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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
  • C08F212/22—Oxygen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/22—Esters containing halogen
• • 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
  • G03F7/038—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
  • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
  • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
  • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/30—Imagewise removal using liquid means
  • G03F7/32—Liquid compositions therefor, e.g. developers
  • G03F7/325—Non-aqueous compositions
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/38—Treatment before imagewise removal, e.g. prebaking
• • 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
  • G03F7/40—Treatment after imagewise removal, e.g. baking

Definitions

• the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, a resist film, a pattern forming method, an electronic device manufacturing method, and an electronic device.
• pattern forming methods using chemical amplification have been used to compensate for the decrease in sensitivity due to light absorption.
• a photoacid generator contained in an exposed area is decomposed by light irradiation to generate acid.
• the post-exposure bake (PEB) process, etc. the alkali-insoluble groups of the resin contained in the actinic ray-sensitive or radiation-sensitive resin composition are converted into alkali-soluble groups by the catalytic action of the generated acid.
• the solubility in the developer is changed by, for example, changing to a base.
• development is performed using, for example, a basic aqueous solution.
• the exposed portion is removed and a desired pattern is obtained.
• the wavelength of exposure light sources has become shorter and the numerical aperture (NA) of projection lenses has become higher.
• NA numerical aperture
• EUV extreme ultraviolet
• EB electron beam
• Patent Document 1 describes a positive resist composition that can form ultrafine patterns (e.g., 40 nm or less) with extremely high resolution as containing "(A) an ionic compound, and (B) A positive type containing a resin that has a repeating unit (b1) having an interactive group that interacts with the ionic group in the above ionic compound and whose main chain is decomposed by irradiation with X-rays, electron beams, or extreme ultraviolet rays.
• “Resist composition” is disclosed.
• a pattern forming method comprising the step of developing the exposed resist film using a developer containing an organic solvent to obtain a pattern.
• the pattern forming method according to [11] further comprising a step 4 of cleaning the pattern using a rinsing liquid containing an organic solvent after the step 3.
• the pattern forming method does not include step 4 of cleaning the pattern using a rinsing solution containing an organic solvent after step 3, the developer contains two or more organic solvents,
• the pattern forming method has a step 4 of cleaning the pattern using a rinsing solution containing an organic solvent after the step 3, at least one of the developer and the rinsing solution contains two or more organic solvents.
• the two or more organic solvents include a first organic solvent and a second organic solvent, The boiling point of the first organic solvent is higher than the boiling point of the second organic solvent, The pattern forming method according to [13], wherein the ClogP value of the first organic solvent is larger than the ClogP value of the second organic solvent.
• a method for manufacturing an electronic device comprising the pattern forming method according to any one of [11] to [14].
• an actinic ray-sensitive or radiation-sensitive resin composition that can form a pattern with excellent LWR performance. Further, according to the present invention, it is possible to provide a resist film, a pattern forming method, an electronic device manufacturing method, and an electronic device related to the actinic ray-sensitive or radiation-sensitive resin composition.
• the present invention will be explained in detail below. Although the description of the constituent elements described below may be made based on typical embodiments of the present invention, the present invention is not limited to such embodiments.
• the "substituent” in this specification is preferably a monovalent substituent.
• organic group refers to a group containing at least one carbon atom.
• active rays or “radiation” include, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet (EUV) light, X-rays, and electron beams (EB). Beam) etc.
• Light as used herein means actinic rays or radiation.
• exposure in this specification refers not only to exposure to bright line spectra of mercury lamps, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays, and X-rays, but also to particle beams such as electron beams and ion beams. Also includes drawings by. In this specification, " ⁇ " is used to include the numerical values described before and after it as a lower limit value and an upper limit value. The direction of bonding of the divalent groups described herein is not limited unless otherwise specified. For example, when Y in the compound represented by the general formula "X-Y-Z" is -COO-, Y may be -CO-O- or -O-CO-. You can. Further, the above compound may be "X-CO-O-Z" or "X-O-CO-Z".
• ppm means “parts-per-million ( 10-6 )
• ppb means “parts-per-billion (10-9)
• ppt means “parts-per-billion ( 10-9 )”. parts-per-trillion (10 ⁇ 12 )”.
• weight average molecular weight (Mw), number average molecular weight (Mn), and polydispersity (also referred to as molecular weight distribution) (Mw/Mn) are measured using a GPC (Gel Permeation Chromatography) device (HLC-8120GPC manufactured by Tosoh).
• GPC measurement solvent: tetrahydrofuran, flow rate (sample injection amount): 10 ⁇ L, column: Tosoh TSK gel Multipore HXL-M, column temperature: 40°C, flow rate: 1.0 mL/min, detector: differential refractive index detector (Refractive Index Detector)) is defined as a polystyrene equivalent value.
• ClogP values were obtained from Daylight Chemical Information System, Inc. This value was calculated using the program "CLOGP” available from. This program provides the value of "calculated logP” calculated by the fragment approach of Hansch, Leo (see below). The fragment approach is based on the chemical structure of a compound and estimates the logP value of the compound by dividing the chemical structure into substructures (fragments) and summing the logP contributions assigned to the fragments. The details are described in the following documents. In this specification, ClogP values calculated by the program CLOGP v4.82 are used. A. J. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammnens, J. B. Taylor and C. A. Ramsden, Eds.
• examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• the solid content is intended to be a component that forms a resist film, and does not include a solvent. Furthermore, if the component forms a resist film, it is considered to be a solid component even if the component is liquid.
• the actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also referred to as “resist composition”) comprises a repeating unit represented by the formula (Ia) described below, and a repeating unit represented by the formula (IIa) described below.
• a resin (hereinafter also referred to as “resin (C)”) that contains the repeating unit represented by the formula and whose main chain is cleaved by exposure to light;
• An ionic compound represented by formula (III) described below hereinafter also referred to as "specific photoacid generator”
• the resin (C) satisfies Requirements 1 and 2, which will be described later.
• the resin (C) when the resin (C) satisfies requirement 1 described below, the resin (C) has a predetermined amount of phenolic hydroxyl groups, and this phenolic hydroxyl group interacts with the specific photoacid generator. This tends to cause dissolution contrast.
• the resin (C) satisfies Requirement 2 described later, the difference in dissolution rate in the developer between the resin (C) and the specific photoacid generator can be easily reduced.
• a pattern with excellent LWR can be obtained.
• the LWR performance when the LWR performance is better, it is also referred to as the effect of the present invention is better.
• the components contained in the resist composition of the present invention will be explained below.
• the resist composition includes a repeating unit represented by formula (Ia) and a repeating unit represented by formula (IIa), and includes a resin (resin (C)) whose main chain is cleaved by exposure to light.
• X a represents a halogen atom.
• the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, preferably a chlorine atom, a bromine atom, or an iodine atom, more preferably a chlorine atom or an iodine atom, and still more preferably a chlorine atom.
• Y a represents a group represented by formula (Y-1) or a group represented by formula (Y-2).
• formula (Y-1) and formula (Y-2) the wavy line portion represents the bonding position.
• Y a in formula (Ia) is a group represented by formula (Y-1)
• it is represented by formula (Ia)
• Y a in formula (Ia) is a group represented by formula (Y-1).
• -2) is represented by formula (Ib).
• R 2a represents a hydrogen atom or a monovalent organic group.
• the monovalent organic group represented by R 2a is not particularly limited, but includes, for example, an alkyl group that may have a substituent, a monovalent aromatic group that may have a substituent, and a substituent.
• An aralkyl group which may have a group can be mentioned.
• substituents hereinafter also referred to as "substituent T" that the alkyl group, monovalent aromatic group, and aralkyl group may each have include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• Halogen atoms such as atoms; alkoxy groups such as methoxy, ethoxy and tert-butoxy groups; aryloxy groups such as phenoxy and p-tolyloxy groups; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl and phenoxycarbonyl groups Acyloxy groups such as acetoxy, propionyloxy and benzoyloxy groups; Acyl groups such as acetyl, benzoyl, isobutyryl, acryloyl, methacryloyl and methoxalyl groups; Alkyl such as methylsulfanyl and tert-butylsulfanyl groups Sulfanyl group; arylsulfanyl group such as phenylsulfanyl group and p-tolylsulfanyl group; alkyl group; cycloalkyl group; aryl group; heteroaryl group; hydroxyl group; carboxy group; for
• the substituent T is preferably a substituent containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom.
