WO2023157712A1 - Composition de résine sensible aux rayons actiniques ou au rayonnement, film de réserve, procédé de formation de motif, procédé de fabrication de dispositif électronique et polymère - Google Patents

Composition de résine sensible aux rayons actiniques ou au rayonnement, film de réserve, procédé de formation de motif, procédé de fabrication de dispositif électronique et polymère Download PDF

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Publication number
WO2023157712A1
WO2023157712A1 PCT/JP2023/003929 JP2023003929W WO2023157712A1 WO 2023157712 A1 WO2023157712 A1 WO 2023157712A1 JP 2023003929 W JP2023003929 W JP 2023003929W WO 2023157712 A1 WO2023157712 A1 WO 2023157712A1
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group
formula
substituent
sensitive
represented
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PCT/JP2023/003929
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English (en)
Japanese (ja)
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洋平 石地
智美 高橋
直也 畠山
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富士フイルム株式会社
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    • 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
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/52—Amides or imides
    • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • 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
    • C08F22/00—Homopolymers and 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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F22/36—Amides or imides
    • C08F22/40—Imides, e.g. cyclic imides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—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, an electronic device manufacturing method, and a polymer.
  • a pattern forming method using chemical amplification has been used in order 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 an acid.
  • the post-exposure baking (PEB: Post Exposure Bake) process or the like 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 the base.
  • the wavelength of the exposure light source is shortened and the numerical aperture (NA) of the projection lens is increased.
  • NA numerical aperture
  • an exposure machine using an ArF excimer laser with a wavelength of 193 nm as a light source has been developed. ing.
  • the pattern formation method which uses extreme ultraviolet rays (EUV light: Extreme Ultraviolet) and an electron beam (EB: Electron Beam) as a light source is also being examined. Under such circumstances, various structures have been proposed as actinic ray-sensitive or radiation-sensitive resin compositions.
  • EUV light Extreme Ultraviolet
  • EB Electron Beam
  • Patent Document 1 discloses a polymer whose main chain is cut by irradiation with EUV light, electron beams, or the like, thereby increasing its solubility in an alkaline aqueous solution.
  • 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 resolution satisfies the level required these days. It is clear that there is a need for further improvement.
  • the repeating unit represented by the above formula (3) contains any one or more repeating units selected from the group consisting of formulas (3)-1 to (3)-4 described later, [6 ] and the actinic ray-sensitive or radiation-sensitive resin composition.
  • a radiation-sensitive resin composition is any one or more repeating units selected from the group consisting of formulas (3)-1 to (3)-4 described later, [6 ] and the actinic ray-sensitive or radiation-sensitive resin composition.
  • an actinic ray-sensitive or radiation-sensitive resin composition which is excellent in the resolution of the formed pattern.
  • the resist film, the pattern formation method, and the manufacturing method of an electronic device regarding the said actinic-ray-sensitive or radiation-sensitive resin composition can be provided.
  • an "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • organic group refers to a group containing at least one carbon atom.
  • the substituent is preferably a monovalent substituent unless otherwise specified.
  • actinic ray or “radiation” as used herein refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV), X-rays, and electron beams (EB: Electron Beam), etc.
  • light means actinic rays or radiation.
  • exposure means, unless otherwise specified, not only exposure by the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, X-rays, and EUV light, but also electron beams, and It also includes drawing with particle beams such as ion beams.
  • ⁇ is used to include the numerical values before and after it as lower and upper limits.
  • the bonding direction of the divalent groups described herein is not limited unless otherwise specified. For example, in the compound represented by the formula "XYZ", when Y is -COO-, Y may be -CO-O- or -O-CO- good too. Further, 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 by a GPC (Gel Permeation Chromatography) device (HLC-8120GPC manufactured by Tosoh Corporation).
  • GPC Gel Permeation Chromatography
  • the acid dissociation constant (pKa) represents the pKa in an aqueous solution. , is a calculated value. All pKa values described herein are calculated using this software package.
  • pKa can also be obtained by molecular orbital calculation.
  • H + dissociation free energy can be calculated by, for example, DFT (density functional theory), but various other methods have been reported in literature, etc., and are not limited to this. .
  • DFT density functional theory
  • Gaussian16 is an example.
  • the pKa in the present specification refers to a value obtained by calculating a value based on a database of Hammett's substituent constants and known literature values using Software Package 1, as described above. If it cannot be calculated, a value obtained by Gaussian 16 based on DFT (density functional theory) is adopted.
  • pKa in this specification refers to "pKa in aqueous solution” as described above, but when pKa in aqueous solution cannot be calculated, “pKa in dimethyl sulfoxide (DMSO) solution” is adopted. It shall be.
  • halogen atoms include, for example, fluorine, chlorine, bromine, and iodine atoms.
  • the solid content is intended to be the component that forms the resist film, and does not include the solvent.
  • it is regarded as a solid content even if its property is liquid.
  • the actinic ray-sensitive or radiation-sensitive resin composition (hereinafter also referred to as “resist composition”) of the present invention is represented by a repeating unit represented by formula (1) described later and a repeating unit represented by formula (2) described later. It contains a polymer (hereinafter also referred to as "specific polymer”) containing a specific repeating unit (hereinafter also referred to as "repeating unit A”) selected from the group consisting of repeating units, and a solvent.
  • the resist composition of the present invention has excellent resolution due to the above constitution.
  • the present inventors presume as follows. Due to the structure of the repeating unit A, when the specific polymer is irradiated with ionizing radiation such as electron beams and extreme ultraviolet rays and light with short wavelengths such as ultraviolet rays, the main chain is scissionable and the molecular weight is easily reduced. , and its solubility in an organic developer is remarkably low when it is not exposed to light. As a result, the resist film formed from the resist composition of the present invention containing the specific polymer has a high dissolution contrast between the unexposed area and the exposed area, and is considered to have excellent resolution of the formed pattern. .
  • the present inventors found that when the resist composition contains a photodecomposable onium salt compound, the interaction between the specific polymer and the photodecomposable onium salt compound causes the unexposed area to It has also been clarified that the dissolution contrast of the exposed area is further increased, and the resolution of the pattern formed as a result is more excellent.
  • the better resolution of the pattern formed from the resist composition and/or the better LWR of the pattern formed from the resist composition is also referred to as "the effect of the present invention is better.” say.
  • the specific polymer contains a specific repeating unit (repeating unit A) selected from the group consisting of repeating units represented by formula (1) and repeating units represented by formula (2).
  • the specific polymer corresponds to a so-called main chain scission type polymer in which the main chain is cut by the action of exposure to light to cause a decrease in molecular weight.
  • the specific polymer further includes a repeating unit represented by formula (3) (hereinafter "repeating unit B" It is also preferable to include The repeating unit represented by formula (1) and the repeating unit represented by formula (2) are described below. ⁇ Repeating Unit Represented by Formula (1) and Repeating Unit Represented by Formula (2) (Repeating Unit A)>
  • X represents a halogen atom.
  • R 1 to R 3 each independently represent a hydrogen atom or a substituent. However, at least one of R 1 and R 2 represents an electron-withdrawing group.
  • the halogen atom represented by X includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.
  • a fluorine atom, a chlorine atom, and an iodine atom are preferred from the viewpoint that the effects of the present invention are more excellent, and a chlorine atom is more preferred from the viewpoint that the storage stability of the resist composition is more excellent.
  • the substituent represented by R 1 to R 3 is not particularly limited, and examples thereof include the groups exemplified for the substituent W below.
  • Substituent W is, for example, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, a cyano group, a nitro group, an alkoxy group, an aryloxy group, a silyloxy group, a heterocyclicoxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, primary to tertiary amino group (including anilino group), alkylthio group, arylthio group, heterocyclicthio group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group,
  • each group described above may further have a substituent (for example, one or more groups among the groups described above), if possible.
