbonyl group eg, preferably having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms.
• a 51a ⁇ , A 51b ⁇ , and A 51c ⁇ each independently represent a monovalent anionic functional group.
• the monovalent anionic functional groups represented by A 51a ⁇ , A 51b ⁇ , and A 51c ⁇ are intended to be monovalent groups containing the above-described anion site A 1 ⁇ .
• the monovalent anionic functional groups represented by A 51a ⁇ , A 51b ⁇ , and A 51c ⁇ are not particularly limited, but are, for example, the group consisting of the above formulas (AX-1) to (AX-3) A selected monovalent anionic functional group can be mentioned.
• a 52a - and A 52b - represent divalent anionic functional groups.
• the divalent anionic functional groups represented by A 52a - and A 52b - are intended to be divalent linking groups containing the above-mentioned anion site A 2 - .
• the divalent anionic functional group represented by A 22 - includes, for example, divalent anionic functional groups selected from the group consisting of the above formulas (BX-8) to (BX-11).
• M 51a + , M 51b + , M 51c + , M 52a + , and M 52b + each independently represent an organic cation.
• the organic cations represented by M 51a + , M 51b + , M 51c + , M 52a + , and M 52b + are synonymous with M 11 + described above, and the preferred embodiments are also the same.
• L51 and L53 each independently represent a divalent organic group.
• the divalent organic groups represented by L 51 and L 53 have the same meanings as L 21 and L 22 in formula (Ia-2) above, and the preferred embodiments are also the same.
• L52 represents a trivalent organic group.
• the trivalent organic group represented by L 52 has the same definition as L 41 in formula (Ia-4) above, and the preferred embodiments are also the same.
• the acid dissociation constants a1-1 to a1-3 correspond to the acid dissociation constant a1 described above, and the acid dissociation constants a2-1 and a2-2 correspond to the acid dissociation constant a2 described above.
• a 51a ⁇ , A 51b ⁇ , and A 51c ⁇ may be the same or different.
• a 52a - and A 52b - may be the same or different.
• M 51a + , M 51b + , M 51c + , M 52a + , and M 52b + may be the same or different.
• M 51b + , M 51c + , M 52a + , M 52b + , A 51a ⁇ , A 51b ⁇ , A 51c ⁇ , L 51 , L 52 and L 53 is an acid-decomposable group as a substituent may have
• Compound (II) is a compound having two or more of the above structural moieties X and one or more of the following structural moieties Z, wherein the first acidic It is a compound that generates an acid containing two or more sites and the structural site Z described above.
• Structural site Z nonionic site capable of neutralizing acid
• the preferred range of the acid dissociation constant a1 derived from the acidic site represented by is the same as the acid dissociation constant a1 in the above compound PI.
• the compound (II) is a compound that generates an acid having two of the first acidic sites derived from the structural site X and the structural site Z
• the compound PII is "two HA 1 It corresponds to "a compound having When the acid dissociation constant of this compound PII is determined, the acid dissociation constant when the compound PII is "a compound having one A 1 - and one HA 1 " and "one A 1 - and one HA
• the acid dissociation constant when the "compound having 1 " becomes "the compound having two A 1 - " corresponds to the acid dissociation constant a1.
• the acid dissociation constant a1 is obtained by the method for measuring the acid dissociation constant described above.
• the above compound PII corresponds to an acid generated when compound (II) is irradiated with actinic rays or radiation.
• the two or more structural sites X may be the same or different.
• Two or more of A 1 ⁇ and two or more of M 1 + may be the same or different.
• the nonionic site capable of neutralizing the acid in the structural site Z is not particularly limited.
• a site containing a group capable of electrostatically interacting with protons or a functional group having electrons is preferred.
• a group capable of electrostatically interacting with protons or a functional group having electrons is a functional group having a macrocyclic structure such as a cyclic polyether, or a lone pair of electrons that does not contribute to ⁇ conjugation.
• a functional group having a nitrogen atom is included.
• a nitrogen atom having a lone pair of electrons that does not contribute to ⁇ -conjugation is, for example, a nitrogen atom having a partial structure represented by the following formula.
• Partial structures of functional groups having electrons or groups capable of electrostatically interacting with protons include, for example, a crown ether structure, an azacrown ether structure, a primary to tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure. Among them, primary to tertiary amine structures are preferred.
• the compound (II) is not particularly limited, but includes, for example, compounds represented by the following formulas (IIa-1) and (IIa-2).
• a 61a - and A 61b - have the same meanings as A 11 - in formula (Ia-1) above, and preferred embodiments are also the same.
• M 61a + and M 61b + have the same meanings as M 11 + in formula (Ia-1) described above, and the preferred embodiments are also the same.
• L 61 and L 62 have the same definitions as L 1 in formula (Ia-1) above, and the preferred embodiments are also the same.
• R 2X represents a monovalent organic group.
• the monovalent organic group represented by R 2X is not particularly limited, and may be an alkyl group (preferably having 1 to 10 carbon atoms, which may be linear or branched), a cycloalkyl group (preferably having 3 to 15), or an alkenyl group (preferably having 2 to 6 carbon atoms).
• —CH 2 — contained in the alkyl group, cycloalkyl group and alkenyl group in the monovalent organic group represented by R 2X is —CO—, —NH—, —O—, —S—, and —SO— , and —SO 2 — may be substituted with one or a combination of two or more.
• the alkylene group, the cycloalkylene group, and the alkenylene group may have a substituent. Examples of substituents include, but are not particularly limited to, halogen atoms (preferably fluorine atoms).
• the acid dissociation constant a1-8 derived from the acidic site represented by a1-7 and A 61b H corresponds to the acid dissociation constant a1 described above.
• the compound PIIa-1 obtained by replacing the cation sites M 61a + and M 61b + in the structural site 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 formula (Ia-1) above, and preferred embodiments are also the same.
• M 71a + , M 71b + , and M 71c + have the same meanings as M 11 + in formula (Ia-1) above, and the preferred embodiments are also the same.
• L 71 , L 72 , and L 73 have the same meanings as L 1 in formula (Ia-1) above, and preferred embodiments are also the same.
• the acid dissociation constant a1-9 derived from, the acid dissociation constant a1-10 derived from the acidic site represented by A 71b H, and the acid dissociation constant a1-11 derived from the acidic site represented by A 71c H are It corresponds to the acid dissociation constant a1 described above.
• a compound PIIa-2 obtained by replacing the cation sites M 71a + , M 71b + , and M 71c + in the structural site X of the compound (IIa-1) with H + is HA 71a -L 71 -N(L 73 -A 71c H) -L 72 -A 71b H.
• compound PIIa-2 is the same as the acid generated from the compound represented by formula (IIa-2) upon exposure to actinic rays or radiation.
• M 71a + , M 71b + , M 71c + , A 71a ⁇ , A 71b ⁇ , A 71c ⁇ , L 71 , L 72 and L 73 has an acid-decomposable group as a substituent; may
• the content is not particularly limited, but since the cross-sectional shape of the formed pattern becomes more rectangular, the total solid content of the composition is , is preferably 0.5% by mass or more, more preferably 1.0% by mass or more.
• the content is preferably 50.0% by mass or less, more preferably 30.0% by mass or less, and even more preferably 25.0% by mass or less, relative to the total solid content of the composition.
• the photoacid generator (B) may be used alone or in combination of two or more.
• the composition of the present invention may contain an acid diffusion control agent.