• substituent containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom include a hydroxyl group, a carboxyl group, a cyano group, a carbonyl group, a formyl group, a carbomoyl group, an ether group, an alkoxycarbonyl group, Examples thereof include an amino group, an imino group, a nitro group, a thiol group, a thioether group, a thioester group, a sulfo group, a sulfonyl group, and a sulfonamide group.
• the monovalent organic group represented by R 2a may be a monovalent organic group containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom.
• R 2a may be a monovalent organic group that may contain at least one of an oxygen atom, a nitrogen atom, and a sulfur atom.
• the monovalent organic group represented by R 2a is an alkyl group that may have a substituent, a monovalent aromatic group that may have a substituent, or an alkyl group that may have a substituent.
• An aralkyl group which may contain at least one of an oxygen atom, a nitrogen atom and a sulfur atom is preferred.
• an alkyl group which may have a substituent or a monovalent aromatic group which may have a substituent is preferred.
• the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 6, even more preferably 1 or 2, and particularly preferably 1.
• the alkyl group may be linear, branched, or cyclic, and includes, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and a t-butyl group. and linear or branched alkyl groups such as n-hexyl groups, monocyclic cycloalkyl groups such as cyclopentyl groups and cyclohexyl groups, and norbornyl groups, tetracyclodecanyl groups, tetracyclododecanyl groups and adamantyl groups. Examples include polycyclic cycloalkyl groups such as.
• the alkyl group is preferably a linear alkyl group.
• the number of carbon atoms in the linear alkyl group is preferably 1 to 20, more preferably 1 to 6, even more preferably 1 or 2, and particularly preferably 1.
• the alkyl group has a substituent, it is preferable to have the substituent at the terminal of the alkyl group.
• the substituent that the alkyl group may have is as described above, and a substituent containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom is preferable.
• the number of substituents is not particularly limited, and is preferably 1 to 4, more preferably 1 to 2.
• the monovalent aromatic group is not particularly limited, and may be either an aryl group or a heteroaryl group.
• the monovalent aromatic group may be either monocyclic or polycyclic, and the number of ring members is preferably 6 to 15, more preferably 6 to 10.
• the monovalent aromatic group is preferably a phenyl group, a naphthyl group, or an anthracenyl group, more preferably a phenyl group or a naphthyl group, and even more preferably a phenyl group.
• the phenyl group has a substituent, it is preferable to have the substituent at the para position of the phenyl group.
• the substituent that the monovalent aromatic group may have is as described above, and a substituent containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom is preferable.
• the number of substituents is not particularly limited, and is preferably 1 to 4, more preferably 1 to 2.
• the monovalent aromatic group which may have a substituent is a monovalent aromatic group which may have a substituent containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom; , a heteroaryl group containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom as a ring member atom, which may have a substituent, is also preferable.
• R 3a and R 4a each independently represent a hydrogen atom or a monovalent organic group.
• the monovalent organic group represented by R 3a and R 4a is not particularly limited, but includes, for example, an alkyl group that may have a substituent, and a monovalent aromatic group that may have a substituent.
• Examples thereof include aralkyl groups which may have a group and a substituent and may contain at least one of an oxygen atom, a nitrogen atom, and a sulfur atom.
• the substituents that each of the alkyl group, monovalent aromatic group, and aralkyl group may have are not particularly limited, and include the groups exemplified as the substituent T described above, such as oxygen atom, nitrogen atom, Substituents containing at least one sulfur atom are preferred.
• the monovalent organic group represented by R 3a and R 4a may be a monovalent organic group containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom.
• R 3a and R 4a may be monovalent organic groups that may contain at least one of an oxygen atom, a nitrogen atom, and a sulfur atom.
• the monovalent organic group represented by R 3a and R 4a is preferably an alkyl group which may have a substituent.
• the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 6, even more preferably 1 or 2, and particularly preferably 1.
• the alkyl group may be linear, branched, or cyclic, and includes, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and a t-butyl group.
• alkyl groups such as n-hexyl groups, monocyclic cycloalkyl groups such as cyclopentyl groups and cyclohexyl groups, and norbornyl groups, tetracyclodecanyl groups, tetracyclododecanyl groups and adamantyl groups.
• Examples include polycyclic cycloalkyl groups such as.
• the alkyl group is preferably a linear alkyl group.
• the number of carbon atoms in the linear alkyl group is preferably 1 to 20, more preferably 1 to 6, even more preferably 1 or 2, and particularly preferably 1.
• the alkyl group has a substituent
• substituents that the above-mentioned alkyl group may have include the groups exemplified as the substituent T, and a substituent containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom is preferable.
• the number of substituents is not particularly limited, and is preferably 1 to 4, more preferably 1 to 2.
• the repeating unit represented by formula (Ia) has a phenolic hydroxyl group.
• the position of the phenolic hydroxyl group in the repeating unit represented by formula (Ia) is not particularly limited, but it is preferable that R 2a in formula (Y-1) is a group having a phenolic hydroxyl group, and R 2a is a group having a phenolic hydroxyl group. More preferably, it is a phenyl group having a hydroxyl group.
• the content of the repeating unit represented by formula (Ia) is preferably 20 to 80 mol%, more preferably 40 to 70 mol%, and 50 to 70 mol% based on the total repeating units in the resin (C). is even more preferable.
• R 1a represents an alkyl group which may have a substituent.
• Ar a represents a monovalent aromatic group which may have a substituent.
• the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 6, even more preferably 1 or 2, and particularly preferably 1.
• the alkyl group may be linear, branched, or cyclic, and includes, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and a t-butyl group.
• alkyl groups such as n-hexyl groups, monocyclic cycloalkyl groups such as cyclopentyl groups and cyclohexyl groups, and norbornyl groups, tetracyclodecanyl groups, tetracyclododecanyl groups, and adamantyl groups.
• Examples include polycyclic cycloalkyl groups such as.
• the alkyl group is preferably a linear alkyl group, more preferably a linear alkyl group having 1 to 5 carbon atoms, even more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
• the substituents that the alkyl group may have are not particularly limited, and include the groups exemplified as the substituent T.
• the number of substituents is not particularly limited, and is preferably 1 to 4, more preferably 1 to 2.
• the alkyl group represented by R 1a may be an alkyl group having a substituent containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom.
• R 1a may be an alkyl group that may have a substituent containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom.
• the monovalent aromatic group represented by Ar a is not particularly limited, and may be either an aryl group that may have a substituent or a heteroaryl group that may have a substituent. .
• the monovalent aromatic group may be either monocyclic or polycyclic, and the number of ring member atoms is preferably 6 to 15, more preferably 6 to 10.
• the monovalent aromatic group is preferably an aryl group that may have a substituent, more preferably a phenyl group, a naphthyl group, or an anthracenyl group that may have a substituent.
• a phenyl group or a naphthyl group which may have a substituent is more preferable, and a phenyl group which may have a substituent is particularly preferable.
• the phenyl group has a substituent, it is preferable to have the substituent at the para position of the phenyl group.
• the number of substituents is not particularly limited, and is preferably 1 to 4, more preferably 1 to 2.
• Examples of the substituent that the above-mentioned monovalent aromatic group may have include the groups exemplified for the above-mentioned substituent T, with a hydroxyl group being preferred and a phenolic hydroxyl group being more preferred.
• the number of substituents is not particularly limited, and is preferably 1 to 4, more preferably 1 to 2.
• the monovalent aromatic group is preferably a phenyl group having a hydroxyl group (preferably a phenolic hydroxyl group) or a naphthyl group having a hydroxyl group (preferably a phenolic hydroxyl group).
• the monovalent aromatic group represented by Ar a is a monovalent aromatic group having a substituent containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom, and may have a substituent. , a heteroaryl group containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom as a ring member atom.
• the monovalent aromatic group represented by Ar a is a monovalent aromatic group that may have a substituent containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom, and a monovalent aromatic group that has a substituent. It may be a heteroaryl group containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom as a ring member atom.
• the repeating unit represented by formula (IIa) has a phenolic hydroxyl group.
• the position of the phenolic hydroxyl group in the repeating unit represented by formula (IIa) is not particularly limited, but it is preferable that Ar a is a monovalent aromatic group having a phenolic hydroxyl group, and phenyl having a phenolic hydroxyl group is preferable. or a naphthyl group having a phenolic hydroxyl group.
• the content of the repeating unit represented by formula (IIa) is preferably 20 to 80 mol%, more preferably 30 to 70 mol%, and 30 to 50 mol% based on the total repeating units in the resin (C). is even more preferable.
• the resin (C) may contain other repeating units that do not correspond to either the repeating unit represented by formula (Ia) or the repeating unit represented by formula (IIa).
