Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • 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
  • C08F220/04—Acids; Metal salts or ammonium salts thereof
  • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• • 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
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor

Definitions

• the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, a resist film, a pattern forming method, and an electronic device manufacturing method.
• pattern forming methods 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 catalytic action of the generated acid converts the alkali-insoluble groups of the resin contained in the actinic ray-sensitive or radiation-sensitive resin composition into alkali-soluble groups.
• 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 Documents 1 and 2 describe polymers whose main chains can be cut by electron beam irradiation, resulting in a decrease in molecular weight.
• the present inventors prepared and studied an actinic ray-sensitive or radiation-sensitive resin composition containing a predetermined polymer with reference to Patent Document 1, and found that the sensitivity did not meet the recently required level. It became clear that there was room for further improvement.
• the patterns formed using the above composition have poor LWR (line width roughness) performance, especially in the formation of ultra-fine patterns (for example, patterns with a line width of 20 nm or less), and there is room for further improvement. It became clear.
• an object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition that has excellent sensitivity and can form a pattern that has excellent LWR performance.
• the present invention also provides a resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition, a pattern forming method using the actinic ray-sensitive or radiation-sensitive resin composition, and an electronic device.
• the objective is to provide a manufacturing method.
• [1] Contains a repeating unit represented by the following formula (a1), and at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (a2) and a repeating unit represented by the following formula (a3).
• X 1 represents a halogen atom.
• W 1 represents an aromatic group.
• R 1 represents a hydrogen atom or a substituent.
• R 1 may be combined with W 1 to form a ring.
• X 2 represents an alkyl group.
• W 2 represents an aromatic group.
• R 2 represents a hydrogen atom or a substituent.
• R 2 may combine with X 2 or W 2 to form a ring.
• X 3 represents a halogen atom, a cyano group, -COOR A1 , -OCOR A2 , -SO 2 R A3 , or an alkyl group.
• R A1 , R A2 and R A3 each independently represent an organic group.
• R 3 represents a hydrogen atom or a substituent.
• L 1 represents a linking group.
• W3 represents an organic group.
• R 3 may combine with X 3 or W 3 to form a ring.
• the actinic ray-sensitive or radiation-sensitive resin according to [1] which contains an ionic compound (B), and the resin (A) has an interactive group that interacts with the ionic compound (B). resin composition.
• a pattern forming method comprising the step of developing using a developer.
• a method for manufacturing an electronic device comprising the pattern forming method according to [7].
• an actinic ray-sensitive or radiation-sensitive resin composition that has excellent sensitivity and can form a pattern that has excellent LWR performance. Further, according to the present invention, there is provided a resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition, a pattern forming method using the actinic ray-sensitive or radiation-sensitive resin composition, and an electronic A method for manufacturing a device can be provided.
• 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 notation that does not indicate substituted or unsubstituted includes groups having a substituent as well as groups having no substituent. do.
• the term "alkyl group” includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
• organic group as used herein refers to a group containing at least one carbon atom.
• the substituent is preferably a monovalent substituent.
• 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), X-rays, and electron beams (EB: Electron Beam), etc.
• Light in this specification means actinic rays or radiation.
• exposure refers not only to exposure to the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays, X-rays, and EUV light, but also to electron beams and It also includes drawing using particle beams such as ion beams.
• ⁇ 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.
• Y in the compound represented by the formula "X-Y-Z" is -COO-
• Y may be -CO-O- or -O-CO- Good too.
• the above compound may be "X-CO-O-Z" or "X-O-CO-Z".
• the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (also referred to as molecular weight distribution) (Mw/Mn) of the resin are measured using a GPC (Gel Permeation Chromatography) apparatus (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 Defined as a polystyrene equivalent value determined by a Refractive Index Detector.
• GPC Gel Permeation Chromatography
• acid dissociation constant refers to pKa in an aqueous solution, and specifically, using the following software package 1, a value based on Hammett's substituent constant and a database of known literature values is calculated. , is a value obtained by calculation. All pKa values described herein are values calculated using this software package.
• pKa can also be determined by molecular orbital calculation method.
• a specific method for this includes a method of calculating H 2 + dissociation free energy in an aqueous solution based on a thermodynamic cycle.
• the H + dissociation free energy can be calculated, for example, by DFT (density functional theory), but various other methods have been reported in the literature, and the method is not limited to this. .
• DFT density functional theory
• there is a plurality of software that can perform DFT and one example is Gaussian 16.
• pKa in this specification refers to a value obtained by calculating a value based on Hammett's substituent constant and a database of known literature values using software package 1. If calculation is not possible, a value obtained by Gaussian 16 based on DFT (density functional theory) is adopted.
• pKa in this specification refers to "pKa in an aqueous solution” as described above, but if pKa in an aqueous solution cannot be calculated, “pKa in a dimethyl sulfoxide (DMSO) solution” is adopted. It shall be.
• 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 (hereinafter also referred to as "resist composition") of the present invention comprises a repeating unit represented by the following formula (a1) and a repeating unit represented by the following formula (a2).
• X 1 represents a halogen atom.
• W 1 represents an aromatic group.
• R 1 represents a hydrogen atom or a substituent.
• R 1 may be combined with W 1 to form a ring.
• X 2 represents an alkyl group.
• W 2 represents an aromatic group.
• R 2 represents a hydrogen atom or a substituent.
• R 2 may combine with X 2 or W 2 to form a ring.
• X 3 represents a halogen atom, a cyano group, -COOR A1 , -OCOR A2 , -SO 2 R A3 , or an alkyl group.
• R A1 , R A2 and R A3 each independently represent an organic group.
• R 3 represents a hydrogen atom or a substituent.
• L 1 represents a linking group.
• W3 represents an organic group.
• R 3 may combine with X 3 or W 3 to form a ring.
• the resist composition of the present invention can form a pattern with excellent sensitivity and LWR performance.
• the resist composition of the present invention contains the resin (A) containing the repeating unit represented by formula (a1), suppresses side reactions (crosslinking reaction and reverse reaction) that occur together with the main chain scission reaction, and suppresses the main chain scission reaction. It is believed that the sensitivity and LWR performance were improved by improving the efficiency of the chain scission reaction.
• the fact that the sensitivity of the resist composition is better and/or the LWR performance of a pattern formed from the resist composition is better is also referred to as "the effect of the present invention is better.”
• the resin (A) contains a repeating unit represented by the above formula (a1).
• the resin (A) contains the repeating unit represented by the above formula (a1), so that the main chain is cleaved by irradiation with actinic rays or radiation (preferably X-rays, electron beams, or extreme ultraviolet rays). It functions as a so-called main chain cleavage type polymer.
• the resin (A) may be a homopolymer or a copolymer. When the resin (A) is a copolymer, it may be a random copolymer, a block copolymer, or an alternating copolymer.
• X 1 represents a halogen atom.
• X 1 is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom or a chlorine atom, and even more preferably a fluorine atom in terms of the stability of the resin (A).
• the resin (A) may contain only one type of repeating unit represented by formula (a1), or may contain two or more types. When the resin (A) contains two or more types of repeating units represented by formula (a1), there may be two or more types of halogen atoms in X 1 (for example, a fluorine atom and a chlorine atom).
• W 1 represents an aromatic group.
• the aromatic group represented by W 1 may be an aromatic hydrocarbon group or an aromatic heterocyclic group.
