Classifications

• • 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
  • C08F20/00—Homopolymers and 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
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F20/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
• • 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
  • C08F20/00—Homopolymers and 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
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/38—Esters containing sulfur
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
  • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
  • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor
  • G03F7/2041—Exposure; Apparatus therefor in the presence of a fluid, e.g. immersion; using fluid cooling means

Definitions

• the present invention relates to a radiation sensitive resin composition, a resist pattern forming method using the radiation sensitive resin composition, a polymer suitably used for the radiation sensitive resin composition, and a raw material monomer of the polymer. Relates to suitable compounds.
• a chemically amplified radiation-sensitive resin composition used for microfabrication by lithography is capable of applying acid to exposed areas by irradiation with far ultraviolet rays such as ArF excimer laser light, electromagnetic waves such as X-rays, and charged particle beams such as electron beams.
• a resist pattern can be formed on the substrate by generating a difference in the dissolution rate of the exposed portion and the unexposed portion with respect to the developer by a chemical reaction using this acid as a catalyst.
• Such a radiation-sensitive resin composition is required to improve lithography performance such as sensitivity, LWR (Line Width Roughness) performance, pattern collapse resistance, and pattern shape as the processing technology becomes finer.
• lithography performance such as sensitivity, LWR (Line Width Roughness) performance, pattern collapse resistance, and pattern shape as the processing technology becomes finer.
• the molecular structure and the like of the polymer used in the radiation-sensitive resin composition have been studied, and the lactone structure is used for the purpose of controlling the solubility of the polymer and enhancing the adhesion between the resist pattern and the substrate.
• NLM norbornane lactone
• a radiation-sensitive resin composition containing a polymer containing a conventional lactone structure such as a norbornane lactone structure satisfies LWR performance and pattern collapse resistance. I can't.
• the present invention has been made based on the circumstances as described above, and an object thereof is to provide a radiation-sensitive resin composition having excellent LWR performance and pattern collapse resistance.
• a polymer (hereinafter also referred to as “[A] polymer”) having a structural unit containing a bislactone structure (hereinafter also referred to as “structural unit (I)”), and a radiation-sensitive acid generator (hereinafter referred to as “[B ] Acid generator " Is a radiation-sensitive resin composition.
• the radiation-sensitive resin composition of the present invention is excellent in LWR performance and pattern collapse resistance by containing a [A] polymer having a structural unit containing a bislactone structure and a [B] acid generator.
• the reason why the [A] polymer of the radiation sensitive resin composition has the above-mentioned specific structure is not necessarily clear, but for example, the [A] polymer has a bislactone structure. It is considered that the polarity of the [A] polymer can be appropriately increased, and as a result, the LWR performance can be improved. Moreover, it is thought that the adhesiveness of a resist pattern and a board
• the bislactone structure is preferably represented by the following formula (a).
• R 2 to R 6 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
• the radiation sensitive resin composition can improve the LWR performance and the pattern collapse resistance by having the specific structure as the bislactone structure of the [A] polymer.
• the structural unit is preferably represented by the following formula (1).
• R 2 to R 6 have the same meaning as the above formula (a).
• R 1 is a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
• Y is a single bond. Or a divalent linking group.
• the said radiation sensitive resin composition can improve LWR performance and pattern collapse tolerance more because [A] polymer has the said specific structural unit.
• the resist pattern forming method of the present invention comprises: A step of forming a photoresist film on the substrate using the radiation-sensitive resin composition; A step of exposing the photoresist film; and a step of developing the exposed photoresist film.
• a step of forming a photoresist film on the substrate using the radiation-sensitive resin composition comprises: A step of exposing the photoresist film; and a step of developing the exposed photoresist film.
• the polymer of the present invention has a structural unit represented by the following formula (1).
• R 1 is a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
• Y is a single bond or a divalent linking group.
• R 2 to R 6 are respectively Independently, it is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
• the polymer has the specific structural unit, it can be suitably used as a polymer component of the radiation-sensitive resin composition described above.
• the compound of the present invention is represented by the following formula (i).
• R 1 is a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
• Y ′ is a divalent linking group.
• R 2 to R 6 are each independently selected. And a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
• the compound Since the compound has the specific structure, it can be suitably used as a raw material monomer for the above-described polymer.
• bislactone structure refers to a structure in which two lactone rings share one or more carbon atoms.
• Organic group refers to a group containing at least one carbon atom.
• a resist pattern having a low LWR and a high resistance to pattern collapse can be formed.
• the polymer of the present invention can be suitably used as a polymer contained in the radiation-sensitive resin composition, and the compound of the present invention can be suitably used as a raw material monomer for the polymer. it can. Therefore, these radiation-sensitive resin compositions, resist pattern formation methods, polymers and compounds can be suitably used for pattern formation in the field of semiconductor processing, for example, where miniaturization will continue to progress in the future.
• the radiation-sensitive resin composition contains a [A] polymer and a [B] acid generator.
• the radiation-sensitive resin composition may contain a [C] acid diffusion controller, a [D] fluorine atom-containing polymer, and a [E] solvent as suitable components, as long as the effects of the present invention are not impaired.
• other optional components may be contained. Hereinafter, each component will be described.
• the polymer is a polymer having the structural unit (I).
• the radiation sensitive resin composition is excellent in LWR performance and pattern collapse resistance because the polymer [A] has the structural unit (I).
• the [A] polymer of the radiation sensitive resin composition has the structural unit (I)
• the above effect is not clear.
• the [A] polymer has a bislactone structure. It is considered that the polarity of the [A] polymer can be appropriately increased as compared with the case of having a conventional lactone structure, and as a result, the LWR performance can be improved.
• substrate can be improved, As a result, pattern collapse tolerance can be improved.
• the polymer preferably has, in addition to the structural unit (I), a structural unit (II) containing an acid dissociable group, a structural unit (III) containing a polar group, and a non-dissociable hydrocarbon group.
• Other structural units such as a structural unit (IV) containing
• each structural unit will be described.
• the structural unit (I) is a structural unit containing a bislactone structure.
• the bislactone structure is not particularly limited as long as the two lactone rings share one or more carbon atoms, and the two lactone rings share only one carbon atom. Two carbons Examples include those that share atoms and those that share three carbon atoms.
• the lactone ring refers to one ring structure containing —COO—.
• Examples of the bislactone structure include a structure represented by the above formula (a).
• R 2 to R 6 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
• Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms represented by R 2 to R 6 include a chain hydrocarbon group having 1 to 10 carbon atoms and an alicyclic hydrocarbon having 3 to 10 carbon atoms. And aromatic hydrocarbon groups having 6 to 10 carbon atoms.
• chain hydrocarbon group examples include: Saturated hydrocarbon groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, and t-butyl; Ethenyl group, 1-propen-1-yl group, 1-propen-2-yl group, 3-propen-1-yl group, 1-buten-1-yl group, 1-buten-2-yl group, 2- And unsaturated hydrocarbon groups such as a methyl-1-buten-2-yl group.
• Examples of the alicyclic hydrocarbon group include: Saturated hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclodecyl group, norbornyl group, adamantyl group; Examples thereof include unsaturated hydrocarbon groups such as a cyclopentenyl group, a cyclohexenyl group, a cyclooctenyl group, a cyclodecyl group, and a norbornenyl group.
• aromatic hydrocarbon group examples include phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, benzyl group, phenethyl group and the like.
• R 2 to R 6 are preferably a hydrogen atom or a chain hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a chain saturated hydrocarbon group having 1 to 6 carbon atoms, a hydrogen atom or a methyl group An ethyl group is more preferable, and a hydrogen atom is particularly preferable.
• Examples of the structural unit (I) include a structural unit represented by the following formula (A).
• R ⁇ 1 > is a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
• Y is a single bond or a divalent linking group.
