Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
  • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
  • C09D125/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
  • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
  • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
  • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/40—Treatment after imagewise removal, e.g. baking
• • 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
  • G03F7/70—Microphotolithographic exposure; Apparatus therefor
  • G03F7/70008—Production of exposure light, i.e. light sources
  • G03F7/70033—Production of exposure light, i.e. light sources by plasma extreme ultraviolet [EUV] sources

Definitions

• the present invention relates to a resist composition and a method of forming a resist pattern.
• Resist materials are required to have lithographic properties such as sensitivity to these exposure light sources and resolution capable of reproducing patterns with fine dimensions.
• a resist material that satisfies such requirements conventionally, a resist composition containing a base component whose solubility in a developing solution is changed by the action of acid and an acid generator component that generates acid upon exposure has been used. ing.
• a resist pattern is formed by forming a thick resist film having a thickness of 1 ⁇ m or more, for example, on the surface of the workpiece. and a step of performing etching or the like.
• Patent Document 1 discloses a resist composition that generates an acid upon exposure and whose solubility in a developer changes due to the action of the acid. It contains component (A) and a polyether compound having a weight average molecular weight of 400 or more, and the content of the polyether compound is 0.8 to 0.8 parts per 100 parts by mass of the base component (A).
• a resist composition is disclosed which is 32 parts by weight and has a solid content concentration of 25% by weight or more. According to this resist composition, a thick resist film can be formed, cracks are less likely to occur, and the resolution is excellent, and a resist pattern forming method using the resist composition. It is disclosed that
• the thicker the resist film the more difficult it is to maintain the sensitivity during exposure, and the lower the resolution for development, the more difficult it is to obtain the desired resist pattern shape.
• the transmittance of the irradiated light decreases, so that the interface portion of the substrate cannot be fully rendered insoluble, and shape deterioration (undercut shape) may occur.
• DOF depth of focus
• the present invention has been made in view of the above circumstances, and uses a resist composition capable of forming a resist pattern having good resolution, DOF, and pattern shape, and the resist composition.
• An object of the present invention is to provide a method for forming a resist pattern.
• the present invention employs the following configurations. That is, the first aspect of the present invention contains a resin (A), an acid generator (B), and a cross-linking agent (C), and the resin (A) has a LogP of 2.8 or less. It is an alkali-soluble resin, and the alkali-soluble resin comprises a structural unit (a10) represented by the following general formula (a10-1) and a structural unit (a20) represented by the following general formula (a20-1).
• the acid generator (B) contains a compound (B0) having a molar extinction coefficient of 10000 mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 or less at a wavelength of 248 nm, and the cross-linking agent (C) is a melamine-based cross-linking agent , a urea-based cross-linking agent, an alkylene urea-based cross-linking agent, a glycoluril-based cross-linking agent, and at least one cross-linking agent selected from the group consisting of an epoxy-based cross-linking agent, and having a solid content concentration of 15% by mass or more. composition.
• the cross-linking agent (C) is a melamine-based cross-linking agent , a urea-based cross-linking agent, an alkylene urea-based cross-linking agent, a glycoluril-based cross-linking agent, and at least one cross-linking agent selected from the group consisting of an epoxy-based cross-linking
• R x1 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
• Ya x1 is a single bond or a divalent linking group.
• Wa x1 is an aromatic hydrocarbon group which may have a substituent.
• n ax1 is an integer of 1 or more.
• R x2 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms.
• Ya x2 is a single bond or a divalent linking group.
• Ra x2 is a hydrocarbon group.
• a second aspect of the present invention comprises the steps of forming a resist film on a support using the resist composition according to the first aspect, exposing the resist film, and exposing the resist film after the exposure. It is a resist pattern forming method including a step of developing to form a resist pattern.
• a resist composition capable of forming a resist pattern with good resolution, DOF and pattern shape, and a method of forming a resist pattern using the resist composition.
• alkyl group includes linear, branched and cyclic monovalent saturated hydrocarbon groups unless otherwise specified. The same applies to the alkyl group in the alkoxy group. Unless otherwise specified, the "alkylene group” includes straight-chain, branched-chain and cyclic divalent saturated hydrocarbon groups.
• halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• a "structural unit” means a monomer unit (monomeric unit) that constitutes a polymer compound (resin, polymer, copolymer).
• polymer compound refers to a polymer having a molecular weight of 1000 or more.
• molecular weight of the polymer a polystyrene-equivalent weight-average molecular weight obtained by GPC (gel permeation chromatography) is used.
• non-polymer one having a molecular weight of 500 or more and less than 4000 is usually used.
• low-molecular-weight compound refers to a non-polymer having a molecular weight of 500 or more and less than 4,000.
• polymer those having a molecular weight of 1000 or more are usually used.
• a "derived structural unit” means a structural unit formed by cleaving a multiple bond between carbon atoms, such as an ethylenic double bond.
• Derivative is a concept that includes those in which the ⁇ -position hydrogen atom of the target compound is substituted with other substituents such as alkyl groups and halogenated alkyl groups, as well as derivatives thereof. Derivatives thereof include those obtained by substituting the hydrogen atom of the hydroxyl group of the target compound, in which the hydrogen atom at the ⁇ -position may be substituted with a substituent, with an organic group; Examples of good target compounds include those to which substituents other than hydroxyl groups are bonded.
• the ⁇ -position refers to the first carbon atom adjacent to the functional group unless otherwise specified.
• the resist composition of this embodiment generates acid upon exposure, and the action of the acid changes the solubility in a developer.
• a resist composition comprises a resin (A) (hereinafter also referred to as “(A) component”), an acid generator (B) (hereinafter also referred to as “(B) component”), and a cross-linking agent (C) (hereinafter referred to as “ (C) Also referred to as “component”).
• the component (A) in the resist composition of this embodiment is an alkali-soluble resin having a LogP value of 2.8 or less.
• the resin (A) is an alkali-soluble resin having a LogP value of 2.8 or less” means that the LogP value is calculated collectively for all the alkali-soluble resins contained in the resist composition of the present embodiment.
• the LogP value should be 2.8 or less when Among them, when the LogP value is calculated collectively for all the resins contained in the resist composition of the present embodiment, the LogP value is preferably 2.8 or less, and the resist composition of the present embodiment contains More preferably, all resins are alkali-soluble resins with a LogP value of 2.8 or less.
• the alkali-soluble resin in the resist composition of the present embodiment has a LogP value of 2.8 or less, preferably 2.0 or more and 2.8 or less, more preferably 2.2 or more and 2.8 or less. It is preferably 2.5 or more and 2.8 or less.
• the LogP value of the alkali-soluble resin in the resist composition of the present embodiment is 2.8 or less, the hydrophilicity of the alkali-soluble resin is moderate, and the removability of the unexposed portion of the resist film with an alkaline developer is improved. By doing so, the DOF is improved while maintaining a good pattern shape.
• the LogP value of the alkali-soluble resin in the resist composition of the present embodiment is at least the above preferable value, the hydrophobicity of the alkali-soluble resin becomes moderate, and the swelling of the alkali-soluble resin by the developer is further suppressed. can do.
• LogP value refers to the logarithmic value of the octanol/water partition coefficient ( Pow ).
• a “LogP value” is a valid parameter that can characterize the hydrophilicity/hydrophobicity of a wide range of compounds. In general, partition coefficients are obtained by calculation rather than experiments.
• LogP value means a value calculated by Software V11.02 manufactured by Calculated using Advanced Chemistry Development (ACD/Labs). As the LogP value increases on the plus side of 0, the hydrophobicity increases, and when the absolute value increases on the minus side, the water solubility increases (high polarity). The LogP value has a negative correlation with the water solubility of organic compounds, and is widely used as a parameter for estimating the hydrophilicity/hydrophobicity of organic compounds.
• the LogP value of the alkali-soluble resin is the LogP value of a plurality of monomers constituting the alkali-soluble resin. can be calculated by the software mentioned above, and these values are multiplied by the ratio of the constituent units derived from each monomer in the alkali-soluble resin and added together.
• the alkali-soluble resin in the resist composition of the present embodiment is a copolymer of hydroxystyrene and styrene
• the LogP value of the alkali-soluble resin (copolymer of hydroxystyrene and styrene) is 2.62 ⁇ 0 .95 + 2.82 x 0.05 gives 2.63.
• the alkali-soluble resin is a blend polymer of homopolymers
• the LogP value of the alkali-soluble resin constitutes each homopolymer. It can be obtained by calculating the LogP value of each monomer using the above-mentioned software, multiplying these values by the ratio of each homopolymer in the blend polymer, and adding them together.
• the alkali-soluble resin in the resist composition of the present embodiment is a blend polymer of a hydroxystyrene homopolymer and a styrene homopolymer, and the mixing ratio (mass ratio) of the blend polymer is the hydroxystyrene homopolymer:
• the homopolymer of styrene is 95:5
• the LogP value of hydroxystyrene calculated by the software described above is 2.62
• the LogP value of styrene is 2.82.
• the LogP value of the blend polymer of homopolymer and homopolymer of styrene is 2.62 ⁇ 0.95+2.82 ⁇ 0.05, which is 2.63.
• each copolymer is first treated in the same manner as in (i) above. LogP values are calculated respectively. Then, in the same manner as in (ii), the LogP value of each copolymer is multiplied by the ratio of each copolymer and summed. Thereby, the LogP value of the alkali-soluble resin (copolymer blend polymer) can be calculated.
• copolymer A a copolymer composition ratio (molar ratio) of hydroxystyrene
• the LogP value is 2.62*0.95+2.82*0.05, which is 2.63.
• the LogP value of Copolymer B is 2.62 ⁇ 0.9+2.82 ⁇ 0.1, which is 2.64. Therefore, the LogP value of the alkali-soluble resin (blend polymer of copolymer A and copolymer B) is 2.63 ⁇ 0.9+2.64 ⁇ 0.1, which is 2.63.
• the alkali-soluble resin in the resist composition of the present embodiment includes a structural unit (a10) represented by the following general formula (a10-1) and a structural unit (a20) represented by the following general formula (a20-1). have
• the structural unit (a10) is a structural unit represented by general formula (a10-1) below.
• R x1 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
• Ya x1 is a single bond or a divalent linking group.
• Wa x1 is an aromatic hydrocarbon group which may have a substituent.
• n ax1 is an integer of 1 or more.
• R x1 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 x1 is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms.
• a group is more preferred, a hydrogen atom or a methyl group is more preferred, and a hydrogen atom is particularly preferred.
• Ya x1 is a single bond or a divalent linking group.
• the divalent linking group for Ya x1 is not particularly limited, but is preferably a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a hetero atom, or the like. It is mentioned as.
• a divalent hydrocarbon group which may have a substituent When Ya x1 is a divalent hydrocarbon group which may have a substituent, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
• the aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity.
• the aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
• Examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, and aliphatic hydrocarbon groups containing rings in their structures.
• linear or branched aliphatic hydrocarbon group The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and Numbers 1 to 4 are more preferred, and carbon numbers 1 to 3 are most preferred.
• a straight-chain alkylene group is preferable, and specifically, a methylene group [ --CH.sub.2-- ], an ethylene group [--( CH.sub.2 ) .sub.2-- ], a trimethylene group [ -(CH 2 ) 3 -], tetramethylene group [-(CH 2 ) 4 -], pentamethylene group [-(CH 2 ) 5 -] and the like.
• the branched chain aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, still more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms.