• Resin (C) is different from either the repeating unit represented by formula (Ia) or the repeating unit represented by formula (IIa), and is composed of a repeating unit having a phenolic hydroxyl group (hereinafter also referred to as "repeating unit Z"). ) is preferable.
• the number of phenolic hydroxyl groups is not particularly limited, and is preferably 1 to 4, more preferably 1 to 2.
• repeating unit Z examples include the following repeating units.
• the content of the repeating unit Z is preferably 0 to 50 mol%, more preferably 0 to 30 mol%, and even more preferably 0 to 10 mol%, based on all repeating units in the resin (C).
• the resin (C) preferably contains at least one of a repeating unit represented by formula (Ib) and a repeating unit represented by formula (IIb) described below.
• X b represents a halogen atom.
• Examples of X b include a halogen atom represented by X a in formula (Ia).
• Y b represents a group represented by formula (Y-3) or a group represented by formula (Y-4).
• the wavy line portion represents the bonding position.
• R 2b represents a hydrogen atom or a monovalent organic group containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom.
• the monovalent organic group containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom represented by R 2b is not particularly limited, but for example, a substituted group containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom
• a substituted group containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom An alkyl group having a group, a monovalent aromatic group having a substituent containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom, or a monovalent aromatic group having a substituent, and an oxygen atom as a ring member atom,
• a heteroaryl group containing at least one of a nitrogen atom and a sulfur atom is preferred.
• the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 6, even more preferably 1 or 2, and particularly preferably 1.
• the alkyl group may be linear, branched, or cyclic, and preferably linear.
• Examples of the alkyl group include linear or branched alkyl groups such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, and n-hexyl 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 tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.
• the alkyl group has include a substituent containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom among the groups exemplified as the substituent T, such as a hydroxyl group, a carboxyl group, a carbonyl group, and a carbomoyl group. , an ether group, an alkoxycarbonyl group, an amino group, a nitro group, a thiol group, a sulfo group, a sulfonyl group, or a sulfonamide group.
• the number of substituents is not particularly limited, and is preferably 1 to 4, more preferably 1 to 2.
• the said alkyl group may have a substituent other than the substituent containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom.
• Examples of the monovalent aromatic group having a substituent containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom include an aryl group having a substituent containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom, and Examples include heteroaryl groups having a substituent containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom.
• the above aryl group may further have a substituent other than the substituent containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom.
• the above aryl group may be monocyclic or polycyclic, and the number of ring member atoms is preferably 6 to 15, more preferably 6 to 10.
• the above-mentioned heteroaryl group may be monocyclic or polycyclic, and the number of ring member atoms is preferably 5 to 15, more preferably 5 to 10.
• the aryl group is preferably a phenyl group, a naphthyl group, or an anthracenyl group having a substituent containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom;
• a phenyl group or a naphthyl group having a substituent containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom is more preferable, and a phenyl group having a substituent containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom is even more preferable.
• heteroaryl group examples include a pyrrolyl group, a furyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, a triazolyl group, and an oxadiazolyl group, which may have a substituent.
• Examples include 5-membered heteroaryl groups such as thiadiazolyl, thiadiazolyl and tetrazolyl groups, and 6-membered heteroaryl groups such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl and triazinyl groups.
• Examples of the substituent containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom, which the aryl group may have and which the heteroaryl group may have, include an oxygen atom, a nitrogen atom, and a nitrogen atom among the groups exemplified as the substituent T.
• Substituents containing at least one of an atom and a sulfur atom include a hydroxyl group, a carboxyl group, a carbonyl group, a carbomoyl group, an ether group, an alkoxycarbonyl group, an amino group, a nitro group, a thiol group, a sulfo group, a sulfonyl group, or a sulfone group.
• An amide group is preferred.
• the number of substituents is not particularly limited, and is preferably 1 to 4, more preferably 1 to 2.
• the said aryl group and the said heteroaryl group may have a substituent other than the substituent containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom.
• a preferred embodiment of the heteroaryl group in a heteroaryl group which may have a substituent and contains at least one of an oxygen atom, a nitrogen atom and a sulfur atom as a ring member atom is a The preferred embodiments are the same as those described for the heteroaryl group having at least one substituent.
• the above heteroaryl group may further have a substituent.
• the above-mentioned substituent is not particularly limited, but includes, for example, the groups exemplified for the above-mentioned substituent T.
• the number of substituents is not particularly limited, and is preferably 1 to 4, more preferably 1 to 2.
• R 3b and R 4b each independently represent a hydrogen atom or a monovalent organic group.
• the monovalent organic groups represented by R 3b and R 4b are not particularly limited, but for example, the monovalent organic groups represented by R 3a and R 4a may have a substituent.
• Good alkyl groups, monovalent aromatic groups that may have substituents, and aralkyl groups that may have substituents and contain at least one of an oxygen atom, a nitrogen atom, and a sulfur atom. can be mentioned.
• the substituents that each of the alkyl group, monovalent aromatic group, and aralkyl group may have are not particularly limited, and include the groups exemplified as the substituent T described above, such as an oxygen atom, a nitrogen Substituents containing at least one of an atom and a sulfur atom are preferred.
• the monovalent organic group represented by R 3b and R 4b may be a monovalent organic group containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom.
• R 3b and R 4b may be a monovalent organic group that may contain at least one of an oxygen atom, a nitrogen atom, and a sulfur atom.
• the monovalent organic group represented by R 3b and R 4b is preferably an alkyl group that may have a substituent containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom.
• the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 6, even more preferably 1 or 2, and particularly preferably 1.
• the alkyl group may be linear, branched, or cyclic, and includes, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and a t-butyl group.
• linear or branched alkyl groups such as n-hexyl groups, monocyclic cycloalkyl groups such as cyclopentyl groups and cyclohexyl groups, and norbornyl groups, tetracyclodecanyl groups, tetracyclododecanyl groups and adamantyl groups.
• Examples include polycyclic cycloalkyl groups such as.
• R 3b and R 4b represents a hydrogen atom or a monovalent organic group containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom.
• the monovalent organic group containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom is preferably an alkyl group having a substituent containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom.
• the alkyl group is preferably an alkyl group having a substituent containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom, as exemplified by the monovalent organic groups represented by R 3b and R 4b .
• R 3b and R 4b represents a hydrogen atom
• the other represents a monovalent organic group not containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom.
• an unsubstituted alkyl group is preferable.
• the number of carbon atoms in the unsubstituted alkyl group is preferably 1 to 20, more preferably 1 to 6, even more preferably 1 or 2, and particularly preferably 1.
• the above-mentioned unsubstituted alkyl group may be linear, branched, or cyclic, such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t - Straight-chain or branched alkyl groups such as butyl and n-hexyl groups, monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, and norbornyl, tetracyclodecanyl, and tetracyclododecanyl groups. and polycyclic cycloalkyl groups such as adamantyl groups.
• the content of the repeating unit represented by formula (Ib) is preferably 1 to 60 mol%, more preferably 5 to 55 mol%, and 5 to 50 mol% based on the total repeating units in the resin (C). is even more preferable.
• R 1b represents an alkyl group that may have a substituent.
• Ar b represents a monovalent aromatic group which may have a substituent.
• Examples of the alkyl group represented by R 1b include the alkyl group which may have a substituent represented by R 1a .
• the alkyl group represented by R 1b is an alkyl group which may have a substituent containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom represented by R 3b and R 4b .
• the monovalent aromatic group represented by Ar b include a monovalent aromatic group optionally having a substituent represented by Ar a .
• the monovalent aromatic group represented by Ar b is a monovalent aromatic group which may have a substituent containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom represented by Ar a .
• An aromatic group or a heteroaryl group which may have a substituent and contains at least one of an oxygen atom, a nitrogen atom and a sulfur atom as a ring member atom is preferable.
• R 1b represents an alkyl group having a substituent containing an oxygen atom, nitrogen atom or sulfur atom
• Ar b represents a monovalent aromatic group having a substituent containing an oxygen atom, nitrogen atom or sulfur atom.
• At least one of watermark and Ar b may have a substituent and represents a heteroaryl group containing an oxygen atom, a nitrogen atom, or a sulfur atom.
• the total content of the repeating unit represented by formula (Ia) and the repeating unit represented by formula (IIa) is preferably 80 to 100 mol%, and 90 to 100 mol%, based on the total repeating units in the resin (C). 100 mol% is more preferable, and even more preferably 95 to 100 mol%.
