WO2015129832A1 - Composition de résine radiosensible, procédé permettant de former un motif de réserve, polymère et composé - Google Patents

Composition de résine radiosensible, procédé permettant de former un motif de réserve, polymère et composé Download PDF

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Publication number
WO2015129832A1
WO2015129832A1 PCT/JP2015/055718 JP2015055718W WO2015129832A1 WO 2015129832 A1 WO2015129832 A1 WO 2015129832A1 JP 2015055718 W JP2015055718 W JP 2015055718W WO 2015129832 A1 WO2015129832 A1 WO 2015129832A1
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group
polymer
structural unit
resin composition
carbon atoms
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PCT/JP2015/055718
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Japanese (ja)
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準人 生井
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Jsr株式会社
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Priority to JP2016505307A priority Critical patent/JP6493386B2/ja
Publication of WO2015129832A1 publication Critical patent/WO2015129832A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/90—Carboxylic acid amides having nitrogen atoms of carboxamide groups further acylated
    • C07C233/91—Carboxylic acid amides having nitrogen atoms of carboxamide groups further acylated with carbon atoms of the carboxamide groups bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/30—Sulfonamides, the carbon skeleton of the acid part being further substituted by singly-bound nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/45—Sulfonamides, the carbon skeleton of the acid part being further substituted by singly-bound nitrogen atoms, not being part of nitro or nitroso groups at least one of the singly-bound nitrogen atoms being part of any of the groups, X being a hetero atom, Y being any atom, e.g. N-acylaminosulfonamides
    • C07C311/46—Y being a hydrogen or a carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/48—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom
    • 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
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/38—Esters containing sulfur
    • C08F220/382—Esters containing sulfur and containing oxygen, e.g. 2-sulfoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/38—Esters containing sulfur
    • C08F220/387—Esters containing sulfur and containing nitrogen and oxygen

Definitions

  • the present invention relates to a radiation sensitive resin composition, a resist pattern forming method, a polymer and a compound.
  • a resist pattern forming method by photolithography For forming various electronic device structures such as semiconductor devices and liquid crystal devices, a resist pattern forming method by photolithography is used.
  • a radiation sensitive resin composition for forming a resist pattern on a substrate is used.
  • the radiation sensitive resin composition generates an acid in an exposed portion by irradiation with radiation such as deep ultraviolet rays such as ArF excimer laser light or an electron beam, and a developing solution for an exposed portion and an unexposed portion by the catalytic action of the acid. A difference in dissolution rate with respect to is formed, and a resist pattern is formed on the substrate.
  • Such a radiation-sensitive resin composition is excellent in resolution and not only in the rectangular shape of the cross-sectional shape of the resist pattern, but also in LWR (Line Width Roughness) performance, CDU (Critical Dimension Uniformity) performance, and the like.
  • LWR Line Width Roughness
  • CDU Critical Dimension Uniformity
  • MEEF Mem Error Enhancement Factor
  • the miniaturization of the resist pattern has progressed to a level of 45 nm or less, the required level of the performance is further increased, and the conventional radiation-sensitive resin composition satisfies these requirements. I can't make it happen.
  • the present invention has been made based on the above-described circumstances, and exhibits excellent MEEF performance, depth of focus, and exposure margin, and is excellent in LWR performance, CDU performance, resolution, and cross-sectional rectangularity. It aims at providing the radiation sensitive resin composition which can form a resist pattern.
  • structural unit (I) containing a group represented by the following formula (1) (hereinafter also referred to as “group (1)”). ) Containing a polymer (hereinafter also referred to as “[A] polymer”) and a radiation-sensitive acid generator (hereinafter also referred to as “[B] acid generator”). is there.
  • group (1) a group represented by the following formula (1)
  • [A] polymer a polymer
  • [B] acid generator a radiation-sensitive acid generator
  • R 1 is a substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms.
  • R 2 is a single bond or a substituted or unsubstituted 2 having 1 to 5 carbon atoms.
  • R 1 and at least one of one or more R 2 form a ring structure having 3 to 20 ring members composed of carbon atoms to which they are bonded together and to which they are bonded.
  • A is an integer of 1 to 3.
  • a is 2 or more, a plurality of R 2 may be the same or different, and A has two or more heteroatoms, (This is a monovalent group bonded to R 2 by a carbon atom. * Indicates a bonding site.)
  • Another invention made in order to solve the above-mentioned problems comprises a step of forming a resist film, a step of exposing the resist film, and a step of developing the exposed resist film, It is the resist pattern formation method formed with a conductive resin composition.
  • R 1 is a substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms.
  • R 2 is a single bond or a substituted or unsubstituted 2 having 1 to 5 carbon atoms.
  • R 1 and at least one of one or more R 2 form a ring structure having 3 to 20 ring members composed of carbon atoms to which they are bonded together and to which they are bonded.
  • A is an integer of 1 to 3.
  • R 10 is a hydrogen atom, a fluorine atom, a methyl group or A is a trifluoromethyl group, and A is a monovalent group having two or more heteroatoms and bonded to R 2 with a carbon atom.
  • R 1 is a substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms.
  • R 2 is a single bond or a substituted or unsubstituted 2 having 1 to 5 carbon atoms.
  • R 1 and at least one of one or more R 2 form a ring structure having 3 to 20 ring members composed of carbon atoms to which they are bonded together and to which they are bonded.
  • A is an integer of 1 to 3.
  • R 10 is a hydrogen atom, a fluorine atom, a methyl group or A is a trifluoromethyl group, and A is a monovalent group having two or more heteroatoms and bonded to R 2 with a carbon atom.
  • organic group means a group containing at least one carbon atom.
  • the “hydrocarbon group” includes a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.
  • the “hydrocarbon group” may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
  • the “chain hydrocarbon group” refers to a hydrocarbon group that does not include a cyclic structure but includes only a chain structure, and includes both a linear hydrocarbon group and a branched hydrocarbon group.
  • alicyclic hydrocarbon group refers to a hydrocarbon group that includes only an alicyclic structure as a ring structure and does not include an aromatic ring structure, and includes a monocyclic alicyclic hydrocarbon group and a polycyclic alicyclic group. Includes both hydrocarbon groups.
  • “Aromatic hydrocarbon group” refers to a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary to be composed only of an aromatic ring structure, and a part thereof may include a chain structure or an alicyclic structure.
  • the “number of ring members” means the number of atoms constituting the ring of the alicyclic structure and the aliphatic heterocyclic structure, and in the case of the polycyclic alicyclic structure and the polycyclic aliphatic heterocyclic structure, The number of atoms that make up.
  • the radiation sensitive resin composition and resist pattern forming method of the present invention excellent MEEF performance, depth of focus and exposure margin are exhibited, and LWR performance, CDU performance, resolution, and cross-sectional rectangularity are obtained.
  • An excellent resist pattern can be formed.
  • the polymer of this invention is used suitably as a polymer component of the said radiation sensitive resin composition. Since the compound of the present invention has a structure represented by the above formula (i), it is suitably used as a monomer compound that incorporates the structural unit (I) into the polymer. Therefore, these can be suitably used for pattern formation in semiconductor device manufacturing or the like, where miniaturization is expected to progress further in the future.
  • the radiation-sensitive resin composition contains a [A] polymer and a [B] acid generator. Moreover, the said radiation sensitive resin composition is also called fluorine atom containing polymer (henceforth "[D] polymer") other than [C] acid diffusion control body and [D] [A] polymer as a suitable component. ) And [E] may contain a solvent, and may contain other optional components as long as the effects of the present invention are not impaired. Hereinafter, each component will be described.
  • the polymer is a polymer having the structural unit (I).
  • the radiation-sensitive resin composition exhibits excellent MEEF performance, depth of focus, and exposure margin due to the [A] polymer having the structural unit (I), LWR performance, CDU performance, and resolution.
  • it is possible to form a resist pattern having a rectangular cross-sectional shape (these performances are also referred to as “lithographic performances” hereinafter).
  • the reason why the polymer exhibits the above-described effect by having the above-described configuration is not necessarily clear, but can be inferred as follows, for example.
  • the structural unit (I) has a monovalent group having two or more heteroatoms, and a ketone structure is formed between the monovalent group and the polymer chain. Since it has the specific structure connected with the spacer which has, it has high polarity. Therefore, [A] polymer can adjust the solubility with respect to a developing solution more appropriately. Furthermore, the radiation sensitive resin composition can shorten the diffusion length of the acid generated from the [B] acid generator more appropriately. As a result, according to the radiation sensitive resin composition, the lithography performance of the resist pattern to be formed can be improved.
  • the polymer is a structural unit other than the structural unit (I) and includes an acid dissociable group (II); a lactone structure, a cyclic carbonate structure, and a sultone structure Or a structural unit (III) containing a combination thereof; a structural unit (IV) containing a polar group and a fluorine atom-containing structural unit (V), and other structural units other than the structural units (I) to (V) It may have a structural unit or the like.
  • the polymer preferably has a structural unit (II) and a structural unit (III) in addition to the structural unit (I).
  • the polymer may have one or more of each structural unit. Hereinafter, each structural unit will be described.
  • the structural unit (I) is a structural unit containing a group represented by the following formula (1).
  • R 1 is a substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms.
  • R 2 is a single bond or a substituted or unsubstituted divalent chain hydrocarbon group having 1 to 5 carbon atoms.
  • R 1 and at least one of one or a plurality of R 2 may be combined with each other to form a ring structure having 3 to 20 ring members that is configured together with the carbon atom to which they are bonded.
  • a is an integer of 1 to 3.
  • a is 2 or more, a plurality of R 2 may be the same or different.
