Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
  • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
  • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
  • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more 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, directly attached to ring carbon atoms
  • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
  • C07D239/47—One nitrogen atom and one oxygen or sulfur atom, e.g. cytosine
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
  • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
  • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
  • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more 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, directly attached to ring carbon atoms
  • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
  • C07D239/52—Two oxygen atoms
  • C07D239/54—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
  • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
  • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
  • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more 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, directly attached to ring carbon atoms
  • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
  • C07D239/52—Two oxygen atoms
  • C07D239/54—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals
  • C07D239/545—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals with other hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
  • C07D239/553—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals with other hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms with halogen atoms or nitro radicals directly attached to ring carbon atoms, e.g. fluorouracil
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
  • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
  • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
  • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more 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, directly attached to ring carbon atoms
  • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
  • C07D239/52—Two oxygen atoms
  • C07D239/54—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals
  • C07D239/545—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals with other hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
  • C07D239/557—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals with other hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms, e.g. orotic acid
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
  • C07D239/70—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings condensed with carbocyclic rings or ring systems
  • C07D239/72—Quinazolines; Hydrogenated quinazolines
  • C07D239/95—Quinazolines; Hydrogenated quinazolines with hetero atoms directly attached in positions 2 and 4
  • C07D239/96—Two oxygen atoms
• • 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
  • C07D493/04—Ortho-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
• • 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
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor

Definitions

• the present invention relates to a radiation-sensitive resin composition, 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 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 with respect to 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 A technology to improve the lithography performance by ArF exposure by blending a quencher (diffusion control agent) in the resist composition and capturing the acid diffused to the unexposed part by salt exchange reaction while the efforts for further technological progress are progressing.
• a quencher diffusion control agent
• EUV extreme ultraviolet
• CDU critical dimension uniformity
• LWR line widow roughness
• An object of the present invention is to provide a radiation-sensitive resin composition and a pattern forming method capable of exhibiting sensitivity, CDU performance, and LWR performance at a sufficient level.
• the present invention in one embodiment, comprises an onium salt compound and A resin containing a structural unit having an acid dissociative group, Containing with solvent,
• the feeling that the onium salt compound is at least one selected from the group consisting of the onium salt compound (1) represented by the following formula (1) and the onium salt compound (2) represented by the following formula (2).
• Radiation resin composition (In the above formula (1), R 1 is a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms.
• R 2 and R 3 are independently hydrogen atoms, halogen atoms, carboxy groups, amino groups or monovalent organic groups having 1 to 40 carbon atoms, or R 2 and R 3 are combined with each other.
• X 1 and X 2 are independently oxygen atoms or sulfur atoms, respectively. However, X 1 and X 2 are not both be a sulfur atom.
• Z 1 + is a monovalent radiation-sensitive onium cation.
• R 4 is a hydrogen atom, a monovalent organic group halogen atoms or 1 to 40 carbon atoms.
• R 5 and R 6 are independently hydrogen atoms or monovalent organic groups having 1 to 40 carbon atoms, or R 5 and R 6 are combined with each other and are composed of nitrogen atoms to which they are bonded. It represents a ring structure having 3 to 8 ring members.
• Z 2 + is a monovalent radiation-sensitive onium cation.
• the radiation-sensitive resin composition contains at least one of an onium salt compound (1) and an onium salt compound (2) as a quencher (acid diffusion control agent), it has excellent sensitivity in forming a resist pattern. , CDU performance, and LWR performance can be demonstrated.
• both onium salt compounds have high transparency in the resist film, so that the sensitivity is good, and because they are relatively basic, they are in the unexposed part. It is presumed that the high acid capture property has an effect.
• the organic group means a group containing at least one carbon atom.
• 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 hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms.
• R 2 and R 3 are independently hydrogen atoms, halogen atoms, carboxy groups, amino groups or monovalent organic groups having 1 to 40 carbon atoms, or R 2 and R 3 are combined with each other.