  • a substituent for example, one or more groups among the groups described above
  • an alkyl group which may have a substituent is also included as one form of the substituent W.
  • the carbon number of the substituent W is, for example, 1 to 20.
  • the number of atoms other than hydrogen atoms possessed by the substituent W is, for example, 1-30.
  • Alkyl groups may be linear, branched, or cyclic.
  • alkyl groups 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, Monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups are included.
  • the substituent which the alkyl group may have is not particularly limited, and examples thereof include groups exemplified for the substituent W.
  • the said phenolic hydroxyl group intends the hydroxyl group substituted by the ring member atom of the aromatic ring (aromatic-hydrocarbon ring and aromatic heterocycle).
  • the alkyl group portion of the alkoxy group, the alkyl group portion of the aralkyl group, the alkyl group portion of the alkylthio group, the alkyl group portion of the alkylsulfinyl group, and the alkyl portion of the alkylsulfonyl group exemplified for the substituent W are the above alkyl groups. preferable.
  • an alkoxy group which may have a substituent an aralkyl group which may have a substituent, an alkylthio group which may have a substituent, an alkylsulfinyl group which may have a substituent, and a substituent
  • the alkoxy group, aralkyl group, alkylthio group, alkylsulfinyl group, and alkylsulfonyl group may have Examples similar to those for substituents can be given.
  • the alkenyl group exemplified for the substituent W may be linear, branched, or cyclic.
  • 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 of the alkyl group which may have a substituent.
  • the alkynyl group exemplified for the substituent W may be linear, branched, or cyclic.
  • the alkynyl group preferably has 2 to 20 carbon atoms. In the alkynyl group which may have a substituent, examples of the substituent which the alkynyl group may have are the same as those of the alkyl group which may have a substituent.
  • the aryl group exemplified for the substituent W may be either monocyclic or polycyclic (eg, 2 to 6 rings).
  • the number of ring member atoms in the aryl group is preferably 6-15, more preferably 6-10.
  • the aryl group is preferably a phenyl group, a naphthyl group, or an anthranyl group, more preferably a phenyl group.
  • examples of the substituent which the aryl group may have are the same as those of the alkyl group which may have a substituent.
  • the same examples as the aryl groups exemplified for the substituent W can be given for the aryl group portion in the substituent containing an aryl group (eg, aryloxy group). be done.
  • the heteroaryl group exemplified for the substituent W may be either monocyclic or polycyclic (eg, 2 to 6 rings).
  • the number of heteroatoms that the heteroaryl group has as ring member atoms is, for example, 1-10.
  • the heteroatom 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 heteroaryl group is preferably 5-15.
  • examples of the substituent which the heteroaryl group may have are the same as those of the alkyl group which may have a substituent.
  • the heterocyclic ring exemplified in the substituent W is intended to be a ring containing a heteroatom as a ring member atom, and unless otherwise specified, may be either an aromatic heterocyclic ring or an aliphatic heterocyclic ring, a monocyclic ring or a polycyclic ring. It may be any ring (eg, 2 to 6 rings).
  • the hetero ring has, for example, 1 to 10 heteroatoms as ring member atoms. Examples of the heteroatom 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 hetero ring is preferably 5-15.
  • examples of the substituent which the heterocycle may have are the same as those of the optionally substituted alkyl group.
  • the lactone group exemplified for the substituent W is preferably a 5- to 7-membered lactone group, and the 5- to 7-membered lactone ring is condensed with another ring structure to form a bicyclo structure or a spiro structure. is more preferable.
  • examples of the substituent which the lactone group may have are the same as those of the optionally substituted alkyl group.
  • the substituents represented by R 1 and R 2 are, among others, optionally substituted alkyl groups, aryl groups, or heteroaryl groups, or electron-withdrawing groups. is preferred.
  • whether or not the substituents represented by R 1 and R 2 are electron-withdrawing groups is determined by calculating the compound represented by the following formula (1-X) as a model compound. is intended to have an acid dissociation constant pKa value of 9.5 or less. That is, for example, when the relevant substituent is a methoxy group , the acid dissociation constant pKa is used to determine whether or not the methoxy group corresponds to an electron-withdrawing group.
  • the method for measuring the acid dissociation constant pKa of the hydroxy group is as described above.
  • R e represents a substituent to be measured.
  • the electron-withdrawing group represented by R 1 and R 2 is preferably a substituent in which the acid dissociation constant pKa of the hydroxy group is 9.0 or less, and 8.5 or less. It is more preferable that it is a substituent that becomes 8.0 or less is more preferable.
  • the lower limit is not particularly limited, and is preferably 4.0 or more, for example.
  • Examples include a halogenated alkyl group, a halogenated aryl group, and the like, and among them, a group represented by any one of the following formulas (a) to (c) and a halogenated alkyl group in that the effects of the present invention are more excellent.
  • a halogenated aryl group and more preferably a group represented by any one of the following formulas (a) to (c).
  • R 1 X represents a hydrogen atom or a substituent.
  • the substituent represented by R X is not particularly limited, and includes the groups exemplified for the substituent W described above, among which an alkyl group, an aryl group, or a heteroaryl group, which may have a substituent. is preferred, an optionally substituted alkyl group or an aryl group is more preferred, and an optionally substituted alkyl group having 1 to 6 carbon atoms or a phenyl group is even more preferred.
  • * represents a bonding site with the nitrogen atom in formula (1).
  • halogenated alkyl group a linear or branched alkyl having 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 6) substituted with one or more halogen atoms groups are preferred. More preferably, the halogenated aryl group is substituted with one or more halogen atoms and has 6 to 15 (preferably 6 to 10) ring member atoms. Examples of the halogenated aryl group include a phenyl group or a naphthyl group substituted with a halogen atom.
  • the halogenated alkyl group and the halogenated aryl group may have substituents other than halogen atoms (for example, the groups exemplified for the substituent W above).
  • R 1 is a hydrogen atom, or an optionally substituted alkyl group, aryl group, or heteroaryl group and R 2 preferably represents an electron-withdrawing group
  • R 1 represents a hydrogen atom or an optionally substituted alkyl group, aryl group, or heteroaryl group
  • R 1 represents an optionally substituted alkyl group or aryl group
  • the substituent is preferably a substituent other than a halogen atom.
  • R 3 is preferably a hydrogen atom or an optionally substituted alkyl group, more preferably a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms.
  • a hydrogen atom is preferred, and a hydrogen atom is more preferred.
  • X represents a halogen atom.
  • R4 represents a hydrogen atom or a substituent.
  • L 1 and L 2 each independently represent -CO-, -SO- or -SO 2 -.
  • L3 represents a single bond or a divalent linking group.
  • the halogen atom represented by X includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. Among them, an iodine atom is preferable because the effects of the present invention are more excellent.
  • the substituent represented by R 4 is not particularly limited, and examples thereof include the groups exemplified for the substituent W above, among which an optionally substituted alkyl group, An aryl group or a heteroaryl group is preferred, and an optionally substituted alkyl group or aryl group is more preferred.
  • L 1 and L 2 preferably represent -CO-.
  • the divalent linking group represented by L 3 is not particularly limited, and examples thereof include -CR S1 R S2 - and -CR S3 R S4 -CR S5 R S6 -.
  • R S1 to R S6 each independently represent a hydrogen atom or a substituent.
  • the substituent represented by R S1 to R S6 is not particularly limited, and examples thereof include the groups exemplified for the substituent W above, preferably an alkyl group optionally having a substituent, and having a substituent An alkyl group having 1 to 6 carbon atoms, which may be R S1 to R S6 are preferably hydrogen atoms.
  • L 3 is preferably a single bond or —CR S1 R S2 —, more preferably a single bond.
