WO2006077705A1 - Composition de photoresine positive et procede de formation de motif en photoresine - Google Patents

Composition de photoresine positive et procede de formation de motif en photoresine Download PDF

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Publication number
WO2006077705A1
WO2006077705A1 PCT/JP2005/023154 JP2005023154W WO2006077705A1 WO 2006077705 A1 WO2006077705 A1 WO 2006077705A1 JP 2005023154 W JP2005023154 W JP 2005023154W WO 2006077705 A1 WO2006077705 A1 WO 2006077705A1
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Prior art keywords
group
component
structural unit
alkyl group
acid
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PCT/JP2005/023154
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English (en)
Japanese (ja)
Inventor
Yohei Kinoshita
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Tokyo Ohka Kogyo Co., Ltd.
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Priority claimed from JP2005010051A external-priority patent/JP4191145B2/ja
Priority claimed from JP2005012053A external-priority patent/JP2006201402A/ja
Application filed by Tokyo Ohka Kogyo Co., Ltd. filed Critical Tokyo Ohka Kogyo Co., Ltd.
Publication of WO2006077705A1 publication Critical patent/WO2006077705A1/fr

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Classifications

    • 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
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate

Definitions

  • the present invention relates to a positive resist composition and a resist pattern forming method.
  • Such a resist for a short wavelength light source is required to have high resolution capable of reproducing a pattern with a fine dimension and high sensitivity to such a short wavelength light source.
  • a chemically amplified resist containing a base resin and an acid generator (PAG) that generates acid upon exposure is known.
  • PAG acid generator
  • Patent Document 1 describes PAGs composed of triphenylsulfonium onium salts, and among them, fluorinated compounds such as triphenylsulfonium nonafluorobutanesulfonate (TPS-PFBS).
  • TPS-PFBS triphenylsulfonium nonafluorobutanesulfonate
  • Onium salt acid generators that use an alkyl sulfonate ion as an anion are the most commonly used.
  • Patent Document 1 Japanese Patent Laid-Open No. 2003-167347
  • the present invention has been made in view of the above circumstances, and provides high resolution.
  • the present invention employs the following configuration.
  • the first aspect (aspect) of the present invention is a positive resist composition, which comprises a resin component (A) whose alkali solubility is increased by the action of an acid, and an acid generator that generates an acid upon exposure.
  • a lower alkyl group, a fluorine atom or a fluorinated lower alkyl group having 1 to 5 carbon atoms; and R 2 each independently represents a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms.
  • Group power consisting of
  • Replacement paper At least one structural unit (al), and
  • the component (B) is represented by the following general formula (b-1)
  • R represents an aralkyl group, an alkoxy group, a halogen atom, or a hydroxyl group
  • R 1 and R 13 each independently represents an optionally substituted aryl group or alkyl group
  • n ′ represents 0 or an integer of 1 to 3 is represented.
  • the second aspect of the present invention includes a step of forming a resist film on a substrate using the positive resist composition of the first aspect of the present invention, a step of exposing the resist film, and A resist pattern forming method including a step of developing the resist film to form a resist pattern is provided.
  • a third aspect of the present invention is a positive resist composition
  • a resin component (A) whose alkali solubility is increased by the action of an acid and an acid generator component (B) which generates an acid upon exposure.
  • the component (A) is a structural unit represented by the following general formula (al-01) and a structural unit represented by the following general formula (a 1 02)
  • Y represents an aliphatic cyclic group
  • n represents 0 or an integer of 1 to 3
  • m represents 0 or 1
  • R independently represents a hydrogen atom or a carbon number of 1 to 5
  • R 1 R 2 independently represents a hydrogen atom or a carbon number :! Represents a lower alkyl group of ⁇ 5.
  • the component (B) is represented by the following general formula (b-3) or (b-4)
  • X represents a C 2-6 alkylene group in which at least one hydrogen atom is substituted with a fluorine atom; ⁇ ", ⁇ "each independently represents at least one hydrogen atom is fluorine.
  • the fourth aspect of the present invention includes a step of forming a resist film on a substrate using the positive resist composition of the third aspect of the present invention, a step of exposing the resist film, and the resist film
  • a resist pattern forming method including a step of developing the resist pattern to form a resist pattern
  • a positive resist composition and a resist pattern forming method capable of obtaining high resolution and improving D0F.
  • the "structural unit” in the claims and the specification means a monomer unit constituting a resin.
  • the “structural unit derived from acrylate ester force” in the claims and the specification means a structural unit formed by cleavage of an ethylenic double bond of an acrylate ester.
  • a structural unit derived from an acrylate ester refers to a structural unit in which a hydrogen atom bonded to a carbon atom at the ⁇ -position is substituted with another substituent such as a halogen atom, an alkyl group, or a halogenated alkyl group.
  • Acrylic ester in which a hydrogen atom is bonded to the carbon atom at the position.
  • spot (a carbon atom at the platter) refers to the carbon atom to which the carboxy group is bonded, unless otherwise specified. That is.
  • alkyl group includes a linear, cyclic or branched alkyl group unless otherwise specified.
  • the positive resist composition of the present invention contains the resin component ( ⁇ ) (hereinafter sometimes referred to as the ( ⁇ ) component) and an acid generator (hereinafter referred to as “acid generator”) that generates an acid upon irradiation (exposure) of radiation. ( ⁇ ) component)).
  • ⁇ resin component
  • acid generator an acid generator that generates an acid upon irradiation (exposure) of radiation.
  • the component (ii) Since the component (ii) has a structural unit (al) having an acid dissociable, dissolution inhibiting group, it is insoluble in alkali before exposure. When the acid generated from the component (B) by exposure acts, The inhibitory group is dissociated, and as a result, the entire component (A) is alkali-insoluble to alkali-soluble. Therefore, in the formation of a resist pattern, if selective exposure is performed on the resist, or if post-exposure heating (PEB) is performed in addition to exposure, the exposed portion turns to alkali-soluble, while the unexposed portion becomes alkaline. It remains insoluble and does not change A positive resist pattern can be formed by alkali development.
  • PEB post-exposure heating
  • Component (A) is at least one structural unit selected from the group consisting of the structural unit represented by the general formula (al-01) and the structural unit represented by the general formula (al-02) (al )
  • the structural unit (al) is a structural unit derived from the acrylate force, and is bonded to the oxygen atom at the terminal of the carbonyloxy group (C ( ⁇ ) —O—) derived from the carboxy group. It has a structure in which an (alkoxyalkyl group) type acid dissociable, dissolution inhibiting group [CO ⁇ R 2 ) — ⁇ — (CH 2 ) Y] is bonded. Therefore, when acid acts, the acid dissociation property
  • the bond is cleaved between the dissolution inhibiting group and the terminal oxygen atom.
