Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
  • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
  • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
  • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
  • C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D307/20—Oxygen atoms
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
  • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/30—Imagewise removal using liquid means
  • G03F7/32—Liquid compositions therefor, e.g. developers
  • G03F7/325—Non-aqueous compositions

Definitions

• the present invention relates to an actinic ray- or radiation-sensitive resin composition, a resist film, a pattern forming method, and a method for manufacturing an electronic device.
• An actinic ray-sensitive or radiation-sensitive resin film (hereinafter also referred to as a "resist film”) formed using an actinic ray-sensitive or radiation-sensitive resin composition (hereinafter also referred to as a "resist composition”) containing a photoacid generator is exposed to light to generate an acid from the photoacid generator.
• the acid is used as a catalyst to change the solubility of the resin contained in the resist composition in a developer (e.g., an alkaline aqueous solution or an organic solvent). Thereafter, the exposed or unexposed portion of the resist film is removed using the developer to obtain a desired pattern.
• Patent Document 1 discloses a resist composition that "contains a base component whose solubility in a developer changes under the action of an acid, a compound having a specific structure and consisting of an anion moiety and a cation moiety, and a fluorine additive that contains a fluorine resin component having specific structural units.”
• the one or more photoacid generators and the first acid diffusion controller or the second acid diffusion controller may be bonded via a covalent bond.
• an actinic ray-sensitive or radiation-sensitive resin composition capable of forming a resist pattern with small LWR.
• the present invention can also provide a resist film formed using the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition, as well as a pattern forming method and a device manufacturing method using the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition.
• a numerical range expressed using “ ⁇ ” means a range that includes the numerical values written before and after " ⁇ " as the lower and upper limits.
• an "alkyl group” includes not only an alkyl group that has no substituents (unsubstituted alkyl group) but also an alkyl group that has a substituent (substituted alkyl group).
• a monovalent substituent is preferred.
• an "organic group” refers to a group containing at least one carbon atom.
• halogen atoms include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
• the bonding direction of the divalent linking group is not limited unless otherwise specified.
• Y when Y is -COO- in a compound represented by the formula "X-Y-Z", Y may be -CO-O- or -O-CO-. That is, the compound may be "X-CO-O-Z" or "X-O-CO-Z".
• (meth)acrylate refers to acrylate and methacrylate
• (meth)acrylic refers to acrylic and methacrylic.
• actinic rays or “radiation” refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light: extreme ultraviolet), X-rays, and electron beams (EB).
• light means actinic rays or radiation.
• exposure includes not only exposure to the emission line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV: extreme ultraviolet), X-rays, and the like, but also drawing with particle beams such as electron beams and ion beams.
• ppm means “parts-per-million (10 -6 )
• ppb means “parts-per-billion (10 -9 )
• ppt means “parts-per-trillion (10 -12 ).”
• 1 ⁇ is equal to 1 ⁇ 10 ⁇ 10 m.
• Mw weight average molecular weight
• Mn number average molecular weight
• dispersity hereinafter also referred to as "molecular weight distribution”
• Mw/Mn polystyrene equivalent values measured using a Gel Permeation Chromatography (GPC) device (Tosoh Corporation HLC-8120GPC) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 ⁇ L, column: Tosoh Corporation TSK gel Multipore HXL-M, column temperature: 40°C, flow rate: 1.0 mL/min, detector: differential refractive index detector).
• GPC Gel Permeation Chromatography
• the acid dissociation constant (pKa) refers to the pKa in an aqueous solution.
• DMSO dimethyl sulfoxide
• the pKa can be calculated, for example, by calculation based on the database of Hammett's substituent constants and known literature values, and by using molecular orbital calculation method.
• Specific methods of molecular orbital calculation method include a method of calculating by calculating H + dissociation free energy in aqueous solution based on thermodynamic cycle.
• the calculation method of H + dissociation free energy can be calculated, for example, by DFT (density functional theory), but there are various other methods reported in literature, etc., and it is not limited thereto.
• pKa is a value calculated using the following software package 1 based on a database of Hammett's substituent constants and known literature values.
• the acid dissociation constants A, B, and C are values calculated using the above-mentioned software package 1 for an acidic compound in which all cationic sites in the complex are replaced with protons. More specifically, for example, in a composite formed by bonding one photoacid generator and one acid diffusion controller via a covalent bond, two acid dissociation constants are calculated using the above-mentioned software package 1 for an acidic compound in which all cations in the composite are replaced with protons, and if the calculated acid dissociation constant is ⁇ 1.50 or less, it is considered to correspond to acid dissociation constant A, and if the calculated acid dissociation constant is more than ⁇ 1.50, it is considered to correspond to acid dissociation constant B (or acid dissociation constant C).
• the ClogP value is a value obtained by calculating the common logarithm logP of the partition coefficient P between 1-octanol and water. Any known method and software can be used to calculate the ClogP value, but unless otherwise specified, in this invention, the structure is drawn using ChemDraw Professional (version 20.1.1.125) manufactured by PerkinElmer, and the value calculated using the above software is used.
• Solids refers to the components that form the resist film, and does not include solvents. In addition, if a component forms a resist film, it is considered to be a solid even if it is in liquid form.
• acid diffusion control agent refers to a concept that includes a first acid diffusion control agent and a second acid diffusion control agent.
• the actinic ray-sensitive or radiation-sensitive resin composition (hereinafter, also referred to as "resist composition") of the present invention will be described in detail below.
• the resist composition of the present invention comprises a resin whose polarity increases under the action of an acid, one or more photoacid generators; a first acid diffusion controller comprising a first cation and a first anion; a second acid diffusion control agent comprising a second cation and a second anion; the photoacid generator is composed of a cation and an anion and generates an acid when irradiated with actinic rays or radiation; an acid dissociation constant A of an acidic compound obtained by replacing a cation in the photoacid generator with a proton is ⁇ 1.50 or less; an acid dissociation constant B of an acidic compound obtained by replacing the first cation of the first acid diffusion controller with a proton, and an acid dissociation constant C of an acidic compound obtained by
• the present inventors speculate as follows.
• the mechanism by which the effects are obtained is not limited by the following speculation. In other words, even if the effects are obtained by a mechanism other than the following, it is included in the scope of the present invention.
• the resist film prepared using the resist composition of the present invention is exposed to light, and the exposed resist film is developed using a developer to obtain a resist pattern.
• the polarity of the specific resin is increased by the acid generated from the photoacid generator, so that the exposed portion becomes more hydrophilic than the unexposed portion, and a difference in solubility in the developer (dissolution contrast) occurs between the exposed portion and the unexposed portion, making it possible to form a pattern.
• the greater the difference in dissolution contrast the better the LWR performance, and therefore it is preferable.
• the above exposure treatment although light is irradiated through a mask, some light leaks, so that acid is generated from a part of the photoacid generator not only in the exposed area but also in the unexposed area.
• the difference in dissolution contrast becomes small, which is not preferable, but it is possible to quench the acid generated in the unexposed area by including an acid diffusion controller.
• the first acid diffusion controller is relatively hydrophilic and therefore easily diffuses into the hydrophilic exposed area, and can quench the acid at the boundary between the exposed area and the unexposed area.
• the second acid diffusion controller is relatively hydrophobic and therefore remains in the hydrophobic unexposed area without diffusing. Even if the first acid diffusion controller diffuses to the exposed area side and acid remains in the unexposed area, it can be quenched by the second acid diffusion controller. Therefore, it is presumed that the first acid diffusion controller quenches the acid in the boundary area, and the second acid diffusion controller quenches the acid in the unexposed area, thereby enabling the formation of a pattern with excellent LWR performance.
• the resist composition of the present invention contains a resin whose polarity increases under the action of an acid (hereinafter, also referred to as a "specific resin”).
• the specific resin preferably has a group that decomposes under the action of an acid to increase its polarity (hereinafter, also referred to as an "acid-decomposable group”), and more preferably contains a repeating unit having an acid-decomposable group.
• an acid-decomposable group typically, in the pattern formation method of the present invention, 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.
• the repeating unit having an acid-decomposable group include a repeating unit having an acid-decomposable group and a repeating unit having an acid-decomposable group containing an unsaturated bond.
• the specific resin preferably contains a repeating unit having an acid-decomposable group.
• the acid-decomposable group refers to a group that is decomposed by the action of an acid to generate a polar group.
• the acid-decomposable group preferably has a structure in which a polar group is protected by a group that is eliminated by the action of an acid (a leaving group).
• the specific resin preferably has a repeating unit having a group that decomposes under the action of an acid to generate a polar group, and the resin having this repeating unit has increased polarity under the action of an acid, thereby increasing its solubility in an alkaline developer and decreasing its solubility in an organic solvent.
• the polar group is preferably an alkali-soluble group, and examples thereof include acidic groups such as a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphate 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(alkylsulfonyl)methylene group, as well as an alcoholic hydroxyl group.
• acidic groups
• the polar group is preferably a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group, and more preferably a carboxy group or a phenolic hydroxyl group.
• Examples of the leaving group which is eliminated by the action of an acid include groups represented by the formulae (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)
• Rx 1 to Rx 3 each preferably independently represent an alkyl group or a cycloalkyl group, and more preferably represent a linear alkyl group.
• the alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group.
• cycloalkyl group examples include monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, and polycyclic cycloalkyl groups such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.
• the aryl group is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.
• the alkenyl group is preferably a vinyl group.
• Rx 1 to Rx 3 may be bonded to form a monocycle or polycycle.
• the ring formed by combining two of Rx 1 to Rx 3 is preferably a cycloalkyl group, more 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 tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms, or a polycyclic cycloalkyl group having 6 to 12 carbon atoms.
• one of the methylene groups constituting the ring may be replaced by a heteroatom such as an oxygen atom or a sulfur atom, a carbonyl group, a group containing a heteroatom such as an -SO2- group or an -SO3- group, or a vinylidene group.
• one or more of the ethylene groups constituting the cycloalkane ring may be replaced by a vinylene group.
• Rx1 is preferably a methyl group or an ethyl group, and Rx2 and Rx3 are bonded to form the above-mentioned cycloalkyl group.
• the resist composition is, for example, a resist composition for EUV exposure, it is also preferable that the groups represented by Rx 1 to Rx 3 and the rings formed by bonding two of Rx 1 to Rx 3 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, and R 37 and R 38 may be bonded to each other to form a ring.
• the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group.
• Preferred embodiments of the alkyl group, cycloalkyl group, aryl group and aralkyl group are the same as those of the groups represented by Rx 1 to Rx 3 above. It is also preferable that R 36 is a hydrogen atom.
• one or more methylene groups may be replaced by a heteroatom-containing group such as an oxygen atom or a sulfur atom, a carbonyl group, a -SO 2 - group, or a -SO 3 - group.
• R 38 may be bonded to another substituent in the main chain of the repeating unit to form a ring.
• the group formed by bonding R 38 to another substituent in the main chain of the repeating unit is preferably an alkylene group such as a methylene group.
• the groups represented by R 36 to R 38 and the ring formed by bonding R 37 and R 38 further have a fluorine atom or an iodine atom as a substituent.
• Ar represents an aromatic ring group.
• Rn represents an alkyl group, a cycloalkyl group, or an aryl group.
• Rn and Ar may be bonded to each other to form a non-aromatic ring.
• Ar is preferably an aryl group.
• the preferred embodiments of the alkyl group, cycloalkyl group, and aryl group are the same as those of the groups represented by Rx 1 to Rx 3 above.
• the group represented by Ar and the group represented by Rn have a fluorine atom or iodine atom as a substituent.
• the ring atom in the non-aromatic ring adjacent to the ring atom directly bonded to the polar group (or a residue thereof) 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 be a 2-cyclopentenyl group having a substituent (such as an alkyl group), such as a 3-methyl-2-cyclopentenyl group, or a cyclohexyl group having a substituent (such as an alkyl group), such as a 1,1,4,4-tetramethylcyclohexyl group.
• the repeating unit having an acid-decomposable group is preferably a repeating unit represented by formula (A).
• L1 represents a divalent linking group
• R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group or an aryl group
• R2 represents a leaving group which is eliminated by the action of an acid.
• L1 represents a divalent linking group.