  • the repeating unit A contains at least one repeating unit selected from the group consisting of the following formula (1)-1 and the following formula (2)-1 in that the effect of the present invention is more excellent. is preferred, and it is more preferred to contain a repeating unit represented by the following formula (2)-1.
  • X and R 1 in formula (1)-1 have the same meanings as X and R 1 in formula (1) described above, and the preferred embodiments are also the same.
  • W in formula (1)-1 represents an electron-withdrawing group represented by either -CO-R X or -SO 2 -R X.
  • R X represents a hydrogen atom or a substituent.
  • R 1 X has the same meaning as R 1 X in formulas (a) to (c) above, and preferred embodiments are also the same.
  • X and R 4 have the same meanings as X and R 4 in formula (2) above, and the preferred embodiments are also the same.
  • the lower limit of the content of the repeating unit A is preferably 10 mol% or more, more preferably 20 mol% or more, and 40 mol% or more, based on the total repeating units. More preferably.
  • the upper limit is 100 mol % or less, preferably 80 mol % or less, more preferably 60 mol % or less, based on all repeating units.
  • the specific polymer preferably further contains a repeating unit (repeating unit B) represented by formula (3).
  • the repeating unit (repeating unit B) represented by Formula (3) will be described below. ⁇ Repeating Unit Represented by Formula (3) (Repeating Unit B)>
  • R5 represents a hydrogen atom or a hydrocarbon group which may have a substituent.
  • R 5 is preferably a hydrocarbon group which may have a substituent.
  • the optionally substituted hydrocarbon group represented by R 5 includes a linear, branched or cyclic alkyl group which may have a substituent, and a substituted and aryl groups that may be used.
  • the linear, branched, or cyclic alkyl group represented by R 5 which may have a substituent is preferably an alkyl group exemplified as the substituent W, and has a substituent.
  • An alkyl group having 1 to 6 carbon atoms which may be substituted is more preferred, and a methyl group or an ethyl group is even more preferred.
  • the aryl group which may have a substituent represented by R 5 is preferably an aryl group exemplified as the substituent W, more preferably a phenyl group or a naphthyl group which may have a substituent. preferable.
  • Z has a group represented by -NR f R g or a substituent in which -CH 2 - may be substituted with a group selected from the group consisting of -O- and -CO- represents a good hydrocarbon group.
  • R f represents a hydrocarbon group which may have a substituent
  • R g may have a hydrogen atom or a substituent represents a good hydrocarbon group.
  • R f and R g may combine with each other to form a ring.
  • -CH 2 - is -O-, -CO-, -SO-, and -SO 2 - It may be substituted with a group selected from the group consisting of
  • the optionally substituted hydrocarbon groups represented by R f and R g include linear, branched or cyclic alkyl groups optionally having substituents, and substituted An aryl group optionally having a group and the like can be mentioned.
  • the linear, branched, or cyclic alkyl group which may have a substituent is preferably an alkyl group exemplified as the substituent W, which may have a substituent.
  • the aryl group which may have a substituent is preferably the aryl group exemplified as the substituent W, and more preferably a phenyl group or a naphthyl group which may have a substituent.
  • the ring formed by combining R f and R g is not particularly limited, and may be either monocyclic or polycyclic.
  • the above ring may contain heteroatoms such as oxygen, nitrogen and sulfur atoms and/or carbonyl carbon as ring member atoms.
  • the above ring is preferably a 5- or 6-membered alicyclic ring.
  • the hydrocarbon group which may be substituted by a group selected from the group consisting of -O- and -CO-, in which -CH 2 - represented by Z is particularly limited to However, for example, an optionally substituted alkyl group (which may be linear, branched, or cyclic), an optionally substituted aryl group, —OR 6 , —COOR 7 , or -OCOR 8 is preferred.
  • R 6 to R 8 above may independently have an optionally substituted alkyl group (which may be linear, branched, or cyclic) or may have a substituent represents an aryl group.
  • Examples of the optionally substituted alkyl group represented by Z and the optionally substituted alkyl group represented by R 6 to R 8 include the alkyl groups exemplified as the substituent W. is preferred, and an optionally substituted alkyl group having 1 to 6 carbon atoms is more preferred.
  • Examples of the substituent that the alkyl group may have include the groups exemplified as the substituent W, and among them, the interactive group described above is preferable.
  • the aryl group optionally having substituents represented by Z and the aryl group optionally having substituents represented by R 6 to R 8 are the aryl groups exemplified as the substituent W. is preferred, and a phenyl group optionally having a substituent is more preferred. Examples of the substituent that the aryl group may have include the groups exemplified as the substituent W, and among them, the interactive group described above is preferable.
  • repeating unit (repeating unit B) represented by formula (3) any one selected from the group consisting of formulas (3)-1 to (3)-4 in that the effects of the present invention are more excellent. It preferably contains one or more repeating units, more preferably contains a repeating unit represented by formula (3)-1, and preferably contains a repeating unit represented by formula (3)-1-1 More preferred.
  • R a represents a hydrocarbon group which may have a substituent.
  • the hydrocarbon group optionally having substituents represented by R a is the same as the hydrocarbon group optionally having substituents represented by R 5 in formula (3), and is a preferred embodiment. is the same.
  • R b represents a substituent.
  • the substituent represented by R b is not particularly limited, and includes the groups exemplified as the substituent W, and among these, an interactive group is preferred.
  • n represents an integer of 0 to 5; n preferably represents an integer of 0 to 3.
  • m represents 0 or 1;
  • R c and R d each independently represent a hydrocarbon group which may have a substituent.
  • —CH 2 — may be substituted with —CO—.
  • the hydrocarbon group optionally having substituents represented by R c is the same as the hydrocarbon group optionally having substituents represented by R 5 in formula (3). is the same.
  • Examples of the optionally substituted hydrocarbon group represented by R d include an optionally substituted alkyl group, an optionally substituted aryl group, and a substituted and an alkylcarbonyl group which may be substituted.
  • alkyl group optionally having substituent(s) and the aryl group optionally having substituent(s) described above alkyl optionally having substituent(s) represented by R 6 to R 8 in formula (3) It is the same as the aryl group optionally having a group and a substituent, and the preferred embodiments are also the same.
  • the alkyl portion of the alkylcarbonyl group optionally having substituents described above is the same as the alkyl group optionally having substituents represented by R 6 to R 8 in formula (3), and is preferably The mode is also the same.
  • R e represents a hydrocarbon group which may have a substituent.
  • the hydrocarbon group optionally having substituents represented by Re is the same as the hydrocarbon group optionally having substituents represented by R 5 in formula (3), and is a preferred embodiment.
  • R f and R g in formula (3)-3 have the same definitions as R f and R g in the group represented by —NR f R g represented by Z in formula (3), and are preferred embodiments. is the same.
  • each R h independently represents a hydrocarbon group which may have a substituent.
  • R i represents a hydrogen atom or a hydrocarbon group which may have a substituent.
  • the optionally substituted hydrocarbon group represented by R h is the same as the optionally substituted hydrocarbon group represented by R 5 in formula (3), and is a preferred embodiment. is the same.
  • Examples of the optionally substituted hydrocarbon group represented by R i include an optionally substituted alkyl group (which may be linear, branched, or cyclic), Alternatively, an aryl group optionally having a substituent may be used.
  • alkyl group optionally having substituent(s) and the aryl group optionally having substituent(s) described above alkyl optionally having substituent(s) represented by R 6 to R 8 in formula (3) It is the same as the aryl group optionally having a group and a substituent, and the preferred embodiments are also the same.
  • the repeating unit (repeating unit B) represented by formula (3) is derived from a monomer selected from the group consisting of ⁇ -methylstyrenes, isopropenyl ethers, isopropenylamines, and methacrylic acid esters. It is also preferred that it is a repeating unit.
  • R a represents a hydrocarbon group which may have a substituent.