  • A has two or more hetero atoms, a monovalent group having a carbon atom bonded to R 2. * Indicates a binding site.
  • Examples of the divalent hydrocarbon group represented by R 1 include a divalent chain hydrocarbon group having 1 to 10 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 10 carbon atoms, and a carbon number. Examples thereof include 6 to 10 divalent aromatic hydrocarbon groups.
  • Examples of the divalent chain hydrocarbon group having 1 to 10 carbon atoms include alkanediyl groups such as methanediyl group, ethanediyl group, propanediyl group, butanediyl group; Alkenediyl groups such as ethenediyl group, propenediyl group, butenediyl group; Examples include alkynediyl groups such as ethynediyl group, propynediyl group, and butynediyl group.
  • Examples of the divalent alicyclic hydrocarbon group having 3 to 10 carbon atoms include monocyclic cycloalkanediyl groups such as cyclopropanediyl group, cyclobutanediyl group, cyclopentanediyl group, and cyclohexanediyl group; A polycyclic cycloalkanediyl group such as a norbornanediyl group or an adamantanediyl group; Monocyclic cycloalkenediyl groups such as cyclopropenediyl group, cyclobutenediyl group, cyclopentenediyl group, cyclohexenediyl group; And polycyclic cycloalkenediyl groups such as norbornenediyl group.
  • monocyclic cycloalkanediyl groups such as cyclopropanediyl group, cyclobutanediyl group, cyclopen
  • divalent aromatic hydrocarbon group having 6 to 10 carbon atoms examples include arylene groups such as a phenylene group and a tolylene group.
  • Examples of the substituent that these groups may have include a hydroxy group, a halogen atom, and an organic group having 1 to 20 carbon atoms.
  • Examples of the organic group having 1 to 20 carbon atoms include alkyl groups such as a methyl group and an ethyl group, and alkanediyl groups bonded to the same carbon atom that R 1 has.
  • R 1 is preferably a substituted or unsubstituted methanediyl group and an unsubstituted ethanediyl group, more preferably an unsubstituted methanediyl group and a methanediyl group substituted with an alkanediyl group bonded to the same carbon atom of R 1 , An unsubstituted methanediyl group is more preferred.
  • Examples of the divalent chain hydrocarbon group represented by R 2 include the same groups as those exemplified as the divalent chain hydrocarbon group for R 1 .
  • Examples of the substituent that these groups may have include the same groups as the substituents exemplified in R 1 above.
  • R 2 is preferably a single bond, an unsubstituted alkanediyl group or an alkanediyl group substituted with an alkyl group, and a single bond, an unsubstituted methanediyl group, an unsubstituted ethanediyl group or a methanediyl group substituted with a methyl group Is more preferable.
  • A is preferably 1 or 2 from the viewpoint of easiness of synthesis or the like, and more preferably 1.
  • Examples of the ring structure having 3 to 20 ring members composed of R 1 and at least one of one or a plurality of R 2 and the carbon atom to which they are bonded include a cyclopropane structure, a cyclobutane structure, and a cyclopentane.
  • Examples thereof include alicyclic structures such as a structure, cyclohexane structure, norbornane structure, and adamantane structure; and aliphatic heterocyclic structures such as an oxacyclopentane structure, a thiacyclopentane structure, and an azacyclopentane structure.
  • an alicyclic structure is preferable and a cyclohexane structure is more preferable.
  • Examples of the monovalent group having two or more heteroatoms represented by A include a monovalent group having a chain structure and a monovalent cyclic group having a heterocyclic structure.
  • hetero atom examples include an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, and a phosphorus atom.
  • an oxygen atom, a sulfur atom, and a nitrogen atom are preferable, and an oxygen atom is more preferable.
  • Examples of the chain structure include a chain structure having an ester group (—COO—); a chain structure having —SO 2 O—; a chain structure having a sulfone group (—SO 2 —); and a sulfoxide group (— Chain structure having SO—); chain structure having amide group (—CONH—); sulfonimide group (—N (SO 2 R) 2 ), carboximide group (—N (COR) 2 ), carvone Examples include a chain structure having an imide group such as an acid sulfonimide group (—N (COR) (SO 2 R)); a chain structure having a sulfonamide group (—NHSO 2 —); and combinations thereof.
  • heterocyclic structure examples include a lactone structure; a lactam structure, a sultone structure; a cyclic sulfone structure; a cyclic sulfoxide structure; a cyclic amine structure; a cyclic sulfonimide structure, a cyclic carboxylic acid imide structure, and a cyclic carboxylic acid sulfonimide structure.
  • the cyclic amine structure includes those in which a carbonyl group or a sulfonyl group is bonded to the nitrogen atom of the cyclic amine structure.
  • Examples of the monovalent cyclic group having a heterocyclic structure include a group consisting only of a heterocyclic structure, a group consisting of a heterocyclic structure and another structure, and the like.
  • Examples of the other group include a monovalent hydrocarbon group having 1 to 10 carbon atoms, —CO—, —COO—, a divalent hydrocarbon group having 1 to 10 carbon atoms, and a group composed of a combination thereof. Is mentioned.
  • Examples of the monovalent hydrocarbon group include a group in which one hydrogen atom is bonded to one of the bonds of the R 1 divalent hydrocarbon group exemplified above.
  • a chain hydrocarbon group and an aromatic hydrocarbon group are preferable, an alkyl group and an aryl group are more preferable, and a methyl group, a tert-butyl group, and a phenyl group are further preferable.
  • divalent hydrocarbon group examples include the same groups as those exemplified as the divalent hydrocarbon group for R 1 .
  • a chain hydrocarbon group is preferable, an alkanediyl group is more preferable, and a methyl group is more preferable.
  • the other group may be bonded to the carbon atom bonded to R 2.
  • the other group may be bonded to the heterocyclic structure at a portion other than the carbon atom bonded to R 2 .
  • the monovalent group having two or more heteroatoms represented by A is preferably a monovalent cyclic group having a heterocyclic structure.
  • a heterocyclic structure a lactone structure, a lactam structure, a sultone structure, a cyclic sulfone structure, a cyclic sulfoxide structure, a cyclic amine structure, a cyclic imide structure, a cyclic sulfonamide structure, and a combination thereof are preferable, and a lactone structure is more preferable.
  • the polymer has, as the structural unit (I), a structural unit represented by the following formula (2-1) (hereinafter also referred to as “structural unit (I-1)”), a structural unit represented by the following formula (2-2): And a combination thereof (hereinafter also referred to as “structural unit (I-2)”). That is, as the structural unit (I), for example, a structural unit represented by at least one of the following formulas (2-1) and (2-2) is preferable.
  • Z is a group represented by the above formula (1).
  • R 10 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
  • L is a single bond, —O—, —COO— or —CONH—.
  • R 10 is preferably a hydrogen atom and a methyl group, more preferably a methyl group, from the viewpoint of copolymerization of the monomer that gives the structural unit (I).
  • structural units (I) structural units represented by the following formulas (2-1-1) to (2-1-24) (hereinafter referred to as “structural units (I-1-1) to (I-1 -24) ”)) and the like.
  • R 10 has the same meaning as in the above formulas (2-1) and (2-2).
  • the lower limit of the content ratio of the structural unit (I) of the polymer is preferably 1 mol%, more preferably 3 mol%, more preferably 5 mol% with respect to all structural units constituting the [A] polymer. Is more preferable, and 10 mol% is particularly preferable. As an upper limit of the said content rate, 90 mol% is preferable, 70 mol% is more preferable, 50 mol% is further more preferable, 30 mol% is especially preferable.
  • Examples of the monomer that gives the structural unit (I) include a compound represented by the following formula (i) (hereinafter also referred to as “compound (i)”).
  • R 1 is a substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms.
  • R 2 is a single bond or a substituted or unsubstituted divalent chain hydrocarbon group having 1 to 5 carbon atoms.
  • R 1 and at least one of one or a plurality of R 2 may be combined with each other to form a ring structure having 3 to 20 ring members that is configured together with the carbon atom to which they are bonded.
  • a is an integer of 1 to 3.
  • R 10 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
  • A has two or more hetero atoms, a monovalent group having a carbon atom bonded to R 2.
  • R 10 when R 10 is a methyl group, R 1 is a methanediyl group, R 2 is a single bond, A is a 3-methyl- ⁇ -butyrolactone-3-yl group, and a is 1, It can be synthesized simply and with good yield.
  • a compound represented by the above formula (i′-b) is reacted with a compound represented by the above formula (i′-a) and iodomethane in a solvent such as acetone in the presence of a base such as potassium carbonate.
  • a base such as potassium carbonate.
  • the compound represented by the above formula (i′-c) can be obtained by reacting this compound (i′-b) with sulfuryl chloride in a solvent such as hexane.
  • the compound (i′-c) and methacrylic acid are reacted in a solvent such as N, N-dimethylformamide (DMF) in the presence of potassium carbonate and potassium iodide to thereby give the compound (i′-c).
  • DMF N, N-dimethylformamide
  • the structural unit (II) is a structural unit other than the structural unit (I) and includes an acid dissociable group.
  • the “acid-dissociable group” is a group that replaces a hydrogen atom of a polar group such as a carboxy group or a phenolic hydroxyl group, and is a group that dissociates by the action of an acid.
  • structural unit (II) examples include a structural unit represented by the following formula (3-1) (hereinafter also referred to as “structural unit (II-1)”) and a structure represented by the following formula (3-2).
  • a unit hereinafter also referred to as “structural unit (II-2)”).
  • R 12 represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
  • R 13 is a monovalent hydrocarbon group having 1 to 20 carbon atoms.
  • R 14 and R 15 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, or 3 to 3 carbon atoms composed of these groups together with the carbon atom to which they are bonded. 20 alicyclic structures are represented.
