Classifications

• • 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
  • C07C309/09—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 etherified hydroxy groups bound to the carbon skeleton
  • C07C309/11—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 etherified hydroxy groups bound to the carbon skeleton with the oxygen atom of at least one of the etherified hydroxy groups further bound to a carbon atom of a six-membered aromatic ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C317/00—Sulfones; Sulfoxides
  • C07C317/02—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to acyclic carbon atoms
  • C07C317/06—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to acyclic carbon atoms of a saturated carbon skeleton containing rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C317/00—Sulfones; Sulfoxides
  • C07C317/12—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to carbon atoms of rings other than six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C317/00—Sulfones; Sulfoxides
  • C07C317/14—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
  • C07C321/12—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms
  • C07C321/16—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms of a saturated carbon skeleton containing rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
  • C07C321/24—Thiols, sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
  • C07C321/28—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
  • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
  • C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
  • C07D307/32—Oxygen atoms
  • C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
  • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
  • C07D317/72—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 spiro-condensed with carbocyclic rings
• • 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
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists

Definitions

• the present invention relates to a radiation-sensitive resin composition, a method for forming a resist pattern using the composition, a sulfonate compound, a radiation-sensitive acid generator containing the same, and the like.
• 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 through 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.
• short-wavelength radiation such as an ArF excimer laser
• an immersion exposure method liquid immersion
• lithography using shorter wavelength radiation such as electron beam, X-ray and EUV (extreme ultraviolet) is also being studied.
• a resin having an alicyclic structure with less absorption as a protecting group is used instead of the hydroxystyrene polymer, but the photoacid generator used in combination with the hydroxystyrene polymer is used. Since the acid strength is insufficient to promote deprotection of the resin having an alicyclic structure, the proximal carbon of the sulfonic acid group is used as a photoacid generator that gives an acid having sufficient acid strength for deprotection.
• An acid generator in which is replaced with fluorine has been put into practical use (Patent Document 2).
• the resist includes the line widow slagness (LWR) performance, which indicates the sensitivity in the exposure process and the variation in the line width of the resist pattern. Further improvement of various performances is required. Further, next-generation exposure techniques such as electron beam exposure are also required to have the same or higher resist performance. However, all the properties of the conventional radiation-sensitive resin composition have not been obtained at a sufficient level.
• LWR line widow slagness
• the present inventors have found that the above object can be achieved by using a radiation-sensitive acid generator having a specific structure in combination, and have completed the present invention. ..
• the present invention relates to a sulfonate compound represented by the following formula (1), a resin containing a structural unit having an acid dissociative group, and a radiation-sensitive resin composition containing a solvent.
• R f is independently a hydrogen atom, a fluorine atom, or a fluoroalkyl group, and at least one R f is a fluorine atom, or a fluoroalkyl group.
• m is 1 or 2 and n is an integer of 4-8.
• L 1 is -O-, -S-, or -SO 2-
• R is an m-valent hydrocarbon group
• X + is a monovalent radiation-sensitive onium cation.
• the radiation-sensitive resin composition of the present invention contains a sulfonate compound represented by the above formula (1), a resin containing a structural unit having an acid dissociative group, and a solvent, the sensitivity and LWR in the exposure process All of the performance etc. can be demonstrated at an excellent level.
• the mechanism of action for the manifestation of the above effects is not clear, and the scope of rights of the present invention is not necessarily limited by this inference, but the radiation-sensitive resin composition of the present invention is a sulfonate having a specific structure that is strongly acidic. It is presumed that various resist performances are improved by containing a compound or the like.
• the present invention Step (1) of forming a resist film with the above radiation-sensitive resin composition,
• the present invention relates to a method for forming a resist pattern, which comprises a step of exposing the resist film (2) and a step of developing the exposed resist film (3).
• a sulfonate compound represented by the above formula (1), a resin containing a structural unit having an acid dissociative group, and a radiation-sensitive resin composition containing a solvent are used as a substrate. Since it includes a step of directly or indirectly applying it onto the resist film to form a resist film, it exhibits excellent levels of sensitivity in the exposure process and line widow roughness (LWR) performance that indicates variations in the line width of the resist pattern. It will be possible.
• LWR line widow roughness
• the mechanism of action of the above-mentioned effect manifestation is not clear, and the scope of rights of the present invention is not necessarily limited by this inference, but the method for forming the resist pattern of the present invention is a strongly acidic sulfonate compound having a specific structure. It is presumed that the resist performance is improved by including the above.
• the present invention further relates to a method for processing a substrate, which comprises a step (4-1) of forming a pattern on the substrate by using the resist pattern formed by the above method as a mask.
• the present invention further relates to a method for producing a metal film pattern, which comprises a step (4-2) of forming a metal film by using the resist pattern formed by the above method as a mask.
• the method for processing the substrate and the method for producing the metal film pattern of the present invention include a sulfonate compound represented by the above formula (1), a resin containing a structural unit having an acid dissociation group, and a solvent. Since the step of directly or indirectly applying the radioactive resin composition onto the substrate to form a resist film is included, it is possible to process a high-quality substrate pattern and a metal film pattern, respectively.
• the present invention relates to a sulfonate compound represented by the following formula (1).
• R f is independently a hydrogen atom, a fluorine atom, or a fluoroalkyl group, and at least one R f is a fluorine atom, or a fluoroalkyl group.
• m is 1 or 2 and n is an integer of 4-8.
• L 1 is -O-, -S-, or -SO 2-
• R is an m-valent hydrocarbon group
• X + is a monovalent radiation-sensitive onium cation.
• the sulfonate compound of the present invention has a structure represented by the above formula (1), for example, by using a radiation-sensitive resin composition containing the sulfonate compound, a resist forming method, or the like, the sensitivity in the exposure step and the LWR All of the performance etc. can be demonstrated at an excellent level.
• the mechanism of action for the manifestation of the above effects is not clear, and the scope of rights of the present invention is not necessarily limited by this inference. For example, it is presumed that it acts as a suitable radiation-sensitive acid generator, and as a result, improves various resist performances.
• the present invention relates to a radiation-sensitive acid generator containing a sulfonate compound represented by the following formula (1).
• R f is independently a hydrogen atom, a fluorine atom, or a fluoroalkyl group, and at least one R f is a fluorine atom, or a fluoroalkyl group.
• m is 1 or 2 and n is an integer of 4-8.
• L 1 is -O-, -S-, or -SO 2-
• R is an m-valent hydrocarbon group
• X + is a monovalent radiation-sensitive onium cation.