  • R b represents a substituent.
  • n represents an integer of 0 to 5;
  • R a , R b , and n in formula (3)-1-1 have the same meanings as R a , R b , and n in formula (3)-1, and preferred embodiments are also the same.
  • the total content of the repeating unit A and the repeating unit B is preferably 90 mol% or more, more preferably 95 mol% or more, relative to all repeating units. In addition, as an upper limit, 100 mol% or less is preferable.
  • the repeating unit A and the repeating unit B may be in any form such as a random copolymer, a block copolymer, and an alternating copolymer (ABAB . . . ). However, among others, it is preferably an alternating copolymer.
  • the ratio of the alternating copolymer in the specific polymer is 90% by mass or more (preferably 100% by mass or more) based on the total mass of the specific polymer. Aspects are also included.
  • the content of the repeating unit (repeating unit B) represented by the above formula (3) is preferably 10 mol% or more, more preferably 20 mol% or more, based on the total repeating units. is more preferable, and 40 mol % or more is even more preferable.
  • the upper limit is less than 100 mol %, preferably 80 mol % or less, more preferably 60 mol % or less, relative to all repeating units.
  • the specific polymer may contain repeating units other than the repeating units described above as long as the effects of the present invention are not impaired.
  • Other repeating units include, for example, repeating units derived from ⁇ -haloacrylates.
  • a specific polymer can be synthesized according to a conventional method (for example, radical polymerization).
  • the lower limit of the weight-average molecular weight of the specific polymer is preferably 1,000 or more, more preferably 2,500 or more, and even more preferably 30,000 or more, as a polystyrene-equivalent value by GPC method.
  • the upper limit is preferably 200,000 or less, more preferably 150,000 or less, still more preferably 80,000 or less, and particularly preferably 65,000 or less.
  • the degree of dispersion (molecular weight distribution) of the specific polymer is usually 1.0 to 5.0, preferably 1.0 to 3.0, more preferably 1.2 to 3.0, and 1.2 to 2.0. 5 is more preferred. When the degree of dispersion is within the above range, the resolution and resist shape are better.
  • the repeating unit A of the specific polymer is a repeating unit represented by the formula (1) (provided that the electron-withdrawing group is 8.5 or less case) and any one or more repeating units represented by formula (2), it preferably satisfies any one or more of the following conditions S1 to S3.
  • S1 The specific polymer contains a repeating unit represented by formula (2)-1.
  • S2 The specific polymer contains a repeating unit represented by formula (3)-1 (preferably formula (3)-1-1).
  • S3 The weight average molecular weight of the specific polymer is 30,000 or more.
  • the content of the specific polymer is preferably 50.0 to 100.0% by mass, more preferably 50.0 to 99.9% by mass, based on the total solid content of the composition. 0 to 99.0% by mass is more preferable, and 70.0 to 99.0% by mass is particularly preferable.
  • the specific polymer may be used alone or in combination. When two or more are used, the total content is preferably within the range of the preferred content.
  • the resist composition contains a solvent.
  • Solvent consists of (M1) propylene glycol monoalkyl ether carboxylate and (M2) propylene glycol monoalkyl ether, lactate, acetate, alkoxypropionate, linear ketone, cyclic ketone, lactone, and alkylene carbonate. It preferably contains 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.
  • PGMEA propylene glycol monomethyl ether acetate
  • PGMEA propylene glycol monomethyl ether propionate
  • PGMEA propylene glycol monoethyl ether acetate
  • Glycol monomethyl ether acetate (PGMEA) is more preferred.
  • propylene glycol monoalkyl ether propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether are preferred.
  • Ethyl lactate, butyl lactate, or propyl lactate is preferred as the lactate ester.
  • Preferred acetic acid esters are methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate and 3-methoxybutyl acetate. Also preferred is butyl butyrate.
  • the alkoxypropionate is preferably methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP).
  • 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.
  • Ketones acetylacetone, acetonylacetone, ionones, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone or methylamylketone are preferred.
  • Preferred cyclic ketones are methylcyclohexanone, isophorone, and cyclohexanone.
  • As the lactone ⁇ -butyrolactone is preferred.
  • Propylene carbonate is preferred as the alkylene carbonate.
  • Propylene glycol monomethyl ether PGME
  • ethyl lactate ethyl 3-ethoxypropionate
  • methyl amyl ketone cyclohexanone
  • butyl acetate pentyl acetate
  • ⁇ -butyrolactone propylene carbonate
  • an ester solvent having 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12, and even more preferably 7 to 10) and having 2 or less heteroatoms. It is also preferred to include Ester-based 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.
  • Component (M2) preferably has a flash point (hereinafter also referred to as fp) of 37° C. or higher.
  • fp flash point
  • Examples of such component (M2) include propylene glycol monomethyl ether (fp: 47° C.), ethyl lactate (fp: 53° C.), ethyl 3-ethoxypropionate (fp: 49° C.), methyl amyl ketone (fp: 42° C.), ° 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 is more preferred, and propylene glycol monoethyl ether or ethyl lactate is even more preferred.
  • flash point means the value described in the reagent catalogs of Tokyo Chemical Industry Co., Ltd. or Sigma-Aldrich.
  • the solvent preferably contains component (M1). More preferably, the solvent consists essentially of component (M1) alone, or is a mixed solvent of component (M1) and other components. In the latter case, the solvent more preferably contains both component (M1) and component (M2).
  • the mass ratio (M1/M2) of the component (M1) and the component (M2) is preferably in the range of "100/0" to "15/85", and "100/0" to "40/60". more preferably in the range of "100/0" to "60/40". That is, it is preferable that the solvent consists only of the component (M1) or contains both the component (M1) and the 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 more preferably 60/40 or more. preferable.
  • the mass ratio of the component (M1) to the component (M2) shall be, for example, 99/1 or less.
  • the content of components other than components (M1) and (M2) is preferably 5 to 30% by mass relative to the total amount of the solvent.
  • the content of the solvent in the resist composition is preferably determined so that the solid content concentration is 0.5 to 30% by mass, and is preferably determined to be 1 to 20% by mass, in terms of better coating properties. is more preferred.
  • the resist composition may contain components other than the specific polymer and solvent.
  • Other components are not particularly limited, and include, for example, photodecomposable onium salt compounds and surfactants.
  • the resist composition preferably contains a compound having an onium salt structure (photodegradable onium salt compound) that generates an acid upon exposure to actinic rays or radiation.
  • an onium salt structure photodegradable onium salt compound
  • the specific polymer in the unexposed portion, the specific polymer is photodecomposed via the interactive group that may be contained in the specific polymer and the nitrogen atom site of the repeating unit A. Easy to aggregate with type onium salt compounds. On the other hand, when exposed to light, the aggregate structure can be released by cleavage of the photodegradable onium salt compound.
  • the specific polymer contained in the resist composition preferably has an interactive group.
  • the interactive group includes the phenolic hydroxyl group, carboxyl group, sulfonic acid group, amide group, sulfonamide group, and the like described above.
  • a photodegradable onium salt compound is a compound that has at least one salt structure site composed of an anion site and a cation site, and that decomposes upon exposure to generate an acid (preferably an organic acid).
  • the above-mentioned salt structure portion of the photodegradable onium salt compound is easily decomposed by exposure to light and has excellent organic acid production properties.
  • the salt structure portion may be a part or the whole of the photodecomposable onium salt compound.
  • the case where the above-mentioned salt structure site is a part of the photodegradable onium salt compound corresponds to, for example, a structure in which two or more salt structure sites are linked, such as the photodegradable onium salt PG2 described later. do.
  • the number of salt structure sites in the photodecomposable onium salt is not particularly limited, but is preferably 1-10, more preferably 1-6, more preferably 1-3.
