Classifications

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

Definitions

• the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and an electronic device manufacturing method. More specifically, the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and an electronic device manufacturing method that can be suitably used in ultra-microlithography processes applicable to ultra-large scale integration (LSI) and high-capacity microchip manufacturing processes, nanoimprint mold manufacturing processes, high-density information recording medium manufacturing processes, and other photofabrication processes.
• LSI ultra-large scale integration
• microchip manufacturing processes nanoimprint mold manufacturing processes
• high-density information recording medium manufacturing processes and other photofabrication processes.
• immersion liquid a liquid with a high refractive index
• Patent Documents 1 and 2 describe resins containing fluorine atoms.
• Patent Document 3 describes a pattern forming method including a step of forming a film from an actinic ray-sensitive or radiation-sensitive resin composition and a step of forming a topcoat layer containing a fluorine atom-containing resin on the film.
• the fluorine atom-containing resin added to the actinic ray-sensitive or radiation-sensitive resin composition is typically a hydrophobic resin, and is unevenly distributed on the surface of the actinic ray-sensitive or radiation-sensitive film to make the surface hydrophobic.
• LWR performance refers to performance that can reduce the LWR of a pattern.
• actinic ray-sensitive or radiation-sensitive resin compositions are required to have little effect on performance due to the passage of time from exposure to post exposure bake (PEB), that is, to have excellent PED (Post Exposure time Delay) stability.
• the present invention has been made in view of the above points, and an object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition that is excellent in LWR performance and PED stability. Another object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and an electronic device manufacturing method using the actinic ray-sensitive or radiation-sensitive resin composition.
• the present inventors found that the above problems can be solved by using a resin containing a repeating unit having an acid group with a pKa of 8.0 or more and 12.0 or less, a repeating unit having an acid group with a pKa of less than 8.0, and a repeating unit containing at least one fluorine atom and having a pKa of 12.0 or less and no acid group.
• An actinic ray-sensitive or radiation-sensitive resin composition containing at least the following (A), (B) and (C).
• A a repeating unit (a1) having an acid group with a pKa of 8.0 or more and 12.0 or less, represented by the following general formula (a1-1) or (a1-2); a repeating unit (a2) having an acid group with a pKa of less than 8.0; a resin containing a repeating unit (a3) containing at least one fluorine atom and having a pKa of 12.0 or less and having no acid group; a repeating unit (b2) having a group that decomposes under the action of an acid and increases in polarity; and does not contain repeating units that generate acid upon irradiation with actinic rays or radiation
• C Compound that generates acid upon irradiation with actinic rays or radiation
• R a1 represents a hydrogen atom or an alkyl group.
• R a2 represents a halogen atom, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an alkylthio group, an alkoxycarbonyl group, or an alkylcarbonyloxy group.
• n1 represents an integer of 1 or more and (5+2m) or less.
• n2 represents an integer of 1-3.
• k1 represents an integer of 0 or more and (5+2m ⁇ n1) or less.
• R a3 represents a hydrogen atom or an alkyl group.
• R a4 represents an alkyl group having 3 or more fluorine atoms as substituents.
• R a5 represents a hydrogen atom or an alkyl group.
• L3 represents a single bond or a linking group consisting of at least one selected from the group consisting of an alkylene group, a cycloalkylene group and an arylene group.
• p represents an integer of 1 to 3;
• An actinic ray-sensitive or radiation-sensitive resin composition containing at least the following (AX), (B) and (C).
• AX a repeating unit (ax1) having an acid group with a pKa of 8.0 or more and 12.0 or less; a repeating unit (a2) having an acid group with a pKa of less than 8.0;
• B a repeating unit (b1) having a phenolic hydroxyl group, and a repeating unit (a3) containing at least one fluorine atom and having no acid group and having a pKa of 12.0 or less, and having a dissolution rate of 0.002 nm/s or more in an alkaline developer for a film of the resin alone.
• a pattern forming method comprising the steps of: forming an actinic ray-sensitive or radiation-sensitive film on a substrate from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [9]; 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 [11].
• the actinic-ray-sensitive or radiation-sensitive resin composition which is excellent in LWR performance and PED stability can be provided. Further, the present invention can provide an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and an electronic device manufacturing method using the actinic ray-sensitive or radiation-sensitive resin composition.
• actinic ray or “radiation” means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV: Extreme Ultraviolet), X-rays, soft X-rays, and electron beams (EB: Electron Beam).
• light means actinic rays or radiation.
• exposure includes not only exposure by the emission line spectrum of a mercury lamp, far ultraviolet rays, extreme ultraviolet rays, X-rays, and EUV represented by excimer lasers, but also drawing by particle beams such as electron beams and ion beams.
• the term " ⁇ " is used to include the numerical values before and after it as lower and upper limits.
• (meth)acrylate represents at least one of acrylate and methacrylate.
• (Meth)acrylic acid represents at least one of acrylic acid and methacrylic acid.
• the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (also referred to as molecular weight distribution) (Mw/Mn) of the resin are measured by GPC (Gel Permeation Chromatography) device (HLC-8120GPC manufactured by Tosoh Corporation) (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 ⁇ L, column: TSK g manufactured by Tosoh Corporation. el Multipore HXL-M, column temperature: 40° C., flow rate: 1.0 mL/min, detector: defined as a polystyrene conversion value by a Refractive Index Detector.
• GPC Gel Permeation Chromatography
• the notation that does not describe substituted or unsubstituted includes groups containing substituents as well as groups without substituents.
• an "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
• the term "organic group” as used herein refers to a group containing at least one carbon atom. As a substituent, a monovalent substituent is preferable unless otherwise specified.
• the bonding direction of the divalent groups indicated is not limited unless otherwise specified.
• Y in a compound represented by the formula "XYZ" is -COO-
• Y may be -CO-O- or -O-CO-.
• the compound may be "X—CO—O—Z” or "X—O—CO—Z.”
• the acid dissociation constant (pKa) represents the pKa in an aqueous solution, and specifically, a value obtained by calculating a value based on a database of Hammett's substituent constants and known literature values using Software Package 1 below. All pKa values described herein are calculated using this software package.
• 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.
• H + dissociation free energy can be calculated by, for example, DFT (density functional theory), but various other methods have been reported in literature, etc., and are not limited to this. 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.
• 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” shall be adopted.
• DMSO dimethyl sulfoxide
• solid content means a component that forms an actinic ray-sensitive or radiation-sensitive film, and does not include a solvent.
• solid content it is regarded as a solid content even if the property is liquid.
• the actinic ray-sensitive or radiation-sensitive resin composition of the present invention (also referred to as “the composition of the present invention") is an actinic ray-sensitive or radiation-sensitive resin composition containing at least the following (A), (B) and (C).
• R a1 represents a hydrogen atom or an alkyl group.
• R a2 represents a halogen atom, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an alkylthio group, an alkoxycarbonyl group, or an alkylcarbonyloxy group. When multiple R a2 are present, the multiple R a2 may be the same or different.
• m represents an integer of 0 to 2;
• n1 represents an integer of 1 or more and (5+2m) or less.
• n2 represents an integer of 1-3.
• k1 represents an integer of 0 or more and (5+2m ⁇ n1) or
• the component (A) of the present invention is a resin containing a repeating unit having an acid group with a pKa of 8.0 or more and 12.0 or less, a repeating unit having an acid group with a pKa of less than 8.0, and at least one fluorine atom. Furthermore, for the same reason, it is considered that the resolution is excellent and that the excellent LWR performance can be maintained even after a certain period of time has passed since the preparation of the actinic ray-sensitive or radiation-sensitive resin composition.
• composition of the present invention (A), (B) and (C) are preferably separate components.
• the composition of the present invention is typically a resist composition, and may be a positive resist composition or a negative resist composition.
• the composition of the present invention may be a resist composition for alkali development or a resist composition for organic solvent development.
• the composition of the present invention may be a chemically amplified resist composition or a non-chemically amplified resist composition.
• the composition of the present invention is typically a chemically amplified resist composition.
• the actinic ray-sensitive or radiation-sensitive film formed from the composition of the present invention is typically a resist film.
• the component (A) contained in the composition of the present invention is a resin containing a repeating unit (a1) having an acid group with a pKa of 8.0 or more and 12.0 or less, a repeating unit (a2) having an acid group having a pKa of less than 8.0, and a repeating unit (a3) containing at least one fluorine atom and having a pKa of 12.0 or less and having no acid group.
• the component (A) is also referred to as "resin (A)".
• the value obtained by calculation using the aforementioned software package 1 (if the pKa cannot be calculated by this method, the value obtained by Gaussian 16 based on DFT) is taken as the pKa of the acid group of each repeating unit.
• the monomer (M) has two or more acid groups, two or more pKa values are calculated. In this case, the minimum pKa is taken as the pKa of the acid group of the repeating unit.
• the repeating unit (a1) is a repeating unit having an acid group with a pKa of 8.0 or more and 12.0 or less represented by the general formula (a1-1) or (a1-2).
• R a1 represents a hydrogen atom or an alkyl group.
• the alkyl group for R a1 is preferably an alkyl group 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, more preferably an alkyl group having 1 to 3 carbon atoms, and still more preferably a methyl group.
• R a2 represents a halogen atom, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an alkylthio group, an alkoxycarbonyl group, or an alkylcarbonyloxy group.
• the halogen atom for R a2 includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, with a fluorine atom being preferred.
• the alkyl group for R a2 is preferably an alkyl group having 1 to 10 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group, more preferably an alkyl group having 1 to 6 carbon atoms.
• the aryl group represented by R a2 is preferably a phenyl group, a naphthyl group, a phenanthryl group, an anthryl group, or the like, and more preferably a phenyl group or a naphthyl group.
• the heteroaryl group of R a2 is preferably a heteroaryl group containing at least one heteroatom selected from the group consisting of a sulfur atom, a nitrogen atom and an oxygen atom.
• a thienyl group, a furanyl group, a benzothienyl group, a benzofuranyl group, a pyrrole group, an oxazolyl group, a thiazolyl group, a pyridyl group and the like are preferred, and a thienyl group, a furanyl group, a benzothienyl group and a benzofuranyl group are more preferred.