  • R is a hydrogen atom, a lower alkyl group having carbon atoms:! To 5, a fluorine atom, or a fluorinated lower alkyl group having 1 to 5 carbon atoms.
  • the fluorinated lower alkyl group is a group in which part or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms, and any of them may be used, but it is preferable that all are fluorinated.
  • Preferred examples of the lower alkyl group as R include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n -butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. It is done. Industrially, a methyl group is preferable.
  • the fluorinated lower alkyl group having 1 to 5 carbon atoms is preferably a trifluoromethyl group such as a trifluoromethyl group, a hexafluoroethyl group, a heptafluoropropyl group, or a nonafluorobutyl group. More preferred.
  • R 1 R 2 is preferably at least one hydrogen atom, more preferably a hydrogen atom.
  • n is preferably 0 or 1, more preferably 0.
  • Y is an aliphatic cyclic group, which may or may not have a substituent on the ring skeleton.
  • aliphatic in the claims and the specification means relative to aromatics. It is defined as a concept that means a group, a compound, or the like that does not have aromaticity.
  • Aliphatic cyclic group means a monocyclic or polycyclic group having no aromaticity.
  • the basic ring structure excluding the substituent of the “aliphatic cyclic group” in the present invention is not limited to a group consisting of carbon and hydrogen (hydrocarbon group). It is preferable that The “hydrocarbon group” may be either saturated or unsaturated, but is usually preferably saturated. A polycyclic group is preferred.
  • Such an aliphatic cyclic group include a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane. Can be illustrated.
  • monocycloalkanes such as cyclopentane and cyclohexane
  • groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. It is done.
  • Y is particularly preferably a group obtained by removing one or more hydrogen atoms from adamantane (which may have a substituent).
  • the substituent is preferably a polar group, particularly in order to suppress pattern collapse.
  • the structural unit (al) is selected from the group consisting of the structural unit represented by the general formula (al-01) and the structural unit represented by the general formula (al_02). Two or more species may be used.
  • the structural unit (al) preferably includes the structural unit represented by the general formula (al_01) from the viewpoint of resolution.
  • the proportion of the structural unit represented by the general formula (al-01) in (al) is preferably 50 mol% or more, and more preferably 80 mol% or more. Most preferably, it is mol%.
  • (A) the amount of the structural during component unit (al) is, (A) relative to all the structural units within the component, 1 0-80 Monore 0/0 force S Preferably, 20-70 Monore 0/0 force more preferably S, 25 ⁇ 50 Monore 0/0 force further good better record,.
  • the component (A) preferably has a structural unit (a2) derived from an acrylate ester having a latathone-containing monocyclic or polycyclic group.
  • the lathetone-containing monocyclic or polycyclic group of the structural unit ( a2 ) is used to enhance the adhesion of the resist film to the substrate or to have an affinity for the developer when the component (A) is used for forming the resist film. It is effective for improving the sex.
  • the ratatone-containing monocyclic or polycyclic group refers to a cyclic group containing one ring (lataton ring) containing a -o-c (o) structure.
  • the rataton ring is counted as the first ring, and when it is a lactone ring alone, it is called a monocyclic group, and when it has another ring structure, it is called a polycyclic group regardless of its structure.
  • any unit can be used without any particular limitation as long as it has both such a rataton structure (one O—C (O) —) and a cyclic group.
  • examples of the latatatone-containing monocyclic group include groups in which one hydrogen atom has been removed from y-peptite latatatone.
  • examples of the latathone-containing polycyclic group include groups in which a bicycloalkane, tricycloalkane or tetracycloalkane having a latathone ring is removed.
  • a group obtained by removing one hydrogen atom from a latathone-containing tricycloalkane having the following structural formula is advantageous in that it is easily available industrially.
  • examples of the structural unit (a2) include structural units represented by the following general formulas (a2_ :! to (a2_5).
  • R is the same as defined above, R ′ each independently represents a hydrogen atom, a lower alkyl group, or an alkoxy group having 1 to 5 carbon atoms, and m is 0 or 1.
  • R ′ is preferably a hydrogen atom in view of industrial availability.
  • the structural unit (a2) it is preferable to use at least one selected from the general formulas (a2— :!) to (a2-5) general formulas (a2—l) to (a2-3) force selections It is more preferable to use one or more of these.
  • chemical formulas (a2-1-1), (a2-1-2), (a2-2-1), (a2-2-2), (a2-3-1), (a2-3-0) It is preferable to use one or more selected from (a2-3-9) and (a2-3-10).
  • component (A) As structural unit (a2), one type may be used alone, or two or more types may be used in combination.
  • the content of the structural unit (a2) is preferably 10 to 80 mol% with respect to the total of all the structural units in the component (A). 50 Monore 0/0 and more preferably fixture 25 to 50 mol% is more preferred. By setting it to the lower limit value or more, the effect of containing the structural unit (a2) can be sufficiently obtained, and by setting the upper limit it or less, it is possible to balance with other structural units.
  • the component (A) is preferably a copolymer having the structural units (al) and (a2).
  • the structural unit (a3) is a structural unit other than the structural unit (al) and the structural unit (a2), includes an aliphatic cyclic group-containing non-acid dissociable, dissolution inhibiting group, and does not include a polar group.
  • Acrylic ester force is a structural unit derived.
  • An aliphatic cyclic group-containing non-acid dissociable, dissolution inhibiting group is a group having an aromaticity, a cyclic group (aliphatic cyclic group), and generated from the component (B). This is a non-acid dissociable, dissolution inhibiting group that cannot be dissociated by acid.
  • the structural unit (a3) for example, a unit in which the aliphatic cyclic group-containing non-acid dissociable, dissolution inhibiting group is bonded to the ester portion of an acrylate ester can be mentioned.
  • the structural unit (a3) reduces the alkali solubility of the entire component (A) before exposure, and is not dissociated by the action of an acid generated from the component (B) after exposure.
  • Acid dissociable, dissolution-inhibiting group (A) When the entire component (A) is changed to alkali-soluble, the group (A) has a solubility-suppressing property that reduces the alkali-solubility of the entire component to the extent that it does not become insoluble in alkali.