• the divalent linking group include -CO-, -O-, -S-, -SO-, -SO 2 -, divalent hydrocarbon groups (e.g., alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups, etc.), and linking groups in which a plurality of these are linked together.
• the divalent hydrocarbon group may have a fluorine atom or an iodine atom as a substituent.
• L1 is preferably -CO-, -Rt-, -COO-Rt-, -COO-Rt-CO- or -Rt-CO-, and more preferably -CO- or -COO-Rt-CO-.
• Rt is a divalent hydrocarbon group, preferably an alkylene group or an arylene group, and more preferably an alkylene group.
• the arylene group is preferably a phenylene group.
• the alkylene group may be linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 3.
• the total number of fluorine atoms and iodine atoms contained in the alkylene group having a fluorine atom or an iodine atom is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.
• R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group, or an aryl group.
• the alkyl group and the aryl group may have a fluorine atom or an iodine atom as a substituent.
• the alkyl group may be either linear or branched.
• the number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 3.
• the total number of fluorine atoms and iodine atoms that the alkyl group may have is not particularly limited, but is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3.
• the alkyl group may contain a heteroatom such as an oxygen atom.
• R2 represents a leaving group which is eliminated by the action of an acid.
• the leaving group may have a fluorine atom or an iodine atom as a substituent.
• Examples of the leaving group include the leaving groups represented by the above formulae (Y1) to (Y4).
• the repeating unit having an acid-decomposable group is preferably a repeating unit represented by formula (AI).
• Xa1 represents a hydrogen atom or an alkyl group which may have a substituent.
• T represents a single bond or a divalent linking group.
• Rx1 to Rx3 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). Two of Rx 1 to Rx 3 may be bonded to form a monocyclic or polycyclic ring (eg, a monocyclic or polycyclic cycloalkyl group).
• Xa1 represents a hydrogen atom or an alkyl group which may have a substituent.
• the alkyl group which may have a substituent include a methyl group or a group represented by -CH 2 -R 11.
• R 11 represents a halogen atom, a hydroxyl group, or a monovalent organic group.
• the monovalent organic group include an alkyl group having 5 or less carbon atoms which may have a halogen atom, an acyl group having 5 or less carbon atoms which may have a halogen atom, and an alkoxy group having 5 or less carbon atoms which may have a halogen atom.
• An alkyl group having 1 to 3 carbon atoms is preferred, and a methyl group is more preferred.
• Xa1 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
• T represents a single bond or a divalent linking group.
• the divalent linking group include an alkylene group, an aromatic ring group, -COO-Rt-, and -O-Rt-, where Rt represents an alkylene group or a cycloalkylene group.
• T is preferably a single bond or --COO--Rt--.
• Rt is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably a methylene group, an ethylene group, or a propylene group.
• Rx 1 to Rx 3 each independently represent an alkyl group (straight-chain or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (straight-chain or branched), or an aryl group (monocyclic or polycyclic). Two of Rx 1 to Rx 3 may be bonded to form a monocyclic or polycyclic ring (eg, a monocyclic or polycyclic cycloalkyl group). Preferred embodiments of the alkyl group, cycloalkyl group, alkenyl group and aryl group represented by Rx 1 to Rx 3 are the same as the groups represented by Rx 1 to Rx 3 in formulae (Y1) and (Y2).
• the cycloalkyl group formed by combining two of Rx1 to Rx3 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 tricyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group.
• a monocyclic cycloalkyl group having 5 to 6 carbon atoms or a polycyclic cycloalkyl group having 6 to 12 carbon atoms is preferable.
• one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom or a sulfur atom, a carbonyl group, a group containing a heteroatom such as an -SO2- group or an -SO3- group, or a vinylidene group.
• one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.
• Rx1 is preferably a methyl group or an ethyl group
• Rx2 and Rx3 are bonded to form the above-mentioned cycloalkyl group.
• the groups represented by Rx1 to Rx3 may have a substituent. Examples of the substituent include an alkyl group having 1 to 4 carbon atoms, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, a carboxy group, and an alkoxycarbonyl group having 2 to 6 carbon atoms.
• the repeating unit represented by formula (AI) is preferably an acid-decomposable tertiary alkyl (meth)acrylate repeating unit (a repeating unit in which Xa1 represents a hydrogen atom or a methyl group and T represents a single bond or -COO-Rt-).
• repeating units having an acid-decomposable group include the repeating units described in paragraphs [0053] to [0057] of WO 2020/158467.
• the specific resin may have, as the repeating unit having an acid-decomposable group, a repeating unit having an acid-decomposable group containing an unsaturated bond.
• a repeating unit represented by formula (B) is preferred.
• Xb represents a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent.
• 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 be bonded to form a monocyclic or polycyclic ring (such as a monocyclic or polycyclic cycloalkyl group or cycloalkenyl group).
• Xb represents a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent.
• the preferred embodiments of Xb are the same as those of Xa1 in formula (AI).
• L represents a single bond or a divalent linking group which may have a substituent.
• the divalent linking group include a -Rt- group, a -CO- group, a -COO-Rt- group, a -COO-Rt-CO- group, a -Rt-CO- group, and a -O-Rt- group.
• Rt represents an alkylene group, a cycloalkylene group, or an aromatic ring group, and is preferably an aromatic ring group.
• Rt may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group.
• L is preferably a -Rt- group, a -CO- group, a -COO-Rt-CO- group, or a -Rt-CO- group.
• Ry 1 to Ry 3 each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group, an alkynyl group, a cycloalkenyl group (monocyclic or polycyclic), or an aryl group (monocyclic or polycyclic), provided that at least one of Ry 1 to Ry 3 represents an alkenyl group, an alkynyl group, a cycloalkenyl group (monocyclic or polycyclic), or an aryl group (monocyclic or polycyclic).
• Two of Ry 1 to Ry 3 may be bonded to form a monocyclic or polycyclic ring (such as a monocyclic or polycyclic cycloalkyl group or cycloalkenyl group).
• a monocyclic or polycyclic ring such as a monocyclic or polycyclic cycloalkyl group or cycloalkenyl group.
• Preferred embodiments of the alkyl group, cycloalkyl group, alkenyl group and aryl group represented by Ry 1 to Ry 3 above are the same as the groups represented by Rx 1 to Rx 3 in formula (Y-1).
• the alkynyl group represented by Ry 1 to Ry 3 is preferably an ethynyl group.
• cycloalkenyl group represented by Ry 1 to Ry 3 a structure containing a double bond in a part of a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group is preferable.
• the cycloalkyl group or cycloalkenyl group formed by combining two of Ry1 to Ry3 for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom or a sulfur atom, a carbonyl group, a group containing a heteroatom such as an -SO2- group or an -SO3- group, a vinylidene group, or a combination thereof.
• cycloalkyl groups or cycloalkenyl groups one or more of the ethylene groups constituting the cycloalkane ring or cycloalkene ring may be replaced with a vinylene group.
• R1 is a methyl group, an ethyl group, a vinyl group, an allyl group, or an aryl group
• Ry2 and Ry3 are bonded to form the above-mentioned cycloalkyl group or cycloalkenyl group.
• the substituent is preferably an alkyl group having 1 to 4 carbon atoms, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, a carboxy group, or an alkoxycarbonyl group having 2 to 6 carbon atoms.
• the repeating unit represented by formula (B) is preferably an acid-decomposable (meth)acrylic acid tertiary ester repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a -CO- group), an acid-decomposable hydroxystyrene tertiary alkyl ether repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a phenyl group), or an acid-decomposable styrene carboxylic acid tertiary ester repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a -Rt-CO- group (Rt is an aromatic group)).
• an acid-decomposable (meth)acrylic acid tertiary ester repeating unit a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents
• the content is preferably 15 to 80 mol %, more preferably 20 to 70 mol %, and even more preferably 30 to 60 mol %, based on the total repeating units in the specific resin.
• the content of the 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, based on the total repeating units in the specific resin.
• the upper limit is preferably 90 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 the total repeating units in the specific resin.
• the specific resin may contain at least one type of repeating unit selected from the group consisting of Group A below, and/or at least one type of repeating unit selected from the group consisting of Group B below.
• Group A A group consisting of the following repeating units (20) to (25).
• a repeating unit having an acid group as described below (21)
• a repeating unit having a photoacid generating group as described below
• a repeating unit represented by formula (V-1) or the following formula (V-2), as described below Group B of repeating units for reducing mobility of the main chain: a group consisting of the following repeating units (30) to (32).
• (32) A repeating unit represented by formula (III), as described below, which has neither a hydroxyl group nor a cyano group.
• the specific resin preferably has an acid group, and preferably contains a repeating unit having an acid group.
• the interaction between the specific resin and the acid generated from the photoacid generator is superior.
• the diffusion of the acid is further suppressed, and the cross-sectional shape of the formed pattern can become more rectangular.
• the specific resin When the resist composition is used for EUV exposure, the specific resin preferably has at least one type of repeating unit selected from Group A above. When the resist composition is used for EUV exposure, the specific resin also preferably contains a fluorine atom or an iodine atom. When the resist composition is used for ArF exposure, the specific resin preferably has one type of repeating unit selected from Group B above. When the resist composition is used for ArF exposure, it is also preferable that the specific resin contains neither fluorine atoms nor silicon atoms. When the resist composition is used for ArF exposure, it is also preferable that the specific resin does not contain an aromatic group.
• the specific resin may have a repeating unit having an acid group.
• the acid dissociation constant of the acid group is preferably 13 or less, more preferably 10 or less, and the lower limit is preferably 3 or more, more preferably 5 or more.
• the content of the acid group in the specific resin is not particularly limited, but is often 0.2 to 6.0 mmol/g. Among them, 0.8 to 6.0 mmol/g is preferable, 1.2 to 5.0 mmol/g is more preferable, and 1.6 to 4.0 mmol/g is even more preferable. When the content of the acid group is within the above range, development proceeds well, and the formed pattern shape and resolution are more excellent.
• the acid group is preferably, for example, a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group.
• a fluorinated alcohol group preferably a hexafluoroisopropanol group
• a sulfonic acid group preferably a sulfonamide group
• an isopropanol group preferably, for example, a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group.
• hexafluoroisopropanol group one or more (preferably one or two) fluorine atoms may be substituted with
• the repeating unit having an acid group preferably has a structure different from that of a repeating unit having an acid-decomposable group and a repeating unit having a lactone group, a sultone group, or a carbonate group, which will be described later.
• the repeating unit having an acid group may have a fluorine atom or an iodine atom.
• the repeating unit having an acid group is preferably a repeating unit represented by the following formula (1):
• A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group.
• R represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkyloxycarbonyl group, or an aryloxycarbonyl group.
• R may be the same or different, and may form a ring together.
• R is preferably a hydrogen atom.
• a represents an integer of 1 to 3.
• b represents an integer of 0 to (5-a).
• repeating units having an acid group examples include the repeating units described in paragraphs [0081] to [0086] of WO 2020/158467.
• the content of repeating units having an acid group is preferably 10 mol% or more, and more preferably 15 mol% or more, based on the total repeating units in the specific resin.
• the upper limit is preferably 70 mol% or less, more preferably 65 mol% or less, and even more preferably 60 mol% or less, based on the total repeating units in the specific resin.
• the specific resin may have a repeating unit (hereinafter also referred to as "unit X") that has neither an acid decomposable group nor an acid group and has a fluorine atom, a bromine atom or an iodine atom, which is different from the above-mentioned ⁇ repeating unit having an acid decomposable group> and ⁇ repeating unit having an acid group>.
• unit X a repeating unit
• the unit X is 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> and the ⁇ repeating unit having a photoacid generating group> described below.
• the repeating unit X is preferably a repeating unit represented by formula (C).
• L5 represents a single bond or -COO-.
• R9 represents a hydrogen atom or an alkyl group which may have a fluorine atom or an iodine atom.
• R10 represents a hydrogen atom, an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a group which combines these.
• Examples of the unit X include the repeating units described in paragraph [0093] of WO2020/158467.
• the content of unit X is preferably 0 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, based on all repeating units in the specific resin.
• the upper limit is preferably 50 mol% or less, more preferably 45 mol% or less, and even more preferably 40 mol% or less, based on all repeating units in the specific resin.
