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
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
• • 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

• CDU critical dimension uniformity
• R 1 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms.
• Y 1 is a single bond or a divalent linking group.
• R f1 and R f2 are each independently a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group having 1 to 5 carbon atoms, a monovalent fluorinated hydrocarbon group having 1 to 5 carbon atoms, a cyano group, or , is a nitro group.
• R f1 and Y 1 may combine with each other to form a ring structure having 3 to 15 carbon atoms.
• R f3 and R f4 are each independently a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group having 1 to 5 carbon atoms, a monovalent fluorinated hydrocarbon group having 1 to 5 carbon atoms, a cyano group, or , is a nitro group.
• X 1 is a monovalent hydrocarbon group having 1 to 5 carbon atoms, a monovalent fluorinated hydrocarbon group having 1 to 5 carbon atoms, a cyano group, or a nitro group.
• R f3 , R f4 and X 1 may together form a ring structure having 3 to 15 carbon atoms.
• at least one of R f1 , R f2 , R f3 , R f4 , or X 1 is a fluorine atom, a monovalent fluorinated hydrocarbon group having 1 to 5 carbon atoms, a cyano group, or a nitro group; .
• R 2 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms.
• Y2 is a divalent linking group.
• R f5 and R f6 are each independently a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group having 1 to 5 carbon atoms, a monovalent fluorinated hydrocarbon group having 1 to 5 carbon atoms, a cyano group, or , is a nitro group.
• X2 is a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, a cyano group or a nitro group. Any two or three of R f5 , R f6 and X 2 may together form a ring structure having 3 to 15 carbon atoms.
• R f5 , R f6 or X 2 is a fluorine atom, a monovalent fluorinated hydrocarbon group having 1 to 5 carbon atoms, a cyano group or a nitro group.
• the radiation-sensitive resin composition it is possible to construct a resist film that satisfies sensitivity, CDU performance, and residual defect performance.
• the reason for this is not certain and is not limited, it is presumed as follows.
• a dissociation reaction occurs in the structural units (1) and (2) in the resin A during the development process, and the solubility can be changed, so that the development defect performance is improved and the contrast between the exposed area and the unexposed area is increased. , excellent pattern formability is exhibited.
• the iodine atoms contained in the acid diffusion control agent absorb radiation such as EUV radiation having a wavelength of 13.5 nm very strongly, thereby increasing the sensitivity of the radiation-sensitive resin composition. It is presumed that the above resist performance can be exhibited by these combined actions.
• the present invention provides, in another embodiment, a step of directly or indirectly applying the radiation-sensitive resin composition onto a substrate to form a resist film; exposing the resist film; and developing the exposed resist film with a developer.
• the radiation-sensitive resin composition (hereinafter also simply referred to as "composition") according to the present embodiment contains resin A, resin B, an acid diffusion controller and a solvent.
• the above composition may contain other optional components as long as they do not impair the effects of the present invention.
• the radiation-sensitive resin composition can impart high levels of sensitivity, CDU performance and development defect performance to the resulting resist film.
• Resin A includes a structural unit represented by the following formula (1) (hereinafter also referred to as “structural unit (1)”), a structural unit represented by the following formula (2) (hereinafter referred to as “structural unit (2) ”), or a polymer assembly containing both.
• structural unit (1) a structural unit represented by the following formula (1)
• structural unit (2) a structural unit represented by the following formula (2)
• Y 1 is a single bond or a divalent linking group.
• R f1 and R f2 are each independently a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group having 1 to 5 carbon atoms, a monovalent fluorinated hydrocarbon group having 1 to 5 carbon atoms, a cyano group, or , is a nitro group.
• R f1 and Y 1 may combine with each other to form a ring structure having 3 to 15 carbon atoms.
• R f3 and R f4 are each independently a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group having 1 to 5 carbon atoms, a monovalent fluorinated hydrocarbon group having 1 to 5 carbon atoms, a cyano group, or , is a nitro group.
• X 1 is a monovalent hydrocarbon group having 1 to 5 carbon atoms, a monovalent fluorinated hydrocarbon group having 1 to 5 carbon atoms, a cyano group, or a nitro group. Any two or three of R f3 , R f4 and X 1 may together form a ring structure having 3 to 15 carbon atoms. provided that at least one of R f1 , R f2 , R f3 , R f4 , or X 1 is a fluorine atom, a monovalent fluorinated hydrocarbon group having 1 to 5 carbon atoms, a cyano group, or a nitro group; .
• R 2 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms.
• Y2 is a divalent linking group.
• R f5 and R f6 are each independently a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group having 1 to 5 carbon atoms, a monovalent fluorinated hydrocarbon group having 1 to 5 carbon atoms, a cyano group, or , is a nitro group.
• Resin A may contain other structural units in addition to structural unit (1) and structural unit (2) as long as the effects of the present invention are not impaired. Each structural unit will be described below.
• Structural unit (1) Structural unit (1) is represented by the following formula (1).
• R 1 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms.
• Y 1 is a single bond or a divalent linking group.
• R f1 and R f2 are each independently a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group having 1 to 5 carbon atoms, a monovalent fluorinated hydrocarbon group having 1 to 5 carbon atoms, a cyano group, or , is a nitro group.
