WO2023095561A1 - Composition de résine sensible au rayonnement et procédé de formation de structure - Google Patents

Composition de résine sensible au rayonnement et procédé de formation de structure Download PDF

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Publication number
WO2023095561A1
WO2023095561A1 PCT/JP2022/040625 JP2022040625W WO2023095561A1 WO 2023095561 A1 WO2023095561 A1 WO 2023095561A1 JP 2022040625 W JP2022040625 W JP 2022040625W WO 2023095561 A1 WO2023095561 A1 WO 2023095561A1
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group
carbon atoms
radiation
monovalent
hydrocarbon group
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PCT/JP2022/040625
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English (en)
Japanese (ja)
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正之 三宅
龍一 根本
奈津美 北野
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Jsr株式会社
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Publication of WO2023095561A1 publication Critical patent/WO2023095561A1/fr

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    • 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
    • G03F7/038—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 a radiation-sensitive resin composition and a pattern forming method.
  • Photolithography technology that uses resist compositions is used to form fine circuits in semiconductor devices.
  • an acid is generated by exposing the film of the resist composition to radiation through a mask pattern, and the acid is used as a catalyst to react with the resin in the exposed area and the unexposed area.
  • a resist pattern is formed on a substrate by creating a difference in solubility in an organic developer.
  • CDU critical dimension uniformity
  • pattern circularity which indicates the roundness of the hole shape
  • LWR Line Width Roughness
  • the present invention is a radiation-sensitive resin capable of forming a resist film that can exhibit sensitivity, CDU performance, pattern circularity, LWR performance, and pattern rectangularity at a sufficient level even when forming a resist pattern with a high aspect ratio.
  • An object is to provide a composition and a pattern forming method.
  • a first onium salt compound represented by the following formula (1) a second onium salt compound represented by the following formula (2); a resin containing a structural unit having an acid-labile group; It relates to a radiation-sensitive resin composition containing a solvent.
  • R 1 is a monovalent chain organic group having 1 to 40 carbon atoms.
  • R 2 and R 3 are each independently a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group or a monovalent fluorinated hydrocarbon group. When multiple R 2 and R 3 are present, multiple R 2 and R 3 are the same or different.
  • R f11 and R f12 are each independently a fluorine atom or a monovalent fluorinated hydrocarbon group. When a plurality of R f11 and R f12 are present, the plurality of R f11 and R f12 are the same or different.
  • m 1 and m 2 are each independently an integer of 1-4.
  • R 4 , R 5 , R 6 and R 7 are each independently a hydrogen atom, a hydroxy group, a halogen atom or a monovalent organic group having 1 to 20 carbon atoms. When a plurality of R 4 , R 5 , R 6 and R 7 are present, the plurality of R 4 , R 5 , R 6 and R 7 are the same or different.
  • R 8 is a hydrogen atom, a hydroxy group, a halogen atom or a monovalent organic group having 1 to 20 carbon atoms.
  • each R 8 is independently a hydrogen atom, a hydroxy group, a halogen atom or a monovalent organic group having 1 to 20 carbon atoms, or two of the multiple R 8 represents a 5- to 20-membered cyclic structure formed together with the two carbon atoms of the benzene ring in the above formula (1) to which they are combined and bonded.
  • n 1 and n 2 are each independently an integer of 1-4.
  • n3 is an integer from 1 to 5;
  • R B is a monovalent organic group having 3 to 40 carbon atoms containing a cyclic structure.
  • R f21 and R f22 are each independently a fluorine atom or a monovalent fluorinated hydrocarbon group. When a plurality of R f21 and R f22 are present, the plurality of R f21 and R f22 are the same or different.
  • p is an integer from 1 to 4;
  • Z + is a monovalent radiation-sensitive onium cation.
  • the radiation-sensitive resin composition contains both the first onium salt compound and the second onium salt compound as radiation-sensitive acid generators, excellent sensitivity and CDU can be obtained even when forming a resist pattern with a high aspect ratio. Performance, pattern circularity, LWR performance, and pattern rectangularity can be exhibited. Although not bound by any theory, the reason for this is presumed as follows. Since the anion portion of the first onium salt compound has a chain structure and is less affected by steric hindrance, the diffusion length of the generated acid is relatively long. As a result, even if the resist film is thick, the generated acid is not unevenly distributed and the acid can be sufficiently distributed.
  • the cation portion of the first onium salt compound has high transparency and high quantum efficiency due to its structure, so that even a thick resist film can efficiently generate acid throughout the thickness direction during exposure. be able to. Furthermore, since it has a thioxane-like structure containing sulfur and oxygen, it has high solubility and can be uniformly dispersed in the resist film.
  • an organic group means a group containing at least one carbon atom.
  • the step of directly or indirectly applying the radiation-sensitive resin composition onto a substrate to form a resist film the 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 capable of forming a resist film having excellent sensitivity, CDU performance, pattern circularity, LWR performance and pattern rectangularity is used, a high-quality resist pattern can be efficiently formed. can be formed into
  • the radiation-sensitive resin composition according to the present embodiment (hereinafter also simply referred to as "composition”) comprises a first onium salt compound, a second onium salt compound, a resin containing a structural unit having an acid-dissociable group, and a solvent. including. Furthermore, an acid diffusion control agent is included as needed.
  • the above composition may contain other optional components as long as they do not impair the effects of the present invention. Since the radiation-sensitive resin composition contains both the first onium salt compound and the second onium salt compound as radiation-sensitive acid generators, the resist film of the radiation-sensitive resin composition has a high level of sensitivity, CDU performance, pattern circularity, LWR performance and pattern rectangularity can be imparted.
  • the first onium salt compound is represented by the above formula (1) and functions as a radiation-sensitive acid generator that generates an acid upon exposure to radiation.
  • the monovalent chain organic group having 1 to 40 carbon atoms represented by R 1 is not particularly limited as long as it has a chain structure.
  • the chain structure includes a monovalent chain hydrocarbon group having 1 to 40 carbon atoms, which may be saturated or unsaturated, linear or branched, and one of the hydrogen atoms contained in the chain hydrocarbon group. groups partially or wholly substituted with substituents, and -CO-, -CS-, -O-, -S-, -SO 2 -, -NR'- Or a group containing a combination of two or more of these, or a combination thereof.
  • R' is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
  • Examples of the chain hydrocarbon group having 1 to 40 carbon atoms include a linear or branched saturated hydrocarbon group having 1 to 40 carbon atoms, or a linear or branched unsaturated hydrocarbon group having 1 to 40 carbon atoms. is mentioned.
  • Examples of the linear or branched saturated hydrocarbon group having 1 to 40 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1- Alkyl groups such as a methylpropyl group, t-butyl group, n-pentyl group, isopentyl group, and neopentyl group are included.
  • linear or branched unsaturated hydrocarbon groups having 1 to 40 carbon atoms examples include alkenyl groups such as ethenyl group, propenyl group and butenyl group; alkynyl groups such as ethynyl group, propynyl group and butynyl group. .
  • the monovalent chain organic group having 1 to 40 carbon atoms represented by R 1 includes the above monovalent chain hydrocarbon group having 1 to 40 carbon atoms and the monovalent chain having 1 to 40 carbon atoms.
  • a group in which at least one of an ether bond (—O—) and a carbonyl group (—CO—) (thus including an ester bond) is incorporated in the chain or at the end of the chain of a hydrocarbon group having 1 carbon It is preferably a group in which some or all of the hydrogen atoms of a monovalent chain hydrocarbon group of ⁇ 40 are substituted with fluorine atoms, or a combination thereof.
  • a group in which at least one of an ether bond (-O-) and a carbonyl group (-CO-) is incorporated in the chain or at the end of the chain of a monovalent chain hydrocarbon group having 1 to 20 carbon atoms A group in which some or all of the hydrogen atoms of a monovalent chain hydrocarbon group having 1 to 20 carbon atoms are substituted with fluorine atoms, or a combination thereof is preferred.
  • the monovalent chain organic group having 1 to 40 carbon atoms represented by R 1 is preferably a linear organic group having 1 to 40 carbon atoms.
  • an ether bond (-O-) and a carbonyl group (-CO-) is incorporated in the chain or at the end of the chain of the monovalent chain hydrocarbon group having 1 to 20 carbon atoms , an alkoxyalkyl group, an alkylcarbonylalkyl group, an alkoxycarbonylalkyl group, an alkylcarbonyloxyalkyl group, an alkylcarbonyloxy group, an alkoxy group, and the like.
  • the alkyl chains of these groups each independently preferably have 1 to 12 carbon atoms.
  • At least one of an ether bond (--O--) and a carbonyl group (--CO--) may be repeatedly incorporated in the chain. Some or all of the hydrogen atoms in these groups may be substituted with halogen atoms.
  • a monovalent fluorinated chain hydrocarbon group having 1 to 20 carbon atoms groups are preferred.