• the acid diffusion control agent traps the acid generated from the photoacid generator or the like during exposure, and acts as a quencher that suppresses the reaction of the acid-decomposable resin in the unexposed area due to excess generated acid.
• the type of acid diffusion controller is not particularly limited, and examples include basic compounds (CA), low-molecular-weight compounds (CB) having nitrogen atoms and groups that leave under the action of acids, and actinic rays or radiation. and a compound (CC) whose ability to control acid diffusion decreases or disappears upon irradiation.
• a basic compound (CA) include, for example, those described in paragraphs [0132] to [0136] of WO2020/066824, and the basicity is reduced or reduced by exposure to actinic rays or radiation.
• Specific examples of the disappearing basic compound (CE) include those described in paragraphs [0137] to [0155] of WO 2020/066824, have a nitrogen atom, and are eliminated by the action of an acid.
• the low-molecular-weight compound having a group include those described in paragraphs [0156] to [0163] of WO 2020/066824, and basicity is obtained by irradiation with actinic rays or radiation.
• Specific examples of the basic compound (CE) that decreases or disappears include those described in paragraph [0164] of WO2020/066824.
• 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% relative to the total solid content of the resist composition. 0% by mass is preferred, and 1.0 to 15.0% by mass is more preferred.
• the acid diffusion controller may be used singly or in combination of two or more.
• the composition of the invention may further comprise a hydrophobic resin different from resin (A).
• Hydrophobic resins are preferably designed to be unevenly distributed on the surface of the resist film. may not contribute to
• the effects of adding a hydrophobic resin include control of the static and dynamic contact angles of the resist film surface with respect to water, and suppression of outgassing.
• the hydrophobic resin preferably has one or more of a fluorine atom, a silicon atom, and a CH3 partial structure contained in the side chain portion of the resin. It is more preferable to have The hydrophobic resin preferably has a hydrocarbon group with 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted on the side chain. Hydrophobic resins include compounds described in paragraphs [0275] to [0279] of WO2020/004306.
• the content of the hydrophobic resin is preferably 0.01 to 20.0% by mass, and 0.1 to 15.0% by mass, based on the total solid content of the composition. % by mass is more preferred.
• the composition of the invention may contain a surfactant.
• a surfactant When a surfactant is contained, it is possible to form a pattern with excellent adhesion and fewer development defects.
• the surfactant is preferably a fluorine-based and/or silicon-based surfactant. Fluorinated and/or silicon-based surfactants include surfactants disclosed in paragraphs [0218] and [0219] of WO2018/193954.
• One type of these surfactants may be used alone, or two or more types may be used.
• the content of the surfactant is preferably 0.0001 to 2.0% by mass, preferably 0.0005 to 1.0%, based on the total solid content of the composition. % by mass is more preferred, and 0.1 to 1.0% by mass is even more preferred.
• the composition of the invention preferably contains a solvent.
• Solvent consists of (M1) propylene glycol monoalkyl ether carboxylate and (M2) propylene glycol monoalkyl ether, lactate, acetate, alkoxypropionate, linear ketone, cyclic ketone, lactone, and alkylene carbonate. It is preferable to include at least one selected from the group.
• the solvent may further contain components other than components (M1) and (M2).
• a combination of the above-described solvent and the above-described resin is preferable from the viewpoint of improving the coatability of the resist composition and reducing the number of development defects in the pattern. Since the solvent described above has a good balance of solubility, boiling point, and viscosity of the resin described above, it is possible to suppress unevenness in the thickness of the resist film and generation of deposits during spin coating. Details of component (M1) and component (M2) are described in paragraphs [0218] to [0226] of WO2020/004306, the contents of which are incorporated herein.
• the content of components other than components (M1) and (M2) is preferably 5 to 30% by mass relative to the total amount of the solvent.
• the content of the solvent in the composition of the present invention is preferably determined so that the solid content concentration is 0.5 to 30% by mass, more preferably 1 to 20% by mass. By doing so, the coatability of the resist composition can be further improved.
• the solid content means all the components other than the solvent, and as described above, the components that form the actinic ray-sensitive or radiation-sensitive film.
• the solid content concentration is the mass percentage of the mass of other components excluding the solvent relative to the total mass of the composition of the present invention.
• Total solid content refers to the total mass of components excluding the solvent from the total composition of the composition of the present invention.
• the “solid content” is the component excluding the solvent, and may be solid or liquid at 25° C., for example.
• the composition of the present invention contains a dissolution-inhibiting compound, a dye, a plasticizer, a photosensitizer, a light-absorbing agent, and/or a compound that promotes solubility in a developer (for example, a phenol compound having a molecular weight of 1000 or less, or An alicyclic or aliphatic compound containing a carboxyl group) may further be included.
• a dissolution-inhibiting compound for example, a dye, a plasticizer, a photosensitizer, a light-absorbing agent, and/or a compound that promotes solubility in a developer (for example, a phenol compound having a molecular weight of 1000 or less, or An alicyclic or aliphatic compound containing a carboxyl group) may further be included.
• the “dissolution-inhibiting compound” is a compound with a molecular weight of 3000 or less, which is decomposed by the action of an acid to reduce its solubility in an organic developer.
• the composition of the specification is suitably used as a photosensitive composition for EUV exposure.
• EUV light has a wavelength of 13.5 nm, which is shorter than ArF (wavelength 193 nm) light and the like, so the number of incident photons is smaller when exposed with the same sensitivity. Therefore, the effect of "photon shot noise", in which the number of photons stochastically varies, is large, leading to deterioration of LER and bridge defects.
• photon shot noise there is a method of increasing the number of incident photons by increasing the amount of exposure, but this is a trade-off with the demand for higher sensitivity.
• the method for producing an actinic ray-sensitive or radiation-sensitive resin composition according to the present invention (hereinafter also referred to as "the method for producing the composition of the present invention” or “the method for producing a composition”) is as described above.
• a method for producing an actinic ray-sensitive or radiation-sensitive resin composition containing the salt (P) as a compound that generates an acid upon exposure to actinic rays or radiation including a method for producing the salt (P).
• the method for producing the composition includes, for example, a compound that is produced by the method for producing the salt (P) described above and generates an acid upon exposure to actinic rays or radiation in the actinic ray-sensitive or radiation-sensitive resin composition, and an actinic ray-sensitive resin composition. It can be produced by mixing each component that may be included in the curable or radiation-sensitive resin composition.
• 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 an acid-decomposable resin, a photoacid generator, an acid diffusion controller, and a solvent
• the acid-decomposable resin, the photoacid generator, and the acid diffusion controller correspond to the solid content. do.
• the total atoms of the total solid content correspond to the sum of all atoms derived from the resin, all atoms derived from the photoacid generator, and all atoms derived from the acid diffusion control agent.
• [H] represents the molar ratio of hydrogen atoms derived from the total solid content to the total atoms of the total solid content.
• hydrogen atoms derived from the acid-decomposable resin, hydrogen atoms derived from the photoacid generator, and the acid with respect to the sum of all atoms derived from the photoacid generator and all atoms derived from the acid diffusion control agent It represents the total molar ratio of hydrogen atoms derived from the diffusion control agent.
• the A value can be calculated by calculating the contained atomic ratio when the structure and content of the constituent components of the total solid content in the resist composition are known. Further, even if the constituent components are unknown, the constituent atomic number ratio can be calculated by analytical methods such as elemental analysis for the resist film obtained by evaporating the solvent component of the resist composition. .