  • R 16 represents a hydrogen atom or a methyl group.
  • L 1 is a single bond, —CCOO— or —CONH—.
  • R 17 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.
  • R 18 and R 19 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent oxyhydrocarbon group having 1 to 20 carbon atoms.
  • R 12 is preferably a hydrogen atom and a methyl group, more preferably a methyl group, from the viewpoint of copolymerization of the monomer that gives the structural unit (II).
  • Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R 13 , R 14 , R 15 , R 17 , R 18 and R 19 include monovalent chain carbonization having 1 to 20 carbon atoms. Examples thereof include a hydrogen group, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms.
  • Examples of the monovalent chain hydrocarbon group having 1 to 20 carbon atoms represented by R 13 , R 14 , R 15 , R 17 , R 18 and R 19 include a methyl group, an ethyl group, and an n-propyl group.
  • Alkyl groups such as i-propyl group;
  • An alkenyl group such as an ethenyl group, a propenyl group, a butenyl group;
  • Examples thereof include alkynyl groups such as ethynyl group, propynyl group and butynyl group.
  • Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R 13 , R 14 , R 15 , R 17 , R 18 and R 19 include monocyclic rings such as a cyclopentyl group and a cyclohexyl group.
  • a polycyclic cycloalkyl group such as a norbornyl group, an adamantyl group and a tricyclodecyl group; Examples thereof include polycyclic cycloalkenyl groups such as norbornenyl group and tricyclodecenyl group.
  • Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R 13 , R 14 , R 15 , R 17 , R 18, and R 19 include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.
  • Examples of the alicyclic structure having 3 to 20 carbon atoms composed of the above-described groups combined with the carbon atom to which they are bonded include, for example, a cyclopropane structure, a cyclobutane structure, a cyclopentane structure, a cyclohexane structure, a cycloheptane structure, a cyclo Monocyclic cycloalkane structures such as octane structures; Examples thereof include polycyclic cycloalkane structures such as a norbornane structure, an adamantane structure, a tricyclodecane structure, and a tetracyclododecane structure.
  • hydrocarbon group represented by R 13 , R 14 and R 15 a chain hydrocarbon group and an alicyclic hydrocarbon group are preferable.
  • Examples of the monovalent oxyhydrocarbon group having 1 to 20 carbon atoms represented by R 18 and R 19 include, for example, 1 carbon atom of R 13 , R 14 , R 15 , R 17 , R 18 and R 19.
  • Examples of the monovalent hydrocarbon group of ⁇ 20 include those containing an oxygen atom at the terminal on the bond side.
  • structural units (II-1) structural units represented by the following formulas (3-1-1) to (3-1-5) (hereinafter referred to as “structural units (II-1-1) to (II-1) ⁇ 5) ”) is preferred.
  • the structural unit (II-2) is preferably a structural unit represented by the following formula (3-2-1) (hereinafter also referred to as “structural unit (II-2-1)”).
  • R 12 to R 15 have the same meanings as the above formula (3-1).
  • R 13 ′ , R 14 ′ and R 15 ′ are each independently a monovalent chain hydrocarbon group having 1 to 10 carbon atoms.
  • np is each independently an integer of 1 to 4.
  • R 16 to R 19 have the same meaning as in the above formula (3-2).
  • Examples of the structural units (II-1-1) to (II-1-5) include structural units represented by the following formulas.
  • R 12 has the same meaning as in the above formula (3-1).
  • structural units derived from 2-alkyl-2-adamantyl (meth) acrylate structural units derived from 1-alkyl-1-cyclopentyl (meth) acrylate, 2- (1-adamantyl) -2-propyl Structural units derived from (meth) acrylate, structural units derived from 2-alkyl-2-tetracyclododecan-yl (meth) acrylate, structures derived from 2- (1-cyclohexyl) -2-propyl (meth) acrylate
  • Examples of the structural unit (II-2) include a structural unit represented by the following formula.
  • R 16 has the same meaning as in the above formula (3-2).
  • the structural unit (II-2) is preferably a structural unit derived from p- (1-cyclohexylethoxyethoxy) styrene.
  • the lower limit of the content ratio of the structural unit (II) is preferably 10 mol% with respect to the total structural units constituting the [A] polymer, Mole% is more preferable, and 30 mol% is more preferable.
  • As an upper limit of the said content rate 90 mol% is preferable, 80 mol% is more preferable, and 75 mol% is further more preferable.
  • the structural unit (III) is a structural unit containing a lactone structure, a cyclic carbonate structure, a sultone structure, or a combination thereof (excluding the structural unit (I)).
  • the polymer further has the structural unit (III), so that the solubility in the developer can be appropriately adjusted. As a result, the lithography performance of the radiation-sensitive resin composition is further improved. be able to. Moreover, the adhesiveness of the resist pattern formed from the said radiation sensitive resin composition and a board
  • Examples of the structural unit (III) include a structural unit represented by the following formula.
  • R L1 represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
  • the structural unit (III) is preferably a structural unit containing a lactone structure, more preferably a structural unit containing a norbornane lactone structure, a structural unit containing an oxynorbornane lactone structure, or a structural unit containing a ⁇ -butyrolactone structure.
  • the lower limit of the content ratio of the structural unit (III) is preferably 5 mol% with respect to all the structural units constituting the [A] polymer, Mole% is more preferable, and 25 mol% is more preferable.
  • As an upper limit of the said content rate 80 mol% is preferable, 70 mol% is more preferable, 60 mol% is further more preferable, 50 mol% is especially preferable.
  • the solubility in the developer can be adjusted more appropriately. As a result, the lithography of the radiation-sensitive resin composition can be performed. The performance can be further improved. Moreover, the adhesiveness of the resist pattern formed from the said radiation sensitive resin composition and a board
  • the structural unit (IV) is a structural unit containing a polar group.
  • the polymer can adjust the solubility in the developer more appropriately, and as a result, improves the lithography performance of the radiation-sensitive resin composition. be able to. Moreover, the adhesiveness of the resist pattern formed from the said radiation sensitive resin composition and a board
  • Examples of the polar group include a hydroxy group, an oxo group ( ⁇ O), a carboxy group, a nitro group, a cyano group, and a sulfonamide group. Among these, a hydroxy group and a keto group are preferable.
  • Examples of the structural unit containing the polar group include a structural unit represented by the following formula.
  • R L2 represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
  • the structural unit (V) is a structural unit containing a fluorine atom.
  • the polymer can further have a structural unit (V) in addition to the structural unit (I) to adjust the fluorine atom content, and as a result, the polymer is formed from the radiation-sensitive resin composition.
  • the dynamic contact angle on the resist film surface can be improved.
  • Examples of the structural unit (V) include the following structural unit (V-1) and structural unit (V-2).
  • the structural unit (V-1) is a structural unit represented by the following formula (4a).
  • RD is a hydrogen atom, a methyl group, or a trifluoromethyl group.
  • G is a single bond, an oxygen atom, a sulfur atom, —CO—O—, —SO 2 —O—NH—, —CO—NH— or —O—CO—NH—.
  • R E is a monovalent chain hydrocarbon group having 1 to 6 carbon atoms having at least one fluorine atom or a monovalent aliphatic cyclic hydrocarbon group having 4 to 20 carbon atoms having at least one fluorine atom. It is.
  • the chain hydrocarbon group having 1 to 6 carbon atoms having at least one fluorine atom represented by R E such as trifluoromethyl group, 2,2,2-trifluoroethyl group, perfluoroethyl group 2,2,3,3,3-pentafluoropropyl group, 1,1,1,3,3,3-hexafluoropropyl group, perfluoro n-propyl group, perfluoro i-propyl group, perfluoro n -Butyl group, perfluoro i-butyl group, perfluoro t-butyl group, 2,2,3,3,4,4,5,5-octafluoropentyl group, perfluorohexyl group and the like.
  • R E fluorine atom represented by R E
  • Examples of the aliphatic cyclic hydrocarbon group having 4 to 20 carbon atoms having at least one fluorine atom represented by R E for example mono-fluoro cyclopentyl group, difluorocyclopentyl groups, perfluorocyclopentyl group, monofluoromethyl cyclohexyl group, Examples thereof include a difluorocyclopentyl group, a perfluorocyclohexylmethyl group, a fluoronorbornyl group, a fluoroadamantyl group, a fluorobornyl group, a fluoroisobornyl group, a fluorotricyclodecyl group, and a fluorotetracyclodecyl group.
  • Examples of the monomer that gives the structural unit (V-1) include trifluoromethyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,2-trimethyl ester, and the like. Fluoroethyloxycarbonylmethyl (meth) acrylic acid ester, perfluoroethyl (meth) acrylic acid ester, perfluoro n-propyl (meth) acrylic acid ester, perfluoro i-propyl (meth) acrylic acid ester, perfluoro n- Butyl (meth) acrylic acid ester, perfluoro i-butyl (meth) acrylic acid ester, perfluoro t-butyl (meth) acrylic acid ester, 2- (1,1,1,3,3,3-hexafluoropropyl ) (Meth) acrylic acid ester, 1- (2,2,3,3,4,4,5,5-octaf) (Olopentyl) (meth) acrylic acid ester,
  • the lower limit of the content ratio of the structural unit (V-1) is 5 mol% with respect to all the structural units constituting the [A] polymer. Is preferable, and 8 mol% is more preferable. As an upper limit of the said content rate, 80 mol% is preferable, 50 mol% is more preferable, 30 mol% is further more preferable, 20 mol% is especially preferable.
  • V-2 The structural unit (V-2) is a structural unit represented by the following formula (4b).
  • R ⁇ F> is a hydrogen atom, a methyl group, or a trifluoromethyl group.