• R A is a monovalent group containing a bislactone structure.
• the R 1 is preferably a hydrogen atom or a methyl group, and more preferably a methyl group, from the viewpoint of copolymerization of the monomer that gives the [A] polymer.
• Examples of the divalent linking group represented by Y include a divalent chain hydrocarbon group having 1 to 10 carbon atoms; a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms; 20 divalent aromatic hydrocarbon groups; a group in which one or more of these groups are combined with a divalent group containing a hetero atom; some or all of the hydrogen atoms of these groups are substituted And the like.
• Examples of the divalent chain hydrocarbon group include: Saturated hydrocarbon groups such as methanediyl group, ethanediyl group, propanediyl group, butanediyl group, dimethylmethanediyl group, methylethanediyl group; Examples thereof include unsaturated hydrocarbon groups such as ethenediyl group, propenediyl group, butenediyl group, methylenemethanediyl group, methyleneethanediyl group, methylenepropanediyl group, ethylideneethanediyl group, ethynediyl group, propynediyl group and butynediyl group. Among these, an ethanediyl group, a methylethanediyl group, a dimethylmethanediyl group, and a methyleneethanediyl group are preferable.
• divalent alicyclic hydrocarbon group examples include: Saturated hydrocarbon groups such as cyclopropanediyl group, cyclobutanediyl group, cyclopentanediyl group, cyclohexanediyl group, methylpentanediyl group, methylhexanediyl group, norbornanediyl group, adamantanediyl group; Examples thereof include unsaturated hydrocarbon groups such as a cyclopentenediyl group, a cyclohexenediyl group, and a norbornenediyl group.
• divalent aromatic hydrocarbon group examples include: Examples thereof include benzenediyl group, toluenediyl group, xylenediyl group, benzenediyl-methanediyl group, benzenediyl-ethanediyl group, naphthalenediyl group, naphthalenediyl-methanediyl group.
• Examples of the divalent group containing a heteroatom include —O—, —S—, —NR—, —CO—, —CS—, —CNR—, —SO—, —SO 2 —, —COO—. , —NR—, —CONR—, —O—CO—O—, —O—CO—NR—, —NR—CO—NR— and the like.
• R is a hydrogen atom or a monovalent hydrocarbon group. Among them, -O -, - S -, - SO 2 -, - COO -, - CONR- are preferred, -S -, - SO 2 - , - COO- is more preferable.
• Examples of the substituent that the above group may have include, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, a hydroxy group, a carboxy group, a cyano group, a nitro group, an alkoxy group, an alkoxycarbonyl group, An alkoxycarbonyloxy group, an acyl group, etc. are mentioned.
• a hydroxy group is preferable from the viewpoint of ease of synthesis of the monomer that gives the structural unit (I).
• Y is preferably a group represented by the following formulas (Y-1) to (Y-4).
• Y is a group represented by the following formula, a monomer that gives the structural unit (I) can be easily synthesized.
• R a , R a ′ , R b and R c are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. is there.
• X is —O—, —S— or —SO 2 —.
• R d is a divalent hydrocarbon group having 1 to 20 carbon atoms.
• Q is each independently —O—, —S—, —NR—, —CO—, —CS—, —CNR—, —SO—, —SO 2 —, —COO—, —NR—, — CONR-, -O-CO-O-, -O-CO-NR- or -NR-CO-NR-. * Shows the site
• Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R a , R a ′ , R b and R c include, for example, an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 20 carbon atoms. Examples thereof include an alkyl group, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms.
• alkyl group examples include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, and a t-butyl group.
• cycloalkyl group examples include monocyclic cycloalkyl groups such as cyclopentyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cyclooctyl group; norbornyl group, adamantyl group, tricyclodecyl group, tetracyclododecyl group, and the like.
• Examples include polycyclic cycloalkyl groups.
• aryl group examples include a phenyl group, a tolyl group, a xylyl group, a mesityl group, a naphthyl group, and an anthryl group.
• aralkyl group examples include a benzyl group, a phenethyl group, a naphthylmethyl group, and an anthrylmethyl group.
• a hydrogen atom and an alkyl group are preferable, a hydrogen atom, a methyl group, and an ethyl group are more preferable, and a hydrogen atom and a methyl group are further more preferable.
• X is preferably —S— or —SO 2 —.
• Examples of the divalent hydrocarbon group represented by R d include the groups exemplified as the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by the above R a , R a ′ , R b and R c. A group obtained by removing one hydrogen atom from
• R d is preferably an alkanediyl group having 1 to 20 carbon atoms, preferably a methanediyl group, an ethanediyl group or a propanediyl group, more preferably a propanediyl group.
• Q is preferably —O—, —CO—, —COO— or —CONR—, more preferably —COO—.
• Y is preferably a group represented by the above formula (Y-4).
• Examples of the monovalent group containing the bislactone structure represented by R A include monovalent groups including those exemplified as the bislactone structure.
• a group represented by the following formula (a ′) is preferable.
• R 2 to R 6 have the same meaning as in the above formula (a). * Shows the site
• structural unit (I) a structural unit represented by the above formula (1) “hereinafter also referred to as“ structural unit (I-1) ”” is preferable.
• R 2 to R 6 have the same meaning as in the above formula (a).
• R 1 is a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
• Y is a single bond or a divalent linking group.
• R 1 and Y include the same groups as those exemplified as R 1 and Y in the formula (A).
• Examples of the structural unit (I-1) include structural units represented by the following formulas (I-1-1) to (I-1-5).
• R 1 has the same meaning as in the above formula (1).
• the structural unit (I-1) is preferably a structural unit represented by the above formula (I-1-5) from the viewpoint of improving the LWR performance and pattern collapse resistance of the radiation-sensitive resin composition.
• Examples of the monomer that provides the structural unit (I-1) include a compound represented by the above formula (i) (hereinafter also referred to as “compound (i)”).
• R ⁇ 1 > is a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
• Y ′ is a divalent linking group.
• R 2 to R 6 are each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms.
• R 1 is preferably a hydrogen atom or a methyl group, more preferably a methyl group, from the viewpoint of copolymerizability of the compound (i).
• Examples of the divalent linking group represented by Y ′ include the same groups as those exemplified as the divalent linking group represented by Y in the formula (A).
• R 2 to R 6 include groups similar to those exemplified as the monovalent hydrocarbon group represented by R 2 to R 6 in the above formula (1).
• Examples of the compound (i) include compounds represented by the following formulas (i-1) to (i-5).
• the compound (i) can be synthesized by various synthesis methods.
• each compound (i) in the case where the divalent linking group Y ′ in the compound (i) is represented by the above formulas (Y-1) to (Y-4) is respectively in accordance with each reaction scheme shown below. Can be synthesized.
• a compound in which Y ′ is represented by the above formula (Y-1) (hereinafter also referred to as “compound (iA)”) (for example, the above compounds (i-1), (i-2), etc.)
• the compound can be synthesized from a bislactone structure-containing compound having a carbon-carbon double bond (hereinafter also referred to as “compound (a)”) according to the following scheme.
• R 1 and R 2 to R 6 are as defined in the above formula (i).
• R a , R b and R c are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms.
• X is —O—, —S— or —SO 2 —.
• R d is a divalent hydrocarbon group having 1 to 20 carbon atoms.
• J is a halogen atom, —OH or —O—COR e .
• Re is a monovalent organic group.
• the compound (a) can be obtained, for example, by reacting propanedicarboxylic acid and methacrylic anhydride in the presence of a catalyst such as a base such as an amine and a polymerization inhibitor such as copper (II) chloride. .
• various compounds (iA) are synthesized by performing a structure conversion reaction on the linking group Y ′ of the compound (iA) such as the compound (i-1) to the compound (i-2). can do.