• the specific resin may have a repeating unit (hereinafter also referred to as "unit Y") having at least one type selected from the group consisting of a lactone group, a sultone group, and a carbonate group. It is also preferred that the unit Y does not have a hydroxyl group or 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 lactone structure or a 5- to 7-membered sultone structure.
• a 5- to 7-membered lactone structure having another ring structure condensed thereto in the form of a bicyclo structure or a spiro structure, or a 5- to 7-membered sultone structure having another ring structure condensed thereto in the form of a bicyclo structure or a spiro structure is more preferred.
• the specific resin preferably has a repeating unit having a lactone group or sultone group obtained by removing one or more hydrogen atoms from a ring member atom of a lactone structure represented by any one of the following formulae (LC1-1) to (LC1-21), or a sultone structure represented by any one of the following formulae (SL1-1) to (SL1-3), and the lactone group or sultone group may be directly bonded to the main chain.
• the ring member atom of the lactone group or sultone group may constitute the main chain of the specific resin.
• the lactone structure or sultone structure may have a substituent (Rb 2 ).
• Preferred substituents (Rb 2 ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, a carboxy group, a halogen atom, a cyano group, and an acid-decomposable group.
• n2 represents an integer of 0 to 4. When n2 is 2 or more, the multiple Rb 2s may be different from each other, or the multiple Rb 2s may be bonded to each other to form a ring.
• An example of a 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) is a repeating unit 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. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb0 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 carboxy group, or a divalent linking group combining these.
• 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, and is preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a 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).
• optical isomers exist in the repeating unit having a lactone group or a sultone group
• any optical isomer may be used.
• one optical isomer may be used alone, or multiple optical isomers may be used in combination.
• the optical purity (ee) is preferably 90 or more, and more preferably 95 or more.
• the carbonate group is preferably a cyclic carbonate ester group.
• Examples of the unit Y include the repeating units described in paragraphs [0104] to [0110] of WO 2020/158467.
• the content of the unit Y is preferably 1 mol% or more, and more preferably 10 mol% or more, based on all repeating units in the specific resin.
• 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 specific resin.
• the specific resin may contain, as a repeating unit other than the above, a repeating unit having a group that generates an acid upon irradiation with actinic rays or radiation (hereinafter, also referred to as a "photoacid generating group").
• a repeating unit having a photoacid generating group is a repeating unit represented by formula (4).
• R 41 represents a hydrogen atom or a methyl group.
• L 41 represents a single bond or a divalent linking group.
• L 42 represents a divalent linking group.
• R 40 represents a structural moiety that is decomposed by irradiation with actinic rays or radiation to generate an acid in a side chain. Examples of the repeating unit having a photoacid generating group are shown below.
• repeating units having a photoacid generating group examples include the repeating units described in paragraphs [0094] to [0105] of JP2014-041327A and the repeating unit described in paragraph [0094] of WO2018/193954.
• the content of the repeating unit having a photoacid generating group is preferably 1 mol% or more, and more preferably 5 mol% or more, based on the total repeating units in the specific resin.
• the upper limit is preferably 40 mol% or less, more preferably 35 mol% or less, and even more preferably 30 mol% or less, based on the total repeating units in the specific resin.
• the specific resin may have a repeating unit represented by the following formula (V-1) or the following formula (V-2).
• the repeating units represented by the following formulae (V-1) and (V-2) are preferably repeating units different from the repeating units described above.
• R6 and R7 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 or a fluorinated alkyl group having 1 to 6 carbon atoms), or a carboxy group.
• the alkyl group a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms is preferable.
• n3 represents an integer of 0 to 6.
• n4 represents an integer of 0 to 4.
• X4 is a methylene group, an oxygen atom, or a sulfur atom.
• Examples of the repeating unit represented by formula (V-1) or (V-2) include the repeating units described in paragraph [0100] of WO 2018/193954.
• the specific resin preferably has a high glass transition temperature (Tg) in order to suppress excessive diffusion of the generated acid or pattern collapse during development.
• Tg is preferably higher than 90° C., more preferably higher than 100° C., even more preferably higher than 110° C., and particularly preferably 125° C. or higher.
• the upper limit is preferably 400° C. or lower, more preferably 350° C. or lower, in order to provide an excellent dissolution rate in the developer.
• the Tg of a polymer such as a specific resin is calculated by the following method. First, the Tg of a homopolymer consisting of only each repeating unit contained in the polymer is calculated by the Bicerano method.
• the mass ratio (%) of each repeating unit to the total repeating units in the polymer is calculated.
• the Tg at each mass ratio is calculated using the Fox formula (described in Materials Letters 62 (2008) 3152, etc.), and these are summed up to obtain the Tg (°C) of the polymer.
• the Bicerano method is described in Prediction of Polymer Properties, Marcel Dekker Inc., New York (1993). Calculation of Tg by the Bicerano method can be performed using polymer property estimation software MDL Polymer (MDL Information Systems, Inc.).
• Methods for reducing the mobility of the main chain of the specific resin include the following methods (a) to (e). (a) introduction of a bulky substituent into the main chain; (b) introduction of a plurality of substituents into the main chain; (c) introduction of a substituent inducing an interaction between specific resins into the vicinity of the main chain; (d) formation of a main chain with a cyclic structure; (e) linking of a cyclic structure to the main chain.
• the specific resin preferably has a repeating unit exhibiting a homopolymer Tg of 130° C. or higher.
• the specific resin may have a repeating unit having a hydroxyl group or a cyano group, in order to further improve the adhesion to the substrate and the affinity for the developer.
• the 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.
• the repeating unit having a hydroxyl group or a cyano group preferably does not have an acid-decomposable group. Examples of the repeating unit having a hydroxyl group or a cyano group include those described in paragraphs [0081] to [0084] of JP2014-098921A.
• the specific resin may have a repeating unit having an alkali-soluble group.
• the alkali-soluble group include a carboxy group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol group (e.g., a hexafluoroisopropanol group) in which the ⁇ -position is substituted with an electron-withdrawing group, and the carboxy group is preferred.
• the specific resin contains a repeating unit having an alkali-soluble group, thereby increasing the resolution in contact hole applications. Examples of the repeating unit having an alkali-soluble group include those described in paragraphs [0085] and [0086] of JP2014-098921A.
• the specific resin may have an alicyclic hydrocarbon structure and a repeating unit that does not exhibit acid decomposability. This can reduce elution of low molecular weight components from the resist film into the immersion liquid during immersion exposure.
• repeating units that have an alicyclic hydrocarbon structure and do not exhibit acid decomposability include repeating units derived from 1-adamantyl (meth)acrylate, diamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, or cyclohexyl (meth)acrylate.
• the specific resin may have a repeating unit represented by formula (III) which does not have either a hydroxyl group or 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, where Ra 2 represents a hydrogen atom, an alkyl group or an acyl group.
• Examples of the repeating unit represented by formula (III) that does not have either a hydroxyl group or a cyano group include the repeating units described in paragraphs [0087] to [0094] of JP2014-098921A.
• the specific resin may have repeating units other than the repeating units described above.
• the specific resin may have a repeating unit selected from the group consisting of a repeating unit having an oxathiane ring group, a repeating unit having an oxazolone ring group, a repeating unit having a dioxane ring group, and a repeating unit having a hydantoin ring group.
• the specific resin may have various repeating structural units for the purpose of adjusting dry etching resistance, suitability for standard developing solutions, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, etc.
• the specific resin can be synthesized according to a conventional method (for example, radical polymerization).
• the weight average molecular weight of the specific resin, as calculated as polystyrene by GPC method, is preferably 30,000 or less, more preferably 1,000 to 30,000, even more preferably 3,000 to 30,000, and particularly preferably 5,000 to 15,000.
• the dispersity (molecular weight distribution) of the specific resin is preferably from 1 to 5, more preferably from 1 to 3, even more preferably from 1.2 to 3.0, and particularly preferably from 1.2 to 2.0. The smaller the dispersity, the better the resolution and resist shape, and furthermore, the smoother the sidewalls of the resist pattern are, and the better the roughness is.
• the content of the specific resin is preferably from 40.0 to 99.9 mass %, and more preferably from 60.0 to 90.0 mass %, based on the total solid content of the resist composition.
• the specific resin may be used alone or in combination of two or more kinds.
• the resist composition contains one or more photoacid generators which are composed of cations and anions and which generate an acid upon exposure to actinic rays or radiation.
• the photoacid generator is an acidic compound obtained by replacing the cation with a proton, and has an acid dissociation constant A (pKa(A)) of ⁇ 1.50 or less.
• the photoacid generator may be in the form of a low molecular weight compound, or may be incorporated into a part of a polymer (e.g., the above-mentioned specific resin).Furthermore, the form of a low molecular weight compound and the form of being incorporated into a part of a polymer may be used in combination.
• the molecular weight of the photoacid generator is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less. There is no particular lower limit, but a molecular weight of 100 or more is preferable. In this specification, the photoacid generator is preferably in the form of a low molecular weight compound.
• photoacid generators include compounds (onium salts) represented by "M + X - ", and are preferably compounds that generate an organic acid upon exposure to light.
• organic acid include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, camphorsulfonic acid, etc.).
• M + represents a cation.
• the cation is preferably an organic cation.
• the organic cation is preferably a cation represented by formula (ZaI) (hereinafter also referred to as “cation (ZaI)”) or a cation represented by formula (ZaII) (hereinafter also referred to as “cation (ZaII)").
• R 201 , R 202 and R 203 each independently represent an organic group.
• the number of carbon atoms in the organic group is preferably 1 to 30, and more preferably 1 to 20.
• Two of R 201 to R 203 may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group.
• Examples of the group formed by bonding two of R 201 to R 203 include an alkylene group (e.g., a butylene group and a pentylene group) and -CH 2 -CH 2 -O-CH 2 -CH 2 -.
• two of R 201 to R 203 may be bonded, for example, by a single bond or an ether bond (-O-) to form a ring structure.
• Suitable embodiments of the organic cation in formula (ZaI) include cation (ZaI-1), cation (ZaI-2), cation (ZaI-3b), and cation (ZaI-4b), which will be described later.
• the cation (ZaI-1) is an arylsulfonium cation in which at least one of R 201 to R 203 in the above formula (ZaI) is an aryl group.
• the arylsulfonium cation all of R 201 to R 203 may be aryl groups, or some of R 201 to R 203 may be aryl groups, with the remainder being alkyl groups or cycloalkyl groups.
• R 201 to R 203 may be an aryl group, and the remaining two of R 201 to R 203 may be bonded to form a ring structure, which may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group in the ring.
• Examples of the group formed by bonding two of R 201 to R 203 include alkylene groups in which one or more methylene groups may be substituted with oxygen atoms, sulfur atoms, ester groups, amide groups, and/or carbonyl groups (e.g., butylene group, pentylene group, and -CH 2 -CH 2 -O-CH 2 -CH 2 -).
• Arylsulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.
• the aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
• the aryl group may be an aryl group having a heterocyclic structure with an oxygen atom, a nitrogen atom, or a sulfur atom.
• the heterocyclic structure may include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue.
• the two or more aryl groups may be the same or different.
• Examples of the alkyl group or cycloalkyl group that the arylsulfonium cation may have include a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, and a cycloalkyl group having 3 to 15 carbon atoms, and a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, or a cyclohexyl group is preferable.
• Examples of the substituent that the aryl group, alkyl group, and cycloalkyl group of R 201 to R 203 may have include an alkyl group (e.g., having 1 to 15 carbon atoms), a cycloalkyl group (e.g., having 3 to 15 carbon atoms), an aryl group (e.g., having 6 to 14 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a cycloalkylalkoxy group (e.g., having 1 to 15 carbon atoms), a halogen atom (e.g., fluorine and iodine), a hydroxyl group, a carboxy group, an ester group, a sulfinyl group, a sulfonyl group, an alkylthio group, and a phenylthio group.
• an alkyl group e.g., having 1 to 15 carbon atoms
• the above-mentioned substituent may further have a substituent, and it is also preferred that the above-mentioned alkyl group has a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group.
