WO2013147266A1 - Composition de résine photosensible d'exposition par immersion, polymère et composé - Google Patents

Composition de résine photosensible d'exposition par immersion, polymère et composé Download PDF

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Publication number
WO2013147266A1
WO2013147266A1 PCT/JP2013/059752 JP2013059752W WO2013147266A1 WO 2013147266 A1 WO2013147266 A1 WO 2013147266A1 JP 2013059752 W JP2013059752 W JP 2013059752W WO 2013147266 A1 WO2013147266 A1 WO 2013147266A1
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group
carbon atoms
polymer
hydrocarbon group
immersion exposure
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PCT/JP2013/059752
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English (en)
Japanese (ja)
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光央 佐藤
信也 峯岸
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Jsr株式会社
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Priority to JP2014508236A priority Critical patent/JP6164211B2/ja
Publication of WO2013147266A1 publication Critical patent/WO2013147266A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • 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
    • G03F7/0046—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

Definitions

  • the present invention relates to a photoresist composition for immersion exposure, a polymer and a compound.
  • a resist film is formed on a substrate with a photoresist composition containing a polymer having an acid-dissociable group, and an excimer laser beam or the like is passed through a mask pattern.
  • a fine resist pattern is formed by exposing a resist film by irradiation with short-wavelength radiation and removing an exposed portion with an alkaline developer.
  • a “chemically amplified resist” is used in which an acid generator that generates an acid upon irradiation with radiation is contained in the photoresist composition, and the sensitivity is improved by the action of the acid.
  • the use of the immersion exposure method is expanding as a method for forming a finer resist pattern.
  • exposure is performed by filling the space between the exposure lens and the resist film with an immersion exposure liquid having a higher refractive index than air or an inert gas.
  • this immersion exposure method there is an advantage that even when the numerical aperture of the lens is increased, the depth of focus is hardly lowered and high resolution is obtained.
  • a photoresist composition used in the above immersion exposure method As a photoresist composition used in the above immersion exposure method, elution of an acid generator and the like from the resist film to the immersion exposure liquid is prevented, and water drainage of the resist film surface is improved, enabling high-speed scanning.
  • a method for increasing the water repellency of the resist film surface has been studied. For example, a highly water-repellent upper layer film is provided on this surface, or the fluorine-containing weight having a high water repellency is applied to the photoresist composition. It has been proposed to contain coalesces (see WO 2007/116664).
  • the liquid immersion upper layer film is also required to improve the resist pattern shape.
  • the present invention has been made based on the circumstances as described above, and an object thereof is to increase the receding contact angle at the time of immersion exposure on the resist film surface in the immersion exposure process and to develop the resist film. It is an object to provide a photoresist composition for immersion exposure, a polymer and a compound that can suppress the occurrence of defects.
  • a polymer (a1) having a structural unit represented by the following formula (1) (hereinafter also referred to as “structural unit (I)”), and a polymer having a smaller fluorine atom content than the polymer (a1) ( a2) a polymer component (hereinafter also referred to as “[A] polymer component”), and a solvent (hereinafter also referred to as “[B] solvent”).
  • R 1 is an alkali dissociable group.
  • X represents a divalent hydrocarbon group having 1 to 20 carbon atoms or a carbon number of 1;
  • a divalent fluorinated hydrocarbon group having ⁇ 20, R 2 is an (n + 1) valent hydrocarbon group having 1 to 20 carbon atoms, an (n + 1) valent fluorinated hydrocarbon group having 1 to 20 carbon atoms, Or at least selected from the group consisting of these groups and —CO—, —COO—, —OCO—, —O—, —NR B —, —CS—, —S—, —SO— and —SO 2 —. is a group which combines with one group.
  • R 2 is may be a single bond .
  • R B is a hydrogen atom or 1 to 10 carbon atoms
  • the monovalent hydrocarbon group is .R 3, and a monovalent hydrocarbon group, a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, or their group having 1 to 20 carbon atoms -CO-, A group in combination with at least one group selected from the group consisting of —COO—, —OCO—, —O—, —NR C —, —CS—, —S—, —SO— and —SO 2 —;
  • R C is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 1 to 3.
  • n is 2 or more, a plurality of R 1 , A and X may be the same or different.
  • the immersion-exposure photoresist composition (hereinafter also referred to as “immersion-exposure film-forming composition (PR)”) includes the polymer (a1) and the base polymer as the polymer component [A].
  • a polymer (a2) can be effectively unevenly distributed on the surface layer of the resist film, and due to its high water repellency, the receding contact angle during immersion exposure of the resist film surface can be further increased.
  • the polymer (a1) is highly hydrophilic due to dissociation of alkali dissociable groups during alkali development. Accordingly, the affinity or solubility of the resist film surface to the developer or rinse liquid is increased, and as a result, development defects can be suppressed. This is considered to be due to the fact that in the photoresist composition for immersion exposure, the structural unit (I) of the polymer (a1) has an alkali dissociable group at the specific site.
  • the polymer (a2) preferably has an acid dissociable group.
  • the shape of the resist pattern formed from the immersion exposure photoresist composition can be further improved.
  • R 1 in the above formula (1) is preferably a fluorinated alkyl group having 1 to 20 carbon atoms or a fluorinated alkylcarbonyl group having 1 to 20 carbon atoms.
  • R 1 contains a fluorine atom
  • the photoresist composition for immersion exposure can further increase the receding contact angle during immersion exposure on the resist film surface and suppress the occurrence of development defects. be able to.
  • X in the above formula (1) is preferably a divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms.
  • the photoresist composition for immersion exposure can further increase the receding contact angle at the time of immersion exposure on the resist film surface and also has the ability to dissociate alkali dissociable groups. As a result, the occurrence of development defects can be further suppressed.
  • R 3 in the above formula (1) preferably has acid dissociation properties. Since the R 3 has acid dissociation property, the immersion exposure photoresist composition can improve the solubility of the polymer (a1) in the alkaline developer in the exposed portion, and as a result, development defects. Can be further suppressed.
  • the polymer (a1) preferably further has a structural unit containing an acid dissociable group (hereinafter also referred to as “structural unit (II)”).
  • structural unit (II) an acid dissociable group
  • the polymer of the present invention has a structural unit (I) represented by the following formula (1).
  • R 1 is an alkali dissociable group.
  • A is —CO—O— *, —O—, —NR A — or —SO 2 —O— *, where R A is , A hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, * represents a bonding site with R 1.
  • X represents a divalent hydrocarbon group having 1 to 20 carbon atoms or a carbon number of 1;
  • a divalent fluorinated hydrocarbon group having ⁇ 20, R 2 is an (n + 1) valent hydrocarbon group having 1 to 20 carbon atoms, an (n + 1) valent fluorinated hydrocarbon group having 1 to 20 carbon atoms, Or at least selected from the group consisting of these groups and —CO—, —COO—, —OCO—, —O—, —NR B —, —CS—, —S—, —SO— and —SO 2 —. is a group which combines with one group.
  • R 2 is may be a single bond .
  • R B is a hydrogen atom or 1 to 10 carbon atoms
  • the monovalent hydrocarbon group is .R 3, and a monovalent hydrocarbon group, a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, or their group having 1 to 20 carbon atoms -CO-, A group in combination with at least one group selected from the group consisting of —COO—, —OCO—, —O—, —NR C —, —CS—, —S—, —SO— and —SO 2 —;
  • R C is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 1 to 3.
  • n is 2 or more, a plurality of R 1 , A and X may be the same or different.
  • the polymer has the specific structural unit described above, for example, the photoresist composition, the polymer, and the solvent described above, which exhibit a large receding contact angle during immersion exposure and can suppress development defects, are included.
  • the composition can be suitably used as a component of a composition for forming a liquid immersion upper layer film (hereinafter also referred to as “the film forming composition for liquid immersion exposure”).
  • R 1 in the above formula (1) is preferably a fluorinated alkyl group having 1 to 20 carbon atoms or a fluorinated alkylcarbonyl group having 1 to 20 carbon atoms.
  • the polymer contains a fluorine atom in R 1 , according to the film forming composition for immersion exposure containing this polymer, the receding contact angle at the time of immersion exposure on the surface of a resist film or the like is further increased. And the occurrence of development defects can be suppressed.
  • X in the above formula (1) is preferably a divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms.
  • the polymer contains a fluorine atom in X
  • the receding contact angle at the time of immersion exposure on the surface of a resist film or the like can be further increased.
  • the dissociation property of the alkali-dissociable group can be enhanced, and as a result, development defects can be further suppressed.
  • R 3 in the above formula (1) preferably has acid dissociation properties.
  • R 3 has acid dissociation properties, according to the film forming composition for immersion exposure containing this polymer, the solubility of the polymer (a1) in the exposed portion in the alkaline developer can be increased. As a result, the occurrence of development defects can be further suppressed.
  • R 1 is an alkali-dissociable group.
  • A is —CO—O— *, —O—, —NR A —, or —SO 2 —O— *, where R A is , A hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, * represents a bonding site with R 1.
  • X represents a divalent hydrocarbon group having 1 to 20 carbon atoms or a carbon number of 1;
  • a divalent fluorinated hydrocarbon group having ⁇ 20, R 2 is an (n + 1) valent hydrocarbon group having 1 to 20 carbon atoms, an (n + 1) valent fluorinated hydrocarbon group having 1 to 20 carbon atoms, Or at least selected from the group consisting of these groups and —CO—, —COO—, —OCO—, —O—, —NR B —, —CS—, —S—, —SO— and —SO 2 —. is a group which combines with one group.
  • R 2 is may be a single bond .
  • R B is a hydrogen atom or 1 to 10 carbon atoms Monovalent and is .R 3 'is a hydrocarbon group, an acid dissociable group .n, when it .n is 2 or an integer of 1 to 3, the plurality of R 1, A and X, respectively They may be the same or different.
  • the compound Since the compound has the above specific structure, it is suitable as a monomer that gives the structural unit (I), for example.
  • the photoresist composition of the present invention in the immersion exposure process, a large receding contact angle can be given to the resist film surface during the immersion exposure, and development defects can be suppressed. Therefore, the photoresist composition for immersion exposure can be suitably used for a manufacturing process in a semiconductor device that is further miniaturized, and can improve product quality and productivity in the immersion exposure process. . Moreover, the said polymer and compound can be used suitably as a component and raw material of the said film formation composition for immersion exposure.
  • the film forming composition for immersion exposure contains a [A] polymer component and a [B] solvent. Moreover, the said film formation composition for immersion exposure may contain arbitrary components in the range which does not impair the effect of this invention. Hereinafter, each component will be described in detail.
  • the polymer component contains a polymer (a1). Moreover, the [A] polymer component may contain other polymers, such as a polymer (a2) mentioned later and (a3), in the range which does not impair the effect of this invention. In addition, the [A] polymer component may contain 2 or more types of said each polymer.
  • the polymer (a1) will be described in detail.
  • the polymer (a1) is a polymer having the structural unit (I). Moreover, the polymer (a1) may have other structural units other than the structural unit (I). In addition, the polymer (a1) may have 2 or more types of each structural unit. Hereinafter, each structural unit will be described in detail.