• a compound in which the linking group Y ′ is represented by the above formula (Y-2) (hereinafter also referred to as “compound (iB)”) (eg, the above compound (i-3) etc.) is, for example, a compound ( It can be synthesized according to the following scheme from a ′).
• R 1 and R 2 to R 6 are as defined in the above formula (i).
• R a ′ , R b and R c are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms.
• a bislactone structure-containing compound (a ′) having a carbon-carbon double bond with, for example, a bromine supplying material such as N-bromosuccinimide (NBS) and a peroxide such as benzoyl peroxide (BPO)
• NBS N-bromosuccinimide
• BPO benzoyl peroxide
• a compound (b ′) in which the allylic position of the carbon-carbon double bond of the compound (a ′) is brominated can be obtained.
• the compound (iB) can be obtained by reacting the compound (b ′) with (meth) acrylic acid in the presence of a base such as potassium carbonate.
• a compound in which the linking group Y ′ is represented by the above formula (Y-3) (hereinafter also referred to as “compound (i-C)”) (for example, the compound (i-4) and the like) is, for example, a compound ( It can be synthesized according to the following scheme from a).
• a compound in which the linking group Y ′ is represented by the above formula (Y-4) (hereinafter also referred to as “compound (i-D)”) (for example, the compound (i-5) and the like) is, for example, It can be synthesized from compound (a) according to the following scheme.
• R 1 and R 2 to R 6 are as defined in the above formula (i).
• R a , R b and R c are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms.
• J is a halogen atom, —OH or —O—COR e .
• Re is a monovalent organic group.
• Compound (b ′′) can be obtained by epoxidizing the carbon-carbon double bond of compound (a) with an oxidizing agent such as m-chloroperbenzoic acid.
• This compound (b ′′) and ( Compound (iC) can be obtained by reacting with (meth) acrylic acid in the presence of a catalyst such as a quaternary ammonium salt.
• a compound (c) having a hydroxy group can be obtained by subjecting the compound (b ′′) to a hydrogenation reaction in the presence of a hydrogenation catalyst such as palladium carbon.
• Compound (iD) can be obtained by reacting a (meth) acrylic acid derivative such as (meth) acrylic acid halide, (meth) acrylic acid or (meth) acrylic anhydride.
• the content ratio of the structural unit (I) is preferably 5 mol% to 95 mol%, more preferably 10 mol% to 90 mol%, more preferably 20 mol% with respect to all the structural units constituting the [A] polymer. ⁇ 80 mol% is more preferred, and 30 mol% ⁇ 70 mol% is particularly preferred.
• the structural unit (II) is a structural unit having an acid dissociable group (except for those corresponding to the structural unit (I)).
• the said radiation sensitive resin composition can improve the sensitivity and pattern formation property of the said radiation sensitive resin composition because a [A] polymer has structural unit (II).
• the “acid-dissociable group” refers to a group that replaces a hydrogen atom such as a carboxy group or a hydroxy group, and dissociates due to the action of an acid or the like generated from the [B] acid generator described later.
• Examples of the structural unit (II) include a structural unit (II-1) represented by the following formula (2).
• R 7 is a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
• R 8 is a monovalent acid dissociable group.
• Examples of the monovalent acid dissociable group represented by R 8 include a group represented by the following formula (p).
• R p1 , R p2 and R p3 are each independently an alkyl group having 1 to 4 carbon atoms or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms. However, R p2 and R p3 may be bonded to each other to form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms together with the carbon atom to which they are bonded.
• Examples of the alkyl group having 1 to 4 carbon atoms represented by R p1 to R p3 include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-methylpropyl group, Examples thereof include a 1-methylpropyl group and a t-butyl group.
• Examples of the alicyclic hydrocarbon group having 4 to 20 carbon atoms represented by R p1 to R p3 include a monocyclic alicyclic hydrocarbon group having a cycloalkane skeleton such as cyclopentane and cyclohexane; And polycyclic alicyclic hydrocarbon groups having a bridged skeleton such as an adamantane skeleton and a norbornane skeleton.
• R p1 is an alkyl group having 1 to 4 carbon atoms
• R p2 and R p3 are bonded to each other, and a divalent group having an adamantane skeleton or a cycloalkane skeleton together with the carbon atom to which they are bonded Is preferably formed.
• structural unit (II-1) examples include structural units represented by the following formulas (2-1) to (2-4) (hereinafter referred to as “structural units (II-1-1) to (II-1-)”. 4) ”)) and the like.
• R 7 has the same meaning as in the above formula (2).
• R p1 , R p2 and R p3 have the same meaning as in the above formula (p).
• n p is an integer of 1 to 4.
• Examples of the structural unit (II-1) include a structural unit represented by the following formula.
• R ⁇ 7 > is synonymous with the said Formula (2).
• the structural unit (II), the structural unit (II-1-1) and the structural unit (II-1-2) are preferable, and the structural unit having a cyclopentane skeleton and the structural unit having an adamantane skeleton are preferable. More preferred are structural units derived from 1-methylcyclohexyl (meth) acrylate, more preferred are structural units derived from 2-methyladamantyl (meth) acrylate, and particularly preferred are structural units derived from 1-methylcyclohexyl (meth) acrylate. .
• the content ratio of the structural unit (II) is preferably 5 mol% to 95 mol%, more preferably 10 mol% to 90 mol%, more preferably 20 mol% with respect to all the structural units constituting the [A] polymer. ⁇ 80 mol% is more preferred, and 30 mol% ⁇ 70 mol% is particularly preferred.
• the structural unit (III) is a structural unit containing a polar group (except for those corresponding to the structural unit (I) and the structural unit (II)).
• the polymer can adjust the solubility in the developer, and as a result, the pattern forming property of the radiation-sensitive resin composition can be improved.
• the polar group include a hydroxy group, a carboxy group, a cyano group, a nitro group, a sulfonamide group, and a carbonyl group.
• Examples of the structural unit (III) include a structural unit represented by the following formula.
• R 9 is a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
• a structural unit containing a hydroxy group is preferred, a structural unit containing a hydroxy group and an adamantane skeleton is more preferred, and a structural unit derived from 3-hydroxy-1-adamantyl (meth) acrylate is more preferred.
• the content ratio of the structural unit (III) is preferably 30 mol% or less, more preferably 20 mol% or less, and still more preferably 10 mol% or less with respect to all the structural units constituting the [A] polymer.
• the structural unit (IV) is a structural unit containing a non-acid dissociable hydrocarbon group.
• Examples of the structural unit (IV) include a structural unit represented by the following formula (3).
• R 10 is a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
• R 11 is a non-acid dissociable monovalent hydrocarbon group having 1 to 20 carbon atoms.
• non-acid dissociable monovalent hydrocarbon group represented by R 11 examples include: Methyl group; Primary or secondary alkyl group such as ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, n-pentyl group, i-pentyl group; Secondary cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl; Aryl groups such as phenyl, tolyl, xylyl, mesityl, naphthyl, anthryl; Examples include aralkyl groups such as benzyl group and phenethyl group. Among these, a methyl group, a primary or secondary alkyl group, and a secondary cycloalkyl group are preferable, and a methyl group is more preferable
• the content ratio of the structural unit (IV) is preferably 0 mol% to 70 mol%, more preferably 0 mol% to 60 mol%, more preferably 30 mol%, based on all structural units constituting the [A] polymer. More preferred is ⁇ 60 mol%.
• the [A] polymer is at least one selected from the group consisting of a monolactone structure, a cyclic carbonate structure, and a sultone structure, in addition to the structural units (III) and (IV).
• the structural unit (V) including the structure may be included.
• “Monolactone structure” refers to a structure in which one lactone ring does not share a carbon atom with another lactone ring.
• the content ratio of the structural unit (V) is preferably 0 mol% to 30 mol%, more preferably 0 mol% to 20 mol%, more preferably 0 mol%, based on all structural units constituting the [A] polymer. More preferred is ⁇ 10 mol%.
