WO2007148525A1 - Composition de réserve positive et procédé de formation d'un motif de réserve - Google Patents

Composition de réserve positive et procédé de formation d'un motif de réserve Download PDF

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Publication number
WO2007148525A1
WO2007148525A1 PCT/JP2007/061284 JP2007061284W WO2007148525A1 WO 2007148525 A1 WO2007148525 A1 WO 2007148525A1 JP 2007061284 W JP2007061284 W JP 2007061284W WO 2007148525 A1 WO2007148525 A1 WO 2007148525A1
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group
alkyl group
acid
carbon atoms
formula
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PCT/JP2007/061284
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English (en)
Japanese (ja)
Inventor
Masaru Takeshita
Ryoji Watanabe
Takeshi Iwai
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Tokyo Ohka Kogyo Co., Ltd.
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Publication of WO2007148525A1 publication Critical patent/WO2007148525A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—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

Definitions

  • the present invention relates to a positive resist composition and a resist pattern forming method.
  • a resist film having a resist material strength is formed on a substrate, and light, electron beam, or the like is passed through a mask on which a predetermined pattern is formed on the resist film.
  • a step of forming a resist pattern having a predetermined shape on the resist film is performed by performing selective exposure with radiation and developing. Resist material that changes its properties so that the exposed part dissolves in the developer is positive, V does not dissolve the exposed part in the developer, and the resist material that changes in characteristics is negative.
  • the wavelength of an exposure light source is generally shortened.
  • the power used in the past typically ultraviolet rays such as g-line and i-line
  • KrF excimer laser and ArF excimer laser have now begun mass production of semiconductor devices using KrF excimer laser and ArF excimer laser.
  • these excimer lasers have shorter wavelength excimer lasers, electron beams, EUV (
  • Resist materials are required to have lithography characteristics such as sensitivity to these exposure light sources and resolution capable of reproducing patterns with fine dimensions.
  • a chemically amplified resist containing a base resin whose alkali solubility is changed by the action of an acid and an acid generator that generates an acid upon exposure is used.
  • a positive chemically amplified resist contains, as a base resin, a resin whose alkali solubility is increased by the action of an acid and an acid generator. When acid is generated from the raw material, the exposed area becomes alkali-soluble.
  • (meth) acrylic acid ester means one or both of an acrylic acid ester having a hydrogen atom bonded to the ⁇ -position and a methacrylic acid ester having a methyl group bonded to the a-position.
  • (Meth) acrylate means either an acrylate having a hydrogen atom bonded to the ⁇ -position or a metatalate having a methyl group bonded to the ⁇ -position.
  • (Meth) acrylic acid” means both acrylic acid having a hydrogen atom bonded to the ⁇ -position and methacrylic acid having a methyl group bonded to the ⁇ -position !.
  • the acid generator has a high acid-generating ability, among others, a cation moiety that also has a trisulfol sulfone (TPS) force, and a fluorinated alkyl sulfonate ion force such as nonafluorobutane sulfonate.
  • TPS trisulfol sulfone
  • fluorinated alkyl sulfonate ion force such as nonafluorobutane sulfonate.
  • An acid salt-based acid generator having a cation moiety is the most common (see, for example, Patent Document 1).
  • Patent Document 1 Japanese Patent Laid-Open No. 2003-241385
  • ⁇ DOF '' is a range of depth of focus where a resist pattern can be formed with a dimension within which a deviation from the target dimension is within a predetermined range when the focus is shifted up and down at the same exposure amount, that is, in the mask pattern. This is the range where a faithful resist pattern can be obtained, and the larger the DOF, the better.
  • the first 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) that generates an acid upon exposure.
  • the acid generator component (B) is represented by the following general formula (b′—1): a cationic moiety, and the following general formula (b-3) and Z or (b-4):
  • a positive resist composition comprising an acid generator (B1) having an anion portion represented.
  • R 1 and R 2 each independently represents an optionally substituted naphthyl group; R 3 represents an alkyl group or an aryl group. ] [0010] [Chemical 2]
  • X represents a C 2-6 alkylene group in which at least one hydrogen atom is substituted with a fluorine atom
  • Y and Z "each independently represents at least one hydrogen atom substituted with a fluorine atom.
  • 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, a step of exposing the resist film, and the resist film.
  • a resist pattern forming method including a step of forming a resist pattern by development.
  • structural unit means a monomer unit (monomer unit) that constitutes the resin component (polymer).
  • Exposure is a concept including general irradiation of radiation.
  • alkylene group includes linear, branched and cyclic divalent saturated hydrocarbon groups.
  • the “lower alkyl group” means an alkyl group having 1 to 5 carbon atoms.
  • a positive resist composition and a resist pattern forming method excellent in depth of focus (DOF) characteristics can be provided.
  • the positive resist composition of the present invention comprises a resin component ( ⁇ ) whose alkali solubility is increased by the action of an acid (hereinafter referred to as ( ⁇ ) component), and an acid generator component ( ⁇ ) that generates an acid upon exposure. (Hereinafter referred to as component (ii)).
  • component (ii) component an acid generator component that generates an acid upon exposure.
  • component (ii) an acid generator component that generates an acid upon exposure.
  • component (ii) the component (A) is alkali-insoluble before exposure
  • an acid is generated from the component (B) by exposure, and the acid acts on the component (A).
  • Alkali solubility of the whole component is increased, and alkali-insoluble and alkali-soluble are changed. Therefore, when a resist film obtained using a positive resist composition is selectively exposed in the formation of a resist pattern, the exposed area turns alkali-soluble while the unexposed area remains alkali-insoluble. However, it can be alkali-developed.
  • the component (A) is not particularly limited, and those that have been proposed as base resins for positive chemically amplified resists can be used, for example, polyhydroxystyrene-based compounds. Examples include rosin and acrylate-based rosin.
  • the component (A) preferably has a structural unit that also induces acrylate power.
  • the "structural unit derived from an acrylate ester force” means a structural unit formed by cleavage of an ethylenic double bond of an acrylate ester. To do.