  • the structural unit (I) is a structural unit represented by the above formula (1).
  • the polymer (a1) has a higher receding contact angle during immersion exposure on the surface of the resist film or the like due to its high water repellency. be able to.
  • the polymer (a1) is highly hydrophilic due to dissociation of alkali dissociable groups during alkali development. Accordingly, the affinity or solubility of the surface of the resist film or the like to the developing solution or rinsing solution is increased, and as a result, development defects can be suppressed. This is considered to be due to the fact that the structural unit (I) of the polymer (a1) has an alkali-dissociable group at the specific site in the film forming composition for immersion exposure.
  • R 1 is an alkali dissociable group.
  • A is —CO—O— *, —O—, —NR A — or —SO 2 —O— *.
  • R A is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. * Indicates a binding site with R 1.
  • X is a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms.
  • R 2 represents an (n + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, an (n + 1) -valent fluorinated hydrocarbon group having 1 to 20 carbon atoms, or these groups and —CO—, —COO—, —
  • the group is a combination of at least one group selected from the group consisting of OCO—, —O—, —NR B —, —CS—, —S—, —SO— and —SO 2 —.
  • R B is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
  • R 3 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, or these groups and —CO—, —COO—, —OCO—, — A group in combination with at least one group selected from the group consisting of O—, —NR C —, —CS—, —S—, —SO— and —SO 2 —.
  • R C is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
  • n is an integer of 1 to 3. When n is 2 or more, the plurality of R 1 , A, and X may be the same or different.
  • the alkali dissociable group is, for example, a group that substitutes a hydrogen atom in a polar functional group such as a hydroxy group or a sulfo group, and is in the presence of an alkali (for example, 2.38% by mass of tetravalent at 23 ° C.
  • a group that dissociates in an aqueous solution of methylammonium hydroxide is, for example, a group that substitutes a hydrogen atom in a polar functional group such as a hydroxy group or a sulfo group.
  • alkali dissociable group examples include groups represented by the following formulas.
  • A when A is —O— or —NR A —, those represented by the following formula (R1-1) are preferable, and A is —CO—O— * or In the case of —SO 2 —O— *, those represented by any of the following formulas (R1-2) to (R1-4) are preferable.
  • R K1 is a monovalent fluorinated alkyl group having 1 to 20 carbon atoms or a fluorinated alicyclic hydrocarbon group having 3 to 20 carbon atoms.
  • R K2 is a substituent. If R K2 is plural, the plurality of R K2 may be the same or different.
  • m1 is an integer of 0 to 5.
  • m2 is an integer of 0-4.
  • R K3 and R K4 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a fluorinated alkyl group having 1 to 20 carbon atoms. However, R K3 and R K4 may be bonded to each other to form a divalent alicyclic hydrocarbon group together with the carbon atom to which they are bonded.
  • Examples of the monovalent fluorinated alkyl group having 1 to 20 carbon atoms represented by R K1 include a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, a 1-butyl group, and a 2-butyl group.
  • 2- (2-methylpropyl) group 1-pentyl group, 2-pentyl group, 3-pentyl group, 1- (2-methylbutyl) group, 1- (3-methylbutyl) group, 2- (2-methylbutyl) ) Group, 2- (3-methylbutyl) group, neopentyl group, 1-hexyl group, 2-hexyl group, 3-hexyl group, 1- (2-methylpentyl) group, 1- (3-methylpentyl) group, 1- (4-methylpentyl) group, 2- (2-methylpentyl) group, 2- (3-methylpentyl) group, 2- (4-methylpentyl) group, 3- (2-methylpentyl) group, 3- (3-methylpentyl) group, octyl group, Examples include a group in which part or all of hydrogen atoms of an alkyl group having 1 to 20 carbon atoms such as nyl group, decyl group, dodecyl group, tetradecy
  • Examples of the fluorinated alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R K1 include a cyclopentyl group, a cyclopentylmethyl group, a 1- (1-cyclopentylethyl) group, and 1- (2-cyclopentylethyl).
  • cyclohexyl group cyclohexylmethyl group, 1- (1-cyclohexylethyl) group, 1- (2-cyclohexylethyl group), cycloheptyl group, cycloheptylmethyl group, 1- (1-cycloheptylethyl) group
  • examples thereof include a group in which part or all of the hydrogen atoms of the 1- (2-cycloheptylethyl) group, 2-norbornyl group, 1-adamantyl group, 2-adamantyl group and the like are substituted with fluorine atoms.
  • R K2 includes —R P1 , —R P2 —O—R P1 , —R P2 —CO—R P1 , —R P2 —CO—OR P1 , —R P2 —O—CO— R P1 , —R P2 —OH, —R P2 —CN, or —R P2 —COOH.
  • R P1 is a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms, a monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms. It is a group.
  • R P1 A part or all of the hydrogen atoms possessed by R P1 may be substituted with fluorine atoms.
  • R P2 represents a single bond, a divalent chain saturated hydrocarbon group having 1 to 10 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a divalent aromatic group having 6 to 30 carbon atoms. Group hydrocarbon group. Some or all of the hydrogen atoms which the R P2 has may be substituted by a fluorine atom.
  • Examples of the divalent alicyclic hydrocarbon group that may be formed together with the carbon atom to which R K3 and R K4 are bonded to each other include a 1,1-cyclopentanediyl group, 1 , 1-cyclohexanediyl group and the like.
  • Examples of the group represented by the above formula (R1-4) include a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, a 1-butyl group, a 2-butyl group, a 1-pentyl group, 2- Pentyl group, 3-pentyl group, 1- (2-methylbutyl) group, 1- (3-methylbutyl) group, 2- (3-methylbutyl) group, neopentyl group, 1-hexyl group, 2-hexyl group, 3- Hexyl group, 1- (2-methylpentyl) group, 1- (3-methylpentyl) group, 1- (4-methylpentyl) group, 2- (3-methylpentyl) group, 2- (4-methylpentyl) ) Group, 3- (2-methylpentyl) group, and a group in which some or all of the hydrogen atoms of these groups are substituted with fluorine atoms.
  • the alkali dissociable group represented by R 1 is preferably a fluorinated alkyl group having 1 to 20 carbon atoms or a fluorinated alkylcarbonyl group having 1 to 20 carbon atoms. That is, R K1 in the above formula (R1-1) is a fluorinated alkyl group having 1 to 20 carbon atoms, or R K3 and R K4 in the above formula (R1-4) are hydrogen atoms and have 1 to 20 carbon atoms. Or a fluorinated alkyl group having 1 to 20 carbon atoms (provided that at least one of R K3 and R K4 contains a fluorine atom).
  • R 1 contains a fluorine atom
  • the film-forming composition for immersion exposure can further increase the receding contact angle during immersion exposure on the surface of a resist film or the like, and suppress the occurrence of development defects. can do.
  • Examples of the fluorinated alkyl group having 1 to 20 carbon atoms represented by R 1 include the same groups as those exemplified as the group represented by the formula (R1-4).
  • Examples of the fluorinated alkylcarbonyl group having 1 to 20 carbon atoms represented by R 1 include alkylcarbonyl groups having 1 to 20 carbon atoms such as a methylcarbonyl group, an ethylcarbonyl group, a propylcarbonyl group, and a butylcarbonyl group. Examples include a group in which part or all of the hydrogen atoms are substituted with fluorine atoms. Among these, a fluorinated alkylcarbonyl group having 1 to 5 carbon atoms is preferable, a fluorinated methylcarbonyl group is more preferable, and a trifluoromethylcarbonyl group is further preferable.
  • Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms represented by R A , R B and RC include, for example, an alkyl group having 1 to 10 carbon atoms and a monovalent alicyclic ring having 3 to 10 carbon atoms.
  • a formula hydrocarbon group and the like are examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms represented by R A , R B and RC.
  • alkyl group having 1 to 10 carbon atoms examples include linear alkyl groups such as methyl group, ethyl group, n-propyl group, and n-butyl group; i-propyl group, i-butyl group, sec- Examples thereof include branched alkyl groups such as a butyl group and a t-butyl group.
  • Examples of the monovalent alicyclic hydrocarbon group having 3 to 10 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, norbornyl group, adamantyl group, and cyclobutyl.
  • a methyl group, a cyclohexylethyl group, etc. are mentioned.
  • Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms represented by X include, for example, an alkanediyl group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and carbon. Examples thereof include a divalent aromatic hydrocarbon group of 6 to 20 or a divalent group obtained by combining two or more of these groups.
  • alkanediyl group having 1 to 20 carbon atoms examples include a methanediyl group, an ethanediyl group, a propanediyl group, a butanediyl group, and a pentanediyl group.
  • Examples of the divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a cyclopropanediyl group, a cyclobutanediyl group, a cyclopentanediyl group, a cyclobutenediyl group, a cyclopentenediyl group, a norbornylene group, and an adamantylene group.
  • Examples of the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenylene group, a biphenylene group, a terphenylene group, a benzylene group, a phenyleneethylene group, a phenylenecyclohexylene group, and a naphthylene group.
  • divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms represented by X a part or all of the hydrogen atoms of the divalent hydrocarbon group having 1 to 20 carbon atoms are substituted with fluorine atoms. It is a group.
  • divalent hydrocarbon group having 1 to 20 carbon atoms include the same groups as those exemplified as the divalent hydrocarbon group having 1 to 20 carbon atoms represented by X above.
  • X is preferably a divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms.
  • the film forming composition for immersion exposure can further increase the receding contact angle at the time of immersion exposure on the surface of a resist film or the like, and the dissociation property of the alkali dissociable group. As a result, development defects can be further suppressed.
  • Examples of the (n + 1) -valent hydrocarbon group having 1 to 20 carbon atoms represented by R 2 include groups obtained by removing (n + 1) hydrogen atoms from hydrocarbons having 1 to 20 carbon atoms. .
  • Examples of the hydrocarbon having 1 to 20 carbon atoms include methane, ethane, propane, butane, propene, 1-butene and 2-methylpropene.
  • the hydrogen atoms of the (n + 1) -valent hydrocarbon group having 1 to 20 carbon atoms are It is a group substituted with a fluorine atom.
  • Examples of the (n + 1) -valent hydrocarbon group having 1 to 20 carbon atoms include the same groups as those exemplified as the (n + 1) -valent hydrocarbon group having 1 to 20 carbon atoms represented by R 2 above. Is mentioned.
  • Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R 3 include the carbon number exemplified as the monovalent organic group having 1 to 20 carbon atoms represented by R K1 to R K4. Examples thereof include the same groups as 1 to 20 monovalent hydrocarbon groups.
  • the monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms represented by R 3 a part or all of the hydrogen atoms of the monovalent hydrocarbon group having 1 to 20 carbon atoms is substituted with a fluorine atom. It is a group that has been.
  • Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include the same groups as those exemplified as the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R 3 .
  • R 3 preferably has acid dissociation properties. Since the R 3 has acid dissociation properties, the immersion exposure film-forming composition can enhance the solubility of the polymer (a1) in the alkaline developer in the exposed portion, and as a result, development defects. Can be further suppressed.