• R f3 , R f4 and X 1 may together form a ring structure having 3 to 15 carbon atoms. provided that at least one of R f1 , R f2 , R f3 , R f4 , or X 1 is a fluorine atom, a monovalent fluorinated hydrocarbon group having 1 to 5 carbon atoms, a cyano group, or a nitro group; . )
• R 1 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms.
• R 1 is preferably a hydrogen atom or a methyl group from the viewpoint of copolymerizability of the monomer that gives the structural unit (1).
• Y 1 is a single bond or a divalent linking group.
• the divalent linking group for Y 1 include a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, and the like.
• the above divalent hydrocarbon group having 1 to 20 carbon atoms as Y 1 is, for example, a divalent chain hydrocarbon group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, groups, divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms, and the like.
• Examples of the divalent chain hydrocarbon group having 1 to 20 carbon atoms include a linear or branched saturated hydrocarbon group having 1 to 20 carbon atoms, or a divalent linear hydrocarbon group having 1 to 20 carbon atoms. Chain or branched unsaturated hydrocarbon groups are included.
• Examples of the divalent linear or branched saturated hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group and 2-methylpropyl group. , a 1-methylpropyl group, a group obtained by removing one hydrogen atom from an alkyl group such as a t-butyl group.
• Examples of the divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a monocyclic or polycyclic bivalent saturated hydrocarbon group or a monocyclic or polycyclic divalent unsaturated hydrocarbon group. be done.
• the monocyclic divalent saturated hydrocarbon group is preferably a group obtained by removing one hydrogen atom from a cyclopentyl group, cyclohexyl group, cycloheptyl group or cyclooctyl group.
• R f1 and R f2 are each independently a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group having 1 to 5 carbon atoms, a monovalent fluorinated hydrocarbon group having 1 to 5 carbon atoms, a cyano group, or , is a nitro group.
• R f3 and R f4 are each independently a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group having 1 to 5 carbon atoms, a monovalent fluorinated hydrocarbon group having 1 to 5 carbon atoms, a cyano group, or , is a nitro group.
• the above monovalent fluorinated hydrocarbon groups having 1 to 5 carbon atoms each independently include, for example, a monovalent fluorinated linear hydrocarbon group having 1 to 5 carbon atoms, a monovalent fluorinated hydrocarbon group having 3 to 5 carbon atoms, and and the like.
• Examples of the above C 3-5 alicyclic hydrocarbon groups include monocyclic saturated hydrocarbon groups and monocyclic or polycyclic unsaturated hydrocarbon groups.
• a cyclopentyl group is preferable as the monocyclic saturated hydrocarbon group.
• R f1 , R f2 , R f3 , R f4 , or X 1 is a fluorine atom, a monovalent fluorinated hydrocarbon group having 1 to 5 carbon atoms, or a cyano group. , or a nitro group.
• examples of monomers forming the structural unit (1) include monomers represented by the following formula.
• Structural unit (2) Structural unit (2) is represented by the following formula (2).
• R 2 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms.
• Y2 is a divalent linking group.
• R f5 and R f6 are each independently a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group having 1 to 5 carbon atoms, a monovalent fluorinated hydrocarbon group having 1 to 5 carbon atoms, a cyano group, or , is a nitro group.
• Y2 is a divalent linking group.
• Y 2 includes, for example, a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, which may contain an ether group or an ester group. .
• the divalent hydrocarbon group and fluorinated hydrocarbon group having 1 to 20 carbon atoms as Y 2 contains an ether group or an ester group, one or more ether groups or ester groups are included in the group. Any hydrocarbon group may be included.
• the divalent hydrocarbon group having 1 to 20 carbon atoms as Y 2 is, for example, a chain divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, groups, divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms, and the like.
• divalent chain hydrocarbon group having 1 to 20 carbon atoms examples include a linear or branched saturated hydrocarbon group having 1 to 20 carbon atoms, or a divalent linear hydrocarbon group having 1 to 20 carbon atoms. Chain or branched unsaturated hydrocarbon groups are included. Specific examples of these groups are the same as those described above.
• divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms examples include a monocyclic or polycyclic bivalent saturated hydrocarbon group or a monocyclic or polycyclic divalent unsaturated hydrocarbon group. be done. Specific examples of these groups are the same as those described above.
• Examples of the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms include phenylene group, tolylene group, xylylene group, naphthylene group, aralkylene group such as anthrylene group; and aralkylene group such as methylphenylene group. .
• the divalent fluorinated hydrocarbon groups having 1 to 20 carbon atoms as Y 2 each independently include, for example, a divalent fluorinated chain hydrocarbon group having 1 to 20 carbon atoms, a chain fluorinated hydrocarbon group having 3 to 3 carbon atoms, 20 divalent fluorinated alicyclic hydrocarbon groups and the like.
• Examples of the chain hydrocarbon groups and alicyclic hydrocarbon groups constituting such divalent fluorinated chain hydrocarbon groups and fluorinated alicyclic hydrocarbon groups include the above-mentioned divalent hydrocarbon groups. be done.