• X 1 and X 2 are independently oxygen atoms or sulfur atoms, respectively. However, X 1 and X 2 are not both be a sulfur atom.
• Z 1 + is a monovalent radiation-sensitive onium cation.
• the present invention relates to an onium salt compound represented by the following formula (2) (that is, an onium salt compound (2)).
• R 4 is a hydrogen atom, a monovalent organic group halogen atoms or 1 to 40 carbon atoms.
• R 5 and R 6 are independently hydrogen atoms or monovalent organic groups having 1 to 40 carbon atoms, or R 5 and R 6 are combined with each other and are composed of nitrogen atoms to which they are bonded. It represents a ring structure having 3 to 8 ring members.
• Z 2 + is a monovalent radiation-sensitive onium cation.
• both the onium salt compounds (1) and (2) can exhibit transparency and strong basicity in the resist film, when blended in a radiation-sensitive resin composition, they have excellent sensitivity at the time of forming a resist pattern. , CDU performance, and LWR performance can be imparted to the composition.
• the radiation-sensitive resin composition according to the present embodiment contains a predetermined onium salt compound, resin and 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 a high level of sensitivity, CDU performance and LWR performance to the radiation-sensitive resin composition.
• the onium salt compound can function as a quencher (also referred to as a "photodisintegrating base” or “acid diffusion control agent”) for capturing an acid before or in an unexposed area.
• a quencher also referred to as a "photodisintegrating base” or “acid diffusion control agent” for capturing an acid before or in an unexposed area.
• the onium salt compound (1) is represented by the following formula (1).
• R 1 is a hydrogen atom or a monovalent organic group having 1 to 40 carbon atoms.
• R 2 and R 3 are independently hydrogen atoms, halogen atoms, carboxy groups, amino groups or monovalent organic groups having 1 to 40 carbon atoms, or R 2 and R 3 are combined with each other.
• X 1 and X 2 are independently oxygen atoms or sulfur atoms, respectively. However, X 1 and X 2 are not both be a sulfur atom.
• Z 1 + is a monovalent radiation-sensitive onium cation.
• the above formula (1) it is not particularly restricted but includes monovalent organic group R 1, R 2 and 1 to 40 carbon atoms represented by R 3, a chain-like structure, or cyclic structure, or combinations thereof There may be.
• the chain structure include chain hydrocarbon groups which are saturated or unsaturated, linear or branched.
• Examples of the cyclic structure include cyclic hydrocarbon groups regardless of whether they are alicyclic, aromatic or heterocyclic.
• the monovalent organic group includes a substituted or unsubstituted monovalent chain hydrocarbon group having 1 to 20 carbon atoms and a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms.
• a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a combination thereof is preferable. Further, a group having a chain structure or a group having a cyclic structure in which a part or all of hydrogen atoms are substituted with a substituent, and CO, CS, O, S, SO between carbon and carbon of these groups. 2 or NR', or a group containing a combination of two or more of these is also mentioned.
• R' is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
• Examples of the substituent that replaces a part or all of the hydrogen atom of the organic group include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxy group; carboxy group; cyano group; nitro group; alkyl.
• 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 alibic alicyclic hydrocarbon group is a polycyclic alicyclic compound in which two carbon atoms that are not adjacent to each other among the carbon atoms constituting the alicyclic are bonded by a bonding chain containing one or more carbon atoms.
• a cyclic hydrocarbon group is a polycyclic alicyclic compound in which two carbon atoms that are not adjacent to each other among the carbon atoms constituting the alicyclic are bonded by a bonding 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.
• heterocyclic cyclic hydrocarbon group examples include a group in which one hydrogen atom is removed from the aromatic heterocyclic structure and a group in which one hydrogen atom is removed from the alicyclic heterocyclic structure.
• the heterocyclic structure also includes a 5-membered aromatic structure having aromaticity by introducing a heteroatom.