  • organic acid generated from the photodegradable onium salt compound by the action of exposure examples include, for example, sulfonic acid (aliphatic sulfonic acid, aromatic sulfonic acid, camphorsulfonic acid, etc.), carboxylic acid (aliphatic 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 polyvalent acid having two or more acid groups.
  • the organic acid generated by decomposition of the photodegradable onium salt compound by exposure becomes a polyvalent acid having two or more acid groups.
  • the cation site constituting the salt structure site is preferably an organic cation site, and among them, an organic cation (cation (ZaI)) represented by the formula (ZaI) described later. Or an organic cation represented by the formula (ZaII) (cation (ZaII)) is preferred.
  • 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 + X ⁇ ” that generates an organic acid upon exposure (hereinafter “photodegradable onium salt compound PG1” Also called).
  • M + represents an organic cation
  • X ⁇ represents an organic anion.
  • the photodegradable onium salt compound PG1 will be described below.
  • the organic cation represented by M + in the photodegradable onium salt compound PG1 includes an organic cation represented by the formula (ZaI) (cation (ZaI)) or an organic cation represented by the formula (ZaII) (cation ( 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 generally 1-30, preferably 1-20.
  • two of R 201 to R 203 may combine to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group.
  • Examples of the group formed by combining two of R 201 to R 203 include an alkylene group (eg, a butylene group and a pentylene group) and —CH 2 —CH 2 —O—CH 2 —CH 2 —. mentioned.
  • Preferred embodiments of the organic cation in formula (ZaI) include cation (ZaI-1), cation (ZaI-2), and organic cations represented by formula (ZaI-3b) (cation (ZaI-3b) ), and an organic cation represented by the formula (ZaI-4b) (cation (ZaI-4b)).
  • Cation (ZaI-1) is an arylsulfonium cation in which at least one of R 201 to R 203 in formula (ZaI) above is an aryl group.
  • R 201 to R 203 may be aryl groups, or part of R 201 to R 203 may be aryl groups and the rest may be alkyl groups or cycloalkyl groups.
  • one of R 201 to R 203 may be an aryl group, and the remaining two of R 201 to R 203 may combine to form a ring structure, in which an oxygen atom, a sulfur atom, It may contain an ester group, an amide group, or a carbonyl group.
  • the group formed by bonding two of R 201 to R 203 includes, for example, one or more methylene groups substituted with an oxygen atom, a sulfur atom, an ester group, an amide group and/or a carbonyl group. alkylene groups (eg, butylene group, pentylene group, or —CH 2 —CH 2 —O—CH 2 —CH 2 —).
  • Arylsulfonium cations include, for example, triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.
  • the aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
  • the aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Heterocyclic structures include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, benzothiophene residues, and the like.
  • the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different.
  • the alkyl group or cycloalkyl group optionally possessed by the arylsulfonium cation is a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or 3 to 15 carbon atoms. is preferred, and for example, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, cyclohexyl group and the like are more preferred.
  • the substituents that the aryl group, alkyl group and cycloalkyl group of R 201 to R 203 may have are each independently an alkyl group (eg, having 1 to 15 carbon atoms) and a cycloalkyl group (eg, having 1 to 15 carbon atoms).
  • aryl groups eg, 6 to 14 carbon atoms
  • alkoxy groups eg, 1 to 15 carbon atoms
  • cycloalkylalkoxy groups eg, 1 to 15 carbon atoms
  • halogen atoms eg, fluorine, iodine
  • hydroxyl groups e.g, a carboxyl group, an ester group, a sulfinyl group, a sulfonyl group, an alkylthio group, a phenylthio group, and the like.
  • the above substituents may further have a substituent if possible.
  • the above alkyl group may have a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group. preferable.
  • Cation (ZaI-2) is a cation in which R 201 to R 203 in formula (ZaI) each independently represents an organic group having no aromatic ring.
  • the aromatic ring also includes an aromatic ring containing a heteroatom.
  • the organic group having no aromatic ring as R 201 to R 203 generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
  • R 201 to R 203 are each independently preferably an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, and a linear or branched 2-oxoalkyl group, 2-oxocycloalkyl group or alkoxy
  • a carbonylmethyl group is more preferred, and a linear or branched 2-oxoalkyl group is even more preferred.
  • alkyl groups and cycloalkyl groups represented by R 201 to R 203 include linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (eg, methyl, ethyl, propyl group, butyl group, and pentyl group), and cycloalkyl groups having 3 to 10 carbon atoms (eg, cyclopentyl group, cyclohexyl group, and norbornyl group).
  • R 201 to R 203 may be further substituted with a halogen atom, an alkoxy group (eg, 1-5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.
  • 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, or a hydroxyl group , represents 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 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 combine with each other to form a ring.
  • the rings may each independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
  • Examples of the ring include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic hetero rings, and polycyclic condensed rings in which two or more of these rings are combined.
  • the ring includes a 3- to 10-membered ring, preferably a 4- to 8-membered ring, more preferably a 5- or 6-membered ring.
  • Examples of groups formed by bonding two or more of R 1c to R 5c , R 6c and R 7c , and R x and R y include alkylene groups such as a butylene group and a pentylene group. A methylene group in this alkylene group may be substituted with a heteroatom such as an oxygen atom.
  • the group formed by combining R 5c and R 6c and R 5c and R x is preferably a single bond or an alkylene group.
  • the alkylene group includes a methylene group, an ethylene group, and the like.
  • R 1c to R 5c , R 6c , R 7c , R x , R y , and two or more of R 1c to R 5c , R 5c and R 6c , R 6c and R 7c , R 5c and R x , and the ring formed by combining R x and R y with each other may have a substituent.
  • the cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).
  • a halogen atom e.g., fluorine atom, iodine atom, etc.
  • R 14 is a hydroxyl group, a halogen atom (e.g., fluorine atom, iodine atom, etc.), an alkyl group, a halogenated alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl group (either a cycloalkyl group itself or a group partially containing a cycloalkyl group). These groups may have a substituent.
  • Each of R 14 independently represents the above group such as a hydroxyl group when a plurality of R 14 are present.
  • Each R 15 independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. Two R 15 may be joined together to form a ring. When two R 15 are combined to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom. In one aspect, two R 15 are alkylene groups, preferably joined together to form a ring structure. The ring formed by combining the alkyl group, the cycloalkyl group, the naphthyl group, and the two R 15 groups may have a substituent.
  • the alkyl groups of R 13 , R 14 and R 15 are preferably linear or branched.
  • the number of carbon atoms in the alkyl group is preferably 1-10.
  • As the alkyl group a methyl group, an ethyl group, an n-butyl group, a t-butyl group, or the like is more preferable.
  • R 204 and R 205 each independently represent an aryl group, an alkyl group or a cycloalkyl group.
  • the aryl group for R 204 and R 205 is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
  • the aryl group for R 204 and R 205 may be an aryl group having a heterocyclic ring having an oxygen atom, a nitrogen atom, a sulfur atom, or the like.
  • Skeletons of heterocyclic aryl groups include, for example, pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
  • the alkyl group and cycloalkyl group for R 204 and R 205 include a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, or pentyl group), or a cycloalkyl group having 3 to 10 carbon atoms (eg, cyclopentyl group, cyclohexyl group, or norbornyl group).
  • the aryl group, alkyl group and cycloalkyl group of R 204 and R 205 may each independently have a substituent.
  • substituents that the aryl group, alkyl group and cycloalkyl group of R 204 and R 205 may have include an alkyl group (eg, 1 to 15 carbon atoms), a cycloalkyl group (eg, 3 to 15), aryl groups (eg, 6 to 15 carbon atoms), alkoxy groups (eg, 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups.
  • the organic anion represented by X 1 ⁇ in the photodecomposable onium salt compound PG1 is preferably a non-nucleophilic anion (an anion having a remarkably low ability to cause a nucleophilic reaction).