  • acid dissociation refers to the property of dissociating in the presence of an acid.
  • Examples of the group having acid dissociability represented by R 3 include the same groups as the acid dissociable groups exemplified as Y in the formula (4) described later.
  • the structural units represented by the formulas (1-2) to (1-6) are preferred from the viewpoint of further increasing the receding contact angle during immersion exposure on the surface of the resist film or the like.
  • the structural units represented by 3) and (1-4) are more preferred.
  • structural units represented by formulas (1-2), (1-4) and (1-6) are more preferable.
  • a compound represented by the above formula (3) is preferable.
  • R 1, A , X, R 2 and n have the same meanings as in formula (1).
  • R 3 ′ is an acid dissociable group.
  • Examples of the acid dissociable group represented by R 3 ′ include the same groups as the acid dissociable groups exemplified as Y in the formula (4) described later.
  • Examples of the compound (monomer) giving the structural unit (I) include compounds represented by the following formulas (i-1) to (i-7).
  • R 2 in the above formula (1) is a hydrocarbon group, for example, in a solvent such as tetrahydrofuran, in the presence of zinc, a halocarboxylic acid ester such as ethyl 2-bromo-2,2-difluoroacetate and 2 Examples thereof include a method of reacting with a haloalkyl acrylate such as ethyl-(bromomethyl) acrylate.
  • the content ratio of the structural unit (I) in the polymer (a1) is preferably 10% by mole to 100% by mole, and preferably 30% by mole to 100% by mole with respect to all the structural units constituting the polymer (a1). More preferred is 50 mol% to 100 mol%.
  • the polymer (a1) may have other structural units such as structural units (II) to (VI) described later as long as the effects of the present invention are not impaired.
  • the content ratio of the other structural units can be appropriately determined according to the purpose.
  • the content of the polymer (a1) is preferably 0.1% by mass to 30% by mass and more preferably 0.5% by mass to 20% by mass with respect to the total polymer constituting the [A] polymer component. Preferably, 1% by mass to 10% by mass is more preferable.
  • each polymer constituting the polymer component is synthesized, for example, by subjecting a predetermined monomer to polymerization such as radical polymerization in a polymerization solvent in the presence of a suitably selected polymerization initiator. Can do.
  • azo radical initiators azobisisobutyronitrile (AIBN), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2-cyclopropylpropio) Nitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate), dimethyl 2,2′-azobisisobutyrate and the like;
  • peroxide radical initiators include benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, and the like.
  • azo radical initiators are preferred, and AIBN is more preferred.
  • Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, ethylene glycol, diethylene glycol, propylene glycol and the like; As cyclic ethers, tetrahydrofuran, dioxane and the like; As alkyl ethers of polyhydric alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, Propylene glycol monomethyl ether, propylene glycol monoethyl ether, etc .; Examples of polyhydric alcohol alkyl ether acetates include ethylene glycol methyl ether acetate,
  • cyclic ethers, polyhydric alcohol alkyl ethers, polyhydric alcohol alkyl ether acetates, ketones or esters are preferred, ketones are more preferred, and 2-butanone is more preferred.
  • the said polymerization solvent can use 1 type (s) or 2 or more types.
  • the weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of each polymer is preferably 1,000 to 50,000, more preferably 1,000 to 30,000, and more preferably 1,000 to 20 1,000 is more preferable, and 2,000 to 10,000 is particularly preferable.
  • Mw weight average molecular weight
  • GPC gel permeation chromatography
  • the ratio (Mw / Mn) of Mw of each polymer to the number average molecular weight (Mn) in terms of polystyrene by GPC is preferably 1 to 5, more preferably 1 to 3, and further preferably 1 to 2.
  • the film-forming composition for immersion exposure is preferably as less as possible as impurities such as halogen ions and metals.
  • impurities such as halogen ions and metals.
  • methods for purifying each polymer in order to reduce impurities include chemical purification methods such as water washing, liquid-liquid extraction, and demetalization filter passage, these chemical purification methods and ultrafiltration, centrifugation, etc. And a combination with a physical purification method.
  • the content of the polymer component is preferably 70% by mass to 100% by mass and more preferably 80% by mass to 100% by mass with respect to the total solid content in the film forming composition for immersion exposure. 90 mass% to 100 mass% is more preferable.
  • the solvent is a solvent that dissolves or uniformly disperses each component such as the polymer component [A].
  • Examples of the solvent include alcohol solvents, ether solvents, hydrocarbon solvents, ketone solvents, ester solvents, water, and the like.
  • the alcohol solvent examples include monohydric alcohols such as butanol, pentanol and 4-methyl-2-pentanol; polyhydric alcohols such as ethylene glycol and propylene glycol.
  • polyhydric alcohol alkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol diethyl ether, and diethylene glycol dimethyl ether;
  • polyhydric alcohol alkyl ether acetates include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether acetate;
  • aliphatic ethers include diethyl ether, dipropyl ether, dibutyl ether, butyl methyl ether, butyl ethyl ether, diisoamyl ether, hexyl methyl ether, octyl methyl ether, cyclopentyl methyl ether, dicyclopentyl
  • hydrocarbon solvent examples include higher hydrocarbons such as decane, dodecene, and untecan.
  • ketone solvent examples include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl- n-hexyl ketone, di-iso-butyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, etc. Can be mentioned.
  • ester solvent examples include methyl acetate, ethyl acetate, n-propyl acetate, iso-propyl acetate, n-butyl acetate, iso-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether, acetic acid Ethylene glycol monoethyl ether, acetic acid diethylene glycol monomethyl ether, acetic acid diethylene glycol monoethyl ether
  • ketone solvents and ester solvents are preferred, the ketone solvent is more preferably cyclohexanone, and the ester solvent is more preferably propylene glycol monomethyl ether acetate.
  • the film forming composition for immersion exposure may contain an optional component.
  • Each optional component may be used alone or in combination of two or more.
  • content of each arbitrary component can be suitably determined according to the objective.
  • the film forming composition for immersion exposure can be prepared by mixing the [A] polymer component, the [B] solvent, and, if necessary, optional components at a predetermined ratio.
  • the solid concentration of the film forming composition for immersion exposure is preferably 0.1% by mass to 50% by mass, more preferably 0.5% by mass to 30% by mass, and further more preferably 1% by mass to 10% by mass. preferable.
  • the film forming composition for immersion exposure can be suitably used as, for example, a photoresist composition (hereinafter referred to as a film forming composition for immersion exposure used as a photoresist composition (for the immersion exposure of the present invention).
  • Photoresist composition is also referred to as “film formation composition for immersion exposure (PR)”).
  • the film-forming composition for immersion exposure becomes a resist film because the polymer (a1) is unevenly distributed on the resist film surface layer. It is possible to increase the receding contact angle during immersion exposure on the surface, and to further reduce the receding contact angle due to dissociation of alkali dissociable groups during alkali development, thereby further suppressing development defects. can do.
  • the film forming composition for immersion exposure includes [C] acid generator, [D] acid diffusion controller, and other optional components as suitable components. It may contain components. Hereinafter, each component will be described in detail.
  • the [B] solvent has been described above in the section ⁇ Film forming composition for immersion exposure>, and will not be described in detail.
  • [A] polymer component (hereinafter, also referred to as “[A1] polymer component”) in the film forming composition for immersion exposure (PR), the following polymer component is preferable.
  • the polymer component is not particularly limited as long as it contains the polymer (a1) and a polymer (a2) having a fluorine atom content smaller than that of the polymer (a1).
  • the polymer (a1) hereinafter also referred to as “polymer (a1-1)”) in the combined component is preferably the following polymer.
  • the polymer (a1-1) preferably has a structural unit (II) in addition to the structural unit (I) described above.
  • the structural unit (II) is a structural unit containing an acid dissociable group. Since the polymer (a1-1) has the structural unit (II), the film-forming composition for immersion exposure (PR) has the solubility of the polymer (a1-1) in the alkaline developer in the exposed area. As a result, the occurrence of development defects can be further suppressed.
  • Examples of the structural unit (II) include a structural unit represented by the following formula (4).
  • R is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
  • Y is an acid dissociable group.
  • the acid dissociable group represented by Y is preferably a group represented by the following formula (Y-1).
  • R a1 , R a2 and R a3 are each independently an alkyl group having 1 to 4 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms. . R a2 and R a3 may be bonded to each other to form a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atom to which they are bonded.
  • Examples of the alkyl group having 1 to 4 carbon atoms represented by R a1 , R a2 and R a3 include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and 2-methyl.
  • a propyl group, a 1-methylpropyl group, a t-butyl group and the like can be mentioned.
  • the divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms to be formed include a bridged skeleton such as an adamantane skeleton and a norbornane skeleton, and a monocyclic cycloalkane skeleton such as cyclopentane and cyclohexane.
  • Group are, for example, one or more of linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms such as methyl group, ethyl group, n-propyl group, i-propyl group, etc. And groups having an alicyclic hydrocarbon skeleton such as a group substituted with.
  • a group having a monocyclic cycloalkane skeleton is preferable in that the shape of the resist pattern after development can be improved.
  • Examples of the structural unit represented by the above formula (4) include structural units represented by the formulas (4-1) to (4-7).
  • R has the same meaning as in formula (4).
  • R a1 , R a2 and R a3 are as defined in the formula (Y-1).
  • Each r is independently an integer of 1 to 3.
  • the structural unit represented by the formula (4-3) is preferable, and r in the formula (4-3) is more preferably 1, and R in the formula (4-3) is preferable.
  • a1 is an ethyl group.
  • the content ratio of the structural unit (II) is preferably 0 mol% to 90 mol%, more preferably 0 mol% to 70 mol%, based on all the structural units constituting the polymer (a1-1). More preferred is mol% to 50 mol%.
  • the polymer (a2) is a polymer having a smaller fluorine atom content than the polymer (a1-1).
  • the immersion exposure film-forming composition (PR) is effective for applying the polymer (a1-1) to the resist film surface layer.
  • the base polymer refers to a polymer that is the main component of the polymer that constitutes the resist film formed from the photoresist composition, and preferably 50% by mass with respect to the total polymer that constitutes the resist film. The polymer which occupies the above is said.
  • the polymer (a2) is not particularly limited as long as it has the above-described configuration, but preferably has an acid-dissociable group, and has the structural unit (II) for the polymer (a1-1) described above. More preferably. Moreover, the polymer (a2) may have another structural unit in the range which does not impair the effect of this invention. The content ratio of other structural units can be appropriately determined according to the purpose. In addition, the polymer (a2) may contain 2 or more types of each structural unit.
  • the content ratio of the structural unit (II) in the polymer (a2) is preferably 10 mol% to 100 mol%, and 20 mol% to 90 mol% with respect to all the structural units constituting the polymer (a2). More preferably, it is more preferably 30 mol% to 80 mol%.
  • Examples of the structural unit other than the structural unit (II) that the polymer (a2) may have include at least one structure selected from the group consisting of a lactone structure, a cyclic carbonate structure, and a sultone structure.