• the hydrocarbon group having 1 to 5 carbon atoms as R f5 and R f6 is, for example, a chain hydrocarbon group having 1 to 5 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 5 carbon atoms. etc.
• chain hydrocarbon group having 1 to 5 carbon atoms examples include a linear or branched saturated hydrocarbon group having 1 to 5 carbon atoms, or a linear or branched unsaturated hydrocarbon group having 1 to 5 carbon atoms. is mentioned. Specific examples of these groups are the same as those described above.
• Examples of the above C 3-5 alicyclic hydrocarbon groups include monocyclic saturated hydrocarbon groups and monocyclic or polycyclic unsaturated hydrocarbon groups.
• a cyclopentyl group is preferable as the monocyclic saturated hydrocarbon group.
• the above monovalent fluorinated hydrocarbon groups having 1 to 5 carbon atoms each independently include, for example, a monovalent fluorinated linear hydrocarbon group having 1 to 20 carbon atoms, a monovalent fluorinated hydrocarbon group having 3 to 5 carbon atoms, and and the like.
• X2 is a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, a cyano group or a nitro group.
• Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms include monocyclic saturated hydrocarbon groups and monocyclic or polycyclic unsaturated hydrocarbon groups.
• a cyclopentyl group is preferable as the monocyclic saturated hydrocarbon group.
• any two or three of R f5 , R f6 and X 2 may together form a ring structure having 3 to 15 carbon atoms.
• At least one of R f5 , R f6 , or X 2 is a fluorine atom, a monovalent fluorinated hydrocarbon group having 1 to 5 carbon atoms, a cyano group, or a nitro group.
• Examples of the structural unit (2) include structural units represented by the following formula.
• the lower limit of the content ratio of the structural unit (2) (the total when there are multiple types of the structural unit (2)) is, among all the structural units constituting the resin, for example, It is 5 mol %, and may be 10 mol %, 15 mol %, 20 mol %, or the like.
• the upper limit of the content ratio is, for example, 100 mol %, and may be 90 mol %, 80 mol %, or 70 mol %.
• the resin A can further have a third structural unit represented by the following formula (3) (hereinafter also referred to as “structural unit (3)”).
• R4 is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.
• R 5 is a monovalent hydrocarbon group having 1 to 20 carbon atoms.
• R 6 and R 7 are each independently a monovalent chain hydrocarbon group having 1 to 10 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or R 6 and R 7 is a divalent alicyclic group having 3 to 20 carbon atoms combined with each other and composed together with the carbon atoms to which they are attached.
• examples of monovalent hydrocarbon groups having 1 to 20 carbon atoms represented by R 5 include aliphatic hydrocarbon groups such as methyl group, ethyl group and isopropyl group; Aromatic hydrocarbon groups can be mentioned.
• the monovalent chain hydrocarbon groups having 1 to 10 carbon atoms represented by R 6 and R 7 each independently include, for example, an alkyl group such as a methyl group or an ethyl group.
• the monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms represented by R 6 and R 7 each independently include, for example, a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group. I can give you a base.
• Examples of the third structural unit include structural units represented by the following formulas (3-1) to (3-6).
• R 4 to R 7 have the same definitions as in formula (3) above.
• i and j are each independently an integer from 0 to 16; k is 0-1.
• R5 is preferably a methyl group, an ethyl group, an isopropyl group or a phenyl group.
• the resin A may contain one or a combination of two or more structural units (3).
• the content of the third structural unit in the resin A is, for example, preferably 1 mol% or more, more preferably 5 mol% or more, relative to the total structural units constituting the resin A. preferable. Moreover, 70 mol% or less is preferable, and 60 mol% or less is more preferable.
• the above resin A can be synthesized, for example, by polymerizing monomers that give each structural unit using a known radical polymerization initiator or the like in an appropriate solvent.
• the Mw and Mn of Resin A are values measured using gel permeation chromatography (GPC) under the following conditions.
• the content of resin A is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, still more preferably 1 part by mass or more, and 1.5 parts by mass or more with respect to 100 parts by mass of the base resin described below. is particularly preferred. Also, it is preferably 15 parts by mass or less, more preferably 12 parts by mass or less, even more preferably 10 parts by mass or less, and particularly preferably 8 parts by mass or less.
• the base resin includes, in addition to the structural unit (I), a structural unit (II) containing at least one selected from the group consisting of a lactone structure, a cyclic carbonate structure and a sultone structure, which will be described later, and structural units (I) and (II ) may have structural units other than Each structural unit will be described below.
• a structural unit (II) containing at least one selected from the group consisting of a lactone structure, a cyclic carbonate structure and a sultone structure, which will be described later, and structural units (I) and (II ) may have structural units other than Each structural unit will be described below.
• examples of monovalent hydrocarbon groups having 1 to 20 carbon atoms represented by R 9 include aliphatic hydrocarbon groups such as methyl group, ethyl group and isopropyl group; Aromatic hydrocarbon groups can be mentioned.
• the divalent alicyclic group having 3 to 20 carbon atoms in which R 10 and R 11 are combined together and formed together with the carbon atoms to which they are bonded includes a hydrocarbon ring having the above carbon number.
• a hydrocarbon ring having the above carbon number There is no particular limitation as long as it is a group obtained by removing two hydrogen atoms from the same constituent carbon atoms.