• the branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specifically, -CH(CH 3 )-, -CH(CH 2 CH 3 )-, -C(CH 3 ) 2- , -C(CH 3 )(CH 2 CH 3 )-, -C(CH 3 )(CH 2 CH 2 CH 3 )-, -C(CH 2 CH 3 ) 2 - and other alkylmethylene groups;- CH(CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 )-, -C(CH 3 ) 2 CH 2 -, -CH(CH 2 CH 3 )CH 2 -, -C(CH 2 Alkylethylene groups such as CH 3 ) 2 -CH
• the linear or branched aliphatic hydrocarbon group may or may not have a substituent.
• substituents include a fluorine atom, a fluorine-substituted fluorinated alkyl group having 1 to 5 carbon atoms, and a carbonyl group.
• Aliphatic hydrocarbon group containing a ring in its structure is a cyclic aliphatic hydrocarbon group which may contain a substituent containing a hetero atom in the ring structure. (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), a group in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, the cyclic aliphatic groups in which a group hydrocarbon group intervenes in the middle of a linear or branched aliphatic hydrocarbon group.
• Examples of the straight-chain or branched-chain aliphatic hydrocarbon group include those mentioned above.
• the cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms.
• a cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group.
• the monocyclic alicyclic hydrocarbon group a group obtained by removing two hydrogen atoms from a monocycloalkane is preferable.
• the monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane.
• the polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms. adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.
• a cyclic aliphatic hydrocarbon group may or may not have a substituent.
• substituents include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group and the like.
• the alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group.
• the alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group and a tert-butoxy group.
• a methoxy group and an ethoxy group are more preferable.
• a fluorine atom is preferable as the halogen atom as the substituent.
• Examples of the halogenated alkyl group as the substituent include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with the halogen atoms.
• a part of the carbon atoms constituting the ring structure of the cyclic aliphatic hydrocarbon group may be substituted with a heteroatom-containing substituent.
• the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
• This aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 ⁇ electrons, and may be monocyclic or polycyclic.
• the aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, still more preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. However, the number of carbon atoms does not include the number of carbon atoms in the substituent.
• Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; mentioned.
• the heteroatom in the aromatic heterocycle includes oxygen atom, sulfur atom, nitrogen atom and the like.
• aromatic heterocycles include pyridine rings and thiophene rings.
• aromatic hydrocarbon groups include groups obtained by removing two hydrogen atoms from the above aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); aromatic compounds containing two or more aromatic rings A group obtained by removing two hydrogen atoms from (e.g., biphenyl, fluorene, etc.); One of the hydrogen atoms of the group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocyclic ring (aryl group or heteroaryl group) A group in which one is substituted with an alkylene group (for example, a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a hydrogen from an arylalkyl group
• a hydrogen atom of the aromatic hydrocarbon group may be substituted with a substituent.
• a hydrogen atom bonded to an aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent.
• the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, and a hydroxyl group.
• the alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group.
• the alkoxy group, halogen atom and halogenated alkyl group as the substituent include those exemplified as the substituent for substituting the hydrogen atom of the cyclic aliphatic hydrocarbon group.
• the H may be substituted with a substituent such as an alkyl group or an acyl group.
• the substituent alkyl group, acyl group, etc. preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 5 carbon atoms.
• Y 21 and Y 22 are each independently a divalent hydrocarbon group which may have a substituent, and the divalent hydrocarbon group includes the divalent linking group for Ya x1 (Divalent hydrocarbon group optionally having substituent(s)) exemplified above.
• Y 21 is preferably a straight-chain aliphatic hydrocarbon group, more preferably a straight-chain alkylene group, more preferably a straight-chain alkylene group having 1 to 5 carbon atoms, particularly a methylene group or an ethylene group.
• Y 22 is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group or an alkylmethylene group.
• the alkyl group in the alkylmethylene group is preferably a straight-chain alkyl group having 1 to 5 carbon atoms, more preferably a straight-chain alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.
• m′′ is an integer of 0 to 3, preferably an integer of 0 to 2, and 0 or 1 is more preferred, and 1 is particularly preferred.
• b' is an integer of 1 to 10, 1 to 8 is preferred, an integer of 1 to 5 is more preferred, 1 or 2 is more preferred, and 1 is most preferred.
• Wa x1 is an aromatic hydrocarbon group which may have a substituent.
• the aromatic hydrocarbon group for Wa x1 includes a group obtained by removing (n ax1 +1) hydrogen atoms from an optionally substituted aromatic ring.
• the aromatic ring here is not particularly limited as long as it is a cyclic conjugated system having 4n+2 ⁇ electrons.
• the aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, still more preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms.
• Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; are mentioned.
• the heteroatom in the aromatic heterocycle includes oxygen atom, sulfur atom, nitrogen atom and the like.
• aromatic heterocycles include pyridine rings and thiophene rings.
• the aromatic hydrocarbon group in Wa x1 is an aromatic compound containing an aromatic ring optionally having two or more substituents (e.g., biphenyl, fluorene, etc.) from which (n ax1 +1) hydrogen atoms are removed. groups are also included.
• Wa x1 is preferably a group obtained by removing (n ax1 +1) hydrogen atoms from benzene, naphthalene, anthracene or biphenyl, and a group obtained by removing ( nax1 +1) hydrogen atoms from benzene or naphthalene. is more preferred, and a group obtained by removing (n ax1 +1) hydrogen atoms from benzene is even more preferred.
• the aromatic hydrocarbon group in Wa x1 may or may not have a substituent.
• substituents include an alkyl group, an alkoxy group, a halogen atom, and a halogenated alkyl group.
• alkyl group, the alkoxy group, the halogen atom, and the halogenated alkyl group as the substituent include the same as those listed as the substituent of the cyclic aliphatic hydrocarbon group in Ya x1 .
• the substituent is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably a linear or branched alkyl group having 1 to 3 carbon atoms, ethyl group or methyl groups are more preferred, and methyl groups are particularly preferred.
• the aromatic hydrocarbon group in Wa x1 preferably has no substituent.
• n ax1 is an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 5, more preferably 1, 2 or 3, and 1 or 2 Especially preferred.
• R ⁇ represents a hydrogen atom, a methyl group or a trifluoromethyl group.
• the structural unit (a10) contained in the alkali-soluble resin in the resist composition of the present embodiment may be of one type or two or more types.
• the ratio of the structural unit (a10) in the alkali-soluble resin is preferably 50 to 99 mol%, more preferably 50 to 98 mol%, relative to the total (100 mol%) of all structural units constituting the alkali-soluble resin. , 60 to 98 mol % is more preferred, and 70 to 98 mol % is particularly preferred.
• the structural unit (a20) is a structural unit represented by the following general formula (a20-1).
• R x2 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
• Ya x2 is a single bond or a divalent linking group.
• Ra x2 is a hydrocarbon group.
• R x2 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 x2 is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms.
• a group is more preferred, a hydrogen atom or a methyl group is more preferred, and a hydrogen atom is particularly preferred.
• Ya x2 is a single bond or a divalent linking group.
• the divalent linking group for Ya x2 is not particularly limited, but may be a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a hetero atom, or the like. are preferred.
• the divalent hydrocarbon group optionally having a substituent and the divalent linking group containing a hetero atom include the above-described divalent hydrocarbon group for Ya x1 and a bivalent hetero atom-containing and the same as the linking group of .
• Ra x2 is a hydrocarbon group.
• the hydrocarbon group for Ra x2 includes linear or branched alkyl groups and cyclic hydrocarbon groups.
• the linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 2 to 5 carbon atoms, and even more preferably 3 to 5 carbon atoms. Specific examples include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group and the like.
• the branched-chain alkyl group preferably has 3 to 10 carbon atoms, more preferably 3 to 5 carbon atoms. Specific examples include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group and a 2,2-dimethylbutyl group, with an isopropyl group being preferred.
• the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group.
• the monocyclic aliphatic hydrocarbon group a group obtained by removing one hydrogen atom from a monocycloalkane is preferable.
• the monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane.
• the aliphatic hydrocarbon group which is a polycyclic group is preferably a group obtained by removing one hydrogen atom from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms. adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.
• the aromatic hydrocarbon group for Ra x2 is an aromatic hydrocarbon group
• the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
• This aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 ⁇ electrons, and may be monocyclic or polycyclic.
• the aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, still more preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms.
• Specific examples of the aromatic hydrocarbon group for Ra x2 include a phenyl group and a naphthyl group.
• the cyclic hydrocarbon group may contain a heteroatom such as a heterocyclic ring.
• Heteroatoms include oxygen atoms, sulfur atoms, nitrogen atoms, and the like.
• Specific examples of the heterocyclic ring include aromatic heterocyclic rings such as pyridine ring and thiophene ring; and aliphatic heterocyclic rings such as tetrahydrofuran, tetrahydropyran and tetrahydrothiophene.
• the hydrocarbon group for Ra x2 is an unsubstituted hydrocarbon group, excluding a hydrocarbon group in which some or all of the hydrogen atoms of the hydrocarbon group for Ra x2 are substituted with a group having a hetero atom. be killed.
• Ra x2 is, among the above, a linear or branched alkyl group having 1 to 5 carbon atoms, a group obtained by removing one hydrogen atom from monocycloalkane, A group obtained by removing one hydrogen atom from a polycycloalkane, a phenyl group, or a naphthyl group, preferably a linear or branched alkyl group having 1 to 5 carbon atoms, or a monocycloalkane A group in which one hydrogen atom has been removed, or a group in which one hydrogen atom has been removed from polycycloalkane, more preferably a linear or branched alkyl group having 1 to 5 carbon atoms , a cyclopentyl group, a cyclohexyl group, or an adamantyl group.
• R ⁇ represents a hydrogen atom, a methyl group or a trifluoromethyl group.
• the structural unit (a20) is preferably a structural unit represented by any one of the general formulas (a20-01-1) to (a20-01-4), and the general formula (a20 -01-2) to (a20-01-4) are more preferred.
• the structural unit (a20) contained in the alkali-soluble resin in the resist composition of the present embodiment may be of one type or two or more types.
• the ratio of the structural unit (a20) in the alkali-soluble resin is preferably 1 to 50 mol%, more preferably 2 to 50 mol%, relative to the total (100 mol%) of all structural units constituting the alkali-soluble resin. , more preferably 2 to 40 mol %, particularly preferably 2 to 30 mol %.
• the alkali-soluble resin in the resist composition of the present embodiment may have structural units other than the structural unit (a10) and the structural unit (a20).
• Examples of compounds that induce such other structural units include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; 2-methacryloyloxyethylsuccinic acid, 2- Methacrylic acid derivatives having a carboxy group and an ester bond, such as methacryloyloxyethyl maleate, 2-methacryloyloxyethyl phthalate, and 2-methacryloyloxyethyl hexahydrophthalic acid; Dicarboxylic acid diesters, such as diethyl maleate and dibutyl fumarate Conjugated diolefins such as butadiene and isoprene; Nitrile group-containing polymerizable compounds such as
• Alkali-soluble resins in the resist composition of the present embodiment may be used singly or in combination of two or more.
• the alkali-soluble resin in the resist composition of the present embodiment includes a polymer compound having a repeating structure of the structural unit (a10) and the structural unit (a20); a polymer compound having the structural unit (a10); and a mixture with a polymer compound having a20).
• a polymer compound with a LogP value of 2.8 or less even if it is a mixture of polymer compounds with a LogP value of 2.8 or less, a polymer compound with a LogP value of 2.8 or less and a polymer compound with a LogP value of more than 2.8 It may be a mixture.
• the alkali-soluble resin in the resist composition of the present embodiment is preferably a polymer compound composed only of a repeating structure of the structural unit (a10) and the structural unit (a20).
• the proportion of the structural unit (a10) is relative to the total (100 mol%) of all structural units constituting the polymer compound.