  • acrylic acid ester a hydrogen atom is bonded to the carbon atom at position a, and in addition to the acrylic acid ester, a substituent (an atom or group other than a hydrogen atom) is bonded to the carbon atom at position a.
  • the concept includes things.
  • the substituent include a halogen atom, a lower alkyl group, and a halogeno-lower alkyl group.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.
  • the ⁇ position (the carbon atom at the position) of the structural unit from which the acrylate force is also derived is a carbon atom to which a carbo group is bonded, unless otherwise specified.
  • the lower alkyl group as the substituent at the ⁇ -position, specifically, methyl group, ethyl group, propyl group, isopropyl group, ⁇ -butyl group, isobutyl group And a lower linear or branched alkyl group such as a ru group, a tert-butyl group, a pentyl group, an isopentyl group, or a neopentyl group.
  • a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group is bonded to the ⁇ -position of the acrylate ester, and a hydrogen atom, a fluorine atom, a lower alkyl group or A fluorinated lower alkyl group is more preferred, and a hydrogen atom or a methyl group is most preferred from the viewpoint of industrial availability.
  • the component (i) preferably has a structural unit (al) derived from an acrylate ester containing an acid dissociable, dissolution inhibiting group.
  • component (A) preferably further comprises a structural unit (a2) derived from an acrylate ester containing a latathone-containing cyclic group, in addition to the structural unit (al).
  • the component (A) preferably further has a structural unit (a3) derived from an acrylate ester containing a polar group-containing aliphatic hydrocarbon group.
  • the component (A) preferably further has a structural unit (aO) represented by the following general formula (aO).
  • R is a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group;
  • Y 1 is an aliphatic cyclic group;
  • Z is a tertiary alkyl group-containing group or an alkoxy group;
  • A is an integer of 1 to 3
  • b is an integer of 0 to 2
  • a + b l to 3;
  • c, d and e are each independently 0 to 3; It is an integer.
  • the structural unit (al) is a structural unit derived from an acrylate ester containing an acid dissociable, dissolution inhibiting group.
  • the acid dissociable, dissolution-inhibiting group in the structural unit (al) has an alkali dissolution inhibiting property that makes the entire component (A) insoluble before dissociation, and after dissociation, the entire (A) component is alkali-soluble.
  • those proposed as acid dissociable, dissolution inhibiting groups for base resins for chemically amplified resists can be used.
  • a group that forms a cyclic or chain tertiary alkyl ester with a carboxy group in (meth) acrylic acid or the like; an acetal type acid dissociable, dissolution inhibiting group such as an alkoxyalkyl group is widely known.
  • (Meth) acrylic acid ester” means either one of an acrylic acid ester having a hydrogen atom bonded to the ⁇ -position and a methacrylic acid ester having a methyl group bonded to the a-position !.
  • the “tertiary alkyl ester” is an ester formed by substitution with a hydrogen atom of a carboxy group, a chain or cyclic alkyl group, and its carboxy group ( A structure in which the tertiary carbon atom of the chain or cyclic alkyl group is bonded to the terminal oxygen atom of 1 C (O) —0—).
  • the bond is broken between the oxygen atom and the tertiary carbon atom.
  • the chain or cyclic alkyl group may have a substituent! /.
  • a group that becomes acid dissociable by constituting a carboxy group and a tertiary alkyl ester will be referred to as a “tertiary alkyl ester type acid dissociable, dissolution inhibiting group” for convenience.
  • the tertiary alkyl ester type acid dissociable, dissolution inhibiting group include aliphatic branched acid dissociable, dissolution inhibiting groups, and acid dissociable, dissolution inhibiting groups containing aliphatic cyclic groups.
  • aliphatic in the claims and the specification is a relative concept with respect to aromatics, and is defined to mean a group, a compound, or the like that does not have aromaticity.
  • “Aliphatic branched” means that it has a branched structure without aromaticity.
  • the structure of the “aliphatic branched acid dissociable, dissolution inhibiting group” consists of carbon and hydrogen-powered groups (carbon Hydrocarbon group), but is preferably a hydrocarbon group. Further, the “hydrocarbon group” may be either saturated or unsaturated, but is usually preferably saturated.
  • a tertiary alkyl group having 4 to 8 carbon atoms is preferred. Specifically, a tert butyl group, a tert-amyl group, a tert-heptyl group, and the like can be given. I can get lost.
  • Aliphatic cyclic group indicates that it is not aromatic !, a monocyclic group or a polycyclic group.
  • the “aliphatic cyclic group” in the structural unit (al) may or may not have a substituent.
  • the basic ring structure is not limited to a group consisting of carbon and hydrogen (hydrocarbon group), but may be a hydrocarbon group.
  • hydrocarbon group may be either saturated or unsaturated, but is usually preferably saturated.
  • aliphatic cyclic group is preferably a polycyclic group.
  • aliphatic cyclic group examples include, for example, a lower alkyl group, a fluorine atom or a fluorinated alkyl group, which may or may not be substituted, monocycloalkane, bicycloalkane.
  • polycycloalkane force such as tricycloalkane and tetracycloalkane include groups in which one or more hydrogen atoms are removed.
  • a monocycloalkane such as cyclopentane or cyclohexane
  • a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane.
  • Examples of the acid dissociable, dissolution inhibiting group containing an aliphatic cyclic group include a group having a tertiary carbon atom on the ring skeleton of a cyclic alkyl group, specifically, 2-methyl 2-adamantyl. Group, 2-ethyl-2-adamantyl group and the like. Or, in a structural unit represented by the following general formula (al "), an aliphatic cyclic group such as an adamantyl group such as a group bonded to an oxygen atom of a carbo-oxy group (-C (O)-0-) Group and this And a group having a branched alkylene group having a tertiary carbon atom, which is bonded to.
  • R represents a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group
  • R 15 and R 16 represent an alkyl group (both linear and branched, preferably carbon number 1 ⁇ 5)).
  • the halogen atom, lower alkyl group or halogenated lower alkyl group of R is the same as the halogen atom, lower alkyl group or halogenated lower alkyl group which may be bonded to the ⁇ -position of the acrylate ester. It is.