• the hydrocarbon ring before removing two hydrogen atoms include cyclopentyl ring, cyclohexyl ring, cycloalkyl ring such as cyclooctyl group ring; polycyclic alicyclic ring such as norbornane ring and adamantyl ring; can.
• R9 is preferably a methyl group, an ethyl group, an isopropyl group or a phenyl group.
• the base resin may contain one or a combination of two or more structural units (I).
• a structural unit containing a lactone structure is preferable, a structural unit containing a norbornanelactone structure is more preferable, and a structural unit derived from norbornanelactone-yl (meth)acrylate is even more preferable.
• Structural units (III) include, for example, structural units represented by the following formula.
• RA is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
• the content of the structural unit (III) is preferably 5 mol% or more, and 8 mol, based on the total structural units constituting the base resin. % or more is more preferable, and 10 mol % or more is even more preferable. Also, it is preferably 40 mol % or less, more preferably 35 mol % or less, and even more preferably 30 mol % or less.
• Structural units (IV) are preferably structural units derived from hydroxystyrene, structural units derived from dihydroxystyrene, and structural units derived from hydroxyphenyl (meth)acrylate.
• the phenolic hydroxyl group is protected by a protective group such as an alkali-dissociable group, and then polymerized, followed by hydrolysis and deprotection to obtain the structural unit (IV).
• a protective group such as an alkali-dissociable group
• the phenolic hydroxyl group may be substituted at any of the p-, m- and o-positions.
• the resin may contain structural units having an organic acid anion moiety and an onium cation moiety as further structural units (VII).
• Structural unit (VII) is preferably represented by the following formula (a71) or (a72).
• R A7 is a hydrogen atom or a methyl group.
• X71 is a single bond or an ester group.
• X 72 is a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms or an arylene group having 6 to 10 carbon atoms, and part of the methylene groups constituting the alkylene group is an ether group, It may be substituted with an ester group or a lactone ring-containing group, and at least one hydrogen atom contained in X 72 may be substituted with an iodine atom.
• X 73 is a single bond, an ether group, an ester group, or a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, and part of the methylene groups constituting the alkylene group is an ether group or It may be substituted with an ester group.
• R f71 to R f74 are each independently a hydrogen atom, a fluorine atom or a trifluoromethyl group, and at least one is a fluorine atom or a fluorinated hydrocarbon group.
• R 73 to R 77 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom, and R 73 and R 74 are bonded to each other and sulfur to which they are bonded A ring may be formed with the atoms.
• the monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom for R 73 to R 77 is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or a carbon Aryl groups having a number of 6 to 20 are preferred, and some or all of the hydrogen atoms in these groups are hydroxy groups, carboxy groups, halogen atoms, oxo groups, cyano groups, amido groups, nitro groups, sultone groups, sulfone groups or They may be substituted with sulfonium salt-containing groups, and some of the methylene groups constituting these groups may be substituted with ether groups, ester groups, carbonyl groups, carbonate groups or sulfonate ester groups.
• the onium cation portion of formula (a71-1) above is preferably represented by formula (Q-1) below.
• Ra 1 and Ra 2 each independently represent a substituent.
• n 1 represents an integer of 0 to 5, and when n 1 is 2 or more, a plurality of Ra 1 may be the same or different.
• n 2 represents an integer of 0 to 5, and when n 2 is 2 or more, a plurality of Ra 2 may be the same or different.
• n 3 represents an integer of 0 to 5, and when n 3 is 2 or more, a plurality of Ra 3 may be the same or different.
• Ra 3 represents a fluorine atom or a group having one or more fluorine atoms. Ra 1 and Ra 2 may be linked together to form a ring.
• n 1 When n 1 is 2 or more, a plurality of Ra 1 may be linked together to form a ring. When n2 is 2 or more, a plurality of Ra2 may be linked together to form a ring. When n 1 is 1 or more and n 2 is 1 or more, Ra 1 and Ra 2 may be linked together to form a ring (ie, a heterocyclic ring containing a sulfur atom).
• Preferred substituents represented by Ra 1 and Ra 2 are alkyl groups, cycloalkyl groups, alkoxy groups, cycloalkyloxy groups, alkoxycarbonyl groups, alkylsulfonyl groups, hydroxyl groups, halogen atoms and halogenated hydrocarbon groups.
• the alkyl groups of Ra 1 and Ra 2 may be straight-chain alkyl groups or branched-chain alkyl groups.
• the alkyl group preferably has 1 to 10 carbon atoms, such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group and 1-methylpropyl group. , t-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl and n-decyl groups.
• methyl group, ethyl group, n-butyl group and t-butyl group are particularly preferred.
• Examples of the alkyl group portion of the alkoxy group for Ra 1 and Ra 2 include those previously listed as the alkyl group for Ra 1 and Ra 2 .
• As this alkoxy group a methoxy group, an ethoxy group, an n-propoxy group and an n-butoxy group are particularly preferred.
• Examples of the cycloalkyl group portion of the cycloalkyloxy groups of Ra 1 and Ra 2 include those previously listed as the cycloalkyl groups of Ra 1 and Ra 2 .