  • Examples of the monovalent fluorinated chain hydrocarbon group having 1 to 20 carbon atoms include trifluoromethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 2,2,3,3, 3-pentafluoropropyl group, 1,1,1,3,3,3-hexafluoropropyl group, heptafluoro n-propyl group, heptafluoro i-propyl group, nonafluoro n-butyl group, nonafluoro i-butyl group, nonafluoro t-butyl group, 2,2,3,3,4,4,5,5-octafluoro n-pentyl group, tridecafluoro n-hexyl group, 5,5,5-trifluoro-1,1- a fluorinated alkyl group such as a diethylpentyl group; fluorinated alkenyl groups such as a trifluoroetheny
  • the monovalent hydrocarbon group represented by R 2 and R 3 includes a monovalent chain hydrocarbon group having 1 to 40 carbon atoms for R 1 and a monovalent alicyclic hydrocarbon group having 3 to 40 carbon atoms.
  • the monovalent alicyclic hydrocarbon group having 3 to 40 carbon atoms includes a monocyclic or polycyclic saturated hydrocarbon group, or a monocyclic or polycyclic unsaturated hydrocarbon group.
  • Preferred monocyclic saturated hydrocarbon groups are cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl groups.
  • Preferred polycyclic cycloalkyl groups are bridged alicyclic hydrocarbon groups such as norbornyl, adamantyl, tricyclodecyl and tetracyclododecyl groups.
  • Monocyclic unsaturated hydrocarbon groups include monocyclic cycloalkenyl groups such as a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group.
  • Polycyclic unsaturated hydrocarbon groups include polycyclic cycloalkenyl groups such as norbornenyl, tricyclodecenyl, and tetracyclododecenyl groups.
  • the bridged alicyclic hydrocarbon group is a polycyclic alicyclic hydrocarbon group in which two carbon atoms that are not adjacent to each other among the carbon atoms constituting the alicyclic ring are linked by a bond chain containing one or more carbon atoms.
  • a cyclic hydrocarbon group is a polycyclic alicyclic hydrocarbon group in which two carbon atoms that are not adjacent to each other among the carbon atoms constituting the alicyclic ring are linked by a bond chain
  • Examples of the monovalent aromatic hydrocarbon group having 6 to 40 carbon atoms include aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group and anthryl group; benzyl group, phenethyl group and naphthylmethyl group; An aralkyl group and the like can be mentioned.
  • the monovalent fluorinated hydrocarbon group represented by R 2 and R 3 includes a monovalent fluorinated chain hydrocarbon group having 1 to 20 carbon atoms for R 1 and a monovalent fluorinated chain hydrocarbon group having 3 to 20 carbon atoms. and the like.
  • Examples of the monovalent fluorinated alicyclic hydrocarbon group having 3 to 20 carbon atoms include a fluorocyclopentyl group, a difluorocyclopentyl group, a nonafluorocyclopentyl group, a fluorocyclohexyl group, a difluorocyclohexyl group, an undecafluorocyclohexylmethyl group, fluorinated cycloalkyl groups such as a fluoronorbornyl group, a fluoroadamantyl group, a fluorobornyl group, a fluoroisobornyl group, and a fluorotricyclodecyl group; and fluorinated cycloalkenyl groups such as a fluorocyclopentenyl group and a nonafluorocyclohexenyl group.
  • the fluorinated hydrocarbon group is preferably a monovalent fluorinated chain hydrocarbon group having 1 to 8 carbon atoms, and more preferably a monovalent fluorinated linear hydrocarbon group having 1 to 5 carbon atoms.
  • R 2 and R 3 are a hydrogen atom, a fluorine atom, or a monovalent fluorinated linear hydrocarbon group having 1 to 5 carbon atoms, from the viewpoint of the degree of freedom of the peripheral structure of the sulfo group and the acidity of the generated acid. preferable.
  • monovalent fluorinated hydrocarbon groups represented by R f11 and R f12 monovalent fluorinated hydrocarbon groups represented by R 2 and R 3 can be preferably employed.
  • n 1 and m 2 are each independently preferably an integer of 1 to 3, more preferably 1 or 2, and particularly preferably 1.
  • anion portion of the first onium salt compound include, but are not limited to, structures represented by the following formulas (1-1-1) to (1-1-20).
  • the above-mentioned C 1 to 40 may be a group corresponding to a structure having 1 to 20 carbon atoms among monovalent chain organic groups, a cyclic structure, or a combination thereof.
  • the above cyclic structures include cyclic hydrocarbon groups which may be alicyclic, aromatic or heterocyclic.
  • the cyclic structure is preferably an alicyclic structure having 3 to 20 carbon atoms, an aromatic ring structure having 6 to 20 carbon atoms, or a combination thereof.
  • R'' is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
  • Examples of the substituent that replaces some or all of the hydrogen atoms of the organic group include substituents that replace some or all of the hydrogen atoms of the chain hydrocarbon group in R 1 .
  • the number of carbon atoms among the monovalent alicyclic hydrocarbon groups having 3 to 40 carbon atoms for R 2 and R 3 Groups corresponding to 3 to 20 can be preferably employed.
  • the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms for R 4 to R 7 includes 6 to 40 carbon atoms among the monovalent aromatic hydrocarbon groups having 6 to 40 carbon atoms for R 2 and R 3 .
  • Groups corresponding to 20 can be suitably employed.
  • heterocyclic cyclic hydrocarbon group for R 4 to R 7 examples include a group obtained by removing one hydrogen atom from an aromatic heterocyclic structure and a group obtained by removing one hydrogen atom from an alicyclic heterocyclic structure.
  • the heterocyclic structure also includes a 5-membered ring aromatic structure having aromaticity by introducing a heteroatom. Heteroatoms include oxygen atoms, nitrogen atoms, sulfur atoms, and the like.
  • aromatic heterocyclic structures examples include oxygen atom-containing aromatic heterocyclic structures such as furan, pyran, benzofuran, and benzopyran; nitrogen atom-containing aromatic heterocyclic structures such as pyrrole, imidazole, pyridine, pyrimidine, pyrazine, indole, quinoline, isoquinoline, acridine, phenazine, carbazole; sulfur atom-containing aromatic heterocyclic structures such as thiophene; Examples include aromatic heterocyclic structures containing multiple heteroatoms such as thiazole, benzothiazole, thiazine, and oxazine.
  • Examples of the alicyclic heterocyclic structures include oxygen atom-containing alicyclic heterocyclic structures such as oxirane, tetrahydrofuran, tetrahydropyran, dioxolane, and dioxane; nitrogen atom-containing alicyclic heterocyclic structures such as aziridine, pyrrolidine, piperidine, piperazine; Sulfur atom-containing alicyclic heterocyclic structures such as thietane, thiolane, and thiane; Examples include alicyclic heterocyclic structures containing multiple heteroatoms such as morpholine, 1,2-oxathiolane, and 1,3-oxathiolane.
  • the cyclic structures also include structures containing lactone structures, cyclic carbonate structures, sultone structures and cyclic acetals.
  • the monovalent organic groups having 1 to 20 carbon atoms represented by R 8 can be preferably employed.
  • the 5- to 20-membered cyclic structure composed together with the two carbon atoms of the benzene ring in the above formula (1) in which two R 8 are combined and bonded together
  • the cyclic structure shown for R 4 to R 7 structures corresponding to 5 to 20 ring members can be preferably employed.
  • the cyclic structure is preferably an alicyclic hydrocarbon structure having 5 to 20 carbon atoms from the viewpoint of the transparency of the cationic portion of the first onium salt compound.
  • the alicyclic hydrocarbon structure having 5 to 20 carbon atoms includes a structure corresponding to 5 to 20 carbon atoms among the monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms shown in R 4 to R 7 . mentioned.
  • R 4 , R 5 , R 6 , R 7 and R 8 are each a hydrogen atom, a halogen atom, the above monovalent chain hydrocarbon group having 1 to 20 carbon atoms or the above monovalent hydrocarbon group having 3 to 20 carbon atoms. Alicyclic hydrocarbon groups are preferred. Among them, R 4 , R 5 , R 6 and R 7 are hydrogen atoms, R 8 is a chain hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 6 to 12 carbon atoms, a fluorine atom or A fluorinated hydrocarbon group having 1 to 10 carbon atoms is more preferred.
  • the monovalent chain hydrocarbon group having 1 to 10 carbon atoms a methyl group, an ethyl group, an iso-propyl group, a tert-butyl group and a 1,1-dimethyl-1-propyl group are preferable.
  • the monovalent alicyclic hydrocarbon group having 6 to 12 carbon atoms a cyclohexyl group and a cycloheptyl group are preferable.
  • fluorinated hydrocarbon group having 1 to 10 carbon atoms examples include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a pentafluoroethyl group, a 2,2,3,3,3-pentafluoropropyl group, A 1,1,1,3,3,3-hexafluoropropyl group and a heptafluoro-n-propyl group are preferred.
  • n 1 and n 2 are each independently preferably an integer of 2 to 4, more preferably 2 or 3.
  • n3 is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, even more preferably 1 or 2.
  • cation portion of the first onium salt compound include, but are not limited to, structures represented by the following formulas (1-2-1) to (1-2-24).
  • the first onium salt compound is obtained by appropriately combining the anion portion and the cation portion.
  • Specific examples include, but are not limited to, structures represented by the following formulas (1-1) to (1-22).