• the radiation-sensitive acid generator of the present invention has a structure represented by the above formula (1), for example, by using a radiation-sensitive resin composition containing the same, a resist forming method, or the like, the sensitivity in the exposure step is achieved. And LWR performance can be demonstrated at an excellent level.
• the mechanism of action for the manifestation of the above effects is not clear, and the scope of rights of the present invention is not necessarily limited by this inference, but the radiation-sensitive acid generator of the present invention has a specific structure that is strongly acidic, etc. Therefore, it is presumed that it acts as a suitable radiation-sensitive acid generator, and as a result, improves various resist performances.
• the radiation-sensitive resin composition according to the present embodiment includes a resin (A), a sulfonate compound (B0) (or a radiation-sensitive acid generator (B)), and the like. And the solvent (D).
• the composition may contain other optional components as long as the effects of the present invention are not impaired.
• the resin (A) in the present invention is a resin containing a structural unit having an acid dissociable group.
• a structural unit (a1) having a phenolic hydroxyl group and a structural unit having an acid dissociable group including a cyclic structure It is an aggregate of polymers having a2) (hereinafter, this resin is also referred to as "base resin").
• the base resin resin (A) may have other structural units other than the structural unit (a1) and the structural unit (a2). Hereinafter, each structural unit will be described.
• the structural unit (a1) is a structural unit containing a phenolic hydroxyl group.
• the resin (A) can more appropriately adjust the solubility in the developing solution, and as a result, the radiation-sensitive resin composition described above. LWR performance and the like can be further improved.
• the resin (A) has the structural unit (a1), so that the structural unit (a1) is used.
• the structural unit (a1) can be a structural unit derived from hydroxystyrene.
• structural unit (a1) for example, a structural unit represented by the following formula (af) can be mentioned.
• R AF1 is a hydrogen atom or a methyl group.
• the LAF is single bond, -COO-, -O- or -CONH-.
• R AF2 is a monovalent organic group having 1 to 20 carbon atoms.
• n f1 is an integer of 0 to 3.
• n f2 is an integer of 1 to 3.
• n f1 + n f2 is 5 or less.
• n af is an integer of 0 to 2.
• the R AF1 is preferably a hydrogen atom from the viewpoint of copolymerizability of the monomer giving the structural unit (a1).
• the L AF it is preferable a single bond and is -COO-.
• the organic group in the resin (A) means a group containing at least one carbon atom.
• Examples of the monovalent organic group having 1 to 20 carbon atoms represented by R AF2 include a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the carbon-carbon group or the bond hand side of the hydrocarbon group. Examples thereof include a group containing a divalent heteroatom-containing group at the terminal, a group in which a part or all of the hydrogen atom of the group and the hydrocarbon group is substituted with a monovalent heteroatom-containing group, and the like.
• Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R AF2 include, for example. Alkyl groups such as methyl group, ethyl group, propyl group and butyl group; Alkenyl groups such as ethenyl group, propenyl group, butenyl group; Chain hydrocarbon groups such as alkynyl groups such as ethynyl group, propynyl group and butynyl group; Cycloalkyl groups such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, norbornyl group, adamantyl group; Alicyclic hydrocarbon groups such as cycloalkenyl groups such as cyclopropenyl group, cyclopentenyl group, cyclohexenyl group, norbornenyl group; Aryl groups such as phenyl group, tolyl group, xsilyl group, naphthy
• a chain hydrocarbon group and a cycloalkyl group are preferable, an alkyl group and a cycloalkyl group are more preferable, and a methyl group, an ethyl group, a propyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group and an adamantyl group are preferable. More preferred.
• divalent heteroatom-containing group examples include -O-, -CO-, -CO-O-, -S-, -CS-, -SO 2-, and -NR'-, and 2 of these.
• a group that combines two or more can be mentioned.
• R' is a hydrogen atom or a monovalent hydrocarbon group.
• Examples of the monovalent heteroatom-containing group include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, hydroxy group, carboxy group, cyano group, amino group and sulfanyl group (-SH). be able to.
• halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, hydroxy group, carboxy group, cyano group, amino group and sulfanyl group (-SH).
• a monovalent chain hydrocarbon group is preferable, an alkyl group is more preferable, and a methyl group is further preferable.
• n f1 is preferably an integer of 0 to 2, more preferably 0 and 1, and even more preferably 0.
• n f2 , 1 and 2 are preferable, and 1 is more preferable.
• naf 0 and 1 are preferable, and 0 is more preferable.
• the structural unit (a1) is preferably a structural unit represented by the following formulas (a1-1) to (a1-6).
• R AF1 is the same as the above formula (af).
• the structural units (a1-1) and (a1-2) are preferable, and (a1-1) is more preferable.
• the lower limit of the content ratio of the structural unit (a1) is preferably 10 mol%, preferably 15 mol%, based on all the structural units constituting the resin (A). Is more preferable, 20 mol% is further preferable, and 25 mol% is particularly preferable.
• the upper limit of the content ratio is preferably 90 mol%, more preferably 80 mol%, further preferably 70 mol%, and particularly preferably 60 mol%.
• the structural unit that gives the structural unit (a1) by hydrolysis is preferably represented by the following formula (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. Examples of the alkoxy group include a methoxy group, an ethoxy group, a tert-butoxy group and the like.
• R 12 is preferably an alkyl group and alkoxy group, and among them methyl group, tert- butoxy group is more preferable.
• the structural unit (a2) is a structural unit containing an acid dissociative group containing a cyclic structure.
• the structural unit (a2) is not particularly limited as long as it contains an acid dissociative group containing a cyclic structure.
• a structural unit having a tertiary alkyl ester moiety and a hydrogen atom of a phenolic hydroxyl group are tertiary alkyl groups. Examples thereof include a structural unit having a substituted structure, a structural unit having an acetal bond, and the like, but from the viewpoint of improving the pattern forming property of the radiation-sensitive resin composition, the structure represented by the following formula (5).
• a unit hereinafter, also referred to as “structural unit (a2-1)” is preferable.
• 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 is 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 (a2).
• R 7 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
• R 8 is a hydrogen atom or 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 is composed of carbon atoms to which these are combined and bonded to each other. It is assumed that one or a plurality of R 8 to R 10 are combined with each other and have at least one or more annular structures.
• L 1 represents a single bond or a divalent linking group. However, when L 1 is a divalent linking group, the structure on the side chain terminal side is -COO-.
• a hydrogen atom preferably a methyl group, more preferably a methyl group.
• Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R 8 include a chain hydrocarbon group having 1 to 10 carbon atoms and a monovalent alicyclic hydrocarbon having 3 to 20 carbon atoms. Groups, monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms and the like can be mentioned.
• the chain hydrocarbon group having 1 to 10 carbon atoms represented by R 8 to R 10 is a linear hydrocarbon group having 1 to 10 carbon atoms or a saturated hydrocarbon group having a branched chain, or a linear hydrocarbon group having 1 to 10 carbon atoms.
• Branched 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 able to.
• As the saturated hydrocarbon group of the monocycle a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group are preferable.
• a bridged alicyclic hydrocarbon group such as a norbornyl group, an adamantyl group, a tricyclodecyl group and a tetracyclododecyl group is preferable.
• the 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 bridged alicyclic hydrocarbon group such as a norbornyl group, an adamantyl group, a tricyclodecyl group and a tetracyclododecyl group.
• Examples of the monovalent aromatic hydrocarbon group in which the R 8 having 6-20 carbon atoms represented by, for example, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an aryl group such as an anthryl group; a benzyl group, a phenethyl group , Aralkyl groups such as naphthylmethyl group can be mentioned.
• R 8 preferably a linear or branched chain saturated hydrocarbon group, an alicyclic hydrocarbon group having 3 to 20 carbon atoms having 1 to 10 carbon atoms.
• a chain hydrocarbon group or an alicyclic hydrocarbon group is combined with each other and formed together with a carbon atom to which they are bonded.
• the divalent alicyclic group having 3 to 20 carbon atoms is 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. If it is a group, it is not particularly limited.
• the condensed alicyclic hydrocarbon group refers to 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 alicyclic saturated hydrocarbon group with a bridge is preferable, and for example, a bicyclo [2.2.1] heptane-2,2-diyl group (norbornane-2,2-diyl) is preferable.
• Group) bicyclo [2.2.2] octane-2,2-diyl group, tricyclo [3.3.1.1 3,7 ] decan-2,2-diyl group (adamantan-2,2-diyl group) ) Etc. are preferable.
• Examples of the divalent linking group represented by L 1 include an alkanediyl group, a cycloalkanediyl group, an arcendyl group, * -R LA O-, * -R LB COO-, and the like (*). Represents the bond on the oxygen side.) A part or all of the hydrogen atoms contained in these groups may be substituted with halogen atoms such as fluorine atoms and chlorine atoms, cyano groups and the like.
• alkanediyl group an alkanediyl group having 1 to 8 carbon atoms is preferable.
• cycloalkanediyl group examples include a monocyclic cycloalkanediyl group such as a cyclopentanediyl group and a cyclohexanediyl group; a polycyclic cycloalkanediyl group such as a norbornanediyl group and an adamantandiyl group. ..
• a cycloalkanediyl group having 5 to 12 carbon atoms is preferable.
• alkenyl group examples include an ethenyl group, a propendyl group, a butenyl group and the like.
• alkendyl group an alkendyl group having 2 to 6 carbon atoms is preferable.
• the * The -R LA O-a R LA mention may be made of the alkanediyl group, the cycloalkanediyl group, said alkenediyl group.
• the * The -R LB COO- R LB it is possible to increase the alkanediyl group, the cycloalkanediyl group, said alkenediyl group, an arenediyl group.
• Examples of the arrangedyl group include a phenylene group, a trilene group, a naphthylene group and the like.
• As the arenediyl group an arenediyl group having 6 to 15 carbon atoms is preferable.
• R 8 is an alkyl group having 1 to 4 carbon atoms, and cycloalkanes having a polycyclic or monocyclic alicyclic structure in which R 9 and R 10 are combined with each other and composed of carbon atoms to which they are bonded. It is preferably a structure.
• L 1 is preferably single bond or * -R LA O-. The R LA alkanediyl group.
• the structural unit (a2-1) is, for example, a structural unit represented by the following formulas (2-1) to (2-4) (hereinafter, "structural unit (a2-1-1) to (a2)”. -1-4) ”), etc. can be mentioned.
• R 7 ⁇ R 10 are as defined in formula (5).
• i and j are each independently an integer of 1 to 4.
• R 8 to R 10 a methyl group, an ethyl group or an isopropyl group is preferable.
• the structural unit (a2-1) is preferably the structural unit (a2-1-1) and the structural unit (a2-1-2), and is a structural unit having a cyclopentane structure and a structure having an adamantan structure.
• Units are more preferred, structural units derived from 1-alkylcyclopentyl (meth) acrylate, structural units derived from 2-alkyladamantyl (meth) acrylate, more preferably structural units derived from 1-methylcyclohexyl (meth) acrylate, Structural units derived from 2-ethyladamantyl (meth) acrylate are particularly preferred.
• the resin (A) may contain one type or a combination of two or more types of structural units (a2).
• the lower limit of the content ratio of the structural unit (a2) 10 mol% is preferable, 15 mol% is more preferable, 20 mol% is further preferable, and 30 mol% is more preferable with respect to all the structural units constituting the resin (A) which is a base resin.
• the upper limit of the content ratio is preferably 90 mol%, more preferably 80 mol%, further preferably 75 mol%, and particularly preferably 70 mol%.
• the structural unit (a3) is a structural unit including a lactone structure, a cyclic carbonate structure, a sultone structure, or a combination thereof.
• the resin (A) has a structural unit (a1) and a structural unit (a2) in addition to the structural unit (a2), the polarity can be made appropriate.
• the radiation-sensitive resin composition can form a resist pattern that is finer and has an excellent rectangular cross-sectional shape as a chemically amplified resist material.
• the lactone structure refers to a structure having one ring (lactone ring) containing a group represented by —O—C (O) —.
• the cyclic carbonate structure refers to a structure having one ring (cyclic carbonate ring) containing a group represented by —O—C (O) —O—.
• the sultone structure refers to a structure having one ring (sultone ring) containing a group represented by —S (O) 2-.
• RAL is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.
• R AL preferably a hydrogen atom and a methyl group from the viewpoint of copolymerizability of the monomer giving the structural unit (a3), more preferably a methyl group.
• the structural unit (a3) includes a structural unit containing a norbornan lactone structure, a structural unit containing an oxanorbornane lactone structure, a structural unit containing a ⁇ -butyrolactone structure, a structural unit containing an ethylene carbonate structure, and a norbornan sulton structure.
• a structural unit containing is preferable, a structural unit derived from norbornan lactone-yl (meth) acrylate, a structural unit derived from oxanorbornene lactone-yl (meth) acrylate, and a structure derived from cyano-substituted norbornan lactone-yl (meth) acrylate.