• a cyclopentyloxy group and a cyclohexyloxy group are particularly preferred as the cycloalkyloxy group.
• alkoxy group portion of the alkoxycarbonyl group for Ra 1 and Ra 2 examples include those previously listed as the alkoxy groups for Ra 1 and Ra 2 .
• this alkoxycarbonyl group a methoxycarbonyl group, an ethoxycarbonyl group and an n-butoxycarbonyl group are particularly preferred.
• Examples of the alkyl group portion of the alkylsulfonyl group for Ra 1 and Ra 2 include those previously listed as the alkyl group for Ra 1 and Ra 2 .
• examples of the cycloalkyl group portion of the cycloalkylsulfonyl groups of Ra 1 and Ra 2 include those previously listed as the cycloalkyl groups of Ra 1 and Ra 2 .
• alkylsulfonyl groups and cycloalkylsulfonyl groups methanesulfonyl group, ethanesulfonyl group, n-propanesulfonyl group, n-butanesulfonyl group, cyclopentanesulfonyl group and cyclohexanesulfonyl group are particularly preferred.
• Each group of Ra 1 and Ra 2 may further have a substituent.
• substituents include a halogen atom such as a fluorine atom (preferably a fluorine atom), a hydroxy group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, a cycloalkyloxy group, an alkoxyalkyl group, and a cycloalkyloxyalkyl group. , alkoxycarbonyl, cycloalkyloxycarbonyl, alkoxycarbonyloxy, and cycloalkyloxycarbonyloxy groups.
• the halogen atoms of Ra 1 and Ra 2 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, with a fluorine atom being preferred.
• Halogenated alkyl groups are preferred as the halogenated hydrocarbon groups for Ra 1 and Ra 2 .
• Examples of the alkyl group and halogen atom that constitute the halogenated alkyl group include those mentioned above. Among them, a fluorinated alkyl group is preferred, and CF3 is more preferred.
• Ra 3 is a fluorine atom or a group having one or more fluorine atoms.
• groups having fluorine atoms include groups in which alkyl groups, cycloalkyl groups, alkoxy groups, cycloalkyloxy groups, alkoxycarbonyl groups and alkylsulfonyl groups as Ra 1 and Ra 2 are substituted with fluorine atoms. .
• fluorinated alkyl groups are preferable, and CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , C 5 F 11 , C 6 F 13 , C 7 F 15 and C 8 F 17 , CH2CF3 , CH2CH2CF3 , CH2C2F5 , CH2CH2C2F5 , CH2C3F7 , CH2CH2C3F7 , CH2C4F _ _ _ _ _ _ _ _ 9 and CH 2 CH 2 C 4 F 9 are more preferred, and CF 3 is particularly preferred.
• Ra3 is preferably a fluorine atom or CF3 , more preferably a fluorine atom.
• n 1 and n 2 are each independently preferably an integer of 0 to 3, preferably an integer of 0 to 2.
• n 1 +n 2 +n 3 3
• n 1 +n 2 +n 3 4
• onium cation moiety represented by the above formula (Q-1) include the following. All of the sulfonium cation moieties shown below are sulfonium cation moieties having a fluorine-substituted aromatic ring structure. Structures substituted with atoms or groups other than fluorine atoms, such as other substituents, can be preferably employed.
• the alkyl group, alkoxy group and alkoxycarbonyl group represented by R d1 and R d2 , and the group having a fluorine atom represented by R d3 and R d4 are the same as those of the above formula (Q-1). mentioned.
• Each of k1 and k2 is preferably 0 to 2, more preferably 0 or 1.
• Each of k3 and k4 is preferably 1 to 3, more preferably 1 or 2.
• (k3+k4) is an integer of 0 to 10, preferably an integer of 1 to 6, more preferably an integer of 1 to 4, and still more preferably 1 or 2.
• onium cation moiety represented by the above formula (Q-2) include the following. All of the iodonium cation moieties shown below are iodonium cation moieties having a fluorine-substituted aromatic ring structure. Structures substituted with atoms or groups other than fluorine atoms, such as other substituents, can be preferably employed.
• the resin may contain structural units derived from styrene in addition to the structural units (I) to (VII). Some or all of the hydrogen atoms of the benzene ring in styrene may be substituted with halogen atoms. An iodine atom is preferred as the halogen atom.
• the molecular weight of the base resin is not particularly limited, but the polystyrene equivalent weight average molecular weight (Mw) by gel permeation chromatography (GPC) is preferably 1,000 or more and 50,000 or less, more preferably 2,000 or more and 30,000 or less. It is preferably 3,000 or more and 15,000 or less, and particularly preferably 4,000 or more and 12,000 or less. If the Mw of the base resin is less than the above lower limit, the resulting resist film may have reduced heat resistance. When the Mw of the base resin exceeds the above upper limit, the developability of the resist film may deteriorate.
• Mw polystyrene equivalent weight average molecular weight
• the ratio (Mw/Mn) of Mw to the polystyrene equivalent number average molecular weight (Mn) of the base resin measured by GPC is usually 1 or more and 5 or less, preferably 1 or more and 3 or less, and more preferably 1 or more and 2 or less.
• the content of the base resin is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 85% by mass or more, relative to the total solid content of the radiation-sensitive resin composition.