• 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.
• the alicyclic heterocyclic structure includes, for example, an oxygen atom-containing alicyclic heterocyclic structure 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; Examples thereof include an alicyclic heterocyclic structure containing a plurality of heteroatoms such as morpholine, 1,2-oxathiolane, and 1,3-oxathiolane.
• an oxygen atom-containing alicyclic heterocyclic structure such as oxylane, tetrahydrofuran, tetrahydropyran, dioxolane, and dioxane
• Nitrogen atom-containing alicyclic heterocyclic structure such as aziridine,
• Examples of the cyclic structure include a lactone structure, a cyclic carbonate structure, a sultone structure, and a structure containing a cyclic acetal.
• Examples of such a structure include structures represented by the following formulas (H-1) to (H-10).
• m is an integer of 1 to 3.
• the ring structure having 5 to 8 ring members, in which R 2 and R 3 are combined with each other and composed of two carbon atoms to which they are bonded, is a double bond between two carbon atoms.
• the unsaturated cyclic hydrocarbon structure from which it is derived is preferably mentioned.
• Examples of the unsaturated cyclic hydrocarbon structure include a monocyclic cycloalkene structure having 5 to 8 carbon atoms such as cyclopentene, cyclohexene, and cycloheptene, and a benzene ring.
• Examples of the halogen atom represented by R 2 and R 3 in the above formula (1) include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
• the amino group represented by R 2 and R 3 may be substituted or unsubstituted.
• the unsubstituted amino group is represented by -NH 2.
• the substituted amino group include an alkylamino group such as a methylamino group and an ethylamino group; a dialkylamino group such as a dimethylamino group, a diethylamino group and a dipropylamino group; and a cycloalkylamino such as a cyclopropylamino group and a cyclobutylamino group.
• Group; Dicycloalkylamino group such as dicyclopropylamino group and dicyclobutylamino group; phenylamino group, diphenylamino group and the like can be mentioned.
• X 1 and X 2 are independently oxygen atoms or sulfur atoms, respectively. Both X 1 and X 2 are preferably oxygen atoms from the viewpoint of compound stability, basicity and the like.
• the monovalent radiation-sensitive onium cation represented by Z 1 + for example, S, I, O, N , P, Cl, Br, F, As, Se, Sn
• examples thereof include radiodegradable onium cations containing elements such as Sb, Te and Bi, and examples thereof include sulfonium cations, tetrahydrothiophenium cations, iodonium cations, phosphonium cations, diazonium cations and pyridinium cations. 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.
• 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 an substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms.
• k1, k2, and k3 are independently integers of 0 to 5.
• R a1 ⁇ R a3 and R P, if R Q and R T is plural respective plurality of R a1 ⁇ R a3 and R P, R Q and R T may have respectively the same or different.
• R b1 is a substituted or unsubstituted linear or branched alkyl group or alkoxy group having 1 to 20 carbon atoms, or 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.
• R b1 is plural, the plurality of R b1 may be the same or different, and plural R b1 may represent a constructed ring aligned 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.
• L C is a single bond or a divalent linking group.
• k5 is an integer from 0 to 4.
• R b2 is plural, the plurality of R b2 may be the same or different, and plural R b2 may represent a keyed configured ring structure.
• 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 is plural, plural R g1 are the the same or different and also, the plurality of R g1 may represent a constructed ring aligned 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 ⁇ 12 monocyclic or polycyclic cycloalkyl groups, substituted or unsubstituted aromatic hydrocarbon groups with 6-12 carbon atoms, hydroxy groups, halogen atoms, or these groups combined with each other.
• k11 and k12 are independently integers of 0 to 4, respectively.
• 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. If R d1 and R d2 is a multiple respectively, it may be different in each of the plurality of R d1 and R d2 same.