  • Examples of the structural unit include a structural unit represented by the following formulas (L-1) and (L-4) to (L-14) as a structural unit containing a lactone structure, and a structural unit containing a cyclic carbonate structure: As a structural unit represented by the following formula (L-2) and a structural unit represented by the following formula (L-3) as a structural unit containing a sultone structure.
  • the polymer (a2) has a structural unit including at least one structure selected from the group consisting of a lactone structure, a cyclic carbonate structure, and a sultone structure, the adhesion of the resist film can be improved.
  • R L1 represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
  • the content of other structural units is preferably 10 mol% to 90 mol%, more preferably 20 mol% to 80 mol%, based on all the structural units constituting the polymer (a2).
  • the content of the polymer (a2) is preferably 300 parts by weight to 5,000 parts by weight and more preferably 1,000 parts by weight to 3,000 parts by weight with respect to 100 parts by weight of the polymer (a1-1). preferable.
  • the polymer (a1-1) can be efficiently unevenly distributed on the resist film surface layer.
  • the acid generator is a radiation-sensitive component that generates an acid upon exposure to radiation. Since the film forming composition for immersion exposure (PR) contains a [C] acid generator, the acid-dissociable group in the polymer is dissociated by the action of the acid generated by exposure, and the generated carboxy group or the like Due to the polarity, the polymer in the exposed area becomes easily soluble in the developer. As a result, a resist pattern with high contrast can be formed.
  • the inclusion form of the [C] acid generator constituting the film forming composition for immersion exposure (PR) may be a compound form as described later (hereinafter also referred to as “[C] acid generator”). It may be a form incorporated as part of the coalescence or both forms. In addition, you may use a [C] acid generator individually or in combination of 2 or more types.
  • Examples of the [C] acid generator include onium salt compounds such as sulfonium salts, tetrahydrothiophenium salts, iodonium salts, and sulfonic acid compounds.
  • sulfonium salt examples include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium perfluoro-n-butanesulfonate, triphenylsulfonium 6-adamantylcarbonyloxy-1,1,2,2-tetrafluorohexanesulfonate, and triphenyl.
  • tetrahydrothiophenium salt examples include 4-hydroxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-hydroxy-1-naphthyltetrahydrothiophenium nonafluoro-n-butanesulfonate, 4-hydroxy-1 -Naphtyltetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (1-naphthylacetomethyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (1-naphthylacetomethyl) tetrahydrothiophenium nonafluoro-n-butane Sulfonate, 1- (1-naphthylacetomethyl) tetrahydrothiophenium perfluoro-n-octane sulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) t
  • iodonium salt examples include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis ( 4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, and the like.
  • sulfonic acid compound examples include trifluoromethanesulfonylbicyclo [2.2.1] hept-5-ene-2,3-dicarbodiimide, nonafluoro-n-butanesulfonylbicyclo [2.2.1] hept-5.
  • the acid generator is preferably an onium salt compound, more preferably a sulfonium salt, and even more preferably triphenylsulfonium perfluoro-n-butanesulfonate.
  • the content of the acid generator is from the viewpoint of ensuring the sensitivity and developability as a resist with respect to 100 parts by mass of the polymer component [A] contained in the film forming composition for immersion exposure (PR). 0.1 to 30 parts by mass is preferable, and 0.1 to 20 parts by mass is more preferable.
  • the content of the [C] acid generator is less than 0.1 parts by mass, the sensitivity and developability of the film forming composition for immersion exposure (PR) tend to be lowered.
  • it exceeds 30 parts by mass the transparency to radiation tends to decrease, and it becomes difficult to obtain a rectangular resist pattern.
  • the acid diffusion controller is a component that controls the diffusion of the acid generated in the resist film during exposure and suppresses an undesirable chemical reaction in the unexposed area.
  • the film forming composition for immersion exposure (PR) contains the [D] acid diffusion controller, the contrast between the exposed portion and the unexposed portion can be increased, and a good resist pattern can be formed.
  • the content of the acid diffusion controller in the immersion exposure film-forming composition (PR) may be a free compound (hereinafter also referred to as “[D] acid diffusion controller”). It may be a form incorporated as part or both of these forms. In addition, you may use [D] acid spreading
  • Examples of the acid diffusion controller include amine compounds, amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, and the like.
  • Examples of the amine compound include mono (cyclo) alkylamines; di (cyclo) alkylamines; tri (cyclo) alkylamines; substituted alkylanilines or derivatives thereof; ethylenediamine, N, N, N ′, N ′.
  • amide group-containing compound examples include Nt-butoxycarbonyl group-containing amide compounds such as Nt-butoxycarbonyl-4-hydroxypiperidine; N-t-amyloxycarbonyl-4-hydroxypiperidine and the like N- t-amyloxycarbonyl group-containing amide compounds; formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone, N-acetyl-1-adamantylamine, tris (2-hydroxyethyl) isocyanurate and the like can be mentioned.
  • Nt-butoxycarbonyl group-containing amide compounds such as Nt-butoxycarbonyl-4-hydroxypiperidine; N-t-amyloxycarbonyl-4-hydroxypiperidine and the like N- t-amyloxycarbonyl group-containing amide compounds; form
  • urea compound examples include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri-n-butyl.
  • nitrogen-containing heterocyclic compound examples include imidazoles such as 2-phenylimidazole; pyridines; piperazines; pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, piperidineethanol, 3-piperidino-1,2 -Propanediol, morpholine, 4-methylmorpholine, 1- (4-morpholinyl) ethanol, 4-acetylmorpholine, 3- (N-morpholino) -1,2-propanediol, 1,4-dimethylpiperazine, 1,4 -Diazabicyclo [2.2.2] octane and the like.
  • imidazoles such as 2-phenylimidazole
  • pyridines piperazines
  • pyrazine pyrazole
  • pyridazine quinosaline
  • purine pyrrolidine
  • piperidine piperidineethanol
  • amide group-containing compounds are preferred, Nt-amyloxycarbonyl group-containing amide compounds are more preferred, and Nt-amyloxycarbonyl-4-hydroxypiperidine is even more preferred.
  • a photodegradable base can also be used as the acid diffusion control agent.
  • This photodegradable base functions as a quencher due to the high acid capturing function by the anion in the unexposed area, and as a result of capturing the acid diffusing from the exposed area, the contrast of the deprotection reaction is improved and the resolution is further improved.
  • Can do As an example of the photodegradable base, an onium salt compound that is decomposed by exposure and loses acid diffusion controllability can be mentioned.
  • the onium salt compound include a sulfonium salt compound represented by the following formula (5-1), an iodonium salt compound represented by the following formula (5-2), and the like.
  • R b1 to R b5 are each independently a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, a halogen atom, or —SO 2 —R X. .
  • R X is an alkyl group, a cycloalkyl group, an alkoxy group or an aryl group.
  • Z ⁇ is OH ⁇ , R b6 —COO ⁇ , R Y —SO 2 —N — —R b6 , R b6 —SO 3 ⁇ , or an anion represented by the following formula (5 ′).
  • R b6 is a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. However, one part or all part of the hydrogen atom which the said alkyl group, cycloalkyl group, aryl group, and aralkyl group have may be substituted.
  • R Y is a linear or branched alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms.
  • some or all of the hydrogen atoms of the alkyl group and cycloalkyl group may be substituted with fluorine atoms.
  • Z ⁇ is R b6 —SO 3 —
  • the fluorine atom is not bonded to the carbon atom to which SO 3 — is bonded.
  • R b7 is a linear or branched alkyl group having 1 to 12 carbon atoms or a linear or branched alkoxy group having 1 to 12 carbon atoms. However, some or all of the hydrogen atoms of the alkyl group and alkoxy group may be substituted with fluorine atoms.
  • u is an integer of 0-2.
  • Examples of the alkyl group represented by R b1 to R b5 include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, an i-butyl group, and a t-butyl group.
  • Examples of the alkoxy group represented by R b1 to R b5 include a methoxy group, an ethoxy group, and a butoxy group.
  • Examples of the halogen atom represented by R b1 to R b5 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • alkyl group and alkoxy group represented by R X for example, the same groups as the groups exemplified for R b1 to R b5 can be applied.
  • Examples of the cycloalkyl group represented by R X include a cyclopentyl group, a cyclohexyl group, a norbornyl group, a tricyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, and the like.
  • Examples of the aryl group represented by R X include a phenyl group, a naphthyl group, and an anthryl group.
  • R b1 to R b5 are preferably a hydrogen atom and —SO 2 —R X. Moreover, as said R ⁇ X >, a cycloalkyl group is preferable and a cyclohexyl group is more preferable.
  • Examples of the alkyl group represented by R b6 include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, an i-butyl group, and a t-butyl group.
  • Examples of the cycloalkyl group represented by R b6 include a cyclopentyl group, a cyclohexyl group, a norbornyl group, a tricyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, and the like.
  • Examples of the aryl group represented by R b6 include a phenyl group, a naphthyl group, and an anthryl group.
  • Examples of the aralkyl group represented by R b6 include a benzyl group, a phenethyl group, and a phenylpropyl group.
  • alkyl group, cycloalkyl group, aryl group and aralkyl group may have include a hydroxy group, a halogen atom, an alkoxy group, a lactone group, and an alkylcarbonyl group.
  • alkyl group and cycloalkyl group represented by R Y for example, the same groups as the groups exemplified for R b6 can be applied.
  • Examples of the sulfonium salt compound represented by the above formula (5-1) include triphenylsulfonium hydroxide, triphenylsulfonium salicylate, triphenylsulfonium 4-trifluoromethyl salicylate, diphenyl-4-hydroxyphenyl. Examples thereof include sulfonium salicylate, triphenylsulfonium 10-camphor sulfonate, 4-t-butoxyphenyl diphenylsulfonium 10-camphor sulfonate, and the like. Of these, triphenylsulfonium salicylate and triphenylsulfonium 10-camphorsulfonate are more preferable. In addition, you may use these sulfonium salt compounds individually or in combination of 2 or more types.
  • Examples of the iodonium salt compound represented by the above formula (5-2) include bis (4-t-butylphenyl) iodonium hydroxide, bis (4-t-butylphenyl) iodonium salicylate, and bis (4- t-butylphenyl) iodonium 4-trifluoromethyl salicylate, bis (4-t-butylphenyl) iodonium 10-camphorsulfonate, and the like.
  • the photodegradable base is preferably a sulfonium salt compound, more preferably triphenylsulfonium salicylate or triphenylsulfonium 10-camphorsulfonate.
  • the content of the acid diffusion controller is preferably 30 parts by mass or less, and 20 parts by mass with respect to 100 parts by mass of the polymer component [A] contained in the film forming composition for immersion exposure (PR). The following is more preferable, and 10 parts by mass or less is more preferable. [D] If the acid diffusion controller is excessively contained, the sensitivity of the formed resist film may be significantly lowered.
  • the film forming composition for immersion exposure (PR) may contain other optional components such as an [E] uneven distribution accelerator as long as the effects of the present invention are not impaired.