• the acid diffusion control agent in the present invention contains an organic acid anion moiety and the cation moiety, the salt contains a carboxylate anion in the organic acid anion moiety, and at least a part of the organic acid anion moiety in the salt is Contains iodine-substituted aromatic ring structures.
• the acid diffusion controller is an acid diffusion controller that generates an acid having a higher pKa than the acid generated from the radiation-sensitive acid generator upon exposure to radiation.
• at least a portion of the organic acid anion moiety in the salt contains an iodine-substituted aromatic ring structure.
• R 1A is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
• R 1B is an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 8 carbon atoms.
• the alkyl group having 1 to 6 carbon atoms may be linear, branched, or cyclic, and specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n- butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group and the like.
• Examples of the alkyl moiety of the alkoxy group having 1 to 6 carbon atoms, the acyloxy group having 2 to 7 carbon atoms, and the alkoxycarbonyl group having 2 to 7 carbon atoms are the same as the specific examples of the alkyl group described above.
• Examples of the alkyl moiety of the alkylsulfonyloxy group having 1 to 4 carbon atoms include those having 1 to 4 carbon atoms among the specific examples of the alkyl group described above.
• the alkenyl group having 2 to 8 carbon atoms may be linear, branched or cyclic, and specific examples thereof include vinyl, 1-propenyl and 2-propenyl groups.
• R 3 , R 4 , R 5 , R 6 and R 7 are each independently a C 1-20 monovalent hydrocarbon group optionally containing a heteroatom.
• the onium cation portion of the acid diffusion control agent has fluorine atoms
• at least one of R 3 , R 4 and R 5 contains one or more fluorine atoms
• at least one of R 6 and R 7 contains one or more fluorine atoms.
• any two of R 3 , R 4 and R 5 may bond with each other to form a ring together with the sulfur atom to which they bond.
• the monovalent hydrocarbon group may be linear, branched, or cyclic, and specific examples thereof include alkyl groups having 1 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, and 2 to 12 carbon atoms. , an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, and the like. Also, some or all of the hydrogen atoms in these groups are substituted with hydroxy groups, carboxy groups, halogen atoms, cyano groups, amido groups, nitro groups, mercapto groups, sultone groups, sulfone groups, or sulfonium salt-containing groups. and some of the carbon atoms of these groups may be substituted with ether bonds, ester bonds, carbonyl groups, carbonate groups or sulfonate ester bonds.
• L 1 is a single bond or a divalent linking group having 1 to 20 carbon atoms
• the divalent linking group is an ether bond, thioether bond, carbonyl group, ester bond, amide bond, sultone ring, lactam ring, carbonate It may contain a bond, a halogen atom, a hydroxy group or a carboxy group.
• a divalent linking group having 1 to 20 carbon atoms is a combination of a group selected from the group consisting of an ether bond, a thioether bond, a carbonyl group, an ester bond and an amide bond and a divalent hydrocarbon group. groups.
• divalent hydrocarbon groups examples include substituted or unsubstituted divalent aliphatic hydrocarbon groups, substituted or unsubstituted divalent alicyclic hydrocarbon groups, and substituted or unsubstituted divalent aromatic hydrocarbon groups. groups. Among them, a divalent alkylene group substituted with one or more fluorine atoms or a substituted or unsubstituted divalent arylene group is preferable.
• L 1 is a group consisting of a combination of a group selected from the group consisting of an ether bond, a thioether bond, a carbonyl group, an ester bond and an amide bond and a substituted or unsubstituted divalent arylene group
• a divalent arylene group is preferably bonded to the carboxy group in the above formulas (S-1) and (S-2).
• n and n are integers satisfying 1 ⁇ m ⁇ 5, 0 ⁇ n ⁇ 3, and 0 ⁇ m+n ⁇ 5, but preferably integers satisfying 1 ⁇ m ⁇ 3 and 0 ⁇ n ⁇ 2.
• anion of the acid diffusion control agent represented by the above formula (S-1) or (S-2) examples include, but are not limited to, the following.
• the acid diffusion control agent may be a metal cation instead of the onium cation moieties represented by the formulas (S-1) and (S-2).
• the acid diffusion controllers represented by the above formulas (S-1) and (S-2) can also be synthesized by known methods, particularly by salt exchange reaction.
• Known acid diffusion control agents can also be used as long as they do not impair the effects of the present invention.
• the acid diffusion control agents may be used alone or in combination of two or more.
• the lower limit of the content of the acid diffusion control agent is preferably 0.5 parts by mass, more preferably 1 part by mass, and even more preferably 1.5 parts by mass with respect to 100 parts by mass of the base resin.
• the upper limit of the content is preferably 15 parts by mass, more preferably 12 parts by mass, and even more preferably 8 parts by mass.
• the radiation-sensitive acid generator preferably contains an organic acid anion portion and an onium cation portion.
• the organic acid anion portion preferably has at least one selected from the group consisting of sulfonate anions and sulfonimide anions. Acids generated by exposure include sulfonic acids and sulfonimides corresponding to the above organic acid anion moieties.
• the organic acid anion moiety preferably contains an iodine-substituted aromatic ring structure.