• 50 to 99 mol % is preferred, 50 to 98 mol % is more preferred, 60 to 98 mol % is even more preferred, and 70 to 98 mol % is particularly preferred.
• the ratio of the structural unit (a20) in the polymer compound is preferably 1 to 50 mol%, preferably 2 to 50 mol, with respect to the total (100 mol%) of all structural units constituting the polymer compound. %, more preferably 2 to 40 mol %, particularly preferably 2 to 30 mol %.
• the molar ratio of the structural unit (a10) to the structural unit (a20) in the polymer compound (structural unit (a10):structural unit (a20)) is preferably 99:1 to 50:50, and 98: It is more preferably 2 to 50:50, even more preferably 98:2 to 60:40, and particularly preferably 98:2 to 70:30.
• the alkali-soluble resin in the resist composition of the present embodiment is obtained by dissolving a monomer that induces each structural unit in a polymerization solvent, and adding, for example, azobisisobutyronitrile (AIBN), dimethyl azobisisobutyrate (eg, V-601 etc.) can be produced by adding a radical polymerization initiator and polymerizing.
• AIBN azobisisobutyronitrile
• dimethyl azobisisobutyrate eg, V-601 etc.
• such an alkali-soluble resin includes a monomer that induces the structural unit (a10), a monomer that induces the structural unit (a20), and optionally a structural unit other than the structural units (a10) and (a20).
• a chain transfer agent such as HS--CH 2 --CH 2 --CH 2 --C(CF 3 ) 2 --OH may be used in combination to form --C(CF 3 ) at the terminal.
• a 2 -OH group may be introduced.
• a copolymer into which a hydroxyalkyl group in which some of the hydrogen atoms of the alkyl group are substituted with fluorine atoms is used to reduce development defects and improve LER (line edge roughness: non-uniform unevenness on the side wall of a line).
• alkali-soluble resins include n-butyllithium, s-butyllithium, t-butyllithium, ethyllithium, ethylsodium, 1,1-diphenylhexyllithium, 1,1-diphenyl-3-methylpentyllithium, and the like. It can also be produced by an anionic polymerization method using an organic alkali metal as a polymerization initiator.
• the weight average molecular weight (Mw) of the alkali-soluble resin in the resist composition of the present embodiment is preferably 1000 or more and less than 4000, more preferably 1500 or more and 3500 or less, and 2000 3000 or less is more preferable.
• Mw polystyrene conversion standard by gel permeation chromatography
• the dispersity (Mw/Mn) of the alkali-soluble resin in the resist composition of the present embodiment is not particularly limited, and is preferably 1.0 to 4.0, more preferably 1.0 to 3.0, and 1.0. ⁇ 2.5 is particularly preferred.
• Mn shows a number average molecular weight.
• the resist composition of the present embodiment may contain a resin other than the alkali-soluble resin described above, but the ratio of the above-described alkali-soluble resin to the total resin contained in the resist composition of the present embodiment is is preferably 95% by mass or more, more preferably 98% by mass or more, still more preferably 99% by mass or more, and may be 100% by mass, relative to the total mass of the resin contained in the resist composition. That is, the resist composition of one embodiment excludes a resist composition in which the proportion of the above-described alkali-soluble resin in the total resin contained in the resist composition is 95% by mass or less.
• the resist composition of one embodiment excludes a resist composition in which the proportion of the above-described alkali-soluble resin in the total resin contained in the resist composition is 98% by mass or less. Moreover, the resist composition of one embodiment excludes a resist composition in which the proportion of the above-described alkali-soluble resin in the total resin contained in the resist composition is 99% by mass or less. Also, the resist composition of one embodiment excludes a resist composition containing an alkali-soluble resin having a LogP of greater than 2.8. Moreover, the resist composition of one embodiment excludes a resist composition containing an alkali-insoluble resin.
• the content of component (A) in the resist composition of the present embodiment may be adjusted according to the resist film thickness to be formed.
• the (B) component in the resist composition of the present embodiment contains a compound (B0) having a molar extinction coefficient of 10000 mol ⁇ 1 L cm ⁇ 1 or less at a wavelength of 248 nm (hereinafter also referred to as “(B0) component”). .
• the molar extinction coefficient of the component (B0) at a wavelength of 248 nm is 10000 mol -1 L cm -1 or less, and is 1000 mol -1 L cm -1 or more and 10000 mol -1 L cm -1 or less. It is preferably 1500 mol -1 L cm -1 or more and 9000 mol -1 L cm -1 or less, and more preferably 1500 mol -1 L cm -1 or more and 5000 mol -1 L cm -1 or less. 2000 mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 or more and 3000 mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 or less is particularly preferable.
• the molar extinction coefficient of the component (B0) at a wavelength of 248 nm is 10000 mol ⁇ 1 L cm ⁇ 1 or less, so that the light of the resist film formed by the resist composition containing the component (B0) (typically In addition, the transmittance of the KrF excimer laser) is improved, and the reaction in which the component (B0) generates acid in the resist film is more likely to occur uniformly, thereby improving the shape and DOF of the resist pattern. Also, the resolution is improved. If the molar extinction coefficient of component (B0) at a wavelength of 248 nm is equal to or less than the above preferable upper limit, the reaction in which acid is generated from the component (B0) in the resist film is performed more uniformly. DOF is further improved. When the molar extinction coefficient of the component (B0) at a wavelength of 248 nm is at least the above preferable lower limit, the sensitivity in resist pattern formation is further improved.
• the molar extinction coefficient of the (B0) component means a value calculated by measuring the absorbance of the (B0) component at a wavelength of 248 nm with a spectrophotometer and using Beer-Lambert's law. Specifically, the (B0) component is dissolved in acetonitrile, this solution is placed in a cell with an optical path length of 10 mm, the UV spectrum is measured with a spectrophotometer (UV-3600, manufactured by Shimadzu Corporation), and the absorbance at a wavelength of 248 nm is measured. get. Then, the molar extinction coefficient ⁇ (mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 ) can be calculated from the obtained absorbance and solution concentration using Beer-Lambert's law.
• the molar extinction coefficient of the (B0) component can typically be controlled by appropriately changing the structure of the cation portion of the (B0) component.
• the (B0) component is preferably a compound (B01) represented by the following general formula (b01) (hereinafter also referred to as "(B01) component").
• X - is a counter anion.
• Rb 01 to Rb 03 are each independently an optionally substituted aryl group, an optionally substituted alkyl group, or an optionally substituted alkenyl group.
• Rb 02 and Rb 03 may form a ring together with the sulfur atom in the formula.
• Lb 01 is a single bond or a divalent linking group.
• Rb 01 to Rb 03 are each independently an aryl group, an alkyl group, or an alkenyl group.
• the aryl group for Rb 01 to Rb 03 is preferably an aryl group having 6 to 20 carbon atoms, more preferably a phenyl group or a naphthyl group.
• the alkyl group for Rb 01 to Rb 03 includes chain or cyclic alkyl groups, preferably alkyl groups having 1 to 30 carbon atoms.
• the alkenyl group for Rb 01 to Rb 03 is preferably an alkenyl group having 2 to 10 carbon atoms.
• substituents that the aryl group, alkyl group, and alkenyl group in Rb 01 to Rb 03 may have include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, and an aryl group.
• group a group represented by the general formula [-Yca0-Rca0] (Yca0 is a single bond or a divalent linking group, Rca0 is a hydrocarbon group), and the like.
• Yca0 is preferably a group consisting of a combination of a single bond or an ether bond (-O-) and a linear or branched alkylene group.
• the hydrocarbon group in Rca0 is preferably a cyclic aliphatic hydrocarbon group, more preferably a group obtained by removing one hydrogen atom from a monocycloalkane. , a cyclopentyl group, or a cyclohexyl group.
• hetero atoms such as a sulfur atom, an oxygen atom and a nitrogen atom, a carbonyl group, —SO—, —SO 2 —, It may be bonded via a functional group such as —SO 3 —, —COO—, —CONH— or —N(R N )— (where R N is an alkyl group having 1 to 5 carbon atoms).
• one ring containing a sulfur atom in the formula in its ring skeleton is preferably a 3- to 10-membered ring, particularly a 5- to 7-membered ring including a sulfur atom. preferable.
• the ring to be formed include, for example, a tetrahydrothiophene ring, a thiane ring, a thiophene ring, a thiazole ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthrene ring, a phenoxathiin ring, A tetrahydrothiopyranium ring and the like can be mentioned.
• Rb 01 is more preferably an unsubstituted aryl group or an aryl group having -Yca0-Rca0 as a substituent.
• Rb 02 and Rb 03 are preferably mutually bonded to form a ring together with the sulfur atom in the formula, and Rb 02 and Rb 03 are mutually bonded It is more preferable to form an aliphatic ring together with the sulfur atom in the formula, more preferably to form a tetrahydrothiophene ring or a thiane ring.
• Lb01 is a single bond or a divalent linking group.
• the cation moiety of the component (B0) is preferably a cation represented by the following general formula (ca-b0-1).
• Rb 01 is an optionally substituted aryl group, an optionally substituted alkyl group, or an optionally substituted alkenyl group.
• Lb 01 is a single bond or a divalent linking group.
• Yb 01 is a group that forms an alicyclic ring together with the sulfur atom in the formula. The aliphatic ring formed by the sulfur atom in the formula and Yb01 may have a substituent.
• Rb 01 in the general formula (ca-b0-1) is the same as Rb 01 in the general formula (b01).
• Lb 01 in the general formula (ca-b0-1) is the same as Lb 01 in the general formula (b01).
• Yb 01 in the general formula (ca-b0-1) is a group forming an aliphatic ring together with the sulfur atom in the formula.
• the aliphatic ring may have a substituent, and examples of the substituent include the same substituents that Rb 01 in the general formula (b01) may have.
• Yb 01 in the general formula (ca-b0-1) is preferably a group forming a tetrahydrothiophene ring or a thiane ring together with the sulfur atom in the formula.
• R′′ 201 is a hydrogen atom or a substituent, and the substituent is an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, or the above general formula ( groups represented by ca-r-1) to (ca-r-7), respectively.]
• the cation moiety of the component (B0) is preferably a cation represented by any one of the chemical formulas (ca-01-1) to (ca-01-3), and the chemical formula (ca-01-1) The cations represented are more preferred.
• X - is a counter anion.
• X ⁇ is not particularly limited, and those proposed as anion moieties of acid generators for resist compositions can be used.
• Examples of X ⁇ include anions represented by the following general formula (b0-1-an), general formula (b0-2-an), or general formula (b0-3-an).
• R 101 and R 104 to R 108 are each independently an optionally substituted cyclic group, an optionally substituted chain alkyl group, or a substituted It is a chain alkenyl group that may be R 104 and R 105 may combine with each other to form a ring structure.
• R 102 is a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom.
• Y 101 is a divalent linking group or single bond containing an oxygen atom.
• V 101 to V 103 are each independently a single bond, an alkylene group or a fluorinated alkylene group.
• L 101 to L 102 are each independently a single bond or an oxygen atom.
• L 103 to L 105 are each independently a single bond, -CO- or -SO 2 -. ]
• R 101 is a cyclic group optionally having a substituent, a chain optionally having a substituent or a chain alkenyl group which may have a substituent.
• the cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group.
• An aliphatic hydrocarbon group means a hydrocarbon group without aromaticity.
• the aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
• the aromatic hydrocarbon group for R 101 is a hydrocarbon group having an aromatic ring.
• the number of carbon atoms in the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, still more preferably 5 to 20, particularly preferably 6 to 15, most preferably 6 to 10. .
• the number of carbon atoms does not include the number of carbon atoms in the substituent.
• Specific examples of the aromatic ring of the aromatic hydrocarbon group for R 101 include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or a portion of the carbon atoms constituting these aromatic rings substituted with heteroatoms. Aromatic heterocycle etc. are mentioned.
• the heteroatom in the aromatic heterocycle includes oxygen atom, sulfur atom, nitrogen atom and the like.
• the aromatic hydrocarbon group for R 101 include a group in which one hydrogen atom is removed from the aromatic ring (aryl group: e.g., phenyl group, naphthyl group, etc.), and one of the hydrogen atoms in the aromatic ring is alkylene groups substituted with groups (for example, arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.), and the like.
• the alkylene group (alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.
• the cyclic aliphatic hydrocarbon group for R 101 includes an aliphatic hydrocarbon group containing a ring in its structure.
• the cyclic aliphatic hydrocarbon group for R 101 preferably has 3 to 50 carbon atoms, preferably 4 to 45 carbon atoms, and more preferably 5 to 40 carbon atoms.
• the aliphatic hydrocarbon group containing a ring in this structure includes an alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon ring), and an alicyclic hydrocarbon group that is linear or branched.