• the above-mentioned substituent may be an acid-decomposable group. The definition and preferred embodiments of the acid-decomposable group are as described above.
• Cation (ZaI-2) is a cation in which R 201 to R 203 in formula (ZaI) each independently represent an organic group not having an aromatic ring.
• the aromatic ring also includes an aromatic ring containing a heteroatom.
• the organic group not having an aromatic ring preferably has 1 to 30 carbon atoms, and more preferably has 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, and still more preferably a linear or branched 2-oxoalkyl group.
• Examples of the alkyl group and cycloalkyl group of R 201 to R 203 include linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, and pentyl groups), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, and norbornyl groups).
• R 201 to R 203 may be further substituted with a halogen atom, an alkoxy group (eg, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group. It is also preferred that the substituents of R 201 to R 203 each independently form an acid-decomposable group through any combination of the substituents.
• the cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).
• R 1c to R 5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group, or an arylthio group.
• R 6c and R 7c each independently represent a hydrogen atom, an alkyl group (eg, a t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group.
• R x and R y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.
• the substituents of R 1c to R 7c and R x and R y may be acid-decomposable groups.
• R 1c to R 5c , and R x and R y may be bonded to each other to form a ring, and each of these rings may independently have an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbon-carbon double bond.
• R 5c and R 6c , and R 5c and R x may be bonded to each other to form a ring, and each of these rings may independently have a carbon-carbon double bond.
• R 6c and R 7c may be bonded to each other to form a ring.
• the formed ring having an oxygen atom or the like means, for example, a form in which two bondable groups (e.g., Rx and Ry ) are bonded to each other to form an alkylene group, and a methylene group in such an alkylene group is substituted with an oxygen atom or the like.
• the ring include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocyclic ring, and a polycyclic condensed ring formed by combining two or more of these rings.
• the ring is preferably a 3- to 10-membered ring, more preferably a 4- to 8-membered ring, and even more preferably a 5- or 6-membered ring.
• Examples of the group formed by combining any two or more of R 1c to R 5c , R 6c and R 7c , and R x and R y include a butylene group, a pentylene group, and -CH 2 -CH 2 -O-CH 2 -CH 2 - .
• the groups formed by combining R5c and R6c , and R5c and Rx are preferably a single bond or an alkylene group.
• Examples of the alkylene group include a methylene group and an ethylene group.
• the cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).
• R 13 represents a hydrogen atom, a halogen atom (e.g., a fluorine atom or an iodine atom), a hydroxyl group, an alkyl group, a halogenated alkyl group, an alkoxy group, a carboxy group, an alkoxycarbonyl group, or a group containing a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as a part). These groups may have a substituent.
• a halogen atom e.g., a fluorine atom or an iodine atom
• R 13 represents a hydrogen atom, a halogen atom (e.g., a fluorine atom or an iodine atom), a hydroxyl group, an alkyl group, a halogenated alkyl group, an alkoxy group, a carboxy group, an alkoxy
• R 14 represents a hydroxyl group, a halogen atom (e.g., a fluorine atom and an iodine atom, etc.), an alkyl group, a halogenated alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group containing a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as a part). These groups may have a substituent. When there are multiple R 14s , the multiple R 14s may be the same or different.
• a halogen atom e.g., a fluorine atom and an iodine atom, etc.
• an alkyl group e.g., a fluorine atom and an iodine atom
• Each R 15 independently represents an alkyl group, a cycloalkyl group, or a naphthyl group.
• Two R 15 may be bonded to each other to form a ring.
• the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom.
• it is preferred that two R 15 are alkylene groups and are bonded to each other to form a ring structure.
• the alkyl group, the cycloalkyl group, the naphthyl group, and the ring formed by bonding two R 15 together may have a substituent.
• the alkyl groups of R 13 , R 14 and R 15 may be either linear or branched.
• the number of carbon atoms in the alkyl group is preferably 1 to 10.
• the alkyl group is preferably a methyl group, an ethyl group, an n-butyl group or a t-butyl group.
• the groups represented by R 13 to R 15 may be acid-decomposable groups.
• R 204 and R 205 each independently represent an aryl group, an alkyl group or a cycloalkyl group.
• the aryl group of R 204 and R 205 is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
• the aryl group of R 204 and R 205 may be an aryl group having a heterocycle with an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the skeleton of the aryl group having a heterocycle include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
• the alkyl group and cycloalkyl group of R 204 and R 205 are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group), or a cycloalkyl group having 3 to 10 carbon atoms (e.g., a cyclopentyl group, a cyclohexyl group, or a norbornyl group).
• a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms e.g., a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group
• a cycloalkyl group having 3 to 10 carbon atoms e.g
• the aryl group, alkyl group, and cycloalkyl group of R 204 and R 205 may each independently have a substituent.
• substituents that the aryl group, alkyl group, and cycloalkyl group of R 204 and R 205 may have include an alkyl group (e.g., having 1 to 15 carbon atoms), a cycloalkyl group (e.g., having 3 to 15 carbon atoms), an aryl group (e.g., having 6 to 15 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.
• the substituent of R 204 and R 205 may be an acid-decomposable group.
• X - is an anion that is bonded to a proton to form an acidic compound A having an acid dissociation constant A (pKa(A)) of -1.50 or less.
• the acid dissociation constant A is not particularly limited as long as it satisfies the above requirements, but is preferably ⁇ 8.00 to ⁇ 1.50, more preferably ⁇ 6.00 to ⁇ 1.50, and even more preferably ⁇ 6.00 to ⁇ 1.90.
• the anion is preferably an organic anion.
• organic anion anions having a significantly low ability to cause a nucleophilic reaction are preferred, and non-nucleophilic anions are more preferred.
• non-nucleophilic anions examples include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc.).
• the aliphatic moiety in the aliphatic sulfonate anion may be any of a linear or branched alkyl group and a cycloalkyl group, and is preferably a linear or branched alkyl group having 1 to 30 carbon atoms, or a cycloalkyl group having 3 to 30 carbon atoms.
• the alkyl group may be, for example, a fluoroalkyl group (which may have a substituent other than a fluorine atom, or may be a perfluoroalkyl group).
• the aryl group in the aromatic sulfonate anion is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.
• the aromatic sulfonate anion may have a diphenyl ether structure in which phenyl groups are bonded to each other via an oxygen atom.
• a benzenesulfonate anion is preferred, and a benzenesulfonate anion substituted with a branched alkyl group or cycloalkyl group is more preferred.
• the alkyl group, cycloalkyl group, and aryl group listed above may have a substituent.
• the substituent is not particularly limited, but examples include a nitro group, a halogen atom such as a fluorine atom or a chlorine atom, a carboxy group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), an alkylthio group (preferably having 1 to 15 carbon atoms), an alkylsulfonyl group (preferably having 1 to 15 carbon
• non-nucleophilic anions include, for example, phosphorus fluorides (eg, PF 6 ⁇ ), boron fluorides (eg, BF 4 ⁇ ), and antimony fluorides (eg, SbF 6 ⁇ ).
• non-nucleophilic anion an aliphatic sulfonate anion in which at least the ⁇ -position of the sulfonic acid is substituted with a fluorine atom, or an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, is preferred.
• a perfluoroaliphatic sulfonate anion (preferably having 4 to 8 carbon atoms) or a benzenesulfonate anion having a fluorine atom is more preferable, and a nonafluorobutanesulfonate anion, a perfluorooctane sulfonate anion, a pentafluorobenzenesulfonate anion, or a 3,5-bis(trifluoromethyl)benzenesulfonate anion is even more preferable.
• an anion represented by the following formula (AN1) is also preferred.
• R 1 and R 2 each independently represent a hydrogen atom or a substituent.
• the substituent is not particularly limited, but is preferably a group that is not an electron-withdrawing group.
• Examples of the group that is not an electron-withdrawing group include a hydrocarbon group, a hydroxyl group, an oxyhydrocarbon group, an oxycarbonylhydrocarbon group, an amino group, a hydrocarbon-substituted amino group, and a hydrocarbon-substituted amide group.
• the groups which are not electron-withdrawing groups are preferably each independently -R', -OH, -OR', -OCOR', -NH 2 , -NR' 2 , -NHR' or -NHCOR', where R' is a monovalent hydrocarbon group.
• Examples of the monovalent hydrocarbon group represented by R' include alkyl groups such as methyl, ethyl, propyl, and butyl; alkenyl groups such as ethenyl, propenyl, and butenyl; alkynyl groups such as ethynyl, propynyl, and butynyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl; cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and norbornenyl; aryl groups such as phenyl, tolyl, xylyl, mesityl, naphthyl, methylnaphthyl, anthryl, and methylanthryl; and aralkyl groups such as benzyl, phenethy
• L represents a divalent linking group.
• the divalent linking group include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO 2 -, alkylene groups (preferably having 1 to 6 carbon atoms), cycloalkylene groups (preferably having 3 to 15 carbon atoms), alkenylene groups (preferably having 2 to 6 carbon atoms), and divalent linking groups combining a plurality of these.
• the divalent linking group is preferably -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -SO 2 -, -O-CO-O-alkylene group-, -COO-alkylene group-, or -CONH-alkylene group-, and more preferably -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, -SO 2 -, or -COO-alkylene group-.
• a group represented by the following formula (AN1-1) is preferable. * a - ( CR2a2 ) X -Q- ( CR2b2 ) Y - * b (AN1-1)
• * a represents the bonding position to R 3 in formula (AN1).
• * b represents the bonding position to --C(R 1 )(R 2 )-- in formula (AN1).
• X and Y each independently represent an integer of 0 to 10, and preferably an integer of 0 to 3.
• R 2a and R 2b each independently represent a hydrogen atom or a substituent. When a plurality of R 2a and a plurality of R 2b are present, the plurality of R 2a and R 2b may be the same or different. However, when Y is 1 or more, R 2b in CR 2b 2 which is directly bonded to —C(R 1 )(R 2 )— in formula (AN1) is other than a fluorine atom.
• Q represents * A -O-CO-O-* B , * A -CO-* B , * A -CO-O-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B , or * A - SO2- * B .
• Q represents * A -O-CO-O-* B , * A -CO-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B , or * A - SO2- * B .
• * A represents the bonding position on the R3 side in formula (AN1)
• * B represents the bonding position on the --SO 3 -- side in formula (AN1).
• R3 represents an organic group.
• the organic group is not particularly limited as long as it has one or more carbon atoms, and may be a linear group (e.g., a linear alkyl group), a branched group (e.g., a branched alkyl group such as a t-butyl group), or a cyclic group.
• the organic group may or may not have a substituent.
• the organic group may or may not have a heteroatom (such as an oxygen atom, a sulfur atom, and/or a nitrogen atom).
• R3 is preferably an organic group having a cyclic structure.
• the cyclic structure may be a monocyclic or polycyclic ring and may have a substituent.
• the ring in the organic group having a cyclic structure is preferably directly bonded to L in formula (AN1).
• the organic group having a cyclic structure may or may not have a heteroatom (such as an oxygen atom, a sulfur atom, and/or a nitrogen atom).
• the heteroatom may substitute for one or more of the carbon atoms forming the cyclic structure.
• the organic group having a cyclic structure is preferably, for example, a hydrocarbon group having a cyclic structure, a lactone ring group, or a sultone ring group, and among these, the organic group having a cyclic structure is preferably a hydrocarbon group having a cyclic structure.
• the cyclic hydrocarbon group is preferably a monocyclic or polycyclic cycloalkyl group, which may have a substituent.
• the cycloalkyl group may be a monocyclic group (such as a cyclohexyl group) or a polycyclic group (such as an adamantyl group), and preferably has 5 to 12 carbon atoms.
• lactone group and sultone group for example, in any of the structures represented by the above-mentioned formulae (LC1-1) to (LC1-21) and the structures represented by the above-mentioned formulae (SL1-1) to (SL1-3), a group in which one hydrogen atom is removed from a ring member atom constituting the lactone structure or the sultone structure is preferable.
• an anion represented by the following formula (AN2) is also preferred.
• o represents an integer from 1 to 3.
• p represents an integer from 0 to 10.
• q represents an integer from 0 to 10.
• Each Xf independently represents a hydrogen atom, a fluorine atom, an alkyl group substituted with at least one fluorine atom, or an organic group having no fluorine atom.