• Step 1 A step of forming an actinic ray- or radiation-sensitive film on a substrate from the actinic ray- or radiation-sensitive resin composition produced by the method for producing an actinic ray- or radiation-sensitive resin composition.
• Step 2 Step of exposing the actinic ray-sensitive or radiation-sensitive film
• Step 3 Step of developing the exposed actinic ray-sensitive or radiation-sensitive film using a developer
• Step 1 actinic ray-sensitive or radiation-sensitive film forming step
• Step 1 is to form an actinic ray- or radiation-sensitive film on a substrate using the actinic ray- or radiation-sensitive resin composition produced by the method for producing an actinic ray- or radiation-sensitive resin composition. It is a process.
• An actinic ray-sensitive or radiation-sensitive film (preferably a resist film) is formed on a substrate using an actinic ray- or radiation-sensitive resin composition produced by a method for producing an actinic ray- or radiation-sensitive resin composition.
• the forming method include a method of coating the composition of the present invention on a substrate.
• the pore size of the filter is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, and even more preferably 0.03 ⁇ m or less.
• Filters are preferably made of polytetrafluoroethylene, polyethylene, or nylon.
• compositions of the present invention can be applied onto substrates such as those used in the manufacture of integrated circuit devices (eg, silicon, silicon dioxide coatings) by any suitable coating method such as a spinner or coater.
• the coating method is preferably spin coating using a spinner.
• the rotation speed for spin coating using a spinner is preferably 1000 to 3000 rpm.
• the substrate may be dried to form an actinic ray-sensitive or radiation-sensitive film. If necessary, various undercoat films (inorganic film, organic film, antireflection film) may be formed under the actinic ray-sensitive or radiation-sensitive film.
• Heating can be carried out by a means provided in a normal exposure machine and/or a developing machine, and may be carried out using a hot plate or the like.
• the heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, even more preferably 80 to 130°C.
• the heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, even more preferably 60 to 600 seconds.
• the film thickness of the actinic ray-sensitive or radiation-sensitive film is not particularly limited, it is preferably 10 to 120 nm from the viewpoint of forming finer patterns with higher precision.
• the film thickness of the actinic ray-sensitive or radiation-sensitive film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm.
• the thickness of the actinic ray-sensitive or radiation-sensitive film is more preferably 10 to 120 nm, still more preferably 15 to 90 nm.
• a topcoat composition may be used to form a topcoat on the upper layer of the actinic ray-sensitive or radiation-sensitive film.
• the topcoat composition does not mix with the actinic ray-sensitive or radiation-sensitive film and can be uniformly applied over the actinic ray- or radiation-sensitive film.
• the topcoat is not particularly limited, and a conventionally known topcoat can be formed by a conventionally known method. can be formed.
• Specific examples of basic compounds that the topcoat may contain include basic compounds that the resist composition may contain.
• the topcoat also preferably contains a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond.
• Step 2 is a step of exposing the actinic ray-sensitive or radiation-sensitive film.
• the exposure method include a method of irradiating the formed actinic ray-sensitive or radiation-sensitive film with actinic rays or radiation through a predetermined mask.
• Actinic rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, preferably 250 nm or less, more preferably 220 nm or less, 1 to 200 nm Particularly preferred are wavelengths of deep UV light, specifically KrF excimer lasers (248 nm), ArF excimer lasers (193 nm), F2 excimer lasers (157 nm), EUV (13.5 nm), X-rays, and electron beams.
• baking is preferably performed before development. Baking accelerates the reaction of the exposed area, resulting in better sensitivity and pattern shape.
• the heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, even more preferably 80 to 130°C.
• the heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, even more preferably 30 to 120 seconds. Heating can be carried out by a means provided in a normal exposing machine and/or developing machine, and may be carried out using a hot plate or the like. This step is also called a post-exposure bake.
• Step 3 is a step of developing the exposed actinic ray-sensitive or radiation-sensitive film using a developer to form a pattern.
• the developer may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer).
• a method of immersing the substrate in a tank filled with a developer for a certain period of time for example, a method of immersing the substrate in a tank filled with a developer for a certain period of time (dip method), a method of developing by standing the developer on the surface of the substrate for a certain period of time using surface tension (puddle method). method), a method of spraying the developer onto the substrate surface (spray method), and a method of continuously discharging the developer while scanning the developer discharge nozzle at a constant speed onto the substrate rotating at a constant speed (dynamic dispensing method). ). Further, after the step of developing, a step of stopping development may be performed while replacing the solvent with another solvent.
• the development time is not particularly limited as long as the resin in the unexposed area is sufficiently dissolved, and is preferably 10 to 300 seconds, more preferably 20 to 120 seconds.
• the temperature of the developer is preferably 0 to 50°C, more preferably 15 to 35°C.
• alkaline aqueous solution containing alkali is not particularly limited, for example, quaternary ammonium salts represented by tetramethylammonium hydroxide, inorganic alkalis, primary amines, secondary amines, tertiary amines, alcohol amines, or cyclic amines. and an alkaline aqueous solution containing Among them, the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt represented by tetramethylammonium hydroxide (TMAH). Suitable amounts of alcohols, surfactants and the like may be added to the alkaline developer.
• the alkali concentration of the alkali developer is usually preferably 0.1 to 20% by mass.
• the pH of the alkaline developer is preferably 10.0 to 15.0.
• the organic developer is a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. Preferably.
• a plurality of the above solvents may be mixed, or may be mixed with a solvent other than the above or water.
• the water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and particularly preferably substantially free of water.
• the content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, and 90% by mass or more and 100% by mass with respect to the total amount of the developer. The following are more preferable, and 95% by mass or more and 100% by mass or less are particularly preferable.
• the pattern forming method preferably includes a step of washing with a rinse after step 3.
• Pure water is an example of the rinse solution used in the rinse step after the step of developing with an alkaline developer.
• An appropriate amount of surfactant may be added to pure water.
• An appropriate amount of surfactant may be added to the rinse solution.
• the rinse solution used in the rinse step after the development step using the organic developer is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used.
• the rinse solution should contain at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. is preferred.
• the method of the rinsing step is not particularly limited. For example, a method of continuously discharging the rinsing liquid onto the substrate rotating at a constant speed (rotation coating method), or a method of immersing the substrate in a tank filled with the rinsing liquid for a certain period of time. a method (dip method) and a method of spraying a rinse liquid onto the substrate surface (spray method).
• the pattern forming method may include a heating step (Post Bake) after the rinsing step. In this step, the developing solution and the rinse solution remaining between the patterns and inside the patterns due to baking are removed. In addition, this process smoothes the resist pattern, and has the effect of improving the roughness of the surface of the pattern.
• the heating step after the rinsing step is usually carried out at 40 to 250° C. (preferably 90 to 200° C.) for 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).
• the substrate may be etched using the formed pattern as a mask. That is, the pattern formed in step 3 may be used as a mask to process the substrate (or the underlying film and substrate) to form a pattern on the substrate.
• the method for processing the substrate (or the underlying film and the substrate) is not particularly limited, but the substrate (or the underlying film and the substrate) is dry-etched using the pattern formed in step 3 as a mask.
• a method of forming a pattern is preferred. Dry etching is preferably oxygen plasma etching.
• the composition of the present invention and various materials used in the pattern forming method of the present specification e.g., solvent, developer, rinse, antireflection film-forming composition, topcoat-forming composition, etc.
• impurities such as The content of impurities contained in these materials is preferably 1 mass ppm or less, more preferably 10 mass ppb or less, still more preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less.