• the alkoxy group represented by R a2 is preferably an alkoxy group having 1 to 10 carbon atoms such as a methoxy group or an ethoxy group, and more preferably an alkoxy group having 1 to 6 carbon atoms.
• the alkylthio group for R a2 is preferably an alkylthio group having 1 to 10 carbon atoms, more preferably an alkylthio group having 1 to 6 carbon atoms.
• the alkoxycarbonyl group for R a2 is preferably an alkoxycarbonyl group having 2 to 10 carbon atoms, more preferably an alkoxycarbonyl group having 2 to 6 carbon atoms.
• the alkylcarbonyloxy group for R a2 is preferably an alkylcarbonyloxy group having 2 to 10 carbon atoms, more preferably an alkylcarbonyloxy group having 2 to 6 carbon atoms. When multiple R a2 are present, the multiple R a2 may be the same or different.
• m represents an integer of 0 to 2, preferably 0 or 1, more preferably 0.
• the aromatic ring in general formula (a1-1) represents benzene.
• the aromatic ring in general formula (a1-1) represents naphthalene.
• the aromatic ring in general formula (a1-1) represents anthracene.
• n1 represents an integer of 1 or more and (5+2m) or less, preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1.
• k1 represents an integer of 0 or more and (5+2m ⁇ n1) or less, preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and still more preferably 0.
• R a1 has the same meaning as R a1 in general formula (a1-1) above, and specific examples and preferred ranges are also the same.
• the alkylene group for L 2 is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and even more preferably an alkylene group having 1 to 3 carbon atoms.
• the cycloalkylene group for L 2 is preferably a cycloalkylene group having 3 to 20 carbon atoms, more preferably a cycloalkylene group having 5 to 15 carbon atoms, and even more preferably a cycloalkylene group having 6 to 10 carbon atoms.
• the arylene group for L 2 is preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 10 carbon atoms, and still more preferably a phenylene group.
• n2 represents an integer of 1 to 3, more preferably 1 or 2.
• the repeating unit (a1) has an acid group with a pKa of 8.0 or more and 12.0 or less. It is preferable that an acid group having a pKa of 8.0 or more and 12.0 or less be covalently bonded to the atomic group constituting the repeating unit (a1).
• Examples of the acid group possessed by the repeating unit (a1) include a phenolic hydroxyl group and a hexafluoroisopropanol group (--C(CF 3 ) 2 OH).
• the pKa of the acid group of the repeating unit (a1) is preferably 8.5 or more and 11.0 or less, more preferably 9.0 or more and 10.5 or less.
• the repeating unit (a1) is preferably represented by general formula (a1-1) above.
• the repeating unit (a1) is represented by the general formula (a1-1), and m in the general formula (a1-1) preferably represents 0 or 1, more preferably 0. More preferably, the repeating unit (a1) is represented by the above general formula (a1-1), and L 1 in the above general formula (a1-1) represents a single bond.
• the repeating unit (a1) is particularly preferably a repeating unit represented by the following general formula (a1-3).
• R a1 represents a hydrogen atom or an alkyl group.
• R a2 represents a halogen atom, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an alkylthio group, an alkoxycarbonyl group, or an alkylcarbonyloxy group.
• n3 represents an integer of 1-3.
• k2 represents an integer from 0 to 4;
• R a1 and R a2 have the same meanings as R a1 and R a2 in general formula (a1-1) above, and specific examples and preferred ranges are also the same.
• n3 represents an integer of 1 to 3, preferably 1 or 2, more preferably 1.
• k2 represents an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0.
• the number of repeating units (a1) contained in the resin (A) may be one or two or more.
• the content of the repeating unit (a1) is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, and still more preferably 20 mol% or more, based on the total repeating units in the resin (A). Moreover, the content of the repeating unit (a1) is preferably 90 mol % or less, more preferably 80 mol % or less, and still more preferably 70 mol % or less, relative to all repeating units in the resin (A).
• the repeating unit (a2) is a repeating unit having an acid group with a pKa of less than 8.0. It is preferable that an acid group having a pKa of less than 8.0 be covalently bonded to the atomic group constituting the repeating unit (a2).
• the acid group that the repeating unit (a2) has include a carboxyl group, a sulfonic acid group, a sulfonamide group, a sulfonimide group, and a hydroxy group.
• a sulfonamide group is preferably represented by —NHSO 2 R 1 .
• R 1 represents an organic group.
• R 1 is preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms.
• the alkyl group preferably has a fluorine atom as a substituent.
• a sulfonimide group is preferably represented by —SO 2 NHSO 2 R 1 .
• R 1 represents an organic group.
• R 1 is preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms.
• the alkyl group preferably has a fluorine atom as a substituent.
• the pKa of the acid group of the repeating unit (a2) is preferably -8.0 or more and 7.0 or less, more preferably 0.0 or more and 6.0 or less.
• the repeating unit (a2) is preferably represented by the following general formula (a2-1).
• R a5 represents a hydrogen atom or an alkyl group.
• L3 represents a single bond or a linking group consisting of at least one selected from the group consisting of an alkylene group, a cycloalkylene group and an arylene group.
• p represents an integer of 1 to 3;
• R a5 in general formula (a2-1) has the same meaning as R a1 in general formula (a1-1) above, and specific examples and preferred ranges are also the same.
• the alkylene group for L 3 is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and even more preferably an alkylene group having 1 to 3 carbon atoms.
• the cycloalkylene group for L 3 is preferably a cycloalkylene group having 3 to 20 carbon atoms, more preferably a cycloalkylene group having 5 to 15 carbon atoms, and even more preferably a cycloalkylene group having 6 to 10 carbon atoms.
• the arylene group of L 3 is preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 10 carbon atoms, and still more preferably a phenylene group.
• p in general formula (a2-1) preferably represents 1 or 2, more preferably 1.
• repeating unit (a2) Specific examples of the monomer corresponding to the repeating unit (a2) are shown below together with their pKa, but the repeating unit (a2) is not limited to these.
• the number of repeating units (a2) contained in the resin (A) may be one or two or more.
• the content of the repeating unit (a2) is not particularly limited, but is preferably 1 mol% or more, more preferably 3 mol% or more, relative to the total repeating units in the resin (A). Moreover, the content of the repeating unit (a2) is preferably 40 mol % or less, more preferably 30 mol % or less, and even more preferably 20 mol % or less, relative to all repeating units in the resin (A).
• the repeating unit (a3) is a repeating unit containing at least one fluorine atom and having a pKa of 12.0 or less and having no acid group.
• the repeating unit (a3) does not have an acid group, or if it does have an acid group, the pKa of the acid group is greater than 12.0.
• the repeating unit (a3) preferably contains an alkyl group or an aryl group having at least one fluorine atom as a substituent.
• the alkyl group an alkyl group having 1 to 20 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable.
• As the aryl group an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 10 carbon atoms is more preferable.
• the repeating unit (a3) preferably contains an alkyl group having 3 or more fluorine atoms as substituents, more preferably contains an alkyl group having 3 to 15 fluorine atoms as substituents, and still more preferably contains an alkyl group having 3 to 10 fluorine atoms as substituents.
• the repeating unit (a3) is preferably represented by the following general formula (a3-1).
• R a3 represents a hydrogen atom or an alkyl group.
• R a4 represents an alkyl group having 3 or more fluorine atoms as substituents.
• R a3 has the same meaning as R a1 in general formula (a1-1) above, and specific examples and preferred ranges are also the same.
• R a4 represents an alkyl group having 3 or more fluorine atoms as substituents, more preferably represents an alkyl group having 3 to 15 fluorine atoms as substituents, and more preferably represents an alkyl group having 3 to 10 fluorine atoms as substituents.
• the alkyl group for R a4 is preferably an alkyl group having 1 to 20 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and 2-ethylhexyl group, more preferably an alkyl group having 1 to 10 carbon atoms.
• repeating unit (a3) Specific examples of the monomer corresponding to the repeating unit (a3) are shown below together with the pKa of the monomer when it contains an acid group, but the repeating unit (a3) is not limited to these.
• the number of repeating units (a3) contained in the resin (A) may be one or two or more.
• the content of the repeating unit (a3) is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, and still more preferably 30 mol% or more, relative to the total repeating units in the resin (A). Moreover, the content of the repeating unit (a3) is preferably 90 mol % or less, more preferably 80 mol % or less, and still more preferably 70 mol % or less, relative to all repeating units in the resin (A).
• the resin (A) may further contain other repeating units in addition to the repeating units (a1), (a2) and (a3).
• the content of other repeating units is preferably 40 mol % or less, more preferably 30 mol % or less, relative to all repeating units in the resin (A). It is preferred that the resin (A) does not contain a repeating unit having a group that decomposes under the action of an acid and increases in polarity. Moreover, it is preferable that the resin (A) does not contain a repeating unit that generates an acid upon exposure to actinic rays or radiation.
• Resin (A) can be synthesized according to a conventional method (for example, radical polymerization).
• the weight average molecular weight of resin (A) is preferably 100,000 or less, more preferably 1,000 to 50,000, even more preferably 3,000 to 40,000, and particularly preferably 4,000 to 30,000.
• the dispersity (molecular weight distribution) of the resin (A) is preferably 1-5, more preferably 1-3, even more preferably 1-2.
• the resin (A) preferably has a dissolution rate of 0.002 nm/s or more, more preferably 0.005 nm/s or more, and even more preferably 0.01 nm/s or more for a film of the resin (A) alone in an alkaline developer.
• the upper limit of the dissolution rate is preferably 100 nm/s or less.
• the resin (A) preferably has a dissolution rate of 0.002 nm/s or more for a film of the resin alone in an alkaline developer, so that the developability is excellent and the LWR performance is further improved.
• the rate of dissolution of the resin-only film in an alkaline developer can be adjusted by the content ratio of the repeating unit (a1), the repeating unit (a2), and the repeating unit (a3), the molecular weight, and the like.
• a method for determining the dissolution rate of a film of resin alone in an alkaline developer will be described below.
• the resin is dissolved in a mixed solvent of propylene glycol monomethyl ether acetate/propylene glycol monomethyl ether (mass ratio 8/2) to prepare a concentration of 3% by mass.