• 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 a combination of an arbitrary anion moiety containing the above-mentioned group having a chain structure, the above-mentioned cyclic structure, or a combination thereof, and the above-mentioned monovalent radiation-sensitive onium cation. .. Specific examples of the onium salt compound (1) include, but are not limited to, the following formulas (1-1) to (1-19).
• the onium salt compound (1) represented by the above formulas (1-1) to (1-11) is preferable.
• Onium salt compound (2) The onium salt compound (2) is represented by the following formula (2).
• R 4 is a hydrogen atom, a monovalent organic group halogen atoms or 1 to 40 carbon atoms.
• R 5 and R 6 are independently hydrogen atoms or monovalent organic groups having 1 to 40 carbon atoms, or R 5 and R 6 are combined with each other and are composed of nitrogen atoms to which they are bonded. It represents a ring structure having 3 to 8 ring members.
• Z 2 + is a monovalent radiation-sensitive onium cation.
• the monovalent organic group having 1 to 40 carbon atoms represented by R 4 , R 5 and R 6 is represented by R 1 , R 2 and R 3 in the above formula (1).
• a monovalent organic group having 1 to 40 carbon atoms can be preferably adopted.
• the ring structure having 3 to 8 ring members, in which R 5 and R 6 are combined with each other and together with the nitrogen atom to which they are bonded includes nitrogen atom-containing fats such as aziridine, pyrrolidine, piperidine, and piperazine.
• nitrogen atom-containing fats such as aziridine, pyrrolidine, piperidine, and piperazine.
• a ring heterocyclic structure can be mentioned.
• the monovalent radiation-sensitive onium cation represented by Z 2 + suitably a monovalent radiation-sensitive onium cation represented by Z 1 + in the above formula (1) Can be adopted.
• the onium salt compound (2) includes an arbitrary anion moiety containing a group having a chain structure similar to that of the above formula (1), a group having a cyclic structure, or a combination thereof, and the monovalent radiation-sensitive onium cation. It is formed by the combination of.
• Specific examples of the onium salt compound (2) include, but are not limited to, the following formulas (2-1) to (2-8) and the like.
• the onium salt compound (2) represented by the above formulas (2-1) to (2-4) is preferable.
• the radiation-sensitive resin composition contains at least one selected from the group consisting of an onium salt compound (1) and an onium salt compound (2) as an acid diffusion control agent.
• the onium salt compound is preferably the onium salt compound (1) in terms of basicity (acid trapping property), transparency and the like.
• an acid diffusion control agent one or both of the onium salt compounds (1) and (2) and other known substances other than the onium salt compounds (1) and (2) are known as long as the action and effect of the present invention are not impaired. It may be used in combination with an acid diffusion control agent.
• the content of the onium salt compound in the radiation-sensitive resin composition according to the present embodiment is 0.01 part by mass or more with respect to 100 parts by mass of the resin described later. It is preferably 30 parts by mass or less. 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. Further, 0.05 parts by mass or more is more preferable, 0.1 parts by mass or more is further preferable, and 0.5 parts by mass or more is particularly preferable.
• the content of the onium salt compound 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, CDU performance, and LWR performance can be exhibited when forming a resist pattern.
• the onium salt compound causes the pyrimidine base derivative (i), which is a precursor of the anion moiety, to react with the onium cation halide corresponding to the onium cation moiety to promote salt exchange.
• the desired onium salt compound (onium salt compound (1) in the case of the following scheme) can be synthesized.
• R 1 , R 2 , R 3 , X 1 , X 2 and Z 1 + are synonymous with the above formula (1) .
• M ⁇ is a halide ion.
• onium salt compounds (1) and onium salt compounds (2) having other structures can be synthesized by appropriately selecting each precursor corresponding to the anion moiety and the onium cation moiety.
• the resin is an aggregate of polymers having a structural unit containing an acid dissociable 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.
• a hydrogen atom preferably a methyl group, more preferably a methyl group.