  • the lower limit of the content of the first onium salt compound (the total thereof when multiple kinds of first onium salt compounds are included) is preferably 0.1 parts by mass, more preferably 1 part by mass, with respect to 100 parts by mass of the resin described later. Preferably, 3 parts by mass is more preferable, and 5 parts by mass is particularly preferable.
  • the upper limit of the content is preferably 100 parts by mass, more preferably 80 parts by mass or less, still more preferably 60 parts by mass or less, and particularly preferably 40 parts by mass.
  • the content of the first onium salt compound is appropriately selected according to the type of resin used, exposure conditions, required sensitivity, and the like. As a result, excellent sensitivity, CDU performance, pattern circularity, LWR performance, and pattern rectangularity can be exhibited when forming a resist pattern.
  • R 4 , R 5 , R 6 and R 7 are hydrogen atoms, n 1 and n 2 are both 2, and n 3 is 1. A case will be described as an example. A representative scheme is shown below.
  • R 1 , R 2 , R 3 , R f11 , R f12 , m 1 , m 2 and R 8 have the same definitions as in formula (1) above.
  • M + is a monovalent metal ion.
  • the (substituted) benzene ring is iodinated under an acid catalyst, and the (substituted) iodobenzene is oxidized with a peroxide, followed by an iodine oxide elimination reaction to obtain an iodonium salt.
  • This undergoes a nucleophilic substitution reaction with thioxane or an analogue thereof to produce the cationic portion of the primary onium salt compound of formula (ia).
  • the first onium salt compound represented by the formula (1') can be synthesized by performing salt exchange with a sulfonate having the structure of the anion portion of the first onium salt compound.
  • Other structures can also be synthesized by appropriately selecting starting materials, thioxane analogs, and sulfonates.
  • the second onium salt compound is represented by the above formula (2) and functions as a radiation-sensitive acid generator that generates an acid upon exposure to radiation.
  • the monovalent organic group having 3 to 40 carbon atoms containing a cyclic structure represented by R B is not particularly limited, and may be either a group containing only a cyclic structure or a group in which a cyclic structure and a chain structure are combined.
  • the cyclic structure may be monocyclic or polycyclic.
  • the cyclic structure may be an aromatic ring structure, an alicyclic structure, a heterocyclic structure, or a combination thereof.
  • Heterocyclic structures include lactone structures, cyclic carbonate structures, sultone structures, or combinations thereof. These structures are preferably included as the minimum basic skeleton of the cyclic structure.
  • the number of cyclic structures as the basic skeleton in the organic group may be one, or two or more.
  • a heteroatom or a heteroatom-containing group may be interposed between the carbon atoms forming the skeleton of the cyclic structure or chain structure or at the end of the carbon chain, and the hydrogen atoms on the carbon atoms of the cyclic structure or chain structure are other It may be substituted with a substituent.
  • the cyclic structures for R 4 , R 5 , R 6 , R 7 and R 8 can be preferably employed.
  • chain structure a monovalent chain organic group having 1 to 40 carbon atoms represented by R 1 can be preferably employed.
  • the heteroatoms or heteroatom-containing groups include -CO-, -CS-, -O-, -S-, -SO 2 -, -NR'''- or combinations of two or more thereof. and the like.
  • R''' is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. Examples of substituents that substitute hydrogen atoms on carbon atoms of the cyclic structure or chain structure include substituents that substitute some or all of the hydrogen atoms of the chain hydrocarbon group in R 1 .
  • the cyclic structure contained in R 2 B is preferably an alicyclic polycyclic structure having 6 to 14 carbon atoms, more preferably a norbornyl group or an adamantyl group.
  • the monovalent fluorinated hydrocarbon groups represented by R f21 and R f22 can be preferably employed.
  • p is preferably an integer of 1 to 3, more preferably 1 or 2.
  • anion portion of the second onium salt compound include, but are not limited to, structures represented by the following formulas (2-1-1) to (2-1-30).
  • the monovalent radiation-sensitive onium cation represented by Z + includes, together with the cation portion of the first onium salt compound, for example, S, I, O, N, P, Cl, Radiation degradable onium cations including elements such as Br, F, As, Se, Sn, Sb, Te, and Bi may be mentioned.
  • radiolytic onium cations include sulfonium cations, tetrahydrothiophenium cations, iodonium cations, phosphonium cations, diazonium cations and pyridinium cations. Among them, a sulfonium cation or an iodonium cation is preferred.
  • Sulfonium cations or iodonium cations are preferably represented by the following formulas (X-1) to (X-6).
  • each R a1 is independently a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, an alkoxy group or an alkoxycarbonyloxy group, a substituted or unsubstituted substituted monocyclic or polycyclic cycloalkyl group having 3 to 12 carbon atoms, substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, hydroxy group, halogen atom, —OSO 2 —R P , —SO 2 —R Q or —S—R T , or represents a ring structure composed of two or more of these groups combined together.
  • the ring structure may contain a heteroatom such as O or S between the carbon-carbon bonds forming the skeleton.
  • R P , R Q and R T are each independently a substituted or unsubstituted linear or branched C 1-12 alkyl group, a substituted or unsubstituted C 5-25 alicyclic It is a hydrocarbon group or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms.
  • k1, k2 and k3 are each independently an integer from 0 to 5; When each of R a1 and R P , R Q and R T is plural, the plural R a1 and R P , R Q and R T may be the same or different.
  • R b1 is a substituted or unsubstituted linear or branched alkyl group or alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted acyl group having 2 to 8 carbon atoms. , or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 8 carbon atoms, or a hydroxy group.
  • nk is 0 or 1; When nk is 0, k4 is an integer of 0-4, and when nk is 1, k4 is an integer of 0-7.
  • R b1 When there are a plurality of R b1 , the plurality of R b1 may be the same or different, and the plurality of R b1 may represent a ring structure formed by being combined with each other.
  • R b2 is a substituted or unsubstituted C 1-7 linear or branched alkyl group or a substituted or unsubstituted C 6 or 7 aromatic hydrocarbon group.
  • LC is a single bond or a divalent linking group.
  • k5 is an integer from 0 to 4;
  • the plurality of Rb2 's may be the same or different, and the plurality of Rb2 's may represent a ring structure formed by being combined with each other.
  • q is an integer from 0 to 3;
  • the ring structure containing S + may contain a heteroatom such as O or S between the carbon-carbon bonds forming the skeleton.
  • R c1 , R c2 and R c3 are each independently a substituted or unsubstituted C 1-12 linear or branched alkyl group.
  • R g1 is a substituted or unsubstituted linear or branched alkyl group or alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted acyl group having 2 to 8 carbon atoms. , or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 8 carbon atoms, or a hydroxy group.
  • nk is 0 or 1; When nk2 is 0, k10 is an integer of 0-4, and when nk2 is 1, k10 is an integer of 0-7.
  • R g1 When there are a plurality of R g1 , the plurality of R g1 may be the same or different, and the plurality of R g1 may represent a ring structure formed by being combined with each other.
  • R g2 and R g3 are each independently a substituted or unsubstituted C 1-12 linear or branched alkyl group, an alkoxy group or an alkoxycarbonyloxy group, a substituted or unsubstituted C 3 -12 monocyclic or polycyclic cycloalkyl groups, substituted or unsubstituted C6-12 aromatic hydrocarbon groups, hydroxy groups, halogen atoms, or these groups combined together Represents a ring structure.
  • k11 and k12 are each independently an integer of 0-4. When each of R g2 and R g3 is plural, the plural R g2 and R g3 may be the same or different.
  • R d1 and R d2 are each independently a substituted or unsubstituted C 1-12 linear or branched alkyl group, alkoxy group or alkoxycarbonyl group, substituted or an unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, a nitro group, or two or more of these groups combined with each other Represents the ring structure that is composed.
  • k6 and k7 are each independently an integer from 0 to 5; When each of R d1 and R d2 is plural, the plural R d1 and R d2 may be the same or different.
  • R e1 and R e2 are each independently a halogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted is an aromatic hydrocarbon group having 6 to 12 carbon atoms.
  • k8 and k9 are each independently an integer of 0-4.
  • radiation-sensitive onium cation examples include, but are not limited to, structures represented by the following formulas (2-2-1) to (2-2-32).
  • Examples of the second onium salt compound include structures in which the anion portion and the radiation-sensitive onium cation are arbitrarily combined.
  • Specific examples of the second onium salt compound include, but are not limited to, onium salt compounds represented by the following formulas (2-1) to (2-30).
  • the lower limit of the content of the secondary onium salt compound (the sum of the secondary onium salt compounds when multiple types of secondary onium salt compounds are included) is preferably 1 part by mass, more preferably 2 parts by mass, with respect to 100 parts by mass of the resin described later. 3 parts by mass is more preferable, and 4 parts by mass is particularly preferable.
  • the upper limit of the content is preferably 40 parts by mass, more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, and particularly preferably 15 parts by mass.
  • the content of the second onium salt compound is appropriately selected according to the type of resin used, exposure conditions, required sensitivity, and the like. As a result, excellent sensitivity, CDU performance, pattern circularity, LWR performance, and pattern rectangularity can be exhibited when forming a resist pattern.