  • R 20 is an (s + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, and an oxygen atom, a sulfur atom, —NR′—, a carbonyl group, —CO—O—, or a terminal at the R 21 side of R 20 Also includes a structure in which —CO—NH— is bonded.
  • R ′ is a hydrogen atom or a monovalent organic group.
  • R 21 is a single bond, a divalent chain hydrocarbon group having 1 to 10 carbon atoms, or a divalent aliphatic cyclic hydrocarbon group having 4 to 20 carbon atoms.
  • X 2 is a C 1-20 divalent chain hydrocarbon group having at least one fluorine atom.
  • a 1 is an oxygen atom, —NR ′′ —, —CO—O— *, or —SO 2 —O— *.
  • R ′′ is a hydrogen atom or a monovalent organic group. * Indicates a binding site that binds to R 22.
  • R 22 is a hydrogen atom or a monovalent organic group.
  • s is an integer of 1 to 3. However, when s is 2 or 3, a plurality of R 21 , X 2 , A 1 and R 22 may be the same or different.
  • R 22 is a hydrogen atom, it is preferable in that the solubility of [A] polymer in an alkaline developer can be improved.
  • Examples of the monovalent organic group represented by R 22 include an acid-dissociable group, an alkali-dissociable group, or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent.
  • Examples of the structural unit (V-2) include structural units represented by the following formulas (4b-1) to (4b-3).
  • R 20 ′ is a divalent linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms.
  • R F , X 2 , R 22 and s are as defined in the above formula (4b). When s is 2 or 3, the plurality of X 2 and R 22 may be the same or different.
  • the lower limit of the content ratio of the structural unit (V-2) is 5 mol% with respect to all structural units constituting the [A] polymer. Is preferred.
  • As an upper limit of the said content rate 80 mol% is preferable, 60 mol% is more preferable, and 40 mol% is further more preferable.
  • the resist film surface formed from the radiation-sensitive resin composition has a reduced degree of dynamic contact angle in alkali development. Can be further improved.
  • the structural unit (VI) is a structural unit containing a group (z) having a hydroxy group at the terminal and a carbon atom adjacent to the hydroxy group having at least one fluorine atom or fluorinated alkyl group (provided that the structure Except unit (I) and structural unit (V)).
  • the polymer can adjust the solubility in the developer more appropriately, and as a result, the lithography performance of the radiation-sensitive resin composition is further improved. be able to. Moreover, the sensitivity of the radiation sensitive resin composition in the case of EUV exposure can be increased.
  • Examples of the group (z) include a group represented by the following formula (z-1).
  • R f1 and R f2 are each independently an alkyl group having 1 to 10 carbon atoms or a fluorinated alkyl group having 1 to 10 carbon atoms. However, at least one of R f1 and R f2 is a fluorinated alkyl group.
  • Examples of the fluorinated alkyl group having 1 to 10 carbon atoms represented by R f1 and R f2 include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a difluoroethyl group, a trifluoroethyl group, Examples include a pentafluoroethyl group, a hexafluoropropyl group, a heptafluoropropyl group, and a nonafluorobutyl group. Among these, a trifluoromethyl group and a pentafluoroethyl group are preferable, and a trifluoromethyl group is more preferable.
  • the group (z) is preferably a hydroxy-di (trifluoromethyl) methyl group, a hydroxy-di (pentafluoroethyl) methyl group or a hydroxy-methyl-trifluoromethylmethyl group, preferably a hydroxy-di (trifluoromethyl) group.
  • a methyl group is more preferred.
  • structural unit (VI) examples include structural units represented by the following formulas (5-1) to (5-9) (hereinafter also referred to as “structural units (VI-1) to (VI-9)”), etc. Is mentioned.
  • R L3 is independently a hydrogen atom or a methyl group.
  • the lower limit of the content ratio of the structural unit (VI) is preferably 20 mol% with respect to all the structural units constituting the polymer [A], 30 Mole% is more preferable.
  • As an upper limit of the said content rate 80 mol% is preferable, 70 mol% is more preferable, and 60 mol% is further more preferable.
  • the solubility in the developer can be further appropriately adjusted. As a result, the lithography of the radiation-sensitive resin composition can be performed. The performance can be further improved. Moreover, the sensitivity of the said radiation sensitive resin composition in the case of EUV exposure can be improved more.
  • the polymer may have other structural units other than the structural units (I) to (VI).
  • the other structural unit include a structural unit containing a non-dissociable alicyclic hydrocarbon group.
  • the upper limit of the content ratio of the above-mentioned other structural units is preferably 20 mol% with respect to all the structural units constituting the [A] polymer. Mole% is more preferable.
  • the lower limit of the content of the [A] polymer in the radiation-sensitive resin composition is preferably 70% by mass, more preferably 80% by mass, based on the total solid content in the radiation-sensitive resin composition. 85 mass% is more preferable.
  • the radiation sensitive resin composition may contain one or more [A] polymers.
  • the polymer can be synthesized, for example, by polymerizing monomers that give each structural unit in a suitable solvent using a radical polymerization initiator or the like.
  • radical polymerization initiator examples include azobisisobutyronitrile (AIBN), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2-cyclopropylpropylene). Pionitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), azo radical initiators such as dimethyl 2,2′-azobisisobutyrate; benzoyl peroxide, t-butyl hydroperoxide, And peroxide radical initiators such as cumene hydroperoxide. Of these, AIBN and dimethyl 2,2'-azobisisobutyrate are preferred, and AIBN is more preferred. These radical initiators can be used alone or in combination 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, hexamethylene dibromide, chlorobenzene; Saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, i-butyl acetate and methyl propionate; Ketones such as acetone, methyl ethyl ketone
  • the lower limit of the reaction temperature in the polymerization is usually 40 ° C., and preferably 50 ° C.
  • the upper limit of the reaction temperature is usually 150 ° C, preferably 120 ° C.
  • the lower limit of the reaction time is usually 1 hour.
  • the upper limit of the reaction time is usually 48 hours, preferably 24 hours.
  • the lower limit of the weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of the polymer is not particularly limited, but is preferably 1,000, more preferably 2,000, and further 3,000. Preferably, 5,000 is particularly preferable.
  • the upper limit of the Mw is not particularly limited, but is preferably 50,000, more preferably 30,000, still more preferably 20,000, and particularly preferably 15,000. [A] By making Mw of a polymer into the said range, the applicability
  • the lower limit of the ratio (Mw / Mn) of Mw to the number average molecular weight (Mn) in terms of polystyrene by GPC of the polymer is usually 1.
  • the upper limit of Mw / Mn is usually 5, preferably 3 and more preferably 2.
  • Mw and Mn of the polymer in this specification are values measured using gel permeation chromatography (GPC) under the following conditions.
  • GPC column 2 "G2000HXL” from Tosoh Corporation, 1 "G3000HXL", 1 "G4000HXL” Column temperature: 40 ° C
  • Elution solvent Tetrahydrofuran (Wako Pure Chemical Industries)
  • Flow rate 1.0 mL / min
  • Sample concentration 1.0% by mass
  • Sample injection volume 100 ⁇ L
  • Detector Differential refractometer Standard material: Monodisperse polystyrene
  • the acid generator is a substance that generates an acid upon exposure.
  • the acid-dissociable group of the [A] polymer or the like is dissociated by the generated acid to generate a carboxy group or the like, and the solubility of the [A] polymer in the developer changes.
  • a resist pattern can be formed from the object.
  • the contained form of the [B] acid generator in the radiation-sensitive resin composition may be a low molecular compound form (hereinafter also referred to as “[B] acid generator” as appropriate), as described later. It may be a form incorporated as a part or both of these forms.
  • 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.
  • [B] acid generator examples include compounds described in paragraphs [0080] to [0113] of JP2009-134088A.
  • the acid generator is preferably a compound represented by the following formula (7).
  • the diffusion length of the acid generated by exposure in the resist film is appropriately shortened by the interaction with the structural unit (I) of the polymer [A]. As a result, the lithography performance of the radiation sensitive resin composition can be improved.
  • R 23 is a monovalent group containing an alicyclic structure having 6 or more ring members or a monovalent group containing an aliphatic heterocyclic structure having 6 or more ring members.
  • R 24 is a fluorinated alkanediyl group having 1 to 10 carbon atoms.
  • X + is a monovalent radiation-sensitive onium cation.
  • the “number of ring members” in R 23 refers to the number of atoms constituting the ring of an alicyclic structure and an aliphatic heterocyclic structure, and in the case of a polycyclic alicyclic structure and a polycyclic aliphatic heterocyclic structure, The number of atoms that make up the ring.
  • Examples of the monovalent group having an alicyclic structure having 6 or more ring members represented by R 23 include monocyclic groups such as a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, and a cyclododecyl group.
  • a cycloalkyl group A monocyclic cycloalkenyl group such as a cyclohexenyl group, a cycloheptenyl group, a cyclooctenyl group, a cyclodecenyl group; A polycyclic cycloalkyl group such as a norbornyl group, an adamantyl group, a tricyclodecyl group, a tetracyclododecyl group; Examples thereof include polycyclic cycloalkenyl groups such as norbornenyl group and tricyclodecenyl group.
  • Examples of the monovalent group containing an aliphatic heterocyclic structure having 6 or more ring members represented by R 23 include a group containing a lactone structure such as a norbornanelactone-yl group; A group containing a sultone structure such as a norbornane sultone-yl group; An oxygen atom-containing heterocyclic group such as an oxacycloheptyl group and an oxanorbornyl group; A nitrogen atom-containing heterocyclic group such as an azacycloheptyl group or a diazabicyclooctane-yl group; And sulfur atom-containing heterocyclic groups such as a thiacycloheptyl group and a thianorbornyl group.