• the number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 4.
• the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.
• each Xf may be the same or different.
• Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably a fluorine atom or CF 3. Of these, it is 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 a plurality of R4s and R5s are present, R4s and R5s may be the same or different.
• the alkyl group preferably has 1 to 4 carbon atoms.
• the alkyl group may have a substituent.
• R4 and R5 are preferably a hydrogen atom.
• L represents a divalent linking group.
• L is defined as the same as L in formula (AN1). When a plurality of L's are present, each L may be the same or different.
• the divalent linking group is preferably --CO--, --O--, --S--, --SO--, --SO 2 --, --CONH-- or a hydrocarbon group having 1 to 17 carbon atoms (for example, an alkylene group, a cycloalkylene group, or an alkenylene group).
• the hydrocarbon group may have a substituent.
• substituents examples include a halogen atom, a hydroxyl group, a carboxy group, an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an acyl group having 1 to 5 carbon atoms, an alkyloxycarbonyl group having 1 to 5 carbon atoms, and an aryl group having 6 to 8 carbon atoms.
• one or more of the methylene groups constituting the cycloalkylene group may be substituted with -O-, -S-, or -CO-.
• the divalent linking group is preferably --O--, --CO--, an alkylene group, or a cycloalkylene group.
• (L) q is preferably, for example, a group represented by formula (AN2-1).
• * a represents the bonding position to C(R 4 )(R 5 ) in formula (AN2)
• * b represents the bonding position to W in formula (AN2).
• x, y, and z each independently represent an integer of 0 to 10, preferably 0 to 3, and more preferably 1 or 2.
• Rt1 and Rt2 each independently represent a divalent hydrocarbon group.
• hydrocarbon group examples include an alkylene group (preferably having 1 to 7 carbon atoms), a cycloalkylene group (preferably having 3 to 17 carbon atoms), and an alkenylene group (preferably having 2 to 8 carbon atoms).
• the hydrocarbon group may have a substituent, and the methylene group constituting the cycloalkylene group may be substituted with -O-, -CO-, -S-, or -SO 2 -.
• Q 1 represents —COO—, —CO—, —O—, —O—CO—O—, —S—, —CONH—, —SO— or —SO 2 —, and is preferably —COO—, —CO— or —O—.
• Q2 represents a single bond when y is 0, and represents a single bond or a divalent linking group mentioned for Q1 when y is an integer of 1 or more.
• Q2 is preferably a single bond, -COO-, -CO- or -O-.
• the plurality of Rt 1 , Rt 2 and Q 2 may be the same or different.
• W represents an organic group containing a cyclic structure, and is preferably a cyclic organic group.
• the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group.
• the alicyclic group may be a monocyclic group or a polycyclic group.
• the monocyclic alicyclic group include a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
• polycyclic alicyclic group examples include a polycyclic cycloalkyl group such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, a decahydronaphthyl group, and an adamantyl group.
• alicyclic groups having a bulky structure with 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group, are preferred.
• the aryl group may be monocyclic or polycyclic, and examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group.
• the heterocyclic group may be monocyclic or polycyclic. In particular, when the heterocyclic group is a polycyclic group, the diffusion of the acid can be more suppressed.
• the heterocyclic group may have aromaticity or may not have aromaticity. Examples of heterocyclic rings having aromaticity include furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, and pyridine ring.
• heterocyclic rings not having aromaticity examples include tetrahydropyran ring, lactone ring, sultone ring, and decahydroisoquinoline ring.
• a monocyclic or polycyclic lactone ring, or a monocyclic or polycyclic sultone ring is preferable.
• the cyclic organic group may have a substituent.
• substituents include an alkyl group (which may be either linear or branched, and preferably has 1 to 12 carbon atoms), a cycloalkyl group (which may be either monocyclic, polycyclic, or spirocyclic, and preferably has 3 to 20 carbon atoms), an aryl group (which preferably has 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonate ester group.
• the carbon that constitutes the cyclic organic group (the carbon that contributes to the ring formation) may be a carbonyl carbon.
• the anion represented by formula (AN2) is preferably SO 3 - -CF 2 -CH 2 -OCO-(L) q' -W, SO 3 - -CF 2 -CHF-CH 2 -OCO-(L) q' -W, SO 3 - -CF 2 -COO-(L) q' -W, SO 3 - -CF 2 -CF 2 -CH 2 -CH 2 -(L) q -W, or SO 3 - -CF 2 -CH(CF 3 )-OCO-(L) q' -W.
• L, q and W are the same as those in formula (AN2).
• q' represents an integer of 0 to 10.
• an aromatic sulfonate anion represented by the following formula (AN3) is also preferred.
• Ar represents an aromatic ring which may have a substituent.
• the aromatic ring represented by Ar may be either a monocyclic ring or a polycyclic ring.
• the aromatic ring represented by Ar may be either an aromatic hydrocarbon ring or an aromatic heterocycle, with an aromatic hydrocarbon ring being preferred.
• the aromatic ring represented by Ar preferably has 5 to 20 member atoms, and more preferably has 6 to 12 member atoms.
• a benzene ring is particularly preferable.
• Examples of the substituent that the aromatic ring represented by Ar may have include a halogen atom (preferably a fluorine atom) and a hydroxyl group.
• n represents an integer of 0 or more. n is preferably 1 to 4, more preferably 2 or 3, and even 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 of these.
• the hydrocarbon group represented by B may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
• the aliphatic hydrocarbon group represented by B may be any one of linear, branched, and cyclic, and is preferably cyclic.
• the aliphatic hydrocarbon group represented by B preferably has 1 to 20 carbon atoms, and more preferably has 1 to 10 carbon atoms.
• an alkyl group having 1 to 10 carbon atoms (such as a methyl group, an isopropyl group, a cyclohexyl group, and a norbornyl group) is preferable, and a cyclic alkyl group having 1 to 10 carbon atoms is more preferable.
• the aromatic hydrocarbon group represented by B may be either a monocyclic or polycyclic group.
• the aromatic hydrocarbon group represented by B preferably has 5 to 20 carbon atoms, more preferably 6 to 12 carbon atoms.
• the aromatic hydrocarbon group represented by B may further have a substituent.
• Examples of the substituent that the aromatic hydrocarbon group may have include an alkyl group having 1 to 10 carbon atoms, a halogen atom (preferably a fluorine atom), and a hydroxyl group.
• a phenyl group which may have a substituent is particularly preferred.
• non-nucleophilic anions include anions represented by the following formula (d1-2):
• Z 2c represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (with the proviso that the carbon atom adjacent to S is not substituted with a fluorine atom or a perfluoroalkyl group).
• the hydrocarbon group in Z 2c may be linear or branched, or may have a cyclic structure.
• the carbon atom in the hydrocarbon group (preferably, when the hydrocarbon group has a cyclic structure, the carbon atom that is a ring atom) may be a carbonyl carbon.
• Examples of the hydrocarbon group include a group having a norbornyl group that may have a substituent.
• the carbon atom forming the norbornyl group may be a carbonyl carbon.
• Z 2c -SO 3 - " in formula (d1-2) is different from the anions represented by the above formulae (AN1) to (AN3).
• Z 2c is preferably other than an aryl group.
• the atoms at the ⁇ -position and ⁇ -position relative to -SO 3 - are preferably atoms other than a carbon atom having a fluorine atom as a substituent.
• the atom at the ⁇ -position and/or the atom at the ⁇ -position relative to -SO 3 - in Z 2c is a ring member atom in a cyclic group.
• the content of the photoacid generator is preferably from 0.5 to 50.0 mass %, more preferably from 1.0 to 30.0 mass %, and even more preferably from 1.0 to 25.0 mass %, relative to the total solids content of the resist composition, from the viewpoint that the cross-sectional shape of the formed pattern becomes more rectangular.
• the photoacid generator may be used alone or in combination of two or more. When the resist composition contains two or more photoacid generators, the total content thereof is preferably within the above range.
• the resist composition of the present invention contains at least two acid diffusion controllers, a first acid diffusion controller and a second acid diffusion controller.
• the acid diffusion controller is an acidic compound consisting of a cation and an anion, in which the cation of the acid diffusion controller is replaced with a proton, and has an acid dissociation constant (pKa(Q)) of greater than -1.50.
• the acid diffusion controller is an onium salt that generates an acid that is weaker than the acid generated by the photoacid generator.
• the first acid diffusion control agent and the second acid diffusion control agent are described in detail below.
• the first acid diffusion controller is an acid diffusion controller comprising a first cation and a first anion.
• the first cation is a cation having a ClogP value between 5.400 and 6.000.
• the first cation becomes appropriately hydrophilic and diffuses into the hydrophilic exposed area, so that the acid can be easily quenched at the boundary between the exposed area and the unexposed area.
• the ClogP value of the first cation is more preferably from 5.600 to 6.000.
• the first cation is not particularly limited as long as it is an organic cation having a ClogP value within the above range, and examples thereof include a sulfonium cation, an ammonium cation, and an iodonium cation. Among these, the sulfonium cation is preferred as the first cation.
• the organic cation for example, an organic cation that can be contained in the photoacid generator can be used.
• the first cation is a sulfonium cation
• the first cation is preferably the above cation (ZaI), more preferably the cation (ZaI-1) or the cation (ZaI-3b), and even more preferably the cation (ZaI-1).
• the first cation is an iodonium cation
• the first cation is preferably the above cation (ZaII).
• the first cation is a sulfonium cation
• the first cation is preferably a cation selected from the group consisting of cations represented by formula (Q-1) to formula (Q-4).
• L Q1 represents a single bond or a divalent linking group, and when n1 is 2 or greater, multiple L Q1 may be the same or different.
• the divalent linking group represented by LQ1 include -CO-, -O-, -S-, -SO-, -SO 2 -, and linking groups in which a plurality of these are linked together (for example, -CO-O-).
• L Q1 is preferably a single bond, —CO—O— (ester bond) or —SO 2 —.
• R Q1 represents an alkyl group. When n1 is 2 or more, multiple R Q1 may be the same or different.
• the alkyl group represented by R 3 Q1 preferably has 1 to 10 carbon atoms, more preferably has 1 to 6 carbon atoms, and even more preferably has 1 to 3 carbon atoms.
• the alkyl group represented by R Q1 may be any of linear, branched, and cyclic, and is preferably linear or cyclic.
• the alkyl group represented by R 3 Q1 may have an ethereal oxygen atom between the carbon-carbon bond. When the alkyl group is cyclic, it may have an ethereal oxygen atom as a ring member atom.
• the alkyl group is preferably a methyl group, an ethyl group, a cyclohexyl group, or a 2-tetrahydropyranyl group.
• n1 represents an integer from 1 to 3. n1 is preferably 1 or 2, and more preferably 1.
• Ar 1 and Ar 2 each independently represent an aryl group.
• Examples of the aryl group represented by Ar 1 and Ar 2 include a phenyl group and a naphthyl group, with a phenyl group being preferred.
• Ar 1 and Ar 2 may be bonded to each other via a single bond or --O--.
• C1 represents an alicyclic structure having 4 or 5 carbon atoms and containing a sulfonium cation moiety.
• L Q2 represents a single bond or a divalent linking group. When n2 is 2 or greater, multiple L Q2 may be the same or different. Examples of the divalent linking group represented by LQ2 include -CO-, -O-, -S-, -SO-, -SO 2 -, and linking groups in which a plurality of these are linked together. LQ2 is preferably a single bond.
• R Q2 represents an alkyl group. When n2 is 2 or greater, a plurality of R Q2 may be the same or different.
• the alkyl group represented by R 3 Q2 preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms.
• the alkyl group represented by RQ2 may be any of linear, branched and cyclic, and is preferably linear or branched.
• the alkyl group is preferably a t-butyl group.
• n2 represents an integer from 1 to 3. n2 is preferably 1 or 2, and more preferably 1.
• C2 represents an alicyclic structure having 4 or 5 carbon atoms and containing a sulfonium cation moiety.
• L Q3 represents a single bond or a divalent linking group. When n3 is 2 or greater, multiple L Q3 may be the same or different. Examples of the divalent linking group represented by LQ3 include -CO-, -O-, -S-, -SO-, -SO 2 -, and linking groups in which a plurality of these are linked together. LQ3 is preferably a single bond.