• the content of the polymer is preferably 70% by mass or more, more preferably 80% by mass or more based on the total solid content in the radiation-sensitive resin composition.
• the polymer can be produced, for example, by polymerizing a monomer corresponding to each predetermined structural unit in a suitable solvent using a radical polymerization initiator.
• a method of dropping a solution containing a monomer and a radical initiator into a reaction solvent or a solution containing the monomer to cause a polymerization reaction, a solution containing the monomer, and a solution containing the radical initiator Separately, a method of dropping a reaction solvent or a monomer-containing solution into a polymerization reaction, a plurality of types of solutions containing each monomer, and a solution containing a radical initiator, It is preferable to synthesize by a method such as a method of dropping it into a reaction solvent or a solution containing a monomer to cause a polymerization reaction.
• 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, hexamethylene dibromide, chlorobenzene; Saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, i-butyl acetate and methyl propionate; Ketones such as acetone, 2-butanone, 4-methyl-2-p
• the reaction temperature in the polymerization may be appropriately determined according to the type of radical initiator, but 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.
• radical initiator used in the polymerization examples include azobisisobutyronitrile (AIBN), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2 -Cyclopropylpropionitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylpropionitrile) and the like. These radical initiators may be used alone or in combination of two or more.
• the polymer obtained by the polymerization reaction is preferably recovered by a reprecipitation method. That is, after completion of the polymerization reaction, the polymer is recovered as a powder by introducing the polymerization solution into a reprecipitation solvent.
• a reprecipitation solvent alcohols, alkanes and the like can be used singly or in combination of two or more.
• the polymer can also be recovered by removing low-molecular components such as monomers and oligomers by a liquid separation operation, a column operation, an ultrafiltration operation, or the like.
• the number average molecular weight (Mn) of the polymer by gel permeation chromatography (GPC) is preferably 1,000 to 100,000, more preferably 1,500 to 60,000, and 2,000 to 40. Is more preferable, and 3,000 to 20,000 is particularly preferable.
• Mn of a polymer By making Mn of a polymer into the said range, the pattern formation property of the said radiation sensitive resin composition can be improved.
• the ratio of the weight average molecular weight (Mw) of the polymer to Mn (Mw / Mn) is usually 1 to 6, preferably 1 to 4.5, more preferably 1 to 3, and more preferably 1 to 2. Is particularly preferred.
• Mn and Mw are GPC columns (2 G2000HXL, 1 G3000HXL, 1 G4000HXL, manufactured by Tosoh), flow rate 1.0 mL / min, elution solvent: tetrahydrofuran, sample concentration: 1.
• the acid generator is a compound that generates an acid upon irradiation with exposure light. By the action of the acid, the acid dissociable group present in the [A] polymer is dissociated to produce a polar group such as a carboxy group, and as a result, the solubility of the [A] polymer in the developer changes.
• the acid generator may be contained in the form of a compound as will be described later (hereinafter also referred to as “[B] acid generator” as appropriate) or in a form incorporated as part of a polymer. Both forms are acceptable.
• Examples of the acid generator include onium salt compounds, N-sulfonyloxyimide compounds, halogen-containing compounds, diazoketone compounds, and the like.
• onium salt compounds examples include sulfonium salts, tetrahydrothiophenium salts, iodonium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like.
• sulfonium salt examples include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium 2-bicyclo [2.2.1] hept.
• tetrahydrothiophenium salt examples include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate and 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium.
• Nonafluoro-n-butanesulfonate 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothio Phenium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium camphor Sulfonate, 1- (6-n-butoxynaphthalene-2-y ) Tetrahydrothiophenium trifluoromethanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydr
• iodonium salt examples include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 2-bicyclo [2.2.1] hept-2-yl.
• onium salts are preferred, sulfonium salts are more preferred, triphenylsulfonium salts are more preferred, and triphenylsulfonium nonafluorobutane sulfonate is particularly preferred.
• the content when the acid generator is a [B] acid generator is from the viewpoint of ensuring the sensitivity and developability of the radiation-sensitive resin composition with respect to 100 parts by mass of the [A] polymer. 0.1 parts by mass or more and 30 parts by mass or less is preferable, 0.5 parts by mass or more and 20 parts by mass or less are more preferable, and 1 part by mass or more and 15 parts by mass or less are more preferable.
• the content of the acid generator is less than 0.1 parts by mass, the sensitivity of the radiation-sensitive resin composition tends to be insufficient. On the other hand, when the content exceeds 30 parts by mass, transparency to exposure light is high. It may become difficult to obtain a desired resist pattern.
• the acid generator may be used alone or in combination of two or more.
• the [C] acid diffusion controller is a component that controls the diffusion phenomenon of the acid generated from the [B] acid generator upon exposure in the photoresist film and suppresses an undesirable chemical reaction in the unexposed area.
• the radiation-sensitive resin composition further improves storage stability and further improves the resolution as a resist.
• [C] acid diffusion controller in the form of a free compound (hereinafter also referred to as “[C] acid diffusion controller” as appropriate), or in a form incorporated as part of the polymer, Both of these forms may be used.
• Examples of the acid diffusion controller include amine compounds, amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, and the like.
• Examples of the amine compound include mono (cyclo) alkylamines; di (cyclo) alkylamines; tri (cyclo) alkylamines; substituted alkylanilines or derivatives thereof; ethylenediamine, N, N, N ′, N′-tetra Methylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenylamine, 2,2-bis (4 -Aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-amino) Phenyl) -2- (4-hydroxyphenyl) propane, 1 4-bis (1- (4-a
• amide group-containing compound examples include Nt-butoxycarbonyl group-containing amino compounds such as Nt-butoxycarbonyl-4-hydroxypiperidine, and Nt-butoxycarbonyl-4-hydroxypiperidine and the like Nt-butoxycarbonyl-4-hydroxypiperidine.
• Nt-butoxycarbonyl group-containing amino compounds such as Nt-butoxycarbonyl-4-hydroxypiperidine, and Nt-butoxycarbonyl-4-hydroxypiperidine and the like Nt-butoxycarbonyl-4-hydroxypiperidine.
• -Amyloxycarbonyl group-containing amino compounds formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone, N -Acetyl-1-adamantylamine, isocyanuric acid tris (2-hydroxyethyl) and the like.
• urea compounds include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri-n-butylthiourea, etc. Is mentioned.
• nitrogen-containing heterocyclic compound examples include imidazoles; pyridines; piperazines; pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, 4-hydroxy-N-amyloxycarbonylpiperidine, piperidineethanol, 3-piperidino- 1,2-propanediol; morpholine, 4-methylmorpholine, 1- (4-morpholinyl) ethanol, 4-acetylmorpholine, N- (2-cyclohexylcarbonyloxyethyl) morpholine, 3- (N-morpholino) -1, Morpholines such as 2-propanediol; 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane and the like.
• amide group-containing compounds and nitrogen-containing heterocyclic compounds are preferred, amide group-containing compounds are more preferred, Nt-amyloxycarbonyl group-containing compounds, and Nt-butoxycarbonyl group-containing compounds are more preferred. Nt-amyloxycarbonyl-4-hydroxypiperidine and Nt-butoxycarbonyl-4-hydroxypiperidine are particularly preferred.
• a photodegradable base that generates a weak acid by exposure can also be used.
• the photodegradable base exhibits a high acid scavenging function by anions in the unexposed area, and captures the acid diffusing from the exposed area. That is, since it functions as an acid diffusion control agent only in the unexposed area, the contrast of the dissociation reaction of the acid dissociable group is improved, and as a result, the resolution of the radiation sensitive resin composition can be further improved.
• the photodegradable base include an onium salt compound that decomposes upon exposure and loses acid diffusion controllability.