• the prepared resin solution is coated on a 6-inch Si wafer previously treated with hexamethyldisilazane (HMDS) using a Tokyo Electron spin coater Mark 8, and dried on a hot plate at 100° C. for 60 seconds to obtain a resin film with a film thickness of 100 nm.
• HMDS hexamethyldisilazane
• the content of the resin (A) in the composition of the present invention is not particularly limited, but is preferably 0.1 to 40.0% by mass, more preferably 1.0 to 30.0% by mass, and still more preferably 5.0 to 20.0% by mass, based on the total solid content of the composition of the present invention.
• the resin (A) contained in the composition of the present invention may be one kind, or two or more kinds.
• the component (B) contained in the composition of the present invention is a resin containing a repeating unit (b1) having a phenolic hydroxyl group and a repeating unit (b2) having a group that decomposes under the action of an acid and increases in polarity, and does not contain a repeating unit that generates an acid upon exposure to actinic rays or radiation.
• the component (B) is also referred to as "resin (B)".
• the repeating unit (b1) is a repeating unit having a phenolic hydroxyl group.
• the repeating unit (b1) preferably has a structure in which a hydroxy group is bonded to an aromatic hydrocarbon ring having 6 to 20 carbon atoms.
• the repeating unit (b1) is preferably a repeating unit represented by the following general formula (b1-1).
• a a1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group.
• R 21 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, and when there are more than one, they may be the same or different. When it has a plurality of R 21 , they may jointly form a ring.
• a hydrogen atom is preferred as R 21 .
• a represents an integer of 1 to 3;
• b represents an integer from 0 to (5-a).
• repeating unit (b1) Specific examples of the repeating unit (b1) are shown below, but are not limited to these.
• a represents an integer of 1-3.
• R represents a hydrogen atom or a methyl group
• a represents an integer of 1-3.
• the content of the repeating unit (b1) is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, and still more preferably 30 mol% or more, based on the total repeating units in the resin (B). Moreover, the content of the repeating unit (b1) is preferably 90 mol % or less, more preferably 85 mol % or less, and still more preferably 80 mol % or less, relative to all repeating units in the resin (B).
• the repeating unit (b2) is a repeating unit having a group that is decomposed by the action of an acid and increases in polarity (also referred to as an "acid-decomposable group”).
• the repeating unit (b2) is also referred to as "a repeating unit having an acid-decomposable group”.
• the resin (B) is an acid-decomposable resin, and in the pattern forming method of the present invention, typically, when an alkaline developer is used as the developer, a positive pattern is preferably formed, and when an organic developer is used as the developer, a negative pattern is preferably formed.
• 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 (B) 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, an (alkylsulfonyl)(alkylcarbonyl)methylene group, an (alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imide group, a tris(alkylcarbonyl)methylene group, and a tris( Examples include acidic groups such as alkylsulfonyl)methylene groups, and alcoholic hydroxyl groups.
• 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), 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 more preferably Rx 1 to Rx 3 each independently represent a linear alkyl group.
• Rx 1 to Rx 3 may combine to form a monocyclic or polycyclic ring.
• Preferred alkyl groups for Rx 1 to Rx 3 are alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group.
• Preferred cycloalkyl groups for Rx 1 to Rx 3 are monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, and polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl.
• 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 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group, more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms.
• one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group.
• 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.
• the alkyl group, cycloalkyl group, alkenyl group, aryl group represented by Rx 1 to Rx 3 and the ring formed by combining two of Rx 1 to Rx 3 preferably further have 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 methylene groups may be replaced with a heteroatom such as an oxygen atom and/or a group containing a heteroatom such as a carbonyl group.
• R 38 may combine with another substituent of the main chain of the repeating unit to form a ring.
• the group formed by bonding R 38 and another substituent of the main chain of the repeating unit to each other is preferably an alkylene group such as a methylene group.
• the monovalent organic groups represented by R 36 to R 38 and the ring formed by combining R 37 and R 38 with each other preferably further have a fluorine atom or an iodine atom as a substituent.
• L 1 and L 2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining these (for example, a group combining an alkyl group and an aryl group).
• M represents a single bond or a divalent linking group.
• Q represents 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 (e.g., 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 preferably further 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 may be replaced with a heteroatom such as an oxygen atom, or a group containing a heteroatom such as a carbonyl group.
• the heteroatom is preferably a heteroatom selected from the group consisting of a fluorine atom, an iodine atom and an oxygen atom in the alkyl group represented by Q which may contain a heteroatom, the cycloalkyl group which may contain a heteroatom, the aryl group which may contain a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, and a group combining these.
• 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 preferably have a fluorine atom or an iodine atom as a substituent.
• the ring member atom adjacent to the ring member atom directly bonded to the polar group (or its residue) in the non-aromatic ring preferably does not have a halogen atom such as a fluorine atom as a substituent.
• the group that is eliminated by the action of an acid may also be a 2-cyclopentenyl group having a substituent (such as an alkyl group) such as a 3-methyl-2-cyclopentenyl group, and a cyclohexyl group having a substituent (such as an alkyl group) such as a 1,1,4,4-tetramethylcyclohexyl group.
• repeating unit having an acid-decomposable group a repeating unit represented by formula (A) is also preferable.
• L 1 represents a divalent linking group which may have a fluorine atom or an iodine atom
• R 1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom
• 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 -, a hydrocarbon group optionally having a fluorine atom or an iodine atom (e.g., 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 more preferably -CO- or an -arylene group-an alkylene group having a fluorine atom or an iodine atom-.
• 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 still more preferably 1 to 3.
• 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 includes leaving groups represented by the above formulas (Y1) to (Y4) and having a fluorine atom or an iodine atom.
• a repeating unit having an acid-decomposable group a repeating unit represented by formula (AI) is also preferable.
• 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 group (monocyclic or polycyclic). However, when all of Rx 1 to Rx 3 are alkyl groups (linear or branched), at least two of Rx 1 to Rx 3 are preferably methyl groups. Two of Rx 1 to Rx 3 may combine to form a monocyclic or polycyclic ring (such as a monocyclic or polycyclic cycloalkyl group).
• Examples of the optionally substituted alkyl group represented by Xa 1 include a methyl group and a group represented by -CH 2 -R 11 .
• R 11 represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group.
• Examples of the monovalent organic group represented by R 11 include an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, an acyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group.
• Xa 1 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
• the divalent linking group for T includes an alkylene group, an aromatic ring group, a --COO--Rt-- group, and a --O--Rt-- group.
• Rt represents an alkylene group or a cycloalkylene group.
• T is preferably a single bond or a -COO-Rt- group.
• Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a -CH 2 - group, a -(CH 2 ) 2 - group, or a -(CH 2 ) 3 - group.
• Preferred alkyl groups for Rx 1 to Rx 3 are alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and t-butyl.
• the cycloalkyl groups of Rx 1 to Rx 3 are preferably monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, or polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group and adamantyl group.
• 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. In the cycloalkyl group formed by combining two of Rx 1 to Rx 3 , for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or 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.
• an acid-decomposable (meth)acrylic acid tertiary alkyl ester-based repeating unit (a repeating unit in which Xa 1 represents a hydrogen atom or a methyl group and T represents a single bond) is preferred.
• Xa 1 and Rx represent a hydrogen atom or a substituent (preferably a linear or branched alkyl group having 1 to 6 carbon atoms, CF 3 , F, or CH 2 OH).
• Rxa and Rxb are each independently a substituent (preferably a linear or branched alkyl group having 1 to 12 carbon atoms, optionally having a linear or branched substituent, an alkenyl group having 1 to 12 carbon atoms, optionally having a linear or branched substituent, an alkynyl group having 1 to 12 carbon atoms, optionally having a linear or branched substituent, an aryl group having 1 to 12 carbon atoms, or a substituent having 1 to 12 carbon atoms.
• p represents an integer of 0 or more.
• Resin (B) 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 optionally substituted by a halogen atom having 5 or less carbon atoms, an acyl group having 5 or less carbon atoms optionally substituted by a halogen atom, and an alkoxy group having 5 or less carbon atoms optionally substituted by a halogen atom, preferably an alkyl group having 3 or less carbon atoms, 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- group.
• 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 of Ry 1 to Ry 3 are preferably 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.
• the cycloalkyl groups represented by Ry 1 to Ry 3 are preferably monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, or polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group and adamantyl group.
• 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 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.
• a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
• cycloalkyl group or cycloalkenyl group formed by combining two of Ry 1 to Ry 3 for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a carbonyl group, a heteroatom-containing group such as —SO 2 — and —SO 3 —, a vinylidene group, or a combination thereof.
• a heteroatom such as an oxygen atom
• a carbonyl group a heteroatom-containing group such as —SO 2 — and —SO 3 —
• 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, ethyl group, vinyl group, allyl group, or aryl group, and Ry 2 and Ry 3 are bonded to form the above-mentioned cycloalkyl group or 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 formula (B) preferably includes 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), an acid-decomposable hydroxystyrene tertiary alkyl ether-based repeating unit (Xb represents a hydrogen atom or a methyl group, and L represents a phenyl group), and an acid-decomposable styrene carboxylic acid tertiary ester-based repeating unit (Xb represents a hydrogen atom or a methyl group, and L represents - It is a repeating unit representing an Rt--CO-- group (Rt is an aromatic group).
• the content of repeating units having an acid-decomposable group containing an unsaturated bond is preferably 15 mol% or more, more preferably 20 mol% or more, and still more preferably 30 mol% or more, relative to all repeating units in the resin (B).
• 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 (B).
• repeating units having an acid-decomposable group containing an unsaturated bond are shown below, but are not limited thereto.
• 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 (B).
• the upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol% or less, and particularly preferably 60 mol% or less, based on all repeating units in the resin (B).
• the resin (B) may contain other repeating units in addition to the repeating units (b1) and (b2). However, the resin (B) does not contain a repeating unit that generates an acid upon exposure to actinic rays or radiation.
• the resin (B) 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.