  • the structural unit (a 3) has a function of suppressing the alkali solubility by increasing the hydrophobicity of the entire component (A) before and after exposure. Specifically, it is a structural unit that can improve (improve hydrophobicity) the contact angle for pure water rinse after PEB (post-exposure heat treatment).
  • the structural unit (a3) needs to contain no polar group.
  • the polar group includes a hydroxyl group, a cyano group, a carboxy group, a “hydroxyalkyl group in which a part of the hydrogen atoms of the alkyl group are replaced by fluorine atoms”, and the like.
  • the structural unit (a3) preferably does not contain an acid dissociable, dissolution inhibiting group.
  • the structural unit (a3) is preferably the following general formula (a3)
  • R is the same as defined above.
  • Z represents an aliphatic cyclic group having 4 to 15 carbon atoms in the basic ring, which may have 1 to 3 alkyl groups having 1 to 10 carbon atoms. ] Is a structural unit.
  • Z is an aliphatic cyclic group (which may be monocyclic or polycyclic) having 4 to 15 carbon atoms in the basic ring (ring structure excluding a substituent), and the aliphatic cyclic group
  • the group is an alkyl group having 1 to 10 carbon atoms and 1 to 10
  • the alkyl group is an alkyl group having 1 to 10 carbon atoms, and a linear or branched alkyl group having 1 to 5 carbon atoms is particularly preferable. Examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a pentyl group, an isopentyl group, and a neopentyl group.
  • the number of the alkyl group is preferably 0 or 1, and more preferably 0.
  • the structural unit (a3) does not overlap with the structural unit (al) and the structural unit (a2). That is, a specific acid dissociable, dissolution inhibiting group in the structural unit (al), and a rataton-containing group in the structural unit (a2), and the same group, and no deviation.
  • the cyclic group constituting the basic skeleton of the aliphatic cyclic group is a monocyclic or polycyclic aliphatic cyclic group conventionally known as an ArF positive resist material. It can be used.
  • Examples of the monocyclic aliphatic cyclic group include groups in which one or more hydrogen atoms have been removed from a monocycloalkane such as cyclohexane or cyclopentane.
  • polycyclic aliphatic cyclic group examples include groups in which one or two or more hydrogen atoms have been removed from a polycycloalkane such as a bicycloalkane, tricycloalkane, or tetracycloalkane. Specific examples include groups in which one or two or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
  • a cyclohexyl group, a cyclopentyl group, an adamantyl group, a norbornyl group, an isobornyl group, a tricyclodecanyl group, and a tetracyclododecanyl group are preferred from the viewpoint of industrial availability.
  • the structural unit represented by the general formula (a3_l) is preferable because the shape of the obtained resist pattern, for example, rectangularity is particularly good. Further, it is preferable from the viewpoint of suppressing pattern collapse. [0050]
  • the structural unit (a3) one type may be used alone, or two or more types may be used in combination.
  • the content of structural unit (a3) is preferably 3 to 50 mol% with respect to the total of all structural units of component (A). More preferred is 15-30 mol%.
  • the component (A) further includes a structural unit (a4) derived from an acrylate ester containing a polar group-containing aliphatic hydrocarbon group. It ’s okay.
  • the structural unit (a4) By having the structural unit (a4), the hydrophilicity of the component (A) is increased, the affinity with the developer is increased, the alkali solubility in the exposed area is improved, and the resolution is improved.
  • the polar group include a hydroxyl group, a cyano group, a carboxy group, and a “hydroxyalkyl group in which a part of the hydrogen atom of the alkyl group is substituted with a fluorine atom”, and a hydroxyl group is particularly preferable.
  • aliphatic hydrocarbon group a linear or branched hydrocarbon group having 1 to 10 carbon atoms (preferably an alkylene group) or a polycyclic aliphatic hydrocarbon group (polycyclic group).
  • polycyclic group for example, a resin for resist compositions for ArF excimer lasers, and many proposed ones can be appropriately selected and used.
  • the structural unit is more preferable.
  • the polycyclic group include groups in which one or more hydrogen atoms have been removed from bicycloalkane, tricycloalkane, tetracycloalkane, or the like.
  • Specific examples include groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane.
  • a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane.
  • Such polycyclic groups can be used by appropriately selecting from among many proposed polymers (resin components) for resist compositions for ArF excimerizers.
  • two or more hydrogen atoms are removed from adamantane and two or more hydrogen atoms are removed from norbornane.
  • a group obtained by removing two or more hydrogen atoms from tetracyclododecane is preferred industrially.
  • the structural unit (a4) when the hydrocarbon group in the polar group-containing aliphatic hydrocarbon group is a linear or branched hydrocarbon group having 1 to 10 carbon atoms, the hydroxy group of acrylic acid is used. Preferred structural unit derived from tilester force When the hydrocarbon group is a polycyclic group, a structural unit represented by the following formula (a4-1), a structural unit represented by (a4-2), The structural unit represented by (a4-3) is preferred.
  • j is preferably 1 or 2, and more preferably 1; When j is 2, it is preferable that the hydroxyl group is bonded to the 3rd and 5th positions of the adamantyl group. When j is 1, it is preferable that the hydroxyl group is bonded to the 3-position of the adamantyl group.
  • j is preferably 1, and it is particularly preferred that the hydroxyl group is bonded to the 3-position of the adamantyl group.
  • k is preferably 1.
  • the Ciano group is the 5-position of the norbornyl group or
  • t ' is preferably 1. Les, preferably 1 is 1.
  • Each s is preferably 1.
  • a bornyl group or a 3_norbornyl group is preferred.
  • the fluorinated alkyl alcohol is preferably bonded to the 5th or 6th position of the norbornyl group.
  • one type may be used alone, or two or more types may be used in combination.
  • component (A) has structural unit (a4)
  • the content of structural unit (a4) in component (A) is 5 to 50 mol% with respect to all structural units in component (A). it is preferably 15 to 45 Monore 0/0 to gesture et preferred, most preferably 15 to 35 Monore 0/0.
  • the conventional chemical amplification type other than the structural units (al) to (a4) can be used as long as the effects of the present invention are not impaired.
  • Used as a di-type resist for the production of acrylic acid derivatives, methacrylic acid derivatives, carboxylic acids having ethylenic double bonds to make them alkali-soluble, such as acrylic acid, metathallic acid, maleic acid, and fumaric acid, and acrylic resins The known monomers and the like can be used in combination as appropriate and copolymerized as necessary.