• Examples thereof include a group bonded to the end of a chain aliphatic hydrocarbon group and a group in which an alicyclic hydrocarbon group intervenes in the middle of a linear or branched aliphatic hydrocarbon group.
• the alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms.
• the alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group.
• the monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane.
• the monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane.
• the polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms.
• the polycycloalkanes include polycycloalkanes having a bridged ring system polycyclic skeleton such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; condensed ring systems such as cyclic groups having a steroid skeleton; Polycycloalkanes having a polycyclic skeleton of are more preferred.
• the cyclic aliphatic hydrocarbon group for R 101 is preferably a group obtained by removing one or more hydrogen atoms from monocycloalkane or polycycloalkane, more preferably a group obtained by removing one hydrogen atom from polycycloalkane.
• An adamantyl group and a norbornyl group are more preferred, and an adamantyl group is particularly preferred.
• the linear aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group, preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. , 1-3 are most preferred.
• a straight-chain alkylene group is preferable, and specifically, a methylene group [ --CH.sub.2-- ], an ethylene group [--( CH.sub.2 ) .sub.2-- ], a trimethylene group [ -(CH 2 ) 3 -], tetramethylene group [-(CH 2 ) 4 -], pentamethylene group [-(CH 2 ) 5 -] and the like.
• the branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group, preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, and still more preferably 3 or 4. , 3 are most preferred.
• the branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specifically, -CH(CH 3 )-, -CH(CH 2 CH 3 )-, -C(CH 3 ) 2- , -C(CH 3 )(CH 2 CH 3 )-, -C(CH 3 )(CH 2 CH 2 CH 3 )-, -C(CH 2 CH 3 ) 2 - and other alkylmethylene groups;- CH(CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 )-, -C(CH 3 ) 2 CH 2 -, -CH(CH 2 CH 3 )CH 2 -, -C(CH 2 Alkylethylene groups such as CH 3 ) 2 -CH 2 -; alkyltrimethylene groups such as -CH(CH 3 )CH 2 CH 2 - and -CH 2 CH(CH 3 )CH 2 -; -CH(CH 3 ) Examples include alkylalky
• the cyclic hydrocarbon group for R 101 may contain a heteroatom such as a heterocyclic ring.
• lactone-containing cyclic groups respectively represented by the following general formulas (b2-r-1) to (b2-r-7), the following general formulas (b5-r-1) to (b5-r- 4), and heterocyclic groups represented by the following chemical formulas (r-hr-1) to (r-hr-16).
• * represents a bond that binds to Y 101 in formula (b0-1-an).
• substituents on the cyclic group of R 101 include alkyl groups, alkoxy groups, halogen atoms, halogenated alkyl groups, hydroxy groups, carbonyl groups, nitro groups and the like.
• the alkyl group as a substituent is preferably an alkyl group having 1 to 5 carbon atoms, most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group.
• the alkoxy group as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group and a tert-butoxy group.
• a methoxy group and an ethoxy group are most preferred.
• a halogen atom as a substituent includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
• halogenated alkyl groups examples include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, tert-butyl, etc., in which some or all of the hydrogen atoms are Groups substituted with the aforementioned halogen atoms are included.
• a carbonyl group as a substituent is a group that substitutes a methylene group ( --CH.sub.2-- ) constituting a cyclic hydrocarbon group.
• the cyclic hydrocarbon group for R 101 may be a condensed cyclic group containing a condensed ring in which an aliphatic hydrocarbon ring and an aromatic ring are condensed.
• the condensed ring include a polycycloalkane having a polycyclic skeleton of a bridged ring system condensed with one or more aromatic rings.
• Specific examples of the bridged ring system polycycloalkanes include bicycloalkanes such as bicyclo[2.2.1]heptane (norbornane) and bicyclo[2.2.2]octane.
• the condensed cyclic group is preferably a group containing a condensed ring in which two or three aromatic rings are condensed to a bicycloalkane, and two or three aromatic rings are condensed to bicyclo[2.2.2]octane. Groups containing a condensed ring are more preferred.
• Specific examples of the condensed cyclic group for R 101 include those represented by the following formulas (r-br-1) to (r-br-2). In the formula, * represents a bond that binds to Y 101 in formula (b0-1-an).
• Substituents that the condensed cyclic group in R 101 may have include, for example, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an aromatic hydrocarbon group, and an alicyclic and hydrocarbon groups of the formula.
• Examples of the alkyl group, alkoxy group, halogen atom, and halogenated alkyl group as the substituent of the condensed cyclic group are the same as those exemplified as the substituent of the cyclic group for R 101 above.
• aromatic hydrocarbon group as a substituent of the condensed cyclic group
• aromatic hydrocarbon group examples include groups obtained by removing one hydrogen atom from the aromatic ring (aryl group: for example, phenyl group, naphthyl group, etc.), Groups one of which is substituted with an alkylene group (e.g., arylalkyl groups such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, etc.), the above Examples thereof include heterocyclic groups represented by formulas (r-hr-1) to (r-hr-6).
• Examples of the alicyclic hydrocarbon group as a substituent of the condensed cyclic group include groups obtained by removing one hydrogen atom from monocycloalkane such as cyclopentane and cyclohexane; adamantane, norbornane, isobornane, tricyclodecane, tetra A group obtained by removing one hydrogen atom from a polycycloalkane such as cyclododecane; a lactone-containing cyclic group represented by each of the general formulas (a2-r-1) to (a2-r-7); —SO 2 —containing cyclic groups respectively represented by (a5-r-1) to (a5-r-4); and heterocyclic groups.
• the cyclic hydrocarbon group for R 101 is a group in which two or more aliphatic rings and/or aromatic rings are linked by a linear or branched aliphatic hydrocarbon group which may have a substituent.
• the straight-chain or branched-chain aliphatic hydrocarbon group that connects the alicyclic hydrocarbon groups is a divalent group in which the methylene group ( --CH.sub.2-- ) constituting the aliphatic hydrocarbon chain contains a heteroatom. may be substituted.
• a chain alkyl group which may have a substituent may be linear or branched.
• the linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms.
• the branched-chain alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms.
• 1-methylethyl group 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group and the like.
• a chain alkenyl group which may have a substituent may be linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, and further preferably 2 to 4 carbon atoms. 3 is particularly preferred.
• linear alkenyl groups include vinyl groups, propenyl groups (allyl groups), and butynyl groups.
• Examples of branched alkenyl groups include 1-methylvinyl group, 2-methylvinyl group, 1-methylpropenyl group, 2-methylpropenyl group and the like.
• the chain alkenyl group is preferably a linear alkenyl group, more preferably a vinyl group or a propenyl group, and particularly preferably a vinyl group.
• substituents on the linear alkyl group or alkenyl group for R 101 include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, a cyclic group for R 101 above, and the like. mentioned.
• R 101 is preferably a chain alkyl group which may have a substituent or an alicyclic hydrocarbon group which may have a substituent, and has a halogen atom.
• a chain alkyl group, which may be substituted, or a group obtained by removing one or more hydrogen atoms from an optionally substituted polycycloalkane is more preferred.
• Y 101 is a divalent linking group containing a single bond or an oxygen atom.
• Y 101 may contain an atom other than an oxygen atom.
• Atoms other than an oxygen atom include, for example, a carbon atom, a hydrogen atom, a sulfur atom, a nitrogen atom, and the like.
• a sulfonyl group ( --SO.sub.2-- ) may be further linked to this combination.
• Such a divalent linking group containing an oxygen atom includes, for example, linking groups represented by the following general formulas (y-al-1) to (y-al-7).
• R 101 in the above formula (b0-1-an) is bound to the following general formula (y-al-1 ) to (y-al- 7 ).
• V′ 101 is a single bond or an alkylene group having 1 to 5 carbon atoms
• V′ 102 is a divalent saturated hydrocarbon group having 1 to 30 carbon atoms.
• the divalent saturated hydrocarbon group for V' 102 is preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and 1 to 5 carbon atoms. is more preferably an alkylene group of
• the alkylene group for V' 101 and V' 102 may be a straight-chain alkylene group or a branched alkylene group, and a straight-chain alkylene group is preferred.
• Specific examples of the alkylene group for V' 101 and V' 102 include a methylene group [-CH 2 -]; -CH(CH 3 )-, -CH(CH 2 CH 3 )-, -C(CH 3 ) 2 -, -C(CH 3 )(CH 2 CH 3 )-, -C(CH 3 )(CH 2 CH 2 CH 3 )-, -C(CH 2 CH 3 ) 2 - and other alkylmethylene groups; ethylene groups [-CH 2 CH 2 -]; -CH(CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 )-, -C(CH 3 ) 2 CH 2 -, -CH(CH 2 CH 3 ) Alkylethylene groups such as CH 2 -; trim
• part of the methylene groups in the alkylene group in V'101 or V'102 may be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms.
• the aliphatic cyclic group is a cyclic aliphatic hydrocarbon group ( monocyclic aliphatic hydrocarbon group, polycyclic aliphatic hydrocarbon group ) with one more hydrogen atom removed, and more preferably a cyclohexylene group, a 1,5-adamantylene group or a 2,6-adamantylene group.
• Y 101 is preferably a single bond, a divalent linking group containing an ester bond, or a divalent linking group containing an ether bond, and may be a single bond or the above formulas (y-al-1) to (y- A connecting group represented by al-5) is more preferable, and a single bond or a connecting group represented by the above formula (y-al-2) is more preferable.
• V 101 is a single bond, an alkylene group or a fluorinated alkylene group.
• the alkylene group and fluorinated alkylene group for V 101 preferably have 1 to 4 carbon atoms.
• the fluorinated alkylene group for V 101 include groups in which some or all of the hydrogen atoms in the alkylene group for V 101 are substituted with fluorine atoms.
• V 101 is preferably a single bond or a fluorinated alkylene group having 1 to 4 carbon atoms, and is a single bond or a linear fluorinated alkylene group having 1 to 4 carbon atoms. is more preferred.
• R 102 is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms.
• R 102 is preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, more preferably a fluorine atom.
• anion moiety represented by the formula (b0-1-an) include, for example, when Y 101 is a single bond, fluorinated alkylsulfonate anions such as trifluoromethanesulfonate anion and perfluorobutanesulfonate anion. and when Y 101 is a divalent linking group containing an oxygen atom, anions represented by any of the following formulas (an-1) to (an-3) can be mentioned.
• R′′ 101 is an optionally substituted aliphatic cyclic group, a monovalent heterocyclic group represented by each of the above chemical formulas (r-hr-1) to (r-hr-6) A cyclic group, a condensed cyclic group represented by the above formula (r-br-1) or (r-br-2), or a chain alkyl group which may have a substituent.
• R′′ 102 is an optionally substituted aliphatic cyclic group, the condensed cyclic group represented by the formula (r-br-1) or (r-br-2), the general formula (a2-r- 1), lactone-containing cyclic groups represented by (a2-r-3) to (a2-r-7), respectively, or the above general formulas (a5-r-1) to (a5-r-4), respectively -SO 2 -containing cyclic group represented.
• R′′ 103 is an optionally substituted aromatic cyclic group, an optionally substituted aliphatic cyclic group, or an optionally substituted chain alkenyl group.
• V′′ 101 is a single bond, an alkylene group having 1 to 4 carbon atoms, or a fluorinated alkylene group having 1 to 4 carbon atoms.
• R 102 is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms.
• Each v′′ is independently an integer of 0 to 3
• each q′′ is independently an integer of 0 to 20, and n′′ is 0 or 1.
• the optionally substituted aliphatic cyclic groups of R′′ 101 , R′′ 102 and R′′ 103 are exemplified as the cyclic aliphatic hydrocarbon group for R 101 in the formula (b0-1-an).
• substituents include the same substituents that may substitute the cyclic aliphatic hydrocarbon group for R 101 in the formula (b0-1-an). .
• the optionally substituted aromatic cyclic group for R′′ 103 is the group exemplified as the aromatic hydrocarbon group for the cyclic hydrocarbon group for R 101 in the formula (b0-1-an).
• substituents include the same substituents that may substitute the aromatic hydrocarbon group for R 101 in the formula (b0-1-an).
• the optionally substituted chain alkyl group for R′′ 101 is preferably a group exemplified as the chain alkyl group for R 101 in the formula (b0-1-an).
• the optionally substituted chain alkenyl group for R′′ 103 is preferably a group exemplified as the chain alkenyl group for R 101 in the formula (b0-1-an).
• R 104 and R 105 each independently represent a cyclic group optionally having a substituent, a substituent It is a chain alkyl group which may have one or a chain alkenyl group which may have a substituent, and examples thereof are the same as those for R 101 in the formula (b0-1-an). However, R 104 and R 105 may combine with each other to form a ring.
• R 104 and R 105 are preferably a chain alkyl group which may have a substituent, and are a linear or branched alkyl group, or a linear or branched fluorinated alkyl group. is more preferred.