• the repeating unit represented by formula (Ib) and the repeating unit represented by formula (IIb) do not have a phenolic hydroxyl group.
• the repeating unit having a phenolic hydroxyl group corresponds to any of the repeating unit represented by formula (Ia), the repeating unit represented by formula (IIa), and the repeating unit Z, and the repeating unit represented by formula (Ib). It does not correspond to either the repeating unit represented by formula (IIb) or the repeating unit represented by formula (IIb).
• R 2b in formula (Y-3) represented by Y b , and R 3b and R 4b in (Y-4) have a phenolic hydroxyl group. Contains no groups.
• the groups represented by R b1 and Ar b do not include a group having a phenolic hydroxyl group.
• Requirement 1 The repeating unit represented by formula (Ia) has a phenolic hydroxyl group, the repeating unit represented by formula (IIa) has a phenolic hydroxyl group, and the resin is represented by formula (Ia).
• the total amount A of the repeating unit represented by formula (Ia) having a phenolic hydroxyl group, the repeating unit represented by formula (IIa) having a phenolic hydroxyl group, and the other repeating unit having a phenolic hydroxyl group is It is 0.10 mmol/g or more based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition.
• a repeating unit represented by formula (Ia) having a phenolic hydroxyl group a repeating unit represented by formula (IIa) having a phenolic hydroxyl group, a repeating unit represented by formula (Ia) and a repeating unit represented by formula (IIa)
• the other repeating units having a phenolic hydroxyl group that are different from any of the repeating units represented by these are also collectively referred to as specific unit 1.
• Requirement 2 The repeating unit represented by formula (Ia) has a phenolic hydroxyl group, the repeating unit represented by formula (IIa) has a phenolic hydroxyl group, or the resin has a repeating unit represented by formula (Ia).
• the total amount B of the repeating unit and the repeating unit represented by formula (IIb) is 0.80 mmol/g or more based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition.
• a repeating unit represented by formula (Ia) having a phenolic hydroxyl group a repeating unit represented by formula (IIa) having a phenolic hydroxyl group, a repeating unit represented by formula (Ia) and a repeating unit represented by formula (IIa)
• Other repeating units having a phenolic hydroxyl group, repeating units represented by formula (Ib), and repeating units represented by formula (IIb), which are different from any of the repeating units represented by formula (Ib), are collectively referred to as specified Also called unit 2.
• requirement 1 is that the resin (C) has at least one repeating unit among the specific units 1, and the total amount A of the specific units 1 is based on the total solid content of the resist composition. It is specified that it is 0.10 mmol/g or more.
• Requirement 2 is that the resin (C) has at least one repeating unit among the specific units 2, and the total amount B of the specific units 2 is based on the total solid content of the resist composition. It is specified that it is 0.80 mmol/g or more.
• the resin (C) has a repeating unit represented by the formula (Ia) having a phenolic hydroxyl group, which corresponds to both specific unit 1 and specific unit 2, and the specific unit 1 and other units other than the repeating unit are If the specific unit 2 is not present, and the total amount of repeating units represented by formula (Ia) having a phenolic hydroxyl group is 0.80 mmol/g or more based on the total solid content of the resist composition, , the resin (C) satisfies Requirements 1 and 2.
• the resin (C) has a repeating unit represented by formula (Ia) having a phenolic hydroxyl group among the specific units 1, and the total amount A of the specific units 1 is Since it is 0.80 mmol/g or more, requirement 1 is satisfied. Further, the resin (C) has a repeating unit represented by formula (Ia) having a phenolic hydroxyl group among the specific units 2, and the total amount B of the specific units 2 is 0.80 mmol/g or more. , also satisfies requirement 2. Therefore, in the above case, the resin (C) satisfies Requirements 1 and 2.
• the resin (C) contains at least one of the repeating units that do not correspond to the specific unit 1 among the specific units 2, that is, the repeating unit represented by the formula (Ib), and the repeating unit represented by the formula (IIb). It is also preferable to have one.
• the repeating unit represented by formula (Ib) and the repeating unit represented by formula (IIb) are also collectively referred to as specific unit 3. Further, the total amount of the specific unit 3 is also referred to as the total amount C.
• the resin (C) has 3 specific units, it is easy to adjust the dissolution rate of the resin (C) in the developer, that is, it is easy to reduce the difference between the dissolution rate of the specific photoacid generator and the developer, and the resin
• the progress of the crosslinking reaction, which is a side reaction, can be further suppressed during the cutting of (C).
• the total amount A is 0.10 mmol/g or more, preferably 0.15 mmol/g or more, and more preferably 0.20 mmol/g or more, based on the total solid content of the resist composition.
• the upper limit is not particularly limited, but may be 5.00 mmol/g or less, preferably 3.00 mmol/g or less, and more preferably 1.50 mmol/g or less.
• the total amount B is 0.80 mmol/g or more, preferably 1.00 mmol/g or more, and more preferably 1.20 mmol/g or more, based on the total solid content of the resist composition.
• the upper limit is not particularly limited, but may be 5.00 mmol/g or less, preferably 4.00 mmol/g or less.
• the total amount C may be 0 mmol/g or more, preferably 0.40 mmol/g or more, and more preferably 0.50 mmol/g or more, based on the total solid content of the resist composition.
• the upper limit is not particularly limited, but may be 5.00 mmol/g or less, preferably 4.00 mmol/g or less, and more preferably 3.00 mmol/g or less.
• the content of specific unit 1 in resin (C) is preferably 1 to 50 mol%, more preferably 5 to 30 mol%, based on all repeating units in resin (C).
• the content of the specific unit 2 in the resin (C) is not particularly limited, and is preferably 10 to 100 mol% with respect to all repeating units in the resin (C). , more preferably 20 to 80 mol%.
• the content of the specific unit 3 in the resin (C) is not particularly limited, and is 0 to 90 mol% with respect to all repeating units in the resin (C). It is preferably 10 to 90 mol%, more preferably 20 to 80 mol%.
• the weight average molecular weight (Mw) of the resin (C) is not particularly limited, but it is preferably 15,000 or more, more preferably 20,000 or more, and even more preferably 30,000 or more, since the effects of the present invention are more excellent.
• the upper limit is not particularly limited, but is preferably 200,000 or less, more preferably 150,000 or less.
• the number average molecular weight (Mn) of the resin (C) is not particularly limited, but is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 15,000 or more.
• the upper limit is not particularly limited, but is preferably 150,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less.
• the polydispersity of the resin (C) is not particularly limited, but it is preferably 2.5 or less, more preferably 2.0 or less, and even more preferably 1.7 or less in terms of the effects of the present invention.
• the lower limit is not particularly limited and may be 1.0 or more.
• the content of the resin (C) is not particularly limited, but it is preferably 40 to 99% by mass, more preferably 60 to 97% by mass, based on the total solid content of the resist composition, since the effects of the present invention are more excellent. , 65 to 97% by mass is more preferable.
• the resist composition may contain only one type of resin (C), or may contain two or more types. When two or more types are included, it is preferable that their total amount falls within the above range.
• the resist composition contains an ionic compound (specific photoacid generator) represented by formula (III).
• B + represents a sulfonium cation or an iodonium cation.
• the cation represented by B + decomposes by absorbing irradiated light, and the generated radical cation species plays the role of extracting hydrogen.
• the cation represented by B + is preferably a cation represented by the formula (ZaI) (cation (ZaI)) or a cation represented by the formula (ZaII) (cation (ZaII)).
• R 201 to R 203 each independently represent an organic group.
• the number of carbon atoms in the organic group represented by R 201 to R 203 is preferably 1 to 30, more preferably 1 to 20.
• two of the organic groups represented by R 201 to R 203 may be combined to form a ring structure, and within the formed ring there may be an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. May contain.
• examples of the group formed by bonding two of the organic groups represented by R 201 to R 203 include an alkylene group (e.g., butylene group and pentylene group), and -CH 2 -CH 2 -O-CH 2 -CH 2 - is mentioned.
• R 204 and R 205 each independently represent a monovalent aromatic group that may have a substituent or an alkyl group that may have a substituent; A monovalent aromatic group is preferable in that the effect is more excellent.
• Examples of the monovalent aromatic group for R 204 and R 205 include an aryl group and a heteroaryl group.
• a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.
• a heteroaryl group has a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom.
• Examples of the ring constituting the heteroaryl group include a pyrrole ring, a furan ring, a thiophene ring, an indole ring, a benzofuran ring, and a benzothiophene ring.
