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
  • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/01—Sulfonic acids
  • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
  • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
  • C07C309/07—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton
  • C07C309/12—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing esterified hydroxy groups bound to the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/01—Sulfonic acids
  • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
  • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
  • C07C309/17—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing carboxyl groups bound to the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/01—Sulfonic acids
  • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
  • C07C309/19—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of a saturated carbon skeleton containing rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
  • C07C381/12—Sulfonium compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
  • C07C65/01—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups
  • C07C65/03—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups monocyclic and having all hydroxy or O-metal groups bound to the ring
  • C07C65/05—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups monocyclic and having all hydroxy or O-metal groups bound to the ring o-Hydroxy carboxylic acids
  • C07C65/10—Salicylic acid
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
  • C07D207/10—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D207/16—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
  • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
  • C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D211/60—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
  • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
  • C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D211/60—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
  • C07D211/62—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals attached in position 4
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
  • C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
  • C07D327/06—Six-membered rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
  • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
  • C07D333/46—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
  • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
  • C07D333/76—Dibenzothiophenes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
  • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
  • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
  • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
  • C07D491/10—Spiro-condensed systems
  • C07D491/113—Spiro-condensed systems with two or more oxygen atoms as ring hetero atoms in the oxygen-containing ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
  • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
  • C07D493/10—Spiro-condensed systems
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1807—C7-(meth)acrylate, e.g. heptyl (meth)acrylate or benzyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
  • C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
  • C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
  • C08F220/365—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate containing further carboxylic moieties
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/38—Esters containing sulfur
  • C08F220/382—Esters containing sulfur and containing oxygen, e.g. 2-sulfoethyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
• • 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
  • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
• • 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
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
  • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—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
  • G03F7/20—Exposure; Apparatus therefor
  • G03F7/2041—Exposure; Apparatus therefor in the presence of a fluid, e.g. immersion; using fluid cooling means

Definitions

• the present invention relates to a radiation-sensitive resin composition, a pattern forming method, and an onium salt compound.
• Photolithography technology using a resist composition is used to form fine circuits in semiconductor devices.
• an acid is generated by exposure to a film of a resist composition by irradiation via a mask pattern, and an alkali-based resin is used in an exposed portion and an unexposed portion by a reaction using the acid as a catalyst.
• a resist pattern is formed on the substrate by causing a difference in solubility in an organic developer.
• the above photolithography technology uses short-wavelength radiation such as an ArF excimer laser, and is an immersion exposure method (liquid immersion) in which the space between the lens of the exposure device and the resist film is filled with a liquid medium.
• short-wavelength radiation such as an ArF excimer laser
• immersion exposure method liquid immersion
• Patent Document 1 lithography using shorter wavelength radiation such as electron beam, X-ray and EUV (extreme ultraviolet) is also being studied.
• LWR line widow roughness
• CDU critical dimension uniformity
• An object of the present invention is to provide a radiation-sensitive resin composition, a pattern forming method, and an onium salt compound capable of exhibiting sensitivity, LWR performance, and CDU performance at a sufficient level.
• the present invention includes an onium salt compound represented by the following formula (1) (hereinafter, also referred to as “onium salt compound (1)”).
• a resin containing a structural unit having an acid dissociative group Regarding a radiation-sensitive resin composition containing a solvent.
• R 1 is a monovalent hydrocarbon group having 1 to 20 carbon atoms.
• R 2 and R 3 are independently monovalent hydrocarbon groups having 1 to 20 carbon atoms, or a ring composed of carbon atoms in which R 2 and R 3 are combined with each other and bonded to each other. It represents an annular structure with 3 to 20 members.
• R 4 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms
• L 1 is a substituted or unsubstituted divalent linking group having 1 to 40 carbon atoms
• R 4 And L 1 represent a group containing a heterocyclic structure having 3 to 20 ring members, which is combined with each other and is composed of a nitrogen atom to which they are bonded.
• L 2 is a single bond or a substituted or unsubstituted divalent linking group having 1 to 40 carbon atoms.
• R f1 and R f2 are independently hydrogen atoms, fluorine atoms, monovalent hydrocarbon groups having 1 to 10 carbon atoms, or monovalent fluorinated hydrocarbon groups having 1 to 10 carbon atoms.
• n is an integer of 1 to 4.
• Z + is a monovalent radiation-sensitive onium cation.
• the radiation-sensitive resin composition can exhibit excellent sensitivity, LWR performance, and CDU performance when forming a resist pattern.
• the onium salt compound (1) is presumed to function as a quencher (acid diffusion control agent).
• the acid generated from the onium salt compound (1) or other radiation-sensitive acid generator by exposure deprotects the tertiary alkoxycarbonyl group that protects the nitrogen atom in the onium salt compound (1) molecule. It is considered that the sulfonic acid anion and the ammonium cation coexist to form an intramolecular salt to be in a dissolved state.
• the onium salt compound (1) in the form of an intramolecular salt no longer has a citric acid function, the generated acid is not captured in the exposed portion, and therefore, the sensitivity of the radiation-sensitive resin composition is increased. ..
• the unexposed portion the protected nitrogen atom maintains an appropriate basicity, and can exhibit an acid trapping function. In this way, the high sensitivity due to the disappearance of the quencher function in the exposed part and the quencher function in the unexposed part combine to increase the contrast between the exposed part and the unexposed part, and the above-mentioned resist performances are exhibited. Inferred. Further, since the solubility in the developing solution is increased in the exposed portion, the generation of residue is suppressed, and it is presumed that this point also contributes to the improvement of the contrast.
• the present invention comprises a step of directly or indirectly applying the radiation-sensitive resin composition onto a substrate to form a resist film.
• the process of exposing the resist film and The present invention relates to a pattern forming method including a step of developing the exposed resist film with a developing solution.
• the present invention relates to an onium salt compound represented by the following formula (1) (that is, an onium salt compound (1)) in still another embodiment.
• R 1 is a monovalent hydrocarbon group having 1 to 20 carbon atoms.
• R 2 and R 3 are independently monovalent hydrocarbon groups having 1 to 20 carbon atoms, or a ring composed of carbon atoms in which R 2 and R 3 are combined with each other and bonded to each other. It represents an annular structure with 3 to 20 members.
• R 4 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms
• L 1 is a substituted or unsubstituted divalent linking group having 1 to 40 carbon atoms
• R 4 And L 1 represent a group containing a heterocyclic structure having 3 to 20 ring members, which is combined with each other and is composed of a nitrogen atom to which they are bonded.
• L 2 is a single bond or a substituted or unsubstituted divalent linking group having 1 to 40 carbon atoms.
• R f1 and R f2 are independently hydrogen atoms, fluorine atoms, monovalent hydrocarbon groups having 1 to 10 carbon atoms, or monovalent fluorinated hydrocarbon groups having 1 to 10 carbon atoms.
• n is an integer of 1 to 4.
• Z + is a monovalent radiation-sensitive onium cation.
• the onium salt compound (1) can exhibit a quencher function disappears in the exposed portion and moderate basicity in the unexposed portion in the resist film, and therefore, when blended in a radiation-sensitive resin composition, a resist pattern is formed. It is possible to impart excellent sensitivity, LWR performance, and CDU performance to the composition.
• the radiation-sensitive resin composition according to the present embodiment contains a predetermined onium salt compound (1), a resin and a solvent. Further, if necessary, a radiation-sensitive acid generator is included.
• the above composition may contain other optional components as long as the effects of the present invention are not impaired.
• the radiation-sensitive resin composition can impart high levels of sensitivity, LWR performance and CDU performance to the radiation-sensitive resin composition.
• the onium salt compound (1) can function as a quencher (also referred to as a "photodisintegrating base” or “acid diffusion control agent") for capturing an acid before exposure or in an unexposed portion.
• the onium salt compound (1) is represented by the above formula (1).
• the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R 1 , R 2 , R 3 and R 4 is not particularly limited, and is a monovalent hydrocarbon group having 1 to 20 carbon atoms. Examples thereof include chain hydrocarbon groups, monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms, monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms, and combinations thereof.
• the monovalent chain hydrocarbon group having 1 to 20 carbon atoms includes, for example, a linear or branched saturated hydrocarbon group having 1 to 20 carbon atoms, or a linear or branched chain unsaturated group having 1 to 20 carbon atoms. Hydrocarbon groups and the like can be mentioned.
• Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a monocyclic or polycyclic saturated hydrocarbon group, a monocyclic or polycyclic unsaturated hydrocarbon group, and the like.