• the chain alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 7 carbon atoms, still more preferably 1 to 3 carbon atoms.
• the number of carbon atoms in the chain alkyl groups of R 104 and R 105 is preferably as small as possible within the above range of the number of carbon atoms, for reasons such as good solubility in resist solvents.
• the greater the number of hydrogen atoms substituted with fluorine atoms the stronger the acid strength. It is preferable because it improves the transparency.
• the proportion of fluorine atoms in the chain alkyl group is preferably 70 to 100%, more preferably 90 to 100%, and most preferably all hydrogen atoms are substituted with fluorine atoms.
• V 102 and V 103 are each independently a single bond, an alkylene group, or a fluorinated alkylene group, and are respectively V 101 and V 101 in formula (b0-1-an). The same can be mentioned.
• L 101 and L 102 are each independently a single bond or an oxygen atom.
• R 106 to R 108 each independently represent a cyclic group optionally having a substituent, a substituent It is a chain alkyl group which may have one or a chain alkenyl group which may have a substituent, and examples thereof are the same as those for R 101 in the formula (b0-1-an).
• L 103 to L 105 are each independently a single bond, —CO— or —SO 2 —.
• an anion represented by the formula (b0-1-an) or (b0-3-an) is preferable as X 1 ⁇ in the general formula (b01).
• the (B0) component is more preferably a compound (B011) represented by the following general formula (b01-1) (hereinafter also referred to as "(B011) component").
• X - is a counter anion.
• Each Rb 01 is independently an aryl group which may have a substituent, an alkyl group which may have a substituent, or an alkenyl group which may have a substituent.
• Lb 01 is a single bond or a divalent linking group.
• Yb 01 is a group that forms an aliphatic ring together with the sulfur atom in the formula. The aliphatic ring formed by the sulfur atom in the formula and Yb01 may have a substituent.
• the anion part of the (B011) component is the same as the anion part of the (B01) component described above.
• the cation portion of component (B011) is the same as the cation represented by general formula (ca-b0-1) above.
• the component (B0) may be used singly or in combination of two or more.
• the content of component (B0) is preferably 1 to 25 parts by mass, more preferably 1 to 20 parts by mass, with respect to 100 parts by mass of component (A). It is preferably from 1 to 15 parts by mass.
• the content of component (B0) is at least the lower limit of the preferred range, lithography properties such as resolution, DOF, and pattern shape are further improved in resist pattern formation.
• it is equal to or less than the upper limit of the preferred range when each component of the resist composition is dissolved in an organic solvent, a uniform solution is easily obtained, and the storage stability of the resist composition is further enhanced.
• the proportion of component (B0) in the total component (B) is, for example, 50% by mass or more, preferably 70% by mass or more, and more preferably 95% by mass or more. is.
• the proportion of component (B0) in the total component (B) may be 100% by mass.
• the (B) component in the resist composition of the present embodiment may contain an acid generator component (B1) (hereinafter also referred to as "(B1) component”) other than the above-described (B0) component.
• B1 component an acid generator component
• Component (B1) is an acid generator having a molar extinction coefficient at a wavelength of 248 nm of more than 10000 mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 , and typically the cation moiety is the cation moiety of component (B0) described above. is a different acid generator.
• Component (B1) includes onium salt-based acid generators such as iodonium salts and sulfonium salts (excluding those corresponding to component (B0)); oxime sulfonate-based acid generators; bisalkyl or bisarylsulfonyl diazomethanes; Diazomethane-based acid generators such as poly(bissulfonyl)diazomethanes; nitrobenzylsulfonate-based acid generators, iminosulfonate-based acid generators, and disulfone-based acid generators.
• onium salt-based acid generators such as iodonium salts and sulfonium salts (excluding those corresponding to component (B0)); oxime sulfonate-based acid generators; bisalkyl or bisarylsulfonyl diazomethanes; Diazomethane-based acid generators such as poly(bissulfonyl)diazomethanes
• onium salt acid generator for example, a compound represented by the following general formula (b-1) (hereinafter also referred to as “component (b-1)”), represented by general formula (b-2)
• component (b-2) A compound (hereinafter also referred to as “(b-2) component”) or a compound represented by general formula (b-3) (hereinafter also referred to as “(b-3) component”) can be mentioned.
• R 101 and R 104 to R 108 are each independently an optionally substituted cyclic group, an optionally substituted chain alkyl group, or a substituted It is a chain alkenyl group that may be R 104 and R 105 may combine with each other to form a ring structure.
• R 102 is a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom.
• Y 101 is a divalent linking group or single bond containing an oxygen atom.
• V 101 to V 103 are each independently a single bond, an alkylene group or a fluorinated alkylene group.
• L 101 to L 102 are each independently a single bond or an oxygen atom.
• L 103 to L 105 are each independently a single bond, -CO- or -SO 2 -.
• m is an integer of 1 or more, and M'm+ is an m-valent onium cation.
• anion portion in the component (b-1) is an anion represented by the formula (b0-1-an).
• Anion in Component (b-2) is an anion represented by the formula (b0-2-an).
• Anion in Component (b-3) is an anion represented by the formula (b0-3-an).
• M′ m+ represents an m-valent onium cation. Among these, sulfonium cations and iodonium cations are preferred. m is an integer of 1 or more.
• Preferred cation moieties include organic cations represented by general formulas (ca-1) to (ca-5) below.
• R 201 to R 207 and R 211 to R 212 each independently represent an optionally substituted aryl group, alkyl group or alkenyl group.
• R 201 to R 203 , R 206 to R 207 and R 211 to R 212 may combine with each other to form a ring together with the sulfur atom in the formula.
• R 208 to R 209 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
• R 210 is an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted —SO 2 — It contains cyclic groups.
• Each Y 201 independently represents an arylene group, an alkylene group or an alkenylene group.
• x is 1 or 2;
• W 201 represents a (x+1)-valent linking group.
• examples of the aryl group for R 201 to R 207 and R 211 to R 212 include unsubstituted aryl groups having 6 to 20 carbon atoms. , phenyl group and naphthyl group are preferred.
• the alkyl group for R 201 to R 207 and R 211 to R 212 is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.
• the alkenyl groups for R 201 to R 207 and R 211 to R 212 preferably have 2 to 10 carbon atoms.
• R 201 to R 207 and R 210 to R 212 may have include alkyl groups, halogen atoms, halogenated alkyl groups, carbonyl groups, cyano groups, amino groups, aryl groups, and the following Examples thereof include groups represented by general formulas (ca-r-1) to (ca-r-7).
• each R′ 201 is independently a hydrogen atom, an optionally substituted cyclic group, an optionally substituted chain alkyl group, or an optionally substituted It is a good chain alkenyl group.
• R 201 to R 203 , R 206 to R 207 , and R 211 to R 212 are mutually bonded to form a ring together with the sulfur atom in the formula.
• a sulfur atom, an oxygen atom, a hetero atom such as a nitrogen atom, a carbonyl group, -SO-, -SO 2 -, -SO 3 -, -COO-, -CONH- or -N(R N )-(
• the R 3 N is an alkyl group having 1 to 5 carbon atoms.).
• one ring containing a sulfur atom in the formula in its ring skeleton is preferably a 3- to 10-membered ring including a sulfur atom, particularly a 5- to 7-membered ring. preferable.
• the ring formed include a thiophene ring, a thiazole ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthrene ring, a phenoxathiin ring, a tetrahydrothiophenium ring, a tetrahydrothio A pyranium ring etc. are mentioned.
• R 208 to R 209 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. may form a ring.
• R 210 is an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted —SO 2 — It contains cyclic groups.
• the aryl group for R 210 includes an unsubstituted aryl group having 6 to 20 carbon atoms, preferably a phenyl group or a naphthyl group.
• the alkyl group for R 210 is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.
• the alkenyl group for R 210 preferably has 2 to 10 carbon atoms.
• the —SO 2 -containing cyclic group optionally having a substituent for R 210 is preferably a “—SO 2 -containing polycyclic group” represented by general formula (a5-r-1) above. is more preferred.
• Each Y 201 independently represents an arylene group, an alkylene group or an alkenylene group.
• the arylene group for Y 201 includes groups obtained by removing one hydrogen atom from the aryl group exemplified as the aromatic hydrocarbon group for R 101 in the above formula (b0-1-an).
• the alkylene group and alkenylene group for Y 201 are groups obtained by removing one hydrogen atom from the groups exemplified as the chain alkyl group and chain alkenyl group for R 101 in the above formula (b0-1-an). mentioned.
• W 201 is a (x+1)-valent, ie divalent or trivalent linking group.
• the divalent linking group in W 201 is preferably a divalent hydrocarbon group which may have a substituent.
• the divalent linking group in W 201 may be linear, branched or cyclic, preferably cyclic. Among them, a group in which two carbonyl groups are combined at both ends of an arylene group is preferable.
• the arylene group includes a phenylene group, a naphthylene group and the like, and a phenylene group is particularly preferred.
• the trivalent linking group for W 201 includes a group obtained by removing one hydrogen atom from the divalent linking group for W 201 , a group obtained by further bonding the divalent linking group to the divalent linking group, and the like. mentioned.
• the trivalent linking group for W 201 is preferably a group in which two carbonyl groups are bonded to an arylene group.
• the cation moiety ((M' m+ ) 1/m ) is preferably a cation represented by general formula (ca-1).
• Suitable cations represented by the formula (ca-1) include cations represented by the following chemical formulas (ca-1-1) to (ca-1-47).
• g1, g2 and g3 represent the number of repetitions, g1 is an integer of 1 to 5, g2 is an integer of 0 to 20, and g3 is an integer of 0 to 20. ]
• the component (B1) may be used singly or in combination of two or more.
• the content of component (B1) is preferably less than 40 parts by mass, more preferably 0 to 20 parts by mass, even more preferably 0 to 5 parts by mass, per 100 parts by mass of component (A).
• Component (C) in the resist composition of the present embodiment is at least one selected from the group consisting of melamine-based cross-linking agents, urea-based cross-linking agents, alkylene urea-based cross-linking agents, glycoluril-based cross-linking agents, and epoxy-based cross-linking agents. is a cross-linking agent.
• melamine-based cross-linking agents include compounds obtained by reacting melamine and formaldehyde and substituting the hydrogen atoms of the amino groups with hydroxymethyl groups; Examples thereof include compounds substituted with a methyl group. Specific examples include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxybutylmelamine, etc. Among them, hexamethoxymethylmelamine is preferred.
• urea-based cross-linking agent urea and formaldehyde are reacted to replace the hydrogen atom of the amino group with a hydroxymethyl group.
• examples thereof include compounds substituted with a methyl group.
• Specific examples include bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, bisbutoxymethylurea, etc. Among them, bismethoxymethylurea is preferred.
• alkylene urea-based cross-linking agents examples include compounds represented by the following general formula (CA-1).
• Rc 1 and Rc 2 are each independently a hydroxyl group or a lower alkoxy group
• Rc 3 and Rc 4 are each independently a hydrogen atom, a hydroxyl group or a lower alkoxy group
• vc is 0 to An integer of 2.
• Rc 1 and Rc 2 are lower alkoxy groups, they are preferably alkoxy groups having 1 to 4 carbon atoms and may be linear or branched. Rc 1 and Rc 2 may be the same or different from each other. More preferably, they are the same.
• Rc 3 and Rc 4 are lower alkoxy groups, they are preferably alkoxy groups having 1 to 4 carbon atoms and may be linear or branched. Rc3 and Rc4 may be the same or different from each other. More preferably, they are the same.
• vc is an integer of 0-2, preferably 0 or 1;
• alkylene urea-based cross-linking agent a compound having vc of 0 (ethylene urea-based cross-linking agent) and/or a compound having vc of 1 (propylene urea-based cross-linking agent) is particularly preferable.
• the compound represented by the above general formula (CA-1) can be obtained by condensation reaction of alkylene urea and formalin, or by reacting this product with a lower alcohol.
• alkylene urea cross-linking agents include mono- and/or dihydroxymethylated ethylene urea, mono- and/or dimethoxymethylated ethylene urea, mono- and/or diethoxymethylated ethylene urea, mono- and/or dipropoxy Ethylene urea cross-linking agents such as methylated ethylene urea, mono and/or dibutoxymethylated ethylene urea; mono and/or dihydroxymethylated propylene urea, mono and/or dimethoxymethylated propylene urea, mono and/or diethoxymethyl propylene urea cross-linking agents such as propylene urea, mono- and/or dipropoxymethylated propylene urea, mono- and/or dibutoxymethylated propylene urea; 1,3-di(methoxymethyl)4,5-dihydroxy-2- imidazolidinone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone and