• a compound in which one or more fluorine atoms or fluorinated hydrocarbon groups are bonded to a carbon atom adjacent to a sulfonate anion can be preferably used as a radiation-sensitive acid generator that gives sulfonic acid upon exposure.
• R 1 is a hydroxy group, a carboxy group, a fluorine atom, a chlorine atom, a bromine atom or an amino group, or a fluorine atom, a chlorine atom, a bromine atom, a hydroxy group, an amino group or an alkoxy group having 1 to 10 carbon atoms;
• R 8 is a hydrogen atom, a halogen atom, a hydroxy group, a carbon an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms which may contain an acyloxy group having 2 to 6 carbon atoms; 16 alkyl group, alkenyl group having 2 to 16 carbon atoms, or aryl group having 6 to 12 carbon atoms, halogen atom, hydroxy group, alkoxy group having 1 to 6 carbon atoms, acyl group having 2 to 6 carbon atoms, Alternatively, it may contain an acyloxy group having 2 to 6 carbon atoms.
• R 2 is a single bond or a divalent linking group having 1 to 20 carbon atoms when p is 1, and a trivalent or tetravalent linking group having 1 to 20 carbon atoms when p is 2 or 3. and the linking group may contain an oxygen atom, a sulfur atom or a nitrogen atom.
• Rf 1 to Rf 4 are each independently a hydrogen atom, a fluorine atom or a trifluoromethyl group, at least one of which is a fluorine atom or a trifluoromethyl group. Also, Rf 1 and Rf 2 may combine to form a carbonyl group. In particular, both Rf3 and Rf4 are preferably fluorine atoms.
• R 3 , R 4 , R 5 , R 6 and R 7 are each independently a C 1-20 monovalent hydrocarbon group optionally containing a heteroatom.
• the onium cation moiety of the radiation-sensitive acid generator contains fluorine
• at least one of R 3 , R 4 and R 5 contains one or more fluorine atoms
• at least one of R 6 and R 7 contains one or more fluorine atoms.
• any two of R 3 , R 4 and R 5 may bond with each other to form a ring together with the sulfur atom to which they bond.
• the monovalent hydrocarbon group may be linear, branched, or cyclic, and specific examples thereof include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms. , an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, and the like. Also, some or all of the hydrogen atoms in these groups are substituted with hydroxy groups, carboxy groups, halogen atoms, cyano groups, amido groups, nitro groups, mercapto groups, sultone groups, sulfone groups, or sulfonium salt-containing groups. and some of the carbon atoms of these groups may be substituted with ether bonds, ester bonds, carbonyl groups, carbonate groups or sulfonate ester bonds.
• p is an integer that satisfies 1 ⁇ p ⁇ 3.
• q and r are integers satisfying 0 ⁇ q ⁇ 5, 0 ⁇ r ⁇ 3, and 0 ⁇ q+r ⁇ 5.
• q is preferably an integer that satisfies 1 ⁇ q ⁇ 3, more preferably 2 or 3.
• r is preferably an integer that satisfies 0 ⁇ r ⁇ 2.
• Examples of the organic acid anion portion of the radiation-sensitive acid generator represented by the above formulas (A-1) and (A-2) include, but are not limited to, those shown below. All of the compounds shown below are organic acid anion moieties having an iodine-substituted aromatic ring structure. A structure substituted with an atom or group other than an iodine atom such as a substituent of can be preferably employed.
• the onium cation moiety in the radiation-sensitive acid generator represented by formula (A-1) above is represented by (Q-1) and (Q-2) above in the structural unit (VII) that may be contained in the resin.
• the structures shown for the onium cation moieties can be suitably employed.
• the lower limit of the content of the radiation-sensitive acid generator is preferably 0.5 parts by mass, more preferably 1 part by mass, still more preferably 1.5 parts by mass, and 2 parts by mass with respect to 100 parts by mass of the base resin.
• the upper limit of the content is preferably 20 parts by mass or less, more preferably 18 parts by mass or less, still more preferably 15 parts by mass or less, and particularly preferably 12 parts by mass or less, relative to 100 parts by mass of the resin.
• alcohol solvents include carbon such as iso-propanol, 4-methyl-2-pentanol, 3-methoxybutanol, n-hexanol, 2-ethylhexanol, furfuryl alcohol, cyclohexanol, 3,3,5-trimethylcyclohexanol, diacetone alcohol; Monoalcoholic solvents of numbers 1 to 18; Polyethylene glycol having 2 to 18 carbon atoms such as ethylene glycol, 1,2-propylene glycol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol and tripropylene glycol. a alcohol-based solvent; A polyhydric alcohol partial ether solvent obtained by etherifying a part of the hydroxy groups of the above polyhydric alcohol solvent may be used.
• ketone solvents examples include chain ketone solvents such as acetone, butanone, and methyl-iso-butyl ketone; Cyclic ketone solvents such as cyclopentanone, cyclohexanone, and methylcyclohexanone; 2,4-pentanedione, acetonylacetone, acetophenone and the like.
• the radiation-sensitive resin composition may contain other optional components in addition to the components described above.