• the lower limit of the content ratio of the structural unit (a3) to all the structural units constituting the resin (A) is preferably 1 mol%, more preferably 10 mol%. , 20 mol% is more preferred, and 25 mol% is particularly preferred.
• the upper limit of the content ratio 70 mol% is preferable, 65 mol% is more preferable, 60 mol% is further preferable, and 55 mol% is particularly preferable.
• the resin (A) may appropriately have other structural units (also referred to as structural units (a4)) other than the structural units (a1) to (a3).
• the structural unit (a4) include structural units having a fluorine atom, an alcoholic hydroxyl group, a carboxy group, a cyano group, a nitro group, a sulfonamide group and the like.
• a structural unit having a fluorine atom, a structural unit having an alcoholic hydroxyl group and a structural unit having a carboxy group are preferable, and a structural unit having a fluorine atom and a structural unit having an alcoholic hydroxyl group are more preferable.
• the lower limit of the content ratio of the structural unit (a4) to all the structural units constituting the resin (A) is preferably 1 mol%, more preferably 20 mol%. , 40 mol% is more preferred.
• the upper limit of the content ratio 80 mol% is preferable, 75 mol% is more preferable, and 70 mol% is further more preferable.
• the resin (A) of the present invention for example, (a) a repeating structure of hydroxyphenyl units obtained by polymerizing a hydroxystyrene monomer protected by an alkali hydrolyzable group and then hydrolyzing it, and , (A) The repeating structure obtained by directly polymerizing the hydroxystyrene monomer can correspond to the above structural unit (a1).
• the content of the resin (A) is preferably 70% by mass or more, more preferably 75% by mass or more, still more preferably 80% by mass or more, based on the total solid content of the radiation-sensitive resin composition.
• the “solid content” refers to all the components contained in the radiation-sensitive resin composition except the solvent.
• the base resin resin (A) can be synthesized, for example, by subjecting a monomer giving each structural unit to a polymerization reaction 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 radical initiators such as cumene hydroperoxide. 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 in the polymerization reaction include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane; cyclohexane, cycloheptan, cyclooctane, and decalin.
• Cycloalkanes such as norbornan
• aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene
• halogenated hydrocarbons such as chlorobutane, bromohexane, dichloroethane, hexamethylenedibromid, chlorobenzene
• acetic acid Saturated carboxylic acid esters such as ethyl, n-butyl acetate, i-butyl acetate, methyl propionate
• ketones such as acetone, methyl ethyl ketone, 4-methyl-2-pentanone, 2-heptanone
• tetrahydrofuran dimethoxyethanes, di Ethers such as ethoxyethanes
• alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 4-methyl-2-pentanol and the like can be mentioned.
• the reaction temperature in the above polymerization reaction 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 resin (A) is not particularly limited, but the polystyrene-equivalent weight average molecular weight (Mw) by gel permeation chromatography (GPC) is preferably 1,000 or more and 50,000 or less, preferably 2,000 or more and 30, It is more preferably 000 or less, further preferably 3,000 or more and 15,000 or less, and particularly preferably 4,000 or more and 12,000 or less. If the Mw of the resin (A) is less than the above lower limit, the heat resistance of the obtained resist film may decrease. If the Mw of the resin (A) exceeds the above upper limit, the developability of the resist film may decrease.
• 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 resin (A) by GPC is usually 1 or more and 5 or less, preferably 1 or more and 3 or less, and 1 or more and 2 or less. More preferred.
• 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
• Detector Differential refractometer Standard material: Monodisperse polystyrene
• the content of the resin (A) 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 contains, as another resin, a resin having a larger mass content of fluorine atoms than the base resin (hereinafter, also referred to as “(E) high fluorine content resin”). You may be.
• the radiation-sensitive resin composition contains a high-fluorine content resin, it can be unevenly distributed on the surface layer of the resist film with respect to the base resin, and as a result, the state of the surface of the resist film and the components in the resist film can be distributed. The distribution can be controlled to the desired state.
• the high fluorine content resin has, for example, the structural unit (a1) and the structural unit (a2) in the base resin, and the structural unit represented by the following formula (4) (hereinafter, “structural unit (a5)””. Also referred to as).
• R 13 is a hydrogen atom, a methyl group or a trifluoromethyl group.
• G is a single bond, an oxygen atom, a sulfur atom, -COO-, -SO 2 ONH-, -CONH- or -OCONH-.
• R 14 is a monovalent fluorinated chain hydrocarbon group having 1 to 20 carbon atoms or a monovalent fluorinated alicyclic hydrocarbon group having 3 to 20 carbon atoms.
• R 13 from the viewpoint of copolymerizability of the monomer giving the structural unit (a5), preferably a hydrogen atom or a methyl group, more preferably a methyl group.
• a single bond and -COO- are preferable, and -COO- is more preferable, from the viewpoint of copolymerizability of the monomer giving the structural unit (a5).
• the monovalent fluorinated alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R 14 is a part of hydrogen atoms of a monocyclic or polycyclic hydrocarbon group having 3 to 20 carbon atoms.
• the ones that are all substituted with fluorine atoms can be mentioned.
• R 14 preferably a fluorinated chain hydrocarbon group, more preferably a fluorinated alkyl group, a 2,2,2-trifluoroethyl group, 1,1,1,3,3,3-hexafluoro-propyl Groups and 5,5,5-trifluoro-1,1-diethylpentyl groups are more preferred.
• the lower limit of the content ratio of the structural unit (a5) is preferably 10 mol%, preferably 15 mol%, based on all the structural units constituting the high fluorine content resin. Is more preferable, 20 mol% is further preferable, and 25 mol% is particularly preferable. As the upper limit of the content ratio, 60 mol% is preferable, 50 mol% is more preferable, and 40 mol% is further more preferable.
• the high fluorine content resin may have a fluorine atom-containing structural unit represented by the following formula (f-1) (hereinafter, also referred to as a structural unit (a6)) in addition to the structural unit (a5). .. Since the high fluorine content resin has a structural unit (f-1), its solubility in an alkaline developer can be improved and the occurrence of development defects can be suppressed.
• the structural unit (a6) may be a group having (x) an alkali-soluble group or a group (y) that dissociates due to the action of an alkali to increase its solubility in an alkaline developer (hereinafter, simply referred to as an "alkali dissociative group"). It is roughly divided into two cases of having). Common to both (x) and (y), in the above formula (f-2), RC is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
• R D is a single bond, having from 1 to 20 carbon atoms (s + 1) -valent hydrocarbon group, an oxygen atom at the terminal of R E side of the hydrocarbon group, a sulfur atom, -NR dd -, carbonyl group, -COO- or 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 by 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.