  • Each optional component may be used alone or in combination of two or more. Further, the content of other optional components can be appropriately determined according to the purpose.
  • the uneven distribution promoter is a component that segregates the polymer (a1-1) more efficiently on the resist film surface.
  • the film formation composition for immersion exposure (PR) contains the [E] uneven distribution accelerator, the blending amount of the polymer (a1-1) can be reduced.
  • Examples of the uneven distribution promoter include lactone compounds, carbonate compounds, nitrile compounds, and polyhydric alcohols. In addition, you may use [E] uneven distribution promoter individually or in combination of 2 or more types.
  • lactone compound examples include ⁇ -butyrolactone, valerolactone, mevalonic lactone, norbornane lactone, and the like.
  • carbonate compound examples include propylene carbonate, ethylene carbonate, butylene carbonate, vinylene carbonate, and the like.
  • nitrile compound examples include succinonitrile.
  • polyhydric alcohol examples include glycerin.
  • lactone compounds are preferred, and ⁇ -butyrolactone is more preferred.
  • the content of the uneven distribution promoter is preferably 5 to 300 parts by mass with respect to 100 parts by mass of the total amount of the polymer.
  • the film forming composition for immersion exposure can be suitably used, for example, as a composition for forming an upper liquid immersion film (hereinafter referred to as a film forming composition for immersion exposure used as a composition for forming an upper film for immersion).
  • a film forming composition for immersion exposure used as a composition for forming an upper film for immersion.
  • film forming composition for liquid immersion exposure (TC) By forming the liquid immersion upper film on the resist film using the film formation composition for liquid immersion exposure (TC), the receding contact angle at the time of liquid immersion exposure on the liquid immersion upper film can be further increased. During alkali development, the receding contact angle can be further reduced by dissociation of the alkali-dissociable group, and as a result, development defects can be further suppressed.
  • the film forming composition for immersion exposure may contain other components in addition to the above [A] polymer component and [B] solvent.
  • each component will be described in detail.
  • the [B] solvent has been described above in the section ⁇ Film forming composition for immersion exposure>, and will not be described in detail.
  • [A] polymer component (hereinafter, also referred to as “[A2] polymer component”) in the film forming composition for immersion exposure (TC), the following polymer components are preferable.
  • the polymer component is particularly limited as long as it contains the polymer (a1) (the polymer in the [A2] polymer component (a1 is also referred to as “polymer (a1-2)”)). However, a polymer different from the polymer (a1) (hereinafter also referred to as “polymer (a3)”) may be included as long as the effects of the present invention are not impaired.
  • the polymer component preferably has structural units (III) to (V) in the same or different polymer (a3) as the polymer (a1-2).
  • the polymer component may have other structural units such as the structural unit (VI) in the same or different polymer (a3) as the polymer (a1-2).
  • each polymer may have 2 or more types of each structural unit, respectively.
  • each structural unit will be described in detail.
  • the structural unit (III) includes a structural unit containing a fluorinated sulfonamide group (hereinafter also referred to as “structural unit (III-1)”) and a structural unit containing an ⁇ -trifluoromethyl alcohol group (hereinafter referred to as “structural unit (III)”. III-2) ”) is at least one structural unit selected from the group consisting of.
  • the film forming composition for liquid immersion exposure (TC) can improve the water repellency and removability of the liquid immersion upper layer film by the [A2] polymer component further having the structural unit (III), Occurrence of development defects can be suppressed.
  • the structural unit (III-1) is preferably a structural unit represented by the following formula (5).
  • RD is a hydrogen atom, a methyl group, a fluorine atom, or a trifluoromethyl group.
  • R n1 is a divalent linking group.
  • R n2 is a fluorinated alkyl group having 1 to 20 carbon atoms.
  • the RD is preferably a hydrogen atom or a methyl group, and more preferably a methyl group, from the viewpoint of the copolymerizability of the monomer that gives the structural unit represented by the formula (5).
  • Examples of the divalent linking group represented by R n1 include a divalent chain hydrocarbon group having 1 to 6 carbon atoms and a divalent alicyclic hydrocarbon group having 4 to 12 carbon atoms. It is done.
  • Examples of the divalent chain hydrocarbon group having 1 to 6 carbon atoms include, for example: As saturated chain hydrocarbon groups, methanediyl group, 1,2-ethanediyl group, 1,1-ethanediyl group, 1,3-propanediyl group, 1,2-propanediyl group, 1,1-propanediyl group, 2 , 2-propanediyl group, 1,4-propanediyl group, 1,5-pentanediyl group, 1,6-hexanediyl group, 1-methyl-1,3-propanediyl group, 2-methyl-1,3- Propanediyl group, 2-methyl-1,2-propanediyl group, 1-methyl-1,4-butanediyl group, 2-methyl-1,4-butanediyl group and the like;
  • Examples of the unsaturated chain hydrocarbon group include a 1,2-ethenediyl group, a 1,3-prop
  • Examples of the divalent alicyclic hydrocarbon group having 4 to 12 carbon atoms include: As monocyclic hydrocarbon group, cyclobutanediyl group such as 1,3-cyclobutanediyl group; cyclopentanediyl group such as 1,3-cyclopentanediyl group; 1,4-cyclohexanediyl group, 1,2-cyclohexanediyl Cyclohexanediyl group such as a group; cyclooctanediyl group such as 1,5-cyclooctanediyl group; Polycyclic hydrocarbon groups such as 1,4-norbornanediyl group, norbornanediyl group such as 2,5-norbornanediyl group, adamantanediyl group such as 1,3-adamantanediyl group, 2,4-adamantanediyl group, etc. Is mentioned. Among
  • R n1 is preferably a divalent chain hydrocarbon group having 1 to 6 carbon atoms, more preferably a divalent chain hydrocarbon group having 1 to 3 carbon atoms, and further preferably a 1,2-ethanediyl group. .
  • Examples of the fluorinated alkyl group having 1 to 20 carbon atoms represented by R n2 include, for example, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a trifluoroethyl group, a pentafluoromethyl group, a heptafluoropropyl group, Nonafluorobutyl group etc. are mentioned. Of these, a trifluoromethyl group is preferred.
  • the structural unit (III-2) may be any structural unit containing an ⁇ -trifluoromethyl alcohol group (—C (R) (OH) (CF 3 ) group, R is a monovalent organic group). Although it does not specifically limit, For example, the structural unit etc. which are represented by following formula (6) are mentioned.
  • RE is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.
  • R t1 is a divalent linking group.
  • R E from the viewpoint of copolymerizability of the monomer giving the structural unit represented by the above formula (6), a hydrogen atom, preferably a methyl group, more preferably a methyl group.
  • Examples of the divalent linking group represented by R t1 include the same groups as those exemplified as R n1 in the above formula (5). Further, the methylene group (—CH 2 —) in these chain hydrocarbon groups and alicyclic hydrocarbon groups may be substituted with an oxygen atom, a carbonyl group or an ester group.
  • R t1 is preferably a divalent chain hydrocarbon group having 1 to 3 carbon atoms or a divalent alicyclic hydrocarbon group having 4 to 12 carbon atoms, and a divalent group containing a propanediyl group or a cyclohexane skeleton.
  • a divalent group containing a norbornene skeleton and a divalent group containing an adamantane skeleton are more preferred, and a 1,2-propanediyl group and a 1-cyclohexyl-1,2-ethanediyl group are more preferred.
  • Examples of the structural unit represented by the above formula (6) include structural units represented by the following formulas (6-1) to (6-8).
  • R E has the same meaning as in the above formula (6).
  • the content ratio of the structural unit (III) in the polymer component is preferably 0 mol% to 90 mol%, preferably 1 mol% to 80 mol%, based on all structural units constituting the [A2] polymer component. % Is more preferable, 4 mol% to 75 mol% is further preferable, and 20 mol% to 70 mol% is particularly preferable. [A2] By making the content ratio of the structural unit (III) in the polymer component within the above range, the water repellency and removability of the liquid immersion upper layer film formed from the film formation composition for liquid immersion exposure (TC) are effective. And development defects can be effectively suppressed.
  • the content ratio of the structural unit (III) in the polymer (a1-2) is preferably 0 mol% to 90 mol%, preferably 5 mol% to the total structural unit constituting the polymer (a1-2). 85 mol% is more preferable, and 15 mol% to 65 mol% is more preferable.
  • the content ratio of the structural unit (III) in the polymer (a3) is preferably from 0 to 90 mol%, preferably from 5 to 85 mol%, based on all the structural units constituting the polymer (a3). More preferably, it is more preferably 15 mol% to 65 mol%.
  • the structural unit (IV) is a structural unit containing a sulfo group.
  • the film forming composition for liquid immersion exposure (TC) can further improve the removability and peeling resistance of the liquid immersion upper layer film by the [A2] polymer component further having the structural unit (IV). The occurrence of development defects can be further suppressed.
  • Examples of the structural unit (IV) include a structural unit represented by the following formula (7).
  • R ⁇ F> is a hydrogen atom, a methyl group, a fluorine atom, or a trifluoromethyl group.
  • R s1 is a single bond, an oxygen atom, a sulfur atom, a divalent chain hydrocarbon group having 1 to 6 carbon atoms, a divalent alicyclic hydrocarbon group having 4 to 12 carbon atoms, or a carbon atom having 6 to 12 carbon atoms.
  • X ′ is an oxygen atom, a sulfur atom or an NH group.
  • R ′ is a single bond, a divalent chain hydrocarbon group having 1 to 6 carbon atoms, a divalent alicyclic hydrocarbon group having 4 to 12 carbon atoms, or a divalent aromatic carbon group having 6 to 12 carbon atoms. It is a hydrogen group.
  • R F a hydrogen atom or a methyl group is preferable from the viewpoint of the copolymerizability of the monomer giving the structural unit (IV).
  • Examples of the divalent chain hydrocarbon group having 1 to 6 carbon atoms and the divalent alicyclic hydrocarbon group having 4 to 12 carbon atoms represented by R s1 and R ′ include, for example, the above formula (5 ), The same groups as those exemplified as R n1 in the above.
  • Examples of the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms represented by R s1 include arylene groups such as a phenylene group and a tolylene group.
  • R s1 is a single bond, a divalent chain hydrocarbon group having 1 to 6 carbon atoms, a divalent aromatic hydrocarbon having 6 to 12 carbon atoms, or a divalent group having 1 to 6 carbon atoms.
  • —C ( ⁇ O) —NH—R′— which is a chain hydrocarbon group, is preferably a single bond, a methanediyl group, a phenylene group, —C ( ⁇ O) —NH—CH (CH 3 ) —CH 2 —. Is more preferable, and a single bond, —C ( ⁇ O) —NH—CH (CH 3 ) —CH 2 — is more preferable.
  • Examples of the structural unit (IV) include structural units represented by the following formulas (7-1) to (7-4).
  • R F has the same meaning as in the above formula (7).
  • the structural unit represented by the above formula (7-1) and the structural unit represented by the above formula (7-4) are preferable.