  • the lower limit of the ring members of groups denoted by R 23, in view to be appropriate diffusion length of the above-mentioned acid is further preferred 8, 9, and still more preferably 10.
  • the upper limit of the number of ring members is preferably 15 and more preferably 13 from the viewpoint that the acid diffusion length becomes more appropriate.
  • R 23 is preferably a monovalent group containing an alicyclic structure having 9 or more ring members and a monovalent group containing an aliphatic heterocyclic structure having 9 or more ring members, an adamantyl group, a hydroxyadamantyl group A norbornanelactone-yl group and a 5-oxo-4-oxatricyclo [4.3.1.1 3,8 ] undecan-yl group are more preferred, and an adamantyl group is more preferred.
  • Examples of the fluorinated alkanediyl group having 1 to 10 carbon atoms represented by R 24 include one or more hydrogen atoms of an alkanediyl group having 1 to 10 carbon atoms such as a methanediyl group, an ethanediyl group, and a propanediyl group. And a group in which is substituted with a fluorine atom.
  • SO 3 - fluorinated alkane diyl group which has a fluorine atom to carbon atom is bonded to adjacent groups are preferred, SO 3 - 2 fluorine atoms to the carbon atom adjacent to the group is attached More preferred are fluorinated alkanediyl groups, 1,1-difluoromethanediyl group, 1,1-difluoroethanediyl group, 1,1,3,3,3-pentafluoro-1,2-propanediyl group, 1,1 1,2,2-tetrafluoroethanediyl group, 1,1,2,2-tetrafluorobutanediyl group and 1,1,2,2-tetrafluorohexanediyl group are more preferable.
  • the monovalent radiation-sensitive onium cation represented by X + is a cation that decomposes upon irradiation with radiation. In the exposed portion, sulfonic acid is generated from protons generated by the decomposition of the radiation-sensitive onium cation and sulfonate anions.
  • Examples of the monovalent radiation-sensitive onium cation represented by X + include elements such as S, I, O, N, P, Cl, Br, F, As, Se, Sn, Sb, Te, and Bi. Examples include radiation-sensitive onium cations.
  • Examples of the cation containing S (sulfur) as an element include a sulfonium cation and a tetrahydrothiophenium cation.
  • Examples of the cation containing I (iodine) as an element include an iodonium cation.
  • an iodonium cation examples include an iodonium cation.
  • a sulfonium cation represented by the following formula (X-1), a tetrahydrothiophenium cation represented by the following formula (X-2), and an iodonium cation represented by the following formula (X-3) are: preferable.
  • R a1 , R a2 and R a3 each independently represent a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted group.
  • aromatic hydrocarbon group having 6 to 12 carbon atoms represents or is a -OSO 2 -R P or -SO 2 -R Q, or two or more are combined with each other configured ring of these groups .
  • R P and R Q are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 25 carbon atoms.
  • R a1 ⁇ R a3 and R P and R Q are a plurality each of the plurality of R a1 ⁇ R a3 and R P and R Q may be the same as or different from each other.
  • R b1 represents a substituted or unsubstituted linear or branched alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 8 carbon atoms. It is. k4 is an integer of 0 to 7. If 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.
  • k5 is an integer of 0 to 6. If 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.
  • R c1 and R c2 each independently represent a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted carbon number of 6 aromatic hydrocarbon group having to 12 represent two or more are combined with each other configured ring of -OSO 2 -R R or -SO 2 -R or S or those groups.
  • R R and R S each independently represent a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 25 carbon atoms.
  • R c1, R c2, R when R and R S is plural respective plurality of R c1, R c2, R R and R S may have respectively the same or different.
  • Examples of the unsubstituted linear alkyl group represented by R a1 to R a3 , R b1 , R b2 , R c1 and R c2 include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group. Etc.
  • Examples of the unsubstituted branched alkyl group represented by R a1 to R a3 , R b1 , R b2 , R c1 and R c2 include i-propyl group, i-butyl group, sec-butyl group, t -A butyl group etc. are mentioned.
  • Examples of the unsubstituted aromatic hydrocarbon group represented by R a1 to R a3 , R c1 and R c2 include aryl groups such as a phenyl group, a tolyl group, a xylyl group, a mesityl group, and a naphthyl group; a benzyl group, And aralkyl groups such as phenethyl group.
  • Examples of the unsubstituted aromatic hydrocarbon group represented by R b1 and R b2 include a phenyl group, a tolyl group, and a benzyl group.
  • Examples of the substituent that may be substituted for the hydrogen atom of the alkyl group and aromatic hydrocarbon group include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, a hydroxy group, a carboxy group, and a cyano group. Nitro group, alkoxy group, alkoxycarbonyl group, alkoxycarbonyloxy group, acyl group, acyloxy group and the like. Among these, a halogen atom is preferable and a fluorine atom is more preferable.
  • R a1 to R a3 , R b1 , R b2 , R c1 and R c2 include an unsubstituted linear or branched alkyl group, a fluorinated alkyl group, and an unsubstituted monovalent aromatic hydrocarbon group.
  • —OSO 2 —R ′′ and —SO 2 —R ′′ are preferred, fluorinated alkyl groups and unsubstituted monovalent aromatic hydrocarbon groups are more preferred, and fluorinated alkyl groups are more preferred.
  • R ′′ is an unsubstituted monovalent alicyclic hydrocarbon group or an unsubstituted monovalent aromatic hydrocarbon group.
  • k1, k2 and k3 are preferably integers of 0 to 2, more preferably 0 and 1, and even more preferably 0.
  • k4 is preferably an integer of 0 to 2, more preferably 0 and 1, and even more preferably 1.
  • k5 is preferably an integer of 0 to 2, more preferably 0 and 1, and still more preferably 0.
  • k6 and k7 are preferably integers of 0 to 2, more preferably 0 and 1, and even more preferably 0.
  • X + is preferably a cation represented by the above formula (X-1), more preferably a triphenylsulfonium cation.
  • Examples of the acid generator represented by the above formula (7) include compounds represented by the following formulas (7-1) to (7-13) (hereinafter referred to as “compounds (7-1) to (7-13)”. ) ”)) And the like.
  • the acid generator is preferably an onium salt compound, more preferably a sulfonium salt or a tetrahydrothiophenium salt, and the compound (7-1), compound (7-2), compound (7-12). And compound (7-13) are more preferable.
  • the [B] acid generator is a [B] acid generator
  • the [A] polymer 0.1 mass part is preferable with respect to 100 mass parts, 0.5 mass part is more preferable, and 1 mass part is further more preferable.
  • As an upper limit of the said content 30 mass parts is preferable, 20 mass parts is more preferable, and 15 mass parts is further more preferable.
  • the radiation-sensitive resin composition may contain one or more [B] acid generators.
  • the said radiation sensitive resin composition may contain a [C] acid diffusion control body as needed.
  • the acid diffusion control body controls the diffusion phenomenon in the resist film of the acid generated from the [B] acid generator by exposure, has the effect of suppressing undesirable chemical reactions in the non-exposed areas, and the radiation sensitivity obtained
  • the storage stability of the photosensitive resin composition is further improved, the resolution of the resist is further improved, and the change in the line width of the resist pattern due to fluctuations in the holding time from exposure to development processing can be suppressed, thereby stabilizing the process.
  • a radiation-sensitive resin composition having excellent properties can be obtained.
  • the content of the acid diffusion controller in the radiation-sensitive resin composition is incorporated as a part of the polymer even in the form of a free compound (hereinafter referred to as “[C] acid diffusion controller” as appropriate). Or both of these forms.
  • a compound represented by the following formula (8) hereinafter also referred to as “nitrogen-containing compound (I)”
  • nitrogen-containing compound (I) a compound having two nitrogen atoms in the same molecule
  • nitrogen-containing compound (II) a compound having three nitrogen atoms
  • nitrogen-containing compound (III) compounds having three nitrogen atoms
  • amide group-containing compounds urea compounds, nitrogen-containing heterocyclic compounds, etc. It is done.
  • R 25 , R 26 and R 27 are each independently a hydrogen atom, an optionally substituted linear, branched or cyclic alkyl group, aryl group or aralkyl group. .
  • nitrogen-containing compound (I) examples include monoalkylamines such as n-hexylamine; dialkylamines such as di-n-butylamine; trialkylamines such as triethylamine; aromatic amines such as aniline. It is done.
  • nitrogen-containing compound (II) examples include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, and the like.
  • nitrogen-containing compound (III) examples include polyamine compounds such as polyethyleneimine and polyallylamine; and polymers such as dimethylaminoethylacrylamide.
  • amide group-containing compound examples include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone and the like. It is done.
  • urea compound examples include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tributylthiourea and the like.
  • nitrogen-containing heterocyclic compound examples include pyridines such as pyridine and 2-methylpyridine; morpholines such as N-propylmorpholine and N- (undecylcarbonyloxyethyl) morpholine; pyrazine, pyrazole and the like.
  • a compound having an acid dissociable group can also be used as the nitrogen-containing organic compound.
  • the nitrogen-containing organic compound having such an acid dissociable group include Nt-butoxycarbonylpiperidine, Nt-butoxycarbonylimidazole, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2 -Phenylbenzimidazole, N- (t-butoxycarbonyl) di-n-octylamine, N- (t-butoxycarbonyl) diethanolamine, N- (t-butoxycarbonyl) dicyclohexylamine, N- (t-butoxycarbonyl) diphenylamine Nt-butoxycarbonyl-4-hydroxypiperidine, Nt-amyloxycarbonyl-4-hydroxypiperidine and the like.
  • a photodegradable base that is exposed to light and generates a weak acid upon exposure can also be used.