  • Acetal type acid dissociable, dissolution inhibiting group is generally bonded to an oxygen atom by substituting a hydrogen atom at the terminal of an alkali-soluble group such as a carboxy group or a hydroxyl group. When an acid is generated by exposure, the acid acts to break the bond between the acetal type acid dissociable, dissolution inhibiting group and the oxygen atom to which the acetal type acid dissociable, dissolution inhibiting group is bonded.
  • Examples of the acetal type acid dissociable, dissolution inhibiting group include a group represented by the following general formula (pi).
  • R 1 ′ and R 2 ′ each independently represent a hydrogen atom or a lower alkyl group, and n is 0 Represents an integer of ⁇ 3, and Y represents a lower alkyl group or an aliphatic cyclic group.
  • n is preferably an integer of 0 to 2, 0 or 1 is more preferable, and 0 is most preferable.
  • R 1 ′ and R 2 ′ the same as the lower alkyl group for R in the above formula (al ′′) can be used, and a methyl group in which a methyl group or an ethyl group is preferred is most preferred.
  • R 1 ′ and R 2 is a hydrogen atom, that is, the acid dissociable, dissolution inhibiting group (pi) is represented by the following general formula (pi-1) It is preferably a group.
  • R 1 ', n, Y is R 1 in the formula (pi)', n, it is the same as Y. ]
  • Examples of the lower alkyl group for Y include the same as the lower alkyl group for R in the above formula (al ").
  • aliphatic cyclic group for Y many conventionally proposed ArF resists and the like can be appropriately selected from monocyclic or polycyclic aliphatic cyclic groups. Examples thereof are the same as the “aliphatic cyclic group”.
  • the acetal type acid dissociable, dissolution inhibiting group includes a group represented by the following general formula (p2).
  • R “and R 18 are each independently a linear or branched alkyl group or a hydrogen atom, and R 19 is a linear, branched or cyclic alkyl group, or R 17 and R 19 are each independently a linear or branched alkylene group, and the end of R 17 and the end of R 19 may be bonded to form a ring.
  • the alkyl group preferably has 1 to 15 carbon atoms, and is preferably a straight-chain or branched-chain ethyl group, and a methyl group is preferred.
  • it is preferable that one of R 17 and R 18 is a hydrogen atom and the other is an S-methyl group.
  • R 19 is a linear, branched or cyclic alkyl group, preferably having 1 to 15 carbon atoms, and may be linear, branched or cyclic.
  • R 19 When R 19 is linear or branched, it preferably has 1 to 5 carbon atoms, more preferably an ethyl group or a methyl group, and most preferably an ethyl group.
  • R 19 is cyclic, it is preferably 4 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and further preferably 5 to carbon atoms: LO is most preferable.
  • one or more polycycloalkanes such as monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane, which may or may not be substituted with a fluorine atom or a fluorinated alkyl group. And the like, in which a hydrogen atom is removed.
  • Specific examples include monocycloalkanes such as cyclopentane and cyclohexane, and groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. It is done. Among them, a group in which one or more hydrogen atoms are removed from adamantane is preferable.
  • R 17 and R 19 are each independently a linear or branched alkylene group (preferably an alkylene group having 1 to 5 carbon atoms), and the end of R 19 and the end of R 17 The end may be bonded.
  • a cyclic group is formed by R 17 and R 19 , the oxygen atom to which R 19 is bonded, and the carbon atom to which the oxygen atom and R 17 are bonded.
  • a 4- to 7-membered ring is preferable, and a 4- to 6-membered ring is more preferable.
  • Specific examples of the cyclic group include a tetrahydrobiranyl group and a tetrahydrofuran group.
  • a structural unit represented by the following general formula (al— 0— 1) and a structural unit force represented by the following general formula (al— 0— 2) are selected. It is preferable to use one or more.
  • R represents a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group
  • X 1 represents an acid dissociable, dissolution inhibiting group
  • R represents a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group
  • X 2 represents an acid dissociable, dissolution inhibiting group
  • Y 2 represents an alkylene group or an aliphatic cyclic group. .
  • the halogen atom, lower alkyl group, or halogenated lower alkyl group of R is a halogen atom, lower alkyl group, or may be bonded to the ⁇ -position of the acrylate ester. This is the same as the halogeno lower alkyl group.
  • X 1 is not particularly limited as long as it is an acid dissociable, dissolution inhibiting group, and examples thereof include the above-described tertiary alkyl ester type acid dissociable, dissolution inhibiting group and acetal type acid dissociable, dissolution inhibiting group. Tertiary alkyl ester type acid dissociable, dissolution inhibiting groups are preferred.
  • R is the same as R in the above formula (al-0-1).
  • X 2 is the same as X 1 in the formula (al-0-1).
  • Y 2 is preferably an alkylene group having 1 to 4 carbon atoms or a divalent aliphatic cyclic group, except that a group in which two or more hydrogen atoms are removed is used as the aliphatic cyclic group.
  • the same as the explanation of the “aliphatic cyclic group” can be used.
  • Specific examples of the structural unit (al) include structural units represented by the following general formulas (al-1) to (al-4).
  • X ′ represents a tertiary alkyl ester type acid dissociable, dissolution inhibiting group
  • Y represents a lower alkyl group having 1 to 5 carbon atoms, or an aliphatic cyclic group
  • n represents 0 to 3
  • M represents 0 or 1
  • R is the same as R in the formula (al ")
  • R 1 'and R 2 ' each independently represents a hydrogen atom or a lower group having 1 to 5 carbon atoms. Represents an alkyl group.
  • At least one of R 1 'and R 2 ' is preferably a hydrogen atom, more preferably a hydrogen atom.
  • n is preferably 0 or 1.
  • X ' is the same as the tertiary alkyl ester type acid dissociable, dissolution inhibiting group exemplified as X 1 in the formula (al-0-1).
  • Examples of the aliphatic cyclic group for Y include the same groups as those exemplified above in the explanation of the “aliphatic cyclic group”.
  • one type may be used alone, or two or more types may be used in combination.
  • the structural unit represented by the general formula (al-1) is preferred, specifically, the structural unit represented by the formula (al-1 1 1) to the formula (al-1 1 7); It is more preferable to use at least one selected from the structural unit forces represented by al-1 1 36) to formula (al-1 1 42).