  • the content ratio of the structural unit (IV) in the polymer component is preferably from 0 mol% to 10 mol%, preferably from 0.1 mol% to the total structural unit constituting the [A2] polymer component. 5 mol% is more preferable, and 0.2 mol% to 2 mol% is more preferable. [A2] By making the content ratio of the structural unit (IV) in the polymer component within the above range, the removability and peeling resistance of the liquid immersion upper layer film can be effectively improved, and the occurrence of development defects is effective. Can be suppressed.
  • the content ratio of the structural unit (IV) in the polymer (a3) is usually 0% by mole to 20% by mole, and 0.2% by mole to the total structural unit constituting the polymer (a3). 10 mol% is more preferable, and 0.5 mol% to 7 mol% is more preferable.
  • the structural unit (V) includes a structural unit containing a carboxy group (hereinafter also referred to as “structural unit (V-1)”) and a structural unit containing a group represented by the following formula (2) (hereinafter referred to as “structural unit ( V-2) ”) is at least one structural unit selected from the group consisting of.
  • the [A2] polymer component further includes the structural unit (V), so that the removability and peeling resistance of the liquid immersion upper layer film can be further improved. The occurrence of development defects can be further suppressed.
  • Examples of the structural unit (V-1) include structural units represented by the following formulas (8-1) to (8-3).
  • R G is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
  • R c1 and R c2 each independently represent a divalent chain hydrocarbon group having 1 to 6 carbon atoms, a divalent alicyclic hydrocarbon group having 4 to 12 carbon atoms, or 2 having 6 to 12 carbon atoms. Valent aromatic hydrocarbon group.
  • a hydrogen atom and a methyl group are preferable and a methyl group is more preferable.
  • Examples of the divalent chain hydrocarbon group having 1 to 6 carbon atoms represented by R c1 and R c2 include the same groups as those exemplified as R n1 in the above formula (5). Of these, saturated chain hydrocarbon groups are preferred, and 1,2-ethanediyl groups are more preferred.
  • Examples of the divalent alicyclic hydrocarbon group having 4 to 12 carbon atoms represented by R c1 and R c2 include groups similar to the groups exemplified as R n1 in the above formula (5). .
  • a monocyclic hydrocarbon group is preferable, a cyclohexanediyl group is more preferable, and a 1,2-cyclohexanediyl group is more preferable.
  • Examples of the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms represented by R c1 and R c2 include the same groups as those exemplified as R s1 in the above formula (7).
  • V-1) examples include structural units represented by the following formulas (8-1-1) to (8-1-3), and the following formulas (8-2-1) and (8- And the structural unit represented by 2-2).
  • R G has the same meaning as the above formulas (8-1) to (8-3).
  • structural units represented by the above formulas (8-1) and (8-3) are preferred.
  • structural units represented by the formula (8-1) the structural unit represented by the formula (8-1-1) is more preferable.
  • the structural unit (V-2) is a structural unit containing a group represented by the following formula (2).
  • R 4 represents a hydrogen atom, a halogen atom, a nitro group, an alkyl group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or 1 to 20 carbon atoms.
  • Some or all of the hydrogen atoms of the alkyl group, alicyclic hydrocarbon group, alkoxy group, acyl group, aralkyl group and aryl group may be substituted.
  • R 5 is —C ( ⁇ O) —R 6 , —S ( ⁇ O) 2 —R 7 , —R 8 —CN, or —R 9 —NO 2 .
  • R 6 and R 7 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a fluorinated alkyl group having 1 to 20 carbon atoms, or a monovalent alicyclic hydrocarbon having 3 to 20 carbon atoms. Group, an alkoxy group having 1 to 20 carbon atoms, a cyano group, a cyanomethyl group, an aralkyl group having 7 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. However, R 6 or R 7 and R 4 may be bonded to each other to form a ring structure.
  • R 8 and R 9 are each independently a single bond, a methylene group or an alkylene group having 2 to 5 carbon atoms.
  • Examples of the halogen atom represented by R 4 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom and a chlorine atom are preferable.
  • Examples of the alkoxy group having 1 to 20 carbon atoms represented by R 4 include a methoxy group and an ethoxy group.
  • Examples of the acyl group having 1 to 20 carbon atoms represented by R 4 include an acetyl group and a propionyl group.
  • Examples of the aralkyl group having 7 to 20 carbon atoms represented by R 4 include a benzyl group, a phenethyl group, and a naphthylmethyl group.
  • Examples of the aryl group having 6 to 20 carbon atoms represented by R 4 include a phenyl group, a tolyl group, a dimethylphenyl group, a 2,4,6-trimethylphenyl group, and a naphthyl group.
  • Examples of the substituent that the alkyl group, monovalent alicyclic hydrocarbon group, alkoxy group, acyl group, aralkyl group and aryl group represented by R 4 may have include a fluorine atom and a chlorine atom. And halogen atoms such as hydroxyl group, nitro group, cyano group and the like.
  • R 4 from the viewpoint of balancing the solubility of the developer in the liquid immersion upper layer film formed from the film forming composition for liquid immersion exposure (TC) and the peeling resistance, among these, a hydrogen atom, a carbon number An alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms are preferable, and a hydrogen atom, a methyl group, an ethyl group, and an acetyl group are more preferable.
  • R 5 is —C ( ⁇ O) —R 6 or —S ( ⁇ O) 2 —R 7
  • the alkyl group represented by R 6 and R 7 a monovalent alicyclic hydrocarbon group, alkoxy
  • the group, the aralkyl group, and the aryl group include the same groups as those exemplified as the respective groups for R 4 .
  • the fluorinated alkyl group represented by R 6 and R 7 include a group in which at least one hydrogen atom of the group exemplified as the alkyl group for R 4 is substituted with a fluorine atom.
  • R 6 and R 7 a hydrogen atom and an alkyl group are preferable, and a hydrogen atom, a methyl group, and an ethyl group are more preferable.
  • the group containing a ring structure formed by bonding R 6 or R 7 and R 4 to each other includes an atom to which R 6 or R 7 and R 4 are bonded, and has 5 carbon atoms having an oxo group.
  • Divalent alicyclic hydrocarbon groups of ⁇ 12 are preferred.
  • R 8 and R 9 are preferably a single bond, a methanediyl group or an ethanediyl group.
  • the structural unit (V-2) is derived from, for example, a (meth) acrylic acid ester derivative having a group represented by the following formula (2), a (meth) acrylamide derivative, a vinyl ether derivative, an olefin derivative, a styrene derivative, or the like. Examples include structural units. Of these, structural units derived from (meth) acrylic acid ester derivatives are preferred. That is, the structural unit (V-2) is preferably a structural unit represented by the following formula (9).
  • R 4 and R 5 is as defined in the above formula (2).
  • m is an integer of 1 to 3.
  • R 4 and R 5 is plural, respectively, it may be different in each of a plurality of R 4 and R 5 are the same.
  • L 1 is a (m + 1) -valent linking group.
  • R H is a hydrogen atom, a methyl group, a fluorine atom or a trifluoromethyl group.
  • the RH is preferably a hydrogen atom or a methyl group, and more preferably a methyl group, from the viewpoint of copolymerizability of the monomer that gives the structural unit represented by the formula (9).
  • Examples of the (m + 1) -valent linking group represented by L 1 include an alkanediyl group, a divalent alicyclic hydrocarbon group, an alkenediyl group, as a divalent linking group (when n is 1), And arenediyl groups. Note that some or all of the hydrogen atoms contained in these groups may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, a cyano group, or the like.
  • alkanediyl group examples include a methanediyl group, an ethanediyl group, a propanediyl group, a butanediyl group, a hexanediyl group, and an octanediyl group.
  • the alkanediyl group is preferably an alkanediyl group having 1 to 8 carbon atoms.
  • divalent alicyclic hydrocarbon group examples include monocyclic alicyclic hydrocarbon groups such as cyclopentanediyl group and cyclohexanediyl group; and polycyclic alicyclic groups such as norbornanediyl group and adamantanediyl group. A hydrocarbon etc. are mentioned.
  • the divalent alicyclic hydrocarbon group is preferably a divalent alicyclic hydrocarbon group having 5 to 12 carbon atoms.
  • alkenediyl group examples include an ethenediyl group, a propenediyl group, and a butenediyl group.
  • the alkenediyl group is preferably an alkenediyl group having 2 to 6 carbon atoms.
  • Examples of the arenediyl group include a phenylene group, a tolylene group, and a naphthylene group.
  • a phenylene group As the above arenediyl group, an arenediyl group having 6 to 15 carbon atoms is preferable.
  • an alkanediyl group a divalent alicyclic hydrocarbon group is preferable, an alkanediyl group having 1 to 4 carbon atoms, and a divalent alicyclic hydrocarbon having 6 to 11 carbon atoms. Groups are more preferred.
  • structural units represented by the following formula (9) As the structural unit represented by the following formula (9), structural units represented by the following formulas (9-1) to (9-10) are preferable.
  • R H has the same meaning as in the above formula (9).
  • the content of the structural unit (V) in the polymer component is preferably 0 mol% to 30 mol%, preferably 1 mol% to 20 mol, based on all structural units constituting the [A2] polymer component. % Is more preferable, and 4 mol% to 15 mol% is more preferable. [A2] By making the content ratio of the structural unit (V) in the polymer component within the above range, the removability and peeling resistance of the liquid immersion upper layer film formed from the film forming composition for liquid immersion exposure (TC) are effective. And development defects can be effectively suppressed.
  • the content ratio of the structural unit (V) in the polymer (a3) is preferably 0% by mole to 60% by mole, and preferably 10% by mole to 55% by mole with respect to all the structural units constituting the polymer (a3). More preferably, it is more preferably 25 mol% to 50 mol%.
  • the polymer component preferably further has a structural unit (VI) represented by the following formula (Z). [A2] When the polymer component further has the structural unit (VI), the water repellency of the formed liquid immersion upper layer film can be increased.
  • R M1 represents a hydrogen atom, a methyl group, a fluorine atom or a trifluoromethyl group.
  • R M2 is a linear or branched alkyl group having 1 to 6 carbon atoms having a fluorine atom or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms having a fluorine atom.
  • one part or all part of the hydrogen atom which the said alkyl group and alicyclic hydrocarbon group have may be substituted by the substituent.
  • Examples include a group in which part or all of the hydrogen atoms of the linear or branched alkyl group are substituted with fluorine atoms.
  • Examples of the monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms having a fluorine atom represented by R M2 include a cyclopentyl group, a cyclopentylpropyl group, a cyclohexyl group, a cyclohexylmethyl group, a cycloheptyl group, a cyclopentyl group, and the like. Examples thereof include a group in which part or all of the hydrogen atoms of a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms such as an octyl group and a cyclooctylmethyl group are substituted with fluorine atoms.
  • substituents examples include a fluorine atom, a hydroxy group, a carboxy group, and an amino group.
  • Examples of the structural unit (VI) include structural units represented by the following formulas (Z-1) to (Z-6).
  • R M1 has the same meaning as in the above formula (Z).