• the lower limit is not particularly limited, and is preferably 0 mass ppt or more.
• examples of metal impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn.
• Methods for reducing impurities such as metals contained in various materials include, for example, a method of selecting raw materials with a low metal content as raw materials constituting various materials, and a method of filtering raw materials constituting various materials with a filter. and a method of performing distillation under conditions in which contamination is suppressed as much as possible by, for example, lining the inside of the apparatus with Teflon (registered trademark).
• impurities may be removed with an adsorbent, or filter filtration and adsorbent may be used in combination.
• adsorbent known adsorbents can be used.
• inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.
• metal impurities such as metals contained in the various materials described above, it is necessary to prevent metal impurities from entering during the manufacturing process. Whether the metal impurities are sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of the metal component contained in the cleaning liquid used for cleaning the manufacturing equipment.
• the content of the metal component contained in the cleaning liquid after use is preferably 100 mass ppt (parts per trillion) or less, more preferably 10 mass ppt or less, and even more preferably 1 mass ppt or less.
• the lower limit is not particularly limited, and is preferably 0 mass ppt or more.
• Organic processing liquids such as rinsing liquids should contain conductive compounds to prevent damage to chemical piping and various parts (filters, O-rings, tubes, etc.) due to electrostatic charging and subsequent electrostatic discharge.
• the conductive compound is not particularly limited, and examples thereof include methanol.
• the amount added is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, from the viewpoint of maintaining preferable developing properties or rinsing properties.
• the lower limit is not particularly limited, and is preferably 0.01% by mass or more.
• chemical liquid pipe for example, SUS (stainless steel), antistatic treated polyethylene, polypropylene, or various pipes coated with fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can be used.
• Antistatic treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can also be used for filters and O-rings.
• the present specification also relates to an electronic device manufacturing method including the pattern forming method described above, and an electronic device manufactured by this manufacturing method.
• a preferred embodiment of the electronic device of the present specification includes a mode in which it is installed in electric/electronic equipment (household appliances, OA (Office Automation), media-related equipment, optical equipment, communication equipment, etc.).
• the molar ratio X (mol%) of the salt (I) to the salt (P) was calculated using the above formulas (1) and (2).
• the above molar ratio X indicates the residual rate (mol%) of salt (I) with respect to 1 mol of salt (P).
• the predetermined standard (predetermined amount) of X was set to 0.5 mol %.
• 1 obtained by the above method was used as the titer of the silver nitrate aqueous solution.
• the concentration Y was measured as follows.
• a solution A is prepared by dissolving 1.6 g of the internal standard substance 1,3,5-trimethoxybenzene in 100 ml of acetonitrile.
• To 0.08 g of the lot to be measured of the product containing salt (P) is added 10 ml of solution A and diluted to 20 ml with acetonitrile to form solution C1.
• the solution C1 is subjected to HPLC measurement under the same conditions as above, and the peak area value SC of the salt (P) cation is calculated with respect to the peak area value of the internal standard substance. The measurement of the same sample solution is repeated two more times, and the average SC value SC AVE is calculated.
• the corresponding sample concentration KC (g/ml) is calculated from the SC AVE and the calibration curve.
• concentration Y (% by mass) of the lot to be measured for the salt (P) in the product containing the salt (P) was calculated from the above formula (3).
• the concentration Z was measured as follows.
• a solution A is prepared by dissolving 12 mg of rhodamine base (manufactured by Sigma-Aldrich) (compound C) in 200 ml of acetonitrile.
• a solution B is prepared by dissolving 50 mg of tosylic acid (compound D) in 200 ml of acetonitrile.
• a solution C is prepared by diluting 5 ml of the solution B 40 times with acetonitrile. 2 ml of solution A and 2 ml of solution C are placed in a 10 ml volumetric flask and diluted to 10 ml with acetonitrile to prepare solution D1.
• the ultraviolet-visible absorption spectrum of solution D1 is measured with "UV-1800 (manufactured by Shimadzu Corporation)" to obtain absorbance Abs D1 at a maximum absorption wavelength of 556 nm.
• solutions D2, D3 and D4 are similarly prepared.
• the ultraviolet-visible absorption spectra of D2, D3 and D4 obtained are similarly measured to obtain Abs D2 , Abs D3 and Abs D4 .
• 2 ml of solution A is taken in a 10 ml volumetric flask and diluted to 10 ml with acetonitrile to prepare solution E.
• the ultraviolet-visible absorption spectrum of Solution E is measured to obtain absorbance Abs E at a wavelength of 556 nm.
• Abs D1 to Abs D4 obtained above, the difference from Abs E is obtained, and the obtained results are defined as Abs DE1 to Abs DE4 , respectively.
• a calibration curve for the molar concentration of tosylic acid in D1, D2, D3 and D4 and the absorbance at a wavelength of 556 nm is prepared from the obtained Abs DE1 to Abs DE4 .
• a solution A is prepared by dissolving 12 mg of rhodamine base (manufactured by Sigma-Aldrich) (compound C) in 200 ml of acetonitrile. Weigh 0.05 g of the product containing salt (P), add 2 ml of solution A, and further add acetonitrile to prepare solution F diluted to 10 ml. As a blank, 2 ml of solution A is taken in a 10 ml volumetric flask and diluted to 10 ml with acetonitrile to prepare solution E.
• the ultraviolet-visible absorption spectra of Solution F and Solution E are measured in the same manner as in preparing the above calibration curve, and absorbances Abs F and Abs E at a wavelength of 556 nm are obtained.
• Abs FE Abs F -Abs E
• the corresponding molar concentration T (mol/l) of tosylic acid is calculated from the calibration curve prepared above.
• the residual acid concentration Z (ppm) in terms of tosylic acid contained in the product containing the salt (P) was calculated.
• the molecular weight of tosylic acid of 172.20 was used for MT (g/mol), and the solvent amount of solution F of 0.01 (l) was used for LB.
• the concentration Z of the residual acid contained in the product containing the salt (P) is the concentration in terms of tosylic acid (compound D).
• the predetermined standard (predetermined amount) of Z was set to 100 ppm.
• Lot 1-b-2 had X of 0.15 mol % and Z of 21 ppm.
• Table 1 the above values (X is 0.15 mol % and Z is 21 ppm) are described in the columns of X and Z for Lot 2 in Synthesis Example 1, Salt B1, "b”.
• Lot 1-b-3 had X of 0.29 mol % and Z of 16 ppm.
• Table 1 the above values (X is 0.29 mol % and Z is 16 ppm) are described in the columns of X and Z for Lot 3 in Synthesis Example 1, Salt B1, "b”.
• X and Z are listed in Table 1, respectively.
• Lot 1-b-2 had a solid content of 99.1% calculated from 1 H NMR measurement
• lot 1-b-3 had a solid content of 98.2%.
• Lot 1-R-1 After adding 100 g of diisopropyl ether to the crude product and stirring, the solid was collected by filtration and dried under reduced pressure for 5 hours. A part of the obtained solid was dissolved in deuterated acetone and subjected to 1 H NMR measurement, and the solid content value was calculated from the integral ratio with the residual diisopropyl ether to be 96.6%. X, Y, Z were not calculated.
• the solid obtained is referred to as Lot 1-R-1.
• Lot 1-R-2 and Lot 1-R-3 were synthesized by the same procedure as above. Lot 1-R-2 had a solids content of 97.6% calculated from 1 H NMR measurement, and lot 1-R-3 had a solids content of 98.8%.