  • the structural unit represented by the general formula (a 1-2) is also preferred, specifically, the formula (al-2-9) It is more preferable to use at least one selected from the structural unit forces represented by formula (al-2-10), formula (al-2-13), and formula (al-2-14).
  • R represents a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group, and R 11 represents a lower alkyl group.
  • R represents a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group
  • R 12 represents a lower alkyl group.
  • h represents an integer of 1 to 3.
  • R represents a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group
  • R 1 ′ and R 2 ′ each independently represent a hydrogen atom or a lower alkyl group
  • R is the same as R in the above formula (al ").
  • the lower alkyl group of R 11 is the same as the lower alkyl group in R, and is a methyl group or Ethyl group is preferred.
  • R is the same as R in the above formula (al ").
  • the lower alkyl group of R 12 is the same as the lower alkyl group in R, and is a methyl group or an ethyl group. I like the group.
  • h is preferably 1 or 2, and most preferably 2.
  • R is the same as R in the above formula (al ").
  • R and R 2 ' are preferably hydrogen atoms.
  • N is preferably 0 or 1. Most preferred is 0.
  • the bond position between adamantane and one C (R) (R 2 ') -0- (CH) — is the 1st or 2nd position of adamantane.
  • the amount of the structural unit (al) is, (A) to the total structural units constituting the component 10 to 80 mol 0/0 preferably fixture 20 to 70 mole 0/0 force more preferably, further preferable arbitrary 25 to 50 mole 0/0.
  • the structural unit (a2) is a structural unit (a2) derived from an acrylate ester containing a latathone-containing cyclic group.
  • the ratatone-containing cyclic 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 if it is only a rataton ring, it is called a monocyclic group, and if it has another ring structure, it is called a polycyclic group regardless of the structure.
  • the Rataton cyclic group in the structural unit (a2) increases the adhesion of the resist film to the substrate or has an affinity for a developer containing water. It is effective for raising.
  • the structural unit (a2) is not particularly limited, and any unit can be used.
  • examples of the latatatone-containing monocyclic group include groups in which y-peptidyl latatone force one hydrogen atom is removed.
  • examples of the latathone-containing polycyclic group include groups in which a bicycloalkane, tricycloalkane, or tetracycloalkane having a latathone ring has one hydrogen atom removed.
  • examples of the structural unit (a2) include structural units represented by the following general formulas (a2l) to (a2-5).
  • R is a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group
  • R ′ is a hydrogen atom, a lower alkyl group, or an alkoxy group having 1 to 5 carbon atoms
  • m is 0. Or an integer of 1, and A is an alkylene group having 1 to 5 carbon atoms or an oxygen atom.
  • R in the general formulas (a2-l) to (a2-5) is the same as R in the formula (al ") in the structural unit (al).
  • the lower alkyl group for R is the same as the lower alkyl group for R in formula (al ") in the structural unit (al).
  • R ′ is preferably a hydrogen atom in view of industrial availability.
  • alkylene group having 1 to 5 carbon atoms of A examples include a methylene group, an ethylene group, an n-propylene group, and an isopropylene group.
  • one type may be used alone, or two or more types may be used in combination.
  • the proportion of (A) the structural unit in the component (a2) is for the total of all structural units constituting the component (A), 5 to 60 mole 0/0 force transducer preferred, 10 to 50 mole 0/0 more preferably the force, preferably 20 to 50 mole 0/0 Gasa et al.
  • the proportion of (A) the structural unit in the component (a2) is for the total of all structural units constituting the component (A), 5 to 60 mole 0/0 force transducer preferred, 10 to 50 mole 0/0 more preferably the force, preferably 20 to 50 mole 0/0 Gasa et al.
  • the structural unit (a3) is a structural unit (a3) derived from an acrylate ester containing a polar group-containing aliphatic hydrocarbon group.
  • Examples of the polar group include a hydroxyl group, a cyano group, a carboxy group, and a hydroxyalkyl group substituted with a partial S hydrogen atom of an alkyl group, and a hydroxyl group is particularly preferred.
  • aliphatic hydrocarbon group examples include a linear or branched hydrocarbon group having 1 to 10 carbon atoms (preferably an alkylene group) and a polycyclic aliphatic hydrocarbon group (polycyclic group).
  • polycyclic group for example, V has been proposed in a variety of resins for resist compositions for ArF excimer lasers, and can be appropriately selected from those used.
  • the structural unit is more preferable.
  • the polycyclic group include groups in which two or more hydrogen atoms are removed from bicycloalkane, tricycloalkane, tetracycloalkane and the like.
  • Specific examples include groups in which two or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
  • adamantane norbornane
  • isobornane tricyclodecane
  • tetracyclododecane a polycycloalkane
  • two or more hydrogen atoms are removed from adamantane
  • two or more hydrogen atoms are removed from norbornane
  • two or more hydrogen atoms are removed from tetracyclododecane.
  • the industrial group is preferred.
  • the structural unit (a3) when the hydrocarbon group in the polar group-containing aliphatic hydrocarbon group is a linear or branched hydrocarbon group having 1 to: LO carbon atoms, the hydroxy group of acrylic acid is used.
  • Preferred structural units derived from tilesters When the hydrocarbon group is a polycyclic group, a structural unit represented by the following formula (a3-1), a structural unit represented by (a3-2), The structural unit represented by (a3-3) is preferable.
  • j is preferably 1 or 2. More preferably, when j is 2, the hydroxyl group is preferably bonded to the 3rd and 5th positions of the adamantyl group, and when j is 1, the hydroxyl group is bonded to the 3rd position of the adamantyl group. Things are preferred.
  • j is preferably 1, and the hydroxyl group is particularly preferably bonded to the 3rd position of the adamantyl group.
  • k is preferably 1.
  • the cyan group is the 5-position of the norbornyl group or
  • t ′ is preferably 1.
  • 1 is preferably 1.
  • s is preferred to be 1,.
  • These preferably have a 2-norbornyl group or a 3-norbornyl group bonded to the terminal of the carboxy group of acrylic acid. It is preferred that the fluorinated alkyl alcohol be bonded to the 5 or 6 position of the norbornyl group! /.