• the aromatic hydrocarbon group (aryl group) of W 1 is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 15 carbon atoms, and phenyl or naphthyl group is more preferable, and phenyl group is particularly preferable.
• the aromatic heterocyclic group (heteroaryl group) of W 1 preferably contains at least one hetero atom selected from the group consisting of a sulfur atom, a nitrogen atom, and an oxygen atom.
• the number of heteroatoms contained in the aromatic heterocyclic group is preferably 1 to 5, more preferably 1 to 3.
• the number of carbon atoms in the aromatic heterocyclic group is not particularly limited, but is preferably from 2 to 20, more preferably from 3 to 15.
• the aromatic heterocyclic group may be monocyclic or polycyclic.
• Examples of the aromatic heterocyclic group of W1 include thienyl group, furanyl group, benzothienyl group, dibenzothienyl group, benzofuranyl group, pyrrole group, oxazolyl group, thiazolyl group, pyridyl group, isothiazolyl group, thiadiazolyl group, etc. It will be done.
• the aromatic group represented by W 1 may have a substituent.
• Substituents are not particularly limited, but include, for example, alkyl groups (for example, alkyl groups having 1 to 10 carbon atoms), cycloalkyl groups (for example, cycloalkyl groups having 3 to 20 carbon atoms), and alkoxy groups (for example, cycloalkyl groups having 1 to 10 carbon atoms). (alkoxy group), hydroxy group, carboxy group, etc.
• R 1 represents a hydrogen atom or a substituent.
• the substituent for R 1 is not particularly limited, but is preferably an organic group.
• the organic group is not particularly limited, and examples thereof include groups exemplified as the organic group W below.
• Organic group W is, for example, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, an aryl group, a heteroaryl group, an aralkyl group, a cyano group, an alkoxy group, an aryloxy group, a heterocycle.
• alkylcarbonyloxy group or arylcarbonyloxy group carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkylthio group, arylthio group group, heterocyclic thio group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, aryloxycarbonyl group, alkoxycarbonyl group, aryl or heterocyclic azo group, sulfonamide group, imide group, acylamino group, carbamoyl group, lactone group etc.
• each of the above-mentioned groups may further have a substituent, if possible.
• an alkyl group which may have a substituent is also included as one form of the organic group W.
• the above substituents are not particularly limited, but include, for example, one or more of the groups shown as the organic group W above, a halogen atom, a nitro group, a primary to tertiary amino group, a phosphino group, a phosphinyl group, Examples include a phosphinyloxy group, a phosphinylamino group, a phosphono group, a silyl group, a hydroxy group, a carboxy group, a sulfonic acid group, and a phosphoric acid group (hereinafter, these are also referred to as "substituent T").
• the number of carbon atoms in the organic group W is, for example, 1 to 20.
• the number of atoms other than hydrogen atoms that the organic group W has is, for example, 1 to 30.
• the number of carbon atoms in the alkyl group exemplified in the organic group W is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6.
• the alkyl group may be either linear or branched. 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. It will be done.
• the substituent which the alkyl group may have is not particularly limited, and includes, for example, the groups exemplified by the above-mentioned substituent T.
• the alkyl group moiety in the alkoxy group (including the alkoxy group moiety in a substituent containing an alkoxy group (e.g., alkoxycarbonyloxy group)), the alkyl group moiety in an aralkyl group, and the alkyl group in an alkylcarbonyl group exemplified in the organic group W
• the alkyl group moiety in the alkylcarbonyloxy group the alkyl group moiety in the alkylthio group, the alkyl group moiety in the alkylsulfinyl group, and the alkyl moiety in the alkylsulfonyl group, the above alkyl groups are preferable.
• an alkoxy group that may have a substituent an aralkyl group that may have a substituent, an alkylcarbonyloxy group that may have a substituent, an alkylthio group that may have a substituent, a substituent
• an alkoxy group, an aralkyl group, an alkylcarbonyloxy group, an alkylthio group, an alkylsulfinyl group, and an alkylsulfonyl group have Examples of the substituent that may be substituted include the same substituents as in the alkyl group which may have a substituent.
• Examples of the cycloalkyl group for the organic group W include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group.
• Examples include alkyl groups.
• the number of carbon atoms in the cycloalkyl group is preferably 5 to 20, more preferably 5 to 15.
• examples of the substituent which the cycloalkyl group may have are the same as those for the alkyl group which may have a substituent.
• the alkenyl group exemplified in the organic group W may be either linear or branched.
• the alkenyl group preferably has 2 to 20 carbon atoms.
• examples of the substituent which the alkenyl group may have are the same as those for the alkyl group which may have a substituent.
• the cycloalkenyl group exemplified in the organic group W preferably has 5 to 20 carbon atoms.
• examples of the substituent which the cycloalkenyl group may have are the same as those for the alkyl group which may have a substituent.
• the alkynyl group exemplified in the organic group W may be either linear or branched.
• the number of carbon atoms in the alkynyl group is preferably 2 to 20.
• examples of the substituent which the alkynyl group may have are the same as those for the alkyl group which may have a substituent.
• the cycloalkynyl group exemplified as the organic group W preferably has 5 to 20 carbon atoms.
• examples of the substituent which the cycloalkynyl group may have are the same as those for the alkyl group which may have a substituent.
• the aryl group exemplified in the organic group W may be either monocyclic or polycyclic (eg, 2-6 rings, etc.) unless otherwise specified.
• the number of ring member atoms in the aryl group is preferably 6 to 15, more preferably 6 to 10.
• the aryl group is preferably a phenyl group, a naphthyl group, or an anthranyl group, and more preferably a phenyl group.
• examples of the substituent which the aryl group may have are the same as those for the alkyl group which may have a substituent.
• the same examples as the aryl group exemplified in the above organic group W are given for the aryl group moiety in a substituent containing an aryl group (for example, an aryloxy group). It will be done.
• the heteroaryl group exemplified in the organic group W may be either monocyclic or polycyclic (eg, 2-6 rings, etc.) unless otherwise specified.
• the number of heteroatoms that the heteroaryl group has as ring member atoms is, for example, 1 to 10.
• the heteroatoms include nitrogen atom, sulfur atom, oxygen atom, selenium atom, tellurium atom, phosphorus atom, silicon atom, and boron atom.
• the number of ring member atoms in the above heteroaryl group is preferably 5 to 15.
• examples of the substituent which the heteroaryl group may have are the same as those for the alkyl group which may have a substituent.
• the heterocycle exemplified in the organic group W is intended to be a ring containing a hetero atom as a ring member atom, and unless otherwise specified, it may be either an aromatic heterocycle or an aliphatic heterocycle, and may include a monocyclic ring and a polycyclic ring. It may be any ring (for example, 2 to 6 rings, etc.).
• the number of heteroatoms that the heterocycle has as ring member atoms is, for example, 1 to 10. Examples of the above heteroatoms include nitrogen atom, sulfur atom, oxygen atom, selenium atom, tellurium atom, Examples include phosphorus atoms, silicon atoms, and boron atoms.
• the number of ring member atoms in the heterocycle is preferably 5 to 15. In the heterocycle which may have a substituent, examples of the substituent which the heterocycle may have are similar to the substituents in the alkyl group which may have a substituent.