• a saturated hydrocarbon group of the monocycle a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group are preferable.
• As the polycyclic cycloalkyl group an alicyclic hydrocarbon group having a bridge such as a norbornyl group, an adamantyl group, a tricyclodecyl group and a tetracyclododecyl group is preferable.
• Examples of the monocyclic unsaturated hydrocarbon group include a monocyclic cycloalkenyl group such as a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group.
• Examples of the polycyclic unsaturated hydrocarbon group include a polycyclic cycloalkenyl group such as a norbornenyl group, a tricyclodecenyl group and a tetracyclododecenyl group.
• the Arihashi alicyclic hydrocarbon group is a polycyclic fat in which two carbon atoms that are not adjacent to each other among the carbon atoms constituting the alicyclic are bonded by a bond chain containing one or more carbon atoms.
• a cyclic hydrocarbon group is a polycyclic fat in which two carbon atoms that are not adjacent to each other among the carbon atoms constituting the alicyclic are bonded by a bond chain containing one or more carbon atoms.
• Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include an aryl group such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group and an anthryl group; a benzyl group, a phenethyl group and a naphthylmethyl group.
• Aralkill groups and the like can be mentioned.
• hydrogen atoms are formed from the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms. There is a structure in which one more is removed.
• R 1 , R 2 and R 3 are preferably chain hydrocarbon groups having 1 to 5 carbon atoms independently from the viewpoint of structural stability of the tertiary alkoxycarbonyl group.
• the substituted or unsubstituted divalent linking group represented by L 1 and L 2 having 1 to 40 carbon atoms for example, for example, a divalent linear chain having 1 to 40 carbon atoms.
• a divalent linear chain having 1 to 40 carbon atoms One selected from a cyclic or branched hydrocarbon group, a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, -CO-, -O-, -NH-, -S- and a cyclic acetal structure. Examples thereof include a group or a group formed by combining two or more of these groups.
• Examples of the divalent linear or branched hydrocarbon group having 1 to 40 carbon atoms include a methanediyl group, an ethanediyl group, a propanediyl group, a butanjiyl group, a hexanediyl group, and an octanediyl group. Of these, an alkanediyl group having 1 to 8 carbon atoms is preferable.
• Examples of the divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms include a monocyclic cycloalkandyl group such as a cyclopentanediyl group and a cyclohexanediyl group; and a polycycle such as a norbornandyl group and an adamantandiyl group. Cycloalkandyl group and the like. Of these, a cycloalkanediyl group having 5 to 12 carbon atoms is preferable.
• Examples of the substituent that replaces a part or all of the hydrogen atom of L 1 and L 2 include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, a hydroxy group, a carboxy group, a cyano group and a nitro group. Examples thereof include a group, an alkoxy group, an alkoxycarbonyl group, an alkoxycarbonyloxy group, an acyl group, and an acyloxy group.
• heterocyclic structure-containing linking group As a group containing a heterocyclic structure having 3 to 20 ring members, which is composed of a nitrogen atom in which R 4 and L 1 are combined with each other and bonded to each other (hereinafter, also referred to as “heterocyclic structure-containing linking group”). Examples thereof include a group containing an aromatic heterocyclic structure and a group containing an aliphatic heterocyclic structure.
• the heterocyclic structure also includes a 5-membered aromatic structure having aromaticity by introducing a heteroatom. Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom and the like.
• aromatic heterocyclic structure examples include oxygen atom-containing aromatic heterocyclic structures such as furan, pyran, benzofuran, and benzopyran; Nitrogen atom-containing aromatic heterocyclic structures such as pyrrole, imidazole, pyridine, pyrimidine, pyrazine, indole, quinoline, isoquinoline, acridine, phenazine, carbazole; Sulfur atom-containing aromatic heterocyclic structure such as thiophene; Examples thereof include an aromatic heterocyclic structure containing a plurality of heteroatoms such as thiazole, benzothiazole, thiazine, and oxazine.
• Examples of the aliphatic heterocyclic structure include oxygen atom-containing alicyclic heterocyclic structures such as oxylane, tetrahydrofuran, tetrahydropyran, dioxolane, and dioxane; Nitrogen atom-containing alicyclic heterocyclic structure such as aziridine, pyrrolidine, piperidine, piperazine; Sulfur atom-containing alicyclic heterocyclic structure such as thietan, thiolan, thian; Alicyclic heterocyclic structure containing multiple heteroatoms such as morpholine, 1,2-oxathiolane, 1,3-oxathiolane; Lactone structure, cyclic carbonate structure, cyclic acetal structure and sultone structure; Examples thereof include a spiro heterocyclic structure in which a plurality of the above aliphatic heterocyclic structures share and bond a quaternary carbon atom.
• the heterocyclic structure-containing linking group includes not only a heterocyclic structure containing a nitrogen atom, but also a heterocyclic structure containing a nitrogen atom, a heterocyclic structure containing a heteroatom other than the nitrogen atom, and the divalent shown as L1.
• a combination with at least one of the linking groups can also be preferably adopted.
• the heterocyclic structure containing a nitrogen atom a pyrrolidine structure or a piperidine structure is preferable.
• L2 is preferably a substituted or unsubstituted divalent chain hydrocarbon group having 1 to 10 carbon atoms.
• the monovalent hydrocarbon group having 1 to 10 carbon atoms represented by R f1 and R f2 is one of the monovalent hydrocarbon groups having 1 to 20 carbon atoms represented by R 1 .
• a structure corresponding to 1 to 10 carbon atoms can be preferably adopted.
• the monovalent fluorinated hydrocarbon group having 1 to 10 carbon atoms represented by R f1 and R f2 is, for example, a monovalent fluorinated chain hydrocarbon group having 1 to 10 carbon atoms.
• a monovalent fluorinated alicyclic hydrocarbon group having 3 to 10 carbon atoms and the like can be mentioned.
• Examples of the monovalent fluorinated chain hydrocarbon group having 1 to 10 carbon atoms include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a pentafluoroethyl group, and 2,2,3,3.
• 3-Pentafluoropropyl group 1,1,1,3,3,3-hexafluoropropyl group, heptafluoron-propyl group, heptafluoroi-propyl group, nonafluoron-butyl group, nonafluoroi-butyl group, Nonafluoro t-butyl group, 2,2,3,3,4,5,5-octafluoro n-pentyl group, tridecafluoro n-hexyl group, 5,5,5-trifluoro-1,1- Fluorinated alkyl groups such as diethylpentyl group; Fluorinated alkenyl groups such as trifluoroethenyl group and pentafluoropropenyl group; Examples thereof include a fluorinated alkynyl group such as a fluoroethynyl group and a trifluoropropynyl group.
• Examples of the monovalent fluorinated alicyclic hydrocarbon group having 3 to 10 carbon atoms include a fluorocyclopentyl group, a difluorocyclopentyl group, a nonafluorocyclopentyl group, a fluorocyclohexyl group, a difluorocyclohexyl group and an undecafluorocyclohexylmethyl group.
• Fluorinated cycloalkyl groups such as fluoronorbornyl group, fluoroadamantyl group, fluorobornyl group, fluoroisobornyl group, fluorotricyclodecyl group; Examples thereof include a fluorinated cycloalkenyl group such as a fluorocyclopentenyl group and a nonafluorocyclohexenyl group.
• the fluorinated hydrocarbon group the monovalent fluorinated chain hydrocarbon group having 1 to 10 carbon atoms is preferable, the monovalent fluorinated alkyl group having 1 to 10 carbon atoms is more preferable, and the fluorinated alkyl group has 1 to 10 carbon atoms.
• a perfluoroalkyl group of 6 is even more preferred, and a linear perfluoroalkyl group having 1 to 6 carbon atoms is particularly preferred.
• N is preferably an integer of 1 to 3, and more preferably 1 or 2.
• the anion moiety of the onium salt compound (1) represented by the above formula (1) is not particularly limited, and examples thereof include structures represented by the following formulas (1a) to (1z).
• Z + has the same meaning as the above formula (1).
• the monovalent radiosensitive onium cation represented by the above Z + includes, for example, S, I, O, N, P, Cl, Br, F, As, Se, Sn, Sb. , Te, Bi and the like, examples thereof include radiodegradable onium cations, and examples thereof include sulfonium cations, tetrahydrothiophenium cations, iodonium cations, phosphonium cations, diazonium cations, pyridinium cations and the like. Of these, sulfonium cations or iodonium cations are preferable.