  • non-nucleophilic anions include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, , and aralkylcarboxylate anions), sulfonylimide anions, bis(alkylsulfonyl)imide anions, tris(alkylsulfonyl)methide anions, and the like.
  • organic anion for example, an organic anion represented by the following formula (DA) is also preferable.
  • 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- represents an anionic group.
  • the anionic group represented by A 31- is not particularly limited, but is preferably, for example, a group selected from the group consisting of groups represented by formulas (B-1) to (B-14). , among others, formula (B-1), formula (B-2), formula (B-3), formula (B-4), formula (B-5), formula (B-6), formula (B- 10), formula (B-12), formula (B-13), or formula (B-14) are more preferred.
  • each R X1 independently represents a monovalent organic group.
  • each R 1 X2 independently represents a hydrogen atom or a substituent other than a fluorine atom and a perfluoroalkyl group. Two R 1 X2 in formula (B-7) may be the same or different.
  • R 1 XF1 represents a hydrogen atom, a fluorine atom, or a perfluoroalkyl group.
  • R XF1 represents a fluorine atom or a perfluoroalkyl group.
  • Two R 1 XF1 in formula (B-8) may be the same or different.
  • R 1 X3 represents a hydrogen atom, a halogen atom, or a monovalent organic group.
  • n1 represents an integer of 0-4.
  • R 1 XF2 represents a fluorine atom or a perfluoroalkyl group.
  • the partner that bonds to the bonding position represented by * in formula (B-14) is preferably a phenylene group that may have a substituent.
  • a halogen atom etc. are mentioned as a substituent which the said phenylene group may have.
  • each R X1 independently represents a monovalent organic group.
  • R X1 is an alkyl group (either linear or branched, preferably having 1 to 15 carbon atoms), a cycloalkyl group (either monocyclic or polycyclic, preferably having 3 to 20 carbon atoms). ), or an aryl group (which may be monocyclic or polycyclic, preferably having 6 to 20 carbon atoms). Further, the above group represented by R X1 may have a substituent.
  • the atom directly bonded to N- in R 1 X1 is preferably neither a carbon atom in -CO- nor a sulfur atom in -SO 2 -.
  • the cycloalkyl group in R X1 may be monocyclic or polycyclic.
  • the cycloalkyl group for R X1 includes, for example, a norbornyl group and an adamantyl group.
  • the substituent that the cycloalkyl group in R 1 X1 may have is not particularly limited, but an alkyl group (either linear or branched, preferably having 1 to 5 carbon atoms) is preferred.
  • One or more 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 1-10, more preferably 1-5.
  • the substituent that the alkyl group in R X1 may have is not particularly limited, but is preferably, for example, a cycloalkyl group, a fluorine atom, or a cyano group.
  • Examples of the cycloalkyl group as the substituent include the cycloalkyl groups described in the case where R 1 X1 is a cycloalkyl group.
  • the alkyl group in R X1 has a fluorine atom as the substituent, the alkyl group may be a perfluoroalkyl group.
  • one or more —CH 2 — of the alkyl group in R X1 may be substituted with a carbonyl group.
  • the aryl group for R X1 is preferably a benzene ring group.
  • the substituent that the aryl group in R X1 may have is not particularly limited, but an alkyl group, a fluorine atom, or a cyano group is preferable. Examples of the alkyl group as the substituent include the alkyl groups described in the case where R 1 X1 is an alkyl group.
  • each R 1 X2 is independently a hydrogen atom, or a substituent other than a fluorine atom and a perfluoroalkyl group (e.g., an alkyl group containing no fluorine atom and a fluorine atom includes a cycloalkyl group that does not contain ).
  • Two R 1 X2 in formula (B-7) may be the same or different.
  • R 1 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 1 XF1 in formula (B-8) may be the same or different.
  • the perfluoroalkyl group represented by R 1 XF1 preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 6 carbon atoms.
  • R 1 X3 represents a hydrogen atom, a halogen atom, or a monovalent organic group.
  • the halogen atom as R 1 X3 includes, for example, 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 of 0-4.
  • n1 is preferably an integer of 0 to 2, preferably 0 or 1. When n1 represents an integer of 2 to 4, multiple R 1 X3 may be the same or different.
  • R 1 XF2 represents a fluorine atom or a perfluoroalkyl group.
  • the perfluoroalkyl group represented by R 1 XF2 preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 6 carbon atoms.
  • the monovalent organic group represented by R a1 is not particularly limited, but generally has 1 to 30 carbon atoms, 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, preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, and still more preferably an alkyl group having 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 further a cycloalkyl group having 3 to 10 carbon atoms. preferable.
  • the aryl group may be monocyclic or polycyclic, preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and even more preferably an aryl group having 6 to 10 carbon atoms.
  • the cycloalkyl group may contain heteroatoms as ring member atoms. Examples of heteroatoms include, but are not limited to, nitrogen atoms, oxygen atoms, and the like.
  • the above alkyl group, cycloalkyl group and aryl group may further have a substituent.
  • the divalent linking group as L a1 is not particularly limited, but includes an alkylene group, a cycloalkylene group, an aromatic group, —O—, —CO—, —COO—, and a group formed by combining two or more of these. represent.
  • 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, 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, 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.
  • a 31- and R a1 may combine with each other to form a ring.
  • Examples of the photodegradable onium salt compound PG1 include, for example, paragraphs [0135] to [0171] of WO2018/193954, paragraphs [0077] to [0116] of WO2020/066824, WO2017/ It is also preferable to use the photoacid generators disclosed in paragraphs [0018] to [0075] and [0334] to [0335] of JP-A-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
  • photodecomposable onium salt compound PG2 the following compound (I) and compound (II) (hereinafter referred to as “compound (I) and compound (II)” will be referred to as “photodecomposable onium salt compound PG2 "Also called.).
  • the photodegradable onium salt compound PG2 is a compound that has two or more of the salt structure sites described above and generates a polyvalent organic acid upon exposure. The photodegradable onium salt compound PG2 will be described below.
  • Compound (I) is a compound having one or more structural moieties X shown below and one or more structural moieties Y shown below, wherein the first acidic It is a compound that generates an acid containing a site and a second acidic site described below derived from the structural site Y described below.
  • Structural site X Structural site consisting of an anionic site A 1 ⁇ and a cation site M 1 + and forming a first acidic site represented by HA 1 upon exposure to actinic rays or radiation
  • Structural site Y Anionic site A A structural moiety consisting of 2 ⁇ and a cationic moiety M 2 + and forming a second acidic site represented by HA 2 upon exposure to actinic rays or radiation provided that compound (I) satisfies condition I below.
  • the above compound PI corresponds to an acid generated when compound (I) is irradiated with actinic rays or radiation.
  • each structural moiety X may be the same or different.
  • Two or more of A 1 ⁇ and two or more of M 1 + may be the same or different.
  • a 1 ⁇ and A 2 ⁇ , and M 1 + and M 2 + may be the same or different, but A 1 ⁇ and A 2 ⁇ may be the same or different.
  • Each A 2 - is preferably different.
  • the anion site A 1 - and the anion site A 2 - are structural sites containing negatively charged atoms or atomic groups, for example, formulas (AA-1) to (AA-3) and formula (BB -1) to (BB-6).
  • * represents a bonding position.
  • RA represents a monovalent organic group.
  • the monovalent organic group represented by RA includes a cyano group, a trifluoromethyl group, a methanesulfonyl group, and the like.
  • the cation site M 1 + and the cation site M 2 + are structural sites containing positively charged atoms or atomic groups, and examples thereof include monovalent organic cations.
  • the organic cation is not particularly limited, the organic cation represented by the formula (ZaI) (cation (ZaI)) or the organic cation represented by the formula (ZaII) (cation (ZaII)) is preferable.