• the lactone group exemplified in the organic group W is preferably a 5- to 7-membered lactone group, and another ring structure is fused to the 5- to 7-membered lactone ring to form a bicyclo structure or a spiro structure. It is more preferable that In the lactone group which may have a substituent, examples of the substituent which the lactone group may have are similar to the substituents in the alkyl group which may have a substituent.
• R 1 a hydrogen atom is preferable.
• R 1 may be combined with W 1 to form a ring.
• the ring formed by combining R 1 with W 1 is not particularly limited, and may be either monocyclic or polycyclic.
• the ring may contain a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom as a ring member atom.
• the above ring may contain carbonyl carbon as a ring member atom.
• the ring is preferably a 5- or 6-membered alicyclic ring.
• repeating unit represented by formula (a1) is not limited thereto.
• the content of the repeating unit represented by formula (a1) is preferably 20 mol% or more, more preferably 30 mol% or more, and 40 mol% or more, based on the total repeating units. More preferably, it is mol% or more. Further, the content of the repeating unit represented by formula (a1) is preferably 90 mol% or less, more preferably 80 mol% or less, and 70 mol% or less based on the total repeating units. It is more preferable that the amount is at least 60 mol %, particularly preferably 60 mol % or less. In the resin (A), one type of repeating unit represented by formula (a1) may be contained alone, or two or more types may be contained. When two or more types are included, the total content is preferably within the above range.
• X 2 represents an alkyl group.
• the number of carbon atoms in the alkyl group of X 2 is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6.
• the alkyl group may be either linear or branched. 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. It will be done.
• the alkyl group may have a substituent, and examples of the substituent include the groups exemplified by the above-mentioned substituent T.
• W 2 represents an aromatic group.
• the explanation, specific example, and preferred range for W 2 are the same as the explanation, specific example, and preferred range for W 1 in the above-mentioned formula (a1).
• R 2 represents a hydrogen atom or a substituent.
• the explanation, specific example, and preferred range for R 2 are the same as the explanation, specific example, and preferred range for R 1 in the above-mentioned formula (a1).
• R 2 may combine with X 2 or W 2 to form a ring.
• the ring formed by combining R 2 with X 2 or W 2 is not particularly limited, and may be either monocyclic or polycyclic.
• the ring may contain a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom as a ring member atom.
• the above ring may contain carbonyl carbon as a ring member atom.
• the ring is preferably a 5- or 6-membered alicyclic ring.
• repeating unit represented by formula (a2)
• the repeating unit is not limited thereto.
• the content of the repeating unit represented by formula (a2) in the resin (A) is preferably 10 mol% or more, more preferably 20 mol% or more, and 30 mol% or more, based on the total repeating units. More preferably, it is mol% or more. Further, the content of the repeating unit represented by formula (a2) is preferably 80 mol% or less, more preferably 70 mol% or less, and 60 mol% or less based on the total repeating units. It is even more preferable that there be. In the resin (A), one type of repeating unit represented by formula (a2) may be contained alone, or two or more types may be contained. When two or more types are included, the total content is preferably within the above range.
• X 3 represents a halogen atom, a cyano group, -COOR A1 , -OCOR A2 , -SO 2 R A3 , or an alkyl group.
• R A1 , R A2 and R A3 each independently represent an organic group.
• the halogen atom for X 3 is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
• the number of carbon atoms in the alkyl group of X 3 is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 6.
• the alkyl group may be either linear or branched. 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. It will be done.
• the alkyl group may have a substituent, and examples of the substituent include the groups exemplified by the above substituent T.
• the organic groups of R A1 , R A2 and R A3 are not particularly limited, and include, for example, the groups exemplified as the organic group W above.
• R 3 represents a hydrogen atom or a substituent.
• the explanation, specific example, and preferred range for R 3 are the same as the explanation, specific example, and preferred range for R 1 in the above-mentioned formula (a1).
• R 3 may combine with X 3 or W 3 to form a ring.
• the ring formed by R 3 bonding with X 3 or W 3 is not particularly limited, and may be either monocyclic or polycyclic.
• the ring may contain a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom as a ring member atom.
• the above ring may contain carbonyl carbon as a ring member atom.
• the ring is preferably a 5- or 6-membered alicyclic ring.
• L 1 represents a linking group.
• L 1 preferably represents -O- or -NR 4 -.
• R 4 represents a hydrogen atom or an organic group.
• the organic group is not particularly limited, and includes, for example, the groups exemplified as the organic group W above. It is particularly preferred that L 1 represents -O-.
• W 3 represents an organic group.
• the organic group is not particularly limited, and includes, for example, the groups exemplified as the organic group W above.
• W 3 preferably represents an alkyl group, a cycloalkyl group or an aryl group.
• repeating unit represented by formula (a3)
• the repeating unit is not limited thereto.
• the content of the repeating unit represented by formula (a3) in the resin (A) is preferably 10 mol% or more, more preferably 20 mol% or more, and 30 mol% or more, based on the total repeating units. More preferably, it is mol% or more. Further, the content of the repeating unit represented by formula (a3) is preferably 80 mol% or less, more preferably 70 mol% or less, and 60 mol% or less based on the total repeating units. It is even more preferable that there be. In the resin (A), one type of repeating unit represented by formula (a3) may be contained alone, or two or more types may be contained. When two or more types are included, the total content is preferably within the above range.
• the content of the repeating unit represented by formula (a1)/the content of the repeating unit represented by formula (a2) may be in a molar ratio of 30/70 to 70/30.
• the ratio is preferably 40/60 to 60/40.
• the content of the repeating unit represented by formula (a1)/the content of the repeating unit represented by formula (a3) is calculated as follows:
• the ratio is preferably 30/70 to 70/30, more preferably 40/60 to 60/40.
• the resin (A) may contain repeating units other than the above-mentioned repeating units as long as the effects of the present invention are not impaired.
• the resin (A) has an interactive group that interacts with the ionic compound (B) described below. Since the resin (A) has an interactive group that interacts with the ionic compound (B), the unexposed areas of the resist film formed using the resist composition of the present invention are difficult to dissolve in the developer. . On the other hand, when exposed to light, the main chain of the resin (A) is decomposed (cut) and the interaction between the resin (A) and the ionic compound (B) is canceled, so it dissolves in the developer. It becomes easier. In other words, it is thought that the above effect increases the dissolution contrast between the unexposed area and the exposed area of the resist film, thereby further improving the LWR performance.
• Examples of the above-mentioned interactive groups include hydroxy groups (alcoholic hydroxyl groups and phenolic hydroxyl groups, etc.), carboxy groups, sulfonic acid groups, alkoxy groups, amide groups, and sulfonamide groups, and phenolic hydroxy groups or carboxy It is preferable that it is a group.
• the above-mentioned phenolic hydroxyl group is a hydroxyl group substituted on a ring member atom of an aromatic ring (aromatic hydrocarbon ring and aromatic heterocycle).
• the alkoxy group is preferably an alkoxy group having 1 to 5 carbon atoms.
• the above-mentioned sulfonamide group is not particularly limited, but includes, for example, -SO 2 -NHR P (R P represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms).
• the weight average molecular weight of the resin (A) is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 20,000 or more. Moreover, the weight average molecular weight of the resin (A) is preferably 200,000 or less, more preferably 150,000 or less, even more preferably 100,000 or less, and particularly preferably 85,000 or less.
• the above weight average molecular weight value is a value determined as a polystyrene equivalent value by GPC method.