• a portion of the obtained solid was dissolved in deuterated acetone and subjected to 1 H NMR measurement, and the solid content was determined from the integral ratio with the remaining diisopropyl ether to be 99.3%.
• X and Z were measured with respect to the solid after drying, X was 0.09 mol% and Z was 10 ppm.
• the resulting solid is referred to as Lot 2-a-0.
• the concentration of the reference lot was the above 99.3%.
• the crude product, salt C2 (0.045 g), 80 g of methylene chloride and 80 g of water were mixed and stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 80 g of 0.1N hydrochloric acid and five times with 80 g of water, and concentrated under reduced pressure. When X was calculated again with respect to the obtained crude product, it was 0.18 mol%. 100 g of diisopropyl ether was added to the crude product and stirred, and the filtered solid was dried under reduced pressure for 5 hours.
• Lot 2-a-3 was synthesized by the same procedure as lot 2-a-1.
• X, Y, and Z were measured for lot 2-a-3, X was 0.24 mol%, Y was 98.2%, and Z was 31 ppm.
• Lot 2-b-2 and Lot 2-b-3 were synthesized in the same manner as above.
• Lot 2-b-2 had X of 0.14 mol % and Z of 44 ppm.
• Lot 2-b-3 had X of 0.28 mol % and Z of 11 ppm.
• Lot 2-b-2 had a solid content of 97.5% calculated from 1 H NMR measurement, and lot 2-b-3 also had a solid content of 98.8%.
• a portion of the obtained solid was dissolved in deuterated acetone and subjected to 1 H NMR measurement, and the solid content value was calculated from the integral ratio with the residual diisopropyl ether to be 99.1%.
• X and Z were measured with respect to the solid after drying, X was 0.08 mol% and Z was 4 ppm.
• the resulting solid is lot 3-a-0.
• the concentration of the reference lot was 99.1% above.
• the crude product was mixed with salt C3 (0.11 g), 100 g of methylene chloride and 100 g of water, and stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100 g of 0.1N hydrochloric acid and three times with 100 g of water, and concentrated under reduced pressure. When X was calculated again with respect to the obtained crude product, it was 0.22 mol %. 120 g of diisopropyl ether was added to the crude product and stirred, and the filtered solid was dried under reduced pressure for 5 hours.
• Lot 3-a-3 was synthesized by the same procedure as lot 3-a-2.
• X, Y, and Z were measured for lot 3-a-3, X was 0.19 mol%, Y was 95.7%, and Z was 19 ppm.
• Lot 3-b-2 and lot 3-b-3 were synthesized by the same procedure as above.
• X was 0.11 mol% and Z was 10 ppm.
• Lot 3-b-3 had X of 0.20 mol % and Z of 16 ppm.
• Lot 3-b-2 had a solid content of 97.5% calculated from 1 H NMR measurement, and lot 3-b-3 also had a solid content of 99.0%.
• a portion of the obtained solid was dissolved in deuterated acetone and subjected to 1 H NMR measurement, and the solid content value was calculated from the integral ratio with the residual diisopropyl ether to be 99.2%.
• X and Z were measured with respect to the solid after drying, X was 0.10 mol% and Z was 5 ppm.
• the resulting solid is lot 4-a-0.
• the concentration of the reference lot was the above 99.2%.
• the crude product was mixed with salt C4 (0.070 g), 160 g of methylene chloride and 160 g of water, and stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 160 g of 0.1N hydrochloric acid and five times with 160 g of water, and concentrated under reduced pressure. When X was calculated again with respect to the obtained crude product, it was 0.10 mol%. 200 g of diisopropyl ether was added to the crude product and stirred, and the filtered solid was dried under reduced pressure for 5 hours.
• Lot 4-a-3 was synthesized by the same procedure as lot 4-a-1.
• X, Y, and Z were measured for lot 4-a-3, X was 0.24 mol%, Y was 96.6%, and Z was 9 ppm.
• Lot 4-b-2 and Lot 4-b-3 were synthesized by the same procedure as above.
• Lot 4-b-2 had X of 0.17 mol % and Z of 35 ppm.
• Lot 4-b-3 had X of 0.14 mol % and Z of 10 ppm.
• Lot 4-b-2 had a solid content of 97.5% calculated from 1 H NMR measurement, and lot 4-b-3 also had a solid content of 98.1%.
• a portion of the obtained solid was dissolved in deuterated acetone and subjected to 1 H NMR measurement, and the solid content value was determined from the integral ratio with residual diisopropyl ether to be 99.0%.
• X and Z were measured with respect to the solid after drying, X was 0.09 mol% and Z was 4 ppm.
• the resulting solid is lot 5-a-0.
• the concentration of the reference lot was 99.0% above.
• the crude product was mixed with salt C5 (0.050 g), 80 g of methylene chloride and 80 g of water, and stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 80 g of 0.1N hydrochloric acid and five times with 80 g of water, and concentrated under reduced pressure. When X was calculated again with respect to the obtained crude product, it was 0.25 mol%. 100 g of diisopropyl ether was added to the crude product and stirred, and the filtered solid was dried under reduced pressure for 5 hours.
• Lot 5-a-3 was synthesized by the same procedure as lot 5-a-1.
• X, Y, and Z were measured for lot 5-a-3, X was 0.13 mol%, Y was 96.0%, and Z was 21 ppm.
• Lot 5-b-2 and lot 5-b-3 were synthesized by the same procedure as above.
• Lot 5-b-2 had X of 0.13 mol % and Z of 18 ppm.
• Lot 5-b-3 had X of 0.15 mol % and Z of 33 ppm.
• Lot 5-b-2 had a solid content of 96.6% calculated from 1 H NMR measurement, and lot 5-b-3 had a solid content of 96.7%.
• a part of the obtained solid was dissolved in deuterated acetone and subjected to 1 H NMR measurement, and the solid content value was calculated from the integral ratio with residual diisopropyl ether to be 99.5%.
• X and Z were measured with respect to the solid after drying, X was 0.09 mol% and Z was 6 ppm.
• the resulting solid is referred to as Lot 6-a-0.
• the concentration of the reference lot was 99.5% above.
• Lot 6-a-2 and Lot 6-a-3 were synthesized in the same manner as Lot 6-a-1, respectively.
• X was 0.09 mol%
• Y was 98.9%
• Z was 13 ppm.
• Lot 6-a-3 had X of 0.14 mol %, Y of 99.4% and Z of 22 ppm.
• Lot 6-b-2 had X of 0.13 mol % and Z of 14 ppm.
• Lot 6-b-3 had X of 0.10 mol % and Z of 10 ppm.
• Lot 6-b-2 had a solid content of 98.8% calculated from 1 H NMR measurement, and lot 6-b-3 had a solid content of 96.8%.
• a portion of the obtained solid was dissolved in deuterated acetone and subjected to 1 H NMR measurement. Since no diisopropyl ether peak was observed, the solid content value was determined from the integral ratio with residual isopropyl alcohol, and was 99.7. %Met. When X and Z were measured for the solid after drying, X was 0.10 mol % and Z was 5 ppm. The resulting solid is lot 7-a-0. The concentration of the reference lot was the above 99.7%.
• Lot 7-a-3 was synthesized by the same procedure as lot 7-a-2.
• X, Y, and Z were measured for lot 7-a-3, X was 0.21 mol%, Y was 98.1%, and Z was 21 ppm.