• the onium salt compound include a sulfonium salt compound represented by the following formula (C1) and an iodonium salt compound represented by the following formula (C2).
• R 12 to R 16 are each independently a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, a halogen atom, or —SO 2 —R ⁇ .
• R ⁇ is an alkyl group, a cycloalkyl group, an alkoxy group or an aryl group.
• Z - and E - are, OH -, R ⁇ -COO - , R ⁇ -SO 2 -N - -R ⁇ , R ⁇ -SO 3 - is an anion represented by or the following formula (C3).
• R ⁇ is a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. Some or all of the hydrogen atoms of the alkyl group, cycloalkyl group, aryl group and aralkyl group may be substituted.
• R ⁇ is a linear or branched alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 20 carbon atoms. Some or all of the hydrogen atoms of the alkyl group and cycloalkyl group may be substituted with fluorine atoms. However, when Z ⁇ and E ⁇ are R ⁇ —SO 3 — , the fluorine atom is not bonded to the carbon atom to which SO 3 — is bonded.
• R 17 represents a linear or branched alkyl group having 1 to 12 carbon atoms in which part or all of the hydrogen atoms may be substituted with fluorine atoms, or a carbon number of 1 to 12 These are linear or branched alkoxy groups.
• u is an integer of 0-2.
• R 12 to R 16 in the above formulas (C1) and (C2) a hydrogen atom and —SO 2 —R ⁇ are preferable. Moreover, as said R ( alpha) , a cycloalkyl group is preferable and a cyclohexyl group is more preferable.
• Examples of the alkyl group represented by R ⁇ include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, an i-butyl group, a t-butyl group, and the like, and hydrogen atoms of these groups. Examples thereof include a group that is partially or wholly substituted.
• the cycloalkyl group represented by R beta such as cyclopentyl group, cyclohexyl group, norbornyl group, tricyclodecanyl group, tetracyclododecanyl group, adamantyl group, etc., and some of the hydrogen atoms of these groups or Examples include groups in which all are substituted.
• aryl group represented by R beta for example, a phenyl group, a naphthyl group, anthranyl group, and some or all of the hydrogen atoms of these groups and the like groups substituted.
• the aralkyl group represented by R beta for example, benzyl, phenylethyl group, phenylpropyl group, and some or all of the hydrogen atoms of these groups and the like groups substituted.
• alkyl group, cycloalkyl group, aryl group, and alkaryl group have include a hydroxy group, a halogen atom, an alkoxy group, a lactone group, and an alkylcarbonyl group.
• Examples of the alkyl group represented by R ⁇ include a methyl group, an ethyl group, a propyl group, and a butyl group.
• Examples of the cycloalkyl group represented by R ⁇ include a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and the like.
• Examples of the photodegradable base include compounds represented by the following formulas.
• triphenylsulfonium salicylate and triphenylsulfonium 10-camphorsulfonate are preferable, and triphenylsulfonium 10-camphorsulfonate is more preferable.
• the content of the acid diffusion controller is preferably 20 parts by mass or less with respect to 100 parts by mass of the polymer [A] when the [C] acid diffusion controller is a [C] acid diffusion controller. 0.1 to 15 parts by mass is more preferable, and 0.5 to 10 parts by mass is even more preferable. [C] If the content of the acid diffusion controller exceeds 20 parts by mass, the sensitivity of the resulting radiation-sensitive resin composition may be reduced. [C]
• the acid diffusion inhibitors may be used alone or in combination of two or more.
• the radiation-sensitive resin composition may contain [D] a fluorine atom-containing polymer (except for those corresponding to the [A] polymer).
• the radiation-sensitive resin composition contains [D] a fluorine atom-containing polymer, so that when the photoresist film is formed, the distribution of the radiation-sensitive resin composition depends on the oil repellency characteristics of the [D] fluorine atom-containing polymer. Since it tends to be unevenly distributed on the surface of the photoresist film, it is possible to suppress elution of the [B] acid generator and [C] acid diffusion controller in the photoresist film into the immersion medium during immersion exposure. Can do. Further, since the radiation sensitive resin composition contains [D] fluorine atom-containing polymer, the receding contact angle on the surface of the formed photoresist film is increased, and immersion exposure can be suitably performed. Scanning is possible.
• the fluorine atom-containing polymer can be formed by polymerizing one or more monomers usually containing fluorine atoms in the structure.
• the fluorine atom-containing polymer preferably has the following structural unit (FI) as a structural unit containing a fluorine atom in the structure.
• the fluorine atom-containing polymer may have a structural unit other than the structural unit containing a fluorine atom in the structure.
• the fluorine atom-containing compound may have one or more of these structural units.
• the structural unit (FI) is a structural unit represented by the following formula (D1).
• R 18 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
• A is a single bond or a divalent linking group.
• R 19 is an alkyl group having 1 to 6 carbon atoms having at least one fluorine atom, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a derivative thereof.
• Examples of the divalent linking group represented by A include —O—, —S—, —COO—, —OCO—, —NHCO—, —CONH—, —SO 2 NHCF 3 , —O—CO. —NH—, —NH—CO—O— are mentioned.
• Preferred monomers that give the structural unit (FI) include trifluoromethyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylic.
• the content ratio of the structural unit (FI) is preferably 5 mol% or more, more preferably 10 mol% or more, and more preferably 15 mol% or more with respect to all the structural units constituting the [D] fluorine atom-containing polymer. Is more preferable.
• the receding contact angle may be less than 70 degrees, and the elution of the acid generator from the photoresist film cannot be suppressed. May occur.
• the fluorine atom-containing polymer may have only one type of structural unit (FI) or two or more types.
• the fluorine atom-containing polymer has a structure having an acid-dissociable group as another structural unit in addition to the above-described structural unit containing a fluorine atom, for example, for controlling the dissolution rate in a developer.
• one or more structural units derived from an aromatic compound can be contained.
• Examples of the structural unit having an acid dissociable group include structural units similar to the structural unit (II) of the [A] polymer.
• Examples of the structural unit containing at least one structure selected from the group consisting of the lactone structure, the cyclic carbonate structure, and the sultone structure include structural units similar to the structural unit (V) of the [A] polymer.
• Examples of the structural unit containing the polar group include structural units similar to the structural unit (III) of the [A] polymer.
• Examples of the structural unit containing the alicyclic hydrocarbon group include a structural unit represented by the following formula (D2).
• R 20 represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
• G is a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms.
• Examples of the monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms represented by G include cyclobutane, cyclopentane, cyclohexane, bicyclo [2.2.1] heptane, bicyclo [2.2.2]. ] Octane, tricyclo [5.2.1.0 2,6 ] decane, tetracyclo [6.2.1.1 3,6 . And a group obtained by removing one hydrogen atom from an alicyclic hydrocarbon such as 0 2,7 ] dodecane and tricyclo [3.3.1.1 3,7 ] decane.
• Some or all of the hydrogen atoms of the monovalent alicyclic hydrocarbon group may be methyl, ethyl, n-propyl, i-propyl, n-butyl, 2-methylpropyl, 1- Straight chain or branched alkyl group having 1 to 4 carbon atoms such as methylpropyl group and t-butyl group, cycloalkyl group having 3 to 10 carbon atoms; hydroxy group, cyano group, hydroxyalkyl having 1 to 10 carbon atoms Group and a carboxy group may be substituted. Further, two hydrogen atoms bonded to the same carbon atom may be substituted with one oxygen atom to form a keto group.
• Preferred monomers that give the structural unit containing the alicyclic hydrocarbon group include (meth) acrylic acid-bicyclo [2.2.1] hept-2-yl ester, (meth) acrylic acid-bicyclo [2 2.2] Oct-2-yl ester, (meth) acrylic acid-tricyclo [5.2.1.02,6] dec-7-yl ester, (meth) acrylic acid-tetracyclo [6.2.1]. .13,6.0 2,7 ] dodeca-9-yl ester, (meth) acrylic acid-tricyclo [3.3.1.1 3,7 ] dec-1-yl ester, (meth) acrylic acid-tricyclo [3.3.1.1 3,7 ] dec-2-yl ester.