  • one type may be used alone, or two or more types may be used in combination.
  • Component (A) the proportion of the structural unit (a3), the (A) against the total of all structural units constituting the component 5 to 50 mol 0/0 it is preferably a tool 40 mol 0 / 0 forces Ri preferably, more preferably 5 to 25 mol 0/0 power.
  • a tool 40 mol 0 / 0 forces Ri preferably, more preferably 5 to 25 mol 0/0 power.
  • the structural unit (aO) is a structural unit represented by the general formula (aO). By having the structural unit (aO), the solubility of the component (A) in the organic solvent is improved.
  • R is a hydrogen atom, a halogen atom, a lower alkyl group, or a halogenated lower alkyl group.
  • R is the same as R in the formula (al ′′) in the structural unit (al). Among them, R is more preferably a hydrogen atom or a methyl group that is preferably a methyl group.
  • Y 1 represents an aliphatic cyclic group.
  • Examples of Y 1 include those similar to the aliphatic cyclic group of Y 2 in the structural unit (al) exemplified in the formula (al-0-2).
  • the aliphatic cyclic group in the structural unit (aO) is preferably a polycyclic group, but is preferably a group obtained by removing two or more hydrogen atoms from adamantane.
  • Z is a tertiary alkyl group-containing group or an alkoxyalkyl group.
  • tertiary alkyl group refers to an alkyl group having a tertiary carbon atom.
  • the “alkyl group” represents a monovalent saturated hydrocarbon group, and includes a chain (straight chain or branched chain) alkyl group and an alkyl group having a cyclic structure.
  • Tertiary alkyl group-containing group refers to a group containing a tertiary alkyl group in its structure.
  • the tertiary alkyl group-containing group is composed of a tertiary alkyl group which may be composed only of the tertiary alkyl group and another atom or group other than the tertiary alkyl group. Good.
  • the “other atom or group other than the tertiary alkyl group” constituting the tertiary alkyl group-containing group together with the tertiary alkyl group includes a carbonyloxy group, a carbonyl group, an alkylene group, an oxygen atom, etc. Is mentioned.
  • tertiary alkyl group-containing group of Z examples include a cyclic structure! /, A tertiary alkyl group-containing group, a tertiary alkyl group-containing group having a cyclic structure, and the like.
  • a tertiary alkyl group-containing group contains a branched tertiary alkyl group as the tertiary alkyl group and does not have a cyclic structure in the structure. is there.
  • Examples of the branched tertiary alkyl group include groups represented by the following general formula (I).
  • R 21 to R 23 are each independently a linear or branched alkyl group.
  • the alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms.
  • the total number of carbon atoms of the group represented by the general formula (I) is preferably 4 to 7, more preferably 4 to 6, and most preferably 4 to 5.
  • Specific examples of the group represented by the general formula (I) include a tert-butyl group and a tert-amyl group, and a tert-butyl group is more preferable.
  • the tertiary alkyl group-containing group includes the above-described branched tertiary alkyl group; the above-described branched tertiary alkyl group is linear or A tertiary alkyl group-containing chain alkyl group bonded to a branched alkylene group; a tertiary alkyloxy having the above-described branched tertiary alkyl group as the tertiary alkyl group; Carbon group; tertiary alkyl group having tertiary branched alkyl group as described above as tertiary alkyl group.
  • alkylene group in the tertiary alkyl group-containing chain alkyl group an alkylene group having 1 to 5 carbon atoms is preferred, and an alkylene group having 1 to 2 carbon atoms is preferred, and an alkylene group having 1 to 2 carbon atoms is more preferred. Even better!
  • Examples of the chain-like tertiary alkyloxycarbonyl group include a group represented by the following general formula (II).
  • R 21 to R 23 in the formula ([pi) is Ru similar der and R 21 to R 23 in general formula (I).
  • As the chain-like tertiary alkyloxycarbonyl group a tert-butyloxycarboxyl group (t-boc) or a tert-amyloxycarboxyl group is preferable.
  • Examples of the chain-like tertiary alkyloxycarbonylalkyl group include a group represented by the following general formula (III).
  • R 21 to R 23 in the formula (III) are the same as R 21 to R 23 in general formula (I).
  • f is an integer of 1 to 3, preferably 1 or 2.
  • Chain tertiary alkyl As the oxyalkyl group, tert butyloxy carboxymethyl group and tert butyl oxycarboxyl group are preferable!
  • the tertiary alkyl group-containing group having no cyclic structure is preferably a tertiary alkyl carboxy group or a tertiary alkyl carboxyalkyl group, and a tertiary alkyl carboxy group.
  • the tert-butyloxy group is most preferred.
  • a tertiary alkyl group-containing group having a cyclic structure is a group having a tertiary carbon atom and a cyclic structure in the structure.
  • the cyclic structure is preferably 4 to 12 carbon atoms constituting the ring, more preferably 5 to 10 carbon atoms, and more preferably 6 to 10 carbon atoms. Most preferred.
  • Examples of the cyclic structure include groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane.
  • Preferable examples include monocycloalkanes such as cyclopentane and cyclohexane, and groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane.
  • Examples of the tertiary alkyl group-containing group having a cyclic structure include a group having the following group (1) or (2) as the tertiary alkyl group.
  • the linear or branched alkyl group has 1 to 5 carbon atoms. 1 to 4 is more preferable and 1 to 3 is more preferable.
  • group (1) examples include a 2-methyl-2-adamantyl group, a 2-ethyl-2-adamantyl group, a 1-methyl-1-cycloalkyl group, and a 1-ethyl-1-cycloalkyl group.
  • a branched alkylene group is bonded to the cycloalkyl group, and the cycloalkyl group may have a substituent.
  • R 25 and R 26 are each independently a linear or branched alkyl group, and the alkyl group is the same as the alkyl group of R 21 to R 23 in the formula (I). Can be mentioned.
  • Examples of the alkoxyalkyl group of Z include a group represented by the following general formula (V).
  • R 41 is a linear, branched or cyclic alkyl group.