• Lot 7-b-2 had X of 0.25 mol % and Z of 14 ppm.
• Lot 7-b-3 had X of 0.11 mol % and Z of 10 ppm.
• Lot 7-b-2 had a solids content of 95.8% calculated from 1 H NMR measurement, and lot 7-b-3 had a solids content of 98.3%.
• Lot 7-c-2 and lot 7-c-3 were synthesized by the same procedure as above.
• Lot 7-c-2 had X of 0.15 mol % and Y of 97.4%.
• Lot 7-c-3 had X of 0.28 mol % and Y of 98.6%.
• Me represents a methyl group.
• a portion of the obtained solid was dissolved in deuterated acetone and subjected to 1 H NMR measurement, and the solid content value was determined from the integral ratio with the residual isopropyl alcohol to be 99.7%.
• X and Z were measured with respect to the solid after drying, X was 0.08 mol% and Z was 7 ppm.
• the resulting solid is lot 8-a-0.
• the concentration of the reference lot was the above 99.7%.
• Lot 8-a-3 was synthesized by the same procedure as lot 8-a-1.
• X, Y, and Z were measured for lot 8-a-3, X was 0.13 mol%, Y was 99.1%, and Z was 10 ppm.
• Lot 8-b-2 and lot 8-b-3 were synthesized by the same procedure as above.
• Lot 8-b-2 had X of 0.15 mol % and Z of 31 ppm.
• Lot 8-b-3 had X of 0.12 mol % and Z of 13 ppm.
• Lot 8-b-2 had a solid content of 99.2% calculated from 1 H NMR measurement, and lot 8-b-3 had a solid content of 98.9%.
• Lot 8-c-2 and lot 8-c-3 were synthesized by the same procedure as above.
• Lot 8-c-2 had X of 0.12 mol % and Y of 98.8%.
• X in lot 8-c-3 was 0.13 mol % and Y was 99.4%.
• Lot 9-a-3 was synthesized by a procedure similar to lot 9-a-1.
• X, Y, and Z were measured for lot 9-a-3, X was 0.11 mol%, Y was 99.2%, and Z was 11 ppm.
• Lot 9-b-2 had X of 0.16 mol % and Z of 9 ppm.
• Lot 9-b-3 had X of 0.16 mol % and Z of 14 ppm.
• Lot 9-b-2 had a solids content of 98.6% calculated from 1 H NMR measurement, and lot 9-b-3 had a solids content of 99.2% as well.
• Lot 9-c-2 and lot 9-c-3 were synthesized by the same procedure as above.
• Lot 9-c-2 had X of 0.16 mol % and Y of 98.6%.
• Lot 9-c-3 had X of 0.10 mol % and Y of 99.2%.
• the solid obtained by repeating this three times was dried under reduced pressure for 8 hours.
• a portion of the obtained solid was dissolved in deuterated acetone and subjected to 1 H NMR measurement, and the solid content value was calculated from the integral ratio with residual diisopropyl ether to be 99.3%.
• X and Z were measured with respect to the solid after drying, X was 0.09 mol% and Z was 8 ppm.
• the resulting solid is lot 10-a-0.
• the concentration of the reference lot was the above 99.3%.
• Lot 10-a-2 and Lot 10-a-3 were synthesized in the same manner as Lot 10-a-1, respectively.
• Lot 10-a-2 had X of 0.16 mol %, Y of 97.2% and Z of 24 ppm.
• Lot 10-a-3 had X of 0.19 mol %, Y of 95.8% and Z of 17 ppm.
• Lot 10-b-2 and lot 10-b-3 were synthesized by the same procedure as above.
• Lot 10-b-2 had X of 0.15 mol % and Z of 11 ppm.
• Lot 10-b-3 had X of 0.13 mol % and Z of 12 ppm.
• Lot 10-b-2 had a solids content of 95.8% calculated from 1 H NMR measurement, and lot 10-b-3 had a solids content of 97.1% as well.
• Lot 10-c-2 and lot 10-c-3 were synthesized by the same procedure as above.
• Lot 10-c-2 had X of 0.18 mol % and Y of 96.9%.
• Lot 10-c-3 had X of 0.22 mol % and Y of 95.5%.
• a portion of the obtained solid was dissolved in deuterated acetone and subjected to 1 H NMR measurement, and the solid content value was determined from the integral ratio with residual chloroform to be 99.8%.
• X and Z were measured with respect to the solid after drying, X was 0.08 mol% and Z was 4 ppm.
• the resulting solid is lot 11-a-0.
• the concentration of the reference lot was 99.8% above.
• the crude product was mixed with salt C10 (0.044 g), 80 g of methylene chloride and 80 g of water, and stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 80 g of 0.1N hydrochloric acid and five times with 80 g of water, and concentrated under reduced pressure. When X was calculated again with respect to the obtained crude product, it was 0.11 mol %. 100 g of diisopropyl ether was added to the crude product and stirred, and the filtered solid was dried under reduced pressure for 5 hours.
• Lot 11-a-3 was synthesized in a manner similar to lot 11-a-1.
• X, Y and Z were measured for lot 11-a-3, X was 0.15 mol%, Y was 99.2%, and Z was 12 ppm.
• Lot 11-b-2 and lot 11-b-3 were synthesized by the same procedure as above.
• Lot 11-b-2 had X of 0.19 mol % and Z of 9 ppm.
• Lot 11-b-3 had X of 0.12 mol % and Z of 14 ppm.
• Lot 11-b-2 had a solids content of 98.8% calculated from 1 H NMR measurement, and lot 11-b-3 had a solids content of 98.0% as well.
• Lot 11-c-2 and lot 11-c-3 were synthesized by the same procedure as above.
• Lot 11-c-2 had X of 0.12 mol % and Y of 98.2%.
• Lot 11-c-3 had X of 0.16 mol % and Y of 98.4%.
• a portion of the obtained solid was dissolved in deuterated acetone and subjected to 1 H NMR measurement, and the solid content value was calculated from the integral ratio with the residual diisopropyl ether to be 99.5%.
• X and Z were measured for the solid after drying, X was 0.09 mol% and Z was 7 ppm.
• the resulting solid is lot 12-a-0.
• the concentration of the reference lot was 99.5% above.
• Lot 12-a-2 and Lot 12-a-3 were each synthesized in the same manner as Lot 12-a-1.
• Lot 12-a-2 had X of 0.18 mol %, Y of 99.4% and Z of 15 ppm.
• Lot 12-a-3 had X of 0.25 mol %, Y of 98.2% and Z of 14 ppm.
• Lot 12-b-2 and lot 12-b-3 were synthesized by the same procedure as above.
• Lot 12-b-2 had X of 0.18 mol % and Z of 30 ppm.
• Lot 12-b-3 had X of 0.16 mol % and Z of 10 ppm.
• Lot 12-b-2 had a solids content of 99.2% calculated from 1 H NMR measurement, and lot 12-b-3 had a solids content of 98.5% as well.
• Lot 12-c-2 and lot 12-c-3 were synthesized by the same procedure as above.
• Lot 12-c-2 had X of 0.19 mol % and Y of 99.3%.
• Lot 12-c-3 had X of 0.16 mol % and Y of 99.2%.
• a portion of the obtained solid was dissolved in deuterated acetone and subjected to 1 H NMR measurement, and the solid content value was calculated from the integral ratio with the residual diisopropyl ether to be 99.4%.
• X and Z were measured with respect to the solid after drying, X was 0.10 mol% and Z was 8 ppm.