• the alkyl group for R 204 and R 205 includes a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group) or a cyclic alkyl group having 3 to 10 carbon atoms (eg, cyclopentyl group, cyclohexyl group, and norbornyl group).
• the monovalent aromatic group and the alkyl group of R 204 and R 205 may further have other substituents, such as an alkyl group (for example, having 1 to 15 carbon atoms). , a monovalent aromatic group (eg, having 6 to 15 carbon atoms), an alkoxy group (eg, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.
• the above-mentioned cation (ZaI) is preferably a cation (ZaI-1), a cation (ZaI-2), or an organic cation represented by the formula (ZaI-3b) or the formula (ZaI-4b).
• R 201 to R 203 represents a monovalent aromatic group which may have a substituent. All of R 201 to R 203 may be a monovalent aromatic group, or some of R 201 to R 203 may be a monovalent aromatic group, and the remainder may have a substituent. It may also be an alkyl group. Further, one of R 201 to R 203 may be a monovalent aromatic group, and the remaining two of R 201 to R 203 may be bonded to form a ring structure, and within the formed ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group.
• the group formed by combining two of R 201 to R 203 includes, for example, one or more methylene groups substituted with an oxygen atom, a sulfur atom, an ester group, an amide group, and/or a carbonyl group. and alkylene groups (eg, butylene group, pentylene group, or -CH 2 -CH 2 -O-CH 2 -CH 2 -).
• examples of the monovalent aromatic group include an aryl group and a heteroaryl group.
• a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.
• a heteroaryl group has a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom.
• examples of the ring constituting the heteroaryl group include a pyrrole ring, a furan ring, a thiophene ring, an indole ring, a benzofuran ring, and a benzothiophene ring.
• the two or more monovalent aromatic groups may be the same or different. .
• the alkyl group is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cyclic alkyl group having 3 to 15 carbon atoms, Examples include methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, and cyclohexyl group.
• the monovalent aromatic groups R 201 to R 203 and the substituents that the alkyl groups may have include, each independently, an alkyl group (for example, having 1 to 15 carbon atoms), a monovalent aromatic group (eg, having 6 to 14 carbon atoms), an alkoxy group (eg, having 1 to 15 carbon atoms), a cycloalkylalkoxy group (eg, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.
• the above substituent may further have another substituent, for example, the above alkyl group may have a halogen atom as a substituent to become a halogenated alkyl group such as a trifluoromethyl group. .
• Examples of the cation (ZaI-1) include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations, but the effects of the present invention Triarylsulfonium cations are preferred in terms of their superiority.
• each of R 201 to R 203 independently represents an organic group having no aromatic ring.
• the aromatic ring also includes a heterocycle containing a heteroatom.
• the organic group having no aromatic ring represented by R 201 to R 203 generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
• R 201 to R 203 are each independently preferably an alkyl group, an allyl group, or a vinyl group, and a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, or an alkoxycarbonylmethyl group. More preferred is a linear or branched 2-oxoalkyl group.
• the alkyl group includes, for example, a linear alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group), and a linear alkyl group having 3 to 10 carbon atoms.
• 10 branched alkyl groups, and cyclic alkyl groups having 3 to 10 carbon atoms eg, cyclopentyl group, cyclohexyl group, and norbornyl group).
• the alkyl group represented by 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.
• R 1c to R 5c each independently represent a hydrogen atom, an alkyl group, a monovalent aromatic group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, or a cycloalkyl group. Represents a carbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group, or an arylthio group.
• R 6c and R 7c each independently represent a hydrogen atom, an alkyl group (such as a t-butyl group), a halogen atom, a cyano group, or an aryl group.
• R x and R y each independently represent an alkyl group, a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.
• R 1c to R 5c , R 5c and R 6c, R 6c and R 7c , R 5c and R x , and R x and R y may be bonded to each other to form a ring.
• the rings formed may each independently contain an oxygen atom, a sulfur atom, a ketone group, an ester group, or an amide bond.
• Examples of the above-mentioned ring include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, and a polycyclic condensed ring formed by combining two or more of these rings.
• the ring include a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and 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 alkylene groups such as a butylene group and a pentylene group.
• the methylene group in this alkylene group may be substituted with a hetero atom such as an oxygen atom.
• the group formed by bonding R 5c and R 6c and R 5c and R x is preferably a single bond or an alkylene group.
• Examples of the alkylene group include a methylene group and an ethylene group.
• R13 is a hydrogen atom, a fluorine atom, a hydroxyl group, a linear or branched alkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group (it may be a cycloalkyl group itself, a cycloalkyl group ). These groups may have substituents.
• R14 is a group having a hydroxyl group, a linear or branched alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl group (not a cycloalkyl group itself). (or a group partially containing a cycloalkyl group). These groups may have substituents. When a plurality of R 14s exist, each independently represents the above group such as a hydroxyl group. R 15 each independently represents an alkyl group or a naphthyl group. These groups may have substituents.
• Two R 15s 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.
• two R 15s are alkylene groups and are preferably bonded to each other to form a ring structure.
• the alkyl group represented by R 15 may be linear, branched, or cyclic.
• the number of carbon atoms in the alkyl group is preferably 1 to 10.
• the alkyl group is preferably a methyl group, ethyl group, n-butyl group, or t-butyl group.
• D ⁇ is a hydroxide ion (OH ⁇ ), an anion formed by dissociating a proton (H + ) from a hydroxyl group in a compound having a hydroxyl group, or a carboxyl group in a compound having a carboxy group. Represents an anion formed by the dissociation of protons from.
• the anion represented by D - is preferably a hydroxide ion or an organic anion represented by the formula (ZbI).
• R a represents a hydrogen atom or a monovalent organic group.
• L a represents a single bond or a divalent linking group.
• a 3 - represents -O - or -COO - .
• the monovalent organic group represented by R a is not particularly limited, but the number of carbon atoms in the monovalent organic group is preferably 1 to 30, more preferably 1 to 20.
• Examples of the monovalent organic group include an alkyl group, a monovalent aromatic group, and an aralkyl group.
• the monovalent organic group represented by R a is preferably an alkyl group or an aryl group.
• the alkyl group and aryl group described above may further have a substituent.
• Substituents that the alkyl group and aryl group may have are not particularly limited, but include the groups exemplified for the substituent T above, such as hydroxyl groups, halogen atoms, and halogen atom-substituted groups. Examples include alkyl groups which may be substituted.
• the alkyl group may be linear, branched, or cyclic.
• the number of carbon atoms in the linear and branched alkyl group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10.
• the cyclic alkyl group (cycloalkyl group) may be monocyclic or polycyclic.
• the number of carbon atoms in the cyclic alkyl group is preferably 3 to 20, more preferably 3 to 15, and even more preferably 3 to 10.
• the aryl group may be monocyclic or polycyclic.
• the number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10.
• the cycloalkyl group may contain a heteroatom as a ring member atom.
• heteroatoms include, but are not limited to, nitrogen atoms, oxygen atoms, and the like.
• the divalent linking group represented by L a is not particularly limited, but includes, for example, an alkylene group, a divalent aromatic group, -O-, -CO-, -COO-, and a combination of two or more of these.
• the following groups are mentioned.
• the alkylene group may be linear, branched, or cyclic.
• the number of carbon atoms in the linear and branched alkylene groups is preferably 1 to 20, more preferably 1 to 10.
• the cyclic alkylene group (cycloalkylene group) may be monocyclic or polycyclic.
• the number of carbon atoms in the cyclic alkylene group is preferably 3 to 20, more preferably 3 to 10.
• the number of carbon atoms in the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15.
• the aromatic ring constituting the divalent aromatic group is not particularly limited, and may be either an aromatic hydrocarbon or an aromatic heterocycle.
• aromatic ring examples include a benzene ring, a naphthalene ring, an anthracene ring, and a thiophene ring, with a benzene ring or a naphthalene ring being preferred, and a benzene ring being more preferred.
• the alkylene group and the divalent aromatic group may further have a substituent.
• Substituents that the alkylene group and the divalent aromatic group may have are not particularly limited, but include the groups exemplified for the substituent T above, with halogen atoms being preferred.
• a 3 - represents -O - or -COO - .
• -O - is a group formed by dissociation of a proton from a hydroxyl group (-OH).
• -COO - is a group formed by dissociating a proton from a carboxy group (-COOH).
• the ClogP value of the specific compound is 3.00 or less.
• the lower limit of the ClogP value of the specific compound is not limited, but is preferably -2.00 or more.
• the specific compound include a compound represented by formula (V) and having a ClogP value of 3.00 or less.
• Formula (V) R-COOH R represents an alkyl group which may have a substituent that does not contain an aromatic ring.