• 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 alibic alicyclic hydrocarbon group is a polycyclic alicyclic compound in which two carbon atoms that are not adjacent to each other among the carbon atoms constituting the alicyclic are bonded by a bonding chain containing one or more carbon atoms.
• a cyclic hydrocarbon group is a polycyclic alicyclic compound in which two carbon atoms that are not adjacent to each other among the carbon atoms constituting the alicyclic are bonded by a bonding chain containing one or more carbon atoms.
• 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 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.
• R 8 a methyl group, an ethyl group or an isopropyl group.
• 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.
• Examples of the divalent alicyclic groups of R L4 and R L5 is keyed 3-8 carbon atoms composed together with the carbon atom to which they are attached to each other, Table with R 9 and R 10 in 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. The group is mentioned.
• 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) as well as a 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.
• R 12 is preferably an alkyl group and alkoxy group, and among them methyl group, tert- butoxy group is 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 and 50,000 or less, and more preferably 2,000 or more and 30,000 or less. , 3,000 or more and 15,000 or less are more preferable, and 4,000 or more and 12,000 or less are particularly preferable. 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.
• R 13 from the viewpoint of copolymerizability of the monomer giving the structural unit (V), 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 (V).
• the monovalent fluorinated alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R 14 may be a part of a hydrogen atom of a monocyclic or polycyclic hydrocarbon group having 3 to 20 carbon atoms. Examples include those entirely substituted with a fluorine atom.
• 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 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. 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 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.
• 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 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.
• 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, 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.
• a plurality of R E, W 1, A 1 and R F is may be respectively the same or different.
• 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.
• (X) As 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.
• R F is a monovalent organic group having 1 to 30 carbon atoms
• a 1 is an oxygen atom, -NR aa -, - COO- *, or -SO 2 O- *.
• R aa is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. * Indicates 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.
• a 1 is an oxygen atom
• W 1, R E 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. If s is 2 or 3, a plurality of R E, W 1, A 1 and R F is may be respectively the same or different.
• 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.
• the structural unit (VI) with (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 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 40 mol% or more, preferably 50 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 lower limit of the content ratio of the structural unit having the alicyclic structure is 10 with respect to all the structural units constituting the high fluorine content resin. Mol% is preferred, 20 mol% is more preferred, and 30 mol% is even more preferred.
• the upper limit of the content ratio is preferably 70 mol%, more preferably 60 mol%, still more preferably 50 mol%.
• 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 the upper limit of the above 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 1.9.
• 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, 10 parts by mass or less is more preferable, 8 parts by mass or less is further preferable, and 5 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 comprises an acid having a pKa smaller than that of the acid generated from the onium salt compound by irradiation (exposure), that is, a radiation-sensitive acid generator that generates a relatively strong acid. Further, it is preferable to include it.
• the resin contains a structural unit (I) having an acid dissociative group
• the acid generated from the radiation-sensitive acid generator by exposure dissociates the acid dissociative group having the structural unit (I), such as a carboxy group. Can be generated.
• This function does not substantially dissociate the acid dissociative 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 of suppressing the diffusion of the acid generated from the acid generator.
• the functions of the onium salt compound and the radiation-sensitive acid generator are distinguished by using 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 the pattern.
• the radiation-sensitive acid generator 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.
• the resin in the exposed portion becomes soluble in the developing solution in the case of developing with an alkaline aqueous solution.
• organic solvent development it becomes sparingly soluble in a developing solution.
• Examples of the radiation-sensitive acid generator include onium salt compounds (however, excluding the above-mentioned onium salt compounds (1) and (2)), 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 compounds in which a carbon atom adjacent to a sulfo group is replaced with one or more fluorine atoms or a fluorinated hydrocarbon group.
• the radiation-sensitive acid generator those having a cyclic structure are particularly preferable.