• the dispersity (molecular weight distribution) of the resin (A) is usually 1.0 to 5.0, preferably 1.0 to 3.0, more preferably 1.0 to 3.0, and 1.0 to 5.0. 2.5 is more preferred. When the degree of dispersion is within the above range, the resolution and resist shape tend to be better.
• the resin (A) can be synthesized according to conventional methods (for example, by radical polymerization). Details of synthesis examples are shown in Examples.
• the content of the resin (A) is preferably 50.0% by mass or more, more preferably 60.0% by mass or more, and 70.0% by mass or more based on the total solid content of the resist composition. More preferably, the amount is % by mass or more. Further, the upper limit of the content of the resin (A) is 100% by mass or less, preferably 99.9% by mass or less.
• the resin (A) may be used alone or in combination. When two or more types are used, it is preferable that the total content is within the above-mentioned preferred content range.
• the resist composition of the present invention preferably contains a solvent.
• the solvent consists of (M1) propylene glycol monoalkyl ether carboxylate, and (M2) propylene glycol monoalkyl ether, lactic acid ester, acetate ester, alkoxypropionic acid ester, chain ketone, cyclic ketone, lactone, and alkylene carbonate.
• M1 propylene glycol monoalkyl ether carboxylate
• M2 propylene glycol monoalkyl ether
• lactic acid ester acetate ester
• alkoxypropionic acid ester chain ketone
• cyclic ketone cyclic ketone
• lactone alkylene carbonate
• alkylene carbonate Preferably, at least one selected from the group .
• this solvent may further contain components other than components (M1) and (M2).
• Component (M1) is preferably at least one selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether acetate; Glycol monomethyl ether acetate (PGMEA) is more preferred.
• component (M2) the following are preferable.
• propylene glycol monoalkyl ether propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether (PGEE) are preferable.
• PGME propylene glycol monomethyl ether
• PGEE propylene glycol monoethyl ether
• lactic acid ester ethyl lactate, butyl lactate, or propyl lactate
• acetic acid ester methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, or 3-methoxybutyl acetate is preferred.
• butyl butyrate is also preferred.
• alkoxypropionate ester methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP) is preferable.
• chain ketones include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, phenylacetone, methyl ethyl ketone, and methyl isobutyl.
• Ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methylnaphthyl ketone, or methyl amyl ketone is preferred.
• cyclic ketone methylcyclohexanone, isophorone, cyclopentanone, or cyclohexanone is preferred.
• lactone ⁇ -butyrolactone is preferred.
• alkylene carbonate propylene carbonate is preferred.
• Component (M2) is more preferably propylene glycol monomethyl ether (PGME), ethyl lactate, ethyl 3-ethoxypropionate, methyl amyl ketone, cyclohexanone, butyl acetate, pentyl acetate, ⁇ -butyrolactone, or propylene carbonate.
• PGME propylene glycol monomethyl ether
• ethyl lactate ethyl 3-ethoxypropionate
• methyl amyl ketone cyclohexanone
• butyl acetate pentyl acetate
• ⁇ -butyrolactone propylene carbonate
• the solvent may include an ester solvent having 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12, even more preferably 7 to 10) and having 2 or less heteroatoms. It is also preferable to include.
• ester solvents having 7 or more carbon atoms and 2 or less heteroatoms include amyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, butyl propionate, and isobutyl isobutyrate. , heptyl propionate, or butyl butanoate are preferred, and isoamyl acetate is more preferred.
• the component (M2) preferably has a flash point (hereinafter also referred to as fp) of 37° C. or higher.
• Such components (M2) include propylene glycol monomethyl ether (fp: 47°C), ethyl lactate (fp: 53°C), ethyl 3-ethoxypropionate (fp: 49°C), and methyl amyl ketone (fp: 42°C). ), cyclohexanone (fp: 44°C), pentyl acetate (fp: 45°C), methyl 2-hydroxyisobutyrate (fp: 45°C), ⁇ -butyrolactone (fp: 101°C), or propylene carbonate (fp: 132°C) is preferred.
• propylene glycol monoethyl ether, ethyl lactate, pentyl acetate, or cyclohexanone are more preferred, and propylene glycol monoethyl ether or ethyl lactate is even more preferred.
• flash point here means the value described in the reagent catalog of Tokyo Chemical Industry Co., Ltd. or Sigma-Aldrich.
• the solvent 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 within the range of "100/0" to "15/85", and is preferably within the range of "100/0" to "40/60”. ”, and even more preferably within the range of “100/0” to “60/40”. That is, it is preferable that the solvent consists only of component (M1) or contains both component (M1) and component (M2), and the mass ratio thereof is as follows.
• the mass ratio of component (M1) to component (M2) is preferably 15/85 or more, more preferably 40/60 or more, and even more preferably 60/40 or more. preferable. If such a configuration is adopted, it becomes possible to further reduce the number of development defects.
• the mass ratio of component (M1) to component (M2) can be, for example, 99/1 or less.
• 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 of the present invention is preferably determined so that the solid content concentration is 0.5 to 30% by mass, and 1 to 20% by mass in terms of better coating properties. It is more preferable to set .
• the resist composition of the present invention may contain components other than the resin (A) and the solvent.
• Other components include, but are not particularly limited to, ionic compounds (specifically, photodegradable onium salt compounds), surfactants, and the like.
• the resist composition of the present invention further contains an ionic compound (B).
• the ionic compound (B) may be a compound that decomposes upon irradiation with actinic rays or radiation, or may be a compound that does not decompose.
• the compound that decomposes upon irradiation with actinic rays or radiation may be a compound that decomposes upon irradiation with actinic rays or radiation to generate an acid, or a compound that decomposes upon irradiation with actinic rays or radiation to generate a base. It may be.
• the ionic compound (B) is preferably a compound with an onium salt structure (photodegradable onium salt compound) that generates an acid upon irradiation with actinic rays or radiation.
• an ionic compound such as a photodegradable onium salt compound
• the resin (A) is capable of absorbing the ionic compound through an interactive group that may be contained in the resin (A). Easily aggregates with (B).
• the aggregation structure may be released due to dissociation between the ionic compound (B) and the interactive group and cleavage of the photodegradable onium salt compound.
• the resin (A) contained in the resist composition preferably has an interactive group.
• the interactive group include the above-mentioned hydroxy group (alcoholic hydroxyl group, phenolic hydroxyl group, etc.), carboxy group, sulfonic acid group, amide group, sulfonamide group, and the like.
• a photodegradable onium salt compound is a compound that has at least one salt structure site consisting of an anion site and a cation site, and that decomposes upon exposure to light and generates an acid (preferably an organic acid).
• an acid preferably an organic acid
• the above-mentioned salt structure moiety of the photodegradable onium salt compound is easily decomposed by exposure to light and has superior ability to produce organic acids, and is particularly composed of an organic cation moiety and an organic anion moiety with extremely low nucleophilicity. It is preferable that The above-mentioned salt structure site may be a part of the photodegradable onium salt compound, or may be the entirety.
• the case where the above-mentioned salt structure part is a part of a photodegradable onium salt compound corresponds to a structure in which two or more salt structure parts are connected, for example, as in the photodegradable onium salt PG2 described below. do.
• the number of salt structural moieties in the photodegradable onium salt is not particularly limited, but is preferably from 1 to 10, preferably from 1 to 6, and more preferably from 1 to 3.