• the sulfonium cation or the iodonium cation is preferably represented by the following formulas (X-1) to (X-6).
• Ra 1 , Ra 2 and Ra 3 are independently substituted or unsubstituted linear or branched alkyl groups having 1 to 12 carbon atoms, alkoxy groups or alkoxycarbonyls.
• Oxy group, substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 12 carbon atoms, substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, hydroxy group, halogen atom, -OSO 2 Represents a ring structure that is -RP , -SO 2 - RQ or -S- RT , or is composed of two or more of these groups combined with each other.
• the ring structure may contain heteroatoms such as O and S between the carbon-carbon bonds forming the skeleton.
• RP , RQ , and RT are independently substituted or unsubstituted linear or branched alkyl groups having 1 to 12 carbon atoms, and substituted or unsubstituted alicyclic groups having 5 to 25 carbon atoms. It is a hydrocarbon group or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms.
• k1, k2, and k3 are independently integers of 0 to 5.
• R b1 is a substituted or unsubstituted linear or branched alkyl group or alkoxy group having 1 to 20 carbon atoms, or an substituted or unsubstituted acyl group having 2 to 8 carbon atoms. , Or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 8 carbon atoms, or a hydroxy group.
• n k is 0 or 1. When n k is 0, k4 is an integer of 0 to 4, and when n k is 1, k4 is an integer of 0 to 7.
• the plurality of R b1s may be the same or different, and the plurality of R b1s may represent a ring structure configured by being combined with each other.
• R b2 is a substituted or unsubstituted linear or branched alkyl group having 1 to 7 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 or 7 carbon atoms.
• LC is a single bond or divalent linking group.
• k5 is an integer from 0 to 4.
• the plurality of R b2s may be the same or different, and the plurality of R b2s may represent a ring structure configured by being combined with each other.
• q is an integer of 0 to 3.
• the ring structure containing S + may contain a heteroatom such as O or S between the carbon-carbon bonds forming the skeleton.
• R c1 , R c2 , and R c3 are independently substituted or unsubstituted linear or branched alkyl groups having 1 to 12 carbon atoms.
• R g1 is a substituted or unsubstituted linear or branched alkyl group or alkoxy group having 1 to 20 carbon atoms, or an substituted or unsubstituted acyl group having 2 to 8 carbon atoms. , Or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 8 carbon atoms, or a hydroxy group.
• n k is 0 or 1. When n k2 is 0, k10 is an integer of 0 to 4, and when n k2 is 1, k10 is an integer of 0 to 7.
• R g1 When there are a plurality of R g1 , the plurality of R g1s may be the same or different, and the plurality of R g1s may represent a ring structure configured by being combined with each other.
• R g2 and R g3 are each independently substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, alkoxy group or alkoxycarbonyloxy group, substituted or unsubstituted carbon number 3 It is a monocyclic or polycyclic cycloalkyl group of ⁇ 12, an substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, a hydroxy group, a halogen atom, or these groups are combined with each other.
• k11 and k12 are independently integers of 0 to 4, respectively.
• R g2 and R g3 are each plural, the plurality of R g2 and R g3 may be the same or different from each other.
• R d1 and R d2 are independently substituted or unsubstituted linear or branched alkyl groups having 1 to 12 carbon atoms, alkoxy groups or alkoxycarbonyl groups, and substituted. Alternatively, it is an unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, a halogen atom, an alkyl halide group having 1 to 4 carbon atoms, a nitro group, or two or more of these groups are combined with each other. Represents a constituent ring structure.
• k6 and k7 are independently integers of 0 to 5. When there are a plurality of R d1 and R d2 , the plurality of R d1 and R d2 may be the same or different from each other.
• R e1 and R e2 are independently halogen atoms, substituted or unsubstituted linear or branched alkyl groups having 1 to 12 carbon atoms, or substituted or unsubstituted. It is an aromatic hydrocarbon group having 6 to 12 carbon atoms.
• k8 and k9 are independently integers of 0 to 4.
• the onium salt compound (1) is formed by any combination of the anion moiety defined by the above formula (1) and the above monovalent radiation-sensitive onium cation.
• Specific examples of the onium salt compound (1) are not particularly limited, but examples thereof include structures represented by the following formulas (1-1) to (1-26).
• the onium salt compound (1) represented by the above formulas (1-1) to (1-24) is preferable.
• the content of the onium salt compound (1) in the radiation-sensitive resin composition according to the present embodiment is 0.05 with respect to 100 parts by mass of the resin described later. More than parts by mass is more preferable, parts by mass of 0.1 parts or more are further preferable, and parts by mass or more are particularly preferable.
• the content is more preferably 25 parts by mass or less, further preferably 20 parts by mass or less, and particularly preferably 15 parts by mass or less.
• the content of the onium salt compound (1) is appropriately selected according to the type of resin used, the exposure conditions and required sensitivity, and the type and content of the radiation-sensitive acid generator described later. As a result, excellent sensitivity, LWR performance, and CDU performance can be exhibited when forming a resist pattern.
• onium salt compound (1) As the onium salt compound (1), a case where R 4 and L 1 form a piperidine ring structure will be described as an example. Typically, as shown in the scheme below, the halogenated alcohol compound is reacted with the protected piperidin carboxylic acid compound to form an ester compound, and the subdithionate is reacted with an oxidizing agent to form a sulfonate compound, and finally.
• the desired onium salt compound (1) can be synthesized by reacting with the onium cation halide corresponding to the onium cation moiety to promote salt exchange.
• R 1 , R 2 , R 3 , L 2 , R f1 , R f 2 and Z + and n are synonymous with the above formula (1).
• X h1 and X h 2 are halogen atoms.
• a halogenated alcohol body as a base of the anion moiety a carboxylic acid compound in which a nitrogen atom is protected, and a precursor corresponding to the onium cation moiety can be appropriately selected. Can be synthesized.
• the radiation-sensitive resin composition may contain other acid diffusion control agents as long as the effects of the present invention are not impaired.
• other acid diffusion control agents include onium salt compounds other than the onium salt compound (1), which generate a relatively weak acid as compared with the radiation-sensitive acid generator described later. Specific examples include compounds represented by the following formulas.
• Examples of other acid diffusion control agents include nitrogen-containing compounds other than the onium salt compound (1), and examples thereof include amine compounds, diamine compounds, polyamine compounds, amide group-containing compounds, urea compounds, and nitrogen-containing heterocyclic compounds. Can be mentioned. These nitrogen-containing compounds may be compounds having a tertiary alkoxycarbonyl group that protects a nitrogen atom. These acid diffusion control agents may be used alone or in combination of two or more.
• the resin is an aggregate of polymers having a structural unit containing an acid dissociative group (hereinafter, also referred to as “structural unit (I)”) (hereinafter, this resin is also referred to as “base resin”).
• the "acid dissociable group” is a group that replaces a hydrogen atom of a carboxy group, a phenolic hydroxyl group, an alcoholic hydroxyl group, a sulfo group, or the like, and means a group that dissociates by the action of an acid.
• the radiation-sensitive resin composition is excellent in pattern-forming property because the resin has a structural unit (I).
• the base resin preferably has a structural unit (II) containing at least one selected from the group consisting of a lactone structure, a cyclic carbonate structure, and a sultone structure, which will be described later, and the structural unit (I). ) And (II) may have other structural units.
• each structural unit will be described.
• the structural unit (I) is a structural unit containing an acid dissociative group.
• the structural unit (I) is not particularly limited as long as it contains an acid dissociative group.
• a structural unit having a tertiary alkyl ester moiety and a structure in which a hydrogen atom of a phenolic hydroxyl group is substituted with a tertiary alkyl group examples thereof include a structural unit having an acetal bond, and a structural unit represented by the following formula (3) from the viewpoint of improving the pattern forming property of the radiation-sensitive resin composition (hereinafter, “structure”).
• Unit (I-1) is preferable.
• R 7 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
• R 8 is a monovalent hydrocarbon group having 1 to 20 carbon atoms.
• R 9 and R 10 are independently monovalent chain hydrocarbon groups having 1 to 10 carbon atoms or monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms, or groups thereof. Represents a divalent alicyclic group having 3 to 20 carbon atoms, which are combined with each other and are composed of carbon atoms to which they are bonded.
• R7 a hydrogen atom and a methyl group are preferable, and a methyl group is more preferable, from the viewpoint of copolymerizability of the monomer giving the structural unit (I-1).
• Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R8 include a chain hydrocarbon group having 1 to 10 carbon atoms and a monovalent alicyclic hydrocarbon having 3 to 20 carbon atoms. Examples thereof include a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms.
• the chain hydrocarbon group having 1 to 10 carbon atoms represented by R 8 to R 10 is a linear or branched saturated hydrocarbon group having 1 to 10 carbon atoms, or a linear hydrocarbon group having 1 to 10 carbon atoms.
• Branch chain unsaturated hydrocarbon groups can be mentioned.
• Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R 8 to R 10 include a monocyclic or polycyclic saturated hydrocarbon group or a monocyclic or polycyclic unsaturated hydrocarbon group. Be done.
• a saturated hydrocarbon group of the monocycle a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group are preferable.
• As the polycyclic cycloalkyl group an alicyclic hydrocarbon group having a bridge such as a norbornyl group, an adamantyl group, a tricyclodecyl group and a tetracyclododecyl group is preferable.
• the Arihashi alicyclic hydrocarbon group is a polycyclic fat in which two carbon atoms that are not adjacent to each other among the carbon atoms constituting the alicyclic are bonded by a bond chain containing one or more carbon atoms.
• a cyclic hydrocarbon group is a polycyclic fat in which two carbon atoms that are not adjacent to each other among the carbon atoms constituting the alicyclic are bonded by a bond chain containing one or more carbon atoms.
• Aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group and anthryl group
• aralkyl groups such as benzyl group, phenethyl group and naphthylmethyl group
• a linear or branched saturated hydrocarbon group having 1 to 10 carbon atoms and an alicyclic hydrocarbon group having 3 to 20 carbon atoms are preferable.
• a divalent alicyclic group having 3 to 20 carbon atoms in which a chain hydrocarbon group represented by R 9 and R 10 or an alicyclic hydrocarbon group is combined with each other and composed of a carbon atom to which these are bonded is formed.
• the group is not particularly limited as long as it is a group obtained by removing two hydrogen atoms from the same carbon atom constituting the carbon ring of the monocyclic or polycyclic alicyclic hydrocarbon having the above carbon number.
• Either a monocyclic hydrocarbon group or a polycyclic hydrocarbon group may be used, and the polycyclic hydrocarbon group may be either an abridged alicyclic hydrocarbon group or a condensed alicyclic hydrocarbon group, and saturated hydrocarbons may be used.
• the condensed alicyclic hydrocarbon group is a polycyclic alicyclic hydrocarbon group in which a plurality of alicyclics share a side (bond between two adjacent carbon atoms).
• the saturated hydrocarbon group is preferably a cyclopentanediyl group, a cyclohexanediyl group, a cycloheptandyl group, a cyclooctanediyl group or the like, and the unsaturated hydrocarbon group is a cyclopentendyl group.
• Cyclohexendyl group, cycloheptendyl group, cyclooctendyl group, cyclodecendyl group and the like are preferable.
• polycyclic alicyclic hydrocarbon group an Aribashi alicyclic saturated hydrocarbon group is preferable, and for example, a bicyclo [2.2.1] heptane-2,2-diyl group (norbornane-2,2-diyl group) is preferable. ), Bicyclo [2.2.2] octane-2,2-diyl group, tricyclo [3.3.1.1 3,7 ] decane-2,2-diyl group (adamantan-2,2-diyl group) Etc. are preferable.
• R 8 is an alkyl group having 1 to 4 carbon atoms
• the alicyclic structure in which R 9 and R 10 are combined with each other and composed of carbon atoms to which they are bonded is a polycyclic or monocyclic cycloalkane. It is preferably a structure.
• the structural unit (I-1) is, for example, a structural unit represented by the following formulas (3-1) to (3-6) (hereinafter, “structural unit (I-1-1) to (I-1-”). 6) ”) and the like.
• R 7 to R 10 have the same meaning as the above formula (3).
• i and j are each independently an integer of 1 to 4.
• k and l are 0 or 1.
• i and j 1 is preferable.
• R8 a methyl group, an ethyl group or an isopropyl group is preferable.
• R 9 and R 10 a methyl group or an ethyl group is preferable.
• the base resin may contain one or a combination of two or more structural units (I).
• the content ratio of the structural unit (I) (the total content ratio when a plurality of types are contained) is preferably 10 mol% or more, more preferably 20 mol% or more, and more preferably 30 mol, based on all the structural units constituting the base resin. % Or more is more preferable, and 35 mol% or more is particularly preferable. Further, 80 mol% or less is preferable, 75 mol% or less is more preferable, 70 mol% or less is further preferable, and 65 mol% or less is particularly preferable. By setting the content ratio of the structural unit (I) in the above range, the pattern-forming property of the radiation-sensitive resin composition can be further improved.
• the structural unit (II) is a structural unit containing at least one selected from the group consisting of a lactone structure, a cyclic carbonate structure and a sultone structure.
• the base resin can adjust the solubility in a developing solution, and as a result, the radiation-sensitive resin composition improves lithography performance such as resolution. be able to.
• the adhesion between the resist pattern formed from the base resin and the substrate can be improved.
• Examples of the structural unit (II) include structural units represented by the following formulas (T-1) to (T-10).
• RL1 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
• RL2 to RL5 are independently composed of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyano group, a trifluoromethyl group, a methoxy group, a methoxycarbonyl group, a hydroxy group, a hydroxymethyl group, and a dimethylamino group.
• RL4 and RL5 may be divalent alicyclic groups having 3 to 8 carbon atoms which are combined with each other and composed of carbon atoms to which they are bonded.
• L 2 is a single bond or divalent linking group.
• X is an oxygen atom or a methylene group.
• k is an integer from 0 to 3.
• m is an integer of 1 to 3.
• the divalent alicyclic group having 3 to 8 carbon atoms in which the above RL4 and RL5 are combined with each other and formed together with the carbon atom to which they are bonded is represented by R9 and R10 in the above formula ( 3 ).
• the chain hydrocarbon groups or alicyclic hydrocarbon groups to be formed are combined with each other and composed of carbon atoms to which they are bonded, and the number of carbon atoms is 3 to 8.
• One or more hydrogen atoms on this alicyclic group may be substituted with a hydroxy group.
• Examples of the divalent linking group represented by L 2 include a divalent linear or branched hydrocarbon group having 1 to 10 carbon atoms and a divalent alicyclic hydrocarbon having 4 to 12 carbon atoms. Examples thereof include a hydrogen group, or a group composed of one or more of these hydrocarbon groups and at least one of -CO-, -O-, -NH- and -S-.
• a structural unit containing a lactone structure is preferable, a structural unit containing a norbornane lactone structure is more preferable, and a structural unit derived from norbornane lactone-yl (meth) acrylate is further preferable.
• the content ratio of the structural unit (II) is preferably 20 mol% or more, more preferably 25 mol% or more, still more preferably 30 mol% or more, based on all the structural units constituting the base resin. Further, 80 mol% or less is preferable, 75 mol% or less is more preferable, and 70 mol% or less is further preferable.
• the radiation-sensitive resin composition can further improve the lithography performance such as resolution and the adhesion of the formed resist pattern to the substrate. ..
• the base resin optionally has other structural units in addition to the structural units (I) and (II).
• the other structural units include structural units (III) containing polar groups (excluding those corresponding to structural units (II)).
• the base resin can adjust the solubility in a developing solution, and as a result, improve the lithography performance such as the resolution of the radiation-sensitive resin composition.
• the polar group include a hydroxy group, a carboxy group, a cyano group, a nitro group, a sulfonamide group and the like. Among these, a hydroxy group and a carboxy group are preferable, and a hydroxy group is more preferable.
• Examples of the structural unit (III) include structural units represented by the following formulas.
• RA is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
• the content ratio of the structural unit (III) is preferably 5 mol% or more, preferably 8 mol, based on all the structural units constituting the base resin. % Or more is more preferable, and 10 mol% or more is further preferable. Further, 40 mol% or less is preferable, 35 mol% or less is more preferable, and 30 mol% or less is further preferable.
• the base resin has a structural unit derived from hydroxystyrene or a structural unit having a phenolic hydroxyl group (hereinafter, both are collectively referred to as “structural unit (IV)” in addition to the structural unit (III) having a polar group. ) ”).
• the structural unit (IV) contributes to the improvement of etching resistance and the difference in developer solubility (dissolution contrast) between the exposed portion and the unexposed portion. In particular, it can be suitably applied to pattern formation using exposure with radiation having a wavelength of 50 nm or less, such as an electron beam or EUV.