• R Q3 represents an alkyl group. When n3 is 2 or greater, a plurality of R Q3 may be the same or different.
• the alkyl group represented by R 3 Q3 preferably has 1 to 10 carbon atoms, and more preferably has 1 to 6 carbon atoms.
• the alkyl group represented by RQ3 may be any of linear, branched and cyclic, and is preferably cyclic.
• the alkyl group is preferably a cyclohexyl group.
• n3 represents an integer from 1 to 3. n3 is preferably 1 or 2, and more preferably 1.
• Each of R and Q4 independently represents an alkyl group.
• the alkyl group represented by R 4 preferably has 1 to 5 carbon atoms, and more preferably 1 or 2 carbon atoms.
• the alkyl group represented by RQ4 may be any of linear, branched and cyclic.
• n41, n42, and n43 each independently represent 0 or 1, and the sum of n41, n42, and n43 is 1 to 3.
• the sum of n41, n42 and n43 is preferably 1 or 3.
• the first cation is an iodonium cation
• the first cation is preferably a cation represented by formula (Q-5).
• L Q5 represents a single bond or a divalent linking group.
• the divalent linking group represented by LQ5 include alkylene groups, -CO-, -O-, -S-, -SO-, -SO 2 -, and linking groups in which a plurality of these are linked together (for example, an O-alkylene group -CO-O-).
• the alkylene group may be linear, branched, or cyclic, but is preferably linear.
• the alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 or 2 carbon atoms.
• R Q5 and R Q6 each independently represent an alkyl group.
• the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms.
• the alkyl group may be linear, branched or cyclic, with branched groups being preferred.
• the alkyl group is preferably a t-butyl group.
• the type of the first anion is not particularly limited as long as the acid dissociation constant B (acid dissociation constant of an acid compound consisting of a first anion and a proton) is greater than ⁇ 1.50.
• the first anion is preferably an organic anion.
• anions having a significantly low ability to cause a nucleophilic reaction are preferred, and non-nucleophilic anions are more preferred.
• the pKa(B) of the acidic compound B formed by combining the first anion and a proton is not particularly limited as long as it is greater than -1.50, but is preferably 0.50 or more greater than pKa(A), more preferably 1.00 or more greater, and even more preferably 2.00 or more greater.
• the upper limit of the difference between pKa(B) and pKa(A) (pKa(B)-pKa(A)) is not particularly limited, and is preferably 15.00 or less, more preferably 10.00 or less.
• the pKa(B) is preferably ⁇ 1.00 or more, more preferably 0.00 or more, and even more preferably 0.50 or more.
• the upper limit is not particularly limited, but is preferably 10.00 or less, more preferably 8.00 or less, and even more preferably 6.00 or less.
• the first anion examples include a sulfonate anion, a carboxylate anion, a sulfonylimide anion, a bis(alkylsulfonyl)imide anion, and a tris(alkylsulfonyl)methide anion.
• the carboxylate anion, the sulfonylimide anion, the bis(alkylsulfonyl)imide anion, and the tris(alkylsulfonyl)methide anion are preferred, and the carboxylate anion is more preferred.
• the first anion is also preferably an anion containing at least one selected from the group consisting of a fluorine atom and an iodine atom (more preferably a fluorine atom).
• the first anion contains a fluorine atom
• the number of fluorine atoms is preferably 1 to 10, and more preferably 1 to 7.
• the first anion is preferably an anion represented by formula (C-1), an anion represented by formula (C-2), or an anion represented by formula (C-3).
• Formula (C-1) R C1 -COO- Formula (C-2) R C2 -L C1 -COO - Formula (C-3) R C3 -CO-N -SO 2 -L C2 -R C4
• R C1 represents an aryl group which may have a substituent, or an alkyl group which may have a substituent.
• the aromatic ring constituting the aryl group represented by R C1 preferably has 5 to 20 member atoms, and more preferably 5 to 10 member atoms.
• the aryl group may be a phenyl group or a naphthyl group, with the phenyl group being preferred.
• the aryl group preferably has 1 to 3 substituents, and more preferably 1 or 2 substituents.
• the substituent that the aryl group may have is not particularly limited, and examples thereof include a hydroxyl group or an alkyl group that may have a halogen atom.
• the alkyl group which may have one or more halogen atoms preferably has 1 to 3 carbon atoms, and more preferably has 1 carbon atom.
• a fluorine atom is preferred.
• the alkyl group which may have an alkyl group may be a perfluoroalkyl group.
• the alkyl group represented by R C1 may be any one of linear, branched, and cyclic, but is preferably a linear alkyl group.
• the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 to 3 carbon atoms.
• the alkyl group preferably has 1 to 10 substituents, and more preferably has 1 to 7 substituents.
• the substituent that the alkyl group may have is not particularly limited, but examples thereof include a hydroxyl group or a halogen atom (preferably a fluorine atom).
• R C2 represents a heterocyclic group.
• the heterocyclic group includes an aromatic heterocyclic ring and a non-aromatic heterocyclic ring, and a non-aromatic heterocyclic ring is preferable.
• the non-aromatic heterocycle preferably has 4 to 8 ring atoms, and more preferably has 4 to 6 ring atoms.
• L C1 represents a single bond or a methylene group.
• R C3 represents an alkyl group which may have a substituent.
• the alkyl group may be linear, branched or cyclic, with linear or branched alkyl groups being preferred.
• the alkyl group represented by R 3 C3 preferably has 1 to 10 carbon atoms, more preferably has 1 to 5 carbon atoms, and further preferably has 1 to 3 carbon atoms.
• the alkyl group preferably has 1 to 10 substituents, and more preferably has 1 to 7 substituents.
• the substituent that the alkyl group may have is not particularly limited, but examples thereof include a hydroxyl group or a halogen atom (preferably a fluorine atom).
• L C2 represents a single bond or a methylene group.
• R C4 represents an alicyclic hydrocarbon ring, and a methylene group in the alicyclic hydrocarbon ring may be substituted with —O—, —CO—, —S—, or —SO 2 —.
• the alicyclic hydrocarbon ring may be a monocyclic ring or a polycyclic ring, and is preferably a polycyclic ring.
• the alicyclic hydrocarbon ring preferably has 1 to 20 carbon atoms, and more preferably has 1 to 10 carbon atoms. Examples of the alicyclic hydrocarbon ring include an adamantane ring and a norbornane ring.
• the methylene groups in the adamantane ring and the norbornane ring may be substituted with -O-, -CO-, -S-, or -SO 2 -.
• the content of the first acid diffusion controller is preferably from 0.1 to 15.0 mass %, and more preferably from 1.0 to 15.0 mass %, relative to the total solid content of the resist composition, in that the cross-sectional shape of the formed pattern becomes more rectangular.
• the first acid diffusion controller may be used alone or in combination of two or more.
• the total content thereof is preferably within the above range.
• the content of the first acid diffusion controller is preferably 15 mol % or less, more preferably 12 mol % or less, and even more preferably 10 mol % or less, based on the total molar amount of the photoacid generator, the first acid diffusion controller, and the second acid diffusion controller.
• the second acid diffusion controller is an acid diffusion controller comprising a second cation and a second anion.
• the second cation is an organic cation having a ClogP value of 8.000 or greater. There is no particular upper limit to the ClogP value, but it is preferably 15,000 or less.
• the second cation is not particularly limited as long as it is an organic cation having a ClogP value within the above range, and examples thereof include a sulfonium cation, an ammonium cation, and an iodonium cation. Among these, the sulfonium cation is preferred as the second cation.
• the second cation is also preferably a cation containing at least one selected from the group consisting of a fluorine atom and an iodine atom (more preferably a fluorine atom).
• a fluorine atom for example, an organic cation that can be contained in the photoacid generator can be used.
• the second cation is a sulfonium cation
• the second cation is preferably the above cation (ZaI), more preferably the above cation (ZaI-1).
• the second cation is preferably the above cation (ZaII).
• L and Q6 each independently represent a single bond or a divalent linking group.
• the divalent linking group represented by LQ6 include alkylene groups having 1 to 10 carbon atoms, -CO-, -O-, -S-, -SO-, -SO 2 -, and linking groups in which a plurality of these are linked together.
• the divalent linking group represented by LQ6 is preferably a single bond, -O-CH 2 -COO-, or -S-CH 2 -COO-.
• Each of R and Q7 independently represents an optionally substituted alkyl group or a halogen atom.
• the alkyl group represented by R may be linear , branched, or cyclic.
• the alkyl group preferably has 1 to 10 carbon atoms, and more preferably has 1 to 4 carbon atoms.
• the alkyl group preferably has 1 to 10 substituents, and more preferably has 1 to 7 substituents.
• the substituent that the alkyl group may have is not particularly limited, and examples thereof include a hydroxyl group or a halogen atom (preferably a fluorine atom).
• R may be a fluoroalkyl group in which one or more hydrogen atoms in the alkyl group are replaced with fluorine atoms, and is preferably a perfluoroalkyl group.
• the alkyl group is preferably a methyl group, an ethyl group, a t-butyl group, a trifluoromethyl group, a group obtained by removing the hydrogen atom at the 2-position of adamantane, or a group obtained by removing the hydrogen atom at the 2-position of 2-methyladamantane.
• Each 1 independently represents an integer of 1 to 5.
• l is preferably 1 to 3, and more preferably 1 or 2.
• the type of the second anion is not particularly limited so long as the acid dissociation constant C (acid dissociation constant of an acid compound consisting of a second anion and a proton) is greater than ⁇ 1.50.
• the second anion is preferably an organic anion.
• anions having a significantly low ability to cause a nucleophilic reaction are preferred, and non-nucleophilic anions are more preferred.
• the pKa(C) of the acidic compound C formed by combining the second anion and a proton is not particularly limited as long as it is greater than -1.50, but is preferably 0.50 or more greater than pKa(A), more preferably 1.00 or more greater, and even more preferably 2.00 or more greater.
• the upper limit of the difference between pKa(C) and pKa(A) (pKa(C)-pKa(A)) is not particularly limited, and is preferably 15.00 or less, more preferably 10.00 or less.
• the pKa(C) is preferably ⁇ 1.00 or more, more preferably 0.00 or more, and even more preferably 0.50 or more.
• the upper limit is not particularly limited, but is preferably 10.00 or less, more preferably 8.00 or less, and even more preferably 6.00 or less.
• the content of the second acid diffusion controller is preferably from 0.1 to 50.0 mass %, more preferably from 1.0 to 50.0 mass %, and even more preferably from 1.0 to 20.0 mass %, relative to the total solids content of the resist composition, from the viewpoint that the cross-sectional shape of the formed pattern becomes more rectangular.
• the second acid diffusion controller may be used alone or in combination of two or more. When the resist composition contains two or more second acid diffusion controllers, the total content thereof is preferably within the above range.
• the resist composition may contain an acid diffusion controller other than those mentioned above.
• acid diffusion control agents other than those mentioned above include basic compounds, low molecular weight compounds having a nitrogen atom and a group that is eliminated by the action of an acid, and compounds whose acid diffusion control ability is reduced or lost by irradiation with actinic rays or radiation.
• the one or more photoacid generators and the first acid diffusion controller or the second acid diffusion controller may be bonded via a covalent bond.
• a compound obtained by bonding a photoacid generator and a first acid diffusion controller or a second acid diffusion controller via a covalent bond is referred to as a "combined product.”
• the combination may be a compound obtained by bonding a photoacid generator and a first acid diffusion controller via a covalent bond, or a compound obtained by bonding a photoacid generator and a second acid diffusion controller via a covalent bond.
• the combination may be a compound obtained by bonding two or more types of photoacid generators and a first acid diffusion controller via a covalent bond, or a compound obtained by bonding two or more types of photoacid generators and a second acid diffusion controller via a covalent bond.
• the resist composition may contain only one type of compound, or two or more types.
• the resist composition may contain another photoacid generator that does not form a compound, or another acid diffusion controller that does not form a compound.
• the following embodiments 1 to 3 are preferred in that the effects of the present invention are more excellent.