  • R 41 When R 41 is linear or branched, it preferably has 1 to 5 carbon atoms, more preferably an ethyl group or a methyl group, and most preferably an ethyl group.
  • R 41 is cyclic, it is preferably 4 to 12 carbon atoms having 4 to 15 carbon atoms.
  • polycyclohexane such as monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane may be substituted with a fluorine atom or a fluorinated alkyl group.
  • alkane forces include groups in which one or more hydrogen atoms have been removed.
  • cyclopentane And monocycloalkanes such as cyclohexane, and groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
  • polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
  • a group in which one or more hydrogen atoms are removed from adamantane is preferable.
  • R 42 is a linear or branched alkylene group. More preferably, the alkylene group has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and more preferably 1 to 2 carbon atoms.
  • alkoxyalkyl group for Z a group represented by the following general formula (VI) is particularly preferable.
  • R 41 is the same as R 41 in the formula (V), and R 43 and R 44 are each independently a linear or branched alkyl group or a hydrogen atom. It is.
  • the alkyl group preferably has 1 to 15 carbon atoms, and is preferably a straight chain or branched chain ethyl group, and a methyl group is preferred.
  • one of R 43 and R 44 is preferably a hydrogen atom and the other is a force methyl group.
  • a tertiary alkyl group-containing group is preferred, and a group represented by the above general formula (II) is more preferred.
  • a tert-butyloxycarbonyl group (t —Boc) is the most preferred.
  • a is an integer of 1 to 3
  • b is an integer of 0 to 2
  • a + b l to 3.
  • b is preferably 0! /.
  • a + b is preferably 1.
  • c is an integer of 0 to 3, preferably 0 or 1, and more preferably 0.
  • d is an integer of 0 to 3, preferably 0 or 1, and more preferably 0.
  • e is an integer of 0 to 3, preferably 0 or 1, and more preferably 0.
  • aO a structural unit represented by the following general formula (aO-1) is particularly preferable.
  • R, Z, b, c, d, and e are the same as R, Z, b, c, d, and e in the formula (aO).
  • the monomer for deriving the structural unit (aO) is, for example, a compound represented by the following general formula (aO ')
  • a part or all of the hydroxyl groups of (an acrylate ester containing an aliphatic cyclic group having 1 to 3 alcoholic hydroxyl groups) is protected with a tertiary alkyl group-containing group using a known technique. It can be synthesized from Kotoko.
  • the structural unit (aO) one type may be used alone, or two or more types may be used in combination.
  • the proportion of the structural unit (aO) in the component (A) is preferably 1 to 25 mol%, preferably 1 to 40 mol%, based on the total of all the structural units constituting the component (A). Is more preferably 5 to 20 mol%.
  • the component (A) may contain other structural units (a4) other than the structural units (al) to (a3) and (aO) as long as the effects of the present invention are not impaired.
  • the structural unit (a4) is not classified into the structural units (al) to (a3) and (aO) described above, and is not particularly limited as long as it is another structural unit.
  • ArF excimer laser KrF excimer laser
  • a number of hitherto known materials can be used as those used for resist resins such as those for use with ArF excimer lasers (preferably for ArF excimer lasers).
  • the structural unit (a4) for example, a structural unit derived from an ester acrylate ester containing an acid non-dissociable aliphatic polycyclic group is preferable.
  • the polycyclic group include those exemplified in the case of the structural unit (al), for ArF excimer laser, for KrF excimer laser (preferably for ArF excimer laser).
  • a large number of conventionally known strengths can be used as the oil component of the resist composition.
  • At least one kind selected from tricyclodecanyl group, adamantyl group, tetracyclododecyl group, isobornyl group and norbornyl group is preferable in terms of industrial availability.
  • These polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.
  • the proportion of the structural unit (a4) is 1 to 30 moles relative to the total of all the structural units constituting the component (A). % and it is preferred instrument 10 to 2 0 mole 0/0 and more preferably is! /,.
  • Such copolymers include, for example, copolymers having structural units (al), (a2) and (a3) forces; co-polymers having structural units (al), ( a2 ), (a3) and (a4) forces.
  • the component (A) preferably includes a copolymer having a combination of structural units represented by the following general formulas (A-11) to (A-17).
  • R is the same as R in the above formula (al "); R 27 is a lower alkyl group.
  • R is the same as R in the above formula (al ′,), 1 ⁇ , R 2 are the same as R 1 ′ R 2 in the above formula (pi); Represents an integer of 3. ]
  • R is the same as R in the formula (al ,,), R 21 ⁇ R 23 is the same R 21 to R in the above formula (I), e is in the formula (aO-) R 28 is a lower alkyl group.
  • examples of the lower alkyl group for R 27 include the same lower alkyl groups as those described above for R 27 .
  • R 27 a methyl group or an ethyl group is preferred, and an ethyl group is most preferred.
  • R 27 is most preferably a methyl group, preferably a methyl group or an ethyl group.
  • R ′′ and R 2 both are preferably hydrogen atoms.
  • N is preferably 0.
  • R 28 the same as the lower alkyl group for R 28 can be exemplified.
  • R 28 a methyl group or an ethyl group is preferred, and an ethyl group is most preferred.
  • R 21 to R 23 are each preferably a methyl group or an ethyl group, and most preferably a methyl group. e is most preferably 0.
  • R is the same as R in the above formula (al "), R to R are the same as R to R in the above formula (I), and R 27 is the same as in the above formula (A-11). It is the same as that of R 27, e is e the same way in the above formula (aO).]
  • R is the same as R in the above formula (al "), R ⁇ R is the same as! ⁇ 1 ⁇ in the above formula (I), and R 27 is the above formula (A-11) The same as R 27 in the above, and e is the same as e in the above formula (aO).]
  • R 27 the same as the lower alkyl group for R can be mentioned, and a methyl group or a methyl group, most preferably a methyl group or an ethyl group, is most preferable.
  • R 21 to R 23 are each preferably a methyl group or an ethyl group, and most preferably a methyl group. e is most preferably 0.
  • R 27 is the same as described above. Among them, a methyl group or an ethyl group is preferred, and an ethyl group is most preferred.