  • the component (A) is obtained, for example, by polymerizing a monomer related to each structural unit by a known radical polymerization using a radical polymerization initiator such as azobisisobutyronitrile (AIB N). be able to.
  • a radical polymerization initiator such as azobisisobutyronitrile (AIB N).
  • component (A) contains, for example, HS—CH 2 —CH 2 —CH _C (CF
  • 3 2 3 2 groups may be introduced.
  • copolymers introduced with hydroxyalkyl groups in which some of the hydrogen atoms in the alkyl group have been replaced with fluorine atoms reduce development defects and LER (Line Edge Roughness: uneven unevenness on the line sidewalls). ).
  • the mass average molecular weight (Mw) of the component (A) is not particularly limited, but preferably 3000 to 50000, more preferably 3000 to 30000 force ⁇ 5,000 to 20000 most preferred.
  • the dispersity (Mw / Mn) of the component (A) is preferably 1.0 to 5.0 force S, more preferably 1.0 to 3.0, and most preferably 1.0 to 2.5.
  • the onion salt acid generator (B1) having a cation moiety represented by the general formula (b_l) is used as an essential component as the component (B). .
  • R 11 represents an aralkyl group, an alkoxy group, a halogen atom, or a hydroxyl group, and n represents 0 or an integer of 1 to 3.
  • n ′ is 2 or 3
  • the plurality of R 11 may be the same as or different from each other.
  • the alkyl group as R 11 is most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group, preferably an alkyl group having 1 to 5 carbon atoms.
  • the alkoxy group as R 11 is most preferably a methoxy group or an ethoxy group, preferably an alkoxy group having 1 to 5 carbon atoms.
  • the halogen atom as R 11 is preferably a fluorine atom.
  • N ′ is preferably 0 or 1, more preferably 1.
  • R 12 and R 13 each independently represents a substituent, aryl group or alkyl group, although they may have a substituent.
  • the aryl group as R 12 and R 13 is not particularly limited, for example, an aryl group having 6 to 20 carbon atoms, and the aryl group has an alkyl group, an alkoxy group, a part or all of the hydrogen atoms of which are It may not be substituted with a halogen atom, a hydroxyl group or the like.
  • an aryl group having 6 to 10 carbon atoms is preferable because it can be synthesized at a low cost. Specific examples include a phenyl group and a naphthyl group.
  • the alkyl group as the substituent is the same as the alkyl group as R 11 .
  • the alkoxy group as the substituent is the same as the alkoxy group as R 11 .
  • the child is the same as the halogen atom as R 11 .
  • the alkyl group as 2 and R 13 is not particularly limited, and examples thereof include linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms. From the viewpoint of excellent resolution, it is preferable that the carbon number is 1 to 5. Specifically, a methinore group, an ethyl group, an n-propyl group, an isopropyl group, an n_butyl group, an isobutyl group, an n_pentyl group, a cyclopentyl group, a hexinole group, a cyclohexinole group, a noninore group, a decanyl group A methyl group is preferable because it is excellent in resolution and can be synthesized at low cost. Most preferably, the 2 and R 13 are both phenyl groups.
  • the anion part in the component (B1) is not particularly limited, and what is known as an anion part of an onion salt-based acid generator can be appropriately used.
  • R M S_ ⁇ _ R 14 is a linear, branched or cyclic alkyl group or fluorinated
  • R M is also linear, branched or cyclic alkyl group
  • the linear or branched alkyl group as R 14 has 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. preferable.
  • the cyclic alkyl group as R 14 is the cyclic alkyl group shown as 2 or R 13 , and preferably has 4 to 15 carbon atoms, preferably 4 to 10 carbon atoms. Even better Most preferably, it is 6 to 10 carbon atoms.
  • the fluorinated alkyl group as R 14 has 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. Also.
  • the fluorination rate of the fluorinated alkyl group (ratio of the number of fluorine atoms substituted by fluorination to the total number of hydrogen atoms in the alkyl group before fluorination, the same shall apply hereinafter) is preferably 10 to 100% More preferably, it is 50 to 100%, and in particular, all hydrogen atoms replaced with fluorine atoms are preferred because the strength of the acid becomes strong.
  • R 14 is most preferably a linear or cyclic alkyl group or a fluorinated alkyl group.
  • X ′′ is a linear or branched alkylene group in which at least one hydrogen atom is replaced with a fluorine atom, and the alkylene group has 2 carbon atoms. -6, preferably 3-5 carbon atoms, most preferably 3 carbon atoms.
  • Y ′′ and ⁇ ′′ are each independently a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkyl group
  • the number of carbons is 1 to: 10, preferably the number of carbons:! To 7, more preferably 1 to 3.
  • the carbon number of the alkylene group of X ′′ or the carbon number of the alkyl group of “ ⁇ ⁇ ⁇ ⁇ ” and “ ⁇ ” is preferably as small as possible within the range of the above-mentioned carbon number for reasons such as good solubility in a resist solvent.
  • the fluorination rate is preferably 70 to 100%, more preferably 90 to 100%, and most preferably a perfluoroalkylene group or a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms. .
  • anion part of the component (B1) an anion part represented by the general formula (b_3) is preferable.
  • X is more preferably a perfluoroalkylene group.
  • the acid generator represented by the chemical formula (bl-07) or (bl-08) is particularly preferable.
  • any of four types may be used. Two or more types may be used in combination.
  • the proportion of the component (B1) in the total component (B) is preferably 50% by mass or more. A more preferable range is 60 to 90% by mass, and 70 to 85% by mass is most preferable.
  • the component (B) preferably contains an acid generator (B2) represented by the following general formula (b-2) in addition to the component (B1).
  • B2 does not overlap with the component (B1). That is, the cation part of the component (B2) does not have “substituent, may, or naphthyl group”.
  • R 4 ′′ represents a linear, branched or cyclic alkyl group or a fluorinated alkyl group; 1 ⁇ ′′ to 1 3 ′′ may each independently have a substituent. Represents a good aryl group or an alkyl group, and at least one of 1 ⁇ "to" represents an aryl group.
  • 1 ⁇ "to 1 ⁇ ” each independently represents an aryl group or an alkyl group which may have a substituent. However! ⁇ 1 When ” ⁇ ! ⁇ ” Is an aryl group, the naphthyl group is excluded.
  • the aryl group as “ ⁇ ” is not particularly limited as long as it is other than a naphthyl group.
  • the aryl group is preferably an aryl group having 6 to 10 carbon atoms because it can be synthesized at low cost. Specifically, a phenyl group is mentioned, for example.