  • the lower limit of the mass-based ratio b/a of the content b of the second onium salt compound to the content a of the first onium salt compound is preferably 0.05, more preferably 0.1, and 0.2. is more preferred, and 0.5 is particularly preferred.
  • the upper limit of the ratio b/a is preferably 20, more preferably 15, even more preferably 10, and particularly preferably 5.
  • the resin is an assembly of polymers containing a structural unit having an acid-labile group (hereinafter also referred to as “structural unit (I)”) (hereinafter also referred to as “base resin”).
  • structural unit (I) structural unit
  • base resin base resin
  • the term “acid-dissociable group” refers to a group that substitutes a hydrogen atom of a carboxy group, a phenolic hydroxyl group, an alcoholic hydroxyl group, a sulfo group, or the like, and is dissociated by the action of an acid.
  • the radiation-sensitive resin composition has excellent pattern formability because the resin has the structural unit (I).
  • the base resin preferably contains 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 (II) may contain other structural units. Each structural unit will be described below.
  • Structural unit (I) is a structural unit containing an acid-labile group.
  • the structural unit (I) is not particularly limited as long as it contains an acid-dissociable group.
  • a structural unit having a tertiary alkyl ester moiety a structure in which a hydrogen atom of a phenolic hydroxyl group is substituted with a tertiary alkyl group and a structural unit having an acetal bond.
  • a structural unit represented by the following formula (3) hereinafter referred to as "structure Unit (I-1)
  • structure Unit (I-1) is preferred.
  • R 17 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
  • R 18 is a monovalent hydrocarbon group having 1 to 20 carbon atoms.
  • R 19 and R 20 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 these groups represents a divalent alicyclic group having 3 to 20 carbon atoms which is combined with the carbon atoms to which they are bonded.
  • R 17 is preferably a hydrogen atom or a methyl group, more preferably a methyl group, from the viewpoint of copolymerizability of the monomer that gives the structural unit (I-1).
  • Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R 18 include a chain hydrocarbon group having 1 to 10 carbon atoms and a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms. groups, monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms, and the like.
  • the chain hydrocarbon group having 1 to 10 carbon atoms represented by R 18 to R 20 includes a linear or branched saturated hydrocarbon group having 1 to 10 carbon atoms, or a linear or branched hydrocarbon group having 1 to 10 carbon atoms.
  • a branched chain unsaturated hydrocarbon group is mentioned.
  • the alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R 18 to R 20 includes monovalent carbonized alicyclic hydrocarbon groups having 3 to 40 carbon atoms in R 2 and R 3 of the above formula (1).
  • groups having 3 to 20 carbon atoms can be preferably employed.
  • the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R 18 includes the monovalent aromatic hydrocarbon group having 6 to 40 carbon atoms for R 2 and R 3 in the above formula (1). Of these, groups having 3 to 20 carbon atoms can be preferably employed.
  • R 18 above is preferably a linear or branched saturated hydrocarbon group having 1 to 10 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms.
  • a divalent alicyclic group having 3 to 20 carbon atoms in which the chain hydrocarbon groups or alicyclic hydrocarbon groups represented by the above R 19 and R 20 are combined with the carbon atoms to which they are bonded, is not particularly limited as long as it is a group obtained by removing two hydrogen atoms from the same carbon atoms constituting the carbocyclic ring of the above-mentioned monocyclic or polycyclic alicyclic hydrocarbon having the number of carbon atoms.
  • Either a monocyclic hydrocarbon group or a polycyclic hydrocarbon group may be used, and the polycyclic hydrocarbon group may be either a bridged alicyclic hydrocarbon group or a condensed alicyclic hydrocarbon group.
  • the condensed alicyclic hydrocarbon group is a polycyclic alicyclic hydrocarbon group in which a plurality of alicyclic rings share a side (a bond between two adjacent carbon atoms).
  • the saturated hydrocarbon group is preferably a cyclopentanediyl group, a cyclohexanediyl group, a cycloheptanediyl group, a cyclooctanediyl group, or the like
  • the unsaturated hydrocarbon group is a cyclopentenediyl group.
  • cyclohexenediyl group, cycloheptenediyl group, cyclooctenediyl group, cyclodecenediyl group and the like are preferable.
  • the polycyclic alicyclic hydrocarbon group is preferably a bridged alicyclic saturated hydrocarbon group, such as a bicyclo[2.2.1]heptane-2,2-diyl group (norbornane-2,2-diyl group ), bicyclo[2.2.2]octane-2,2-diyl group, tricyclo[3.3.1.1 3,7 ]decane-2,2-diyl group (adamantane-2,2-diyl group) etc. are preferred.
  • a bridged alicyclic saturated hydrocarbon group such as a bicyclo[2.2.1]heptane-2,2-diyl group (norbornane-2,2-diyl group ), bicyclo[2.2.2]octane-2,2-diyl group, tricyclo[3.3.1.1 3,7 ]decane-2,2-diyl group (adamantane-2,2-diyl group) etc.
  • R 18 is an alkyl group having 1 to 4 carbon atoms
  • R 19 and R 20 are combined with each other and the alicyclic structure composed together with the carbon atom to which they are bonded is a polycyclic or monocyclic cycloalkane.
  • a structure is preferred.
  • structural unit (I-1) for example, structural units represented by the following formulas (3-1) to (3-6) (hereinafter referred to as “structural units (I-1-1) to (I-1- 6)”) and the like.
  • R 17 to R 20 have the same meanings as in formula (3).
  • i and j are each independently an integer of 1 to 4;
  • k and l are 0 or 1;
  • R 18 is preferably a methyl group, an ethyl group, an isopropyl group or a cyclopentyl group.
  • R 19 and R 20 are preferably a methyl group or an ethyl group.
  • the base resin may contain one or a combination of two or more structural units (I).
  • the lower limit of the content of structural units (I) is preferably 10 mol%, more preferably 20 mol%, and 30 mol, relative to all structural units constituting the base resin. % is more preferred, and 35 mol % is particularly preferred.
  • the upper limit of the content ratio is preferably 80 mol %, more preferably 75 mol %, still more preferably 70 mol %, and particularly preferably 65 mol %.
  • Structural unit (II) is a structural unit containing at least one selected from the group consisting of a lactone structure, a cyclic carbonate structure and a sultone structure.
  • the base resin can adjust the solubility in the developer, and as a result, the radiation-sensitive resin composition improves lithography performance such as resolution. be able to.
  • the adhesion between the resist pattern formed from the base resin and the substrate can be improved.
  • Structural units (II) include, for example, structural units represented by the following formulas (T-1) to (T-10).
  • R L1 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
  • R L2 to R L5 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyano group, a trifluoromethyl group, a methoxy group, a methoxycarbonyl group, a hydroxy group, a hydroxymethyl group, or a dimethylamino group; be.
  • R L4 and R L5 may be a divalent alicyclic group having 3 to 8 carbon atoms combined with each other and composed together with the carbon atoms to which they are attached.
  • L2 is a single bond or a divalent linking group.
  • X is an oxygen atom or a methylene group.
  • k is an integer from 0 to 3;
  • m is an integer of 1-3.
  • the divalent alicyclic group having 3 to 8 carbon atoms formed by combining the above R L4 and R L5 together with the carbon atoms to which they are bonded is represented by R 19 and R 20 in the above formula (3).
  • One or more hydrogen atoms on this alicyclic group may be replaced with a hydroxy group.
  • Examples of the divalent linking group represented by L 2 include a divalent linear or branched hydrocarbon group having 1 to 10 carbon atoms, and a bivalent alicyclic carbonized group having 4 to 12 carbon atoms.
  • a hydrogen group, or a group composed of one or more of these hydrocarbon groups and at least one group selected from -CO-, -O-, -NH- and -S- may be mentioned.
  • 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.
  • the lower limit of the content of structural unit (II) is preferably 20 mol%, more preferably 30 mol%, and even more preferably 35 mol%, relative to all structural units constituting the base resin.
  • the upper limit of the content ratio is preferably 75 mol %, more preferably 70 mol %, and even more preferably 65 mol %.
  • the base resin optionally has other structural units in addition to the structural units (I) and (II).
  • Examples of other structural units above include structural units (III) containing a polar group (excluding structural units (II)).
  • the base resin can adjust the solubility in the developer, and as a result, the lithography performance such as the resolution of the radiation-sensitive resin composition can be improved. can be done.
  • the polar group include a hydroxy group, a carboxyl group, a cyano group, a nitro group, a sulfonamide group and the like. Among these, a hydroxy group and a carboxy group are preferred, and a hydroxy group is more preferred.
  • 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 lower limit of the content of the structural unit (III) is preferably 5 mol% with respect to the total structural units constituting the base resin. mol % is more preferred, and 10 mol % is even more preferred. Moreover, the upper limit of the content ratio is preferably 40 mol %, more preferably 35 mol %, and even more preferably 30 mol %.