  • the content of the structural unit (VI) in the polymer component is preferably 0 mol% to 50 mol%, preferably 1 mol% to 40 mol, based on all structural units constituting the [A2] polymer component. % Is more preferable, and 2 mol% to 30 mol% is more preferable. [A2] By making the content ratio of the structural unit (VI) in the polymer component within the above range, the water repellency and removability of the liquid immersion upper film formed from the liquid immersion upper film formation composition (TC) are further improved. As a result, development defects can be further suppressed.
  • the content ratio of the structural unit (VI) in the polymer (a1-2) is preferably 0 mol% to 70 mol%, preferably 5 mol% to the total structural unit constituting the polymer (a1-2). 65 mol% is more preferable, and 10 mol% to 60 mol% is more preferable.
  • the film forming composition (TC) for immersion exposure may contain other components other than the above-mentioned [A2] polymer component and [B] solvent as long as the effects of the present invention are not impaired.
  • Other components may be used alone or in combination of two or more.
  • the polymer of the present invention is a polymer having the structural unit (I) represented by the above formula (1). Since the polymer has the structural unit (I), for example, it is suitably used as a component of a film forming composition for immersion exposure that exhibits a large receding contact angle during immersion exposure and can suppress development defects. be able to.
  • the compound of the present invention is a compound represented by the above formula (3). Since the compound has the above structure, it is suitable as a monomer that gives the structural unit (I), for example.
  • the resist pattern formation method (I) using the immersion exposure film-forming composition (PR) and the resist pattern formation method (II) using the immersion exposure film-forming composition (TC) are respectively divided. It is shown below.
  • the method of forming a resist pattern using the film forming composition for immersion exposure (PR) is as follows: (A1) A step of forming a resist film on a substrate using the film formation composition for immersion exposure (PR) (hereinafter also referred to as “step (A1)”), (A2) immersion exposure of the resist film by irradiation with radiation through an immersion exposure liquid (hereinafter also referred to as “process (A2)”), and (A3) development of the immersion exposed resist film. And a step of developing with a liquid to form a resist pattern (hereinafter also referred to as “step (A3)”).
  • a resist film is formed on the substrate using the film forming composition for immersion exposure (PR).
  • the substrate include a silicon wafer and a wafer coated with aluminum.
  • a resist film is formed by applying a film forming composition (PR) for immersion exposure on this substrate.
  • the method for applying the film forming composition for immersion exposure (PR) is not particularly limited, and for example, it can be applied by a known method such as a spin coating method.
  • the amount of the film forming composition (PR) to be applied is adjusted so that the resist film to be formed has a desired thickness. To do.
  • SB soft baking
  • Step (A2) the resist film formed in the step (A1) is subjected to immersion exposure by irradiation with radiation through the immersion exposure solution.
  • the immersion exposure liquid a liquid having a higher refractive index than air is usually used. Specific examples include pure water, long chain or cyclic aliphatic compounds, and the like.
  • the exposure apparatus irradiates radiation, and the resist film is formed through a mask having a predetermined pattern. Exposure.
  • the radiation is appropriately selected from visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams, and the like.
  • Far ultraviolet rays represented by ArF excimer laser light (wavelength 193 nm) and KrF excimer laser light (wavelength 248 nm) are preferable, and ArF excimer laser light (wavelength 193 nm) is more preferable.
  • exposure conditions, such as exposure amount can be suitably selected according to the compounding composition of the resist composition for immersion exposure, the kind of additive, etc.
  • PEB heat treatment
  • Step (A3) the resist film subjected to the immersion exposure in the above step (A2) is developed with a developer to form a resist pattern.
  • the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyl Diethylamine, ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH), pyrrole, piperidine, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [ 4.3.0]
  • An alkaline aqueous solution in which at least one alkaline compound such as 5-nonene is dissolved is preferable.
  • a suitable amount of a water-soluble organic solvent such as alcohols such
  • the method of forming a resist pattern using the film forming composition for immersion exposure is as follows: (B1) A step of forming a resist film on a substrate using a photoresist composition (hereinafter also referred to as “step (B1)”), (B2) a step of forming an immersion upper layer film on the resist film using the film formation composition for immersion exposure (TC) (hereinafter also referred to as “step (B2)”), (B3) immersion exposure of the resist film and immersion upper layer film by irradiation with radiation through the immersion exposure liquid (hereinafter also referred to as “process (B3)”), and (B4) the immersion exposure.
  • the resist film and the immersion upper layer film are developed with a developer to form a resist pattern (hereinafter also referred to as “process (B4)”).
  • process (B4) each process is explained in full detail.
  • a photoresist film is used to form a resist film on the substrate.
  • the photoresist composition include a positive or negative chemically amplified resist composition containing an acid generator, a positive resist composition comprising an alkali-soluble resin and a quinonediazide-based photosensitizer, and an alkali-soluble resin. Examples thereof include a negative resist composition composed of a crosslinking agent.
  • a commercially available photoresist composition can also be used as this photoresist composition.
  • it does not specifically limit as a coating method of the said photoresist composition, The method similar to the method used at the said process (A1) is employable.
  • substrate you may perform SB by the method similar to the method used at the said process (A1).
  • Step (B2) In this step, an immersion upper film is formed on the resist film using a film forming composition (TC) for immersion exposure.
  • TC film forming composition
  • the method for forming the liquid immersion upper film is the same as the method for forming the resist film except that the film forming composition for liquid immersion exposure (TC) is used in place of the photoresist composition. Can do.
  • Step (B3) and Step (B4) In the step (B3), the resist film and the immersion upper layer film are subjected to immersion exposure by irradiation of radiation through the immersion exposure liquid. In the step (B4), the resist film and the liquid immersion upper layer film that have been subjected to the liquid immersion exposure are developed with a developing solution to form a resist pattern.
  • the same method as that used in the step (A2) and the step (A3) can be employed.
  • Mw and Mn of the polymer were measured by gel permeation chromatography (GPC) under the following conditions.
  • the degree of dispersion (Mw / Mn) was calculated from the measurement results of Mw and Mn.
  • GPC column 2 G2000HXL, 1 G3000HXL, 1 G4000HXL (manufactured by Tosoh)
  • Elution solvent Tetrahydrofuran Flow rate: 1.0 mL / min
  • Standard material Monodisperse polystyrene Detector: Differential refractometer
  • 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. This polymerization solution was put into 200 g of methanol, and the precipitated white powder was separated by filtration. The filtered white powder was washed twice with 40 g of methanol, filtered, and dried at 50 ° C. for 17 hours to obtain a white powdery polymer (a1-1-1) (6.3 g, yield). 63%).
  • Mw of the polymer (a1-1-1) was 4,000, and Mw / Mn was 1.39.
  • the polymerization solution was cooled with water and cooled to 30 ° C. or lower. This polymerization solution was put into 2,000 g of methanol, and the precipitated white powder was separated by filtration. The filtered white powder was washed twice with 400 g of methanol, filtered, and dried at 50 ° C. for 17 hours to obtain a white powdery polymer (a2-1) (62.3 g, yield 62). %). Mw of the polymer (a2-1) was 5,500, and Mw / Mn was 1.41. As a result of 13 C-NMR analysis, the content ratios of structural units derived from (M-1) and (M-6) were 48.2 mol% and 51.8 mol%, respectively. As a result of 13 C-NMR analysis, the fluorine atom content of the polymer (a2-1) was 0% by mass.
  • the recovered lower layer solution was replaced with 4-methyl-2-pentanol to obtain a solution containing the polymer component (a1-2-1).
  • the solid content concentration of the solution containing the polymer component (a1-2-1) is determined from the mass of the residue after 0.5 g of the polymer solution is placed on an aluminum dish and heated on a hot plate heated to 155 ° C. for 30 minutes.
  • the solid content concentration value was used for the subsequent preparation of the protective film-forming composition solution and the yield calculation.
  • Mw of the obtained polymer (a1-2-1) was 10,000, Mw / Mn was 1.51, and the yield was 75%.
  • the content of each structural unit derived from the compound (Q-1), the compound (M-7) and the compound (M-8) was 4.9 mol% and 34. They were 9 mol% and 60.2 mol%.
  • Example 11 and Synthesis Example 9 Synthesis of polymers (a1-2-2) and (ca-2)
  • Polymers (a1-2-2) and (ca-2) were obtained in the same manner as in Example 10 except that a predetermined amount of the compounds shown in Table 3 were blended.
  • the content rate of each structural unit of each obtained polymer, Mw, and Mw / Mn ratio are shown according to Table 3.
  • This lower layer solution was diluted with isopropanol to 100 g, and again transferred to a separatory funnel. Thereafter, 50 g of methanol and 600 g of n-hexane were put into the above separatory funnel, separation and purification were performed, and the lower layer liquid was recovered after separation.
  • the recovered lower layer solution was replaced with 4-methyl-2-pentanol, and the total amount was adjusted to 250 g. After the adjustment, 250 g of water was added for separation and purification. After separation, the upper layer liquid was recovered. The recovered upper layer liquid was substituted with 4-methyl-2-pentanol to obtain a solution containing the polymer (a3-1).
  • Mw of the obtained polymer (a3-1) was 8,000, Mw / Mn was 1.51, and the yield was 80%.
  • the contents of the structural units derived from (M-7) and (M-9) were 98 mol% and 2 mol%, respectively.
  • Example 12 [A] (a1-1-1) 5 parts by mass and (a2-1) 100 parts by mass as a polymer component, [B] (B-1) 2,590 parts by mass and (B-2) as a solvent 1,110 parts by mass, 9.9 parts by mass of (C-1) as [C] acid generator, and 7.9 parts by mass of (D-1) as [D] acid diffusion controller
  • the obtained mixed solution was filtered through a filter having a pore size of 0.20 ⁇ m to prepare a film forming composition (PR) for immersion exposure.
  • Examples 13 to 19 and Comparative Examples 1 and 2 Except having used each component of the kind and compounding quantity shown in following Table 4, it operated similarly to Example 12 and prepared each film
  • Example 20 20 parts by mass of the polymer (a1-2-1) as the polymer (a1-2), 80 parts by mass of the polymer (a3-1) as the polymer (a3), and (B- 3) 1,000 parts by mass and (B-4) 4,000 parts by mass were mixed, stirred for 2 hours, and then filtered through a filter having a pore size of 0.2 ⁇ m to form a film for immersion exposure in Example 20.
  • a composition (TC) was obtained.
  • Example 21 and Comparative Example 3 Except having mixed each component of the kind and compounding quantity shown in Table 5, it carried out similarly to Example 20, and obtained each film formation composition (TC) for immersion exposure.
  • a photoresist composition ( ⁇ ) used for evaluation of film forming composition (TC) for each immersion exposure was prepared by the following method.
  • this polymer (P-1) has a content ratio of each structural unit derived from the compound (M-6), the compound (M-3) and the compound (M-10).
  • the copolymer was 53.0: 37.2: 9.8 (molar ratio).
  • content of the low molecular weight component derived from each monomer in this polymer was 0.03 mass% with respect to 100 mass% of this polymer.
  • a photoresist composition ( ⁇ ) was prepared.
  • the receding contact angle (°) was measured using a receding contact angle measuring device (DSA-10, manufactured by KRUSS) under the conditions of a temperature of 23 ° C., a relative humidity of 45%, and 1 atm.