• Group A A group consisting of the following repeating units (20) to (24). (20) A repeating unit having an acid group, which will be described later. (21) A repeating unit, which has neither an acid-decomposable group nor an acid group, and has a fluorine atom, a bromine atom, or an iodine atom. ) to formula (E) correspond to (24) 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 (B) may have at least one type of repeating unit selected from the group consisting of Group A above.
• the resin (B) preferably has at least one repeating unit selected from the group consisting of Group A above.
• Resin (B) may contain at least one of a fluorine atom and an iodine atom.
• the resin (B) preferably contains at least one of a fluorine atom and an iodine atom.
• the resin (B) may contain one repeating unit containing both a fluorine atom and an iodine atom, or the resin (B) may contain two types of repeating units: a repeating unit containing a fluorine atom and a repeating unit containing an iodine atom.
• Resin (B) 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 (B) has a repeating unit having an aromatic group.
• the resin (B) may have at least one type of repeating unit selected from the group consisting of Group B above.
• the resin (B) preferably has at least one repeating unit selected from the group consisting of the above B groups.
• the resin (B) preferably contains neither fluorine atoms nor silicon atoms.
• the resin (B) preferably has no aromatic group.
• the resin (B) may have a repeating unit having an acid group in addition to the repeating unit (b1) and the repeating unit (b2).
• As the 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 (B) is not particularly limited, but is often 0.2 to 6.0 mmol/g.
• the acid group is preferably, for example, a carboxyl group, a fluoroalcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group.
• one or more (preferably 1 to 2) fluorine atoms may be substituted with a group other than a fluorine atom (such as an alkoxycarbonyl group).
• a fluorine atom such as an alkoxycarbonyl group.
• the acid group is -C(CF 3 )(OH)-CF 2 - thus formed.
• one or more fluorine atoms may be substituted with a group other than a fluorine atom to form a ring containing -C(CF 3 )(OH)-CF 2 -.
• the repeating unit having an acid group is preferably a repeating unit different from the repeating unit having a structure in which the polar group is protected by a group that is released by 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.
• 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.
• 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 (B). 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 (B).
• the resin (B) may have a repeating unit having neither an acid-decomposable group nor an acid group and having a fluorine atom, a bromine atom, or an iodine atom (hereinafter also referred to as unit X), apart from the above-described ⁇ repeating unit having an acid-decomposable group> and ⁇ repeating unit having an acid group>.
• 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> is preferably different from other types of repeating units belonging to Group A, such as the ⁇ repeating unit having a lactone group, a sultone group, or a carbonate group> described below.
• 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 represents 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, an aryl group optionally having a fluorine atom or an iodine atom, 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 (B). 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 (B).
• 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, more preferably 20 mol% or more, still more preferably 30 mol% or more, and particularly preferably 40 mol% or more, based on the total repeating units of the resin (B).
• the upper limit is not particularly limited, it is, for example, 100 mol % or less with respect to all repeating units of the resin (B).
• 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 repeating unit having a fluorine atom, a bromine atom or an iodine atom and having an acid group, and a repeating unit having a fluorine atom, a bromine atom or an iodine atom.
• Resin (B) 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.
• a 5- to 7-membered lactone structure is condensed with another ring structure to form a bicyclo structure or spiro structure, or a 5- to 7-membered sultone structure in which another ring structure is condensed to form a bicyclo structure or spiro structure.
• the resin (B) preferably has a repeating unit having a lactone group or a sultone group obtained by abstracting one or more hydrogen atoms from a ring member atom of a lactone structure represented by any of the following formulas (LC1-1) to (LC1-21) or a sultone structure represented by any of the following formulas (SL1-1) to (SL1-3), 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 the resin (B).
• 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, carboxyl groups, halogen atoms, cyano groups, and acid-decomposable 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.
• Examples of the repeating unit having a group containing a lactone structure represented by any one of formulas (LC1-1) to (LC1-21) or a sultone structure represented by any one of formulas (SL1-1) to (SL1-3) include repeating units represented by the following formula (AI).
• 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 represents 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 linking groups.
• 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 represents a group obtained by removing one hydrogen atom from a ring member atom of a lactone structure represented by any of formulas (LC1-1) to (LC1-21), or a group obtained by removing one hydrogen atom from a ring member atom of a sultone structure represented by any of formulas (SL1-1) to (SL1-3).
• any optical isomer may be used. Moreover, one optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, its optical purity (ee) is preferably 90 or more, more preferably 95 or more.
• a cyclic carbonate group is preferred.
• a repeating unit having a cyclic carbonate group a repeating unit represented by the following formula (A-1) is preferable.
• R A 1 represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group).
• n represents an integer of 0 or more.
• R A 2 represents a substituent. When n is 2 or more, a plurality of R A 2 may be the same or different.
• A represents a single bond or a divalent linking group.
• the divalent linking group is preferably 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.
• 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 (B).
• the upper limit is preferably 85 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 60 mol% or less, based on all repeating units in the resin (B).
• the resin (B) may have a repeating unit represented by the following formula (V-1) or the following formula (V-2).
• Repeating units represented by the following formulas (V-1) and (V-2) below are preferably different repeating units from the repeating units described above.
• R 6 and R 7 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR:
• R is an alkyl group having 1 to 6 carbon atoms or a fluorinated alkyl group), or a carboxyl group.
• the alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.
• n3 represents an integer of 0-6.
• n4 represents an integer of 0-4.
• X4 is a methylene group, an oxygen atom, or a sulfur atom.
• the repeating units represented by formula (V-1) or (V-2) are exemplified below. Examples of the repeating unit represented by formula (V-1) or (V-2) include repeating units described in paragraph [0100] of WO 2018/193954.
• the resin (B) preferably has a high glass transition temperature (Tg) from the viewpoint of suppressing excessive diffusion of generated acid or pattern collapse during development.
• Tg is preferably greater than 90°C, more preferably greater than 100°C, even more preferably greater than 110°C, and particularly preferably greater than 125°C.
• the Tg is preferably 400° C. or less, more preferably 350° C. or less, from the viewpoint of excellent dissolution rate in the developer.
• Tg of repeating unit is calculated by the following method.
• the Tg of a homopolymer consisting only of each repeating unit contained in the polymer is calculated by the Bicerano method.
• the mass ratio (%) of each repeating unit to all repeating units in the polymer is calculated.
• the Fox formula (described in Materials Letters 62 (2008) 3152, etc.) is used to calculate the Tg at each mass ratio, and these are totaled to obtain the Tg (°C) of the polymer.
• the Bicerano method is described in Prediction of polymer properties, Marcel Dekker Inc, New York (1993). Calculation of Tg by the Bicerano method can be performed using a polymer physical property estimation software MDL Polymer (MDL Information Systems, Inc.).
• Methods for reducing the mobility of the main chain of the resin (B) include the following methods (a) to (e).
• (a) Introduction of a bulky substituent to the main chain (b) Introduction of a plurality of substituents to the main chain (c) Introduction of a substituent that induces interaction between the resin (B) in the vicinity of the main chain (d) Formation of the main chain in the cyclic structure (e) Coupling of the cyclic structure to the main chain
• the resin (B) preferably has a repeating unit exhibiting a homopolymer Tg of 130°C or higher.
• the type of repeating unit exhibiting a homopolymer Tg of 130° C. or higher is not particularly limited as long as it is a repeating unit having a homopolymer Tg of 130° C. or higher as calculated by the Bicerano method.
• the homopolymers correspond to repeating units exhibiting a homopolymer Tg of 130° C. or higher.
• a specific example of means for achieving the above (a) is a method of introducing a repeating unit represented by the formula (A) into the resin (B).
• RA represents a group containing a polycyclic structure.
• R x represents a hydrogen atom, a methyl group, or an ethyl group.
• a group containing a polycyclic structure is a group containing multiple ring structures, and the multiple ring structures may or may not be condensed.
• Specific examples of the repeating unit represented by formula (A) include those described in paragraphs [0107] to [0119] of WO2018/193954.
• a specific example of means for achieving (b) above is a method of introducing a repeating unit represented by the formula (B) into the resin (B).
• R b1 to R b4 each independently represent a hydrogen atom or an organic group, and at least two or more of R b1 to R b4 represent an organic group.
• the type of other organic group is not particularly limited.
• at least two or more of the organic groups are substituents having three or more constituent atoms excluding hydrogen atoms.
• Specific examples of the repeating unit represented by formula (B) include those described in paragraphs [0113] to [0115] of WO2018/193954.
• a specific example of means for achieving the above (c) is a method of introducing a repeating unit represented by the formula (C) into the resin (B).
• R c1 to R c4 each independently represent a hydrogen atom or an organic group, and at least one of R c1 to R c4 is a group containing a hydrogen bonding hydrogen atom within 3 atoms from the main chain carbon. Above all, it is preferable to have a hydrogen-bonding hydrogen atom within 2 atoms (closer to the main chain side) in order to induce interaction between the main chains of the resin (B).
• Specific examples of the repeating unit represented by formula (C) include those described in paragraphs [0119] to [0121] of WO2018/193954.
• a specific example of means for achieving (d) above is a method of introducing a repeating unit represented by the formula (D) into the resin (B).
• Cyclic represents a group forming a main chain with a cyclic structure.
• the number of constituent atoms of the ring is not particularly limited.
• Specific examples of the repeating unit represented by formula (D) include those described in paragraphs [0126] to [0127] of WO2018/193954.
• a specific example of means for achieving (e) above is a method of introducing a repeating unit represented by formula (E) into the resin (B).
• each Re independently represents a hydrogen atom or an organic group.
• organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups, which may have substituents.
• a "Cyclic” is a cyclic group containing carbon atoms in the main chain. The number of atoms contained in the cyclic group is not particularly limited. Specific examples of the repeating unit represented by formula (E) include those described in paragraphs [0131] to [0133] of WO2018/193954.
• the resin (B) 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, sultone group, or carbonate group that the resin (B) 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 (B) 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 (B) 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 (e.g., a hexafluoroisopropanol group) substituted with an electron-withdrawing group at the ⁇ -position, with a carboxyl group being preferred.
• the resin (B) contains a repeating unit having an alkali-soluble group, the resolution for contact holes is increased. Repeating units having an alkali-soluble group include those described in paragraphs [0085] and [0086] of JP-A-2014-098921.