  • Structural unit (IV) In the base resin, as other structural units, in addition to the structural unit (III) having a polar group, a structural unit derived from hydroxystyrene or a structural unit having a phenolic hydroxyl group (hereinafter both are collectively referred to as "structural unit (IV )”). Structural unit (IV) contributes to improvement of etching resistance and improvement of developer solubility difference (dissolution contrast) between exposed and unexposed areas. In particular, it can be suitably applied to pattern formation using exposure to radiation with a wavelength of 50 nm or less, such as electron beams and EUV. In this case, the resin preferably has the structural unit (I) together with the structural unit (IV).
  • Structural units derived from hydroxystyrene are represented by, for example, the following formulas (4-1) to (4-2), and structural units having a phenolic hydroxyl group are represented by, for example, the following formulas (4-3) to (4-4 ) etc.
  • R 11 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
  • the phenolic hydroxyl group is protected by a protective group such as an alkali dissociable group (e.g., an acyl group) during polymerization, and then hydrolyzed to deprotect the structure. It is preferred to obtain the unit (IV).
  • a protective group such as an alkali dissociable group (e.g., an acyl group) during polymerization, and then hydrolyzed to deprotect the structure. It is preferred to obtain the unit (IV).
  • the lower limit of the content of the structural unit (IV) is preferably 10 mol%, more preferably 20 mol%, based on the total structural units constituting the resin.
  • the upper limit of the content ratio is preferably 70 mol %, more preferably 60 mol %.
  • the base resin can be synthesized, for example, by polymerizing monomers that give each structural unit using a radical polymerization initiator or the like in an appropriate solvent.
  • radical polymerization initiator examples include azobisisobutyronitrile (AIBN), 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis(2-cyclopropylpropyl pionitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), azo radical initiators such as dimethyl 2,2'-azobis isobutyrate; benzoyl peroxide, t-butyl hydroperoxide, Examples include peroxide-based radical initiators such as cumene hydroperoxide. Among these, AIBN and dimethyl 2,2'-azobisisobutyrate are preferred, and AIBN is more preferred. These radical initiators can be used individually by 1 type or in mixture of 2 or more types.
  • Solvents used in the above polymerization include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane and n-decane; Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and cumene; Halogenated hydrocarbons such as chlorobutanes, bromohexanes, dichloroethanes, hexamethylene dibromide, chlorobenzene; saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, i-butyl acetate and methyl propionate; Ketones such as acetone, methyl ethyl ketone, 2-but
  • the reaction temperature in the above polymerization is usually 40°C to 150°C, preferably 50°C to 120°C.
  • the reaction time is generally 1 hour to 48 hours, preferably 1 hour to 24 hours.
  • the molecular weight of the base resin is not particularly limited, but the lower limit of the polystyrene equivalent weight average molecular weight (Mw) by gel permeation chromatography (GPC) is preferably 1,000, more preferably 2,000, and more preferably 3,000. Preferably, 4,000 is particularly preferred.
  • the upper limit of Mw is preferably 50,000, more preferably 30,000, still more preferably 15,000, and particularly preferably 12,000. If the Mw of the base resin is less than the above lower limit, the resulting resist film may have reduced heat resistance. If the Mw of the base resin exceeds the above upper limit, the developability of the resist film may deteriorate.
  • 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 Mw and Mn of the resin herein are values measured using gel permeation chromatography (GPC) under the following conditions.
  • 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 radiation-sensitive resin composition of the present embodiment may contain, as another resin, a resin having a higher mass content of fluorine atoms than the base resin (hereinafter also referred to as "high fluorine content resin"). good.
  • high fluorine content resin a resin having a higher mass content of fluorine atoms than the base resin.
  • structural unit (V) As the high fluorine content resin, for example, it is preferable to have a structural unit represented by the following formula (5) (hereinafter also referred to as “structural unit (V)”), and if necessary, the structural unit in the base resin It may have (I) or structural unit (III).
  • R 13 is a hydrogen atom, a methyl group or a trifluoromethyl group.
  • G L is a single bond, an oxygen atom, a sulfur atom, -COO-, -SO 2 ONH-, -CONH- or -OCONH-.
  • R 14 is a monovalent fluorinated chain hydrocarbon group having 1 to 20 carbon atoms or a monovalent fluorinated alicyclic hydrocarbon group having 3 to 20 carbon atoms.
  • R 13 is preferably a hydrogen atom and a methyl group, more preferably a methyl group, from the viewpoint of copolymerizability of the monomer that provides the structural unit (V).
  • GL is preferably a single bond or -COO-, more preferably -COO-, from the viewpoint of copolymerizability of the monomer providing the structural unit (V).
  • R 14 As the monovalent fluorinated chain hydrocarbon group having 1 to 20 carbon atoms represented by R 14 , some or all of the hydrogen atoms possessed by a linear or branched alkyl group having 1 to 20 carbon atoms are fluorine Those substituted by atoms are included.
  • the monovalent fluorinated alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R 14 includes a part of the hydrogen atoms of a monocyclic or polycyclic hydrocarbon group having 3 to 20 carbon atoms, or Those completely substituted with fluorine atoms are included.
  • R 14 above is preferably a fluorinated chain hydrocarbon group, more preferably a fluorinated alkyl group, 2,2,2-trifluoroethyl group, 1,1,1,3,3,3-hexafluoropropyl and 5,5,5-trifluoro-1,1-diethylpentyl groups are more preferred.
  • the content of the structural unit (V) is preferably 30 mol% or more, preferably 40 mol%, based on the total structural units constituting the high fluorine content resin.
  • the above is more preferable, 45 mol % or more is still more preferable, and 50 mol % or more is particularly preferable.
  • it is preferably 90 mol % or less, more preferably 85 mol % or less, and even more preferably 80 mol % or less.
  • the high fluorine content resin has a fluorine atom-containing structural unit (hereinafter also referred to as structural unit (VI)) represented by the following formula (f-2) together with or in place of the structural unit (V). ). Since the high fluorine content resin has the structural unit (f-2), the solubility in an alkaline developer is improved, and the occurrence of development defects can be suppressed.
  • structural unit (VI) fluorine atom-containing structural unit represented by the following formula (f-2)
  • Structural unit (VI) has (x) an alkali-soluble group and (y) a group that dissociates under the action of an alkali to increase solubility in an alkali developing solution (hereinafter also simply referred to as an "alkali-dissociable group"). ) is roughly divided into two cases. Common to both (x) and (y), in the above formula (f-2), R 1 C is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
  • R D is a single bond, a (s+1)-valent hydrocarbon group having 1 to 20 carbon atoms, an oxygen atom, a sulfur atom, -NR dd -, a carbonyl group, -COO- or It is a structure in which -CONH- is bonded, or a structure in which some of the hydrogen atoms of this hydrocarbon group are replaced with an organic group having a heteroatom.
  • R dd is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. s is an integer from 1 to 3;
  • R F is a hydrogen atom and A 1 is an oxygen atom, —COO-* or —SO 2 O-*. * indicates the site that binds to RF .
  • W 1 is a single bond, a hydrocarbon group having 1 to 20 carbon atoms or a divalent fluorinated hydrocarbon group.
  • a 1 is an oxygen atom
  • W 1 is a fluorinated hydrocarbon group having a fluorine atom or a fluoroalkyl group at the carbon atom to which A 1 is bonded.
  • R E is a single bond or a divalent organic group having 1 to 20 carbon atoms.
  • a plurality of R E , W 1 , A 1 and R F may be the same or different.
  • the affinity for an alkaline developer can be increased and development defects can be suppressed.
  • Structural unit (VI) having an alkali-soluble group when A 1 is an oxygen atom and W 1 is a 1,1,1,3,3,3-hexafluoro-2,2-methanediyl group is particularly preferred.
  • R F is a monovalent organic group having 1 to 30 carbon atoms
  • a 1 is an oxygen atom, -NR aa -, -COO-* or —SO 2 O—*.
  • R aa is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. * indicates the site that binds to RF .
  • W 1 is a single bond or a divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms.
  • R E is a single bond or a divalent organic group having 1 to 20 carbon atoms.
  • W 1 or R F has a fluorine atom on the carbon atom bonded to A 1 or on the adjacent carbon atom.
  • a 1 is an oxygen atom
  • W 1 and R E are single bonds
  • R D is a hydrocarbon group having 1 to 20 carbon atoms and a carbonyl group is attached to the end of the R E side
  • R F is an organic group having a fluorine atom.
  • s is 2 or 3
  • a plurality of R E , W 1 , A 1 and R F may be the same or different.
  • Structural units (VI) having an alkali-dissociable group are particularly preferably those in which A 1 is —COO-* and R F or W 1 or both of them have a fluorine atom.
  • R C is preferably a hydrogen atom or a methyl group, more preferably a methyl group, from the viewpoint of copolymerizability of the monomer that gives the structural unit (VI).
  • R E is a divalent organic group
  • a group having a lactone structure is preferred, a group having a polycyclic lactone structure is more preferred, and a group having a norbornane lactone structure is more preferred.
  • the content of the structural unit (VI) is preferably 40 mol% or more, preferably 50 mol%, based on the total structural units constituting the high fluorine content resin.
  • the above is more preferable, and 60 mol % or more is even more preferable. Also, it is preferably 95 mol % or less, more preferably 90 mol % or less, and even more preferably 85 mol % or less.