  • Compound (II) is a compound having two or more of the above structural moieties X and one or more of the following structural moieties Z, wherein the first acidic It is a compound that generates an acid containing two or more sites and the structural site Z described above.
  • Structural site Z nonionic site capable of neutralizing acid
  • the compound (II) is a compound PII (acid) having an acidic site represented by HA 1 in which the cation site M 1 + in the structural site X is replaced with H + by irradiation with actinic rays or radiation. can occur.
  • compound PII represents a compound having an acidic site represented by HA 1 above and structural site Z, which is a nonionic site capable of neutralizing acid.
  • the definition of structural site X and the definitions of A 1 - and M 1 + in compound (II) are the same as the definition of structural site X in compound (I) described above, and A 1 - and M 1 + is synonymous with the definition of and the preferred embodiment is also the same.
  • the two or more structural moieties X may be the same or different.
  • Two or more of A 1 ⁇ and two or more of M 1 + may be the same or different.
  • the acid-neutralizable nonionic site in structural site Z is not particularly limited, and for example, a site containing a group capable of electrostatically interacting with protons or a functional group having electrons is preferable.
  • a group capable of electrostatically interacting 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.
  • a functional group having a A nitrogen atom having a lone pair of electrons that does not contribute to ⁇ -conjugation is, for example, a nitrogen atom having a partial structure represented by the following formula.
  • Partial structures of functional groups having electrons or groups capable of electrostatically interacting with protons include, for example, a crown ether structure, an azacrown ether structure, a primary to tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure. etc., among which primary to tertiary amine structures are preferred.
  • the molecular weight of the photodegradable onium salt compound PG2 is preferably from 100 to 10,000, more preferably from 100 to 2,500, even more preferably from 100 to 1,500.
  • the content is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, based on the total solid content of the composition. Preferably, 5.0% by mass or more is more preferable. Moreover, the content is preferably 40.0% by mass or less, more preferably 30.0% by mass or less.
  • the photodegradable onium salt compounds may be used singly or in combination of two or more. When two or more are used, the total content is preferably within the range of the preferred content.
  • the resist composition may contain a surfactant.
  • a surfactant is contained, the adhesion is better and a pattern with fewer development defects can be formed.
  • the surfactant is preferably a fluorine-based and/or silicon-based surfactant. Fluorinated and/or silicon-based surfactants include surfactants disclosed in paragraphs [0218] and [0219] of WO2018/193954.
  • One type of these surfactants may be used alone, or two or more types may be used.
  • the content of the surfactant is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass, based on the total solid content of the composition.
  • 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.
  • a method of forming a resist film on a substrate using a resist composition includes, for example, a method of coating the substrate with the resist composition.
  • 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 substrates such as those used in the manufacture of integrated circuit devices (eg, silicon, silicon dioxide coatings) by a suitable coating method such as a spinner or coater.
  • the coating method is preferably spin coating using a spinner.
  • the rotation speed for spin coating using a spinner is preferably 1000 to 3000 rpm.
  • the substrate may be dried to form a resist film. If necessary, various base films (inorganic film, organic film, antireflection film) may be formed under the resist film.
  • Heating can be carried out by a means provided in a normal exposure machine and/or a developing machine, and may be carried out using a hot plate or the like.
  • the heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, even more preferably 80 to 130°C.
  • the heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, even more preferably 60 to 600 seconds.
  • the film thickness of the resist film is not particularly limited, it is preferably 10 to 120 nm from the viewpoint of forming fine patterns with higher precision.
  • the film thickness of the resist film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm.
  • the film thickness of the resist film is more preferably 10 to 120 nm, still more preferably 15 to 90 nm.
  • a topcoat composition may be used to form a topcoat on the upper layer of the resist film. It is preferable that the topcoat composition does not mix with the resist film and can be uniformly coated on the upper layer of the resist film.
  • the topcoat is not particularly limited, and a conventionally known topcoat can be formed by a conventionally known method. can be formed. For example, it is preferable to form a top coat containing a basic compound as described in JP-A-2013-061648 on the resist film. Specific examples of basic compounds that the topcoat may contain include basic compounds that the resist composition may contain.
  • the topcoat preferably contains a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond.
  • Step 2 is a step of exposing the resist film.
  • the exposure method include a method of irradiating the formed resist film with actinic rays or radiation through a predetermined mask.
  • Actinic rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, preferably 250 nm or less, more preferably 220 nm or less, particularly preferably 1 -200 nm wavelength deep UV light, 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 of the exposed area, resulting in better sensitivity and pattern shape.
  • the heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, even more preferably 80 to 130°C.
  • the heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, even more preferably 30 to 120 seconds. Heating can be carried out by a means provided in a normal exposing machine and/or developing machine, and may be carried out using a hot plate or the like.
  • Step 3 is a step of developing the exposed resist film using a developer to form a pattern.
  • the developer is a developer containing an organic solvent (hereinafter also referred to as an organic developer).
  • Examples of the development method include a method in which the substrate is immersed in a tank filled with a developer for a certain period of time (dip method), and a method in which the developer is piled up on the surface of the substrate by surface tension and remains stationary for a certain period of time for development (paddle method). ), a method of spraying the developer onto the surface of the substrate (spray method), and a method of continuously ejecting the developer while scanning the developer ejection nozzle at a constant speed onto the substrate rotating at a constant speed (dynamic dispensing method). is mentioned. Further, after the step of developing, a step of stopping development may be performed while replacing the solvent with another solvent.
  • the development time is not particularly limited as long as the resin in the unexposed area is sufficiently dissolved, and is preferably 10 to 300 seconds, more preferably 20 to 120 seconds.
  • the temperature of the developer is preferably 0 to 50°C, more preferably 15 to 35°C.
  • the organic developer is a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. It is preferable to have
  • a plurality of the above solvents may be mixed, or may be mixed with a solvent other than the above or water.
  • the water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and particularly preferably substantially free of water.
  • the content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, and 90% by mass or more and 100% by mass with respect to the total amount of the developer. The following are more preferable, and 95% by mass or more and 100% by mass or less are particularly preferable.
  • the pattern forming method preferably includes a step of washing with a rinse after step 3.
  • the rinse solution used in the rinse step after the development step using the organic developer is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used.
  • the rinse liquid contains at least one organic solvent selected from the group consisting of hydrocarbon-based solvents, ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, and ether-based solvents. is preferred.
  • the method of the rinsing step is not particularly limited. For example, a method of continuously discharging the rinsing liquid onto the substrate rotating at a constant speed (rotation coating method), or a method of immersing the substrate in a tank filled with the rinsing liquid for a certain period of time. method (dip method), and method of spraying a rinse 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 developing solution and the rinse solution remaining between the patterns and inside the patterns due to baking are removed. In addition, this process smoothes the resist pattern, and has the effect of improving the roughness of the surface of the pattern.
  • the heating step after the rinsing step is usually carried out at 40 to 250° C. (preferably 90 to 200° C.) for 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).
  • the substrate may be etched using the formed pattern as a mask. That is, the pattern formed in step 3 may be used as a mask to process the substrate (or the underlying film and substrate) to form a pattern on the substrate.
  • the method for processing the substrate (or the underlying film and the substrate) is not particularly limited, but the substrate (or the underlying film and the substrate) is dry-etched using the pattern formed in step 3 as a mask.
  • a method of forming a pattern is preferred. Dry etching is preferably oxygen plasma etching.
  • Various materials used in the resist composition and the pattern forming method of the present invention contain impurities such as metals. preferably does not contain The content of impurities contained in these materials is preferably 1 mass ppm or less, more preferably 10 mass ppb or less, still more preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less.
  • impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, Zn, and the like.