• Preferred monomers that give structural units derived from the aromatic compound include styrene, ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, 4- (2-t-butoxycarbonylethyloxy) styrene 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene, 2-hydroxy- ⁇ -methylstyrene, 3-hydroxy- ⁇ -methylstyrene 4-hydroxy- ⁇ -methylstyrene, 2-methyl-3-hydroxystyrene, 4-methyl-3-hydroxystyrene, 5-methyl-3-hydroxystyrene, 2-methyl-4-hydroxystyrene, 3-methyl- 4-hydroxystyrene, 3,4-dihydroxystyrene, , 4,6-trihydroxystyrene, 4-t-butoxysty
• the content ratio of the other structural units is usually 80 mol% or less, preferably 75 mol% or less, and more preferably 70 mol% or less.
• the content of the fluorine atom-containing polymer is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the [A] polymer. 1 to 10 parts by mass is more preferable.
• the fluorine atom-containing polymer can be synthesized, for example, by polymerizing a monomer corresponding to each predetermined structural unit in a suitable solvent using a radical polymerization initiator.
• a polymerization initiator a solvent, etc. used for the synthesis
• combination of a [D] fluorine atom containing polymer the thing similar to what was illustrated in the synthesis method of the said [A] polymer is mentioned.
• 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 polystyrene equivalent weight average molecular weight (Mw) of the fluorine atom-containing polymer by GPC method is preferably 1,000 to 50,000, more preferably 1,000 to 30,000, and more preferably 1,000 to 10,000. 000 is more preferable.
• Mw of the fluorine atom-containing polymer is less than 1,000, the formed photoresist film surface may not be able to obtain a sufficient advancing contact angle. On the other hand, when Mw exceeds 50,000, the developability of the resulting radiation-sensitive resin composition tends to decrease.
• the Mw / Mn ratio of the fluorine atom-containing polymer is usually 1 to 3, and preferably 1 to 2.5.
• the radiation-sensitive resin composition usually contains an [E] solvent.
• Solvent is at least [A] polymer, [B] acid generator, [C] acid diffusion controller contained as needed, [D] fluorine atom-containing polymer, and other optional components described later If it can melt
• Examples of the solvent include alcohol solvents, ether solvents, ketone solvents, amide solvents, ester solvents, hydrocarbon solvents, and the like.
• an alcohol solvent for example, Methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-pentanol, iso-pentanol, 2-methylbutanol, sec-pentanol, tert- Pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n- Nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptan
• ether solvent for example, Dialiphatic ether solvents such as diethyl ether, dipropyl ether, dibutyl ether; Aromatic ring ether solvents such as anisole and diphenyl ether; Examples thereof include cyclic ether solvents such as tetrahydrofuran and dioxane.
• ketone solvents include: Acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, methyl-n-amyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-iso-butyl ketone Chain ketone solvents such as trimethylnonanone and acetophenone; Cyclic ketone solvents such as cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone; And diketone solvents such as 2,4-pentanedione and acetonylacetone.
• amide solvent examples include Chain amide solvents such as N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide; And cyclic amide solvents such as N-methylpyrrolidone and N, N′-dimethylimidazolidinone.
• ester solvents include: Methyl acetate, ethyl acetate, n-propyl acetate, iso-propyl acetate, n-butyl acetate, iso-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n propionate -Butyl, iso-amyl propionate, diethyl o
• Carboxylate solvent Acetic acid ethylene glycol monomethyl ether, acetic acid ethylene glycol monoethyl ether, acetic acid diethylene glycol monomethyl ether, acetic acid diethylene glycol monoethyl ether, acetic acid diethylene glycol mono-n-butyl ether, acetic acid propylene glycol monomethyl ether, acetic acid propylene glycol monoethyl ether, acetic acid propylene glycol monopropyl ether
• Carboxylic acid ester solvents of polyhydric alcohol partial ethers such as ether, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate; Lactone solvents such as ⁇ -butyrolactone and ⁇ -valerolactone; Examples thereof include carbonate solvents such as diethyl carbonate and propylene carbonate.
• hydrocarbon solvent examples include Aliphatic carbonization such as n-pentane, iso-pentane, n-hexane, iso-hexane, n-heptane, iso-heptane, 2,2,4-trimethylpentane, n-octane, iso-octane, cyclohexane, methylcyclohexane A hydrogen-based solvent; Fragrances such as benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, iso-propylbenzene, diethylbenzene, iso-butylbenzene, triethylbenzene, di-iso-propylbenzene, n-amylnaphthalene Group hydrocarbon solvents and the like.
• Aliphatic carbonization such as n-p
• ester solvents and ketone solvents are preferable, carboxylic acid ester solvents and cyclic ketone solvents of polyhydric alcohol partial ethers are more preferable, and propylene glycol monomethyl ether acetate and cyclohexanone are more preferable.
• a solvent can be used individually by 1 type or in mixture of 2 or more types.
• the radiation sensitive resin composition can contain a surfactant, an alicyclic skeleton-containing compound, a sensitizer and the like as other components.
• the said radiation sensitive resin composition may contain another arbitrary component individually by 1 type or 2 types or more, respectively.
• the surfactant exhibits the effect of improving the coating property, striation, developability and the like of the radiation sensitive resin composition.
• the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol diacrylate.
• Nonionic surfactants such as stearate, commercially available products such as KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no.
• the alicyclic skeleton-containing compound has an effect of improving the dry etching resistance, pattern shape, adhesion to the substrate, and the like of the radiation-sensitive resin composition.
• Examples of the alicyclic skeleton-containing compound include adamantane derivatives such as 1-adamantanecarboxylic acid, 2-adamantanone, and 1-adamantanecarboxylic acid t-butyl; Deoxycholic acid esters such as t-butyl deoxycholic acid, t-butoxycarbonylmethyl deoxycholic acid, 2-ethoxyethyl deoxycholic acid; Lithocholic acid esters such as tert-butyl lithocholic acid, tert-butoxycarbonylmethyl lithocholic acid, 2-ethoxyethyl lithocholic acid; 3- [2-hydroxy-2,2-bis (trifluoromethyl) ethyl] tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodecane, 2-hydroxy-9-methoxycarbonyl-5-oxo-4-oxa-tricyclo [4.2.1.0 3,7 ] nonane, and the like.
• sensitizer exhibits the effect
• sensitizer examples include carbazoles, acetophenones, benzophenones, naphthalenes, phenols, biacetyl, eosin, rose bengal, pyrenes, anthracenes, phenothiazines, and the like.
• the radiation sensitive resin composition includes, for example, [E] solvent, [A] polymer, [B] acid generator, [C] acid diffusion controller, [D] fluorine atom-containing polymer, if necessary. And other optional components can be prepared by mixing them at a predetermined ratio.
• the prepared radiation-sensitive resin composition is preferably used after being filtered through a filter having a pore diameter of about 0.20 ⁇ m, for example.
• the solid content concentration of the radiation-sensitive resin composition is preferably 0.1% by mass to 50% by mass, more preferably 0.5% by mass to 30% by mass, and further preferably 1% by mass to 15% by mass.
• the resist pattern forming method of the present invention comprises: A step of forming a photoresist film on a substrate using the radiation-sensitive resin composition (hereinafter, also referred to as a “photoresist film forming step”), A step of exposing the photoresist film (hereinafter also referred to as an “exposure step”), and a step of developing the exposed photoresist film (hereinafter also referred to as a “development step”).