  • the high fluorine content resin may contain a structural unit having an alicyclic structure represented by the following formula (6) as a structural unit other than the structural units listed above.
  • R 1 ⁇ is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
  • R 2 ⁇ is a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms.
  • the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R 2 ⁇ includes 1 of 3 to 40 carbon atoms in R 2 and R 3 of the above formula (1).
  • a group corresponding to 3 to 20 carbon atoms among alicyclic hydrocarbon groups having a valency can be preferably employed.
  • the content of the structural unit having the alicyclic structure is 10 mol% or more with respect to the total structural units constituting the high fluorine content resin. is preferred, 20 mol % or more is more preferred, and 30 mol % or more is even more preferred. Moreover, it is preferably 70 mol % or less, more preferably 60 mol % or less, and even more preferably 50 mol % or less.
  • the lower limit of Mw of the high fluorine content resin is preferably 1,000, more preferably 2,000, still more preferably 3,000, and particularly preferably 5,000.
  • the upper limit of Mw is preferably 50,000, more preferably 30,000, even more preferably 20,000, and particularly preferably 15,000.
  • the Mw/Mn of the high fluorine content resin is usually 1 or more, more preferably 1.1 or more. Moreover, it is usually 5 or less, preferably 3 or less, more preferably 2 or less, and still more preferably 1.9 or less.
  • the content of the high fluorine content resin 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 with respect to 100 parts by mass of the base resin. Part by mass or more is particularly preferred. Also, it is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 8 parts by mass or less, and particularly preferably 5 parts by mass or less.
  • the radiation-sensitive resin composition may contain one or more high fluorine content resins.
  • the high fluorine content resin can be synthesized by a method similar to the method for synthesizing the base resin described above.
  • the radiation-sensitive resin composition may contain an acid diffusion controller, if necessary.
  • the acid diffusion control agent has the effect of controlling the diffusion phenomenon in the resist film of the acid generated from the first onium salt compound and the second onium salt compound upon exposure, and suppressing unfavorable chemical reactions in the unexposed areas.
  • the storage stability of the resulting radiation-sensitive resin composition is improved.
  • the resolution of the resist pattern is further improved, and the line width change of the resist pattern due to the fluctuation of the holding time from exposure to development can be suppressed, and a radiation-sensitive resin composition excellent in process stability is obtained. be done.
  • nitrogen-containing compound (I) a compound represented by the following formula (7)
  • nitrogen-containing compounds (II) a compound having two nitrogen atoms in the same molecule
  • nitrogen-containing compounds (III) compounds having three nitrogen atoms
  • amide group-containing compounds urea compounds, nitrogen-containing heterocyclic compounds, and the like.
  • R 22 , R 23 and R 24 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or It is a substituted or unsubstituted aralkyl group.
  • nitrogen-containing compound (I) examples include monoalkylamines such as n-hexylamine; dialkylamines such as di-n-butylamine; trialkylamines such as triethylamine; and aromatic amines such as aniline. be done.
  • nitrogen-containing compound (II) examples include ethylenediamine and N,N,N',N'-tetramethylethylenediamine.
  • nitrogen-containing compound (III) examples include polyamine compounds such as polyethyleneimine and polyallylamine; polymers such as dimethylaminoethylacrylamide.
  • amide group-containing compounds include formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone and the like. be done.
  • Urea compounds include, for example, urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, and tributylthiourea.
  • nitrogen-containing heterocyclic compounds examples include pyridines such as pyridine and 2-methylpyridine; morpholines such as N-propylmorpholine and N-(undecylcarbonyloxyethyl)morpholine; pyrazine and pyrazole.
  • a compound having an acid dissociable group can also be used as the nitrogen-containing organic compound.
  • Nitrogen-containing organic compounds having such an acid-labile group include, for example, Nt-butoxycarbonylpiperidine, Nt-butoxycarbonylimidazole, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2 -Phenylbenzimidazole, N-(t-butoxycarbonyl)di-n-octylamine, N-(t-butoxycarbonyl)diethanolamine, N-(t-butoxycarbonyl)dicyclohexylamine, N-(t-butoxycarbonyl)diphenylamine , Nt-butoxycarbonyl-4-hydroxypiperidine, Nt-butoxycarbonyl-4-acetoxypiperidine, Nt-amyloxycarbonyl-4-hydroxypiperidine and the like.
  • a radiation-sensitive weak acid generator that generates a weak acid upon exposure
  • the acid generated from the radiation-sensitive acid generator is a weak acid that does not induce the dissociation of the acid-dissociable groups in the resin under the conditions for dissociating the acid-dissociable groups.
  • "dissociation" of an acid-dissociable group means dissociation upon post-exposure baking at 110°C for 60 seconds.
  • Examples of radiation-sensitive weak acid generators include onium salt compounds that are decomposed by exposure to lose acid diffusion controllability.
  • onium salt compounds include sulfonium salt compounds represented by the following formula (8-1) and iodonium salt compounds represented by the following formula (8-2).
  • J + is a sulfonium cation and U + is an iodonium cation.
  • Sulfonium cations represented by J + include sulfonium cations represented by the above formulas (X-1) to (X-3), and examples of iodonium cations represented by U + include the above formulas (X- 4) to (X-5) include iodonium cations.
  • E - and Q - are each independently anions represented by OH - , R ⁇ -COO - and R ⁇ -SO 3 - .
  • R ⁇ is a monovalent chain organic group having 1 to 40 carbon atoms or a monovalent organic group having 3 to 40 carbon atoms containing a cyclic structure.
  • a monovalent chain organic group having 1 to 40 carbon atoms for R ⁇ a monovalent chain organic group having 1 to 40 carbon atoms represented by R 1 in the above formula (1) can be preferably used.
  • R B a monovalent organic group having 3 to 40 carbon atoms and containing a cyclic structure represented by R B in the above formula (2) can be preferably used.
  • R B a monovalent organic structure represented by R B in the above formula (2)
  • Examples of the radiation-sensitive weak acid generator include compounds represented by the following formula.
  • the radiation-sensitive weak acid generator is preferably a sulfonium salt, more preferably a triarylsulfonium salt, and more preferably triphenylsulfonium salicylate and triphenylsulfonium 10-camphorsulfonate.
  • the lower limit of the content of the acid diffusion control agent is preferably 0.1 parts by mass, more preferably 0.5 parts by mass, still more preferably 1 part by mass, and particularly preferably 2 parts by mass with respect to 100 parts by mass of the resin. .
  • the upper limit of the content is preferably 20 parts by mass, more preferably 15 parts by mass, and even more preferably 10 parts by mass.
  • the radiation-sensitive resin composition may contain one or more acid diffusion control agents.
  • the radiation-sensitive resin composition according to this embodiment contains a solvent.
  • the solvent is not particularly limited as long as it can dissolve or disperse at least the compound (1), the resin, and optionally the radiation-sensitive acid generator and the like.
  • solvents examples include alcohol-based solvents, ether-based solvents, ketone-based solvents, amide-based solvents, ester-based solvents, and hydrocarbon-based solvents.
  • 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; C2-C18 poly(ethylene glycol) 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.
  • ether solvents examples include Dialkyl ether solvents such as diethyl ether, dipropyl ether, dibutyl ether; Cyclic ether solvents such as tetrahydrofuran and tetrahydropyran; Aromatic ring-containing ether solvents such as diphenyl ether and anisole (methylphenyl ether); Examples thereof include polyhydric alcohol ether solvents obtained by etherifying the hydroxy groups of the above polyhydric alcohol solvents.
  • ketone solvents include linear 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.
  • amide solvents include cyclic amide solvents such as N,N'-dimethylimidazolidinone and N-methylpyrrolidone; Chain amide solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and the like.
  • ester solvents include monocarboxylic acid ester solvents such as n-butyl acetate and ethyl lactate; Polyhydric alcohol partial ether acetate solvents such as diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate; Lactone solvents such as ⁇ -butyrolactone and valerolactone; Carbonate solvents such as diethyl carbonate, ethylene carbonate, propylene carbonate; Polyvalent carboxylic acid diester solvents such as propylene glycol diacetate, methoxytriglycol acetate, diethyl oxalate, ethyl acetoacetate, ethyl lactate and diethyl phthalate can be used.
  • monocarboxylic acid ester solvents such as n-butyl acetate and ethyl lactate
  • hydrocarbon solvents examples include aliphatic hydrocarbon solvents such as n-hexane, cyclohexane, and methylcyclohexane; Aromatic hydrocarbon solvents such as benzene, toluene, di-iso-propylbenzene, n-amylnaphthalene and the like are included.
  • ester-based solvents and ketone-based solvents are preferred, polyhydric alcohol partial ether acetate-based solvents, cyclic ketone-based solvents, and lactone-based solvents are more preferred, and propylene glycol monomethyl ether acetate, cyclohexanone, and ⁇ -butyrolactone are even more preferred.
  • the radiation-sensitive resin composition may contain one or more solvents.