• Glycoluril cross-linking agents include glycoluril derivatives substituted with one or both of a hydroxyalkyl group and an alkoxyalkyl group having 1 to 4 carbon atoms at the N-position.
• Such a glycoluril derivative can be obtained by condensation reaction of glycoluril and formalin, or by reacting this product with a lower alcohol.
• glycoluril cross-linking agents include mono-, di-, tri- and/or tetrahydroxymethylated glycoluril; mono-, di-, tri- and/or tetramethoxymethylated glycoluril; mono-, di-, tri- and/or tetraethoxymethylated glycoluril; mono-, di-, tri- and/or tetrapropoxy-methylated glycoluril; mono-, di-, tri- and/or tetrabutoxymethylated glycoluril.
• the epoxy-based cross-linking agent is not particularly limited as long as it has an epoxy group, and can be arbitrarily selected and used. Among them, those having two or more epoxy groups are preferable. Having two or more epoxy groups improves cross-linking reactivity.
• the number of epoxy groups is preferably two or more, more preferably two to four, most preferably two. Suitable epoxy-based cross-linking agents are shown below.
• glycoluril-based cross-linking agents are preferred as component (C).
• component (C) Component may be used individually by 1 type, and may be used in combination of 2 or more type.
• the content of component (C) is preferably 1 to 50 parts by mass, more preferably 3 to 40 parts by mass, with respect to 100 parts by mass of component (A). 30 parts by weight is more preferred, and 3 to 25 parts by weight is most preferred.
• the content of the component (C) is at least the lower limit, the formation of crosslinks will proceed sufficiently, and the resolution performance and lithography properties will be further improved. Also, a good resist pattern with less swelling can be obtained.
• the storage stability of the resist composition is good, and deterioration of sensitivity over time is easily suppressed.
• the resist composition of this embodiment may further contain other components in addition to the components (A), (B) and (C) described above.
• Other components include, for example, the following components (D), (E), (F), and (S).
• the resist composition of the present embodiment preferably further contains a base component (hereinafter also referred to as "component (D)”) that traps acid generated by exposure (that is, controls acid diffusion).
• component (D) acts as a quencher (acid diffusion control agent) that traps acid generated by exposure in the resist composition.
• Component (D) includes, for example, a photodegradable base (D1) that decomposes upon exposure to lose acid diffusion controllability (hereinafter referred to as "(D1) component”), and a nitrogen-containing organic base that does not fall under component (D1).
• Compound (D2) hereinafter referred to as "component (D2)
• component (D2) hereinafter referred to as "component (D2)
• the component (D1) is not particularly limited as long as it is decomposed by exposure to light and loses the acid diffusion controllability.
• a compound represented by the following general formula (d1-2) hereinafter referred to as “(d1-2) component”
• d1-3 a compound represented by the following general formula (d1- 3)
• One or more compounds selected from the group consisting of "components" are preferred.
• Components (d1-1) to (d1-3) do not act as quenchers because they decompose in the exposed areas of the resist film and lose acid diffusion controllability (basicity), and quench in the unexposed areas of the resist film. Acts as a char.
• Rd 1 to Rd 4 are a cyclic group optionally having a substituent, a chain alkyl group optionally having a substituent, or a chain alkenyl group optionally having a substituent is. However, it is assumed that no fluorine atom is bonded to the carbon atom adjacent to the S atom in Rd 2 in formula (d1-2).
• Yd 1 is a single bond or a divalent linking group.
• m is an integer of 1 or more, and each M m+ is independently an m-valent organic cation.
• Rd 1 is an optionally substituted cyclic group, an optionally substituted chain alkyl group, or an optionally substituted cyclic group. It is a good chain-like alkenyl group, and examples thereof are the same as those for R' 201 above. Among these, Rd 1 is an optionally substituted aromatic hydrocarbon group, an optionally substituted aliphatic cyclic group, or an optionally substituted chain-like Alkyl groups are preferred.
• substituents that these groups may have include a hydroxyl group, an oxo group, an alkyl group, an aryl group, a fluorine atom, a fluorinated alkyl group, and general formulas (a2-r-1) to (a2-r-7). ), an ether bond, an ester bond, or a combination thereof.
• it may be via an alkylene group, and the substituents in this case are represented by the above formulas (y-al-1) to (y-al-5), respectively. is preferred.
• the aromatic hydrocarbon group, aliphatic cyclic group, or chain alkyl group in Rd 1 is represented by the above general formulas (y-al-1) to (y-al-7) as substituents.
• an aromatic hydrocarbon group in Rd 1 in formula (d3-1), an aliphatic cyclic group , or V′ 101 in the above general formulas (y-al-1) to (y-al-7) is bonded to a carbon atom constituting a chain alkyl group.
• the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and a polycyclic structure containing a bicyclooctane skeleton (a polycyclic structure consisting of a bicyclooctane skeleton and a ring structure other than this). More preferably, the aliphatic cyclic group is a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
• a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
• the chain alkyl group preferably has 1 to 10 carbon atoms, and specific examples thereof include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group and octyl group.
• nonyl group linear alkyl group such as decyl group; 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1- Examples include branched chain alkyl groups such as ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, and 4-methylpentyl.
• the chain alkyl group is a fluorinated alkyl group having a fluorine atom or a fluorinated alkyl group as a substituent
• the number of carbon atoms in the fluorinated alkyl group is preferably 1 to 11, more preferably 1 to 8, 1 to 4 are more preferred.
• the fluorinated alkyl group may contain atoms other than fluorine atoms. Atoms other than a fluorine atom include, for example, an oxygen atom, a sulfur atom, a nitrogen atom, and the like.
• M m+ is an m-valent organic cation.
• the same cations as those represented by the general formulas (ca-1) to (ca-5) are preferably exemplified, and represented by the general formula (ca-1).
• Cationic is more preferred.
• Component (d1-1) may be used alone or in combination of two or more.
• Rd 2 is an optionally substituted cyclic group, an optionally substituted chain alkyl group, or an optionally substituted cyclic group. It is a good chain alkenyl group, and examples thereof are the same as those described above for R'201 .
• the carbon atom adjacent to the S atom in Rd 2 is not bonded to a fluorine atom (not fluorine-substituted).
• the anion of component (d1-2) becomes a moderately weak acid anion, and the quenching ability of component (D) is improved.
• Rd 2 is preferably a chain alkyl group optionally having a substituent or an aliphatic cyclic group optionally having a substituent, and an aliphatic ring optionally having a substituent More preferably, it is a formula group.
• the chain alkyl group preferably has 1 to 10 carbon atoms, more preferably 3 to 10 carbon atoms.
• Examples of the aliphatic cyclic group include groups obtained by removing one or more hydrogen atoms from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. (optionally having a substituent); is more preferably a group from which a hydrogen atom is removed.
• the hydrocarbon group of Rd 2 may have a substituent, and examples of the substituent include the hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group , a chain alkyl group) may have the same substituents.
• M m+ is an m-valent organic cation and is the same as M m+ in formula (d1-1).
• Component (d1-2) may be used alone or in combination of two or more.
• Rd 3 is an optionally substituted cyclic group, an optionally substituted chain alkyl group, or an optionally substituted It is a chain alkenyl group, and includes the same groups as those described above for R' 201 , preferably a cyclic group containing a fluorine atom, a chain alkyl group, or a chain alkenyl group. Among them, a fluorinated alkyl group is preferred, and the same fluorinated alkyl group as Rd 1 is more preferred.
• Rd 4 is an optionally substituted cyclic group, an optionally substituted chain alkyl group, or an optionally substituted chain It is an alkenyl group, and examples thereof are the same as those described above for R'201 . Among them, an optionally substituted alkyl group, alkoxy group, alkenyl group, and cyclic group are preferable.
• the alkyl group for Rd 4 is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specifically, a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like.
• a portion of the hydrogen atoms of the alkyl group of Rd4 may be substituted with a hydroxyl group, a cyano group, or the like.
• the alkoxy group for Rd 4 is preferably an alkoxy group having 1 to 5 carbon atoms, and specific examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, Examples include n-butoxy group and tert-butoxy group. Among them, a methoxy group and an ethoxy group are preferable.
• the alkenyl group for Rd 4 includes the same alkenyl groups as those for R' 201 , preferably vinyl, propenyl (allyl), 1-methylpropenyl and 2-methylpropenyl groups. These groups may further have an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms as a substituent.
• the cyclic group for Rd 4 includes the same cyclic group as the cyclic group for R' 201 , and one or more selected from cycloalkanes such as cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. or an aromatic group such as a phenyl group or a naphthyl group.
• cycloalkanes such as cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
• an aromatic group such as a phenyl group or a naphthyl group.
• Yd 1 is a single bond or a divalent linking group.
• the divalent linking group for Yd 1 is not particularly limited, but may be a divalent hydrocarbon group (aliphatic hydrocarbon group, aromatic hydrocarbon group) optionally having a substituent, a bivalent heteroatom-containing and the like. Each of these is a divalent hydrocarbon group optionally having a substituent, a heteroatom-containing 2 The same as the valence linking group can be mentioned.
• Yd 1 is preferably a carbonyl group, an ester bond, an amide bond, an alkylene group, or a combination thereof.
• the alkylene group is more preferably a linear or branched alkylene group, more preferably a methylene group or an ethylene group.
• M m+ is an m-valent organic cation and is the same as M m+ in formula (d1-1).
• Component (d1-3) may be used alone or in combination of two or more.
• any one of the above components (d1-1) to (d1-3) may be used alone, or two or more of them may be used in combination.
• the content of the component (D1) in the resist composition is preferably 0.5 to 20 parts by mass, preferably 1 to 20 parts by mass, per 100 parts by mass of the component (A). 15 parts by mass is more preferable, and 3 to 10 parts by mass is even more preferable.
• the content of component (D1) is at least the preferred lower limit, particularly good lithography properties and resist pattern shape can be easily obtained. On the other hand, if it is equal to or less than the upper limit, the sensitivity can be maintained well, and the throughput is also excellent.
• (D1) Component manufacturing method The method for producing the components (d1-1) and (d1-2) is not particularly limited, and they can be produced by known methods. In addition, the method for producing component (d1-3) is not particularly limited, and for example, it is produced in the same manner as the method described in US2012-0149916.
• Component (D2) may contain a nitrogen-containing organic compound component (hereinafter referred to as "component (D2)") that does not correspond to component (D1) above.
• Component (D2) is not particularly limited as long as it acts as an acid diffusion control agent and does not correspond to component (D1), and any known component may be used.
• aliphatic amines are preferable, and among these, secondary aliphatic amines and tertiary aliphatic amines are more preferable.
• Aliphatic amines are amines having one or more aliphatic groups, which preferably have from 1 to 12 carbon atoms.
• Aliphatic amines include amines (alkylamines or alkylalcohol amines) in which at least one hydrogen atom of ammonia NH3 is substituted with an alkyl or hydroxyalkyl group having 12 or less carbon atoms, or cyclic amines.
• alkylamines and alkylalcoholamines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine and n-decylamine; - dialkylamines such as n-heptylamine, di-n-octylamine, dicyclohexylamine; trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine , tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, tri-n-dodecylamine; diethanolamine, triethanolamine, diisopropanolamine, trialkylamine; Alkyl alcohol amines such as isopropanolamine, di-n-n
• Cyclic amines include, for example, heterocyclic compounds containing a nitrogen atom as a heteroatom.
• the heterocyclic compound may be monocyclic (aliphatic monocyclic amine) or polycyclic (aliphatic polycyclic amine).
• Specific examples of aliphatic monocyclic amines include piperidine and piperazine.
• As the aliphatic polycyclic amine those having 6 to 10 carbon atoms are preferred. Specifically, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5 .4.0]-7-undecene, hexamethylenetetramine, 1,4-diazabicyclo[2.2.2]octane and the like.
• aliphatic amines include tris(2-methoxymethoxyethyl)amine, tris ⁇ 2-(2-methoxyethoxy)ethyl ⁇ amine, tris ⁇ 2-(2-methoxyethoxymethoxy)ethyl ⁇ amine, tris ⁇ 2 -(1-methoxyethoxy)ethyl ⁇ amine, tris ⁇ 2-(1-ethoxyethoxy)ethyl ⁇ amine, tris ⁇ 2-(1-ethoxypropoxy)ethyl ⁇ amine, tris[2- ⁇ 2-(2-hydroxy ethoxy)ethoxy ⁇ ethyl]amine, triethanolamine triacetate and the like, and triethanolamine triacetate is preferred.