  • the photodegradable base include an onium salt compound that loses acid diffusion controllability by being decomposed by exposure.
  • the onium salt compound include a sulfonium salt compound represented by the following formula (9-1), an iodonium salt compound represented by the following formula (9-2), and the like.
  • R 28 to R 32 are each independently a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, or a halogen atom.
  • E ⁇ and Q ⁇ are each independently OH ⁇ , R ⁇ —COO ⁇ , R ⁇ —SO 3 — or an anion represented by the following formula (9-3).
  • R ( beta) is an alkyl group, an aryl group, or an aralkyl group.
  • R 33 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 1 to 12 linear or branched alkoxyl groups.
  • u is an integer of 0-2.
  • Examples of the photodegradable base include compounds represented by the following formulas.
  • the photodegradable base is preferably a sulfonium salt, more preferably a triarylsulfonium salt, and triphenylsulfonium 2.4.6. More preferred are triisopropyl phenyl sulfonate and triphenyl sulfonium 10-camphor sulfonate.
  • the lower limit of the content of the [C] acid diffusion controller is 100 masses of the [A] polymer. 0.1 parts by mass is preferable with respect to parts, and 0.3 parts by mass is more preferable. As an upper limit of the said content, 20 mass parts is preferable, 15 mass parts is more preferable, and 10 mass parts is further more preferable. [C] By making content of an acid diffusion control agent into the said range, the lithography performance of the said radiation sensitive resin composition can be improved. [C] When the content of the acid diffusion controller exceeds the upper limit, the sensitivity of the radiation-sensitive resin composition may be lowered.
  • the radiation-sensitive resin composition may contain one or more [C] acid diffusion controllers.
  • the polymer is a polymer containing a fluorine atom (except for those corresponding to the [A] polymer).
  • the radiation-sensitive composition contains the [D] polymer
  • the distribution is near the resist film surface due to the oil-repellent characteristics of the [D] polymer in the film.
  • the acid generator, the acid diffusion controller, and the like from being eluted into the immersion medium during immersion exposure.
  • the water repellency characteristics of the [D] polymer due to the water repellency characteristics of the [D] polymer, the advancing contact angle between the resist film and the immersion medium can be controlled within a desired range, and the occurrence of bubble defects can be suppressed.
  • the receding contact angle between the resist film and the immersion medium is increased, and high-speed scanning exposure is possible without leaving water droplets.
  • the said radiation sensitive resin composition contains a [D] polymer
  • the resist film suitable for an immersion exposure method can be formed.
  • the polymer is not particularly limited as long as it is a polymer having a fluorine atom, but the fluorine atom content (% by mass) is higher than that of the [A] polymer in the radiation-sensitive resin composition. It is preferable.
  • the fluorine atom content is higher than that of the polymer, the degree of uneven distribution described above becomes higher, and characteristics such as water repellency and elution suppression of the resulting resist film are improved.
  • the lower limit of the fluorine atom content of the polymer is preferably 1% by mass, more preferably 2% by mass, further preferably 4% by mass, and particularly preferably 7% by mass. As an upper limit of the said content rate, 60 mass% is preferable, 40 mass% is more preferable, and 30 mass% is further more preferable. [D] If the fluorine atom content of the polymer is less than the lower limit, the hydrophobicity of the resist film surface may be lowered.
  • the fluorine atom content (% by mass) of the polymer can be calculated from the structure of the polymer obtained by 13 C-NMR spectrum measurement.
  • the polymer preferably has the fluorine atom-containing structural unit (V) in the above-mentioned [A] polymer.
  • the polymer may have one or more structural units (V).
  • the lower limit of the content ratio of the structural unit (V) in the [D] polymer is 5 for all structural units constituting the [D] polymer.
  • Mol% is preferable and 10 mol% is more preferable.
  • As an upper limit of the said content rate 90 mol% is preferable, 85 mol% is more preferable, and 80 mol% is further more preferable.
  • the polymer may further have a structural unit containing an acid dissociable group.
  • the shape of the resulting resist pattern becomes better.
  • the structural unit containing an acid dissociable group include the structural unit (II) in the above-described [A] polymer.
  • the lower limit of the content ratio of the structural unit containing the acid dissociable group is [D] with respect to all structural units constituting the polymer. 5 mol% is preferable, 10 mol% is more preferable, and 15 mol% is further more preferable. As an upper limit of the said content rate, 90 mol% is preferable, 70 mol% is more preferable, 60 mol% is further more preferable, 50 mol% is especially preferable.
  • the content ratio of the structural unit containing an acid dissociable group is less than the above lower limit, development defects in the resist pattern may not be sufficiently suppressed.
  • the content ratio of the structural unit containing an acid dissociable group exceeds the above upper limit, the hydrophobicity of the resulting resist film surface may be lowered.
  • the [D] polymer is, for example, a structural unit containing an alkali-soluble group; a structural unit containing a lactone structure, a cyclic carbonate structure, a sultone structure, or a combination thereof; a structure containing an alicyclic group You may have other structural units, such as a unit.
  • the alkali-soluble group include a carboxy group, a sulfonamido group, and a sulfo group.
  • the upper limit of the content ratio of the above other structural units is usually 30 mol%, preferably 20 mol%, based on all structural units constituting the [D] polymer. When the content rate of said other structural unit exceeds the said upper limit, the pattern formation property of the said radiation sensitive resin composition may fall.
  • the said radiation sensitive resin composition contains a [D] polymer
  • a [D] polymer as a minimum of content of the [D] polymer in the said radiation sensitive resin composition, with respect to 100 mass parts of a [A] polymer. 0.5 parts by mass is preferable, and 1 part by mass is more preferable. As an upper limit of the said content, 20 mass parts is preferable, 15 mass parts is more preferable, and 10 mass parts is further more preferable. [D] If the content of the polymer exceeds the above upper limit, the pattern-forming property of the radiation-sensitive resin composition may be lowered.
  • the radiation-sensitive resin composition usually contains an [E] solvent.
  • the solvent is particularly a solvent that can dissolve or disperse at least the [A] polymer, the [B] acid generator and the optionally contained [C] acid diffusion controller, [D] polymer, and the like. It is not limited.
  • the radiation-sensitive resin composition may contain one or more [E] solvents.
  • Examples of the solvent include alcohol solvents, ether solvents, ketone organic solvents, amide solvents, ester organic solvents, hydrocarbon solvents, and the like.
  • alcohol solvents examples include aliphatic monoalcohol solvents having 1 to 18 carbon atoms such as 4-methyl-2-pentanol and n-hexanol; An alicyclic monoalcohol solvent having 3 to 18 carbon atoms such as cyclohexanol; A polyhydric alcohol solvent having 2 to 18 carbon atoms such as 1,2-propylene glycol; Examples thereof include polyhydric alcohol partial ether solvents having 3 to 19 carbon atoms such as propylene glycol monomethyl ether.
  • ether solvents include dialkyl ether solvents such as diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, diisoamyl ether, dihexyl ether, and diheptyl ether; Cyclic ether solvents such as tetrahydrofuran and tetrahydropyran; And aromatic ring-containing ether solvents such as diphenyl ether and anisole.
  • dialkyl ether solvents such as diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, diisoamyl ether, dihexyl ether, and diheptyl ether
  • Cyclic ether solvents such as tetrahydrofuran and tetrahydropyran
  • aromatic ring-containing ether solvents such as diphenyl ether and anisole.
  • ketone solvent examples include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, 2-heptanone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, Linear ketone solvents such as di-iso-butyl ketone and trimethylnonanone; Cyclic ketone solvents such as cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone; Examples include 2,4-pentanedione, acetonylacetone, acetophenone, and the like.
  • 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.
  • cyclic amide solvents such as N, N′-dimethylimidazolidinone and N-methylpyrrolidone
  • chain amide solvents such as N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, and N-methylpropionamide.
  • ester solvents include monocarboxylic acid ester solvents such as n-butyl acetate and ethyl lactate; Polyhydric alcohol carboxylate solvents such as propylene glycol acetate; Polyhydric alcohol partial ether carboxylate solvents such as propylene glycol monomethyl ether acetate; Polycarboxylic acid diester solvents such as diethyl oxalate; Examples thereof include carbonate solvents such as dimethyl carbonate and diethyl carbonate.
  • monocarboxylic acid ester solvents such as n-butyl acetate and ethyl lactate
  • Polyhydric alcohol carboxylate solvents such as propylene glycol acetate
  • Polyhydric alcohol partial ether carboxylate solvents such as propylene glycol monomethyl ether acetate
  • Polycarboxylic acid diester solvents such as diethyl oxalate
  • Examples thereof include carbonate solvents such as dimethyl carbonate and diethyl carbonate.
  • hydrocarbon solvent examples include aliphatic hydrocarbon solvents having 5 to 12 carbon atoms such as n-pentane and n-hexane; Examples thereof include aromatic hydrocarbon solvents having 6 to 16 carbon atoms such as toluene and xylene.
  • ester solvents, ketone solvents and alcohol solvents are preferable, polyhydric alcohol partial ether acetate solvents, lactone solvents, cyclic ketone solvents and polyhydric alcohol partial ether solvents are more preferable, and propylene glycol. More preferred are monomethyl ether acetate, propylene glycol monomethyl ether, ⁇ -butyrolactone and cyclohexanone.
  • the radiation-sensitive resin composition may contain other optional components in addition to the components [A] to [E].
  • the other optional components include uneven distribution accelerators, surfactants, alicyclic skeleton-containing compounds, and sensitizers. Each of these other optional components may be used alone or in combination of two or more.
  • the uneven distribution accelerator is used to more efficiently apply the water-repellent polymer additive to the resist film surface when the radiation-sensitive resin composition contains the water-repellent polymer additive as the [D] polymer. It has an effect of segregation.