• photoresist film forming step A step of exposing the photoresist film
• exposure step a step of developing the exposed photoresist film
• a photoresist film is formed on the substrate using the radiation sensitive resin composition.
• the substrate for example, a conventionally known substrate such as a silicon wafer or a wafer coated with aluminum can be used.
• an organic or inorganic antireflection film disclosed in Japanese Patent Publication No. 6-12452 and Japanese Patent Application Laid-Open No. 59-93448 may be formed on the substrate.
• the thickness of the resist film to be formed is usually 0.01 ⁇ m to 1 ⁇ m, preferably 0.01 ⁇ m to 0.5 ⁇ m.
• the solvent in the coating film may be volatilized by pre-baking (PB) as necessary.
• PB temperature is appropriately selected depending on the composition of the radiation sensitive resin composition, but is usually 30 ° C. to 200 ° C., preferably 50 ° C. to 150 ° C.
• the PB time is usually 5 seconds to 600 seconds, and preferably 10 seconds to 300 seconds.
• a protective film disclosed in, for example, Japanese Patent Laid-Open No. 5-188598 can be provided on the photoresist film.
• a liquid immersion protective film disclosed in, for example, JP-A-2005-352384 can be provided on the photoresist film.
• an isotrench pattern can be formed by performing reduced projection exposure on a desired region through an isoline pattern mask. Moreover, you may perform exposure twice or more with a desired pattern and a mask pattern. When performing exposure twice or more, it is preferable to perform exposure continuously. In the case of performing multiple exposures, for example, a first reduced projection exposure is performed on a desired area via a line and space pattern mask, and then the second is so that the line intersects the exposed portion where the first exposure has been performed. Reduced projection exposure is performed.
• the first exposure part and the second exposure part are preferably orthogonal.
• the immersion liquid used for exposure examples 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 that is as small as possible so as to minimize distortion of the optical image projected onto the film.
• excimer laser light wavelength 193 nm
• water it is preferable to use water from the viewpoints of availability and easy handling in addition to the above-described viewpoints.
• an additive that decreases the surface tension of water and increases the surface activity may be added in a small proportion.
• This additive is preferably one that does not dissolve the photoresist film on the wafer and can ignore the influence on the optical coating on the lower surface of the lens.
• the water used is preferably distilled water.
• the electromagnetic wave or charged particle beam used for the exposure is appropriately selected according to the type of the [B] acid generator.
• the electromagnetic wave includes ultraviolet rays, far ultraviolet rays, visible rays, X rays, ⁇ rays, and the like.
• the charged particle beam include an electron beam and an ⁇ ray.
• far ultraviolet rays represented by ArF excimer laser and KrF excimer laser (wavelength 248 nm) are preferable, and ArF excimer laser is more preferable.
• the exposure conditions such as the exposure amount are appropriately selected according to the composition of the composition, the type of additive, and the like.
• the exposure process may be performed a plurality of times, and the plurality of exposures may be performed using the same light source or different light sources, but ArF excimer laser light is used for the first exposure. It is preferable to use it.
• PEB post-exposure baking
• the PEB temperature is usually 30 ° C. to 200 ° C., preferably 50 ° C. to 170 ° C.
• the PEB time is usually 5 seconds to 600 seconds, and preferably 10 seconds to 300 seconds.
• the photoresist film exposed in the above exposure step is developed using a developer to obtain a resist pattern.
• alkali development 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, and 1,5-diazabicyclo- [ 4.3.0] -5-nonene and an alkaline aqueous solution in which at least one selected from the group consisting of alkaline compounds is dissolved.
• TMAH tetramethylammonium hydroxide
• the concentration of the alkaline aqueous solution is preferably 10% by mass or less. When the concentration of the alkaline aqueous solution exceeds 10% by mass, the unexposed area may be dissolved in the developer.
• An organic solvent can also be added to the alkaline aqueous solution. In the case of organic solvent development, for example, one or two or more of the solvents exemplified as the [E] solvent of the above-described radiation-sensitive resin composition can be used. As content of the organic solvent in a developing solution, 80 mass% or more is preferable, 90 mass% or more is more preferable, 95 mass% or more is further more preferable.
• a surfactant can be added to the developer as necessary.
• a surfactant for example, an ionic or nonionic fluorine-based and / or silicon-based surfactant can be used.
• a developing method for example, a method in which a substrate is immersed in a tank filled with a developer for a certain time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is allowed to stand for a certain time (a paddle method) ), A method of spraying the developer on the substrate surface (spray method), a method of continuously applying the developer while scanning the developer coating nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc.
• dip method a method in which a substrate is immersed in a tank filled with a developer for a certain time
• a paddle method a method in which the developer is raised on the surface of the substrate by surface tension and is allowed to stand for a certain time
• a method of spraying the developer on the substrate surface spray method
• a method of continuously applying the developer while scanning the developer coating nozzle on the substrate rotating at a constant speed dynamic dispensing method
• a rinse solution water is preferable in the case of alkali development, and pure water is more preferable.
• alcohol solvents and ester solvents are preferable, monovalent alcohol solvents having 6 to 8 carbon atoms are more preferable, and 1-hexanol, 2-hexanol, 2-heptanol, 4-methyl-2 -Pentanol is more preferred.
• a cleaning method for example, a method of continuously applying a rinse liquid onto a substrate rotating at a constant speed (rotary coating method), a method of immersing the substrate in a tank filled with the rinse liquid for a predetermined time (dip method) ), A method (spray method) of spraying a rinse liquid on the substrate surface, and the like.
• the polymer of the present invention has the structural unit (I-1) represented by the above formula (1).
• R ⁇ 1 > is a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
• Y is a single bond or a divalent linking group.
• R 2 to R 6 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
• the polymer has the structural unit (I-1), it can be suitably used as a polymer component of the above-mentioned radiation-sensitive resin composition.
• the content ratio of the structural unit (I-1) in the polymer is preferably 50 mol% or more based on the total structural units constituting the polymer. 70 mol% or more is more preferable, and 90 mol% or more is further more preferable.
• R ⁇ 1 > is a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
• Y ′ is a divalent linking group.
• R 2 to R 6 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
• the compound Since the compound has the above structure, it can be suitably used, for example, as a monomer that gives the structural unit (I-1).
• reaction solution was washed with a saturated aqueous sodium sulfite solution and an aqueous sodium hydrogen carbonate solution in this order to extract by-products and unreacted products.
• organic phase was dried over anhydrous magnesium sulfate, and then the solvent was distilled off.
• the obtained crude product was recrystallized from 20 mL of toluene to obtain compound (b3) (isolation yield 53%).
• Compounds (i-1) to (i-5) are structural units (I), compounds (m-1) and (m-2) are structural units (II), and compounds (m-3) are structural units. (IV) is given respectively.
• the polymer (A-1) had an Mn of 19,000 and an Mw / Mn ratio of 3.9. Moreover, Tg calculated
• the methanol-insoluble part was collected by centrifugation and vacuum dried to obtain a polymer (A-2) (yield 80%).
• the polymer (A-2) had an Mn of 9,300 and an Mw / Mn ratio of 2.3.
• the content ratios of the structural unit derived from the compound (i-1) and the structural unit derived from MMA determined by 1 H-NMR analysis were 48 mol% and 52 mol%, respectively.
• T g determined by DSC is 73 ° C.
• DTA T calculated in (differential thermal analysis) d5 (5 wt% loss temperature) was 223 ° C..
• Example 8 (Synthesis of polymer (A-3)) In a 10 mL volume ampoule containing a stir bar, 372 mg (1.13 mmol) of compound (i-1), 190 mg (1.13 mmol) of compound (m-1), 7.43 mg (45.2 ⁇ mol) of AIBN and 2.26 mL of DMF were added. Then, after deaeration, the tube was sealed and stirred at 80 ° C. for 6 hours to conduct a polymerization reaction. After completion of the reaction, the reaction solution was cooled to room temperature, diluted with DMF added to the polymerization reaction solution, and poured into a large amount of methanol for reprecipitation.