• the content of the radiation-sensitive acid generator is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and further preferably 5 parts by mass or more with respect to 100 parts by mass of the base resin. 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, CDU performance, and LWR 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 onium salt compounds (1) and / or (2), the resin, and the radiation-sensitive acid generating agent 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 1-18 monoalcohol 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, 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 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, 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 cross-linking agent is a compound having two or more functional groups, and in the baking step after the batch exposure step, a cross-linking reaction is caused in the resin component by an acid catalytic reaction, and the molecular weight of the resin component is increased to cause pattern exposure. It reduces the solubility of the part in the developer.
• the functional group include (meth) acryloyl group, hydroxymethyl group, alkoxymethyl group, epoxy group, 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 membrane to the immersion medium, and to perform immersion exposure at a higher speed by high-speed scanning. As a result, the hydrophobicity of the resist film surface that suppresses immersion-derived defects such as watermark defects can be improved.
• Examples of the compound 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.
• polyhydric alcohol examples include glycerin and the like.
• the content of the uneven distribution accelerator is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, still more preferably 20 parts by mass or more, based on 100 parts by mass of the total amount of the resin in the radiation-sensitive resin composition. More than 25 parts by mass is more preferable. Further, 300 parts by mass or less is preferable, 200 parts by mass or less is more preferable, 100 parts by mass or less is further preferable, and 80 parts by mass or less is particularly preferable.
• the radiation-sensitive resin composition may contain one or more of the uneven distribution accelerator.
• the surfactant has an 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 Shinetsu 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, for example.
• 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, onium salt compounds (1) and / or (2), a resin, a radiation-sensitive acid generator, 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 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 depends on the line width of the target pattern, for example, 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. 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 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 organic solvent and the obtained pattern is a negative 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 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 continuously ejecting the developer while scanning the developer discharge nozzle at a constant speed on the substrate rotating at a constant speed
• dynamic discharge method a method of continuously ejecting the developer while scanning the developer discharge nozzle at a constant speed on the substrate rotating at a constant speed
• 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.
• 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. ) 3.0 parts by mass, [E] 3.0 parts by mass (solid content) as a high fluorine content resin, and [D] (D-1) / (D-2) as a 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 hole 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.
• 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 CDU 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 CDU 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 good CDU performance can be formed with high sensitivity.
• Example 43 [Preparation of positive radiation-sensitive resin composition for extreme ultraviolet (EUV) exposure] [Example 43] [A] 100 parts by mass of (A-12) as a resin, [B] 15.0 parts by mass of (B-3) as a radiation-sensitive acid generator, and [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-43) 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.
• PEB was performed at 120 ° C. for 60 seconds.
• the resist film is alkaline-developed with a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution as an alkaline developer, washed with water after development, and further dried to form a positive resist pattern (. A 32 nm line and space pattern) was formed.
• TMAH tetramethylammonium hydroxide
• 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 ). bottom.
• 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.
• [Preparation of positive radiation-sensitive resin composition for ArF exposure, formation and evaluation of resist pattern using this composition] [Example 54] [A] 100 parts by mass of (A-5) as a resin, [B] 12.0 parts by mass of (B-1) as a radiation-sensitive acid generator, and [C] (C-1) as an acid diffusion control agent. ) 2.0 parts by mass, [E] 3.0 parts by mass (solid content) as a high fluorine content resin, and [D] (D-1) / (D-2) as a solvent.
• a radiation-sensitive resin composition (J-54) 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
• LWR performance A 40 nm line-and-space pattern and a 105 nm pitch resist pattern were 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 radiation-sensitive resin composition of Example 54 formed a positive resist pattern by ArF exposure. Even in this case, the LWR performance was good.
• Example 55 [A] 100 parts by mass of (A-15) as a resin, [B] 20.0 parts by mass of (B-5) as a radiation-sensitive acid generator, and (C-7) 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] (D-1) / (D-4) as a solvent.
• a radiation-sensitive resin composition (J-55) 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 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 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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