• organic acids generated from the photodegradable onium salt compound due to the action of exposure mentioned above include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, camphor sulfonic acids, etc.), carboxylic acids (aliphatic sulfonic acids, etc.), carboxylic acid, aromatic carboxylic acid, aralkylcarboxylic acid, etc.), carbonylsulfonylimidic acid, bis(alkylsulfonyl)imidic acid, tris(alkylsulfonyl)methide acid, and the like.
• the organic acid generated from the photodegradable onium salt compound by the action of exposure may be a polyhydric acid having two or more acid groups.
• the photodegradable onium salt compound is the photodegradable onium salt compound PG2 described below
• the organic acid generated by decomposition of the photodegradable onium salt compound due to exposure to light becomes a polyhydric acid having two or more acid groups.
• the cation moiety constituting the salt structure moiety is preferably an organic cation moiety, and in particular, an organic cation (cation (ZaI)) represented by the formula (ZaI) described below.
• an organic cation (cation (ZaII)) represented by formula (ZaII) is preferable.
• Photodegradable onium salt compound PG1 An example of a preferred embodiment of the photodegradable onium salt compound is an onium salt compound represented by "M + ). In the compound represented by "M + X - ", M + represents an organic cation and X - represents an organic anion.
• the photodegradable onium salt compound PG1 will be explained below.
• the organic cation represented by M + in the photodegradable onium salt compound PG1 is an organic cation represented by the formula (ZaI) (cation (ZaI)) or an organic cation (cation (ZaI)) represented by the formula (ZaII). ZaII)) is preferred.
• R 201 , R 202 and R 203 each independently represent an organic group.
• the number of carbon atoms in the organic groups as R 201 , R 202 and R 203 is usually 1 to 30, preferably 1 to 20.
• two of R 201 to R 203 may be combined to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group.
• Examples of the group formed by combining two of R 201 to R 203 include an alkylene group (for example, a butylene group and a pentylene group), and -CH 2 -CH 2 -O-CH 2 -CH 2 -. Can be mentioned.
• Preferred embodiments of the organic cation in formula (ZaI) include cation (ZaI-1), cation (ZaI-2), and organic cation (cation (ZaI-3b)) represented by formula (ZaI-3b), which will be described later. ), and an organic cation (cation (ZaI-4b)) represented by the formula (ZaI-4b).
• the cation (ZaI-1) is an arylsulfonium cation in which at least one of R 201 to R 203 in the above formula (ZaI) is an aryl group.
• the arylsulfonium cation all of R 201 to R 203 may be an aryl group, or some of R 201 to R 203 may be an aryl group, and the remainder may be an alkyl group or a cycloalkyl group.
• R 201 to R 203 may be an aryl group, and the remaining two of R 201 to R 203 may be bonded to form a ring structure, with an oxygen atom, a sulfur atom, It may contain 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 -).
• arylsulfonium cation examples include triarylsulfonium cation, diarylalkylsulfonium cation, aryldialkylsulfonium cation, diarylcycloalkylsulfonium cation, and aryldicycloalkylsulfonium cation.
• the aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
• the aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the heterocyclic structure include pyrrole residue, furan residue, thiophene residue, indole residue, benzofuran residue, and benzothiophene residue.
• the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different.
• the alkyl group or cycloalkyl group that the arylsulfonium cation has as necessary is a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a branched alkyl group having 3 to 15 carbon atoms.
• a cycloalkyl group is preferred, and for example, a methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, and cyclohexyl group are more preferred.
• the substituents that the aryl group, alkyl group, and cycloalkyl group of R 201 to R 203 may each independently include an alkyl group (for example, carbon number 1 to 15), a cycloalkyl group (for example, carbon number 3-15), aryl group (e.g. 6-14 carbon atoms), alkoxy group (e.g. 1-15 carbon atoms), cycloalkylalkoxy group (e.g. 1-15 carbon atoms), halogen atom (e.g.
• the above substituent may further have a substituent if possible.
• the above alkyl group may have a halogen atom as a substituent to become a halogenated alkyl group such as a trifluoromethyl group. preferable.
• the cation (ZaI-2) is a cation in which R 201 to R 203 in the formula (ZaI) each independently represent an organic group having no aromatic ring.
• the aromatic ring includes an aromatic ring containing a hetero atom.
• the organic group having no aromatic ring as R 201 to R 203 generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
• R 201 to R 203 are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, and a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, or an alkoxy
• a carbonylmethyl group is more preferred, and a linear or branched 2-oxoalkyl group is even more preferred.
• the alkyl group and cycloalkyl group of R 201 to R 203 include, for example, a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group). group, butyl group, and pentyl group), and cycloalkyl groups having 3 to 10 carbon atoms (eg, cyclopentyl group, cyclohexyl group, and norbornyl group).
• R 201 to R 203 may be further substituted with a halogen atom, an alkoxy group (eg, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.
• the cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).
• R 1c to R 5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, and a hydroxyl group.
• R 1c to R 5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, and a hydroxyl group.
• R 6c and R 7c each independently represent a hydrogen atom, an alkyl group (such as a t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group.
• R x and R y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.
• R 1c to R 5c , R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y may be bonded to each other to form a ring.
• the rings may each independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
• the 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.
• R 1c to R 5c , R 6c , R 7c , R x , R y , and any two or more of R 1c to R 5c , R 5c and R 6c , R 6c and R 7c , R 5c and R x , and the ring formed by bonding R x and R y to each other may have a substituent.
• the cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).
• R13 is a group having a hydrogen atom, a halogen atom (e.g., a fluorine atom, an iodine atom, etc.), a hydroxyl group, an alkyl group, a halogenated alkyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a cycloalkyl group (cycloalkyl It may be a group itself or a group partially containing a cycloalkyl group). These groups may have substituents.
• a halogen atom e.g., a fluorine atom, an iodine atom, etc.
• R14 is a hydroxyl group, a halogen atom (e.g., a fluorine atom, an iodine atom, etc.), an alkyl group, a halogenated alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl group.
• R 15 each independently represents the above group such as a hydroxyl group.
• R 15 each independently represents an alkyl group, a cycloalkyl group, or a naphthyl group.
• 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 ring formed by bonding the alkyl group, cycloalkyl group, naphthyl group, and two R 15s to each other may have a substituent.
• the alkyl groups of R 13 , R 14 and R 15 are preferably linear or branched.
• the number of carbon atoms in the alkyl group is preferably 1 to 10.
• As the alkyl group a methyl group, ethyl group, n-butyl group, or t-butyl group is more preferable.
• R 204 and R 205 each independently represent an aryl group, an alkyl group, or a cycloalkyl group.
• the aryl group for R 204 and R 205 is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
• the aryl group of R 204 and R 205 may be an aryl group having a heterocycle having an oxygen atom, a nitrogen atom, a sulfur atom, or the like.
• Examples of the skeleton of the aryl group having a heterocycle include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
• the alkyl group and cycloalkyl group of R 204 and R 205 include a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, butyl group, pentyl group), or a cycloalkyl group having 3 to 10 carbon atoms (eg, cyclopentyl group, cyclohexyl group, or norbornyl group).
• the aryl group, alkyl group, and cycloalkyl group of R 204 and R 205 may each independently have a substituent.
• substituents that the aryl group, alkyl group, and cycloalkyl group of R 204 and R 205 may have include an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms), 15), an aryl group (for example, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.