• the resin preferably has a structural unit (I) and a structural unit (III) together with the structural unit (IV).
• a structural unit (IV) by polymerizing in a state where the phenolic hydroxyl group is protected by a protecting group such as an alkaline dissociative group at the time of polymerization, and then hydrolyzing to deprotect.
• a protecting group such as an alkaline dissociative group at the time of polymerization
• the structural unit that gives the structural unit (IV) by hydrolysis is preferably represented by the following formulas (4-1) and (4-2).
• R 11 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
• R 12 is a monovalent hydrocarbon group or an alkoxy group having 1 to 20 carbon atoms. Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms of R 12 include a monovalent hydrocarbon group having 1 to 20 carbon atoms of R 8 in the structural unit (I). Examples of the alkoxy group include a methoxy group, an ethoxy group, a tert-butoxy group and the like.
• an alkyl group and an alkoxy group are preferable, and a methyl group and a tert-butoxy group are more preferable.
• the content ratio of the structural unit (IV) is preferably 10 mol% or more, more preferably 20 mol% or more, based on all the structural units constituting the resin. Further, 70 mol% or less is preferable, and 60 mol% or less is more preferable.
• the base resin can be synthesized, for example, by polymerizing a monomer giving each structural unit in an appropriate solvent using a radical polymerization initiator or the like.
• radical polymerization initiator examples include azobisisobutyronitrile (AIBN), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), and 2,2'-azobis (2-cyclopropylpro). Pionitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate and other azo radical initiators; benzoyl peroxide, t-butyl hydroperoxide, Examples thereof include peroxide-based radical initiators such as cumenehydroperoxide. Among these, AIBN and dimethyl 2,2'-azobisisobutyrate are preferable, and AIBN is more preferable. These radical initiators can be used alone or in admixture of two or more.
• Examples of the solvent used for the polymerization include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane; Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; Halogenated hydrocarbons such as chlorobutanes, bromohexanes, dichloroethanes, hexamethylenedibromid, chlorobenzene; Saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, i-butyl acetate, methyl propionate; Ketones such as acetone, methyl ethyl ket
• the reaction temperature in the above polymerization is usually 40 ° C. to 150 ° C., preferably 50 ° C. to 120 ° C.
• the reaction time is usually 1 hour to 48 hours, preferably 1 hour to 24 hours.
• the molecular weight of the base resin is not particularly limited, but the polystyrene-equivalent weight average molecular weight (Mw) by gel permeation chromatography (GPC) is preferably 1,000 or more, more preferably 2,000 or more, still more preferably 3,000 or more. , 4,000 or more is particularly preferable. Further, Mw is preferably 50,000 or less, more preferably 30,000 or less, further preferably 15,000 or less, and particularly preferably 12,000 or less. If the Mw of the base resin is less than the above lower limit, the heat resistance of the obtained resist film may decrease. If the Mw of the base resin exceeds the above upper limit, the developability of the resist film may deteriorate.
• Mw polystyrene-equivalent weight average molecular weight
• the ratio (Mw / Mn) of Mw to the polystyrene-equivalent number average molecular weight (Mn) of the base resin by GPC is usually 1 or more and 5 or less, preferably 1 or more and 3 or less, and more preferably 1 or more and 2 or less.
• the Mw and Mn of the resin in the present specification are values measured by gel permeation chromatography (GPC) under the following conditions.
• GPC column 2 G2000HXL, 1 G3000HXL, 1 G4000HXL (all manufactured by Tosoh) Column temperature: 40 ° C Elution solvent: Tetrahydrofuran Flow rate: 1.0 mL / min Sample concentration: 1.0% by mass Sample injection amount: 100 ⁇ L Detector: Differential refractometer Standard material: Monodisperse polystyrene
• the content ratio of the base resin is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 85% by mass or more, based on the total solid content of the radiation-sensitive resin composition.
• the radiation-sensitive resin composition of the present embodiment may contain, as another resin, a resin having a larger mass content of fluorine atoms than the base resin (hereinafter, also referred to as “high fluorine content resin”). good.
• a resin having a larger mass content of fluorine atoms than the base resin hereinafter, also referred to as “high fluorine content resin”.
• the high fluorine content resin preferably has, for example, a structural unit represented by the following formula (5) (hereinafter, also referred to as “structural unit (V)”), and if necessary, the structural unit in the base resin. It may have (I) or a structural unit (II).
• R 13 is a hydrogen atom, a methyl group or a trifluoromethyl group.
• GL is a single bond, an oxygen atom, a sulfur atom, -COO-, -SO 2 ONH-, -CONH- or -OCONH-.
• R 14 is a monovalent fluorinated chain hydrocarbon group having 1 to 20 carbon atoms or a monovalent fluorinated alicyclic hydrocarbon group having 3 to 20 carbon atoms.
• a hydrogen atom and a methyl group are preferable, and a methyl group is more preferable, from the viewpoint of copolymerizability of the monomer giving the structural unit ( V).
• a single bond and —COO ⁇ are preferable, and —COO ⁇ is more preferable, from the viewpoint of copolymerizability of the monomer giving the structural unit (V).
• a part or all of the hydrogen atoms of the linear or branched alkyl group having 1 to 20 carbon atoms are fluorine. Examples include those substituted with atoms.
• the monovalent fluorinated alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R 14 may be a part of hydrogen atoms of a monocyclic or polycyclic hydrocarbon group having 3 to 20 carbon atoms. Examples include those all substituted with fluorine atoms.
• a fluorinated chain hydrocarbon group is preferable, a fluorinated alkyl group is more preferable, a 2,2,2-trifluoroethyl group, 1,1,1,3,3,3-hexafluoro-. 2-propyl groups and 5,5,5-trifluoro-1,1-diethylpentyl groups are more preferred.
• the content ratio of the structural unit (V) is preferably 30 mol% or more, preferably 40 mol%, based on all the structural units constituting the high fluorine content resin.
• the above is more preferable, 45 mol% or more is further preferable, and 50 mol% or more is particularly preferable.
• 90 mol% or less is preferable, 85 mol% or less is more preferable, and 80 mol% or less is further preferable.
• the high fluorine content resin is also referred to as a fluorine atom-containing structural unit (hereinafter, structural unit (VI)) represented by the following formula (f-2) together with the structural unit (V) or instead of the structural unit (V). ) May have. Since the high fluorine content resin has a structural unit (f-2), its solubility in an alkaline developer can be improved and the occurrence of development defects can be suppressed.
• structural unit (VI) fluorine atom-containing structural unit represented by the following formula (f-2) together with the structural unit (V) or instead of the structural unit (V).
• the structural unit (VI) is also referred to as (x) a group having an alkali-soluble group and (y) a group that dissociates due to the action of an alkali and increases its solubility in an alkaline developer (hereinafter, simply "alkali dissociative group”). It is roughly divided into two cases of having).
• RC is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
• RD is a single bond, a (s + 1) valent hydrocarbon group with 1 to 20 carbon atoms, and an oxygen atom, sulfur atom, -NR dd- , carbonyl group, -COO- or at the end of this hydrocarbon group on the RE side. It is a structure in which -CONH- is bonded, or a structure in which a part of the hydrogen atom of this hydrocarbon group is replaced with an organic group having a hetero atom.
• R dd is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. s is an integer of 1 to 3.
• RF is a hydrogen atom and A 1 is an oxygen atom, -COO- * or -SO 2 O- *. * Indicates a site that binds to RF.
• W 1 is a single bond, a hydrocarbon group having 1 to 20 carbon atoms, or a divalent fluorinated hydrocarbon group.
• a 1 is an oxygen atom
• W 1 is a fluorinated hydrocarbon group having a fluorine atom or a fluoroalkyl group at the carbon atom to which A 1 is bonded.
• RE is a single bond or a divalent organic group having 1 to 20 carbon atoms.
• the plurality of REs , W1, A1 and RF may be the same or different, respectively.
• the structural unit (VI) has (x) an alkali-soluble group, the affinity for the alkaline developer can be enhanced and development defects can be suppressed.
• the structural unit (VI) having an alkali-soluble group when A 1 is an oxygen atom and W 1 is a 1,1,1,3,3,3-hexafluoro-2,2-methanediyl group. Is particularly preferable.
• RF is a monovalent organic group having 1 to 30 carbon atoms
• a 1 is an oxygen atom, -NR aa- , -COO- * or. -SO 2 O- *.
• R aa is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. * Indicates a site that binds to RF.
• W 1 is a single bond or a divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms.