  • the alkyl group as a substituent of the hydrogen atom of the aryl group is a methinole group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group, which is preferably an alkyl group having from 5 to 5 carbon atoms. Most preferred.
  • the alkoxy group as a substituent for the hydrogen atom of the aryl group is most preferably a methoxy group or an ethoxy group, preferably an alkoxy group having from 5 to 5 carbon atoms.
  • the halogen atom as a substituent for the hydrogen atom of the aryl group is preferably a fluorine atom.
  • the alkyl group as ⁇ " ⁇ " is not particularly limited, and examples thereof include linear, branched or cyclic alkyl groups having carbon numbers:! -10. From the viewpoint of excellent resolution, it is preferably 1 to 5 carbon atoms. Specifically, methylol group, ethyl group, n-propyl group, isop Lopinole group, n_butyl group, isobutyl group, n_pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, noninole group, decanyl group, etc. are listed, and it has excellent resolution and can be synthesized at low cost. Among them, a methyl group can be mentioned as a preferred one.
  • R 4 represents a linear, branched or cyclic alkyl group or fluorinated alkyl group.
  • the linear or branched alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms.
  • the cyclic alkyl group is a cyclic group as indicated by R 1 ′′, and preferably has 4 to 10 carbon atoms, more preferably 4 to 10 carbon atoms. Most preferably, it has 6 to 10 carbon atoms.
  • the fluorinated alkyl group is most preferably 1 to 4 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. Also.
  • the fluorination rate of the fluorinated alkyl group is preferably 10 to 100%, more preferably 50 to 100%.
  • the one in which all hydrogen atoms are substituted with fluorine atoms has a strong acid strength. This is preferable.
  • R 4 ′′ is most preferably a linear or cyclic alkyl group or a fluorinated alkyl group.
  • component (B2) include trifluoromethane sulfonate of triphenylsulfone, heptafluoropropane sulfonate or nonafluorobutane sulfonate, tri (4-methylphenol).
  • onium salts in which the anion portion of these onium salts is replaced with methanesulfonate, n-propanesulfonate, n-butanesulfonate, or n-octanesulfonate can be used.
  • any of four types of forces may be used, or two or more types may be used in combination.
  • the proportion of the component (B2) in the total component (B) is preferably 10 to 40% by mass, and 15 to 30% by mass is more preferably 15 to 25% by mass. Is most preferred.
  • the component (B) further contains a known acid generator (hereinafter sometimes referred to as other acid generator (B3)) used in a chemically amplified resist composition.
  • a known acid generator hereinafter sometimes referred to as other acid generator (B3)
  • the total ratio of the component (B1) and the component (B2) in the whole component (B) is 80% by mass or more. Is more preferable.
  • Other acid generators (B3) include onium salt acid generators (B1) and (B2) other than the above-mentioned acid salt acid generators (for example, odonium salts), and oxime sulfonate acid generators.
  • Lj bisalkyl or bisarylsulfonyldiazomethanes, poly (bissulfonyl) diazomethanes and other diazomethane acid generators, nitrobenzyl sulfonate acid generators, iminosulfonate acid generators, disulfone Known acid generators such as acid generators can be used as appropriate.
  • an onium salt acid generator (B4) having an anion moiety represented by the general formula (b_3) or (b-4) as the component (B) Is used as an essential ingredient is used as an essential ingredient.
  • X ′′ is a linear or branched alkylene group in which at least one hydrogen atom is replaced with a fluorine atom, and the alkylene group has 2 to 2 carbon atoms. 6, preferably 3 to 5 carbon atoms, most preferably 3 carbon atoms.
  • Y ′′ and ⁇ ′′ are each independently a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and the number of carbon atoms of the alkyl group Is 1 to: 10, preferably carbon numbers:! To 7, more preferably 1 to 3 carbon atoms.
  • the carbon number of the alkylene group of X ′′ or the carbon number of the alkyl group of “ ⁇ ⁇ ⁇ ⁇ ” and “ ⁇ ” is preferably as small as possible within the range of the above-mentioned carbon number for reasons such as good solubility in a resist solvent.
  • the fluorination rate is preferably 70 to 100%, more preferably 90 to 100%, and most preferably a perfluoroalkylene group or a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms. .
  • anion part of the component ( ⁇ 4) an anion part represented by the general formula (b-3) is preferable.
  • the cation moiety in the component (B4) is not particularly limited, and what is known as an anion moiety of an onion salt-based acid generator can be appropriately used.
  • R n to R lj and R 15 to R 16 each independently represent an aryl group or an alkyl group; at least one of R ′′ to R 13 represents an aryl group, R 15 to R At least one of 16 represents an aryl group.
  • R ′′ to R 13 each independently represents an aryl group or an alkyl group. Among these, at least one represents an aryl group. Of RU to R ld , two or more are preferably aryl groups. Most preferably, all of R U to R 13 are aryl groups. .
  • the aryl group of RU R 13 is not particularly limited, for example, an aryl group having 6 to 20 carbon atoms, in which part or all of the hydrogen atoms are alkyl groups, alkoxy groups, halogen atoms. It does not need to be substituted with an atom or the like.
  • the aryl group is preferably an aryl group having 6 to 10 carbon atoms because it can be synthesized at low cost. Specific examples include a phenyl group and a naphthyl group. It is most preferable that at least one of the aryl groups of R m ′′ to R 13 is a naphthyl group. By using a naphthyl group, the transparency to ArF excimer laser light is improved and resolution is improved.
  • the alkyl group in which the hydrogen atom of the aryl group may be substituted is preferably a methyl group, an ethyl group or a propyl group, preferably an alkyl group having 1 to 5 carbon atoms.
  • the n-butyl group and the tert-butyl group are most preferred, and the alkoxy group optionally substituted with a hydrogen atom in the aryl group is preferably an alkoxy group having 1 to 5 carbon atoms.
  • a methoxy group and an ethoxy group are most preferred, and the halogen atom that may be substituted for the hydrogen atom of the aryl group is preferably a fluorine atom.
  • the alkyl group of RUR 13 is not particularly limited, and examples thereof include linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms. From the viewpoint of excellent resolution, it is preferably 1 to 5 carbon atoms. Specifically, methylol group, ethyl group, n-propyl group, isopropylinole group, n_butyl group, isobutyl group, n_pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, noninole group, decanyl Groups, and the like, and is preferable because it is excellent in resolution and can be synthesized at low cost.
  • R 15 to R 16 each independently represents an aryl group or an alkyl group.