• the resin (B) may have a repeating unit that has an alicyclic hydrocarbon structure and does not exhibit acid decomposability. This can reduce the elution of low-molecular-weight components from the resist film into the immersion liquid during immersion exposure.
• Repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposability include, for example, repeating units derived from 1-adamantyl (meth)acrylate, diamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, or cyclohexyl (meth)acrylate.
• Resin (B) may have a repeating unit represented by formula (III) that has neither a hydroxyl group nor a cyano group.
• R5 represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxyl group nor a cyano group.
• Ra represents a hydrogen atom, an alkyl group or a --CH 2 --O--Ra 2 group.
• Ra2 represents a hydrogen atom, an alkyl group or an acyl group. Examples of the repeating unit represented by formula (III) having neither a hydroxyl group nor a cyano group include those described in paragraphs [0087] to [0094] of JP-A-2014-098921.
• the resin (B) may have repeating units other than the repeating units described above.
• the resin (B) may have 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. Specific examples of repeating units other than the repeating units described above are shown below.
• the resin (B) may have various repeating structural units for the purpose of adjusting dry etching resistance, standard developer suitability, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, etc.
• all repeating units are preferably composed of repeating units derived from a compound having an ethylenically unsaturated bond.
• all of the repeating units are composed of (meth)acrylate repeating units.
• all of the repeating units may be methacrylate repeating units, all of the repeating units may be acrylate repeating units, or all of the repeating units may be methacrylate repeating units and acrylate repeating units.
• Resin (B) can be synthesized according to a conventional method (for example, radical polymerization).
• the weight average molecular weight of the resin (B) is preferably 30,000 or less, more preferably 1,000 to 30,000, still more preferably 3,000 to 30,000, and particularly preferably 5,000 to 15,000, as a polystyrene equivalent by GPC method.
• the dispersity (molecular weight distribution) of the resin (B) is preferably 1 to 5, more preferably 1 to 3, even more preferably 1.2 to 3.0, and particularly preferably 1.2 to 2.0. The smaller the degree of dispersion, the better the resolution and resist shape, the smoother the side walls of the resist pattern, and the better the roughness.
• the content of resin (B) 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 of the present invention.
• the resin (B) may be used singly or in combination.
• the component (C) contained in the composition of the present invention is a compound (photoacid generator) that generates an acid upon exposure to actinic rays or radiation.
• the component (C) is also referred to as “compound (C)” or "photoacid generator”.
• the photoacid generator is preferably a compound that generates an organic acid upon exposure to actinic rays or radiation.
• examples include sulfonium salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imidosulfonate compounds, oximesulfonate compounds, diazodisulfone compounds, disulfone compounds, and o-nitrobenzylsulfonate compounds.
• a known compound that generates an acid upon exposure to actinic rays or radiation can be appropriately selected and used either singly or as a mixture thereof.
• the known compounds disclosed in paragraphs [0125] to [0319] of US Patent Application Publication No. 2016/0070167A1, paragraphs [0086] to [0094] of US Patent Application Publication No. 2015/0004544A1, and paragraphs [0323] to [0402] of US Patent Application Publication No. 2016/0237190A1 are preferably used. I can.
• photoacid generator for example, compounds represented by the following general formula (ZI), general formula (ZII), or general formula (ZIII) are preferred.
• R 201 , R 202 and R 203 each independently represent an organic group.
• the number of carbon atoms in the organic groups as R 201 , R 202 and R 203 is generally 1-30, preferably 1-20.
• two of R 201 to R 203 may combine to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group.
• Groups formed by combining two of R 201 to R 203 include alkylene groups (eg, butylene group and pentylene group) and —CH 2 —CH 2 —O—CH 2 —CH 2 —.
• Z ⁇ represents an anion (preferably a non-nucleophilic anion).
• Preferred embodiments of the cation in the general formula (ZI) include the compound (ZI-1), the compound (ZI-2), the compound represented by the general formula (ZI-3) (compound (ZI-3)) and the corresponding group in the compound represented by the general formula (ZI-4) (compound (ZI-4)).
• the photoacid generator may be a compound having a plurality of structures represented by general formula (ZI). For example, it may be a compound having a structure in which at least one of R 201 to R 203 of the compound represented by general formula (ZI) and at least one of R 201 to R 203 of another compound represented by general formula (ZI) are bonded via a single bond or a linking group.
• Compound (ZI-1) is an arylsulfonium compound in which at least one of R 201 to R 203 in general formula (ZI) is an aryl group, that is, a compound having an arylsulfonium cation.
• 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.
• Arylsulfonium compounds include, for example, triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.
• the aryl group contained in the arylsulfonium compound 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 residues, furan residues, thiophene residues, indole residues, benzofuran residues, benzothiophene residues, and the like.
• the two or more aryl groups may be the same or different.
• the alkyl group or cycloalkyl group optionally possessed by the arylsulfonium compound is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms.
• the aryl group, alkyl group, and cycloalkyl group of R 201 to R 203 may each independently have an alkyl group (eg, 1 to 15 carbon atoms), a cycloalkyl group (eg, 3 to 15 carbon atoms), an aryl group (eg, 6 to 14 carbon atoms), an alkoxy group (eg, 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group as a substituent.
• Compound (ZI-2) is a compound in which R 201 to R 203 in formula (ZI) each independently represents an organic group having no aromatic ring.
• the aromatic ring also includes an aromatic ring containing a heteroatom.
• the organic group having no aromatic ring as R 201 to R 203 generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
• R 201 to R 203 are each independently preferably an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group or an alkoxycarbonylmethyl group, still more preferably a linear or branched 2-oxoalkyl group.
• the alkyl groups and cycloalkyl groups of R 201 to R 203 are preferably 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 (e.g., 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.
• M represents an alkyl group, a cycloalkyl group, or an aryl group, and when it has a ring structure, the ring structure may contain at least one of an oxygen atom, a sulfur atom, an ester bond, an amide bond, and a carbon-carbon double bond.
• R6c and R7c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
• R 6c and R 7c may combine to form a ring.
• R x and R y each independently represent an alkyl group, a cycloalkyl group, or an alkenyl group.
• R x and R y may combine to form a ring. Further, at least two selected from M, R 6c and R 7c may combine to form a ring structure, and the ring structure may contain a carbon-carbon double bond. Z ⁇ represents an anion.
• the alkyl group and cycloalkyl group represented by M are preferably a linear alkyl group having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms), a branched alkyl group having 3 to 15 carbon atoms (preferably 3 to 10 carbon atoms), or a cycloalkyl group having 3 to 15 carbon atoms (preferably 1 to 10 carbon atoms).
• the aryl group represented by M 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 sulfur atom, or the like.
• Heterocyclic structures include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, and the like.
• M above may further have a substituent.
• M may be a benzyl group.
• the ring structure may contain at least one of an oxygen atom, a sulfur atom, an ester bond, an amide bond, and a carbon-carbon double bond.
• Examples of the alkyl group, cycloalkyl group, and aryl group represented by R 6c and R 7c are the same as those for M described above, and preferred embodiments thereof are also the same. Also, R 6c and R 7c may combine to form a ring.
• Halogen atoms represented by R 6c and R 7c include, for example, fluorine, chlorine, bromine and iodine atoms.
• Examples of the alkyl group and cycloalkyl group represented by R x and R y are the same as those for M described above, and preferred embodiments thereof are also the same.
• the alkenyl group represented by R x and R y is preferably an allyl group or a vinyl group.
• R x and R y may further have a substituent.
• Examples of this embodiment include a 2-oxoalkyl group or an alkoxycarbonylalkyl group as R x and R y .
• Examples of the 2-oxoalkyl group represented by R x and R y include those having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms), and specific examples include 2-oxopropyl group and 2-oxobutyl group.
• Alkoxycarbonylalkyl groups represented by R x and R y include, for example, those having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms). Also, R x and R y may combine to form a ring. The ring structure formed by combining R x and R y may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbon-carbon double bond.
• M and R 6c may combine to form a ring structure, and the formed ring structure may contain a carbon-carbon double bond.
• Compound (ZI-3) above is preferably compound (ZI-3A).
• Compound (ZI-3A) is a compound represented by the following general formula (ZI-3A) and having a phenacylsulfonium salt structure.
• 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 cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group or an arylthio group.
• R 6c and R 7c have the same definitions as R 6c and R 7c in general formula (ZI-3) described above, and preferred embodiments thereof are also the same.
• R x and R y have the same meanings as R x and R y in general formula (ZI-3) described above, and preferred embodiments thereof are also the same.
• R 1c to R 5c and R x and R y may each be combined to form a ring structure, and this ring structure may each independently contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbon-carbon double bond.
• R 5c and R 6c , R 5c and R x may each combine to form a ring structure, and this ring structure may each independently contain a carbon-carbon double bond.
• R 6c and R 7c may be combined to form a ring structure.
• the ring structure include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocyclic rings, and polycyclic condensed rings in which two or more of these rings are combined.
• the ring structure includes a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.
• 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 a butylene group and a pentylene group.
• 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.
• the alkylene group includes a methylene group, an ethylene group, and the like.
• Zc- represents an anion.
• the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom.
• two R 15 are alkylene groups, preferably joined together to form a ring structure.
• Z ⁇ represents an anion.
• the alkyl groups of R 13 , R 14 and R 15 are linear or branched.
• the number of carbon atoms in the alkyl group is preferably 1-10.
• As the alkyl group a methyl group, an ethyl group, an n-butyl group, a t-butyl group, or the like is more preferable.
• R 204 to R 207 each independently represent an aryl group, an alkyl group or a cycloalkyl group.
• the aryl group represented by R 204 to R 207 is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
• the aryl group of R 204 to R 207 may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom, or the like.
• Skeletons of aryl groups having a heterocyclic structure include, for example, pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
• the alkyl and cycloalkyl groups represented by R 204 to R 207 are preferably linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, and pentyl groups), or cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, and norbornyl groups).
• Each of the aryl groups, alkyl groups and cycloalkyl groups of R 204 to R 207 may independently have a substituent.