• RE is a single bond or a divalent organic group having 1 to 20 carbon atoms.
• W 1 or RF has a fluorine atom on the carbon atom bonded to A 1 or the carbon atom adjacent thereto.
• a 1 is an oxygen atom
• W 1 and RE are single bonds
• RD is a structure in which a carbonyl group is bonded to the end of a hydrocarbon group having 1 to 20 carbon atoms on the RE side
• R F is an organic group having a fluorine atom.
• the structural unit (VI) has (y) an alkaline dissociative group, the surface of the resist film changes from hydrophobic to hydrophilic in the alkaline developing step. As a result, the affinity for the developing solution can be significantly increased, and development defects can be suppressed more efficiently.
• a 1 is -COO- * and RF or W 1 or both of them have a fluorine atom.
• a hydrogen atom and a methyl group are preferable, and a methyl group is more preferable, from the viewpoint of copolymerizability of the monomer giving a structural unit (VI).
• RE is a divalent organic group
• a group having a lactone structure is preferable, a group having a polycyclic lactone structure is more preferable, and a group having a norbornane lactone structure is more preferable.
• the content ratio of the structural unit (VI) is preferably 50 mol% or more, preferably 55 mol%, based on all the structural units constituting the high fluorine content resin.
• the above is more preferable, and 60 mol% or more is further preferable. Further, 95 mol% or less is preferable, 90 mol% or less is more preferable, and 85 mol% or less is further preferable.
• the high fluorine content resin may contain a structural unit having an alicyclic structure represented by the following formula (6) as a structural unit other than the structural units listed above.
• R 1 ⁇ is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
• R 2 ⁇ is a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms.
• the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R 2 ⁇ is 1 of 3 to 20 carbon atoms represented by R 8 in the above formula (1).
• Valuable alicyclic hydrocarbon groups can be suitably adopted.
• the content ratio of the structural unit having the alicyclic structure is 10 mol% or more with respect to all the structural units constituting the high fluorine content resin. Is preferable, 20 mol% or more is more preferable, and 30 mol% or more is further preferable. Further, 60 mol% or less is preferable, 50 mol% or less is more preferable, and 450 mol% or less is further preferable.
• the Mw of the high fluorine content resin is preferably 1,000 or more, more preferably 2,000 or more, further preferably 3,000 or more, and particularly preferably 5,000 or more.
• the Mw is preferably 50,000 or less, more preferably 30,000 or less, further preferably 15,000 or less, and particularly preferably 12,000 or less.
• the lower limit of Mw / Mn of the high fluorine content resin is usually 1, and 1.1 is more preferable.
• the upper limit of Mw / Mn is usually 5, preferably 3, more preferably 2, and even more preferably 1.9.
• the content of the high fluorine content resin is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, still more preferably 1 part by mass or more, and 1.5 parts by mass with respect to 100 parts by mass of the base resin. More than parts by mass is particularly preferable. Further, 15 parts by mass or less is preferable, 12 parts by mass or less is more preferable, 10 parts by mass or less is further preferable, and 8 parts by mass or less is particularly preferable.
• the radiation-sensitive resin composition may contain one or more high-fluorine content resins.
• the high fluorine content resin can be synthesized by the same method as the above-mentioned method for synthesizing the base resin.
• the radiation-sensitive resin composition of the present embodiment is an acid having a smaller pKa than the acid generated from the onium salt compound (1) or the like acting as the acid diffusion control agent by irradiation (exposure) of radiation, that is, a relatively strong acid. It is preferable to further contain a radiation-sensitive acid generator that generates radiation.
• the resin contains a structural unit (I) having an acid dissociating group
• the acid generated from the radiation-sensitive acid generator by exposure dissociates the acid dissociating group having the structural unit (I), such as a carboxy group. Can be generated.
• This function does not substantially dissociate the acid dissociating group of the structural unit (I) of the resin or the like under the pattern forming conditions using the radiation-sensitive resin composition, and the radiation-sensitive portion in the unexposed portion. It is different from the function of the onium salt compound (1) of suppressing the diffusion of the acid generated from the acid generator.
• the functions of the onium salt compound (1) and the radiation-sensitive acid generator are the energy required for the acid dissociative group of the structural unit (I) of the resin to dissociate, and the radiation-sensitive resin composition. It is determined by the thermal energy conditions given when forming a pattern using an object.
• the radiation-sensitive acid generating agent contained in the radiation-sensitive resin composition may be a form that exists alone as a compound (liberated from the polymer) or a form incorporated as a part of the polymer. Both forms may be used, but a form that exists alone as a compound is preferable.
• the radiation-sensitive resin composition contains the above-mentioned radiation-sensitive acid generator, the polarity of the resin in the exposed portion is increased, and the resin in the exposed portion becomes soluble in the developing solution in the case of developing with an alkaline aqueous solution. On the other hand, in the case of organic solvent development, it becomes sparingly soluble in the developing solution.
• Examples of the radiation-sensitive acid generator include onium salt compounds (however, excluding the above-mentioned onium salt compound (1)), sulfoneimide compounds, halogen-containing compounds, diazoketone compounds and the like.
• Examples of the onium salt compound include sulfonium salt, tetrahydrothiophenium salt, iodonium salt, phosphonium salt, diazonium salt, pyridinium salt and the like. Of these, sulfonium salts and iodonium salts are preferable.
• Examples of the acid generated by exposure include those that generate sulfonic acid by exposure.
• Examples of such an acid include a sulfonium salt having an anion in which a carbon atom adjacent to a sulfo group is substituted with one or more fluorine atoms or a fluorinated hydrocarbon group.
• the radiation-sensitive acid generator those having a cyclic structure in cations and anions are particularly preferable.
• the content of the radiation-sensitive acid generator (in the case of the combined use of a plurality of radiation-sensitive acid generators, the total thereof) is preferably 0.1 part by mass or more with respect to 100 parts by mass of the base resin. More than parts by mass is more preferable, and more than 5 parts by mass is even more preferable. Further, 40 parts by mass or less is preferable, 35 parts by mass or less is more preferable, 30 parts by mass or less is further preferable, and 20 parts by mass or less is particularly preferable with respect to 100 parts by mass of the resin. As a result, excellent sensitivity, LWR performance, and CDU performance can be exhibited when forming a resist pattern.
• the radiation-sensitive resin composition according to this embodiment contains a solvent.
• the solvent is not particularly limited as long as it is a solvent capable of dissolving or dispersing at least the compound (1), the resin, and the radiation-sensitive acid generator contained if desired.
• solvent examples include alcohol-based solvents, ether-based solvents, ketone-based solvents, amide-based solvents, ester-based solvents, hydrocarbon-based solvents, and the like.
• an alcohol solvent for example, Carbons such as iso-propanol, 4-methyl-2-pentanol, 3-methoxybutanol, n-hexanol, 2-ethylhexanol, furfuryl alcohol, cyclohexanol, 3,3,5-trimethylcyclohexanol, diacetone alcohol, etc. Numbers 1 to 18 of monoalcoholic solvents; Ethylene glycol, 1,2-propylene glycol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, etc.
• Propylene alcohol solvent examples thereof include a polyhydric alcohol partially ether-based solvent obtained by etherifying a part of the hydroxy group of the polyhydric alcohol-based solvent.
• ether solvent examples include, for example. Dialkyl ether solvents such as diethyl ether, dipropyl ether and dibutyl ether; Cyclic ether solvent such as tetrahydrofuran and tetrahydropyran; Aromatic ring-containing ether solvents such as diphenyl ether and anisole (methylphenyl ether); Examples thereof include a polyhydric alcohol ether solvent obtained by etherifying the hydroxy group of the polyhydric alcohol solvent.
• ketone solvent examples include chain ketone solvents such as acetone, butanone, and methyl-iso-butyl ketone: Cyclic ketone solvents such as cyclopentanone, cyclohexanone, and methylcyclohexanone: Examples thereof include 2,4-pentandione, acetonylacetone and acetophenone.
• amide solvent examples include cyclic amide solvents such as N, N'-dimethylimidazolidinone and N-methylpyrrolidone; Examples thereof include chain amide solvents such as N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpropionamide.
• ester solvent examples include, for example. Monocarboxylic acid ester solvent such as n-butyl acetate and ethyl lactate; Polyhydric alcohol partial ether acetate solvent such as diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate; Lactone-based solvents such as ⁇ -butyrolactone and valerolactone; Carbonate-based solvents such as diethyl carbonate, ethylene carbonate, and propylene carbonate; Examples thereof include polyvalent carboxylic acid diester solvents such as propylene glycol diacetate, methoxytriglycolacetate acetate, diethyl oxalate, ethyl acetoacetate, ethyl lactate, and diethyl phthalate.