  • At least one of R 15 to R 16 represents an aryl group. All of R 15 to R 16 are preferably aryl groups.
  • Examples of the aryl group of R 15 to R 16 include those similar to the aryl group of R ′′ to R 13.
  • Examples of the alkyl group of R 15 to R 16 include those similar to the alkyl group of R ′′ to R 13. Is mentioned. Of these, it is most preferred that R 15 to R 16 are all phenyl groups.
  • the acid generator represented by the chemical formula (B1-07) or (B108) is particularly preferable.
  • Component (B4) can be used with 4 types of displacement and displacement force, or 2 or more types can be used together.
  • the proportion of the component (B4) in the total component (B) of the third embodiment is preferably 50% by mass or more, and may be 100% by mass. A more preferable range is 60 to 90% by mass, and 70 to 85% by mass is most preferable.
  • the component (B) of the third embodiment preferably contains an acid generator (B5) represented by the following general formula (b-20) in addition to the component (B4).
  • R 4 are linear, branched or cyclic alkyl groups or fluorinated alkyl groups; 1 ⁇ ′ ′′ to 1 3 ′ ′′ are each independently substituted Represents an aryl group or an alkyl group which may have a group, and at least one of R 1 ′ ′′ to R 3 ′ ′′ represents an aryl group.
  • R 1 ′ ′ ′ to R 3 ′ ′ ′ each independently represents an aryl group or an alkyl group which may have a substituent. At least one of R 1 '''to R 3 ' To express. Of R 1 '''to R 3 '', it is preferred that 2 or more are aryl groups. Most preferably, all of R 1 '"to R 3 ''' are aryl groups.
  • the aryl group as R 1 ′ ′′ to R 3 ′ ′ ′ is, for example, an aryl group having 6 to 20 carbon atoms, and the aryl group is an alkyl group, an alkoxy group, a part or all of the hydrogen atoms of which are It may or may not be substituted with a halogen atom, etc.
  • the aryl group is preferably an aryl group having 6 to 10 carbon atoms because it can be synthesized at low cost.
  • Examples of the alkyl group as a substituent of the hydrogen atom of the aryl group include a methyl group, an ethyl group, a propyl group, and an alkyl group having 1 to 5 carbon atoms.
  • the alkoxy group as a substituent for the hydrogen atom of the aryl group is preferably a methoxy group or an ethoxy group, preferably an alkoxy group having 1 to 5 carbon atoms.
  • the water based on the aryl is preferably a fluorine atom.
  • the alkyl groups as R 1 '"to R 3 ''' are not particularly limited, and examples thereof include straight chain, branched or cyclic alkyl groups having carbon numbers:! To 10 and the like. From the point of being excellent, the carbon number is preferably 1 to 5. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, cyclopentyl group And a hexynole group, a cyclohexenole group, a nonyl group, a decanyl group, and the like, which are excellent in resolution and can be synthesized at a low cost.
  • R 1 ′ ′ ′ to R 3 ′ are most preferably all phenyl groups.
  • R 4 ' represents a linear, branched or cyclic alkyl group or a fluorinated alkyl group.
  • the linear or branched alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms.
  • the cyclic alkyl group is a cyclic group as indicated by R 1 ′ ′ ′, preferably having 4 to 15 carbon atoms, and more preferably 4 to 10 carbon atoms. Most preferably, it has 6 to 10 carbon atoms.
  • the fluorinated alkyl group is most preferably 1 to 4 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. Also.
  • the fluorination rate of the fluorine alkyl group is preferably 10 to 100%, more preferably 50 to 100%. In particular, those in which all of the hydrogen atoms are substituted with fluorine atoms are preferred because the strength of the acid is increased.
  • R 4 ''' is most preferably a linear or cyclic alkyl group or a fluorinated alkyl group.
  • component (B5) include trifluoromethane sulfonate of triphenylsulfone, heptafluoropropane sulfonate or nonafluorobutane sulfonate, tri (4-methylphenol).
  • onium salts in which the anion portion of these onium salts is replaced with methanesulfonate, n-propanesulfonate, n-butanesulfonate, or n-octanesulfonate can be used.
  • any of four types may be used. Two or more types may be used in combination.
  • the proportion of the component (B5) in the whole component (B) is preferably 10 to 40% by mass, and 15 to 30% by mass is more preferably 15 to 25% by mass. Is most preferred.
  • the component (B) of the third aspect of the present invention is a known acid generator (hereinafter referred to as other acid generator (B6) used in conventional chemically amplified resist compositions. ) And les may be contained), but for the effect of the present invention, the component (B4) in the whole component (B) And the total proportion of the components (B5) is preferably 80% by mass or more, more preferably 100% by mass.
  • Other acid generators (B6) include onium salt acid generators (B4) and (B5) other than the above-mentioned onium salt acid generators (eg, odonium salts), and oxime sulfonate acid generators.
  • diazomethane acid generators such as bisalkyl or bisarylsulfonyldiazomethanes, poly (bissulfonyl) diazomethanes, nitrobenzyl sulfonate acid generators, iminosulfonate acid generators, disulfone
  • acid generators such as acid generators can be used as appropriate.
  • the content of the component (B) in the positive resist composition of the present invention is preferably 2 to 20 parts by mass with respect to 100 parts by mass of the component (A) 5 to 15 parts by mass is more preferable. 5 to 13 parts by mass is most preferable. By setting it within the above range, pattern formation is sufficiently performed and good characteristics can be obtained. In addition, it is preferable because a uniform solution can be obtained and storage stability is improved.
  • the positive resist composition of the present invention further includes a resist pattern shape, a post-image stability of the latent image for the a by the pattern-wise exposure of the resist layer, and the like.
  • a nitrogen-containing organic compound (D) can be blended as an optional component.
  • aliphatic amines particularly secondary aliphatic amines and tertiary aliphatic amines are preferred. .
  • Aliphatic amines contain at least one hydrogen atom of ammonia NH and have 12 or more carbon atoms.
  • Examples include amines substituted with an alkyl group or hydroxyalkyl group below (alkylamines or alkylalcoholamines). Specific examples thereof include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine; jetylamine, di-n-propylamine, di-n-heptylamine, di- _n—dialkylamines such as octylamine, dicyclohexylamine; trimethylamine, triethnoreamine, tri_n-propylamine, tri_n-butynoleamine, tri-n_hexylamine, tri-n-pentylamine, tri-n- Trialkylamines such as heptylamine, tri-n-octylamine, tri-n_noninoleamine, tri_n-decanylamine, tri_n
  • Component (D) is usually used in the range of 0.01 to 5.0 parts by mass per 100 parts by mass of component (A).