• substituents that the aryl group, alkyl group and cycloalkyl group of R 204 to R 207 may have include an alkyl group (eg, 1 to 15 carbon atoms), a cycloalkyl group (eg, 3 to 15 carbon atoms), an aryl group (eg, 6 to 15 carbon atoms), an alkoxy group (eg, 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.
• Z ⁇ represents an anion.
• Z - in general formula (ZI), Z - in general formula (ZII), Z - in general formula (ZI-3), Zc - in general formula (ZI-3A), and Z - in general formula (ZI-4) are preferably anions represented by the following general formula (3).
• Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
• the number of carbon atoms in this alkyl group is preferably 1-10, more preferably 1-4.
• a perfluoroalkyl group is preferable as the alkyl group substituted with at least one fluorine atom.
• Xf is preferably a fluorine atom or a C 1-4 perfluoroalkyl group, more preferably a fluorine atom or CF 3 . In particular, it is more preferable that 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 may have substituents and preferably have 1 to 4 carbon atoms.
• R 4 and R 5 are preferably hydrogen atoms. Specific examples and preferred aspects of the alkyl group substituted with at least one fluorine atom are the same as the specific examples and preferred aspects of Xf in general formula (3).
• L represents a divalent linking group.
• each L may be the same or different.
• -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO 2 -, -COO-alkylene group-, -OCO-alkylene group-, -CONH-alkylene group- or -NHCO-alkylene group- is preferable, and -COO-, -OCO-, -CONH-, -SO 2 -, -COO-alkylene group- or -OCO-alkylene group- is more preferable.
• 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.
• Alicyclic groups may be monocyclic or polycyclic.
• Monocyclic alicyclic groups include, for example, monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
• polycyclic alicyclic groups examples include polycyclic cycloalkyl groups such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups.
• polycyclic cycloalkyl groups such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups.
• alicyclic groups having a bulky structure with 7 or more carbon atoms such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups, are preferred.
• Aryl groups may be monocyclic or polycyclic.
• the aryl group includes, for example, phenyl group, naphthyl group, phenanthryl group and anthryl group.
• a heterocyclic group may be monocyclic or polycyclic. The polycyclic type can further suppress acid diffusion. Moreover, the heterocyclic group may or may not have aromaticity. Heterocyclic rings having aromaticity include, for example, furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, and pyridine ring.
• Non-aromatic heterocycles include, for example, tetrahydropyran, lactone, sultone and decahydroisoquinoline rings.
• lactone ring and sultone ring include the lactone structure and sultone structure exemplified in the resins described above.
• the heterocyclic ring in the heterocyclic group is particularly 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 (which may be linear or branched, preferably having 1 to 12 carbon atoms), cycloalkyl groups (which may be monocyclic, polycyclic, or spirocyclic, preferably having 3 to 20 carbon atoms), aryl groups (preferably having 6 to 14 carbon atoms), hydroxyl groups, alkoxy groups, ester groups, amide groups, urethane groups, ureido groups, thioether groups, sulfonamide groups, and sulfonate ester groups.
• carbonyl carbon may be sufficient as carbon (carbon which contributes to ring formation) which comprises a cyclic
• the anions represented by the general formula (3) 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)qW, SO 3 — —C F 2 -CH(CF 3 )-OCO-(L)q'-W is preferred.
• L, q and W are the same as in general formula (3).
• q' represents an integer from 0 to 10;
• Z ⁇ in general formula (ZI), Z ⁇ in general formula (ZII), Z ⁇ in general formula (ZI-3), Zc ⁇ in general formula (ZI-3A), and Z ⁇ in general formula (ZI-4) are also preferably anions represented by the following general formula (4).
• X B1 and X B2 each independently represent a hydrogen atom or a monovalent organic group having no fluorine atom.
• X B1 and X B2 are preferably hydrogen atoms.
• X B3 and X B4 each independently represent a hydrogen atom or a monovalent organic group.
• At least one of X B3 and X B4 is preferably a fluorine atom or a monovalent organic group having a fluorine atom, more preferably both X B3 and X B4 are a fluorine atom or a monovalent organic group having a fluorine atom. More preferably, both X B3 and X B4 are fluorine-substituted alkyl groups.
• L, q and W are the same as in general formula (3).
• Z ⁇ in general formula (ZI), Z ⁇ in general formula (ZII), Z ⁇ in general formula (ZI-3), Zc ⁇ in general formula (ZI-3A), and Z ⁇ in general formula (ZI-4) may be a benzenesulfonate anion, preferably a benzenesulfonate anion substituted with a branched-chain alkyl group or a cycloalkyl group.
• Z - in general formula (ZI), Z - in general formula (ZII), Z - in general formula ( ZI-3), Zc - in general formula (ZI-3A), and Z - in general formula (ZI-4) are also preferably aromatic sulfonate anions represented by the following general formula (SA1).
• Ar represents an aryl group and may further have a substituent other than the sulfonate anion and -(D-B) group.
• Substituents which may be further included include 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
• D is a single bond and B is an aliphatic hydrocarbon structure.
• B is more preferably an isopropyl group or a cyclohexyl group.
• Any combination of the above cations and anions can be used as a photoacid generator.
• the above cations or anions may have a lactone group.
• the lactone group any group having a lactone structure can be used, but a group having a 5- to 7-membered ring lactone structure is preferable, and the 5- to 7-membered lactone structure is preferably condensed with another ring structure to form a bicyclo structure or a spiro structure.
• a group having a lactone structure represented by any one of the following general formulas (LC1-1) to (LC1-17) is more preferred.
• the lactone structure groups represented by general formula (LC1-1), general formula (LC1-4), general formula (LC1-5), general formula (LC1-6), general formula (LC1-13), and general formula (LC1-14) are preferred.
• the lactone structure portion 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, carboxyl groups, halogen atoms, hydroxyl groups, cyano groups, and acid-decomposable groups.
• n2 represents an integer of 0-4. When n2 is 2 or more, multiple Rb 2 may be different, and multiple Rb 2 may combine to form a ring.
• the pKa of the acid generated from the photoacid generator is preferably -10 or more and 5 or less, more preferably -5 or more and 1 or less.
• the photoacid generator may be in the form of a low-molecular-weight compound, or may be in the form of being incorporated into a part of the polymer. Moreover, the form of a low-molecular-weight compound and the form incorporated into a part of a polymer may be used in combination.
• the photoacid generator is preferably in the form of a low molecular weight compound. When the photoacid generator is in the form of a low-molecular-weight compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, even more preferably 1,000 or less.
• a photo-acid generator may be used individually by 1 type, and may use 2 or more types together.
• Compound (C) 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 of the following structural moieties X and one or more of the following structural moieties Y, and is a compound that generates an acid containing the following first acidic moieties derived from the following structural moieties X and the following second acidic moieties derived from the following structural moieties Y upon irradiation with actinic rays or radiation.
• Structural site X A structural site consisting of an anionic site A 1 ⁇ and a cationic site M 1 + and forming a first acidic site represented by HA 1 upon irradiation with actinic rays or radiation.
• Structural site Y A structural site consisting of an anionic site A 2 ⁇ and a cation site M 2 + and forming a second acidic site represented by HA 2 upon irradiation with actinic rays or radiation.
• the 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 + is represented by HA 2 in which the acid dissociation constant a1 derived from the acidic site is represented by HA 1 in which the cation site M 1 + in the structural site X is replaced by H + and HA 2 in which the cation site M 2 + in the structural site Y is replaced by H + . It has an acid dissociation constant a2 derived from an acidic site, and the acid dissociation constant a2 is greater than the acid dissociation constant a1.
• compound (I) is a compound that generates an acid having one first acidic site derived from structural site X and one second acidic site derived from structural site Y
• compound PI corresponds to "a compound having HA 1 and HA 2 ".
• the acid dissociation constant a1 and the acid dissociation constant a2 of the compound PI are determined, the pKa when the compound PI becomes a "compound containing A 1 - and HA 2 " is the acid dissociation constant a1, and the pKa when the above "compound containing A 1 - and HA 2 " becomes a "compound containing A 1 - and A 2 - " is the acid dissociation constant a2.
• compound (I) is a compound that generates an acid having two first acidic sites derived from structural site X and one second acidic site derived from structural site Y
• compound PI corresponds to "a compound having two HA 1 and one HA 2 ".
• the acid dissociation constant of the compound PI is determined, the acid dissociation constant when the compound PI becomes "a compound having one A 1 - , one HA 1 and one HA 2" and the acid dissociation constant when "a compound having one A 1 -, one HA 1 and one HA 2 " becomes a "compound having two A 1 - and one HA 2 " correspond 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 compound PI, when it has a plurality of acid dissociation constants derived from the acidic site HA 1 obtained by replacing the cationic site M 1 + in the structural site X with H + , the value of the acid dissociation constant a2 is larger than the largest value among the plurality of acid dissociation constants a1.
• 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, more preferably 0.5 or more, and even more preferably 1.0 or more.
• 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.
• Anion site A 1 - and anion site A 2 - are structural sites containing negatively charged atoms or atomic groups, and examples thereof include structural sites selected from the group consisting of formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6) shown below.
• the anion site A 1 - is preferably one capable of forming an acidic site with a small acid dissociation constant, more preferably one of the formulas (AA-1) to (AA-3), more preferably one of the formulas (AA-1) and (AA-3).
• the anion site A 2 - is preferably one capable of forming an acidic site having a larger acid dissociation constant than the anion site A 1 - , more preferably any one of the formulas (BB-1) to (BB-6), further preferably any one of the formulas (BB-1) and (BB-4).
• * represents a bonding position.
• RA represents a monovalent organic group.
• the monovalent organic group represented by RA is not particularly limited, examples thereof include a cyano group, a trifluoromethyl group and a methanesulfonyl group.
• the cation site M 1 + and the cation site M 2 + are structural sites containing positively charged atoms or atomic groups, such as monovalent organic cations.
• Examples of organic cations include organic cations represented by M + described above.
• Compound (II) is a compound having two or more of the above structural moieties X and one or more of the following structural moieties Z, and is a compound that generates an acid containing two or more of the above first acidic moieties derived from the above structural moieties X and the above structural moieties Z upon exposure to actinic rays or radiation.