• the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 3 to 10.
• the substituent include substituents that do not contain an aromatic ring among the groups exemplified for the substituent T described above, and a halogen atom is preferred.
• the ClogP value of the compound (D ⁇ H + ) formed by bonding the proton to the anion is not particularly limited. , is preferably 5.00 or less, more preferably 4.00 or less, and even more preferably 3.00 or less. Further, the lower limit is not particularly limited, but may be -2.00 or more.
• the content of the specific photoacid generator in the resist composition is not particularly limited, and may be 0.01 to 1.50 mmol/g based on the total solid content of the resist composition, so that the effect of the present invention can be achieved. In terms of superiority, 0.10 to 1.00 mmol/g is preferable.
• the resist composition may contain only one type of specific photoacid generator, or may contain two or more types of specific photoacid generators. When two or more types are included, it is preferable that their total amount falls within the above range.
• the resist composition may contain a solvent.
• the solvents include (M1) propylene glycol monoalkyl ether carboxylate (such as propylene glycol monomethyl ether acetate (PGMEA)), and (M2) propylene glycol monoalkyl ether (propylene glycol monomethyl ether (PGME) or propylene glycol monoethyl ether).
• this solvent may further contain components other than components (M1) and (M2).
• the solvent preferably contains component (M1). It is more preferable that the solvent consists essentially of component (M1) only, or is a mixed solvent of component (M1) and other components. In the latter case, it is more preferable that the solvent contains both component (M1) and component (M2).
• the mass ratio (M1/M2) of component (M1) and component (M2) is preferably "100/0" to "0/100", more preferably “100/0” to "15/85", and " The range is more preferably 100/0 to 40/60, and particularly preferably 100/0 to 60/40.
• the solvent may further contain components other than components (M1) and (M2).
• the content of components other than components (M1) and (M2) is preferably 5 to 30% by mass based on the total amount of the solvent.
• the content of the solvent in the resist composition is preferably determined so that the solid content concentration is 0.5 to 30% by mass, more preferably 1 to 20% by mass.
• the resist composition may further contain a surfactant.
• the surfactant is preferably a fluorine-based and/or silicon-based surfactant.
• Examples of the fluorine-based and/or silicon-based surfactants include the surfactants disclosed in paragraphs [0218] and [0219] of International Publication No. 2018/193954.
• the content of the surfactant is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass, based on the total solid content of the composition.
• the resist composition may contain only one kind of surfactant, or may contain two or more kinds of surfactants. When two or more types are included, it is preferable that their total amount falls within the above range.
• the resist composition may further contain a dissolution-inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and/or a compound that promotes solubility in a developer.
• the resist composition preferably satisfies the following requirement 3.
• Requirement 3 The polydispersity of the resin contained in the resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition is PDI 0 , When the resist film is exposed to light under irradiation conditions such that the weight average molecular weight of the product obtained by cutting the resin in the resist film is 1/2 of the weight average molecular weight of the resin, the resin is cut.
• the polydispersity of the product obtained is PDI 2 , When the resist film is exposed to light under irradiation conditions such that the weight average molecular weight of the product obtained by cutting the resin in the resist film is 1/3 of the weight average molecular weight of the resin, the resin is cut.
• the polydispersity of the product obtained is PDI 3 , When the resist film is exposed to light under irradiation conditions such that the weight average molecular weight of the product obtained by cutting the resin in the resist film is 1/4 of the weight average molecular weight of the resin, the resin is cut.
• the polydispersity of the product obtained is PDI 4 , When the resist film is exposed to light under irradiation conditions such that the weight average molecular weight of the product obtained by cutting the resin in the resist film is 1/5 of the weight average molecular weight of the resin, the resin is cut.
• the polydispersity of the product obtained is PDI 5 , When the largest value among PDI 2 to PDI 5 is set as PDI max , the relationship of equation (1) is satisfied.
• the polydispersity expressed by PDI 0 and PDI 2 to PDI 5 can be measured by the GPC device described above.
• a predetermined resist composition is applied onto a silicon wafer to form a resist film.
• the thickness of the resist film is preferably 15 to 100 nm.
• a drying process may be performed as necessary after applying the resist composition.
• the conditions for the drying treatment include the conditions described in step 1 below.
• the resist film is irradiated with light at a predetermined exposure amount.
• the light for the light irradiation light that can cleave the main chain of the resin (C) is used, and EUV light is preferable.
• the resist film after exposure is immersed in a predetermined solvent (for example, N-methylpyrrolidone) to dissolve the resist film, and the resulting solution sample is used to determine the product obtained by cutting the resin (C). Measure the weight average molecular weight.
• the weight average molecular weight of the product obtained by cutting the resin (C) is 1/2, 1/3, 1/4, Then, find the irradiation conditions (exposure amount) that are 1/5, and find the polydispersities PDI 2 to PDI 5 of the products obtained by cutting the resin (C) under each irradiation condition.
• the one with the largest value among the obtained polydispersities PDI 2 to PDI 5 is selected as PDI max , and PDI max is compared with the polydispersity PDI 0 of the resin (C) before light irradiation, and the above Check whether the relationship in equation (1) is satisfied.
• the crosslinking reaction is difficult to proceed during cutting of the resin (C), and as a result, the decrease in dissolution contrast is small, and the LWR performance is more excellent.
• the resist composition preferably satisfies the following requirement 4.
• Requirement 4 The dissolution rate in butyl acetate of the resist film obtained by applying an actinic ray-sensitive or radiation-sensitive resin composition on a silicon wafer and heating it at 80°C for 60 seconds is DR 1 , and the actinic ray-sensitive or radiation-sensitive resin composition is When the dissolution rate in butyl acetate of a resist film obtained by applying a photosensitive or radiation-sensitive resin composition onto a silicon wafer and heating it at 130°C for 60 seconds is DR 2 , the relationship of formula (2) is obtained. satisfy.
• a method for contacting the resist film with butyl acetate includes a method of immersing a silicon wafer with a resist film in butyl acetate.
• the immersion time is preferably 100 to 2000 seconds.
• the temperature of butyl acetate during dipping is preferably 0 to 50°C.
• the resist film after immersion is dried using a spin coater (rotation speed: 400 rpm, rotation time: 30 seconds), and the film thickness FT 1 of the obtained resist film is measured.
• the dissolution rate DR 1 is calculated from the following formula using the thickness of the resist film before contact with butyl acetate (initial thickness), the above film thickness FT 1 , and the immersion time.
• Dissolution rate DR 1 (Initial film thickness - FT 1 ) ⁇ (immersion time) (nm/sec)
• the dissolution rate DR 2 is calculated according to the same procedure as above, except that the heat treatment conditions of 80° C. for 60 seconds were changed to 130° C. for 60 seconds. It is examined whether the calculated dissolution rates DR 1 and DR 2 satisfy the relationship of the above formula (2).
• the resist composition satisfies requirement 4 above, when the resist film is heated at a higher temperature, the dissolution rate in the organic solvent is low, and the interaction between the resin (C) and the ionic compound in the resist film is reduced by heating. It can be said that the effect has become stronger.
• the strong interaction means that the dissolution contrast between the unexposed area and the exposed area is high during exposure, so that the LWR performance of the resist film is better.
• the interaction between the resin (C) and the ionic compound is strengthened. There is a way.
• Step 1 Forming a resist film on a substrate using a resist composition
• Step 2 Exposing the resist film to light
• Step 3 Developing the exposed resist film using a developer containing an organic solvent , Step of Obtaining a Pattern
• Step 1 is a step of forming a resist film on a substrate using a resist composition.
• the definition of the resist composition is as described above.
• Examples of methods for forming a resist film on a substrate using a resist composition include a method of applying a resist composition onto a substrate. Note that it is preferable to filter the resist composition before coating, if 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 resist composition can be applied by any suitable application method, such as a spinner or coater, onto a substrate (eg, silicon, silicon dioxide coated) such as those used in the manufacture of integrated circuit devices.
• the coating method is preferably spin coating using a spinner.
• the rotation speed during spin coating using a spinner is preferably 1000 to 3000 rpm.
• the substrate may be dried to form a resist film. Note that, if necessary, various base films (inorganic film, organic film, antireflection film) may be formed under the resist film.
• a silicon wafer in the case of a semiconductor wafer, can be used as the material constituting the substrate to be processed and its outermost layer, and examples of the material forming the outermost layer include Si, SiO 2 , SiN, SiON, TiN, Examples include WSi, BPSG (Boro-Phospho. Silicate Glass), SOG (Spin On Glass), and organic antireflection films.