• Monocarboxylic acid ester solvent such as n-butyl acetate and ethyl lactate
• hydrocarbon solvent examples include aliphatic hydrocarbon solvents such as n-hexane, cyclohexane, and methylcyclohexane; Examples thereof include aromatic hydrocarbon solvents such as benzene, toluene, di-iso-propylbenzene and n-amylnaphthalene.
• ester-based solvents and ketone-based solvents are preferable, polyhydric alcohol partially ether acetate-based solvents, cyclic ketone-based solvents, and lactone-based solvents are more preferable, and propylene glycol monomethyl ether acetate, cyclohexanone, and ⁇ -butyrolactone are even more preferable. ..
• the radiation-sensitive resin composition may contain one kind or two or more kinds of solvents.
• the radiation-sensitive resin composition may contain other optional components in addition to the above components.
• the other optional components include a cross-linking agent, an uneven distribution accelerator, a surfactant, an alicyclic skeleton-containing compound, a sensitizer, and the like. These other optional components may be used alone or in combination of two or more.
• the radiation-sensitive resin composition is prepared by mixing, for example, an onium salt compound (1), a resin, a radiation-sensitive acid generator, a high-fluorine content resin or the like, if necessary, and a solvent in a predetermined ratio. can. After mixing, the radiation-sensitive resin composition is preferably filtered with, for example, a filter having a pore size of about 0.05 ⁇ m to 0.2 ⁇ m.
• the solid content concentration of the radiation-sensitive resin composition is usually 0.1% by mass to 50% by mass, preferably 0.5% by mass to 30% by mass, and more preferably 1% by mass to 20% by mass.
• the pattern forming method according to the embodiment of the present invention is A step (1) of directly or indirectly applying the radiation-sensitive resin composition onto a substrate to form a resist film (hereinafter, also referred to as a “resist film forming step”).
• the step (2) of exposing the resist film (hereinafter, also referred to as “exposure step”) and It includes a step (3) (hereinafter, also referred to as a “development step”) of developing the exposed resist film.
• the resist pattern forming method since the radiation-sensitive resin composition having excellent sensitivity, CDU performance, and LWR performance in the exposure process is used, a high-quality resist pattern can be formed.
• each step will be described.
• a resist film is formed from the radiation-sensitive resin composition.
• the substrate on which the resist film is formed include conventionally known wafers such as silicon wafers, silicon dioxide, and wafers coated with aluminum. Further, for example, an organic or inorganic antireflection film disclosed in JP-A-6-12452 and JP-A-59-93448 may be formed on the substrate.
• the coating method include rotary coating (spin coating), cast coating, roll coating and the like.
• prebaking (PB) may be performed to volatilize the solvent in the coating film.
• the PB temperature is usually 60 ° C. to 140 ° C., preferably 80 ° C. to 120 ° C.
• the PB time is usually 5 seconds to 600 seconds, preferably 10 seconds to 300 seconds.
• the film thickness of the resist film to be formed is preferably 10 nm to 1,000 nm, more preferably 10 nm to 500 nm.
• the immersion liquid and the resist film are formed on the formed resist film regardless of the presence or absence of the water-repellent polymer additive such as the high fluorine content resin in the radiation-sensitive resin composition.
• An insoluble protective film for immersion may be provided in the immersion liquid for the purpose of avoiding direct contact with the liquid.
• a solvent peeling type protective film that is peeled off by a solvent before the developing step see, for example, Japanese Patent Application Laid-Open No. 2006-227632
• a developer peeling type protective film that is peeled off at the same time as the development in the developing step (see, for example, Japanese Patent Application Laid-Open No. 2006-227632).
• any of WO2005-069076 and WO2006-305790 may be used.
• the exposure step which is the next step, is performed with radiation having a wavelength of 50 nm or less
• the resist film formed in the resist film forming step in the above step (1) is passed through a photomask (in some cases, via an immersion medium such as water). , Irradiate and expose.
• the radiation used for exposure is, for example, electromagnetic waves such as visible light, ultraviolet rays, far ultraviolet rays, EUV (extreme ultraviolet rays), X-rays, and ⁇ -rays; electron beams, ⁇ -rays, etc., depending on the line width of the target pattern. Charged particle beams can be mentioned.
• far ultraviolet rays, electron beams, and EUVs are preferable, ArF excimer laser light (wavelength 193 nm), KrF excimer laser light (wavelength 248 nm), electron beams, and EUV are more preferable, and a wavelength of 50 nm, which is positioned as a next-generation exposure technology.
• the following electron beams and UVs are more preferable.
• the immersion liquid to be used include water and a fluorine-based inert liquid.
• the liquid immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has a refractive index as small as possible so as to minimize the distortion of the optical image projected on the film.
• the exposure light source is ArF.
• excima laser light wavelength 193 nm
• water it is preferable to use water from the viewpoints of easy availability and handling in addition to the above viewpoints.
• an additive that reduces the surface tension of water and increases the surface activity may be added in a small proportion. It is preferable that this additive does not dissolve the resist film on the wafer and the influence on the optical coating on the lower surface of the lens can be ignored. Distilled water is preferable as the water to be used.
• PEB post-exposure baking
• the PEB temperature is usually 50 ° C to 180 ° C, preferably 80 ° C to 130 ° C.
• the PEB time is usually 5 seconds to 600 seconds, preferably 10 seconds to 300 seconds.
• the resist film exposed in the exposure step which is the step (2) is developed. This makes it possible to form a predetermined resist pattern. After development, it is generally washed with a rinsing solution such as water or alcohol and dried.
• a rinsing solution such as water or alcohol
• the developing solution used for the above development is, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-.
• n-propylamine, triethylamine, methyldiethylamine, ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH), pyrrole, piperidine, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene , 1,5-diazabicyclo- [4.3.0] -5-nonen and the like may be mentioned as an alkaline aqueous solution in which at least one of the alkaline compounds is dissolved.
• the TMAH aqueous solution is preferable, and the 2.38 mass% TMAH aqueous solution is more preferable.
• an organic solvent such as a hydrocarbon solvent, an ether solvent, an ester solvent, a ketone solvent, an alcohol solvent, or a solvent containing an organic solvent
• the organic solvent include one or more of the solvents listed as the solvent of the above-mentioned radiation-sensitive resin composition.
• ether-based solvents, ester-based solvents, and ketone-based solvents are preferable.
• the ether solvent a glycol ether solvent is preferable, and ethylene glycol monomethyl ether and propylene glycol monomethyl ether are more preferable.
• ester solvent an acetate ester solvent is preferable, and n-butyl acetate and amyl acetate are more preferable.
• ketone solvent a chain ketone is preferable, and 2-heptanone is more preferable.
• the content of the organic solvent in the developing solution is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and particularly preferably 99% by mass or more.
• the components other than the organic solvent in the developing solution include water, silicone oil and the like.
• the developer may be either an alkaline developer or an organic solvent developer, but it is preferable that the developer contains an alkaline aqueous solution and the obtained pattern is a positive pattern.
• Examples of the developing method include a method of immersing the substrate in a tank filled with a developing solution for a certain period of time (dip method), and a method of raising the developing solution on the surface of the substrate by surface tension and allowing it to stand still for a certain period of time (paddle).
• dip method a method of immersing the substrate in a tank filled with a developing solution for a certain period of time
• piddle a method of raising the developing solution on the surface of the substrate by surface tension and allowing it to stand still for a certain period of time
• Method a method of spraying the developer on the surface of the substrate
• spray method a method of continuously spraying the developer on the substrate rotating at a constant speed while scanning the developer dispensing nozzle at a constant speed
• dynamic discharge method a method of continuously spraying the developer on the substrate rotating at a constant speed while scanning the developer dispensing nozzle at a constant speed
• the onium salt compound represented by the above formula (1) can be preferably used.
• Mw Weight average molecular weight
• Mn number average molecular weight
• the start of dropping was set as the start time of the polymerization reaction, and the polymerization reaction was carried out for 6 hours.
• the polymerization solution was water-cooled and cooled to 30 ° C. or lower.
• the cooled polymerization solution was put into methanol (2,000 parts by mass), and the precipitated white powder was filtered off.
• the filtered white powder was washed twice with methanol, filtered, and dried at 50 ° C. for 24 hours to obtain a white powdery resin (A-1) (yield: 83%).