  • 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 radiation-sensitive resin composition can be prepared, for example, by mixing a first onium salt compound, a second onium salt compound, a resin, and, if necessary, a high fluorine content resin, etc., and a solvent in a predetermined ratio. . After mixing, the radiation-sensitive resin composition is preferably filtered through a filter having a pore size of about 0.05 ⁇ m to 0.40 ⁇ m.
  • the solid content concentration of the radiation-sensitive resin composition is usually 0.1% by mass to 50% by mass, preferably 0.5% by mass to 30% by mass, more preferably 1% by mass to 20% by mass.
  • the lower limit of the viscosity of the radiation-sensitive resin composition is preferably 1.0 mPa ⁇ s, more preferably 1.2 mPa ⁇ s, and even more preferably 1.4 mPa ⁇ s.
  • the upper limit of the viscosity is preferably 15 mPa ⁇ s, more preferably 10 mPa ⁇ s, and even more preferably 5 mPa ⁇ s.
  • a pattern forming method comprises: A 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 a “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 “development step”).
  • the radiation-sensitive resin composition capable of forming a resist film having excellent sensitivity, LWR performance, CDU performance, pattern rectangularity, and etching resistance in the exposure process is used, a high quality resist pattern is obtained. can form a resist pattern.
  • a high quality resist pattern is obtained. can form a resist pattern.
  • 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.
  • the coating method for forming the resist film 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 140°C, preferably 80°C to 120°C.
  • the PB time is usually 5 to 600 seconds, preferably 10 to 300 seconds.
  • the lower limit of the thickness of the resist film to be formed is preferably 10 nm, more preferably 15 nm, and even more preferably 20 nm.
  • the upper limit of the film thickness is preferably 500 nm, more preferably 400 nm, and even more preferably 300 nm.
  • the lower limit of the film thickness may be 100 nm, 150 nm, or 200 nm. good.
  • the immersion liquid and the resist film are placed on the formed resist film.
  • an immersion protective film that is insoluble in the immersion liquid may be provided.
  • a solvent peelable protective film that is peeled off with a solvent before the development process see, for example, JP-A-2006-227632
  • a developer peelable protective film that is peeled off at the same time as development in the development process For example, see WO2005-069076 and WO2006-035790
  • the exposure step which is the next step, is performed with radiation having a wavelength of 50 nm or less
  • 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.
  • the immersion liquid used When exposure is performed by immersion exposure, examples of the immersion liquid used include water and fluorine-based inert liquids.
  • the immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has a temperature coefficient of refractive index as small as possible so as to minimize distortion of the optical image projected onto the film.
  • excimer laser light wavelength: 193 nm
  • water it is preferable to use water from the viewpoints of availability and ease of handling in addition to the above viewpoints.
  • an additive that reduces the surface tension of water and increases surface activity may be added in a small proportion. This additive preferably does not dissolve the resist film on the wafer and has negligible effect on the optical coating on the bottom surface of the lens. Distilled water is preferred as the water used.
  • 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
  • TMAH tetramethylammonium hydroxide
  • a TMAH aqueous solution is preferable, and a 2.38% by mass TMAH aqueous solution is more preferable.
  • organic solvents such as hydrocarbon solvents, ether solvents, ester solvents, ketone solvents, alcohol solvents, or solvents containing organic solvents can be used.
  • the organic solvent include one or more of the solvents listed above as the solvent for the radiation-sensitive resin composition.
  • ether-based solvents, ester-based solvents, and ketone-based solvents are preferred.
  • the ether solvent a glycol ether solvent is preferable, and ethylene glycol monomethyl ether and propylene glycol monomethyl ether are more preferable.
  • ester solvent an acetate solvent is preferable, and n-butyl acetate and amyl acetate are more preferable.
  • ketone solvent a chain ketone is preferred, and 2-heptanone is more preferred.
  • 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, for example, water and silicon oil.
  • the developer may be either an alkaline developer or an organic solvent developer. It can be appropriately selected depending on whether the desired positive pattern or negative pattern is desired.
  • 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
  • spray method a method in which the developer is sprayed onto the surface of the substrate
  • dynamic dispensing method a method in which the developer is continuously applied while scanning the developer dispensing nozzle at a constant speed on the substrate rotating at a constant speed
  • Mw and Mn of the polymer were measured under the conditions described above. Further, the degree of dispersion (Mw/Mn) was calculated from the measurement results of Mw and Mn.
  • 13 C-NMR analysis 13 C-NMR analysis of the polymer was performed using a nuclear magnetic resonance apparatus (“JNM-Delta400” manufactured by JEOL Ltd.).
  • the polymerization solution was cooled with water to 30° C. or lower.
  • the cooled polymerization solution was poured into methanol (2,000 parts by mass), and the precipitated white powder was separated by filtration.
  • the filtered white powder was washed twice with methanol, filtered, and dried at 50° C. for 24 hours to obtain a white powdery resin (A-1) (yield: 83%).
  • Resin (A-1) had Mw of 8,800 and Mw/Mn of 1.50.
  • the content ratio of each structural unit derived from (M-1), (M-2) and (M-13) is 41.3 mol% and 13.8 mol%, respectively. and 44.9 mol%.
  • the polymerization solution was cooled with water to 30° C. or lower.
  • the cooled polymerization solution was poured into hexane (2,000 parts by mass), and the precipitated white powder was separated by filtration.
  • the filtered white powder was washed twice with hexane, filtered, and dissolved in 1-methoxy-2-propanol (300 parts by mass).
  • methanol 500 parts by mass
  • triethylamine 50 parts by mass
  • ultrapure water 10 parts by mass
  • Resin (A-12) had an Mw of 5,200 and an Mw/Mn of 1.60.
  • the contents of the structural units derived from (M-1) and (M-18) were 51.3 mol % and 48.7 mol %, respectively.
  • the polymerization solution was cooled with water to 30° C. or lower.
  • the operation of adding hexane (100 parts by mass) and stirring to recover the acetonitrile layer was repeated three times.
  • the high fluorine content resin (F-1) had Mw of 6,000 and Mw/Mn of 1.62.
  • the contents of the structural units derived from (M-1) and (M-20) were 19.9 mol % and 80.1 mol %, respectively.
  • the sodium sulfonate compound was obtained by extracting with acetonitrile and distilling off the solvent. 20.0 mmol of the salt represented by the above formula (B-1-a) was added to the above sulfonic acid sodium salt compound, and a mixture of water:dichloromethane (1:3 (mass ratio)) was added to obtain a 0.5 M solution. and After vigorously stirring at room temperature for 3 hours, dichloromethane was added for extraction, and the organic layer was separated. After drying the resulting organic layer with sodium sulfate, the solvent was distilled off and the residue was purified by column chromatography to obtain an onium salt in good yield.
  • D-1 to D-10 compounds represented by the following formulas (D-1) to (D-10) and d-1 to d-9: the following formulas (d-1) to (d-9)
  • D-1 to D-10 compounds represented by the following formulas (D-1) to (D-10) and d-1 to d-9: the following formulas (d-1) to (d-9)
  • D-1 to D-10 compounds represented by the following formulas (D-1) to (D-10) and d-1 to d-9: the following formulas (d-1) to (d-9)
  • E-1 Propylene glycol monomethyl ether acetate
  • E-2 Propylene glycol monomethyl ether
  • E-3 ⁇ -butyrolactone
  • E-4 Ethyl lactate
  • Example 1 [A] 100 parts by mass of (A-1) as a resin, [B] 6.0 parts by mass of (B-1) as a first onium salt compound, [C] (C-1 as a second onium salt compound ) 6.0 parts by mass, [D] 6.0 parts by mass of (D-1) as an acid diffusion control agent, [F] 3.0 parts by mass of (F-1) as a high fluorine content resin (solid content ), and [E] 3,230 parts by mass of a mixed solvent of (E-1) / (E-2) / (E-3) as a solvent are mixed and filtered through a membrane filter with a pore size of 0.2 ⁇ m. , to prepare a radiation-sensitive resin composition (J-1).
  • Viscosity measurement The viscosity (mPa ⁇ s) of the radiation-sensitive resin composition was measured at 25° C. using a Canon Fenske viscometer.
  • a spin coater (“CLEAN TRACK ACT12" available from Tokyo Electron Co., Ltd.) was used to apply a composition for forming a lower antireflection film ("ARC66" available from Bulwer Science).
  • a lower antireflection film having an average thickness of 100 nm was formed by heating at 205° C. for 60 seconds.
  • the positive radiation-sensitive resin composition for ArF exposure prepared above was applied onto the lower antireflection film using the spin coater, and PB (pre-baking) was performed at 100° C. for 60 seconds. Then, by cooling at 23° C. for 30 seconds, a resist film with an average thickness of 160 nm was formed.
  • PEB post-exposure bake
  • the exposure dose for forming 80 nm holes and contact holes with a pitch of 150 nm is the optimum exposure dose, and the optimum exposure dose is the sensitivity (mJ/cm 2 ).
  • the sensitivity was evaluated as "good” when it was 30 mJ/cm 2 or less, and as “bad” when it exceeded 30 mJ/cm 2 .