• Aspect 1 An aspect including a first conjugate formed by covalently bonding two types of photoacid generators and either one of a first acid diffusion controller or a second acid diffusion controller (hereinafter also referred to as acid diffusion controller X), a second conjugate formed by covalently bonding one type of photoacid generator and acid diffusion controller X, and the other of the first acid diffusion controller and the second acid diffusion controller.
• Aspect 2 An aspect including a composite formed by bonding one type of photoacid generator to either a first acid diffusion controller or a second acid diffusion controller via a covalent bond, the other of the first acid diffusion controller and the second acid diffusion controller, and a photoacid generator that is a compound different from the composite.
• Aspect 3 An aspect including a composite formed by bonding one type of photoacid generator to either a first acid diffusion controller or a second acid diffusion controller via a covalent bond, and the other of the first acid diffusion controller and the second acid diffusion controller.
• the photoacid generator and the first acid diffusion controller When the photoacid generator and the first acid diffusion controller are bonded via a covalent bond, they may be bonded via a single bond or a divalent linking group.
• the divalent linking group include -CO-, -O-, -S-, -SO-, -SO 2 -, divalent hydrocarbon groups (e.g., alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups, etc.), and linking groups in which a plurality of these groups are bonded together.
• the divalent hydrocarbon group may have a fluorine atom or an iodine atom as a substituent.
• the anion in the photoacid generator and the first anion in the first acid diffusion controller may be bonded via a covalent bond, or the cation in the photoacid generator and the first cation in the first acid diffusion controller may be bonded via a covalent bond.
• a bond obtained by bonding the anion in the photoacid generator and the first anion in the first acid diffusion controller via a covalent bond is preferred.
• An example of a mode in which the photoacid generator and the first acid diffusion controller are covalently bonded is a mode in which a residue formed by removing one atom from the photoacid generator and a residue formed by removing one atom from the first acid diffusion controller are bonded via a single bond or a divalent linking group.
• a residue formed by removing one atom from the photoacid generator and a residue formed by removing one atom from the first acid diffusion controller are bonded via a single bond or a divalent linking group.
• anions in the two types of photoacid generators and a first anion in the first acid diffusion controller may be bonded via a covalent bond, or a cation in the two types of photoacid generators and a first cation in the first acid diffusion controller may be bonded via a covalent bond.
• the photoacid generator and the second acid diffusion controller When the photoacid generator and the second acid diffusion controller are bonded via a covalent bond, they may be bonded via a single bond or a divalent linking group.
• the divalent linking group include -CO-, -O-, -S-, -SO-, -SO 2 -, divalent hydrocarbon groups (e.g., alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups, etc.), and linking groups in which a plurality of these are bonded together.
• the divalent hydrocarbon group may have a fluorine atom or an iodine atom as a substituent.
• the anion in the photoacid generator and the second anion in the second acid diffusion controller may be bonded via a covalent bond, or the cation in the photoacid generator and the second cation in the second acid diffusion controller may be bonded via a covalent bond. From the viewpoint of ease of synthesis, a bond obtained by bonding the anion in the photoacid generator and the second anion in the second acid diffusion controller via a covalent bond is preferred.
• An example of a mode in which the photoacid generator and the second acid diffusion controller are covalently bonded is a mode in which a residue formed by removing one atom from the photoacid generator and a residue formed by removing one atom from the second acid diffusion controller are bonded via a single bond or a divalent linking group.
• a residue formed by removing one atom from the photoacid generator and a residue formed by removing one atom from the second acid diffusion controller are bonded via a single bond or a divalent linking group.
• anions in the two types of photoacid generators and a second anion in the second acid diffusion controller may be bonded via a covalent bond, or a cation in the two types of photoacid generators and a second cation in the second acid diffusion controller may be bonded via a covalent bond.
• the content of the binder is preferably 0.1 to 50.0 mass % relative to the total solid content of the resist composition, more preferably 1.0 to 40.0 mass %, even more preferably 1.0 to 35.0 mass %, and particularly preferably 1.0 to 35.0 mass %.
• the resist composition may contain a hydrophobic resin that is different from the specific resin.
• the hydrophobic resin is preferably designed to be unevenly distributed on the surface of the resist film, but unlike a surfactant, it does not necessarily have to have a hydrophilic group in the molecule, and does not necessarily have to contribute to uniform mixing of polar and non-polar substances.
• the effects of adding a hydrophobic resin include control of the static and dynamic contact angle of water on the resist film surface, and suppression of outgassing.
• the hydrophobic resin preferably has one or more of a fluorine atom, a silicon atom, and a CH3 partial structure contained in the side chain portion of the resin, and more preferably has two or more of them.
• the hydrophobic resin preferably has a hydrocarbon group having at least 5 carbon atoms. Such a group may be present in the main chain of the resin, or may be substituted on a side chain. Examples of hydrophobic resins include the compounds described in paragraphs [0275] to [0279] of WO 2020/004306.
• the hydrophobic resin may be used alone or in combination of two or more kinds.
• the content of the hydrophobic resin is preferably from 0.01 to 20.0 mass %, and more preferably from 0.1 to 15.0 mass %, based on the total solid content of the resist composition.
• the resist composition may contain a surfactant.
• a surfactant When a surfactant is contained, a pattern having superior adhesion and fewer development defects can be formed.
• the surfactant is preferably a fluorine-based and/or silicon-based surfactant, and from the standpoint of environmental regulations, a silicon-based surfactant is more preferred. Examples of the fluorine-based and/or silicon-based surfactant include the surfactants described in paragraphs [0218] and [0219] of WO 2018/193954.
• the surfactant may be used alone or in combination of two or more kinds.
• the content of the surfactant is preferably from 0.0001 to 2.0 mass %, more preferably from 0.0005 to 1.0 mass %, and even more preferably from 0.1 to 1.0 mass %, relative to the total solid content of the resist composition.
• the resist composition preferably contains a solvent.
• the solvent preferably contains (CP) propylene glycol monoalkyl ether carboxylate, and (M2) at least one selected from the group consisting of propylene glycol monoalkyl ether, lactate ester, acetate ester, alkoxypropionate ester, chain ketone, cyclic ketone, lactone, and alkylene carbonate.
• the combination of the above-mentioned solvent and the specific resin is preferable in terms of improving the coatability of the resist composition and reducing the number of development defects of the pattern.
• the above-mentioned solvent has a good balance of the solubility, boiling point, and viscosity of the above-mentioned resin, so that it can suppress unevenness in the thickness of the resist film and the occurrence of precipitates during spin coating. Details of the components (CP) and (M2) are described in paragraphs [0218] to [0226] of WO 2020/004306, the contents of which are incorporated herein by reference.
• the solvent may further contain a component other than the component (CP) and the component (M2).
• the content of the component other than the component (CP) and the component (M2) is preferably 5 to 30 mass % based on the total amount of the solvent.
• the content of the solvent in the resist composition is preferably 70 to 95.5% by mass, and more preferably 80 to 99% by mass.
• the resist composition may contain additives other than those mentioned above.
• additives include dissolution-inhibiting compounds (compounds with a molecular weight of 3000 or less that are decomposed by the action of acid and have reduced solubility in organic developers), dyes, plasticizers, photosensitizers, light absorbers, and compounds that promote solubility in developers (for example, phenol compounds with a molecular weight of 1000 or less, and alicyclic or aliphatic compounds containing a carbonyl group).
• the resist composition may contain water, but it is preferable that the water content is small.
• the content of water is often 1 to 30,000 ppm by mass relative to the total mass of the resist composition, and is preferably 10,000 ppm by mass or less, more preferably 5,000 ppm by mass or less, and even more preferably 1,000 ppm by mass or less. There is no particular lower limit, and 0 ppm by mass is preferable.
• the resist composition may contain residual monomers, but the content thereof is preferably small.
• the residual monomers include monomers used in the synthesis of the specific resin.
• the content of the residual monomer is often 1 to 30,000 ppm by mass relative to the total mass of the resist composition, and is preferably 10,000 ppm by mass or less, more preferably 5,000 ppm by mass or less, and even more preferably 1,000 ppm by mass or less. There is no particular lower limit, and 0 ppm by mass is preferable.
• the resist composition of the present specification is suitably used as a resist composition for EUV exposure.
• EUV light has a wavelength of 13.5 nm, which is shorter than ArF light (wavelength 193 nm) and the like, and therefore the number of incident photons is smaller when exposed at the same sensitivity. Therefore, the effect of "photon shot noise," which is the stochastic variation in the number of photons, is large, leading to deterioration of LER and bridge defects.
• One method of reducing photon shot noise is to increase the exposure dose to increase the number of incident photons, but this is a trade-off with the demand for higher sensitivity.
• the pattern forming method of the present invention includes the following steps.
• Step 1 A step of forming a resist film on a substrate using a resist composition.
• Step 2 A step of exposing the resist film.
• Step 3 A step of developing the exposed resist film using a developer to form a resist pattern. Each step may be performed only once or multiple times. Each step will be described in detail below.
• Step 1 is a step of forming a resist film on a substrate using a resist composition.
• the resist composition is as defined above.
• An example of a method for forming a resist film on a substrate using a resist composition is a method in which the resist composition is applied onto a substrate. It is preferable to filter the resist composition before coating as necessary.
• the pore size of the filter is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, and even more preferably 0.03 ⁇ m or less.
• the filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.
• the substrate is not particularly limited, and may be a substrate generally used in the manufacturing process of semiconductors such as ICs, or circuit boards such as liquid crystal or thermal heads, and in other lithography processes for photofabrication, etc.
• Specific examples include inorganic substrates such as silicon, SiO 2 , and SiN.
• an undercoat film for example, an inorganic film, an organic film, or an anti-reflective film may be formed under the resist film.
• the resist composition can be applied onto a substrate, for example, using a spinner or coater.
• the preferred application method is spin coating using a spinner.
• the rotation speed when spin coating using a spinner is preferably 1000 to 3000 rpm.
• a drying treatment may be carried out to form a resist film.
• a drying method for example, a method of drying by heating may be mentioned. Heating may 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., and even more preferably 80 to 130° C.
• the heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.
• a top coat may be formed on the resist film using a top coat composition.
• the top coat composition is preferably a composition that does not mix with the resist film and can be applied uniformly onto the resist film.
• the thickness of the top coat is preferably from 10 to 200 nm, more preferably from 20 to 100 nm, and even more preferably from 40 to 80 nm.
• the composition and method of forming the top coat are not particularly limited, and a known top coat can be formed using a known method.
• the top coat can be formed based on the description in paragraphs [0072] to [0082] of JP2014-059543A.
• the top coat 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 group, and an ester group.
• Step 2 is a step of exposing the resist film to light.
• the exposure method may be a method in which the formed resist film is irradiated with actinic rays or radiation through a predetermined mask.
• the actinic ray or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, preferably having a wavelength of 250 nm or less, more preferably having a wavelength of 220 nm or less, and particularly preferably having 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.
• post-exposure baking Post Exposure Bake
• the post-exposure baking promotes the reaction of the exposed area, resulting in better sensitivity and pattern shape.
• Heating can be performed by a means provided in a normal exposure machine and/or development machine, and may be performed using a hot plate or the like.
• the heating temperature is preferably from 80 to 150°C, more preferably from 80 to 140°C, and even more preferably from 80 to 130°C.
• the heating time is preferably from 10 to 1,000 seconds, more preferably from 10 to 180 seconds, and even more preferably from 30 to 120 seconds.
• Step 3 is a step of developing the exposed resist film with a developer to obtain a resist pattern.
• the developer may be an alkaline developer or a developer containing an organic solvent (hereinafter, also referred to as an "organic developer").
• Examples of the developing method include a method of immersing a substrate in a tank filled with a developing solution for a certain period of time (dip method), a method of piling up the developing solution on the substrate surface by surface tension and leaving it still for a certain period of time to develop (paddle method), a method of spraying the developing solution on the substrate surface (spray method), and a method of continuously discharging the developing solution while scanning a developing solution discharge nozzle at a constant speed onto a substrate rotating at a constant speed (dynamic dispense method).
• a step of stopping the development may be carried out while replacing the developer with another solvent.