• the methanol-insoluble part was recovered by centrifugation and vacuum dried to obtain a polymer (A-3) (yield 89%).
• the polymer (A-3) had a Mn of 12,200 and a Mw / Mn ratio of 2.5.
• the content ratios of the structural unit derived from the compound (i-1) and the structural unit derived from the compound (m-1) determined by 1 H-NMR analysis were 48 mol% and 52 mol%, respectively.
• required by DSC was 97 degreeC
• the methanol-insoluble part was collected by centrifugation and vacuum dried to obtain a polymer (A-4) (yield 82%).
• the polymer (A-4) had an Mn of 11,500 and an Mw / Mn ratio of 2.5.
• the content ratios of the structural unit derived from the compound (i-1) and the structural unit derived from the compound (m-2) determined by 1 H-NMR analysis were 59 mol% and 41 mol%, respectively.
• T g determined by DSC differential scanning calorimetry
• T d5 determined by DTA differential thermal analysis
• the polymer (A-5) had an Mn of 23,000 and an Mw / Mn ratio of 5.2. Further, T g determined by DSC (differential scanning calorimetry) is 119 ° C., DTA T calculated in (differential thermal analysis) d5 (5 wt% loss temperature) was 282 ° C..
• Example 11 (Synthesis of polymer (A-6)) In a 10 mL ampoule containing a stir bar, 39.4 mg (240 ⁇ mol) of compound (i-3), 0.49 mg (2.98 ⁇ mol) of AIBN and 0.15 mL of DMF were put, and after deaeration, the tube was sealed and sealed at 80 ° C. The polymerization reaction was carried out with stirring for 6 hours. After completion of the reaction, the reaction solution was cooled to room temperature, diluted with DMF added to the polymerization reaction solution, and poured into a large amount of methanol for reprecipitation.
• the methanol-insoluble part was recovered by centrifugation and vacuum dried to obtain a polymer (A-6) (yield 99%).
• Mn of the polymer (A-6) was 20,000, and Mw / Mn ratio was 1.9.
• T g is 120 ° C. as determined by DSC (differential scanning calorimetry)
• T d5 determined by DTA (differential thermal analysis) (5 mass% reduction temperature) was 248 ° C..
• the polymer (A-7) had a Mn of 49,000 and a Mw / Mn ratio of 2.9. Further, T g determined by DSC (differential scanning calorimetry) is 133 ° C., DTA T calculated in (differential thermal analysis) d5 (5 wt% loss temperature) was 285 ° C..
• Example 14 (Synthesis of polymer (A-9)) 18.4 g (50 mol%) of the above compound (i-5) and 11.6 g (50 mol%) of the above compound (m-1) were dissolved in 80 g of 2-butanone, and 1.13 g of AIBN was further dissolved to obtain a simple substance. A meter solution was prepared. Subsequently, a 200 mL three-necked flask containing 40 g of 2-butanone was purged with nitrogen for 30 minutes, and then heated to 80 ° C. with stirring, and the monomer solution prepared above was added dropwise over 3 hours using a dropping funnel.
• the dripping start was set as the polymerization reaction start time, and the polymerization reaction was carried out for 6 hours.
• the polymerization reaction solution was cooled with water and cooled to 30 ° C. or lower.
• the cooled polymerization reaction solution was put into 800 g of methanol, and the precipitated white powder was separated by filtration.
• the filtered white powder was washed twice with 160 g of methanol, filtered, and dried at 50 ° C. for 17 hours to synthesize a white powdery polymer (A-9) (yield 79%).
• Mn of the polymer (A-9) was 3,900, and Mw / Mn was 1.41.
• the respective content ratios of the structural unit derived from the compound (i-5) and the structural unit derived from the compound (m-1) obtained by 13 C-NMR analysis were 47.8 mol% and 52.2 mol%, respectively. there were. Further, DSC T g determined in (differential scanning calorimetry) is 143 ° C., DTA T calculated in (differential thermal analysis) d5 (5 wt% loss temperature) was 206 ° C..
• the polymerization reaction solution was cooled with water and cooled to 30 ° C. or lower.
• a cooled polymerization reaction solution was put into 800 g of methanol, and the precipitated white powder was separated by filtration.
• the filtered white powder was washed twice with 160 g of methanol, filtered, and dried at 50 ° C. for 17 hours to synthesize a white powdery polymer (a-1) (yield 86%).
• Mn of the polymer (a-1) was 3,930, and Mw / Mn was 1.40.
• the respective content ratios of the structural unit derived from the compound (m-1) and the structural unit derived from the compound (m-4) determined by 13 C-NMR analysis were 48.2 mol% and 51.8 mol%, respectively. there were. Further, T g determined by DSC (differential scanning calorimetry) is 122 ° C., DTA T calculated in (differential thermal analysis) d5 (5 wt% loss temperature) was 182 ° C..
• Example 15 (Preparation of radiation-sensitive resin composition (J-1)) [A] (A-9) 100 parts by mass as a polymer, [B] (B-1) 9.9 parts by mass as an acid generator, [C] (C-1) 7 as an acid diffusion controller , 9 parts by mass and (E-1) 2,590 parts by mass and (E-2) 1,110 parts by mass as [E] solvent, and the resulting mixture was filtered with a filter having a pore size of 0.20 ⁇ m. A radiation sensitive resin composition (J-1) was prepared by filtration.
• Example 15 In Example 15, instead of 100 parts by mass of the polymer (A-9), 100 parts by mass of the polymer (a-1) was added, and the radiation sensitive resin composition ( CJ-1) was prepared.
• Table 2 below shows the types and amounts of each component used for the preparation of each radiation-sensitive resin composition.
• the resist pattern was formed according to the following method, and the LWR performance and pattern collapse resistance of the radiation sensitive resin composition were evaluated by measuring this resist pattern. The evaluation results are shown in Table 2 below.
• a lower antireflection film having a thickness of 77 nm was formed on the surface of a 12-inch silicon wafer using a composition for forming an antireflection film for lower layer (ARC29A, manufactured by Nissan Chemical Industries). Each radiation-sensitive resin composition was applied on this lower antireflection film, and SB was performed at 100 ° C. for 60 seconds to form a 75 nm-thick photoresist film. Further, a liquid immersion upper film material (NFC TCX091-7, manufactured by JSR) was applied on the formed photoresist film, and SB was performed at 90 ° C. for 60 seconds to form a liquid immersion upper film having a film thickness of 30 nm.
• NFC TCX091-7 manufactured by JSR
• This positive resist pattern is a one-to-one line-and-space with a line width of 50 nm formed through a mask.
• LWR performance The resist pattern formed with the optimum exposure amount was observed from above the pattern using the scanning electron microscope. A total of 50 line widths were measured at arbitrary points, a 3 sigma value was obtained from the distribution of the measured values, and this value was defined as LWR performance (nm). In addition, it shows that LWR performance is so high that this value is small. The LWR performance can be evaluated as “good” when it is less than 4.5 nm and “bad” when it is 4.5 nm or more.
• the radiation-sensitive resin compositions of Examples containing a polymer having a structural unit containing a bislactone structure are more resistant to LWR and pattern collapse than those containing a norbornane lactone structure of Comparative Example. It turns out that it is excellent.
• a resist pattern having a low LWR and a high resistance to pattern collapse can be formed.
• the polymer of the present invention can be suitably used as a polymer contained in the radiation-sensitive resin composition, and the compound of the present invention can be suitably used as a raw material monomer for the polymer. it can. Therefore, these radiation-sensitive resin compositions, resist pattern formation methods, polymers and compounds can be suitably used for pattern formation in the field of semiconductor processing, for example, where miniaturization will continue to progress in the future.

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