• Aromatic amines include 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or derivatives thereof, tribenzylamine, 2,6-diisopropylaniline, 2,6-di-tert-butylpyridine, N-tert- butoxycarbonylpyrrolidine and the like.
• the (D2) component is preferably an alkylamine, more preferably a trialkylamine having 6 to 30 carbon atoms.
• the (D2) component may be used individually by 1 type, and may be used in combination of 2 or more type.
• the content of the component (D2) in the resist composition is preferably 0.01 to 5 parts by mass and 0.01 to 5 parts by mass per 100 parts by mass of the component (A). 1 to 5 parts by mass is more preferable, and 0.1 to 1 part by mass is even more preferable.
• the content of the component (D2) is at least the preferred lower limit, particularly good lithography properties and resist pattern shape are likely to be obtained. On the other hand, if it is equal to or less than the upper limit, the sensitivity can be maintained well, and the throughput is also excellent.
• the component (D) preferably contains the component (D2).
• the content of component (D2) is preferably 50% by mass or more, preferably 70% by mass or more, and 90% by mass. More preferably, the component (D) may consist of the component (D2) only.
• the resist composition of the present embodiment contains, as optional components, an organic carboxylic acid and a phosphorus oxoacid and its derivatives for the purpose of preventing deterioration in sensitivity and improving resist pattern shape, storage stability over time, and the like.
• At least one compound (E) selected from the group consisting of (hereinafter referred to as "component (E)") can be contained.
• organic carboxylic acids include acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like, with salicylic acid being preferred.
• Phosphorus oxoacids include phosphoric acid, phosphonic acid, phosphinic acid, etc. Among these, phosphonic acid is particularly preferred.
• Examples of the oxoacid derivative of phosphorus include esters obtained by substituting a hydrogen atom of the above oxoacid with a hydrocarbon group. 6 to 15 aryl groups and the like.
• Derivatives of phosphoric acid include phosphoric acid esters such as di-n-butyl phosphate and diphenyl phosphate.
• Phosphonic acid derivatives include phosphonic acid esters such as dimethyl phosphonic acid, di-n-butyl phosphonic acid, phenylphosphonic acid, diphenyl phosphonic acid and dibenzyl phosphonic acid.
• Phosphinic acid derivatives include phosphinic acid esters and phenylphosphinic acid.
• the component (E) may be used alone or in combination of two or more.
• the content of component (E) is preferably 0.01 to 5 parts by mass, preferably 0.05 to 3 parts by mass, per 100 parts by mass of component (A). is more preferred.
• the resist composition of the present embodiment may contain a fluorine additive component (hereinafter referred to as "component (F)").
• Component (F) is used to impart water repellency to the resist film, and is used as a resin separate from component (A) to improve lithography properties.
• component (F) for example, JP-A-2010-002870, JP-A-2010-032994, JP-A-2010-277043, JP-A-2011-13569, JP-A-2011-128226. can be used. More specific examples of component (F) include polymers having a structural unit (f1) represented by the following general formula (f1-1).
• this polymer examples include a polymer (homopolymer) consisting only of a structural unit (f1) represented by the following formula (f1-1); a copolymer of the structural unit (f1) and the structural unit (a1). it is preferably a copolymer of the structural unit (f1), a structural unit derived from acrylic acid or methacrylic acid, and the structural unit (a1), and the structural unit (f1) and the structural unit (a1) It is more preferably a copolymer with.
• the structural unit (a1) to be copolymerized with the structural unit (f1) a structural unit derived from 1-ethyl-1-cyclooctyl (meth)acrylate, 1-methyl-1-adamantyl ( Structural units derived from meth)acrylate are preferred, and structural units derived from 1-ethyl-1-cyclooctyl (meth)acrylate are more preferred.
• R is the same as defined above, and Rf 102 and Rf 103 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. and Rf 102 and Rf 103 may be the same or different.
• nf 1 is an integer of 0 to 5
• Rf 101 is an organic group containing a fluorine atom.
• R bonded to the ⁇ -position carbon atom is the same as described above.
• R is preferably a hydrogen atom or a methyl group.
• a fluorine atom is preferable as the halogen atom for Rf102 and Rf103 .
• Examples of the alkyl group having 1 to 5 carbon atoms for Rf 102 and Rf 103 include the same alkyl groups having 1 to 5 carbon atoms as the above R, and a methyl group or an ethyl group is preferable.
• halogenated alkyl group having 1 to 5 carbon atoms for Rf 102 and Rf 103 , specifically, a group in which some or all of the hydrogen atoms in the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. is mentioned.
• a fluorine atom is preferable as the halogen atom.
• Rf 102 and Rf 103 are preferably a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom, a fluorine atom, a methyl group, or an ethyl group, and still more preferably a hydrogen atom.
• nf 1 is an integer of 0 to 5, preferably an integer of 0 to 3, more preferably 1 or 2.
• Rf 101 is an organic group containing a fluorine atom, preferably a hydrocarbon group containing a fluorine atom.
• the hydrocarbon group containing a fluorine atom may be linear, branched or cyclic, and preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms. More preferably, one having 1 to 10 carbon atoms is particularly preferred.
• 25% or more of the hydrogen atoms in the hydrocarbon group are preferably fluorinated, more preferably 50% or more are fluorinated, and 60% or more are Fluorination is particularly preferred because the hydrophobicity of the resist film during immersion exposure increases.
• Rf 101 is more preferably a fluorinated hydrocarbon group having 1 to 6 carbon atoms, such as a trifluoromethyl group, —CH 2 —CF 3 , —CH 2 —CF 2 —CF 3 , —CH(CF 3 ) 2 , -CH 2 -CH 2 -CF 3 , -CH 2 -CH 2 -CF 2 -CF 2 -CF 3 are particularly preferred.
• the weight-average molecular weight (Mw) of component (F) is preferably 1,000 to 50,000, more preferably 5,000 to 40,000, and most preferably 10,000 to 30,000. When it is at most the upper limit of this range, it has sufficient solubility in a resist solvent for use as a resist, and when it is at least the lower limit of this range, the resist film has good water repellency.
• the dispersity (Mw/Mn) of component (F) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.0 to 2.5.
• the component (F) may be used alone or in combination of two or more.
• the content of component (F) is preferably 0.5 to 10 parts by mass, preferably 1 to 10 parts by mass, per 100 parts by mass of component (A). Part is more preferred.
• the resist composition of the present embodiment can be produced by dissolving a resist material in an organic solvent component (hereinafter referred to as "(S) component").
• the component (S) is not particularly limited as long as it can dissolve each component to be used to form a uniform solution. can be used.
• Examples of component (S) include lactones such as ⁇ -butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; ethylene glycol, diethylene glycol, propylene glycol.
• polyhydric alcohols such as dipropylene glycol; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; Derivatives of polyhydric alcohols such as compounds having an ether bond such as monoalkyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether of compounds [among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred]; cyclic ethers such as dioxane, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate , methyl methoxypropionate, ethyl ethoxypropionat
• the (S) component may be used singly or as a mixed solvent of two or more.
• PGMEA, PGME, ⁇ -butyrolactone, EL, and cyclohexanone are preferred.
• a mixed solvent obtained by mixing PGMEA and a polar solvent is also preferable as the component (S).
• the blending ratio (mass ratio) thereof may be appropriately determined in consideration of compatibility between PGMEA and the polar solvent, etc., preferably 1:9 to 9:1, more preferably 2:8 to 8:2. It is preferable to be within the range. More specifically, when EL or cyclohexanone is blended as a polar solvent, the mass ratio of PGMEA:EL or cyclohexanone is preferably 1:9 to 9:1, more preferably 2:8 to 8:2. .
• the mass ratio of PGMEA:PGME is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, still more preferably 3:7 to 7: 3.
• a mixed solvent of PGMEA, PGME and cyclohexanone is also preferred.
• a mixed solvent of at least one selected from PGMEA and EL and ⁇ -butyrolactone is also preferable.
• the mass ratio of the former to the latter is preferably 70:30 to 95:5.
• the content of the (S) component in the resist composition of the present embodiment is appropriately adjusted so that the solid content concentration of the resist composition is 15% by mass or more.
• the resist composition of the present invention further optionally contains miscible additives such as additional resins, dissolution inhibitors, plasticizers, stabilizers, colorants, antihalation agents to improve the performance of the resist film. , dyes, etc. can be added and contained as appropriate.
• miscible additives such as additional resins, dissolution inhibitors, plasticizers, stabilizers, colorants, antihalation agents to improve the performance of the resist film. , dyes, etc. can be added and contained as appropriate.
• the resist composition of the present embodiment after dissolving the resist material in the (S) component, impurities and the like may be removed using a polyimide porous film, a polyamideimide porous film, or the like.
• the resist composition may be filtered using a filter composed of a polyimide porous membrane, a filter composed of a polyamideimide porous membrane, a filter composed of a polyimide porous membrane and a polyamideimide porous membrane, or the like.
• the polyimide porous film and the polyamideimide porous film include those described in JP-A-2016-155121.
• the resist composition of the present embodiment described above contains a resin (A), an acid generator (B), and a cross-linking agent (C), and the resin (A) has a LogP of 2.8 or less.
• the acid generator (B), which is an alkali-soluble resin contains a compound (B0) having a molar extinction coefficient of 10000 mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 or less at a wavelength of 248 nm.
• the compound (B0) Since the compound (B0) has a molar absorption coefficient of 10000 mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 or less at a wavelength of 248 nm, the light of the resist film formed by the resist composition containing the compound (B0) (typically (KrF excimer laser) improves the transmittance, and the reaction of generating acid from the compound (B0) is more likely to occur uniformly. Therefore, even in the resist composition of the present embodiment, which has a solid content concentration of 15% by mass or more and is suitable for forming a thick film, even near the support interface of the resist film formed using the resist composition, acid reaction is sufficiently carried out.
• the resist composition of the present embodiment which has a solid content concentration of 15% by mass or more and is suitable for forming a thick film, even near the support interface of the resist film formed using the resist composition, acid reaction is sufficiently carried out.
• the alkali-soluble resin has a LogP of 2.8 or less and has the structural unit (a20) in addition to the structural unit (a10), so that the solubility in the developer is moderate. Therefore, it is presumed that the resist composition of the present embodiment containing the (B0) component and the alkali-soluble resin can form a resist pattern with good resolution, DOF, and pattern shape. .
• a method for forming a resist pattern according to a second aspect of the present invention comprises the steps of forming a resist film on a support using the resist composition according to the first aspect of the present invention described above, and exposing the resist film to light. and developing the resist film after the exposure to form a resist pattern.
• a resist pattern forming method includes, for example, a resist pattern forming method performed as follows.
• the resist composition of the above-described embodiment is applied onto a support with a spinner or the like, and is then baked (post-apply bake (PAB)) at a temperature of, for example, 80 to 150° C. for 40 to 120 seconds, preferably. is applied for 60 to 100 seconds to form a resist film.
• the resist film is exposed through a mask having a predetermined pattern (mask pattern) using an exposure apparatus such as a KrF exposure apparatus, or is drawn by direct electron beam irradiation without a mask pattern.
• baking post-exposure baking (PEB)) treatment is performed at a temperature of 80 to 150° C. for 40 to 120 seconds, preferably 40 to 90 seconds.
• the developing process is performed using an alkaline developer in the case of the alkali development process, and using a developer containing an organic solvent (organic developer) in the case of the solvent development process.
• the content of the organic solvent in the organic developer is preferably 95% by mass or more, more preferably 99% by mass or more, still more preferably over 99.9% by mass, and 100% by mass. That is, the organic developer may consist of only an organic solvent.
• Rinsing treatment is preferably performed after the development treatment.
• the rinsing treatment water rinsing using pure water is preferable in the case of the alkali developing process, and a rinsing solution containing an organic solvent is preferably used in the case of the solvent developing process.
• a processing for removing the developer or the rinsing liquid adhering to the pattern with a supercritical fluid may be performed.
• drying is performed.
• baking treatment post-baking