• 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 HA 1 in which the cationic site M + in the structural site X is replaced with H + is the same as the acid dissociation constant a1 in the compound PI.
• compound (II) is, for example, a compound that generates an acid having two first acidic sites derived from structural site X and structural site Z
• compound PII corresponds to "a compound having two HA 1 ".
• the acid dissociation constant when the compound PII becomes a "compound having one A 1 - and one HA 1 " and the acid dissociation constant when a "compound having one A 1 - and one HA 1 " becomes a "compound having two A 1 - " correspond to the acid dissociation constant a1.
• the acid dissociation constant a1 is obtained by the method for measuring the acid dissociation constant described above.
• the above compound PII corresponds to an acid generated when compound (II) is irradiated with actinic rays or radiation.
• the two or more structural sites X may be the same or different.
• Two or more of A 1 ⁇ and two or more of M 1 + may be the same or different.
• the acid-neutralizing nonionic site in the structural site Z is not particularly limited, and is preferably, for example, a group capable of electrostatically interacting with protons or a site containing a functional group having electrons.
• Groups capable of electrostatically interacting with protons or functional groups having electrons include functional groups having macrocyclic structures such as cyclic polyethers, or functional groups having nitrogen atoms with lone pairs of electrons that do not contribute to ⁇ conjugation.
• 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.
• Examples of partial structures of functional groups having electrons or groups capable of electrostatically interacting with protons include crown ether structures, azacrown ether structures, primary to tertiary amine structures, pyridine structures, imidazole structures, and pyrazine structures, among which primary to tertiary amine structures are preferred.
• the content of the component (C) (photoacid generator) (the total when multiple types are present) is based on the total solid content of the composition of the present invention.
• a photoacid generator when the compound represented by the general formula (ZI-3) or (ZI-4) is contained, the content of the photoacid generator contained in the composition (if there are multiple types, the total) is preferably 1 to 35% by mass, more preferably 1 to 30% by mass, based on the total solid content of the composition.
• the composition of the present invention may contain an acid diffusion control agent.
• the acid diffusion control agent traps the acid generated from the photoacid generator or the like during exposure, and acts as a quencher that suppresses the reaction of the acid-decomposable resin in the unexposed area due to excess generated acid.
• the type of acid diffusion control agent is not particularly limited, and examples thereof include basic compounds (CA), low-molecular-weight compounds (CB) having a group that has a nitrogen atom and leaves by the action of an acid, and compounds (CC) whose acid diffusion control ability is reduced or lost by irradiation with actinic rays or radiation.
• Examples of the compound (CC) include onium salt compounds (CD), which are relatively weak acids with respect to the photoacid generator, and basic compounds (CE), whose basicity is reduced or lost by irradiation with actinic rays or radiation.
• Specific examples of the basic compound (CA) include, for example, those described in paragraphs [0132] to [0136] of WO 2020/066824, and specific examples of the basic compound (CE) whose basicity is reduced or lost by irradiation with actinic rays or radiation include those described in paragraphs [0137] to [0155] of WO 2020/066824, and WO 2020/ Those described in paragraph [0164] of JP-A-066824 can be mentioned, and specific examples of the low-molecular compound (CB) having a nitrogen atom and a group that leaves under the action of an acid include those described in paragraphs [0156] to [0163] of International Publication No. 2020/066824.
• 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 [0403] to [0423] of US Patent Application Publication No. 2016/0237190A1 paragraphs [0403] to [0423] of US Patent Application Publication No. 2016/0237190A1
• US Patent Application Publication No. 2016 The known compounds disclosed in paragraphs [0259] to [0328] of JP/0274458A1 can be suitably used as the acid diffusion control agent.
• the content of the acid diffusion control agent (the total when multiple types are present) is preferably 0.1 to 15.0% by mass, more preferably 1.0 to 15.0% by mass, based on the total solid content of the composition of the present invention.
• one type of acid diffusion control agent may be used alone, or two or more types may be used in combination.
• the composition of the present invention may further contain a hydrophobic resin (also referred to as “hydrophobic resin (D)”) different from resin (A).
• the hydrophobic resin (D) is preferably designed to be unevenly distributed on the surface of the resist film, but unlike surfactants, it does not necessarily have a hydrophilic group in its molecule, and it does not have to contribute to uniform mixing of polar and non-polar substances.
• the effects of adding the hydrophobic resin (D) 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 (D) preferably has one or more of fluorine atoms, silicon atoms, and CH3 partial structures contained in the side chain portion of the resin, more preferably two or more.
• 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.
• the hydrophobic resin (D) includes compounds described in paragraphs [0275] to [0279] of WO2020/004306.
• the content of the hydrophobic resin (D) is preferably 0.01 to 20.0% by mass, more preferably 0.1 to 15.0% by mass, based on the total solid content of the composition of the present invention.
• 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 surfactant may be used alone, or two or more types may be used.
• the content of the surfactant is preferably 0.0001 to 2.0% by mass, more preferably 0.0005 to 1.0% by mass, and even more preferably 0.1 to 1.0% by mass, relative to the total solid content of the composition of the present invention.
• the composition of the invention preferably contains a solvent.
• the solvent preferably contains at least one selected from the group consisting of (M1) propylene glycol monoalkyl ether carboxylate and (M2) propylene glycol monoalkyl ether, lactic acid ester, acetic acid ester, alkoxypropionic acid ester, chain ketone, cyclic ketone, lactone, and alkylene carbonate.
• the solvent may further contain components other than components (M1) and (M2).
• a combination of the above-described solvent and the above-described resin is preferable from the viewpoint of improving the coatability of the composition of the present invention and reducing the number of pattern development defects. Since the solvent described above has a good balance of solubility, boiling point, and viscosity of the resin described above, it is possible to suppress unevenness in the thickness of the resist film and generation of deposits during spin coating. Details of component (M1) and component (M2) are described in paragraphs [0218] to [0226] of WO2020/004306, the contents of which are incorporated herein.
• the content of components other than components (M1) and (M2) is preferably 5 to 30% by mass relative to the total amount of the solvent.
• the content of the solvent in the composition of the present invention is preferably determined so that the solid content concentration is 0.5 to 30% by mass, more preferably 1 to 20% by mass. By doing so, the coatability of the composition of the present invention can be further improved.
• composition of the present invention may further contain a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and/or a compound that promotes solubility in a developer (e.g., a phenol compound having a molecular weight of 1000 or less, or an alicyclic or aliphatic compound containing a carboxyl group).
• a dissolution inhibiting compound e.g., a phenol compound having a molecular weight of 1000 or less, or an alicyclic or aliphatic compound containing a carboxyl group.
• the “dissolution-inhibiting compound” is a compound with a molecular weight of 3000 or less, which is decomposed by the action of an acid to reduce its solubility in an organic developer.
• the composition of the present invention 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 influence of "photon shot noise", in which the number of photons stochastically varies, is large, leading to deterioration of line edge roughness (LER) and bridge defects.
• LER line edge roughness
• To reduce the photon shot noise there is a method of increasing the number of incident photons by increasing the amount of exposure, but this is a trade-off with the demand for higher sensitivity.
• the EUV light and electron beam absorption efficiency of the resist film formed from the resist composition increases, which is effective in reducing photon shot noise.
• the A value represents the absorption efficiency of the EUV light and the electron beam relative to the mass ratio of the resist film.
• A ([H] x 0.04 + [C] x 1.0 + [N] x 2.1 + [O] x 3.6 + [F] x 5.6 + [S] x 1.5 + [I] x 39.5) / ([H] x 1 + [C] x 12 + [N] x 14 + [O] x 16 + [F] x 19 + [S] x 32 + [I] x 127)
• the A value is preferably 0.120 or more. Although 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.
• [H] represents the molar ratio of hydrogen atoms derived from the total solid content with respect 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 with respect to the total atoms of the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition
• [O] represents the molar ratio of oxygen atoms derived from all solids to all atoms of all solids in the actinic ray- or radiation-sensitive resin composition
• [F] represents the molar ratio of fluorine atoms derived from all solids to all atoms of all solids in the actinic ray-sensitive or radiation-sensitive resin composition
• [S] represents the molar ratio of sulfur atoms derived from all solids to all atoms of all solids in the actinic ray-sensitive or radiation-sensitive resin composition
• [I] represents actinic ray-sensitive.
• 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. That is, 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 all atoms in the total solid content
• [H] represents the total molar ratio of the hydrogen atoms derived from the acid-decomposable resin, the photoacid generator-derived hydrogen atoms, and the acid diffusion control agent-derived hydrogen atoms to the total of all atoms derived from the acid-decomposable resin, all atoms derived from the photoacid generator, and all atoms derived from the acid 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. Moreover, even if the constituent components are unknown, it is possible to calculate the constituent atomic number ratio of the resist film obtained by evaporating the solvent component of the resist composition by analytical techniques such as elemental analysis.
• the actinic ray-sensitive or radiation-sensitive resin composition of the present invention may be in the mode shown below (also referred to as "the composition of the second mode").
• Second aspect Actinic ray-sensitive or radiation-sensitive resin composition containing at least the following (AX), (B) and (C).
• AX a repeating unit (ax1) having an acid group with a pKa of 8.0 or more and 12.0 or less; a repeating unit (a2) having an acid group with a pKa of less than 8.0;
• B a repeating unit (b1) having a phenolic hydroxyl group, and a repeating unit (a3) containing at least one fluorine atom and having no acid group and having a pKa of 12.0 or less, and having a dissolution rate of 0.002 nm/s or more in an alkaline developer for a film of the resin alone.
• a repeating unit (b2) having a group that decomposes under the action of an acid and increases in polarity; and does not contain repeating units that generate acid upon irradiation with actinic rays or radiation
• C Compound that generates acid upon irradiation with actinic rays or radiation
• the composition of the second aspect is the same as the composition of the present invention described above, except that the component (AX) is included instead of the component (A).
• the (AX) component is also called resin (AX).
• the resin (AX) has a dissolution rate of 0.002 nm/s or more, preferably 0.005 nm/s or more, more preferably 0.01 nm/s or more, in an alkaline developer for a film of the resin (AX) alone.