• R F is a hydrogen atom
• a 1 is an oxygen atom
• -COO- * or -SO 2 O-* is. * Indicates a site which binds to R F.
• W 1 is a single bond, 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 RE , W 1 , A 1 and RF may be the same or different, respectively.
• the structural unit (a6) has the (x) alkali-soluble group, the affinity for the alkaline developer can be enhanced and development defects can be suppressed.
• (X) As the structural unit (a6) 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.
• R F is a monovalent organic group having 1 to 30 carbon atoms
• a 1 is an oxygen atom, -NR aa -, - COO- *, or -SO 2 O- *.
• Raa is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. * Indicates a site which binds to R F.
• 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 R F is a fluorine atom on the carbon atom adjacent to the carbon atoms or which binds to A 1.
• W 1 is an oxygen atom
• W 1 is a single bond
• R D is a structure bonded carbonyl group at the terminal of R E side of the hydrocarbon group having 1 to 20 carbon atoms
• R F is an organic group having a fluorine atom.
• the plurality of RE , W 1 , A 1 and RF may be the same or different, respectively.
• the structural unit (a6) has the (y) alkali dissociative group, the surface of the resist film changes from hydrophobic to hydrophilic in the alkaline development step. As a result, the affinity for the developing solution can be significantly increased, and development defects can be suppressed more efficiently.
• the structural unit (a6) having (y) alkali dissociative group, A 1 is -COO- *, which both R F or W 1 or they have a fluorine atom is particularly preferred.
• 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 (a6).
• 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 lower limit of the content ratio of the structural unit (a6) is preferably 10 mol%, preferably 20 mol%, based on all the structural units constituting the high fluorine content resin. Is more preferable, 30 mol% is further preferable, and 35 mol% is particularly preferable.
• the upper limit of the content ratio 90 mol% is preferable, 75 mol% is more preferable, and 60 mol% is further more preferable.
• Mw of the high fluorine content resin 1,000 is preferable, 2,000 is more preferable, 3,000 is further preferable, and 5,000 is particularly preferable.
• Mw 50,000 is preferable, 30,000 is more preferable, 20,000 is further preferable, and 15,000 is particularly preferable.
• 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 1.7.
• the lower limit of the content of the high fluorine content resin is preferably 0.1% by mass, more preferably 0.5% by mass, and 1% by mass with respect to the total solid content in the radiation-sensitive resin composition. More preferably, 1.5% by mass is further preferable.
• the upper limit of the content is preferably 20% by mass, more preferably 15% by mass, further preferably 10% by mass, and particularly preferably 7% by mass.
• the lower limit of the content of the high fluorine content resin 0.1 part by mass is preferable, 0.5 part by mass is more preferable, and 1 part by mass is further preferable, 1.5 parts by mass with respect to 100 parts by mass of the base resin. Parts by mass are particularly preferred.
• the upper limit of the content is preferably 15 parts by mass, more preferably 10 parts by mass, further preferably 8 parts by mass, and particularly preferably 5 parts by mass.
• 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 sulfonate compound (B0) in the present invention is a compound represented by the following formula (1).
• R f is independently a hydrogen atom, a fluorine atom, or a fluoroalkyl group, and at least one R f is a fluorine atom, or a fluoroalkyl group.
• m is 1 or 2 and n is an integer of 4-8.
• L 1 is -O-, -S-, or -SO 2-
• R is an m-valent hydrocarbon group
• X + is a monovalent radiation-sensitive onium cation.
• R f is independently a hydrogen atom, a fluorine atom, or a fluoroalkyl group, and at least one R f is a fluorine atom or a fluoroalkyl group.
• R fs is independently a fluorine atom or a fluoroalkyl group.
• the fluoroalkyl group in the above formula (1) means an alkyl group containing at least one fluorine atom.
• Examples of the fluoroalkyl group include fluoroalkyl groups having 1 to 10 carbon atoms.
• M in the above formula (1) is 1 or 2.
• N in the above formula (1) is an integer of 4 to 8.
• L 1 in the above formula (1) is -O-, -S-, or -SO 2- .
• the L 1 is, -SO 2 - can be cited as a case where a preferred example.
• R in the above formula (1) is an m-valent hydrocarbon group.
• R for example, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted alicyclic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted heterocyclic group.
• a certain case can be given as a preferable example.
• Alkyl groups such as methyl group, ethyl group, propyl group and butyl group; alkenyl groups such as ethenyl group, propenyl group and butenyl group; aliphatic hydrocarbon groups such as alkynyl group such as ethynyl group, propynyl group and butynyl group; Cycloalkyl groups such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group; Alicyclic hydrocarbon groups such as cycloalkenyl groups such as cyclopropenyl group, cyclopentenyl group, cyclohexenyl group; Bridged alicyclic hydrocarbon groups such as norbornyl group, tricyclodecyl group, adamantyl group, norbornenyl group; Aromatic hydrocarbon groups such as aralkyl groups such as phenyl group, tolyl group,
• the above-mentioned aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or unsubstituted heterocyclic group may be an alkyl group such as a methyl group, a cyclic acetal structure, a ketal structure or the like. through including such form which is bound to the L 1.
• X + in the above formula (1) is a monovalent radiation-sensitive onium cation.
• Examples of the compound in the above formula (1) include, but are not limited to, the following compounds.
• the total content of the sulfonate compound (B0) in the resin composition is preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the resin (A). It can be 1 to 20 parts by mass, and can be 3 to 15 parts by mass. Further, the sulfonate compound (B0) may be used alone or in combination of two or more.
• the radiation-sensitive acid generator (B) in the present invention is a radiation-sensitive acid generator containing a sulfonate compound represented by the following formula (1).
• R f is independently a hydrogen atom, a fluorine atom, or a fluoroalkyl group, and at least one R f is a fluorine atom, or a fluoroalkyl group.
• m is 1 or 2 and n is an integer of 4-8.
• L 1 is -O-, -S-, or -SO 2-
• R is an m-valent hydrocarbon group
• X + is a monovalent radiation-sensitive onium cation.
• the radiation-sensitive acid generator (B) is a radiation-sensitive acid generator that generates acid by irradiation with radiation.