  • the amount of the water-repellent polymer additive added can be reduced as compared with the conventional case. Therefore, it is possible to further suppress the elution of components from the resist film to the immersion liquid without impairing the resolution, LWR performance, and defect suppression, or to perform immersion exposure at a higher speed by high-speed scanning. As a result, it is possible to improve the hydrophobicity of the resist film surface that suppresses immersion-derived defects such as watermark defects.
  • Examples of such an uneven distribution promoter include low molecular compounds having a relative dielectric constant of 30 or more and 200 or less and a boiling point at 1 atm of 100 ° C. or more.
  • Specific examples of such compounds include lactone compounds, carbonate compounds, nitrile compounds, and polyhydric alcohols.
  • lactone compound examples include ⁇ -butyrolactone, valerolactone, 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.
  • the lower limit of the content of the uneven distribution accelerator is 10 mass with respect to 100 parts by mass of the total amount of the polymer in the radiation-sensitive resin composition. Part is preferable, 15 parts by mass is more preferable, 20 parts by mass is further preferable, and 25 parts by mass is particularly preferable.
  • As an upper limit of the said content 500 mass parts is preferable, 300 mass parts is more preferable, 200 mass parts is further more preferable, 100 mass parts is especially preferable.
  • Surfactant Surfactants have the effect of improving coatability, striation, developability, and the like.
  • the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol diacrylate.
  • Nonionic surfactants such as stearate; commercially available products include “KP341” from Shin-Etsu Chemical Co., Ltd., “Polyflow No. 75, No.
  • the radiation sensitive resin composition contains a surfactant
  • the upper limit of the content of the surfactant in the radiation sensitive resin composition is usually 2 parts by mass with respect to 100 parts by mass of the polymer [A]. It is.
  • the alicyclic skeleton-containing compound has an effect of improving dry etching resistance, pattern shape, adhesion to the substrate, and the like.
  • 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 .
  • adamantane derivatives such as 1-adamantanecarboxylic acid, 2-adamantanone, and 1-adamantanecarboxylic acid t-butyl
  • Deoxycholic acid esters such
  • the said radiation sensitive resin composition contains an alicyclic skeleton containing compound, as an upper limit of content of the alicyclic skeleton containing compound in the said radiation sensitive resin composition, it is [A] 100 mass parts of polymers. On the other hand, it is usually 5 parts by mass.
  • sensitizer exhibits the effect
  • the sensitizer examples include carbazoles, acetophenones, benzophenones, naphthalenes, phenols, biacetyl, eosin, rose bengal, pyrenes, anthracenes, phenothiazines, and the like. These sensitizers may be used alone or in combination of two or more.
  • the said radiation sensitive resin composition contains a sensitizer, as an upper limit of content of the sensitizer in the said radiation sensitive resin composition, it is 2 mass parts normally with respect to 100 mass parts of [A] polymers. It is.
  • the said radiation sensitive resin composition can be prepared by mixing a [A] polymer, a [B] acid generator, the arbitrary component contained as needed, and a [E] solvent in a predetermined ratio, for example.
  • the radiation-sensitive resin composition is preferably filtered after mixing with, for example, a filter having a pore size of about 0.2 ⁇ m.
  • a filter having a pore size of about 0.2 ⁇ m As a minimum of solid content concentration of the radiation sensitive resin composition, 0.1 mass% is preferred, 0.5 mass% is more preferred, 1 mass% is still more preferred, and 1.5 mass% is especially preferred.
  • the upper limit of the solid content concentration of the radiation-sensitive resin composition is preferably 50% by mass, more preferably 30% by mass, still more preferably 20% by mass, and particularly preferably 10% by mass.
  • the resist pattern forming method includes a step of forming a resist film (hereinafter also referred to as “resist film forming step”), a step of exposing the resist film (hereinafter also referred to as “exposure step”), and the exposed resist. Process of developing the film (hereinafter also referred to as “development process”) The resist film is formed from the radiation-sensitive resin composition.
  • the resist pattern forming method since the radiation sensitive resin composition described above is used, while exhibiting excellent MEEF performance, depth of focus, and exposure margin, LWR and CDU are small, resolution is high, It is possible to form a resist pattern that is excellent in rectangular shape in cross section.
  • each step of the resist pattern forming method 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 ones such as a silicon wafer, silicon dioxide, and a wafer coated with aluminum.
  • 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 coating method include spin coating (spin coating), cast coating, and roll coating.
  • pre-baking (PB) may be performed as needed to volatilize the solvent in the coating film. As a minimum of PB temperature, it is usually 60 ° C and 80 ° C is preferred.
  • PB temperature As an upper limit of PB temperature, it is 140 degreeC normally and 120 degreeC is preferable.
  • the lower limit of the PB time is usually 5 seconds, and preferably 10 seconds.
  • the upper limit of the PB time is usually 600 seconds, and preferably 300 seconds.
  • the lower limit of the average thickness of the resist film to be formed is preferably 10 nm.
  • the upper limit of the average thickness is preferably 1,000 nm, and more preferably 500 nm.
  • the resist film formed in the resist film forming step is exposed by irradiation with radiation through a photomask or the like (in some cases through an immersion medium such as water).
  • radiation include electromagnetic waves such as visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (EUV), X-rays, and ⁇ rays, and charged particle beams such as electron beams and ⁇ rays, depending on the line width of the target pattern. Is mentioned.
  • ArF excimer laser light (wavelength 193 nm)
  • KrF excimer laser light (wavelength 248 nm)
  • EUV and electron beams are more preferable
  • ArF excimer laser light, EUV and electron beams are more preferable. Further preferred.
  • the immersion liquid to be used include water and a fluorine-based inert liquid.
  • the immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has a refractive index temperature coefficient 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 reduces 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 resist 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.
  • PEB post-exposure baking
  • the acid-dissociable group of the [A] polymer and the like by the acid generated from the [B] acid generator by exposure is dissociated. Is preferably promoted.
  • This PEB causes a difference in solubility in the developer between the exposed area and the unexposed area.
  • As a minimum of PEB temperature it is 50 ° C usually and 80 ° C is preferred.
  • the upper limit of the PEB temperature is usually 180 ° C, preferably 130 ° C.
  • the lower limit of the PEB time is usually 5 seconds, and preferably 10 seconds.
  • the upper limit of the PEB time is usually 600 seconds, and preferably 300 seconds.
  • the resist film exposed in the exposure step is developed. Thereby, a predetermined resist pattern can be formed. After development, it is common to wash with water or a rinse solution such as alcohol and then dry.
  • 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,
  • TMAH tetramethylammonium hydroxide
  • Examples thereof include an alkaline aqueous solution in which at least one alkaline compound such as 1,5-diazabicyclo- [4.3.0] -5-nonene is dissolved.
  • a TMAH aqueous solution is preferable, and a 2.38 mass% TMAH aqueous solution is more preferable.
  • organic solvents such as hydrocarbon solvents, ether solvents, ester solvents, ketone solvents, alcohol solvents and the like or solvents containing organic solvents can be mentioned.
  • organic solvent the 1 type (s) or 2 or more types of the solvent enumerated as the [B] solvent of the above-mentioned resin composition are mentioned, for example.
  • ester solvents and ketone solvents are preferable.
  • the ester solvent an acetate solvent is preferable, and n-butyl acetate is more preferable.
  • the ketone solvent is preferably a chain ketone, more preferably 2-heptanone.
  • 80 mass% is preferred, 90 mass% is more preferred, 95 mass% is still more preferred, and 99 mass% is especially preferred.
  • components other than the organic solvent in the developer include water and silicone oil.
  • a developing method for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (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.
  • the polymer of the present invention has a structural unit represented by the above formula (I).
  • the said polymer can be used suitably as a polymer component of the said radiation sensitive resin composition mentioned above.
  • the polymer is described above as the [A] polymer in the radiation-sensitive resin composition.
  • the compound of the present invention is represented by the above formula (i). Since the compound has a structure represented by the above formula (i), it is suitably used as a monomer compound in which the structural unit (I) is incorporated into the polymer. The compound is described above as a monomer that gives the structural unit (I) in the [A] polymer of the radiation-sensitive resin composition.
  • the compounds (M-1), (M-5) to (M-7), (M-9), (M-12), and (M-13) represent the structural unit (II) and the compound ( M-2), (M-8), and (M-10) represent the structural unit (III), the compound (M-3) represents the structural unit (IV), and the compound (M-15) represents the structural unit (III). V), and the compound (M-4) gives other structural units.
  • Compound (M-14) incorporates a structural unit having the structure of [B] acid generator in [A] polymer.
  • the compound (M-16) is a monomer used in place of the structural unit (I) in the following synthesis examples.
  • the dripping start was set as the polymerization reaction start time, and the polymerization reaction was carried out for 6 hours.
  • the polymerization solution was cooled with water and cooled to 30 ° C. or lower.
  • the polymerization solution cooled in 400 g of methanol was added, and the precipitated white powder was separated by filtration.
  • the filtered white powder was washed twice with 80 g of methanol, filtered, and dried at 50 ° C. for 17 hours to synthesize a white powdery polymer (A-1) (15.2 g, yield 76). %).
  • Mw of the polymer (A-1) was 7,300, and Mw / Mn was 1.53.
  • the content ratio of each structural unit derived from (M-1), (M-2), (M-3) and (Z-1) was 34.3 mol%, respectively. 35.1 mol%, 14.6 mol% and 16.0 mol%.
  • the dripping start was set as the polymerization reaction start time, and the polymerization reaction was carried out for 6 hours.
  • the polymerization solution was cooled with water and cooled to 30 ° C. or lower.