• the upper limit of the dissolution rate is preferably 100 nm/s or less.
• the method of determining the dissolution rate of a film of resin alone in an alkaline developer is as described above.
• the resin (AX) is preferable because the dissolution rate of the film of the resin alone in an alkaline developer is 0.002 nm/s or more, so that the developability is excellent and the LWR performance is further improved.
• the rate of dissolution of the resin-only film in an alkaline developer can be adjusted by the content ratio of the repeating unit (ax1), the repeating unit (a2) and the repeating unit (a3), the molecular weight, and the like.
• the resin (AX) is the same as the resin (A) described above except that it contains a repeating unit (ax1) instead of the repeating unit (a1).
• the structure of the repeating unit (ax1) of the resin (AX) is not particularly limited, it is preferably represented by the general formula (a1-1) or (a1-2).
• the description, specific examples and preferred range of the repeating unit (ax1) of the resin (AX) are the same as those described for the repeating unit (a1) above.
• the present invention also relates to an actinic ray-sensitive or radiation-sensitive film formed from the composition of the present invention (hereinafter, "the composition of the present invention” also includes the aforementioned "second aspect composition”).
• the actinic ray-sensitive or radiation-sensitive film of the present invention is preferably a resist film.
• the procedure of the pattern forming method using the composition of the present invention is not particularly limited, it preferably includes the following steps.
• Step 1 Using the composition of the present invention, a step of forming a resist film on a substrate
• Step 2 A step of exposing the resist film
• Step 3 A step of developing the exposed resist film using a developer
• Step 1 is a step of forming a resist film on a substrate using the composition of the present invention.
• Examples of the method of forming a resist film on a substrate using the composition of the present invention include a method of applying the composition of the present invention onto 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 number of rotations for spin coating using a spinner is preferably 1000 to 3000 rpm (rotations per minute).
• the substrate may be dried to form a resist film. If necessary, various base films (inorganic film, organic film, antireflection film) may be formed under the resist film.
• Heating can be carried out by a means provided in a normal exposure machine and/or a developing machine, and may be carried out using a hot plate or the like.
• the heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, even more preferably 80 to 130°C.
• the heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, even more preferably 60 to 600 seconds.
• the film thickness of the resist film is not particularly limited, it is preferably 10 to 120 nm from the viewpoint of forming fine patterns with higher precision.
• the film thickness of the resist film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm.
• the film thickness of the resist 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 resist film. It is preferable that the topcoat composition does not mix with the resist film and can be uniformly coated on the upper layer of the resist film.
• the topcoat is not particularly limited, and a conventionally known topcoat can be formed by a conventionally known method. For example, it is preferable to form a topcoat containing a basic compound as described in JP-A-2013-61648 on the resist film.
• Specific examples of basic compounds that the topcoat may contain include basic compounds that the composition of the present invention may contain.
• the topcoat also preferably contains a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond.
• Step 2 is a step of exposing the resist film.
• the exposure method include a method of irradiating the formed resist film with actinic rays or radiation through a predetermined mask.
• Actinic rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, preferably 250 nm or less, more preferably 220 nm or less, far ultraviolet light with a wavelength of 1 to 200 nm, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), EUV (13.5 nm). , X-rays and electron beams are particularly preferred.
• baking is preferably performed before development. Baking accelerates the reaction in the exposed area, resulting in better sensitivity and pattern shape.
• the heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, even more preferably 80 to 130°C.
• the heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, even more preferably 30 to 120 seconds. Heating can be carried out by a means provided in a normal exposing machine and/or developing machine, and may be carried out using a hot plate or the like. This step is also called a post-exposure bake.
• Step 3 is a step of developing the exposed resist film using a developer to form a pattern.
• the developer may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer).
• Examples of the development method include a method of immersing the substrate in a tank filled with the developer for a certain period of time (dip method), a method of building up the developer on the substrate surface by surface tension and allowing it to stand still for a certain period of time (paddle 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 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, but examples include aqueous alkaline solutions containing quaternary ammonium salts typified by tetramethylammonium hydroxide, inorganic alkalis, primary amines, secondary amines, tertiary amines, alcohol amines, or cyclic amines.
• the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt represented by tetramethylammonium hydroxide (TMAH). Suitable amounts of alcohols, surfactants and the like may be added to the alkaline developer.
• the alkali concentration of the alkali developer is usually preferably 0.1 to 20% by mass.
• the pH of the alkaline developer is preferably 10.0 to 15.0.
• the organic developer is preferably 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.
• 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, more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less.
• 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. It is preferable to use a rinse solution containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.
• the method of the rinsing step is not particularly limited, and examples thereof include a method of continuously discharging the rinsing liquid onto the substrate rotating at a constant speed (rotation coating method), a method of immersing the substrate in a bath filled with the rinsing liquid for a certain period of time (dip method), and a method of spraying the rinsing 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 of processing the substrate (or the underlying film and the substrate) is not particularly limited, but a method of forming a pattern on the substrate by dry etching the substrate (or the underlying film and the substrate) using the pattern formed in step 3 as a mask is preferred. Dry etching is preferably oxygen plasma etching.
• the composition of the present invention and various materials used in the pattern forming method preferably do not contain impurities such as metals.
• the content of impurities contained in these materials is preferably 1 mass ppm (parts per million) or less, more preferably 10 mass ppb (parts per billion) or less, even more preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, 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 that constitute various materials, a method of filtering the raw materials that constitute various materials, and a method of performing distillation under conditions that suppress contamination as much as possible by lining the inside of the equipment 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.
• a conductive compound may be added to the organic treatment liquid such as the rinse liquid in order to prevent damage to the 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 solution 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.).
• AP-1 to AP-13 were used as the resin (A).
• RAP-1 to RAP-4 were used as resins other than resin (A).
• RAP-1 to RAP-4 are also listed in the column of resin (A) in Table 3 below.
• AP-1 to AP-13 and RAP-1 to RAP-4 each contain repeating units shown in Table 1 below in the molar ratio shown in Table 1. Each repeating unit is indicated by the structure of the corresponding monomer. Although the repeating unit formed by the corresponding monomer MX contained in RAP-2 does not correspond to the repeating unit (a1), it is described in the repeating unit (a1) column for convenience.
• Table 1 also shows the dissolution rate of the film of each resin alone in an alkaline developer (referred to as "V A " in Table 1).
• the weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) (in terms of polystyrene).
• the content of repeating units was measured by 13 C-NMR (nuclear magnetic resonance).
• V A Dissolution rate (V A ) of film of resin alone in alkaline developer
• HMDS hexamethyldisilazane
• Table 2 shows the content (mol %), weight average molecular weight (Mw), and degree of dispersion (Mw/Mn) of each repeating unit contained in each resin.
• the content of repeating units is the ratio (molar ratio) of each repeating unit to all repeating units contained in each resin.
• the value of the repeating unit content of each resin corresponds to the order of description of the repeating unit in the structural formula of each resin shown below.
• the weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) (in terms of polystyrene).
• the content of repeating units was measured by 13 C-NMR (nuclear magnetic resonance).
• ⁇ Preparation of resist composition> The components shown in Table 3 were dissolved in the solvent shown in Table 3 to prepare a solution having a solid concentration shown in Table 3, and filtered through a polyethylene filter having a pore size of 0.02 ⁇ m to prepare a resist composition.
• solid content means all the components other than a solvent.
• the resulting resist compositions were used in Examples and Comparative Examples.
• the "% by mass” column indicates the content (% by mass) of each component with respect to the total solid content in the resist composition.
• the type of each compound used and its ratio (mass ratio) are described. When a surfactant was used, it was added in an amount of 0.1% by mass relative to the total solid content in the resist composition.
• ⁇ Pattern Forming Method (1) EB Exposure, Alkaline Development (Positive)>
• the prepared resist composition was coated on a 6-inch Si wafer previously treated with hexamethyldisilazane (HMDS) using a Tokyo Electron spin coater Mark 8, and dried on a hot plate at 100° C. for 60 seconds to obtain a resist film with a thickness of 100 nm. Similar results can be obtained by replacing the Si wafer with a chromium substrate.
• the wafer coated with the resist film obtained above was subjected to pattern irradiation using an electron beam lithography system (HL750 manufactured by Hitachi, Ltd., acceleration voltage 50 keV). At this time, drawing was performed so as to form a line and space of 1:1.
• HL750 electron beam lithography system
• the wafer was heated on a hot plate at 100° C. for 60 seconds, developed with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide for 30 seconds, rinsed with pure water, rotated at 4000 rpm for 30 seconds, and then heated at 95° C. for 60 seconds to obtain a 1:1 line-and-space resist pattern with a line width of 50 nm.
• the cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-4300 manufactured by Hitachi, Ltd.).
• the sensitivity (Eopt) was defined as the exposure dose (electron beam dose) when resolving a 1:1 line-and-space resist pattern with a line width of 50 nm.
• the line width dimension of a 1:1 line and space pattern with a line width of 50 nm and a space width of 50 nm was 50 nm.
• the line width dimension (L0h) when PEB processing was performed immediately after exposure and the line width dimension (L2h) when PEB processing was performed 1 hour after exposure were measured, and the line width change rate was calculated by the following formula.
• Heating was performed at 100° C. for 60 seconds.
• Line width change rate (%) 100 ⁇ (L2h - L0h) nm / 50 nm A smaller value indicates better performance and was used as an indicator of PED stability.
• B or more is preferable practically, and A is more preferable.
• C Line width change rate is 5% or more and less than 10%
• D Line width change rate is 10% or more
• the prepared resist composition was coated on a 6-inch Si wafer previously treated with hexamethyldisilazane (HMDS) using a Tokyo Electron spin coater Mark 8, and dried on a hot plate at 100° C. for 60 seconds to obtain a resist film with a thickness of 100 nm.
• TMAH tetramethylammonium hydroxide
• the actinic-ray-sensitive or radiation-sensitive resin composition which is excellent in LWR performance and PED stability can be provided. Further, the present invention can provide an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and an electronic device manufacturing method using the actinic ray-sensitive or radiation-sensitive resin composition.

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  • 2023-01-13 WO PCT/JP2023/000787 patent/WO2023140191A1/ja unknown
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