• the total content of the radiation-sensitive acid generator (B) in the resin composition is 0.5 to 30 parts by mass with respect to 100 parts by mass of the resin (A). Preferably, it can be 1 to 20 parts by mass, and can be 3 to 15 parts by mass. If the blending amount or content ratio is smaller than the above lower limit, the sensitivity may decrease. On the contrary, if the blending amount or the content ratio exceeds the upper limit, it may be difficult to form a resist film, or the rectangularity of the cross-sectional shape of the resist pattern may be deteriorated. Further, the radiation-sensitive acid generator (B) may be used alone or in combination of two or more. Further, a known radiation-sensitive acid generator may be used in combination as long as the action and effect of the present invention are not impaired.
• the radiation-sensitive resin composition contains a solvent.
• the solvent is not particularly limited as long as it is a solvent capable of dissolving or dispersing at least a resin, a radiation-sensitive acid generator, an acid diffusion control agent contained if desired, and the like.
• 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. Hydrate alcohol solvent; Examples thereof include a polyhydric alcohol partial ether solvent obtained by etherifying a part of the hydroxy groups of the polyhydric alcohol solvent.
• ether solvent 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: 2,4-Pentandione, acetonylacetone, acetophenone and the like can be mentioned.
• amide solvent examples include cyclic amide solvents such as N, N'-dimethylimidazolidinone and N-methylpyrrolidone; Chain amide solvents such as N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, and N-methylpropionamide can be mentioned. can.
• ester solvent examples include Monocarboxylic acid ester solvents 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 valero lactone; 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, methoxytriglycol acetate, diethyl oxalate, ethyl acetoacetate, ethyl lactate, and diethyl phthalate.
• Monocarboxylic acid ester solvents such as n-butyl acetate and ethyl lactate
• hydrocarbon solvent examples include, for example. 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 partial 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 or more solvents.
• the radiation-sensitive resin composition may contain other optional components in addition to the above components.
• the other optional components include acid diffusion control agents, cross-linking agents, uneven distribution accelerators, surfactants, alicyclic skeleton-containing compounds, and sensitizers. These other optional components may be used alone or in combination of two or more.
• the radiation-sensitive resin composition may contain an acid diffusion control agent, if necessary.
• the acid diffusion control agent has the effect of controlling the diffusion phenomenon of the acid generated from the radiation-sensitive acid generator by exposure in the resist film and suppressing an unfavorable chemical reaction in the non-exposed region.
• the storage stability of the obtained radiation-sensitive resin composition is improved.
• the resolution of the resist pattern is further improved, and the change in the line width of the resist pattern due to the fluctuation of the leaving time from the exposure to the development process can be suppressed, so that a radiation-sensitive resin composition having excellent process stability can be obtained. Be done.
• Examples of the acid diffusion control agent include a compound represented by the following formula (5) (hereinafter, also referred to as “nitrogen-containing compound (I)”) and a compound having two nitrogen atoms in the same molecule (hereinafter, “containing”. "Nitrogen compound (II)”), a compound having three nitrogen atoms (hereinafter, also referred to as “nitrogen-containing compound (III)”), an amide group-containing compound, a urea compound, a nitrogen-containing heterocyclic compound and the like can be mentioned. can.
• R 22 , R 23, and R 24 are independently hydrogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted aryl groups, or It is a substituted or unsubstituted aralkyl group.
• nitrogen-containing compound (I) examples include monoalkylamines such as n-hexylamine; dialkylamines such as di-n-butylamine; trialkylamines such as triethylamine; aromatic amines such as aniline. I can give it.
• nitrogen-containing compound (II) examples include ethylenediamine, N, N, N', N'-tetramethylethylenediamine and the like.
• nitrogen-containing compound (III) examples include polyamine compounds such as polyethyleneimine and polyallylamine; and polymers such as dimethylaminoethylacrylamide.
• amide group-containing compound examples include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone and the like. I can give it.
• urea compound examples include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tributylthiourea and the like. Can be done.
• nitrogen-containing heterocyclic compound examples include pyridines such as pyridine and 2-methylpyridine; morpholines such as N-propylmorpholin and N- (undecylcarbonyloxyethyl) morpholin; pyrazine, pyrazole and the like. ..
• nitrogen-containing organic compound a compound having an acid dissociative group can also be used.
• the nitrogen-containing organic compound having such an acid dissociative group include tert-butoxycarbonylpiperidin, tert-butoxycarbonylimidazole, tert-butoxycarbonylbenzimidazole, and tert-butoxycarbonyl-.
• 2-Phenylbenzimidazole N- (t-butoxycarbonyl) di-n-octylamine, N- (t-butoxycarbonyl) diethanolamine, N- (t-butoxycarbonyl) dicyclohexylamine, N- (t-butoxycarbonyl) Examples thereof include diphenylamine, tert-butoxycarbonyl-4-hydroxypiperidine, tert-amyloxycarbonyl-4-hydroxypiperidine and the like.
• a photodisintegrating base that generates a weak acid upon exposure
• the photodisintegrating base include compounds containing a radiation-sensitive onium cation and a weak acid anion that are decomposed by exposure.
• weak acid is generated from the proton generated by the decomposition of the radiation-sensitive onium cation and the anion of the weak acid in the exposed portion, so that the acid diffusion controllability is lowered.
• Examples of the photodisintegrating base include a sulfonium salt compound represented by the following formula (6-1), an iodonium salt compound represented by the following formula (6-2), and the like.
• J + is a sulfonium cation and U + is an iodonium cation.
• the sulfonium cation represented by J + includes the sulfonium cation represented by the following formulas (1-1-a) and (1-1-b) and the sulfonium cation represented by the following formula (X-1).
• Examples of the iodonium cation represented by U + include the iodonium cation represented by the above formula (1-1-c) and the iodonium cation represented by the following formula (X-2). .. E- and Q- are independently anions represented by OH-, R ⁇ -COO-, and R ⁇ -SO3-.
• R ⁇ is an alkyl group, an aryl group or an aralkyl group.
• the hydrogen atom of the aromatic ring of the aryl group or the aralkyl group represented by R ⁇ is substituted with a hydroxy group, a fluorine atom substituted or unsubstituted alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. May be good.
• R c1 , R c2, and R c3 are independently 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.
• 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.
• substituents which may replace the hydrogen atom of each of the above groups include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, hydroxy group, carboxy group, cyano group, nitro group and alkyl.
• halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, hydroxy group, carboxy group, cyano group, nitro group and alkyl.
• Group when substituting a hydrogen atom of a cycloalkyl group or aromatic hydrocarbon group
• aryl group when substituting a hydrogen atom of an alkyl group
• alkoxy group, alkoxycarbonyl group, alkoxycarbonyloxy group, acyl group, acyloxy The group etc. can be mentioned.