• a resist pattern can be formed.
• the support is not particularly limited, and conventionally known ones can be used. Examples thereof include substrates for electronic components and substrates on which a predetermined wiring pattern is formed. More specifically, silicon wafers, metal substrates such as copper, chromium, iron, and aluminum substrates, glass substrates, and the like can be used. As a material for the wiring pattern, for example, copper, aluminum, nickel, gold or the like can be used.
• the wavelength used for exposure is not particularly limited, and includes ArF excimer laser, KrF excimer laser, F2 excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-rays, soft X-rays, and the like. It can be done with radiation.
• the resist composition is highly useful for KrF excimer laser, ArF excimer laser, EB or EUV, and the resist composition has a molar extinction coefficient of 10000 mol ⁇ 1 L cm ⁇ 1 or less at a wavelength of 248 nm. Since it contains the compound (B0), it is more useful as a KrF excimer laser.
• the exposure method of the resist film may be normal exposure (dry exposure) performed in air or an inert gas such as nitrogen, or may be liquid immersion lithography.
• immersion exposure the space between the resist film and the lowest lens of the exposure device is filled in advance with a solvent (immersion medium) having a refractive index greater than that of air, and exposure (immersion exposure) is performed in this state.
• a solvent having a refractive index higher than that of air and lower than that of the resist film to be exposed is preferable. Examples include hydrogen-based solvents. Water is preferably used as the immersion medium.
• Examples of the alkaline developer used for development processing in the alkaline development process include a 0.1 to 10% by mass tetramethylammonium hydroxide (TMAH) aqueous solution.
• the organic solvent contained in the organic developer used for development in the solvent development process may be any one capable of dissolving the component (A) (component (A) before exposure), and may be selected from known organic solvents. It can be selected as appropriate. Specific examples include polar solvents such as ketone-based solvents, ester-based solvents, alcohol-based solvents, nitrile-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents.
• An alcoholic solvent is an organic solvent containing an alcoholic hydroxyl group in its structure.
• "Alcoholic hydroxyl group” means a hydroxyl group attached to a carbon atom of an aliphatic hydrocarbon group.
• a nitrile-based solvent is an organic solvent containing a nitrile group in its structure.
• An amide-based solvent is an organic solvent containing an amide group in its structure.
• Ether-based solvents are organic solvents containing C—O—C in their structure.
• organic solvents there are also organic solvents that contain a plurality of types of functional groups that characterize each of the above solvents in their structures.
• diethylene glycol monomethyl ether corresponds to both alcohol-based solvents and ether-based solvents in the above classification.
• the hydrocarbon-based solvent is a hydrocarbon solvent that is composed of an optionally halogenated hydrocarbon and has no substituents other than halogen atoms. A fluorine atom is preferable as the halogen atom.
• the organic solvent contained in the organic developer among the above, polar solvents are preferable, and ketone-based solvents, ester-based solvents, nitrile-based solvents and the like are preferable.
• ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, and methyl ethyl ketone.
• methyl amyl ketone (2-heptanone) is preferable as the ketone solvent.
• ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol.
• nitrile-based solvents examples include acetonitrile, propionitrile, valeronitrile, and butyronitrile.
• additives can be added to the organic developer as needed.
• additives include surfactants.
• the surfactant is not particularly limited, for example, ionic or nonionic fluorine-based and/or silicon-based surfactants can be used.
• a nonionic surfactant is preferable, and a nonionic fluorine-based surfactant or a nonionic silicon-based surfactant is more preferable.
• a surfactant When a surfactant is blended, its blending amount is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and 0.01 to 0.5% by mass, relative to the total amount of the organic developer. 5% by mass is more preferred.
• the development treatment can be carried out by a known development method, for example, a method of immersing the support in a developer for a certain period of time (dip method), or a method in which the developer is piled up on the surface of the support by surface tension and remains stationary for a certain period of time. method (paddle method), method of spraying the developer onto the surface of the support (spray method), and application of the developer while scanning the developer dispensing nozzle at a constant speed onto the support rotating at a constant speed.
• a continuous method dynamic dispensing method
• the organic solvent contained in the rinsing solution used for the rinsing treatment after the development treatment in the solvent development process for example, among the organic solvents exemplified as the organic solvents used for the organic developer, those that hardly dissolve the resist pattern are appropriately selected.
• the organic solvents exemplified as the organic solvents used for the organic developer those that hardly dissolve the resist pattern are appropriately selected.
• at least one solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents is used.
• at least one selected from hydrocarbon-based solvents, ketone-based solvents, ester-based solvents, alcohol-based solvents and amide-based solvents is preferable, and at least one selected from alcohol-based solvents and ester-based solvents is preferable.
• the alcohol-based solvent used in the rinse liquid is preferably a monohydric alcohol having 6 to 8 carbon atoms, and the monohydric alcohol may be linear, branched or cyclic. Specific examples include 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, and benzyl alcohol. be done. Among these, 1-hexanol, 2-heptanol and 2-hexanol are preferred, and 1-hexanol and 2-hexanol are more preferred.
• any one of these organic solvents may be used alone, or two or more thereof may be used in combination. Moreover, you may mix with organic solvents and water other than the above, and you may use it. However, considering development characteristics, the amount of water in the rinse solution is preferably 30% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and 3% by mass, relative to the total amount of the rinse solution. % or less is particularly preferred.
• Known additives can be added to the rinse solution as needed. Examples of such additives include surfactants. Examples of surfactants include those mentioned above, preferably nonionic surfactants, more preferably nonionic fluorine-based surfactants or nonionic silicon-based surfactants. When a surfactant is blended, its blending amount is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and 0.01 to 0.5% by mass, relative to the total amount of the rinse liquid. % is more preferred.
• the rinsing treatment (cleaning treatment) using the rinsing liquid can be performed by a known rinsing method.
• the rinsing method include a method of continuously applying a rinse solution onto a support rotating at a constant speed (rotation coating method), a method of immersing a support in a rinse solution for a given period of time (dip method), A method of spraying a rinsing liquid onto the support surface (spray method) and the like can be mentioned.
• the resist pattern forming method of the present embodiment described above since the resist composition described above is used, it is possible to form a resist pattern having excellent resolution, DOF, and pattern shape. . Also, for example, a resist pattern with a film thickness of 1 to 10 ⁇ m can be produced with good resolution, DOF, and pattern shape.
• the material does not contain impurities such as metals, metal salts containing halogens, acids, alkalis, components containing sulfur atoms or phosphorus atoms.
• impurities containing metal atoms include Na, K, Ca, Fe, Cu, Mn, Mg, Al, Cr, Ni, Zn, Ag, Sn, Pb, Li, and salts thereof. can.
• the content of impurities contained in these materials is preferably 200 ppb or less, more preferably 1 ppb or less, still more preferably 100 ppt (parts per trillion) or less, particularly preferably 10 ppt or less, and substantially free (of the measuring device). below the detection limit) is most preferred.
• the numbers in [ ] are compounding amounts (mass parts).
• (A)-1 A polymer compound represented by the following chemical formula (A-1).
• the weight average molecular weight (Mw) in terms of standard polystyrene obtained by GPC measurement was 2500, and the degree of dispersion (Mw/Mn) was 1.2.
• the LogP value of the polymer compound calculated by the method described above is 2.63.
• (A)-2 A polymer compound represented by the following chemical formula (A-2).
• the weight average molecular weight (Mw) in terms of standard polystyrene obtained by GPC measurement was 2500, and the degree of dispersion (Mw/Mn) was 1.2.
• the LogP value of the polymer compound calculated by the method described above is 2.65.
• the weight average molecular weight (Mw) in terms of standard polystyrene obtained by GPC measurement was 2500, and the degree of dispersion (Mw/Mn) was 1.5.
• the LogP value of the polymer compound calculated by the method described above is 2.64.
• (A)-4 A polymer compound represented by the following chemical formula (A-4).
• the weight average molecular weight (Mw) in terms of standard polystyrene obtained by GPC measurement was 2500, and the degree of dispersion (Mw/Mn) was 1.5.
• the LogP value of the polymer compound calculated by the method described above is 2.78.
• (A)-5 A polymer compound represented by the following chemical formula (A-5).
• the weight average molecular weight (Mw) in terms of standard polystyrene obtained by GPC measurement was 2500, and the degree of dispersion (Mw/Mn) was 1.5.
• (A)-11 A polymer compound represented by the following chemical formula (A-11).
• the weight average molecular weight (Mw) in terms of standard polystyrene obtained by GPC measurement was 2500, and the degree of dispersion (Mw/Mn) was 1.2.
• the LogP value of the polymer compound calculated by the method described above is 2.62.
• (A)-12 A polymer compound represented by the following chemical formula (A-12).
• the weight average molecular weight (Mw) in terms of standard polystyrene obtained by GPC measurement was 2500, and the degree of dispersion (Mw/Mn) was 1.2.
• the LogP value of the polymer compound calculated by the method described above is 2.92.
• the molar extinction coefficient of the component (B) was calculated by measuring the absorbance of the component (B) at a wavelength of 248 nm with a spectrophotometer and using the Beer-Lambert law. Specifically, the component (B) is dissolved in acetonitrile, this solution is placed in a cell with an optical path length of 10 mm, the UV spectrum is measured with a spectrophotometer (UV-3600, manufactured by Shimadzu Corporation), and the absorbance at a wavelength of 248 nm is measured. Acquired.
• the molar extinction coefficient ⁇ (mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 ) was calculated from the obtained absorbance and solution concentration using the Beer-Lambert law.
• the molar extinction coefficient ⁇ (mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 ) calculated by the above method is also shown below the chemical formula below.
• (B0)-1 Acid generator comprising a compound represented by the following chemical formula (B0-1).
• (B0)-2 An acid generator comprising a compound represented by the following chemical formula (B0-2).
• (B0)-3 Acid generator comprising a compound represented by the following chemical formula (B0-3).
• (B0)-4 Acid generator comprising a compound represented by the following chemical formula (B0-4).
• (B0)-5 Acid generator comprising a compound represented by the following chemical formula (B0-5).
• (B0)-6 An acid generator comprising a compound represented by the following chemical formula (B0-6).
• (B0)-7 Acid generator comprising a compound represented by the following chemical formula (B0-7).
• (B1)-1 an acid generator comprising a compound represented by the following chemical formula (B1-1).
• (B1)-2 an acid generator comprising a compound represented by the following chemical formula (B1-2).
• (C)-1 A cross-linking agent comprising a compound represented by the following chemical formula (C-1).
• (D)-1 tri-n-pentylamine.
• (S)-1 propylene glycol monomethyl ether acetate
• (S)-2 propylene glycol monomethyl ether
• ⁇ Formation of resist pattern> Each resist composition of each example was applied using a spinner onto an 8-inch silicon wafer that had been treated with hexamethyldisilazane (HMDS) at 110° C. for 60 seconds.
• a pre-baking (PAB) treatment was performed on a hot plate at 90° C. for 60 seconds and dried to form a resist film having a thickness of 2 ⁇ m.
• TMAH tetramethylammonium hydroxide
• NMD-3 aqueous solution
• post-baking was performed at 100° C. for 60 seconds. As a result, an isolated space pattern with a width of 500 nm was formed.

Landscapes

• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Materials For Photolithography (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Publications (1)

Family

ID=86999107

Family Applications (1)

Country Status (5)

Citations (8)

Family Cites Families (1)

• 2022
  • 2022-12-22 CN CN202280085974.7A patent/CN118451370A/zh active Pending
  • 2022-12-22 WO PCT/JP2022/047424 patent/WO2023127692A1/ja not_active Ceased
  • 2022-12-22 JP JP2023570936A patent/JPWO2023127692A1/ja active Pending
  • 2022-12-22 KR KR1020247021251A patent/KR20240127977A/ko active Pending
  • 2022-12-22 US US18/714,420 patent/US20250355354A1/en active Pending

Patent Citations (8)

Also Published As

Similar Documents

Legal Events