• the resulting solid is lot 13-a-0.
• the concentration of the reference lot was the above 99.4%.
• the crude product was mixed with salt C12 (0.046 g), 80 g of methylene chloride and 80 g of water, and stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 80 g of 0.1N hydrochloric acid and five times with 80 g of water, and concentrated under reduced pressure. When X was calculated again with respect to the obtained crude product, it was 0.12 mol %. 100 g of diisopropyl ether was added to the crude product and stirred, and the filtered solid was dried under reduced pressure for 5 hours.
• Lot 13-a-3 was synthesized by a procedure similar to lot 13-a-1.
• X, Y, and Z were measured for lot 13-a-3, X was 0.18 mol%, Y was 99.0%, and Z was 11 ppm.
• Lot 13-b-2 and Lot 13-b-3 were synthesized in the same manner as above.
• Lot 13-b-2 had X of 0.10 mol % and Z of 29 ppm.
• Lot 13-b-3 had X of 0.13 mol % and Z of 28 ppm.
• Lot 13-b-2 had a solids content of 96.8% calculated from 1 H NMR measurements, and lot 13-b-3 had a solids content of 98.1% as well.
• Lot 13-c-2 and lot 13-c-3 were synthesized by the same procedure as above.
• Lot 13-c-2 had X of 0.12 mol % and Y of 99.5%.
• Lot 13-c-3 had X of 0.13 mol % and Y of 98.8%.
• the crude product was mixed with salt C13 (0.051 g), 80 g of methylene chloride and 80 g of water, and stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 80 g of 0.1N hydrochloric acid and five times with 80 g of water, and concentrated under reduced pressure. When X was calculated again with respect to the obtained crude product, it was 0.19 mol%. 100 g of diisopropyl ether was added to the crude product and stirred, and the filtered solid was dried under reduced pressure for 5 hours.
• a portion of the obtained solid was dissolved in deuterated acetone and subjected to 1 H NMR measurement, and the solid content value was determined from the integral ratio with the residual diisopropyl ether to be 98.9%.
• X, Y, and Z were measured for the solid after drying, X was 0.19 mol%, Y was 98.1%, and Z was 21 ppm.
• the resulting solid is lot 14-a-1.
• Lot 14-a-3 was synthesized by a procedure similar to lot 14-a-1.
• X, Y and Z were measured for lot 14-a-3, X was 0.19 mol%, Y was 99.1%, and Z was 12 ppm.
• Lot 14-b-2 and lot 14-b-3 were synthesized by the same procedure as above.
• Lot 14-b-2 had X of 0.26 mol % and Z of 19 ppm.
• Lot 14-b-3 had X of 0.12 mol % and Z of 18 ppm.
• Lot 14-b-2 had a solids content of 98.7% calculated from 1 H NMR measurement, and lot 14-b-3 had a solids content of 98.3%.
• Lot 14-c-2 and lot 14-c-3 were synthesized by the same procedure as above.
• Lot 14-c-2 had X of 0.19 mol % and Y of 99.4%.
• Lot 14-c-3 had X of 0.15 mol % and Y of 98.0%.
• a portion of the obtained solid was dissolved in deuterated acetone and subjected to 1 H NMR measurement, and the solid content value was calculated from the integral ratio with the remaining isopropyl alcohol to be 99.3%.
• X and Z were measured for the solid after drying, X was 0.08 mol% and Z was 8 ppm.
• the resulting solid is designated Lot 15-a-0.
• the concentration of the reference lot was the above 99.3%.
• the crude product was mixed with salt C14 (0.050 g), 100 g of methylene chloride and 100 g of water, and stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 100 g of 0.1N hydrochloric acid and five times with 100 g of water, and concentrated under reduced pressure. When X was calculated again with respect to the obtained crude product, it was 0.11 mol %. 120 g of diisopropyl ether was added to the crude product and stirred, and the filtered solid was dried under reduced pressure for 5 hours.
• Lot 15-b-2 had X of 0.16 mol % and Z of 12 ppm.
• Lot 15-b-3 had X of 0.16 mol % and Z of 20 ppm.
• Lot 15-b-2 had a solids content of 98.5% calculated from 1 H NMR measurement, and lot 15-b-3 had a solids content of 96.9% as well.
• Lot 15-c-2 and lot 15-c-3 were synthesized by the same procedure as above.
• Lot 15-c-2 had X of 0.16 mol % and Y of 96.9%.
• Lot 15-c-3 had X of 0.11 mol % and Y of 97.5%.
• a portion of the obtained solid was dissolved in deuterated acetone and subjected to 1 H NMR measurement, and the solid content value was calculated from the integral ratio with the residual diisopropyl ether to be 99.4%.
• X and Z were measured with respect to the solid after drying, X was 0.09 mol% and Z was 6 ppm.
• the resulting solid is lot 16-a-0.
• the concentration of the reference lot was the above 99.4%.
• Lot 16-a-2 and Lot 16-a-3 were synthesized by the same procedure as Lot 16-a-1, respectively.
• Lot 16-a-2 had X of 0.15 mol %, Y of 98.7%, and Z of 11 ppm.
• Lot 16-a-3 had X of 0.14 mol %, Y of 99.2% and Z of 11 ppm.
• Lot 16-b-2 had X of 0.19 mol % and Z of 12 ppm.
• Lot 16-b-3 had X of 0.12 mol % and Z of 21 ppm.
• Lot 16-b-2 had a solids content of 99.4% calculated from 1 H NMR measurement, and lot 16-b-3 had a solids content of 99.8% as well.
• Lot 16-c-2 and lot 16-c-3 were synthesized by the same procedure as above.
• Lot 16-c-2 had X of 0.21 mol % and Y of 99.4%.
• Lot 16-c-3 had X of 0.10 mol % and Y of 99.4%.
• the crude product was mixed with salt C16 (0.020 g), 80 g of methylene chloride, and 80 g of water, and stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 80 g of 0.1N hydrochloric acid and five times with 80 g of water, and concentrated under reduced pressure. When X was calculated again with respect to the obtained crude product, it was 0.27 mol%. 100 g of diisopropyl ether was added to the crude product and stirred, and the filtered solid was dried under reduced pressure for 5 hours.
• Lot 17-a-3 was synthesized by a procedure similar to lot 17-a-1.
• X, Y, and Z were measured for lot 17-a-3, X was 0.14 mol%, Y was 99.1%, and Z was 13 ppm.
• Lot 17-b-2 and lot 17-b-3 were synthesized by the same procedure as above.
• Lot 17-b-2 had X of 0.15 mol % and Z of 10 ppm.
• Lot 17-b-3 had X of 0.13 mol % and Z of 13 ppm.
• Lot 17-b-2 had a solids content of 98.2% calculated from 1 H NMR measurement, and lot 17-b-3 had a solids content of 97.2% as well.
• the crude product was mixed with salt C17 (0.030 g), 80 g of methylene chloride, and 80 g of water, and stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 80 g of 0.1N hydrochloric acid and five times with 80 g of water, and concentrated under reduced pressure. When X was calculated again with respect to the obtained crude product, it was 0.12 mol %. 100 g of diisopropyl ether was added to the crude product and stirred, and the filtered solid was dried under reduced pressure for 5 hours.
• Lot 18-a-3 was synthesized following the same procedure as lot 18-a-2.
• X, Y, and Z were measured for lot 18-a-3, X was 0.12 mol%, Y was 98.3%, and Z was 11 ppm.