• the developing time is not particularly limited as long as the resin in the unexposed area is sufficiently dissolved, and is preferably from 10 to 300 seconds, more preferably from 20 to 120 seconds.
• the temperature of the developer is preferably from 0 to 50°C, and more preferably from 15 to 35°C.
• the alkaline developer is preferably an aqueous alkaline solution containing an alkali.
• examples of the type of the aqueous alkaline solution include an alkaline solution containing a quaternary ammonium salt such as tetramethylammonium hydroxide, an inorganic alkali, a primary amine, a secondary amine, a tertiary amine, an alcohol amine, or a cyclic amine.
• the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide (TMAH).
• TMAH tetramethylammonium hydroxide
• the alkaline developer may contain an appropriate amount of alcohol.
• the alkaline developer usually has a basic compound concentration of 0.1 to 20% by mass.
• the alkaline developer usually has a pH of 10.0 to 15.0.
• the organic developer preferably contains at least one selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.
• ketone solvents and ester solvents the organic solvents described in paragraphs [0179] to [0180] of JP 2022-125078 A can be used, and as the alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents, the solvents disclosed in paragraphs ⁇ 0715> to ⁇ 0718> of US Patent Application Publication No. 2016/0070167 A1 can be used.
• the organic solvent contained in the organic developer may be a mixture of two or more organic solvents, or may be mixed with water.
• the water content of the entire organic developer 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 from 50 to 100% by mass, more preferably from 80 to 100% by mass, still more preferably from 90 to 100% by mass, and particularly preferably from 95 to 100% by mass, based on the total mass of the developer.
• the developer may contain a surfactant, if necessary.
• the above pattern forming method preferably includes, after step 3, a rinsing step of cleaning the pattern with a rinsing liquid.
• the rinsing liquid is not particularly limited as long as it does not dissolve the pattern.
• the rinsing liquid used in the rinsing step after the development step using an alkaline developer is, for example, pure water.
• a rinse liquid used in a rinse step following a development step using an organic developer a solution containing a general organic solvent that does not dissolve the pattern can be used.
• the organic solvent contained in the rinse liquid is preferably at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.
• a suitable amount of a surfactant may be added to the rinse solution.
• the above cleaning method is not particularly limited, and examples include a method in which the rinse solution is continuously discharged onto a substrate rotating at a constant speed (spin coating method), a method in which the substrate is immersed in a tank filled with the rinse solution for a certain period of time (dip method), and a method in which the rinse solution is sprayed onto the substrate surface (spray method).
• the pattern forming method may include a heating step (Post Bake) after the rinsing step. This step removes the developer and rinsing solution remaining between and inside the patterns. This step also anneals the resist pattern, improving the surface roughness of the pattern.
• the heating step after the rinsing step is preferably 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 formed pattern may be used as a mask to perform an etching process on the substrate, which is the object to be etched.
• the pattern formed in step 3 may be used as a mask to process the substrate (or the underlayer film and the substrate) to form a pattern on the substrate.
• the method for processing the substrate (or the underlayer film and the substrate) is not particularly limited, a method is preferred in which the substrate (or the underlayer film and the substrate) is dry-etched using the pattern formed in step 3 as a mask to form a pattern on the substrate.
• the dry etching is preferably oxygen plasma etching.
• the resist composition and various materials used in the pattern formation method of the present invention preferably do not contain impurities such as metals.
• the content of impurities contained in these materials is preferably 1 mass ppm or less, more preferably 10 mass ppb or less, even more preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less.
• 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.
• An example of a method for removing impurities such as metals from various materials is filtration using a filter.
• the method described in paragraph [0321] of WO 2020/004306 can be used.
• Methods for reducing metal and other impurities contained in various materials include, for example, selecting raw materials with low metal content as the raw materials that make up the various materials, filtering the raw materials that make up the various materials, and performing distillation under conditions that minimize contamination as much as possible, such as lining the inside of the equipment with Teflon (registered trademark).
• impurities may be removed using an adsorbent, or a combination of filtration and an adsorbent may be used.
• adsorbent known adsorbents may be used, for example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
• inorganic adsorbents such as silica gel and zeolite
• organic adsorbents such as activated carbon.
• a conductive compound may be added to an organic processing liquid such as a developer and a rinse liquid in order to prevent breakdown of chemical piping and various parts (filters, O-rings, tubes, etc.) due to static charging and subsequent static discharge.
• the conductive compound is not particularly limited, but an example thereof is methanol.
• the amount added is not particularly limited, but from the viewpoint of maintaining favorable development characteristics or rinsing characteristics, it is preferably 10% by mass or less, and more preferably 5% by mass or less.
• the lower limit is not particularly limited, but 0.01% by mass or more is preferable.
• the chemical liquid piping may be made of, for example, stainless steel (SUS), or various piping coated with antistatic polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.).
• the filter and O-ring may be made of antistatic polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.).
• the present invention also relates to a method for manufacturing an electronic device, which includes the above-mentioned pattern formation method, and an electronic device manufactured by this manufacturing method.
• the electronic device of the present invention is suitably mounted in electric and electronic equipment (such as home appliances, OA (Office Automation), media-related equipment, optical equipment, and communication equipment).
• Table 1 shows the type, composition ratio (mass ratio; corresponding from left to right), weight average molecular weight (Mw), and dispersity (Mw/Mn) of each repeating unit in resins E-1 to E-14 used as specific resins.
• the weight average molecular weight (Mw) and dispersity (Mw/Mn) of the specific resin were measured by GPC (carrier: tetrahydrofuran (THF)) (polystyrene equivalent amount).
• the composition ratio (mass%) was measured by 13 C-NMR (nuclear magnetic resonance).
• Resins E-1 to E-14 were synthesized according to the synthesis method of Resin E-1 (Synthesis Example 1) described below.
• Resin E-1 was synthesized according to the following scheme:
• Synthesis Example 1 Synthesis of Resin E-1 Cyclohexanone (113 g) was heated to 80° C. under a nitrogen stream. While stirring this liquid, a mixed solution of Monomer U-1 (25.5 g), Monomer U-2 (31.6 g), cyclohexanone (210 g), and dimethyl 2,2′-azobisisobutyrate [V-601, manufactured by Wako Pure Chemical Industries, Ltd.] (6.21 g) was added dropwise over 6 hours to obtain a reaction liquid. After the dropwise addition was completed, the reaction liquid was further stirred at 80° C. for 2 hours. The resulting reaction liquid was allowed to cool, and then reprecipitated with a large amount of methanol/water (mass ratio 9:1), followed by filtration.
• the resulting solid was dried in vacuum to obtain 52 g of Resin E-1.
• the weight average molecular weight (Mw: polystyrene equivalent) of the obtained resin E-1 determined by GPC (carrier: tetrahydrofuran (THF)) was 6,500, and the dispersity (Mw/Mn) was 1.52.
• the composition ratio measured by 13 C-NMR (nuclear magnetic resonance) was 50/50 by mass.
• the structures of the first anions CA1-1 to CA1-9 of the first acid diffusion control agent are shown below.
• the cations in the conjugates are selected from the first cations CQ1-4 to CQ1-12, or the second cations CQ2-1, CQ2-2, and CQ2-4 to CQ2-9, and the combinations with the anions CA3-1 to CA3-6 are shown in Tables 2 to 4 below.
• the resist solution used was a mixture of the following solvents in the following ratios.
• S1 Propylene glycol monomethyl ether acetate
• S2 Propylene glycol monomethyl ether
• S3 ⁇ -butyrolactone
• S1/S2/S3 85/10/5
• the above-mentioned various components were mixed in the ratios shown in Tables 2 to 4 so that the total content of components other than the solvent was 1.5 mass% relative to the total mass of the resist composition.
• the resulting mixture was then filtered through a polyethylene filter with a pore size of 0.03 ⁇ m to prepare a resist composition.
• the resulting resist composition was used in the examples and comparative examples.
• the exposure mask used had a line width of 20 nm and a 1:1 line and space pattern.
• the exposed resist film was baked at 90° C. for 60 seconds, developed with n-butyl acetate for 30 seconds, and then spin-dried to obtain a negative pattern.
• LWR performance evaluation The line and space pattern resolved at the optimum exposure dose was observed from above the pattern using a critical dimension scanning electron microscope (SEM (S-9380II, Hitachi, Ltd.)). The line width of the line and space pattern was measured at any point, and 3 ⁇ (nm) was calculated when ⁇ was the standard deviation of all the measured values obtained. From the obtained 3 ⁇ value, the LWR was evaluated according to the following evaluation criteria. The LWR was evaluated according to the following five-level scale, with 3 or more indicating good LWR performance, 4 or more being preferable, and 5 being more preferable.
• Examples 1 to 25 in Table 2 show the evaluation results of resist compositions containing one type each of a photoacid generator, a first acid diffusion controller, and a second acid diffusion controller.
• Examples 26 to 55 in Table 3 show the evaluation results of examples using a conjugate in which an anion in a photoacid generator and a second anion in a second acid diffusion controller are bound via a covalent bond. Note that in Examples 26 to 55, a conjugate is used that is composed of an anion shown in the "Structure (Conjugate)" column and cations shown in the second cation column in a number corresponding to the number of anion sites in the anion.
• Examples 50 to 52 are embodiments that include two types of conjugates
• Examples 53 to 55 are embodiments that include, in addition to a conjugate, another photoacid generator that does not form a conjugate.
• Examples 56 to 59 in Table 4 show the evaluation results of examples using a composite in which an anion in a photoacid generator and a first anion in a first acid diffusion controller are bound via a covalent bond. Note that in Examples 56 to 59, a composite is used that is made up of the anion shown in the "Structure (combined compound)" column and the number of cations shown in the "First cation" column that corresponds to the number of anionic sites in the anion.
• the numerical value shown in the "wt %” column of the “Q1 amount” column of the "First acid diffusion controller (Q1)” column indicates the content (mass %) of the first acid diffusion controller relative to the solid content of the resist composition.
• the numerical value shown in the “wt %” column of the “Q2 amount” column of the “Second acid diffusion controller (Q2)” column indicates the content (mass %) of the second acid diffusion controller relative to the solid content of the resist composition.
• the numerical value shown in the "wt %” column of the "Photoacid Generator” column indicates the content (mass %) of the photoacid generator relative to the solid content of the resist composition.
• the values shown in the "wt %" column of the "Photoacid Generator” column indicate the content (mass %) of the bond relative to the solid content of the resist composition.
• the numerical values shown in the "wt %” column of the “specific resin” column indicate the content (mass %) of the specific resin relative to the solid content of the resist composition.
• the numerical value shown in the "mol %” column of the “Q1 amount” column of the "First acid diffusion controller (Q1)” column indicates the content (mol %) of the first acid diffusion controller relative to the total molar amount of the photoacid generator, the first acid diffusion controller, and the second acid diffusion controller.
• the numerical values shown in the "anion pKa (A)” column, the “anion pKa (B)” column, and the “anion pKa (C)” column indicate the acid dissociation constant A, the acid dissociation constant B, and the acid dissociation constant C, respectively.
• the numerical values in the "ClogP value” column of the “First cation” and “Second cation” columns indicate the ClogP value of the first cation or the ClogP value of the second cation.
• the ClogP value is a value calculated using ChemDraw Professional (version 20.1.1.125, manufactured by PerkinElmer).
• An underlayer film-forming composition AL412 (manufactured by Brewer Science) was applied onto a silicon wafer (12 inches) and baked at 205° C. for 60 seconds to form an undercoat film with a thickness of 20 nm.
• the resist composition prepared as described above was applied thereon and baked at 100° C. for 60 seconds to form a resist film with a thickness of 30 nm.
• the wafer coated with the resist film obtained above was subjected to pattern exposure using an EUV exposure device (Micro Exposure Tool, NA (numerical aperture) 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36) manufactured by Exitech Corp.
• EUV exposure device Micro Exposure Tool, NA (numerical aperture) 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36
• the exposure mask used had a line width of 20 nm and a 1:1 line and space pattern.
• the exposed resist film was baked at 90° C. for 60 seconds, developed with an aqueous solution of tetramethylammonium hydroxide (2.38% by mass) for 30 seconds, rinsed with pure water for 30 seconds, and then spin-dried to obtain a positive pattern.

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