• drying method examples include a method of drying by heating. Heating can be carried out using a means provided in an ordinary exposure machine and/or developing machine, or may be carried out using a hot plate or the like.
• the heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, even more preferably 80 to 130°C.
• the heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, even more preferably 60 to 600 seconds.
• the resist film can be formed by prebaking, for example, at 60 to 150° C. for 1 to 20 minutes, preferably at 80 to 120° C. for 1 to 10 minutes.
• the thickness of the resist film is not particularly limited, but is preferably 10 to 120 nm from the standpoint of forming fine patterns with higher precision. Among these, in the case of EUV exposure, the thickness of the resist film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm.
• a top coat may be formed on the upper layer of the resist film using a top coat composition.
• the top coat composition does not mix with the resist film and can be uniformly applied to the upper layer of the resist film.
• the thickness of the top coat is preferably 10 to 200 nm, more preferably 20 to 100 nm, and even more preferably 40 to 80 nm.
• the top coat is not particularly limited, and a conventionally known top coat can be formed by a conventionally known method. Can be formed.
• Specific examples of basic compounds that may be included in the top coat include basic compounds that may be included in the resist composition.
• 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.
• the exposure method include a method of irradiating the formed resist film with actinic rays or radiation through a predetermined mask.
• Actinic light or radiation includes infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, preferably 250 nm or less, more preferably 220 nm or less, particularly preferably 1 Deep ultraviolet light with a wavelength of ⁇ 200 nm, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), EUV (13 nm), X-rays, and electron beams. .
• post-exposure heat treatment also referred to as post-exposure bake
• the post-exposure heat treatment accelerates the reaction in the exposed area, resulting in better sensitivity and pattern shape.
• the heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, even more preferably 80 to 130°C.
• the heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds. Heating can be carried out using means provided in a normal exposure machine and/or developing machine, and may be carried out using a hot plate or the like. This step is also called post-exposure bake.
• Step 3 is a step of developing the exposed resist film using a developer containing an organic solvent to obtain a pattern.
• Development methods include, for example, a method in which the substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is heaped up on the surface of the substrate by surface tension and developed by standing still for a certain period of time (paddle method). ), a method of spraying the developer onto the substrate surface (spray method), and a method of continuously discharging the developer while scanning the developer discharge nozzle at a constant speed onto the rotating substrate (dynamic dispensing method).
• dip method a method in which the substrate is immersed in a tank filled with a developer for a certain period of time
• paddle method a method in which the developer is heaped up on the surface of the substrate by surface tension and developed by standing still for a certain period of time
• spray method a method of spraying the developer onto the substrate surface
• dynamic dispensing method a method of continuously discharging the developer while scanning the developer discharge nozzle at a constant speed onto the rotating substrate
• the development time is not particularly limited as long as the resin in the unexposed area is sufficiently dissolved, and is preferably 10 to 300 seconds, more preferably 20 to 120 seconds.
• the temperature of the developer is preferably 0 to 50°C, more preferably 15 to 35°C.
• the organic solvent contained in the developer is preferably at least one selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.
• the ClogP value of the organic solvent contained in the developer is not particularly limited, but is preferably 0.00 or more, more preferably 1.00 or more. When two or more types of organic solvents are included, it is preferable that the ClogP value of the mixed solvent falls within the above range.
• ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Examples include cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methylnaphthyl ketone, isophorone, and propylene carbonate.
• ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl Ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butanoic acid
• Examples include butyl, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.
• the alcohol solvent amide solvent, ether solvent, and hydrocarbon solvent
• the solvents disclosed in paragraphs [0715] to [0718] of US Patent Application Publication No. 2016/0070167 are used. can.
• a plurality of the above-mentioned solvents may be mixed together, or may be mixed with a solvent other than the above-mentioned ones or water.
• the water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and particularly preferably substantially free of water.
• the content of the organic solvent in the developer is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, even more preferably 90 to 100% by mass, and even more preferably 95 to 100% by mass, based on the total amount of the developer. is particularly preferred.
• the developer contains a first organic solvent and a second organic solvent, and the boiling point of the first organic solvent is higher than the boiling point of the second organic solvent, and It is more preferable that the ClogP value of the first organic solvent is larger than the ClogP value of the second organic solvent.
• the said boiling point means the boiling point under 1 atmosphere (760 mmHg).
• the content ratio of the first organic solvent and the second organic solvent in the developer is not particularly limited, the effect of the present invention is better when the content ratio of the second organic solvent to the content of the first organic solvent is
• the mass ratio is preferably 1 to 50, more preferably 3 to 20.
• the ketone solvent or the ester solvent is preferable, the ester solvent is more preferable, and butyl acetate or isoamyl butyrate is more preferable, since the effect of the present invention is more excellent.
• the first organic solvent is not particularly limited, but an organic solvent having a ClogP value of 3.00 or more is preferable, and a hydrocarbon solvent is more preferable.
• the pattern forming method includes, after step 3, step 4 of cleaning the pattern using a rinsing liquid containing an organic solvent.
• the rinsing liquid contains an organic solvent.
• the organic solvent contained in the rinsing 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.
• Examples of the hydrocarbon solvent, ketone solvent, ester solvent, alcohol solvent, amide solvent, and ether solvent include those described for the developer containing an organic solvent.
• the rinsing liquid contains a first organic solvent and a second organic solvent, and the boiling point of the first organic solvent is higher than the boiling point of the second organic solvent, and It is more preferable that the ClogP value of the first organic solvent is larger than the ClogP value of the second organic solvent.
• the said boiling point means the boiling point under 1 atmosphere (760 mmHg).
• the content ratio of the first organic solvent and the second organic solvent in the rinsing liquid is not particularly limited, the effect of the present invention is better when the content ratio of the second organic solvent to the content of the first organic solvent
• the mass ratio is preferably 1 to 50, more preferably 3 to 20.
• the second organic solvent in the rinsing liquid the ketone solvent or the ester solvent is preferable, the ester solvent is more preferable, and butyl acetate or isoamyl butyrate is more preferable, since the effects of the present invention are more excellent.
• the first organic solvent is not particularly limited, but an organic solvent having a ClogP value of 3.00 or more is preferable, and a hydrocarbon solvent is more preferable.
• the method of the rinsing process is not particularly limited, and examples include a method in which the rinsing liquid is continuously discharged onto the substrate rotating at a constant speed (rotary coating method), and a method in which the substrate is immersed in a tank filled with the rinsing liquid for a certain period of time. (dip method), and a method of spraying a rinsing liquid onto the substrate surface (spray method).
• the pattern forming method of the present invention may include a heating step (Post Bake) after the rinsing step. In this step, the developer and rinse solution remaining between patterns and inside the patterns due to baking are removed. This step also has the effect of smoothing the resist pattern and improving 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 etching process may be performed on the substrate, which is the object to be etched, using the formed pattern as a mask. That is, the pattern formed in step 3 may be used as an etching mask to process the substrate (or the underlying film and the substrate) to form a pattern on the substrate.
• the method of processing the substrate (or the lower layer film and the substrate) is not particularly limited, but by performing dry etching on the substrate (or the lower layer film and the substrate) using the pattern formed in step 3 as a mask, the substrate can be processed.
• a method of forming a pattern is preferred.
• the dry etching is preferably oxygen plasma etching.
• the developer contains two or more organic solvents
• the resist composition and various materials used in the pattern forming method of the present invention do not contain impurities such as metals. It is preferable not to include it.
• the content of impurities contained in these materials is preferably 1 mass ppm or less, more preferably 10 mass ppt 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.
• examples of metal impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, Zn, etc. are mentioned.
• Examples of methods for removing impurities such as metals from various materials include filtration using a filter. Details of filtration using a filter are described in paragraph [0321] of International Publication No. 2020/004306.
• methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with low metal content as raw materials constituting various materials, and filtering raw materials constituting various materials. and a method in which distillation is carried out under conditions where contamination is suppressed as much as possible by lining the inside of the apparatus with Teflon (registered trademark).
• impurities may be removed using an adsorbent, or a combination of filter filtration and an adsorbent may be used.
• adsorbent known adsorbents can be used, such as 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.
• metal impurities have been sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of metal components contained in the cleaning liquid used to clean the manufacturing equipment.
• the content of metal components contained in the cleaning solution after use is preferably 100 parts per trillion or less, more preferably 10 parts per trillion or less, and even more preferably 1 parts per trillion or less.
• a method for improving pattern surface roughness may be applied to the pattern formed by the method of the present invention.