• the other optional components include a cross-linking agent, an uneven distribution promoter, a surfactant, an alicyclic skeleton-containing compound, a sensitizer, and the like. These other optional components may be used alone or in combination of two or more.
• the pattern formation method in this embodiment includes: Step (1) of directly or indirectly coating the radiation-sensitive resin composition on a substrate to form a resist film (hereinafter also referred to as “resist film forming step”); Step (2) of exposing the resist film (hereinafter also referred to as “exposure step”), and A step (3) of developing the exposed resist film (hereinafter also referred to as a “development step”) is included.
• a resist film is formed from the radiation-sensitive resin composition.
• the substrate on which the resist film is formed include conventionally known substrates such as silicon wafers, silicon dioxide, and aluminum-coated wafers. Further, for example, an organic or inorganic antireflection film disclosed in JP-B-6-12452, JP-A-59-93448, etc. may be formed on the substrate. Examples of coating methods include spin coating, casting coating, and roll coating. After coating, if necessary, prebaking (PB) may be performed in order to volatilize the solvent in the coating film.
• the PB temperature is usually 60°C to 150°C, preferably 80°C to 140°C.
• the PB time is usually 5 to 600 seconds, preferably 10 to 300 seconds.
• the thickness of the resist film to be formed is preferably 10 nm to 1,000 nm, more preferably 10 nm to 500 nm.
• the resist film formed in the resist film forming step (step (1) above) is coated through a photomask (in some cases, through an immersion medium such as water). , emit radiation and expose. Radiation used for exposure depends on the line width of the desired pattern. A charged particle beam and the like can be mentioned. Among these, far ultraviolet rays, electron beams, and EUV are preferred, and ArF excimer laser light (wavelength 193 nm), KrF excimer laser light (wavelength 248 nm), electron beams, and EUV are more preferred. The following electron beams and EUV are more preferable.
• a post-exposure bake is performed to accelerate the dissociation of the acid-dissociable groups of the resin or the like by the acid generated from the radiation-sensitive acid generator upon exposure in the exposed portions of the resist film.
• This PEB causes a difference in solubility in a developer between the exposed area and the unexposed area.
• the PEB temperature is usually 50°C to 180°C, preferably 80°C to 130°C.
• the PEB time is usually 5 to 600 seconds, preferably 10 to 300 seconds.
• step (3) above the resist film exposed in the exposure step (step (2) above) is developed. Thereby, a predetermined resist pattern can be formed. After development, it is common to wash with a rinsing liquid such as water or alcohol and dry.
• a rinsing liquid such as water or alcohol
• the content of the organic solvent in the developer is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly preferably 99% by mass or more.
• components other than the organic solvent in the developer include water and silicon oil.
• Examples of the developing method include a method of immersing the substrate in a tank filled with a developer for a certain period of time (dip method), and a method of developing by standing still for a certain period of time while the developer is heaped up on the surface of the substrate by surface tension (puddle method).
• dip method a method of immersing the substrate in a tank filled with a developer for a certain period of time
• puddle method a method of developing by standing still for a certain period of time while the developer is heaped up on the surface of the substrate by surface tension
• method a method of spraying the developer onto the substrate surface
• spray method a method of continuously discharging the developer while scanning the developer discharge nozzle at a constant speed onto the substrate rotating at a constant speed
• dynamic dispensing method a method of continuously discharging the developer while scanning the developer discharge nozzle at a constant speed onto the substrate rotating at a constant speed
• a radiation-sensitive resin composition was prepared by filtering a solution obtained by dissolving each component with the composition shown in Table 1 in a solvent in which 100 ppm of FC-4430 manufactured by 3M was dissolved as a surfactant and filtered through a 0.2 ⁇ m size filter. was prepared.
• This resist film was scanned with an EUV scanner ("NXE3300" by ASML (NA 0.33, ⁇ 0.9/0.6, quadruple pole illumination, pitch 46 nm on wafer, +20% bias hole pattern mask)). was exposed using PEB was performed on a hot plate at 120° C. for 60 seconds, and development was performed with a 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solution for 30 seconds to form a resist pattern with 23 nm holes and a 46 nm pitch.
• TMAH tetramethylammonium hydroxide
• the exposure dose for forming the resist pattern of 23 nm holes with a pitch of 46 nm was defined as the optimum exposure dose (Eop), and the optimum exposure dose was defined as the sensitivity (mJ/cm 2 ).
• the number of development defects per 1 cm 2 was measured using a defect inspection apparatus (KLA-Tencor "KLA2810"). Then, the measured development defects were classified into those judged to be derived from the resist film and foreign substances derived from the outside, and the number of defects judged to be derived from the resist film was calculated. The fewer the number of development defects, the better.
• the development defect is "A” when it is 0.05/ cm2 or less, "B” when it is more than 0.05/ cm2 and 0.1/ cm2 or less, and 0.1/ cm2 . "C” if it exceeds
• PEB was performed on a hot plate at 120° C. for 60 seconds. and developed with a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 30 seconds to form a positive resist pattern (32 nm line and space pattern). This 32 nm line and space pattern is formed.
• the exposure dose was taken as the optimum exposure dose (Eop2).

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  • 2022-08-31 JP JP2023552745A patent/JPWO2023058365A1/ja active Pending
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