  • R 21 to R 23 are each preferably a methyl group or an ethyl group, and most preferably a methyl group. e is most preferably 0.
  • R 28 is preferably a methyl group or an ethyl group.
  • the component (A) one type of rosin (polymer) may be used alone, or two or more types may be used in combination.
  • a copolymer represented by the formula (A 11) and a copolymer represented by the formula (A-12) And a mixture of the copolymer represented by the formula (A-13) and the copolymer represented by the formula (A-14) is particularly preferable.
  • the mixing ratio of the copolymer represented by the formula (A-11) and the copolymer represented by the formula (A-12) is 9 by mass ratio because the effect of the present invention is particularly improved. : 1 to 1: 9 is preferred 8: 2 to 2: 8 is more preferred 6: 4 to 4: 6 is particularly preferred In the above formula (A-13)
  • the mixing ratio of the copolymer represented by the formula (A-14) and the copolymer represented by the above formula (A-14) is 9: 1 to 1: 9 in mass ratio because the effect of the present invention is particularly improved. 8: 2 to 2: 8 is more preferable. 7: 3 to 5: 5 is particularly preferable.
  • the component (A) has the effect of the present invention.
  • a mixture of the copolymer represented by the above formula (A-12) and the copolymer represented by the above formula (A-15) is preferably a copolymer represented by the above formula (A-15).
  • Mixing of a polymer and a copolymer represented by the above formula (A-17) Also particularly preferred.
  • the mixing ratio of the copolymer represented by the formula (A-12) and the copolymer represented by the formula (A-15) is 9 by mass ratio because the effect of the present invention is particularly improved. : 1 to 1: 9 is preferred 8: 2 to 2: 8 is more preferred 6: 4 to 4: 6 is particularly preferred In the above formula (A-15)
  • the mixing ratio of the copolymer to be prepared and the copolymer represented by the above formula (A-17) is 9: 1 to 1: 9 in mass ratio because the effect of the present invention is particularly improved. 9: 1 to 3: 7 is more preferable 9: 1 to 6: 4 is particularly preferable
  • the component (A) can be obtained by polymerizing a monomer for deriving each structural unit, for example, by known radical polymerization using a radical polymerization initiator such as azobisisobutyl-tolyl (AIBN). .
  • the component (A) includes, for example, HS—CH—CH—CH—C (CF
  • component (A) when the component (A) is a mixture, it can be obtained, for example, by synthesizing each polymer by polymerizing a monomer for deriving each structural unit using the above method and mixing the polymers.
  • the weight average molecular weight (Mw) of component (A) is not particularly limited, but 2,000-50,000 is preferred ⁇ , 3, ⁇ 000 to 30,000 power is preferred ⁇ , 5,000 to 20,000 power ⁇ most preferred! / ⁇ .
  • the degree of dispersion (Mw / Mn) i is preferably 1.0 to 5.0 force S, more preferably 1.0 to 3.0 force S, and most preferably 1.2 to 2.5.
  • Mn represents a number average molecular weight.
  • the content of the component (A) should be adjusted according to the thickness of the resist film to be formed.
  • the component (B) includes a cation moiety represented by the general formula (b′-1), and the general formula (b-3) and Z or (b-4). And an acid generator (B1) (hereinafter referred to as component (B1)) having an anion portion.
  • the component (B1) By including the component (B1), excellent depth of focus (DOF) characteristics can be obtained. In particular, the DOF characteristics of isolated hole patterns are improved. In addition, a resist pattern having a good shape can be easily obtained.
  • DOF depth of focus
  • R 1 and R 2 each independently represents a naphthyl group which may have a substituent.
  • part or all of its hydrogen atoms are alkyl groups, alkoxy groups, It may or may not be substituted with a halogen atom or the like.
  • the hydrogen atom of the naphthyl group may be substituted, and the alkyl group is preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. It is more preferable.
  • the alkoxy group is more preferably a methoxy group or an ethoxy group, preferably an alkoxy group having 1 to 5 carbon atoms.
  • the halogen atom is preferably a fluorine atom.
  • R 1 and R 2 are most preferably naphthyl groups having no substituent.
  • R 3 represents an alkyl group or an aryl group.
  • the alkyl group for R 3 is not particularly limited, and examples thereof include a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. Especially, it is preferable that it is C1-C5 from the point which is excellent in resolution. Specifically, methyl group, ethyl group, n-propyl group, isopyl pill group, n butyl group, isobutyl group, n pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, nonyl group, decanyl group A methyl group is preferable because it is excellent in resolution and can be synthesized at low cost.
  • the aryl group for R 3 is not particularly limited, for example, an aryl group having 6 to 20 carbon atoms, and in the aryl group, part or all of the hydrogen atoms are alkyl groups, alkoxy groups, halogen atoms, etc. It may or may not be replaced.
  • an aryl group having 6 to carbon atoms and LO is preferable because it can be synthesized at low cost.
  • Examples thereof include a phenol group and a naphthyl group.
  • alkyl group, alkoxy group and halogen atom in which the hydrogen atom of the aryl group may be substituted are the same as the alkyl group, alkoxy group and halogen atom exemplified in the above R 1 and R 2. Can be mentioned.
  • R 3 is most preferably a phenyl group or a naphthyl group, more preferably a aryl group, and most preferably a phenyl group.
  • X represents that at least one hydrogen atom is a fluorine atom. It is a substituted linear or branched alkylene group, and the alkylene group has 2 to 6 carbon atoms, preferably 3 to 5 carbon atoms, and 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 carbon of the alkyl group
  • the number is 1 to 10, preferably 1 to 7 carbon atoms, and particularly 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 because the solubility in the resist solvent is good within the above carbon number range.
  • the fluorination rate of the alkylene group or alkyl group is preferably 70 to 100%, more preferably 90%. And most preferably a perfluoroalkylene group or a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms.
  • At least one selected from the acid generator power represented by the chemical formulas (b'l-01) to (b'l-04) is particularly preferable.
  • Component (B1) can be used alone or in combination.