  • CDU performance An 80 nm hole and a contact hole with a pitch of 150 nm were formed by irradiating with the optimum exposure amount determined by the evaluation of the sensitivity. The formed resist pattern was observed from above the pattern using the scanning electron microscope. A total of 500 contact hole variations were measured, a 3 sigma value was obtained from the distribution of the measured values, and this 3 sigma value was defined as CDU (nm). CDU indicates that the smaller the value, the smaller the roughness of the hole and the better. CDU performance was evaluated as "good” when less than 5.0 nm and "bad” when greater than or equal to 5.0 nm.
  • the radiation-sensitive resin compositions of Examples had good sensitivity, CDU performance, and pattern circularity when used for ArF exposure.
  • the comparative examples were inferior to the examples in each characteristic. Therefore, when the radiation-sensitive resin composition of the example is used for ArF exposure, a resist pattern having high CDU performance and good pattern circularity can be formed.
  • Example 66 [A] 100 parts by mass of (A-12) as a resin, [B] 9.0 parts by mass of (B-1) as a first onium salt compound, [C] (C-1 as a second onium salt compound ) 9.0 parts by mass, [D] 3.0 parts by mass of (D-5) as an acid diffusion control agent, [F] 3.0 parts by mass of (F-5) as a high fluorine content resin (solid content ) and [E] 6,110 parts by mass of a mixed solvent of (E-1)/(E-4) as a solvent are mixed and filtered through a membrane filter having a pore size of 0.2 ⁇ m to obtain a radiation-sensitive resin composition. (J-66) was prepared.
  • Viscosity measurement The viscosity (mPa ⁇ s) of the radiation-sensitive resin composition was measured at 25° C. using a Canon Fenske viscometer.
  • a spin coater (“CLEAN TRACK ACT12" available from Tokyo Electron Co., Ltd.) was used to apply a composition for forming a lower antireflection film ("ARC66" available from Bulwer Science).
  • a lower antireflection film having an average thickness of 105 nm was formed by heating at 205° C. for 60 seconds.
  • the above-prepared radiation-sensitive resin composition for EUV exposure was applied onto this lower anti-reflection film using the spin coater, followed by PB at 130° C. for 60 seconds. Then, by cooling at 23° C. for 30 seconds, a resist film with an average thickness of 55 nm was formed.
  • the exposure dose for forming a 32 nm line-and-space pattern is defined as the optimum exposure dose, and this optimum exposure dose is defined as sensitivity (mJ/cm 2 ). bottom.
  • the sensitivity was evaluated as "good” when it was 30 mJ/cm 2 or less, and as “bad” when it exceeded 30 mJ/cm 2 .
  • LWR performance A resist pattern was formed by adjusting the mask size so as to form a 32 nm line-and-space pattern by irradiating with the optimum exposure amount determined by the evaluation of sensitivity. The formed resist pattern was observed from above the pattern using the scanning electron microscope. Line width variation was measured at a total of 500 points, a 3 sigma value was obtained from the distribution of the measured values, and this 3 sigma value was defined as LWR (nm). LWR indicates that the smaller the value, the smaller the jolting of the line and the better. The LWR performance was evaluated as "good” when less than or equal to 3.0 nm, and as “poor” when greater than 3.0 nm.
  • a 32 nm line-and-space resist pattern formed by irradiating the optimum exposure dose determined in the evaluation of sensitivity was observed using the scanning electron microscope, and the cross-sectional shape of the line-and-space pattern was evaluated.
  • the rectangularity of the resist pattern is "A" (very good) if the ratio of the length of the lower side to the length of the upper side in the cross-sectional shape is 1 or more and 1.05 or less, and if it is more than 1.05 and 1.10 or less. If it is more than 1.10, it is evaluated as "B" (good), and if it exceeds 1.10, it is evaluated as "C" (bad).
  • a spin coater (“CLEAN TRACK ACT 12" from Tokyo Electron Co., Ltd.) was used to apply a composition for forming a lower anti-reflection film ("ARC66" from Bulwer Science).
  • a lower antireflection film having an average thickness of 100 nm was formed by heating at 205° C. for 60 seconds.
  • the negative type radiation-sensitive resin composition for ArF exposure (J-83) prepared above was applied onto this lower antireflection film using the above spin coater, and PB (pre-baking) was performed at 100° C. for 60 seconds. Then, by cooling at 23° C. for 30 seconds, a resist film with an average thickness of 90 nm was formed.
  • PEB post-exposure bake
  • the resist pattern using the negative radiation-sensitive resin composition for ArF exposure was evaluated in the same manner as the resist pattern using the positive radiation-sensitive resin composition for ArF exposure.
  • the radiation-sensitive resin composition of Example 83 was excellent in sensitivity, CDU performance and pattern circularity even when a negative resist pattern was formed by ArF exposure.
  • Example 84 [A] 100 parts by mass of (A-15) as a resin, [B] 9.0 parts by mass of (B-1) as a first onium salt compound, [C] (C-11 as a second onium salt compound ) 9.0 parts by mass, [D] 3.0 parts by mass of (D-5) as an acid diffusion control agent, [F] 3.0 parts by mass of (F-5) as a high fluorine content resin (solid content ) and [E] 6,110 parts by mass of a mixed solvent of (E-1)/(E-4) as a solvent are mixed and filtered through a membrane filter having a pore size of 0.2 ⁇ m to obtain a radiation-sensitive resin composition. (J-84) was prepared.
  • a spin coater (“CLEAN TRACK ACT 12" from Tokyo Electron Co., Ltd.) was used to apply a composition for forming a lower anti-reflection film ("ARC66" from Bulwer Science).
  • a lower antireflection film having an average thickness of 105 nm was formed by heating at 205° C. for 60 seconds.
  • the negative type radiation-sensitive resin composition for EUV exposure (J-84) prepared above was applied onto this lower antireflection film using the above spin coater, and PB was performed at 130° C. for 60 seconds. Then, by cooling at 23° C. for 30 seconds, a resist film with an average thickness of 55 nm was formed.
  • the resist pattern using the negative radiation-sensitive resin composition for EUV exposure was evaluated in the same manner as the resist pattern using the positive radiation-sensitive resin composition for EUV exposure.
  • the radiation-sensitive resin composition of Example 84 was excellent in sensitivity, LWR performance, and pattern rectangularity even when a negative resist pattern was formed by EUV exposure.
  • the radiation-sensitive resin composition and resist pattern forming method described above it is possible to form a resist pattern that has good sensitivity to exposure light and excellent CDU performance, pattern circularity, LWR performance, and pattern rectangularity. can. Therefore, these materials can be suitably used in the processing of semiconductor devices, which are expected to further miniaturize in the future.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Materials For Photolithography (AREA)

Abstract

La présente invention concerne : une composition de résine sensible au rayonnement qui peut former un film de résine photosensible qui présente des niveaux satisfaisants de sensibilité, de performance de CDU, de circularité de structure, de performance de LWR et de rectangularité de structure même lors de la formation d'un motif de résine photosensible à haut rapport d'aspect ; et un procédé de formation de structure. La composition de résine sensible au rayonnement selon l'invention comprend : un premier composé du type sel d'onium représenté par la formule (1) ; un second composé du type sel d'onium représenté par la formule (2) ; une résine contenant un motif structural contenant un groupe pouvant être dissocié par un acide ; et un solvant.　(Dans la formule (1), R1 représente un groupe organique monovalent en forme de chaîne en C1-40. R2 et R3 représentent chacun un atome d'hydrogène, un atome de fluor, un groupe hydrocarboné monovalent ou un groupe hydrocarboné fluoré monovalent. Rf11 et Rf12 représentent chacun un atome de fluor ou un groupe hydrocarboné fluoré monovalent. R4, R5, R6, R7 et R8 représentent chacun un atome d'hydrogène, un groupe hydroxyle, un atome d'halogène ou un groupe organique monovalent en C1-20. En variante, si une pluralité de R8 est présente, deux éléments parmi la pluralité de R8 s'associent mutuellement pour former une structure cyclique contenant de 5 à 20 chaînons et conçue également par deux atomes de carbone du cycle benzénique de la formule (1) auxquels ces fractions sont liées.)　(Dans la formule (2), RB représente un groupe organique monovalent en C3-40 comprenant une structure cyclique. Rf21 et Rf22 représentent chacun un atome de fluor ou un groupe hydrocarboné fluoré monovalent. Z+ représente un cation d'onium monovalent sensible au rayonnement.)
PCT/JP2022/040625 2021-11-25 2022-10-31 Composition de résine sensible au rayonnement et procédé de formation de structure WO2023095561A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013116885A (ja) * 2011-10-31 2013-06-13 Sumitomo Chemical Co Ltd 塩、レジスト組成物及びレジストパターンの製造方法
JP2020149048A (ja) * 2019-03-06 2020-09-17 信越化学工業株式会社 ポジ型レジスト組成物及びパターン形成方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013116885A (ja) * 2011-10-31 2013-06-13 Sumitomo Chemical Co Ltd 塩、レジスト組成物及びレジストパターンの製造方法
JP2020149048A (ja) * 2019-03-06 2020-09-17 信越化学工業株式会社 ポジ型レジスト組成物及びパターン形成方法

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