• the Mw of the resin (A-1) was 8,800, and the Mw / Mn was 1.50.
• the content ratios of the structural units derived from (M-1), (M-2) and (M-13) were 41.3 mol% and 13.8 mol%, respectively. And 44.9 mol%.
• the polymerization solution was water-cooled and cooled to 30 ° C. or lower.
• the cooled polymerization solution was put into hexane (2,000 parts by mass), and the precipitated white powder was filtered off.
• the filtered white powder was washed twice with hexane, filtered, and dissolved in 1-methoxy-2-propanol (300 parts by mass).
• methanol (500 parts by mass), triethylamine (50 parts by mass) and ultrapure water (10 parts by mass) were added, and a hydrolysis reaction was carried out at 70 ° C. for 6 hours with stirring.
• the polymerization solution was water-cooled and cooled to 30 ° C. or lower.
• hexane 100 parts by mass was added and stirred, and the operation of recovering the acetonitrile layer was repeated three times.
• the solvent By substituting the solvent with propylene glycol monomethyl ether acetate, a solution of the high fluorine content resin (E-1) was obtained (yield: 69%).
• the Mw of the high fluorine content resin (E-1) was 6,000, and the Mw / Mn was 1.62.
• the content ratios of the structural units derived from (M-1) and (M-20) were 19.9 mol% and 80.1 mol%, respectively.
• a mixed solution of acetonitrile: water (1: 1 (mass ratio)) was added to the above bromo form to make a 1M solution, then 40.0 mmol of sodium dithionite and 60.0 mmol of sodium hydrogen carbonate were added, and the temperature was 70 ° C. for 4 hours. It was reacted.
• a mixed solution of acetonitrile: water (3: 1 (mass ratio)) was added to prepare a 0.5 M solution. 60.0 mmol of hydrogen peroxide solution and 2.00 mmol of sodium tungstate were added, and the mixture was heated and stirred at 50 ° C. for 12 hours.
• Example 1 [A] 100 parts by mass of (A-1) as a resin, [B] 12.0 parts by mass of (B-1) as a radiation-sensitive acid generator, and (C-1) as an acid diffusion control agent. ) 5.0 parts by mass, [E] 3.0 parts by mass (solid content) as a high fluorine content resin, and (D-1) / (D-2) as a [D] solvent.
• a radiation-sensitive resin composition (J-1) was prepared by mixing 3,230 parts by mass of the mixed solvent of / (D-3) and filtering with a membrane filter having a pore size of 0.2 ⁇ m.
• ASML's "TWINSCAN XT-1900i” ArF excimer laser immersion exposure device
• the exposure amount for forming the 40 nm line and space pattern is defined as the optimum exposure amount, and this optimum exposure amount is defined as the sensitivity (mJ / cm 2 ). did.
• the sensitivity was evaluated as "good” when it was 25 mJ / cm 2 or less, and as “poor” when it exceeded 25 mJ / cm 2 .
• LWR performance A 40 nm line-and-space resist pattern was formed by irradiating with the optimum exposure amount obtained in the above sensitivity evaluation. The formed resist pattern was observed from above the pattern using the scanning electron microscope. A total of 500 points of variation in line width were measured, and 3 sigma values were obtained from the distribution of the measured values, and these 3 sigma values were defined as LWR (nm). The LWR indicates that the smaller the value, the smaller and better the roughness of the line. The LWR performance was evaluated as "good” when it was 3.0 nm or less, and as “poor” when it exceeded 3.0 nm.
• the radiation-sensitive resin composition of the example had good sensitivity and LWR performance when used for ArF exposure, whereas in the comparative example, each characteristic was the example. Was inferior to. Therefore, when the radiation-sensitive resin composition of the example is used for ArF exposure, a resist pattern having high sensitivity and good LWR performance can be formed.
• Example 52 [Preparation of positive radiation-sensitive resin composition for extreme ultraviolet (EUV) exposure] [Example 52] [A] 100 parts by mass of (A-12) as a resin, [B] 15.0 parts by mass of (B-1) as a radiation-sensitive acid generator, [C] (C-1) as an acid diffusion control agent. ) 3.0 parts by mass, [E] 3.0 parts by mass (solid content) as a high fluorine content resin, and [D] (D-1) / (D-4) as a solvent.
• a radiation-sensitive resin composition (J-52) was prepared by mixing 6,110 parts by mass of the mixed solvent of No. 1 and filtering with a membrane filter having a pore size of 0.2 ⁇ m.
• Example 53 to 62 and Comparative Examples 13 to 16 Radiation-sensitive resin compositions (J-53) to (J-62) and (CJ-13) to (CJ-13) in the same manner as in Example 52 except that the components of the types and contents shown in Table 6 below were used. (CJ-16) was prepared.
• PEB was performed at 120 ° C. for 60 seconds.
• the resist film is alkaline-developed with a 2.38 mass% TMAH aqueous solution as an alkaline developer, washed with water after development, and further dried to form a positive resist pattern (32 nm line and space pattern). Formed.
• the exposure amount for forming the 32 nm line and space pattern is defined as the optimum exposure amount, and this optimum exposure amount is defined as the sensitivity (mJ / cm 2 ). did. The sensitivity was evaluated as "good” when it was 30 mJ / cm 2 or less, and “poor” when it exceeded 30 mJ / cm 2 .
• LWR performance A resist pattern was formed by irradiating the optimum exposure amount obtained in the above sensitivity evaluation and adjusting the mask size so as to form a 32 nm line-and-space pattern. The formed resist pattern was observed from above the pattern using the scanning electron microscope. A total of 500 points of variation in line width were measured, and 3 sigma values were obtained from the distribution of the measured values, and these 3 sigma values were defined as LWR (nm). The LWR indicates that the smaller the value, the smaller the rattling of the line and the better. The LWR performance was evaluated as "good” when it was 3.0 nm or less, and as “poor” when it exceeded 3.0 nm.
• the radiation-sensitive resin composition of the example had good sensitivity and LWR performance when used for EUV exposure, whereas in the comparative example, each characteristic was the example. It was inferior to.
• ASML's "TWINSCAN XT-1900i” ArF excimer laser immersion exposure device
• the exposure amount for forming the 40 nm hole pattern was defined as the optimum exposure amount, and this optimum exposure amount was defined as the sensitivity (mJ / cm 2 ).
• CDU performance A total of 1,800 resist patterns with 40 nm holes and 105 nm pitches were measured at arbitrary points from the upper part of the pattern using the scanning electron microscope. The dimensional variation (3 ⁇ ) was obtained and used as the CDU performance (nm). The CDU shows that the smaller the value, the smaller the variation in the hole diameter in the long period and the better.
• the radiation-sensitive resin composition of Example 63 formed a negative resist pattern by ArF exposure. Even in this case, the sensitivity and CDU performance were good.
• [Preparation of negative radiation-sensitive resin composition for EUV exposure, formation and evaluation of resist pattern using this composition] [Example 64] [A] 100 parts by mass of (A-13) as a resin, [B] 20.0 parts by mass of (B-6) as a radiation-sensitive acid generator, and (C-1) as an acid diffusion control agent. ) 10.0 parts by mass, [E] 7.0 parts by mass (solid content) as a high fluorine content resin, and (D-1) / (D-4) as a [D] solvent.
• a radiation-sensitive resin composition (J-64) was prepared by mixing 6,110 parts by mass of the mixed solvent of No. 1 and filtering with a membrane filter having a pore size of 0.2 ⁇ m.
• EUV exposure apparatus NXE3300” manufactured by ASML
• NA 0.33
• mask imageDEFECT32FFR02.
• PEB was performed at 120 ° C. for 60 seconds.
• the resist film was developed with an organic solvent using n-butyl acetate as an organic solvent developer and dried to form a negative resist pattern (40 nm hole, 105 nm pitch).
• the resist pattern using the negative-type radiation-sensitive resin composition for EUV exposure was evaluated in the same manner as the evaluation of the resist pattern using the negative-type radiation-sensitive resin composition for ArF exposure.
• the radiation-sensitive resin composition of Example 64 had good sensitivity and CDU performance even when a negative resist pattern was formed by EUV exposure.
• the radiation-sensitive resin composition and the resist pattern forming method described above it is possible to form a resist pattern having good sensitivity to exposure light and excellent LWR performance and CDU performance. Therefore, these can be suitably used for processing processes of semiconductor devices, which are expected to be further miniaturized in the future.

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