  • the positive resist composition of the present invention prevents the deterioration of sensitivity due to the blending of the component (D), and the resist pattern shape and stability over time (post exposure stability of the latent image formed oy the pattern-wise).
  • an organic carboxylic acid or phosphorus oxoacid or derivative thereof) (referred to as component (E) in this specification) can be added as an optional component.
  • the component (D) and the component (E) can be used in combination, or one kind of force can be used.
  • organic carboxylic acid for example, malonic acid, citrate, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable.
  • Phosphoric acid or its derivatives include phosphoric acid, phosphoric acid di_n_butyl ester, phosphoric acid diphenyl ester, and the like, derivatives such as phosphonic acid, phosphonic acid dimethyl ester, phosphonic acid.
  • Phosphoric acid and its derivatives such as phosphonic acid, phenylphosphinic acid such as phosphonic acid, phenylphosphonic acid, phosphonic acid diphenyl ester, phosphonic acid dibenzyl ester, etc. And derivatives such as those esters.
  • phosphonic acid is especially preferred.
  • Component (E) is used at a ratio of 0.0 :! to 5.0 parts by mass per 100 parts by mass of component (A).
  • the positive resist composition of the present invention can be produced by dissolving the material in an organic solvent.
  • organic solvent it is sufficient if it can dissolve each component to be used to make a uniform solution. These can be appropriately selected and used.
  • latones such as ⁇ -butyrolatatatone
  • ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone
  • ethylene glycol ethylene glycol monoacetate, diethylene glycol, diethylene glycol monomono
  • Polyhydric alcohols such as acetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, or monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether of dipropylene glycol monoacetate and derivatives thereof
  • Cyclic esters such as: methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, pyruvin Echiru, methyl methoxypropionate, and esters such as ethoxy propyl propi
  • organic solvents may be used alone or as a mixed solvent of two or more.
  • a mixed solvent obtained by mixing propylene glycol monomethyl ether acetate (PGMEA) and a polar solvent is preferable.
  • the mixing ratio may be appropriately determined in consideration of the compatibility between PGMEA and the polar solvent, but is preferably 1: 9 to 9: 1, more preferably 2
  • the mass ratio of PGMEA: EL is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2.
  • organic solvent in addition, at least selected from PGMEA and EL
  • a mixed solvent of one kind and ⁇ _petit-mouthed rataton is also preferable.
  • the mixing ratio of the former and the latter is preferably 70: 30-95: 5.
  • the amount of the organic solvent used is not particularly limited, but is a concentration that can be applied to a substrate and the like, and is appropriately set according to the coating film thickness.
  • the solid content concentration of the resist composition is 2 to 20%. It is used so that it may fall within the range of 5% by mass, preferably 5 to 15% by mass.
  • the positive resist composition of the present invention may further contain, if desired, miscible additives such as an additional resin for improving the performance of the resist film, a surfactant for improving coatability, and a dissolution inhibitor.
  • miscible additives such as an additional resin for improving the performance of the resist film, a surfactant for improving coatability, and a dissolution inhibitor.
  • Plasticizers, stabilizers, colorants, antihalation agents, dyes, and the like can be appropriately added and contained.
  • the resist pattern forming method of the present invention can be performed, for example, as follows. That is, first, the positive resist composition (the positive resist composition of the first or third embodiment) is applied onto a substrate such as a silicon wafer with a spinner or the like, and a temperature condition of 80 to 150 ° C. is applied. Then, a pre-beta is applied for 40 to 120 seconds, preferably 60 to 90 seconds, to form a resist film.
  • the resist film is selectively exposed with a single ArF excimer laser beam through a desired mask pattern using, for example, an ArF exposure apparatus or the like, and then subjected to PEB (after exposure at a temperature of 80 to 150 ° C. (Heating) is applied for 40 to 120 seconds, preferably 60 to 90 seconds.
  • an alkali developer for example, an aqueous solution of 0.1 to 10% by mass of tetramethylammonium hydroxide. If necessary, post-beta may be applied after development processing.
  • An organic or inorganic antireflection layer can be provided between the substrate and the coating layer of the resist composition.
  • the wavelength used for the exposure is not particularly limited, ArF excimer laser, KrF excimer laser, F excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam),
  • the positive resist composition according to the present invention is effective for an ArF excimer laser.
  • the positive resist composition of the present invention high resolution can be obtained and DOF can be improved. Can be raised.
  • the resist pattern is less likely to fall and the exposure margin can be improved. The reason is not clear, but is presumed as follows.
  • the component (B1) which is an essential component of the positive resist composition, has a substituent derived from naphthalene in the cation part, and therefore, a triphenylsulfonium-based onium salt.
  • the acid generator component comprising, the light absorption in the exposure wavelength band is suppressed, and in particular, the light absorption is effectively suppressed in the wavelength band of the ArF excimer laser (especially for ArF excimer laser light). It is estimated that transparency will improve. Therefore, if the exposure amount is the same, the acid generation amount per mole of the acid generator component can be suppressed, and the variation of the acid generation amount relative to the variation of the exposure amount is considered to be relatively small.
  • the structural unit (al) of the component (A) has an acetal group (alkoxyalkyl group) type acid dissociable, dissolution inhibiting group. Since the deprotection energy of the acid dissociable, dissolution inhibiting group of the acetal group type is lower than that of the tertiary ester type acid dissociable, dissolution inhibiting group, the structural unit (al) is It is presumed that the acid dissociable, dissolution inhibiting group can be eliminated to increase alkali solubility and resolve fine patterns. In addition, it is considered that the allowable range of the amount of acid generation for obtaining good resolution is relatively wide.
  • the combination of the powerful component (B1) and the component (A) can be used to achieve both high resolution and improved DOF due to the synergistic effect of both. Therefore, it is considered that the above-described multiple good characteristics can be achieved simultaneously.
  • the component (B4) which is an essential component of the positive resist composition, has a skeleton represented by the general formula (b_3) or (b_4) in the anion portion.
  • the acid diffusion length is expected to be shorter than that of the acid generator component comprising an onium salt having a fluorinated alkyl sulfonate ion as an anion.
  • the structural unit (al) of the component (A) has an acetal group (alkoxyalkyl group) type acid dissociable, dissolution inhibiting group.