  • the operation of adding 100 g of hexane and stirring to recover the acetonitrile layer was repeated three times.
  • the solvent By replacing the solvent with propylene glycol monomethyl ether acetate, a solution containing 60.1 g of the polymer (D-1) was obtained (yield 60%).
  • Mw of the polymer (D-1) was 15,000, and Mw / Mn was 1.90.
  • the content ratios of structural units derived from (M-15) and (M-12) were 70.3 mol% and 29.7 mol%, respectively.
  • B-1 Triphenylsulfonium 2- (adamantan-1-ylcarbonyloxy) -1,1,3,3,3-pentafluoropropane-1-sulfonate
  • B-2 Triphenylsulfonium norbornane sultone-2-yloxy Carbonyl difluoromethanesulfonate
  • B-3 Triphenylsulfonium 3- (piperidin-1-ylsulfonyl) -1,1,2,2,3,3-hexafluoropropane-1-sulfonate
  • B-4 Triphenylsulfonium adamantane 1-yloxycarbonyldifluoromethanesulfonate
  • C-1 Triphenylsulfonium 2.4.6. Triisopropylphenylsulfonate
  • C-2 Triphenylsulfonium 10-camphorsulfonate
  • C-3 N- (n-undecan-1-ylcarbonyloxyethyl) morpholine
  • C-4 Tri-n-pentylamine
  • [Example 50] [A] 100 parts by mass of (A-1) as a polymer, [B] 8.5 parts by mass of (B-1) as an acid generator, [C] (C-1) 2 as an acid diffusion controller 3 parts by weight, (D-1) 3 parts by weight as a [D] polymer, (E-1) 2,240 parts by weight and (E-2) 960 parts by weight as a solvent and [F]
  • a radiation-sensitive resin composition (J-1) was prepared by mixing 30 parts by mass of (F-1) as an uneven distribution accelerator and filtering the obtained mixed solution through a membrane filter having a pore size of 0.2 ⁇ m. .
  • Example 51 to 74 and Comparative Examples 1 to 5 Each radiation-sensitive resin composition was prepared in the same manner as in Example 50 except that the components having the types and contents shown in Table 2 were used.
  • Example 75 [A] 100 parts by mass of (A-1) as a polymer, [B] 20 parts by mass of (B-1) as an acid generator, [C] (C-1) 3.6 as an acid diffusion controller
  • the radiation sensitive resin is obtained by mixing 4 parts by mass and (E-1) 4,280 parts by mass and (E-2) 1,830 parts by mass as [E] solvent and filtering through a membrane filter having a pore size of 0.2 ⁇ m.
  • a composition (J-26) was prepared.
  • Example 76 to 102 and Comparative Examples 6 to 13 Each radiation-sensitive resin composition was prepared in the same manner as in Example 75 except that the components of the types and contents shown in Table 3 were used.
  • NSR-S610C ArF excimer laser immersion exposure apparatus
  • the exposure amount formed in a one-to-one line and space with a line width of 40 nm and a line width formed through a one-to-one line and space mask with a target dimension of 40 nm is an optimum exposure amount ( Eop).
  • Comparative Example 1 for Example 72, Comparative Example 3 for Example 72, Comparative Example 4 for Example 73, Comparative Example 5 for Example 74, Comparative Example 6 and Comparative Example 7 for Example 75, and Examples 76-96.
  • Comparative Example 6 for Example 97, Comparative Example 8 for Example 97, Comparative Example 9 for Example 98, Comparative Example 10 for Example 99, Comparative Example 11 for Example 100, Comparative Example 12 for Example 101 Example 102 is Comparative Example 13.
  • LWR performance The resist pattern formed by irradiating the exposure amount of Eop was observed from above the pattern using the scanning electron microscope. A total of 50 line widths were measured at arbitrary points, and a 3-sigma value was obtained from the distribution of the measured values, and this was defined as LWR performance. The LWR performance indicates that the smaller the value, the smaller the backlash of the line. When the LWR performance is 10% or more (LWR performance is 90% or less) when compared with the comparative example, the LWR performance is “good” and less than 10% (LWR performance is improved). When the value was over 90%), it was evaluated as “bad”.
  • the line width of the resist pattern formed by using the mask pattern having the line widths of 51 nm, 53 nm, 55 nm, 57 nm, and 59 nm is plotted on the vertical axis.
  • the slope of the straight line when the pattern size was plotted on the horizontal axis was calculated, and this was taken as the MEEF performance.
  • the MEEF performance indicates that the closer the value is to 1, the better the mask reproducibility.
  • the MEEF performance is 10% or more when the value is compared with that of the comparative example (MEEF performance value is 90% or less), the MEEF performance is less than 10% (MEEF performance is improved). When the value was over 90%), it was evaluated as “bad”.
  • CDU performance The resist pattern formed by irradiating the exposure amount of Eop was observed from above the pattern using the scanning electron microscope.
  • the line width is measured at 20 points in the range of 400 nm, the average value is obtained, the average value is measured at a total of 500 points, and the 3 sigma value is obtained from the distribution of the measured values, which is taken as the CDU performance. .
  • the CDU performance indicates that the smaller the value, the smaller the line width variation in a long cycle.
  • the CDU performance is improved by 10% or more (the CDU performance value is 90% or less) when the value is compared with that of the comparative example, the improvement is less than 10% (the CDU performance is improved). When the value was over 90%), it was evaluated as “bad”.
  • the radiation sensitive resin composition and resist pattern forming method of the present invention excellent MEEF performance, depth of focus and exposure margin are exhibited, and LWR performance, CDU performance, resolution, and cross-sectional rectangularity are obtained.
  • An excellent resist pattern can be formed.
  • the polymer of this invention is used suitably as a polymer component of the said radiation sensitive resin composition. Since the compound of the present invention has a structure represented by the above formula (i), it is suitably used as a monomer compound that incorporates the structural unit (I) into the polymer. Therefore, these can be suitably used for pattern formation in semiconductor device manufacturing or the like, where miniaturization is expected to progress further in the future.

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Abstract

　La présente invention concerne une composition de résine radiosensible contenant : un polymère ayant une unité structurelle qui contient le groupe représenté par la formule (1) ; et un générateur d'acide radiosensible. Dans la formule (1), R1 est un groupe hydrocarboné divalent en C1-C10 substitué ou non substitué. R2 est un groupe hydrocarboné à chaîne divalente en C1-C5 substitué ou non substitué ou une liaison simple. R1 et un ou plusieurs de R2 peuvent être combinés et, conjointement avec les atomes de carbone liés à ces derniers, forment une structure cyclique ayant de 3 à 20 chaînons. a est un nombre entier compris entre 1 et 3. A est un groupe monovalent ayant au moins deux hétéroatomes et est lié à R2 par l'intermédiaire d'atomes de carbone. Le symbole astérisque indique le site de liaison. Dans la formule (1) ci-dessous, A est de préférence un groupe cyclique monovalent ayant une structure hétérocyclique.
PCT/JP2015/055718 2014-02-26 2015-02-26 Composition de résine radiosensible, procédé permettant de former un motif de réserve, polymère et composé WO2015129832A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021131655A1 (fr) * 2019-12-27 2021-07-01 富士フイルム株式会社 Composition de résine sensible aux rayons actiniques ou sensible au rayonnement, film sensible aux rayons actiniques ou sensible au rayonnement, procédé de formation de motif et procédé de fabrication de dispositif électronique

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001235861A (ja) * 2000-02-21 2001-08-31 Hitachi Ltd パターン形成方法及びそれを用いた半導体装置の製造方法
JP2011059674A (ja) * 2009-08-10 2011-03-24 Sumitomo Chemical Co Ltd レジスト組成物
JP2012215722A (ja) * 2011-03-31 2012-11-08 Jsr Corp 液浸用上層膜形成用組成物
JP2014085642A (ja) * 2012-10-26 2014-05-12 Tokyo Ohka Kogyo Co Ltd レジスト組成物、レジストパターン形成方法、高分子化合物、化合物
JP2014136708A (ja) * 2013-01-15 2014-07-28 Shin Etsu Chem Co Ltd 単量体、高分子化合物、レジスト材料及びパターン形成方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006310500A (ja) * 2005-04-27 2006-11-09 Konica Minolta Holdings Inc 配線基板、圧電性セラミック素子及びそれらの製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001235861A (ja) * 2000-02-21 2001-08-31 Hitachi Ltd パターン形成方法及びそれを用いた半導体装置の製造方法
JP2011059674A (ja) * 2009-08-10 2011-03-24 Sumitomo Chemical Co Ltd レジスト組成物
JP2012215722A (ja) * 2011-03-31 2012-11-08 Jsr Corp 液浸用上層膜形成用組成物
JP2014085642A (ja) * 2012-10-26 2014-05-12 Tokyo Ohka Kogyo Co Ltd レジスト組成物、レジストパターン形成方法、高分子化合物、化合物
JP2014136708A (ja) * 2013-01-15 2014-07-28 Shin Etsu Chem Co Ltd 単量体、高分子化合物、レジスト材料及びパターン形成方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021131655A1 (fr) * 2019-12-27 2021-07-01 富士フイルム株式会社 Composition de résine sensible aux rayons actiniques ou sensible au rayonnement, film sensible aux rayons actiniques ou sensible au rayonnement, procédé de formation de motif et procédé de fabrication de dispositif électronique
JPWO2021131655A1 (fr) * 2019-12-27 2021-07-01
JP7379536B2 (ja) 2019-12-27 2023-11-14 富士フイルム株式会社 感活性光線性又は感放射線性樹脂組成物、感活性光線性又は感放射線性膜、パターン形成方法、及び電子デバイスの製造方法

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