  • DSA-10 receding contact angle measuring device
  • the needle was washed with acetone and isopropyl alcohol, then water was injected into the needle, and a silicon wafer as a measurement target was set on the wafer stage of the receding contact angle measuring device. Thereafter, the height of the stage is adjusted so that the distance between the resist film surface and the tip of the needle is 1 mm or less, and water is discharged from the needle to form a 20 ⁇ L water droplet on the wafer.
  • the contact angle was measured every second. A total of 20 contact angles were measured from the time when the contact angle was stabilized, and the average value was defined as the receding contact angle (°).
  • Table 4 shows the receding contact angle of a resist film having a thickness of 110 nm formed by spin-coating each immersion exposure film-forming composition (PR) on an 8-inch silicon wafer and performing SB at 110 ° C. for 60 seconds. “After SB”. When the receding contact angle after SB is 75 ° or more, the water repellency can be evaluated as good, and when it is less than 75 °, it can be evaluated as defective.
  • Each immersion exposure film-forming composition (PR) was spin-coated on an 8-inch silicon wafer, and SB was performed at 110 ° C. for 60 seconds to form a resist film having a thickness of 110 nm. Then, using a developing device (Clean Track ACT8, manufactured by Tokyo Electron), developed with a 2.38 mass% TMAH aqueous solution for 30 seconds, rinsed with pure water for 15 seconds, shaken and dried at 2,000 rpm, and then the resist pattern receded.
  • the contact angle was defined as “after development” in Table 4. The receding contact angle after development can be evaluated as good when it is less than 10 °, and as poor when it is 10 ° or more.
  • a lower antireflection film is formed on a 12-inch silicon wafer using an antireflection film forming composition (ARC66, manufactured by Nissan Chemical Industries), and each immersion exposure film forming composition (PR ) And spin-coated at 110 ° C. for 60 seconds to form a resist film having a thickness of 110 nm.
  • ARC66 antireflection film forming composition
  • PR immersion exposure film forming composition
  • development defects on the development defect inspection wafer were measured using a development defect inspection apparatus (KLA2810, manufactured by KLA-Tencor). After classifying the measured development defects into those derived from resist and foreign matter derived from the outside, the total number of those determined to be derived from resist is totaled. When this value is 50 / wafer or less, the development defect suppression is good. In the case of more than 50 / wafer, it can be evaluated as defective.
  • KLA2810 manufactured by KLA-Tencor
  • Example 4 the receding contact angle was good both after SB and after development, whereas in Comparative Example, at least one after SB and after development was poor. In addition, the development defect suppression property was good in the examples, whereas all of the comparative examples were bad.
  • Each film forming composition (TC) for immersion exposure is spin-coated on an 8-inch silicon wafer with CLEAN TRACK ACT8 (manufactured by Tokyo Electron), SB is performed at 90 ° C. for 60 seconds, and an immersion upper layer having a film thickness of 90 nm A film was formed.
  • the film thickness was measured using Lambda Ace VM90 (Dainippon Screen).
  • the liquid immersion upper layer film was subjected to paddle development for 60 seconds using a 2.38 mass% TMAH aqueous solution, spin-dried by shaking, and the wafer surface was observed. At this time, if there was no residue and it was developed, the solubility in the developer was “A (good)”, and if the residue was observed, it was evaluated as “B (bad)”.
  • Each immersion exposure film-forming composition (TC) was spin-coated on an 8-inch silicon wafer, and subjected to SB at 90 ° C. for 60 seconds on a hot plate to form an immersion upper film having a thickness of 30 nm. Thereafter, using DSA-10 (manufactured by KRUS), the receding contact angle (°) was promptly measured in an environment of 23 ° C., humidity 45%, and normal pressure. That is, the wafer stage position of DSA-10 was adjusted, and the wafer was set on the adjusted stage. Next, water was injected into the needle, and the position of the needle was finely adjusted to an initial position where water droplets could be formed on the set wafer.
  • a composition for a lower antireflection film (ARC29A, manufactured by Brewer Science) was applied in advance so as to form a lower antireflection film having a film thickness of 77 nm using CLEAN TRACK ACT8.
  • the prepared photoresist composition ( ⁇ ) was spin-coated on the lower antireflection film, and SB was performed at 115 ° C. for 60 seconds to form a resist film having a thickness of 205 nm.
  • membrane formation composition (TC) for immersion exposure was apply
  • the liquid immersion upper layer side was stacked so as to come into contact with the ultrapure water in the silicon rubber sheet of the prepared wafer, and kept in that state for 10 seconds. Thereafter, ultrapure water was collected with a glass syringe and used as a sample for analysis. The recovery rate of ultrapure water after the evaluation was 95% or more.
  • the peak intensity of the anion part of the acid generator in ultrapure water was measured using LC-MS (liquid chromatograph mass spectrometer, LC part: SERIES1100 manufactured by AGILENT, MS part: Mariner manufactured by Perseptive Biosystems, Inc.) as follows. Measured under measurement conditions.
  • the peak intensity of the 1 ppb, 10 ppb, and 100 ppb aqueous solutions of the acid generator was measured under the following measurement conditions to prepare a calibration curve, and the elution amount was calculated from the peak intensity using the calibration curve.
  • each peak intensity of the 1 ppb, 10 ppb, and 100 ppb aqueous solutions of the acid diffusion control agent is measured under the following measurement conditions to create a calibration curve, and the calibration curve is used to calculate the acid diffusion control agent from the peak intensity. The amount of elution was calculated.
  • the elution suppression performance of the photoresist composition was “A (good)”, at least one of which was 5.0 ⁇ 10 ⁇ When it was larger than 12 mol / cm 2 , it was evaluated as defective “B (defective)”.
  • Ultrapure water was discharged from a rinse nozzle of CLEAN TRACK ACT8 on the immersion upper layer film for 60 seconds, and spin drying was performed by shaking off at 4,000 rpm for 15 seconds.
  • paddle development was performed with an LD nozzle for 30 seconds to remove the liquid immersion upper layer film.
  • TMAH aqueous solution was used as a developer.
  • KLA2351 manufactured by KLA Tencor
  • a 12-inch silicon wafer surface was spin-coated with a lower antireflection film (ARC66, manufactured by Nissan Chemical Co., Ltd.) using a coating apparatus (Lithius Pro-i, manufactured by Tokyo Electron), and then SB (205 ° C., 60 seconds). As a result, a lower antireflection film having a film thickness of 105 nm was formed.
  • the photoresist composition ( ⁇ ) prepared above is spin-coated using CLEAN TRACK ACT12, SB is performed at 100 ° C. for 60 seconds, and cooled at 23 ° C. for 30 seconds to form a resist film having a thickness of 100 nm. did.
  • membrane formation composition (TC) for immersion exposure was apply
  • an ArF immersion exposure apparatus S610C, manufactured by NIKON
  • the dimension of the pattern projected by the mask is referred to as the “pattern dimension.”
  • a mask having a pattern dimension of 40 nm line / 84 nm pitch is a mask for projecting a pattern of 40 nm line / 84 nm pitch.
  • PEB is performed on the hot plate of the coating apparatus at 100 ° C.
  • each film forming composition (TC) for immersion exposure is spin-coated with the CLEAN TRACK ACT8, and then SB is performed at 90 ° C. for 60 seconds to form an immersion upper layer film having a thickness of 30 nm. Formed. Thereafter, rinsing with pure water was performed for 60 seconds in CLEAN TRACK ACT8, and drying by shaking was performed. “C (defect)” when peeling is observed at the center after rinsing by visual inspection, “B (somewhat good)” when peeling is observed only at the edge, and “A” when no peeling is observed. (Good) ”.
  • each immersion exposure film-forming composition (TC) was spin-coated, and SB (90 ° C., 60 seconds) was performed to form an immersion upper layer film having a thickness of 30 nm.
  • SB 90 ° C., 60 seconds
  • exposure was performed through a mask for projecting a pattern of 45 nm line / 90 nm pitch.
  • PEB is performed on the hot plate of the coating apparatus at 100 ° C. for 60 seconds, cooled at 23 ° C. for 30 seconds, and then paddle developed with a 2.38 mass% TMAH aqueous solution as a developer at the GP nozzle of the developing cup. For 10 seconds and rinsed with ultrapure water.
  • An evaluation substrate on which a resist pattern was formed was obtained by spin-drying at 2,000 rpm for 15 seconds.
  • the exposure amount for forming a line-and-space pattern (1L1S) having a line width of 90 nm in a one-to-one line width was determined as the optimum exposure amount.
  • a scanning electron microscope CG-4000, manufactured by Hitachi Instruments
  • S-4800 manufactured by Hitachi Keiki Co., Ltd.
  • the present invention can be used as a photoresist composition or the like to give a large receding contact angle to the surface of the resist film or the liquid immersion upper film during the liquid immersion exposure process in the liquid immersion exposure process, and to suppress development defects.
  • a composition for forming a liquid immersion upper layer film a resist pattern having a better shape can be formed. Therefore, the film-forming composition, polymer and compound for immersion exposure can be suitably used for a manufacturing process in a semiconductor device that is further miniaturized, and the product quality and productivity in the immersion exposure process can be improved. Can be improved.

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  • Polymers & Plastics (AREA)
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  • Photosensitive Polymer And Photoresist Processing (AREA)

Abstract

La présente invention concerne une composition de résine photosensible d'exposition par immersion contenant un solvant et un constituant polymère contenant à la fois un polymère (a1) possédant une unité structurelle représentée dans la formule (1) et un polymère (a2) ayant une teneur en atomes de fluor inférieure à celle du polymère (a1). Dans la formule (1), R1 est un groupe dissociable sous l'action d'un alcali. A est -CO-O-*, -O-, -NRA- ou -SO2-O-*. X est un groupe hydrocarbure divalent ayant un nombre d'atomes de carbone de 1 à 20 ou un groupe hydrocarbure fluoré divalent ayant un nombre d'atomes de carbone de 1 à 20.
PCT/JP2013/059752 2012-03-30 2013-03-29 Composition de résine photosensible d'exposition par immersion, polymère et composé WO2013147266A1 (fr)

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JP2016099482A (ja) * 2014-11-20 2016-05-30 Jsr株式会社 感放射線性樹脂組成物及びレジストパターン形成方法
JP2017214580A (ja) * 2017-06-09 2017-12-07 Jsr株式会社 樹脂組成物、レジストパターン形成方法、重合体及び化合物
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JP6304347B2 (ja) * 2016-11-10 2018-04-04 Jsr株式会社 樹脂組成物及びレジストパターン形成方法
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JP2014044414A (ja) * 2012-08-01 2014-03-13 Sumitomo Chemical Co Ltd レジスト組成物及びレジストパターンの製造方法
JP2016099482A (ja) * 2014-11-20 2016-05-30 Jsr株式会社 感放射線性樹脂組成物及びレジストパターン形成方法
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JP7421195B2 (ja) 2018-06-22 2024-01-24 ダイキン工業株式会社 含フッ素化合物の製造方法

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