  • the structural unit (al) Since the deprotection energy of the acid dissociable, dissolution inhibiting group of the acetal group type is lower than that of the tertiary ester type, acid dissociable, dissolution inhibiting group, the structural unit (al) has a low acid strength. It is presumed that the acid dissociable, dissolution inhibiting group can be eliminated to increase alkali solubility and resolve a fine pattern.
  • the powerful component (B4) and component (A) it is possible to achieve both high resolution and improved DOF due to their synergistic effects. Therefore, it is considered that the above-described multiple good characteristics can be achieved at the same time.
  • the obtained compound 1 ((2-adamantoxymethyl) metatalylate) is represented by the following chemical formula.
  • Resin 1 had a weight average molecular weight (Mw) of 7000 and a dispersity (Mw / Mn) of 2.2.
  • Mw weight average molecular weight
  • Mw / Mn dispersity
  • 13 C-NMR carbon 13 nuclear magnetic resonance spectrum
  • a positive resist composition was prepared by mixing the resin 1 synthesized in Synthesis Example 2, the acid generators 1 and 2 shown below, a nitrogen-containing organic compound, and a solvent.
  • Resin 1 100 parts by mass
  • Acid generator 1 6.0 parts by mass
  • Acid generator 2 1.6 parts by mass
  • Triethanolamine as a nitrogen-containing organic compound 0.38 parts by mass
  • the acid generator 1 is a compound represented by the chemical formula (bl—08), and the acid generator 2 is (4 Methylphenyl) diphenylsulfonium trifluoromethanesulfonate.
  • PMEA propylene glycol monomethyl ether acetate
  • EL represents ethyl lactate
  • a resist pattern was formed using the positive resist composition obtained above.
  • ARC_ 29 A (trade name, manufactured by Plue Science Co., Ltd.) on an 8-inch silicon wafer using a spinner, and 215 ° C on a hot plate.
  • An organic antireflection film having a thickness of 90 nm was formed by baking for 90 seconds and drying.
  • the positive resist composition obtained above was applied onto an antireflection film using a spinner, pre-beta (PAB) at 105 ° C. for 90 seconds on a hot plate, and dried to obtain a film thickness of 180 nm.
  • the resist film was formed.
  • a PEB treatment was conducted under conditions of 90 seconds, further 23 ° C at 2.38 mass 0/0 tetramethylammonium Niu arm hydroxide (TMAH) 60 seconds and puddle developed with an aqueous solution, then 20 seconds It was washed with water and shaken and dried. Further, it was heated at 100 ° C. for 60 seconds and dried to form a 1: 1 90 nm line and space pattern (hereinafter referred to as L / S pattern).
  • TMAH tetramethylammonium Niu arm hydroxide
  • Eop is the exposure (sensitivity) when a 90nm LZS pattern is formed 1: 1.
  • the focus was shifted up and down as appropriate, and the range of depth of focus (D0F) in which the 90 nm L / S pattern was obtained within the range of dimensional change rate of ⁇ 10% was determined in nm.
  • 3 ⁇ which is a measure of LER
  • LER line edge roughness
  • 3 ⁇ was calculated from the result of measuring the width of the resist pattern of the sample at 32 locations using a side SEM (measuring SEM) (trade name “S_ 9 220” manufactured by Hitachi, Ltd.).
  • the standard deviation is 3 times the standard deviation (3 ⁇ ). This 3 ⁇ means that the smaller the value, the smaller the roughness and the uniform width resist pattern was obtained. Measurement was performed at two measurement voltages of 800V and 300V.
  • Exposure margin (%) [E (81nm) —E (99nm)] X 100 / Eop
  • E (99 nm) is the sensitivity when obtaining a 99 nm L / S pattern (mj / cm 2 )
  • E (81 nm) is the sensitivity when obtaining an L / S pattern of 81 nm (mj / cm 2 ).
  • Example 1 3.5 parts by mass of triphenylsulfoumonium fluorobutanesulfonate (TPS-PFBS) was used in place of the acid generators 1 and 2, and the blending amount of triethanolamine was 0.35.
  • a positive resist composition was prepared in the same manner as in Example 1 except for changing to parts by mass, and a resist pattern was formed using the resist composition.
  • the 90nm LZS pattern was resolved.
  • the exposure (sensitivity) when a 90 nm LZS pattern was formed 1: 1 was defined as Eop, and the characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 1 below.
  • Example 1 and Comparative Example 1 have better resolution, and LER is slightly better in Example 1.
  • Example 1 is greatly improved compared to Comparative Example 1.
  • Example 1 is superior.

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Abstract

L’invention décrit une composition de photorésine positive ayant une résolution élevée, qui permet d'améliorer le DDF. Cette composition contient un composant de résine (A), dont la solubilité dans les alcalis est augmentée par l’action d’un acide et d’un composant générateur d’acide (B) qui génère un acide lorsqu’il est exposé à la lumière. Le composant de résine (A) possède au moins un motif constitutif (a1) choisi parmi les motifs de formules générales (a1-01) et (a1-02) ci-dessous. Le composant générateur d’acide (B) est composé d’un générateur d'acide (B1) au sel d'onium ayant un composant cationique de formule générale (b-1) ci-dessous, ou d’un générateur d’acide (B4) au sel d’onium ayant un composant anionique de formule générale (b-3) ou (b-4) ci-dessous. Dans ces formules, Y représente un groupe alicyclique ; n vaut 0 ou un entier de 1 à 3 ; m vaut 0 ou 1 ; R représente un atome d’hydrogène, un groupe alkyle inférieur, un atome de fluor ou un groupe alkyle inférieur fluoré ; R1 et R2 représentent respectivement un atome d’hydrogène ou un groupe alkyle inférieur ; R11 représente un groupe alkyle, un groupe alcoxy, un atome d’halogène ou un groupe hydroxyle ; R12 et R13 représentent respectivement un groupe aryle ou un groupe alkyle ; enfin, n' vaut 0 ou représente un entier de 1 à 3. (a1-01) (a1-02) (b-1) (b-3) (b-4)
PCT/JP2005/023154 2005-01-18 2005-12-16 Composition de photoresine positive et procede de formation de motif en photoresine WO2006077705A1 (fr)

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JP2005-010051 2005-01-18
JP2005010051A JP4191145B2 (ja) 2005-01-18 2005-01-18 ポジ型レジスト組成物およびレジストパターン形成方法
JP2005-012053 2005-01-19
JP2005012053A JP2006201402A (ja) 2005-01-19 2005-01-19 ポジ型レジスト組成物およびレジストパターン形成方法

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