• Examples of a method for improving surface roughness of a pattern include a method of treating a pattern with plasma of a gas containing hydrogen, which is disclosed in International Publication No. 2014/002808.
• Japanese Patent Application Publication No. 2004-235468, US Patent Application Publication No. 2010/0020297, Japanese Patent Application Publication No. 2008-83384, and Proc. of SPIE Vol. 8328 83280N-1 "EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement" Examples include known methods such as:
• the present invention also relates to an electronic device manufacturing method including the above-described pattern forming method, and an electronic device manufactured by this manufacturing method.
• the electronic device of the present invention is preferably installed in electrical and electronic equipment (home appliances, office automation (OA), media-related equipment, optical equipment, communication equipment, etc.).
• the method for synthesizing resin C-1 (Synthesis Example 1) is as described below.
• Resin C-2 to Resin C-14 were each synthesized according to the synthesis method of Resin C-1 (Synthesis Example 1 below) or a known method.
• Table 1 shows the composition ratio (mol% ratio), weight average molecular weight (Mw 0 ), number average molecular weight (Mn 0 ), and polydispersity (Mw 0 /Mn) of each repeating unit of Resin C-1 to Resin C-14. 0 ).
• the composition ratio (mol% ratio) of each repeating unit of Resin C-1 to Resin C-14 was measured by 13 C-NMR (Nuclear Magnetic Resonance).
• the weight average molecular weight (Mw 0 ), number average molecular weight (Mn 0 ), and polydispersity (Mw 0 /Mn 0 ) of Resin C-1 to Resin C-14 were measured using a GPC (Gel Permeation Chromatography) apparatus (Tosoh Corporation).
• GPC measurement Solvent: Tetrahydrofuran, Flow rate (sample injection amount): 10 ⁇ L, Column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, Column temperature: 40°C, Flow rate: 1.0 mL/min, Detection Instrument: Measured as a polystyrene equivalent value using a differential refractive index detector.
• SL-1 Propylene glycol monomethyl ether acetate (PGMEA)
• PGME Propylene glycol monomethyl ether
• SL-3 Cyclohexanone
• SL-4 ⁇ -butyrolactone
• SL-5 Ethyl lactate
• SL-6 Diacetone alcohol
• a resist composition was prepared by mixing various components shown in the table below to obtain a mixed solution, and filtering the obtained mixed solution through a polyethylene filter having a pore size of 0.03 ⁇ m.
• the solid content concentration of the resist composition was appropriately adjusted so that the resist composition could be coated with the film thickness shown in Table 4. Solid content means all components other than the solvent.
• the column “ClogP of anion conjugate acid” shows the ClogP value of the conjugate acid of the anion in the specific photoacid generator and other additives. Specifically, in the case of a specific photoacid generator, the ClogP value of the conjugate acid (D ⁇ H + ) of the anion represented by D ⁇ in formula (III) is shown.
• the "Total amount A (mmol/g)" column indicates the repeating unit represented by formula (Ia) having a phenolic hydroxyl group in Requirement 1, the repeating unit represented by formula (IIa) having a phenolic hydroxyl group, and the formula (IIa ) and another repeating unit having a phenolic hydroxyl group (repeat unit Z).
• Total amount B (mmol/g) column indicates the repeating unit represented by formula (Ia) having a phenolic hydroxyl group in requirement 2, the formula (IIa) having a phenolic hydroxyl group, based on the total solid content of the resist composition. ), another repeating unit having a phenolic hydroxyl group (repeat unit Z), a repeating unit represented by formula (Ib), and a repeating unit represented by formula (IIb). show.
• the column “Total amount C (mmol/g)” indicates the total amount of the repeating unit represented by formula (Ib) and the repeating unit represented by formula (IIb) with respect to the total solid content of the resist composition. show.
• the column "Content of specific photoacid generator” indicates the content (mmol/g) of the specific photoacid generator relative to the total solid content of the resist composition.
• the resist components were extracted by immersing the exposed silicon wafer in N-methylpyrrolidone. Using the obtained extract as a sample, the weight average molecular weight, number average molecular weight, and polydispersity of the product obtained by cutting the resin (C) were measured by GPC under the above-mentioned conditions . ⁇ PDI 5 and PDI max were calculated. If the relationship of formula (1) below holds between the calculated PDI max and PDI 0 , the resist composition satisfies Requirement 3.
• the silicon wafer with the resist film obtained by the above procedure was immersed in butyl acetate for 600 seconds, then the wafer was rotated at a rotation speed of 4000 rpm for 30 seconds, and the resist film was developed using the ellipso-type film thickness measuring device again.
• the thickness (FT 1 ) was measured, and the dissolution rate DR 1 of the resist film was calculated using the following formula (A).
• the same operation was performed except that the baking temperature after applying the resist composition was changed to 130°C, the resist film thickness (FT 2 ) after development was measured, and the dissolution rate DR of the resist film was calculated using the following formula (B). 2 was calculated.
• a lower layer film forming composition SHB-A940 (manufactured by Shin-Etsu Chemical Co., Ltd.) was applied onto a silicon wafer and baked at 205° C. for 60 seconds to form a lower layer film with a thickness of 20 nm.
• a resist composition shown in the above table was applied thereon to form a resist film under the conditions (film thickness and PreBake) shown in the above table. As a result, a silicon wafer having a resist film was formed.
• a silicon wafer having a resist film obtained by the above procedure was subjected to pattern irradiation using an EUV scanner NXE3300 manufactured by ASML (NA 0.33, ⁇ 0.9/0.7, dipole illumination).
• an EUV scanner NXE3300 manufactured by ASML NA 0.33, ⁇ 0.9/0.7, dipole illumination.
• a mask with a line size of 20 nm and a line:space ratio of 1:1 was used.
• Optimal exposure amount The line width of the line-and-space pattern was measured while changing the exposure amount using a length-measuring scanning electron microscope (SEM: CG-4100, manufactured by Hitachi High-Technologies) to form the pattern by EUV exposure. Then, the exposure amount when the line width was 20 nm was determined, and this was defined as the optimum exposure amount (mJ/cm 2 ).
• the "Mw 0 " column indicates the weight average molecular weight of the resin (C).
• the “Mn 0” column indicates the number average molecular weight of the resin (C).
• the column “Mw 0 /Mn 0” indicates the polydispersity of the resin (C).
• the “content” column of "specific photoacid generator” indicates the content (mmol/g) of the specific photoacid generator relative to the total solid content of the resist composition.
• “ClogP of anionic conjugate acid”, “total amount A”, “total amount B”, and “total amount C” have the same meanings as each description in Table 3.
• Equation (1) if the relationship of Equation (1) in Requirement 3 is satisfied, it is marked as "A”, and when the relationship of Equation (1) is not satisfied, it is marked as "B".
• Equation (2) if the relationship of Equation (2) in Requirement 4 is satisfied, it is marked as "A”, and if the relationship of Equation (2) is not satisfied, it is marked as "B”.
• the effect of the present invention is more excellent when the polydispersity of the resin is 2.0 or less. Furthermore, it was confirmed that the effects of the present invention were even more excellent when the polydispersity of the resin was 1.7 or less (Examples 4 to 6). It was confirmed that the effect of the present invention is more excellent when the content of the specific photoacid generator is 0.10 to 1.00 mmol/g based on the total solid content of the resist composition (Example 1) , 7 and 8). It was confirmed that the effects of the present invention were more excellent when the pattern forming method further included a step 4 of cleaning the pattern using a rinsing liquid containing an organic solvent after step 3 (Examples 6 and 10).
• the developing solution contains two or more organic solvents
• the pattern forming method does not include Step 4 of cleaning the pattern using a rinsing liquid containing an organic solvent after Step 3
• the developing solution contains two or more organic solvents
• the effects of the present invention are even more excellent when at least one of the developer and the rinsing liquid contains two or more kinds of organic solvents. was confirmed (Examples 6, 9 and 10).
• the developing solution or the rinsing solution contains a first organic solvent and a second organic solvent, and the boiling point of the first organic solvent is higher than the boiling point of the second organic solvent, and the ClogP value of the first organic solvent is higher than the boiling point of the second organic solvent. It was confirmed that the effect of the present invention is more excellent when the ClogP value is larger than the ClogP value of the two organic solvents (Examples 9 and 10).

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• 2023
  • 2023-03-13 JP JP2024510028A patent/JPWO2023182040A1/ja active Pending
  • 2023-03-13 WO PCT/JP2023/009567 patent/WO2023182040A1/ja not_active Ceased
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• 2024
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