• the organic anion represented by X - in the photodegradable onium salt compound PG1 is preferably a non-nucleophilic anion (an anion with extremely low ability to cause a nucleophilic reaction).
• non-nucleophilic anions include sulfonic acid anions (aliphatic sulfonic acid anions, aromatic sulfonic acid anions, camphor sulfonic acid anions, etc.), carboxylic acid anions (aliphatic carboxylic acid anions, aromatic carboxylic acid anions) , and aralkylcarboxylic acid anions), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methide anions.
• organic anion is, for example, an organic anion represented by the following formula (DA).
• a 31- represents an anionic group.
• R a1 represents a hydrogen atom or a monovalent organic group.
• L a1 represents a single bond or a divalent linking group.
• a 31- and R a1 may be bonded to each other to form a ring.
• a 31- represents an anionic group.
• the anionic group represented by A 31- is not particularly limited, but is preferably a group selected from the group consisting of groups represented by formulas (BA-1) to (BA-14), for example. , Formula (BA-1), Formula (BA-2), Formula (BA-3), Formula (BA-4), Formula (BA-5), Formula (BA-6), Formula (BA-10), Formula (BA-12), formula (BA-13), and formula (BA-14) are more preferred.
• R X1 each independently represents a monovalent organic group.
• R X2 each independently represents a hydrogen atom or a substituent other than a fluorine atom and a perfluoroalkyl group. Two R X2 's in formula (BA-7) may be the same or different.
• R XF1 represents a hydrogen atom, a fluorine atom, or a perfluoroalkyl group.
• R XF1 represents a fluorine atom or a perfluoroalkyl group.
• Two R XF1 's in formula (BA-8) may be the same or different.
• R X3 represents a hydrogen atom, a halogen atom, or a monovalent organic group.
• n1 represents an integer from 0 to 4.
• R XF2 represents a fluorine atom or a perfluoroalkyl group.
• the partner to which the bonding position represented by * in formula (BA-14) is bonded is preferably a phenylene group which may have a substituent. Examples of the substituent that the phenylene group may have include a halogen atom.
• R X1 each independently represents a monovalent organic group.
• R X1 is an alkyl group (which may be linear or branched, preferably having 1 to 15 carbon atoms), or a cycloalkyl group (which may be monocyclic or polycyclic, preferably having 3 to 20 carbon atoms). ), or an aryl group (which may be monocyclic or polycyclic. The number of carbon atoms is preferably 6 to 20). Further, the above group represented by R X1 may have a substituent.
• it is also preferable that the atom directly bonded to N- in R X1 is neither the carbon atom in -CO- nor the sulfur atom in -SO 2 -.
• the cycloalkyl group in R X1 may be monocyclic or polycyclic.
• Examples of the cycloalkyl group for R X1 include a norbornyl group and an adamantyl group.
• the substituent that the cycloalkyl group in R One or more of the carbon atoms that are ring member atoms of the cycloalkyl group in R X1 may be replaced with a carbonyl carbon atom.
• the number of carbon atoms in the alkyl group in R X1 is preferably 1 to 10, more preferably 1 to 5.
• the substituent that the alkyl group in R X1 may have is not particularly limited, but is preferably a cycloalkyl group, a fluorine atom, or a cyano group. Examples of the cycloalkyl group as the substituent are the same as the cycloalkyl group explained in the case where R X1 is a cycloalkyl group. When the alkyl group in R X1 has a fluorine atom as the substituent, the alkyl group may be a perfluoroalkyl group. Furthermore, in the alkyl group in R X1 , one or more -CH 2 - may be substituted with a carbonyl group.
• the aryl group for R X1 is preferably a phenyl group.
• the substituent that the aryl group in R X1 may have is not particularly limited, but is preferably an alkyl group, a fluorine atom, or a cyano group. Examples of the alkyl group as the substituent are the same as the alkyl group explained in the case where R X1 is an alkyl group.
• R In formulas (BA-7) and (BA-11), R ). Two R X2 's in formula (BA-7) may be the same or different.
• R XF1 represents a hydrogen atom, a fluorine atom, or a perfluoroalkyl group. However, at least one of the plurality of R XF1 represents a fluorine atom or a perfluoroalkyl group. Two R XF1 's in formula (BA-8) may be the same or different.
• the number of carbon atoms in the perfluoroalkyl group represented by R XF1 is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 6.
• R X3 represents a hydrogen atom, a halogen atom, or a monovalent organic group.
• the halogen atom as R X3 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred.
• the monovalent organic group as R X3 is the same as the monovalent organic group described as R X1 .
• n1 represents an integer from 0 to 4.
• n1 is preferably an integer of 0 to 2, and preferably 0 or 1. When n1 represents an integer of 2 to 4, a plurality of R X3 may be the same or different.
• R XF2 represents a fluorine atom or a perfluoroalkyl group.
• the number of carbon atoms in the perfluoroalkyl group represented by R XF2 is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 6.
• the number of carbon atoms in the monovalent organic group R a1 is not particularly limited, but preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms.
• R a1 is preferably an alkyl group, a cycloalkyl group, or an aryl group.
• the alkyl group may be linear or branched, and preferably has 1 to 20 carbon atoms, more preferably has 1 to 15 carbon atoms, and even more preferably has 1 to 10 carbon atoms.
• the cycloalkyl group may be monocyclic or polycyclic, preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 3 to 15 carbon atoms, and still more preferably a cycloalkyl group having 3 to 10 carbon atoms.
• the aryl group may be monocyclic or polycyclic, preferably having 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and even more preferably 6 to 10 carbon atoms.
• the cycloalkyl group may contain a heteroatom as a ring member atom. Heteroatoms include, but are not particularly limited to, nitrogen atoms, oxygen atoms, and the like.
• the alkyl group, cycloalkyl group, and aryl group described above may further have a substituent.
• a 31- and R a1 may be bonded to each other to form a ring.
• the divalent linking group as L a1 is not particularly limited, but includes, for example, an alkylene group, a cycloalkylene group, an aromatic group, -O-, -CO-, -COO-, and a combination of two or more of these.
• the alkylene group may be linear or branched and preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms.
• the cycloalkylene group may be monocyclic or polycyclic, and preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms.
• the aromatic group is a divalent aromatic group, preferably an aromatic group having 6 to 20 carbon atoms, and more preferably an aromatic group having 6 to 15 carbon atoms.
• the aromatic ring constituting the aromatic group is not particularly limited, but examples include aromatic rings having 6 to 20 carbon atoms, and specific examples include benzene ring, naphthalene ring, anthracene ring, and thiophene ring. .
• the aromatic ring constituting the aromatic group is preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring.
• the alkylene group, cycloalkylene group, and aromatic group may further have a substituent, and the substituent is preferably a halogen atom.
• L a1 preferably represents a single bond.
• Examples of the photodegradable onium salt compound PG1 include paragraphs [0135] to [0171] of International Publication No. 2018/193954, paragraphs [0077] to [0116] of International Publication No. 2020/066824, and International Publication No. 2017 It is also preferable to use the photoacid generators disclosed in paragraphs [0018] to [0075] and [0334] to [0335] of No./154345.
• the molecular weight of the photodegradable onium salt compound PG1 is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less.