• Lot 18-b-2 and lot 18-b-3 were synthesized by the same procedure as above.
• Lot 18-b-2 had X of 0.14 mol % and Z of 14 ppm.
• Lot 18-b-3 had X of 0.14 mol % and Z of 9 ppm.
• Lot 18-b-2 had a solids content of 98.5% calculated from 1 H NMR measurement, and lot 18-b-3 had a solids content of 99.0% as well.
• Lot 18-c-2 and lot 18-c-3 were synthesized by the same procedure as above.
• Lot 18-c-2 had X of 0.17 mol % and Y of 98.3%.
• Lot 18-c-3 had X of 0.12 mol % and Y of 99.0%.
• the crude product was mixed with salt C18 (0.026 g), 80 g of methylene chloride and 80 g of water, and stirred at room temperature for 30 minutes. After removing the aqueous layer, the organic layer was washed once with 80 g of 0.1N hydrochloric acid and five times with 80 g of water, and concentrated under reduced pressure. When X was calculated again with respect to the obtained crude product, it was 0.19 mol%. 100 g of diisopropyl ether was added to the crude product and stirred, and the filtered solid was dried under reduced pressure for 5 hours.
• Lot 19-a-3 was synthesized by a procedure similar to lot 19-a-1.
• X, Y, and Z were measured for lot 19-a-3, X was 0.18 mol%, Y was 99.0%, and Z was 12 ppm.
• Lot 19-b-2 and lot 19-b-3 were synthesized by the same procedure as above.
• Lot 19-b-2 had X of 0.10 mol % and Z of 24 ppm.
• Lot 19-b-3 had X of 0.19 mol % and Z of 11 ppm.
• Lot 19-b-2 had a solids content of 97.4% calculated from 1 H NMR measurement, and lot 19-b-3 had a solids content of 98.6% as well.
• Lot 19-c-2 and lot 19-c-3 were synthesized by the same procedure as above.
• Lot 19-c-2 had X of 0.17 mol % and Y of 98.8%.
• Lot 19-c-3 had X of 0.19 mol % and Y of 98.3%.
• Lot 20-a-3 was synthesized following the same procedure as lot 20-a-2.
• X, Y, and Z were measured for lot 20-a-3, X was 0.14 mol%, Y was 98.8%, and Z was 15 ppm.
• Lot 20-b-2 had X of 0.11 mol % and Z of 10 ppm.
• Lot 20-b-3 had X of 0.11 mol % and Z of 23 ppm.
• Lot 20-b-2 had a solids content of 98.3% calculated from 1 H NMR measurement, and lot 20-b-3 had a solids content of 99.9% as well.
• Lot 20-c-2 had X of 0.16 mol % and Y of 99.4%.
• Lot 20-c-3 had X of 0.21 mol % and Y of 98.5%.
• Table 1 shows the results of X, Y, and Z for each lot in each synthesis example.
• S-1 Propylene glycol monomethyl ether acetate (PGMEA)
• S-2 Propylene glycol monomethyl ether (PGME)
• S-3 ⁇ -butyrolactone
• S-4 ethyl lactate
• S-5 cyclohexanone
• S-6 2-heptanone
• Examples 1-20 and Comparative Examples 1-20 Preparation of actinic ray-sensitive or radiation-sensitive resin composition
• Each component shown in Table 2 was mixed so that the solid content concentration was 2.0% by mass.
• the resulting mixture is first filtered through a polyethylene filter with a pore size of 50 nm, then with a nylon filter with a pore size of 10 nm, and finally with a polyethylene filter with a pore size of 5 nm, in order to obtain an actinic ray-sensitive or radiation-sensitive
• a flexible resin composition (resist composition) was prepared.
• the amount of salt (P) was calculated from the solid content value and weighed so that the amount shown in Table 2 was obtained.
• Y was measured in each lot, Y was taken as the solid content value.
• the "% by mass" column indicates the content (% by mass) of each component with respect to the total solid content in the resist composition.
• the amounts (mass parts) of the solvents used are shown in the table.
• ⁇ Sensitivity fluctuation evaluation> The difference ⁇ CD (nm) between the pattern line width of each lot of each salt (P) and the target pattern size of 25 nm was calculated, and the average value ⁇ CD AVE of ⁇ CD between each lot was calculated.
• a positive value of ⁇ CD indicates a shift to the low sensitivity side
• a negative value of ⁇ CD indicates a shift to the high sensitivity side.
• the absolute value of ⁇ CD AVE is preferably as low as possible, preferably 0.5 nm or less, more preferably 0.2 nm or less.
• Example 1 one of each lot ((1-a-1) to (1-a-3)) of (a-1) to (a-3) related to salt B1 is selected.
• the sensitivity (Eop) was defined as the irradiation energy for resolving a 1:1 line-and-space pattern with a line width of 25 nm.
• Two lots other than the selected lots were exposed at the above Eop, the line width of the resulting pattern size was measured, and the difference ⁇ CD (nm) from 25 nm was calculated.
• An average value ⁇ CD AVE of ⁇ CD between each lot was calculated. The value obtained is reported as " ⁇ CD AVE " for Lot a in Example 1 of Table 3.
• Example 1 select one of each lot ((1-b-1) to (1-b-3)) of (b-1) to (b-3) related to salt B1.
• the sensitivity (Eop) was defined as the irradiation energy for resolving a 1:1 line-and-space pattern with a line width of 25 nm.
• Two lots other than the selected lots were exposed at the above Eop, the line width of the resulting pattern size was measured, and the difference ⁇ CD (nm) from 25 nm was calculated.
• An average value ⁇ CD AVE of ⁇ CD between each lot was calculated. The value obtained is reported as " ⁇ CD AVE " for Lot b in Example 1 of Table 3.
• Example 1 select one of each lot ((1-c-1) to (1-c-3)) of (c-1) to (c-3) related to salt B1.
• the sensitivity (Eop) was defined as the irradiation energy for resolving a 1:1 line-and-space pattern with a line width of 25 nm. Two lots other than the selected lots were exposed at the above Eop, the line width of the resulting pattern size was measured, and the difference ⁇ CD (nm) from 25 nm was calculated. An average value ⁇ CD AVE of ⁇ CD between each lot was calculated. The value obtained is reported as " ⁇ CD AVE " for Lot c in Example 1 of Table 3. In each of lots a to c of Example 1, the smaller the absolute value of " ⁇ CD AVE " is, the smaller the variation in sensitivity is, which is preferable. Examples 2 to 20 were also evaluated in the same manner as in Example 1.
• Comparative Example 1 one of each lot ((1-R-1) to (1-R-3)) of (R-1) to (R-3) related to salt B1 is selected,
• the sensitivity (Eop) was defined as the irradiation energy for resolving a 1:1 line-and-space pattern with a line width of 25 nm.
• Two lots other than the selected lots were exposed at the above Eop, the line width of the resulting pattern size was measured, and the difference ⁇ CD (nm) from 25 nm was calculated.
• An average value ⁇ CD AVE of ⁇ CD between each lot was calculated. The obtained value is listed as " ⁇ CD AVE " for Lot R in Comparative Example 1 in Table 3.
• Comparative Examples 2 to 20 were evaluated in the same manner as in Comparative Example 1. Table 3 shows the evaluation results.
• the manufacturing method of the salt which can suppress the fluctuation
• the manufacturing method of the said actinic-ray-sensitive or radiation-sensitive resin composition, the pattern formation method, and the manufacturing method of an electronic device can be provided.

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