  • a method of reducing impurities such as metals contained in various materials for example, a method of selecting a raw material with a low metal content as a raw material constituting various materials, a method of filtering the raw materials constituting various materials with a filter and a method of performing distillation under conditions in which contamination is suppressed as much as possible by, for example, lining the inside of the apparatus with Teflon (registered trademark).
  • impurities may be removed with an adsorbent, or filter filtration and adsorbent may be used in combination.
  • adsorbent known adsorbents can be used.
  • inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.
  • Whether the metal impurities are sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of the metal component contained in the cleaning liquid used for cleaning the manufacturing equipment.
  • the content of the metal component contained in the cleaning liquid after use is preferably 100 mass ppt (parts per trillion) or less, more preferably 10 mass ppt or less, and even more preferably 1 mass ppt or less.
  • Conductive compounds are added to organic treatment liquids such as rinsing liquids in order to prevent damage to chemical piping and various parts (filters, O-rings, tubes, etc.) due to electrostatic charging and subsequent electrostatic discharge.
  • the conductive compound is not particularly limited, and examples thereof include methanol.
  • the amount added is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, from the viewpoint of maintaining preferable developing properties or rinsing properties.
  • Examples of chemical pipes include SUS (stainless steel), or antistatic polyethylene, polypropylene, or various pipes coated with fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.). can be used.
  • Antistatic treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can also be used for filters and O-rings.
  • the present invention also relates to an electronic device manufacturing method including the pattern forming method described above, and an electronic device manufactured by this manufacturing method.
  • the electronic device of the present invention is preferably mounted in electric/electronic equipment (household appliances, OA (Office Automation), media-related equipment, optical equipment, communication equipment, etc.).
  • the present invention also relates to a polymer (specific polymer) containing a repeating unit represented by either formula (1) or (2).
  • the specific polymer is as described above. That is, it includes specific repeating units selected from the group consisting of repeating units represented by formula (1) and repeating units represented by formula (2).
  • the specific polymer can be used as a so-called main chain scission type polymer.
  • N-phenylmaleimide (17.3 g) was added to dichloroethane (1,2-DCE, 100 ml) to obtain a mixed solution.
  • Bromine (17.56 g) was added dropwise to the resulting mixture at room temperature. After completion of the dropwise addition, the mixture was heated to reflux for 1 hour. After refluxing, dichloroethane was distilled off with an evaporator, then tetrahydrofuran (THF, 300 ml) was added to dissolve the contents, and triethylamine (21.23 g) was added dropwise under ice water.
  • the mixture was heated to room temperature and reacted for 2 hours, then the reaction was quenched with an aqueous ammonium chloride solution (300 ml), and the THF layer was recovered using a separating funnel.
  • the recovered THF layer was concentrated by an evaporator, and the concentrate was reslurried with methanol (100 ml) and filtered to obtain the desired product, 3-Bromo-1-phenyl-1H-pyrrole-2,5-dione. (10.2 g yield, 40.5% yield).
  • Polymer [Various Components of Actinic Ray-Sensitive or Radiation-Sensitive Resin Composition]
  • the polymers (A-1 to A-25 and RA-1) shown in Table 15 were synthesized by known methods.
  • Polymer RA-1 corresponds to a comparative polymer.
  • Table 14 shows the compositions of the polymers A-1 to A-25 and RA-1 (raw material monomer, composition ratio of repeating units (mol% ratio), weight average molecular weight (Mw), and degree of dispersion (Mw/Mn)).
  • the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of the polymers A-1 to A-25 and RA-1 were measured by GPC (carrier: tetrahydrofuran (THF)) (in terms of polystyrene ). Also, the composition ratio (mol% ratio) of the polymer was measured by 13 C-NMR (Nuclear Magnetic Resonance).
  • each raw material monomer in Table 14 above is as follows.
  • the number of each raw material monomer shown in the "repeating unit 1" column is the upper part as a specific example of the repeating unit represented by either formula (1) or formula (2). It corresponds to the number of the monomer indicated in the part.
  • the structure of the raw material monomer (H-3) shown in the "repeating unit 1" column is as follows.
  • Photodegradable onium salt compound The structures of the photodegradable onium salt compounds (PAG-1 to PAG-3) shown in Table 15 are shown below.
  • a silicon wafer having a resist film obtained by the above procedure was exposed using an EUV exposure apparatus (Exitech, Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36). Pattern irradiation was performed.
  • As the reticle a mask having a line size of 20 nm and a line:space ratio of 1:1 was used.
  • the exposed resist film was baked at 90° C. for 60 seconds, developed with butyl acetate for 30 seconds, rinsed with butyl acetate, and spin-dried to obtain a pattern.
  • LWR (nm) The pattern obtained in ⁇ pattern formation> was observed from above using a scanning electron microscope (SEM (Hitachi Ltd. S-9380II)). The line width of the pattern was observed at 250 points, and the measurement variation was evaluated by 3 ⁇ to obtain LWR (nm). The smaller the value of LWR, the better the LWR performance.
  • the LWR evaluation is preferably 5.2 nm or less, more preferably 4.0 nm or less, particularly preferably 3.4 nm or less, and most preferably 2.9 nm or less.
  • the repeating unit A of the specific polymer contained in the resist composition is a repeating unit represented by formula (1) (provided that the electron-withdrawing group is 8.5 or less) and When any one or more of the repeating units represented by formula (2) are present, and the resist composition satisfies any two or more (preferably four or more) of the following conditions A1 to A4, resolution It was confirmed that the properties are better and/or the LWR of the pattern formed is better.
  • the resist composition contains a photodegradable onium salt compound.
  • the specific polymer in the resist composition contains a repeating unit represented by formula (2)-1.
  • the specific polymer in the resist composition contains a repeating unit represented by formula (3)-1 (preferably formula (3)-1-1).
  • the weight-average molecular weight of the specific polymer in the resist composition is 30,000 or more.

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Abstract

La présente invention aborde un premier problème consistant à fournir une composition de résine sensible aux rayons actiniques ou au rayonnement à partir de laquelle un motif ayant une excellente résolution est formé. La présente invention aborde également un deuxième problème consistant à fournir un film de réserve, un procédé de formation de motif et un procédé de fabrication de dispositif électronique qui impliquent tous la composition de résine sensible aux rayons actiniques ou au rayonnement. La présente invention aborde en outre un troisième problème consistant à fournir un polymère dont peut être dotée la composition de résine sensible aux rayons actiniques ou au rayonnement.　Une composition de résine sensible aux rayons actiniques ou au rayonnement selon la présente invention contient un solvant et un polymère comprenant un motif récurrent représenté par la formule (1) ou la formule (2). Dans la formule (1), X représente un atome d'halogène. R1-R3 représentent chacun indépendamment un atome d'hydrogène ou un groupe substituant. Cependant, au moins l'un des R1 et des R2 représente un groupe attracteur d'électrons. Dans la formule (2), X représente un atome d'halogène. R4 représente un atome d'hydrogène ou un groupe substituant. L1 et L2 représentent chacun indépendamment -CO-, -SO-, ou -SO2-. L3 représente une liaison simple ou un groupe de liaison divalent.
PCT/JP2023/003929 2022-02-15 2023-02-07 Composition de résine sensible aux rayons actiniques ou au rayonnement, film de réserve, procédé de formation de motif, procédé de fabrication de dispositif électronique et polymère WO2023157712A1 (fr)

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WO2019187803A1 (fr) * 2018-03-30 2019-10-03 富士フイルム株式会社 Composition de résine sensible aux rayons actifs ou sensible au rayonnement, film de réserve, procédé permettant de former un motif, et procédé permettant de fabriquer un dispositif électronique

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019187803A1 (fr) * 2018-03-30 2019-10-03 富士フイルム株式会社 Composition de résine sensible aux rayons actifs ou sensible au rayonnement, film de réserve, procédé permettant de former un motif, et procédé permettant de fabriquer un dispositif électronique

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