• Photodegradable onium salt compound PG2 Photodegradable onium salt compound PG2
• compound (I) and compound (II) hereinafter, “compound (I) and compound (II)
• photodegradable onium salt compound PG2 is a compound that has two or more of the above-described salt structure sites and generates a polyvalent organic acid upon exposure to light.
• the photodegradable onium salt compound PG2 will be explained below.
• Compound (I) is a compound having one or more of the following structural moieties X and one or more of the following structural moieties Y, and the following first acidic acid derived from the following structural moiety This is a compound that generates an acid containing the following second acidic site derived from the structural site Y below.
• Structural site X A structural site consisting of an anionic site A 1 - and a cationic site M 1 + , and which forms a first acidic site represented by HA 1 by irradiation with actinic rays or radiation
• Structural site Y Anionic site A 2 - and a cationic site M 2 + , and forms a second acidic site represented by HA 2 by irradiation with actinic rays or radiation.
• compound (I) satisfies the following condition I.
• a compound PI obtained by replacing the cation moiety M 1 + in the structural moiety X and the cation moiety M 2 + in the structural moiety Y with H + in the compound (I) is The acid dissociation constant a1 derived from the acidic site represented by HA 1 is obtained by replacing the cationic site M 1 + with H + , and the acid dissociation constant a1 derived from the acidic site represented by HA 1 is obtained by replacing the cationic site M 2 + in the structural site Y with H + It has an acid dissociation constant a2 derived from the acidic site represented by HA 2 , and the acid dissociation constant a2 is larger than the acid dissociation constant a1.
• the above-mentioned compound PI corresponds to an acid generated when compound (I) is irradiated with actinic rays or radiation.
• compound (I) has two or more structural sites X
• the structural sites X may be the same or different.
• the two or more A 1 ⁇ and the two or more M 1 + may be the same or different.
• the above A 1 - and the above A 2 - , and the above M 1 + and the above M 2 + may be the same or different, but the above A 1 - and the above Preferably, each A 2 - is different.
• the anionic moiety A 1 - and the anionic moiety A 2 - are structural moieties containing negatively charged atoms or atomic groups, for example, the formulas (AA-1) to (AA-3) and the formula (BB Examples include structural sites selected from the group consisting of -1) to (BB-6). Note that in the following formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6), * represents the bonding position.
• R A represents a monovalent organic group. Examples of the monovalent organic group represented by R A include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.
• the cationic site M 1 + and the cationic site M 2 + are structural sites containing positively charged atoms or atomic groups, such as monovalent organic cations.
• the organic cation is not particularly limited, but is preferably an organic cation (cation (ZaI)) represented by the above-mentioned formula (ZaI) or an organic cation (cation (ZaII)) represented by the formula (ZaII).
• Compound (II) is a compound having two or more of the above structural moieties It is a compound that generates an acid containing two or more sites and the above structural site Z.
• Structural site Z nonionic site capable of neutralizing acids
• the above compound (II) is a compound PII (acid) having an acidic site represented by HA 1 obtained by replacing the above cation site M 1 + in the above structural site X with H + by irradiation with actinic rays or radiation. It can occur. That is, compound PII represents a compound having the acidic site represented by HA 1 above and the structural site Z, which is a nonionic site capable of neutralizing acid.
• the definition of the structural moiety X and the definitions of A 1 - and M 1 + in compound (II) are the same as the definition of the structural moiety X and A 1 - and M 1 + in compound (I) described above. It has the same meaning as the definition, and the preferred embodiments are also the same.
• the two or more structural sites X may be the same or different.
• the two or more A 1 ⁇ and the two or more M 1 + may be the same or different.
• the nonionic site that can neutralize the acid in the structural site Z is not particularly limited, and is preferably a site that contains a group that can electrostatically interact with protons or a functional group that has electrons. .
• a group capable of electrostatic interaction with protons or a functional group having electrons a functional group having a macrocyclic structure such as a cyclic polyether, or a nitrogen atom having a lone pair of electrons that does not contribute to ⁇ conjugation is used. Examples include functional groups having such a functional group.
• a nitrogen atom having a lone pair of electrons that does not contribute to ⁇ conjugation is, for example, a nitrogen atom having a partial structure shown in the following formula.
• partial structures of functional groups having groups or electrons that can electrostatically interact with protons include crown ether structures, aza crown ether structures, primary to tertiary amine structures, pyridine structures, imidazole structures, and pyrazine structures. Among them, primary to tertiary amine structures are preferred.
• the molecular weight of the photodegradable onium salt compound PG2 is preferably 100 to 10,000, more preferably 100 to 2,500, even more preferably 100 to 1,500.
• the content of the ionic compound (B) is not particularly limited, but is 0.5% by mass or more based on the total solid content of the resist composition. It is preferably 1.0% by mass or more, more preferably 5.0% by mass or more. Further, the content of the ionic compound (B) is preferably 50.0% by mass or less, more preferably 40.0% by mass or less, based on the total solid content of the resist composition.
• the ionic compounds (B) may be used alone or in combination of two or more. When two or more types are used, it is preferable that the total content is within the above-mentioned preferred content range.
• the resist composition of the present invention may further contain a hydrophobic resin different from the resin (A).
• the hydrophobic resin is preferably designed so that it is unevenly distributed on the surface of the resist film, but unlike a surfactant, it does not necessarily have to have a hydrophilic group in the molecule, and it is necessary to uniformly mix polar and non-polar substances. does not have to contribute to
• the effects of adding a hydrophobic resin include controlling the static and dynamic contact angle of the resist film surface with the developer and suppressing outgassing.
• the hydrophobic resin preferably has one or more of a fluorine atom, a silicon atom, and a CH3 partial structure contained in the side chain portion of the resin, and preferably has two or more of them. It is more preferable to have the above.
• the hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted on the side chains. Examples of the hydrophobic resin include compounds described in paragraphs [0275] to [0279] of International Publication No. 2020/004306.
• the content of the hydrophobic resin is preferably 0.01 to 20.0% by mass, and 0.1 to 15% by mass based on the total solid content of the resist composition. .0% by mass is more preferable.
• the hydrophobic resins may be used alone or in combination of two or more. When two or more types are used, it is preferable that the total content is within the above-mentioned preferred content range.
• the resist composition may contain a surfactant.
• a surfactant is included, a pattern with better adhesion and fewer development defects can be formed.
• 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 resist composition. .
• One kind of surfactant may be used, or two or more kinds of surfactants may be used. When two or more types are used, it is preferable that the total content is within the above-mentioned preferred content range.
• the present invention also relates to a resist film formed using the above resist composition.
• the present invention also provides a pattern forming method comprising the steps of forming a film using the resist composition, exposing the film, and developing the exposed film using a developer. Also related.
• Step 1 Step of forming a resist film on a substrate using a resist composition
• Step 2 Step of exposing the resist film
• Step 3 Step of developing the exposed resist film using a developer containing an organic solvent
• 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 as necessary before coating.
• 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 onto a substrate (eg, silicon, silicon dioxide coated), such as those used in the manufacture of integrated circuit devices, by any suitable application method, such as a spinner or coater.
• 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 (rotations per minute).
• 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.
• 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 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 and EB exposure, the thickness of the resist film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm. Further, in the case of ArF immersion exposure, the thickness of the resist film is more preferably 10 to 120 nm, and even more preferably 15 to 90 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 top coat is not particularly limited, and a conventionally known top coat can be formed by a conventionally known method. Can be formed.