• a hydroxy group, an alkoxy group, an alkoxycarbonyl group, an alkoxycarbonyloxy group, an acyl group, and an acyloxy group are preferable, and an alkoxy group or an alkoxycarbonyl group is more preferable.
• Examples of the photodisintegrating base include compounds represented by the following formulas.
• a sulfonium salt is preferable, a triarylsulfonium salt is more preferable, and triphenylsulfonium salicylate and triphenylsulfonium 10-camphorsulfonate are further preferable.
• the lower limit of the content of the acid diffusion control agent 3 parts by mass is preferable, 4 parts by mass is more preferable, and 5 parts by mass is further preferable with respect to 100 parts by mass in total of the radiation-sensitive acid generator.
• the upper limit of the content 150 parts by mass is preferable, 120 parts by mass is more preferable, and 110 parts by mass is further preferable.
• the radiation-sensitive resin composition may contain one or more acid diffusion control agents.
• the cross-linking agent is a compound having two or more functional groups, and in the baking step after the batch exposure step, an acid-catalyzed reaction causes (1) a cross-linking reaction in the polymer component and (1) increases the molecular weight of the polymer component. By doing so, the solubility of the pattern exposed portion in the developing solution is lowered.
• the functional group include a (meth) acryloyl group, a hydroxymethyl group, an alkoxymethyl group, an epoxy group, a vinyl ether group and the like.
• the uneven distribution accelerator has the effect of more efficiently unevenly distributing the high fluorine content resin on the surface of the resist film.
• this uneven distribution accelerator in the radiation-sensitive resin composition, the amount of the high-fluorine-containing resin added can be reduced as compared with the conventional case. Therefore, while maintaining the lithography performance of the radiation-sensitive resin composition, it is possible to further suppress the elution of components from the resist film to the immersion medium, and to perform immersion exposure at a higher speed by high-speed scanning. As a result, the hydrophobicity of the surface of the resist film that suppresses immersion-derived defects such as watermark defects can be improved.
• Examples of those that can be used as such an uneven distribution accelerator include low molecular weight compounds having a relative permittivity of 30 or more and 200 or less and a boiling point of 100 ° C. or more at 1 atm.
• Specific examples of such a compound include a lactone compound, a carbonate compound, a nitrile compound, and a polyhydric alcohol.
• lactone compound examples include ⁇ -butyrolactone, valero lactone, mevalonic lactone, norbornane lactone and the like.
• Examples of the carbonate compound include propylene carbonate, ethylene carbonate, butylene carbonate, vinylene carbonate and the like.
• nitrile compound examples include succinonitrile.
• Examples of the above-mentioned polyhydric alcohol include glycerin and the like.
• the lower limit of the content of the uneven distribution accelerator 10 parts by mass is preferable, 15 parts by mass is more preferable, and 20 parts by mass is further preferable with respect to 100 parts by mass of the total amount of the resin in the radiation-sensitive resin composition. 25 parts by mass is more preferable.
• the upper limit of the content is preferably 300 parts by mass, more preferably 200 parts by mass, further preferably 100 parts by mass, and particularly preferably 80 parts by mass.
• the radiation-sensitive resin composition may contain one or more of the uneven distribution accelerators.
• Surfactant Surfactants have the effect of improving coatability, striation, developability and the like.
• the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, and polyethylene glycol.
• Nonionic surfactants such as distearate; commercially available products include KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), Polyflow No. 75, No.
• the content of the surfactant in the radiation-sensitive resin composition is usually 2 parts by mass or less with respect to 100 parts by mass of the resin.
• the alicyclic skeleton-containing compound has the effect of improving dry etching resistance, pattern shape, adhesiveness to a substrate, and the like.
• Examples of the alicyclic skeleton-containing compound include Adamantane derivatives such as 1-adamantane carboxylic acid, 2-adamantanone, 1-adamantane carboxylic acid t-butyl; Deoxycholic acid esters such as t-butyl deoxycholic acid, t-butoxycarbonylmethyl deoxycholic acid, and 2-ethoxyethyl deoxycholic acid; Lithocholic acid esters such as t-butyl lithocholic acid, t-butoxycarbonylmethyl lithocholic acid, 2-ethoxyethyl lithocholic acid; 3- [2-Hydroxy-2,2-bis (trifluoromethyl) ethyl] tetracyclo [4.4.0.1 (2,5).
• the content of the alicyclic skeleton-containing compound in the radiation-sensitive resin composition is usually 5 parts by mass or less with respect to 100 parts by mass of the resin.
• the sensitizer has an effect of increasing the amount of acid produced from a radiation-sensitive acid generator or the like, and has an effect of improving the "apparent sensitivity" of the radiation-sensitive resin composition.
• sensitizer examples include carbazoles, acetophenones, benzophenones, naphthalenes, phenols, biacetyls, eosin, rose bengal, pyrenes, anthracenes, phenothiazines and the like. These sensitizers may be used alone or in combination of two or more.
• the content of the sensitizer in the radiation-sensitive resin composition is usually 2 parts by mass or less with respect to 100 parts by mass of the resin.
• the radiation-sensitive resin composition contains, for example, a resin, the sulfonate compound (or a radiation-sensitive acid generator), an acid diffusion control agent, a high-fluorine content resin, or the like, if necessary, and a solvent in a predetermined ratio. It can be prepared by mixing with. After mixing, the radiation-sensitive resin composition is preferably filtered with, for example, a filter having a pore size of about 0.05 ⁇ 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 resist pattern forming method in the present invention is Steps of forming a resist film with the radiation-sensitive resin composition (1) (hereinafter, also referred to as “resist film forming step”), The step (2) of exposing the resist film (hereinafter, also referred to as “exposure step”) is included.
• the radiation-sensitive resin composition since the radiation-sensitive resin composition is used, it is possible to form a resist pattern capable of exhibiting sensitivity and LWR performance in the exposure process at an excellent level.
• each step will be described.
• a resist film is formed from the radiation-sensitive resin composition. More specifically, it is a step of directly or indirectly applying the radiation-sensitive resin composition on a substrate to form a resist film.
• the substrate on which the resist film is formed include conventionally known wafers such as silicon wafers, silicon dioxide, and wafers coated with aluminum.
• an organic or inorganic antireflection film disclosed in Japanese Patent Application Laid-Open No. 6-12452 and Japanese Patent Application Laid-Open No. 59-93448 may be formed on the substrate.
• the coating method include rotary coating (spin coating), cast coating, roll coating and the like.