• 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 bond, and an ester bond.
• Step 2 is a step of exposing the resist film.
• the exposure method include a method of irradiating the formed resist film with actinic rays or radiation through a predetermined mask.
• Actinic 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 to 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.
• Step 3 is a step of developing the exposed resist film using a developer to form a pattern.
• the developer may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer), but is preferably an organic developer.
• 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 raised on the surface of the substrate by surface tension and the substrate is left still for a certain period of time for development (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). can be mentioned. Furthermore, after the step of developing, a step of stopping the development may be carried out while substituting another solvent.
• the development time is not particularly limited as long as the resin in the unexposed areas is sufficiently dissolved, and is preferably 10 to 300 seconds, more preferably 20 to 120 seconds.
• the temperature of the developer is preferably 0 to 50°C, more preferably 15 to 35°C.
• alkaline developer it is preferable to use an alkaline aqueous solution containing an alkali.
• the type of alkaline aqueous solution is not particularly limited, but examples include quaternary ammonium salts represented by tetramethylammonium hydroxide, inorganic alkalis, primary amines, secondary amines, tertiary amines, alcohol amines, or cyclic amines. Examples include alkaline aqueous solutions containing.
• the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt typified by tetramethylammonium hydroxide (TMAH). Appropriate amounts of alcohols, surfactants, etc. may be added to the alkaline developer.
• the alkaline concentration of the alkaline developer is usually preferably 0.1 to 20% by mass.
• the pH of the alkaline developer is usually preferably 10.0 to 15.0.
• Organic developers include ketone solvents, ester solvents, alcohol solvents, amide solvents,
• the developer preferably contains at least one organic solvent selected from the group consisting of ether solvents and hydrocarbon solvents.
• 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 organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, and 90% by mass or more and 100% by mass, based on the total amount of the developer. The following is more preferable, and 95% by mass or more and 100% by mass or less is particularly preferable.
• the pattern forming method preferably includes a step of cleaning using a rinsing liquid after step 3.
• Examples of the rinsing solution used in the rinsing step after the step of developing using an alkaline developer include pure water. Note that an appropriate amount of a surfactant may be added to the pure water. An appropriate amount of surfactant may be added to the rinse liquid.
• the rinsing solution used in the rinsing step after the development step using an organic developer is not particularly limited as long as it does not dissolve the pattern, and solutions containing common organic solvents can be used.
• the rinsing liquid contains at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. is preferred.
• 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 usually carried out at 40 to 250°C (preferably 90 to 200°C) for 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).
• the substrate may be etched using the formed pattern as a mask. That is, the pattern formed in step 3 may be used as a mask to process the substrate (or the lower 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 is processed.
• a method of forming a pattern is preferred.
• the dry etching is preferably oxygen plasma etching.
• the resist composition and various materials used in the pattern forming method of the present invention do not contain impurities such as metals. Preferably, it does not contain.
• the content of impurities contained in these materials is preferably 1 mass ppm (parts per million) or less, more preferably 10 mass ppb (parts per billion) or less, even more preferably 100 mass ppt (parts per trillion) or less, and 10 mass ppm (parts per million) or less.
• a mass ppt or less is particularly preferred, and a mass ppt or less is most preferred.
• 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, Examples include W, and Zn.
• 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 liquid after use is preferably 100 mass ppt or less, more preferably 10 mass ppt or less, and even more preferably 1 mass ppt or less.
• the resist composition may contain water as an impurity.
• water When water is contained as an impurity, the water content is preferably as small as possible, but may be contained in an amount of 1 to 30,000 ppm by mass based on the entire resist composition.
• the resist composition may contain residual monomers (for example, monomers derived from raw material monomers used in the synthesis of resin (A)) as impurities.
• the content of the residual monomer is preferably as small as possible, but it may be contained in an amount of 1 to 30,000 ppm by mass based on the total solid content of the resist composition.
• Conductive compounds are added to organic processing solutions such as rinse solutions to prevent damage to chemical piping and various parts (filters, O-rings, tubes, etc.) due to static electricity charging and subsequent electrostatic discharge. You may.
• the conductive compound is not particularly limited, and for example, methanol may be mentioned.
• the amount added is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less in terms of maintaining favorable development characteristics or rinsing characteristics.
• Examples of chemical liquid piping include SUS (stainless steel), polyethylene or polypropylene treated with antistatic treatment, or various types of piping coated with fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.). can be used.
• antistatically treated polyethylene, polypropylene, or fluororesin polytetrafluoroethylene, perfluoroalkoxy resin, etc.
• 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 weight average molecular weight (Mw) and dispersity (Mw/Mn) of A-1 to A-13 and RA-1 were measured by GPC (carrier: tetrahydrofuran (THF)) (the amount is in terms of polystyrene). . Further, the content of each repeating unit was measured by 13 C-NMR (Nuclear Magnetic Resonance).
• A-1 to A-13 correspond to resin (A).
• RA-1 does not fall under resin (A).
• Table 3 below RA-1 is listed in the resin (A) column for convenience.
• Table 2 shows the type and content (mole ratio) of repeating units of the hydrophobic resin (C-1 to C-4), weight average molecular weight (Mw), and degree of dispersion (Mw/Mn).
• the types of repeating units are indicated by the types of monomers corresponding to each repeating unit listed below.
• W-1 Megafac F176 (manufactured by DIC Corporation; fluorine-based)
• W-2 Megafac R08 (manufactured by DIC Corporation; fluorine and silicone-based)
• 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 silicon wafer having a resist film obtained by the above procedure was exposed using an EUV exposure device (manufactured by Exitech, Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36). Pattern irradiation was performed. Note that a mask with a line size of 16 nm and a line:space ratio of 1:1 was used as the reticle. Thereafter, only if there is a description, after baking (Post Exposure Bake; PEB) under the conditions shown in Table 4 below, develop by paddling for 30 seconds with the developer shown in Table 4 below.
• PEB Post Exposure Bake
• the line size (width) can be reduced by rinsing the wafer by pouring the rinsing liquid shown in Table 4 below for 10 seconds while rotating the wafer at a rotation speed of 1000 rpm, and then rotating the wafer for 30 seconds at a rotation speed of 4000 rpm.
• the pattern obtained in the above ⁇ Pattern Formation> was observed from above the pattern using a length-measuring scanning electron microscope (SEM (S-9380II, manufactured by Hitachi, Ltd.)).
• SEM scanning electron microscope
• the line width of the pattern was observed at 250 locations, and its standard deviation ( ⁇ ) was determined. Measurement variations in line width were evaluated using 3 ⁇ , and the value of 3 ⁇ was defined as LWR (nm).
• the results are shown in Table 4. The smaller the LWR value, the better the LWR performance.
• the LWR evaluation is preferably 4.0 or less, more preferably 3.6 or less, even more preferably 3.3 or less, particularly preferably 3.1 or less, and most preferably 2.9 or less.
• Examples 1A to 15A A resist film was formed using each resist composition, patterned, and evaluated in the same manner as in Examples 1 to 15, except that an electron beam (EB) was used instead of EUV as the exposure light source. .
• EB electron beam
• an actinic ray-sensitive or radiation-sensitive resin composition that has excellent sensitivity and can form a pattern that has excellent LWR performance. Further, according to the present invention, a resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition, a pattern forming method using the actinic ray-sensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device.

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