• prebaking 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 of the 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 includes electromagnetic waves such as visible light, ultraviolet rays, far ultraviolet rays, EUV (extreme ultraviolet rays), X-rays, and ⁇ -rays; electron beams, ⁇ -rays, and the like, 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 EUVs are more preferable.
• the immersion liquid to be used include water and a fluorine-based inert liquid.
• the immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has a refractive index temperature coefficient as small as possible so as to minimize 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.
• a step (3) (hereinafter, also referred to as “development step”) for developing the exposed resist film can be included.
• the resist film exposed in the exposure step which is the step (2) is developed.
• a predetermined resist pattern can be formed.
• it is generally washed with a rinse solution such as water or alcohol and dried.
• 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-.
• TMAH tetramethylammonium hydroxide
• pyrrole pyrrole
• piperidine choline
• 1,8-diazabicyclo- [5.4.0] -7-undecene 1,5-Diazabicyclo- [4.3.0] -5-None and the like
• 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.
• organic solvents such as hydrocarbon solvents, ether solvents, ester solvents, ketone solvents, alcohol solvents, etc., or solvents containing organic solvents can be mentioned.
• organic solvent include one or more of the solvents listed as the solvent of the above-mentioned radiation-sensitive resin composition.
• ester-based solvents and ketone-based solvents are preferable.
• the 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.
• 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 developing by 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
• paddle a method of developing by 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 continuing to apply the developer on the substrate rotating at a constant speed while scanning the developer application nozzle at a constant speed
• the substrate processing method in the present invention is Further, the step (4-1) of forming a pattern on the substrate by using the resist pattern formed by the above method as a mask is included.
• the method for producing a metal film pattern in the present invention is as follows. Further, the step (4-2) of forming a metal film by using the resist pattern formed by the above method as a mask is included.
• the radiation-sensitive resin composition is used in the substrate processing method and the metal film pattern manufacturing method, high-quality substrate patterns and metal film patterns can be processed, respectively.
• the above step (4-1) is a step of forming a pattern on the substrate by using the resist pattern formed by any of the methods as a mask as a mask, but as a method of forming a pattern on the substrate by using the resist pattern as a mask.
• a method of forming a resist pattern on a substrate and then forming a pattern on the substrate by a method such as dry etching on a portion without a resist, or a method of forming a resist pattern and then applying a substrate component to a portion without a resist by CVD or the like examples thereof include a method of forming a part or all of a substrate by depositing a metal or attaching a metal by a method such as electroless plating.
• the above step (4-2) is a step of forming a metal film by using the resist pattern formed by any of the methods as a mask as a mask.
• a method of forming a metal film by using the resist pattern as a mask for example.
• a metal film is formed by adhering metal to the part without resist by a method such as electroless plating, or a resist pattern is formed on the metal film and the metal film of the part without resist is formed.
• a method of forming a metal film by removing the metal film by a method such as dry etching can be mentioned.
• Mw weight average molecular weight
• Mn number average molecular weight
• dispersity Mw / Mn
• a GPC column manufactured by Toso Co., Ltd. G2000HXL: 2, G3000HXL: 1, and G4000HXL: 1 was used, the flow rate was 1.0 mL / min, and the elution solvent was tetrahydrofuran.
• sample concentration 1.0% by mass
• sample injection volume 100 ⁇ L
• column temperature 40 ° C.
• detector under the analysis conditions of a differential refractometer
• measurement was performed by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard.
• the dispersity (Mw / Mn) was calculated from the measurement results of Mw and Mn.
• 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 obtained 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%, 13.8 mol% and 13.8 mol%, respectively. It was 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 Mw of the obtained resin (A-12) was 5,200, and the Mw / Mn was 1.60.
• the content ratios of the structural units derived from (M-1) and (M-18) were 51.3 mol% and 48.7 mol%, respectively.
• the Mw of the obtained 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 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. Extraction with acetonitrile and distilling off the solvent gave a sodium sulfonic acid salt compound.
• C-1 to C-5 Compounds represented by the following formulas (C-1) to (C-5).
• Example 1 [A] 100 parts by mass of (A-1) as a resin, [B] 10.0 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-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 apparatus
• the exposure amount for forming the 40 nm line-and-space pattern is set as the optimum exposure amount, and this optimum exposure amount is defined as the sensitivity (mJ / cm 2 ). bottom.
• the sensitivity was evaluated as "good” when it was 20 mJ / cm 2 or less, and as “poor” when it exceeded 20 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 the upper part of 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 3.5 nm or less, and as “poor” when it exceeded 3.5 nm.
• the radiation-sensitive resin composition of the examples had good sensitivity and LWR performance when used for ArF exposure, whereas in the comparative example, each characteristic had each characteristic. It 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 45 [A] 100 parts by mass of (A-12) as a resin, [B] 13.0 parts by mass of (B-3) as a radiation-sensitive acid generator, [C] (C-2) 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-1) / (D-4) as a [D] solvent.
• a radiation-sensitive resin composition (J-45) was prepared by mixing 6,110 parts by mass of the mixed solvent of No. 6 and filtering with a membrane filter having a pore size of 0.2 ⁇ m.
• 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 was defined as the optimum exposure amount, and this optimum exposure amount was defined as the sensitivity (mJ / cm 2 ).
• 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 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 the upper part of 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 4.0 nm or less and “poor” when it exceeded 4.0 nm.
• the radiation-sensitive resin composition of the examples had good sensitivity and LWR performance when used for EUV exposure, whereas in the comparative example, each characteristic had each characteristic. It was inferior to.
• ASML's "TWINSCAN XT-1900i” ArF excimer laser immersion exposure apparatus
• 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 determined 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 54 formed a negative type resist pattern by ArF exposure. Even in this case, the sensitivity and CDU performance were good.
• Example 55 [A] 100 parts by mass of (A-13) as a resin, [B] 20.0 parts by mass of (B-17) as a radiation-sensitive acid generator, [C] (C-2) as an acid diffusion control agent ) 5.0 parts by mass, [E] 3.0 parts by mass (solid content) of (E-5) as a high fluorine content resin, and (D-1) / (D-4) as a [D] solvent.
• a radiation-sensitive resin composition (J-55) was prepared by mixing 6,110 parts by mass of the mixed solvent of No. 6 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 55 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 of the present invention it is possible to form a resist pattern having good sensitivity to light and excellent LWR performance and CDU performance.
• the radiation-sensitive resin composition and the resist pattern forming method of the present invention can be suitably used for a processing process of a semiconductor device or the like, which is expected to be further miniaturized in the future.

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