  • the content of the component (B1) in the entire component (B) is preferably 30% by mass or more, more preferably 40% by mass or more, and 70% by mass. may be the most preferred tool 1 00 mass 0/0 that is not less than% is particularly preferred instrument 80 mass% or more. By being above the lower limit of the range, the DOF characteristics of the resist pattern are improved.
  • the content of the component (B1) is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the component (A).
  • the most preferred is 5 to 15 parts by mass.
  • an acid generator (B2) other than the component (B1) (hereinafter referred to as the component (B2)) may be used in combination with the component (B1). Good.
  • the component (B2) is not particularly limited as long as it is other than the component (B1).
  • Those proposed as acid generators for amplification resists can be used.
  • Examples of such acid generators include onium salt-based acid generators such as odonium salts and sulfo-um salts, oxime sulfonate-based acid generators, bisalkyl or bis-aryl sulfo-diazomethanes,
  • diazomethane acid generators such as poly (bissulfol) diazomethanes, nitrobenzyl sulfonate acid generators, imino sulfonate acid generators, and disulfone acid generators.
  • an acid generator represented by the following general formula (b-0) can be preferably used.
  • 1 represents a linear, branched, or cyclic alkyl group, or a linear, branched, or cyclic fluorinated alkyl group
  • R 52 represents a hydrogen atom, a hydroxyl group, or a halogen atom.
  • R 53 may have a substituent.
  • U is an integer from 1 to 3.
  • R 51 represents a linear, branched or cyclic alkyl group, or a linear, branched or cyclic 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 preferably has 4 to 12 carbon atoms, more preferably 5 to 10 carbon atoms, and still more preferably 6 to carbon atoms: LO.
  • the fluorinated alkyl group is most preferably 1 to 4 carbon atoms, more preferably 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms.
  • the fluorination rate of the alkyl group (the ratio of the number of substituted fluorine atoms to the total number of hydrogen atoms in the alkyl group) is preferably 10 to 100%, more preferably 50 to 100%.
  • R 51 is most preferably a linear alkyl group or a fluorinated alkyl group.
  • R 52 is a hydrogen atom, a hydroxyl group, a halogen atom, a linear or branched alkyl group, a linear or branched halogenoalkyl group, or a linear or branched alkoxy group. .
  • examples of the halogen atom include a fluorine atom, a bromine atom, a chlorine atom, and an iodine atom, and a fluorine atom is preferable.
  • the alkyl group is linear or branched, and the carbon number thereof is preferably 1 to 5, particularly 1 to 4, and more preferably 1 to 3.
  • the halogenated alkyl group is a group in which part or all of the hydrogen atoms in the alkyl group are substituted with halogen atoms.
  • the alkyl group here are the same as the “alkyl group” in R 52 .
  • the halogen atom to be substituted include the same as those described above for the “norogen atom”.
  • the alkoxy group is linear or branched, and the carbon number thereof is preferably 1 to 5, particularly 1 to 4, and more preferably 1 to 3.
  • R 52 is preferably a hydrogen atom.
  • R 53 is an aryl group which may have a substituent, preferably an aryl group having 6 to 20 carbon atoms.
  • the structure of the basic ring (matrix ring) excluding the substituent includes a naphthyl group, Examples thereof include a phenyl group and an anthracenyl group, and a phenyl group is desirable from the viewpoint of the effects of the present invention and the absorption of exposure light such as an ArF excimer laser.
  • substituents examples include a hydroxyl group and a lower alkyl group (straight or branched chain, preferably having 5 or less carbon atoms, particularly preferably a methyl group).
  • aryl group for R 53 those having no substituent are more preferable.
  • u is an integer of 1 to 3, 2 or 3 is preferred and 3 is particularly desirable.
  • Preferred examples of the acid generator represented by the general formula (b-0) include the following.
  • the acid generators represented by the general formula (b-0) can be used singly or in combination of two or more.
  • R 1 " ⁇ 3 ", R 5 “and” each independently represents an aryl group or an alkyl group;
  • R 4 represents a linear, branched or cyclic alkyl group or a fluorinated alkyl group;
  • at least one of,, ⁇ represents an aryl group, and at least one of R 5 "and R 6 " represents an aryl group.
  • the aryl group of R lw to R 3 is not particularly limited, for example, an aryl group having 6 to 20 carbon atoms.
  • part or all of the hydrogen atoms may or may not be substituted with an alkyl group, an alkoxy group, a halogen atom, or the like.
  • the aryl group is preferably an aryl group having 6 to L0 carbon atoms because it can be synthesized at a low cost. Specific examples include a phenyl group and a naphthyl group.
  • alkyl group on which the hydrogen atom of the aryl group may be substituted examples include a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group, which are preferably alkyl groups having 1 to 5 carbon atoms. That is the most preferred.
  • alkoxy group that may be substituted with a hydrogen atom of the aryl group, a methoxy group and an ethoxy group are preferred, with an alkoxy group having 1 to 5 carbon atoms being preferred.
  • the halogen atom that may be substituted for the hydrogen atom of the aryl group is preferably a fluorine atom.
  • the “ ⁇ ” alkyl group is not particularly limited, and examples thereof include a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. From the viewpoint of excellent resolution, the number of carbon atoms is preferably 1 to 5. Specifically, a methyl 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 hexyl group, a cyclohexyl group, a nonyl group, A decanyl group and the like can be mentioned, and a methyl group can be mentioned as a preferable one because it is excellent in resolution and can be synthesized at low cost.
  • R lw to R 3 ′′ are most preferably a phenyl group or a naphthyl group, respectively.
  • 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. Most preferably, it is 1 to 4 carbon atoms.
  • the cyclic alkyl group is a cyclic group as shown by the above R 1 ′′, preferably a carbon number of 4 to 15 carbon atoms, more preferably a carbon number of 4 to 10 carbon atoms. Most preferably, the number is from 6 to 10.
  • the fluorinated alkyl group is most preferably 1 to 4 carbon atoms, more preferably 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. Further, the fluorination rate of the alkyl group (ratio of fluorine atoms in the alkyl group) is preferably 10 to: L0 0%, more preferably 50 to 100%, and in particular, all hydrogen atoms substituted with fluorine atoms are preferred because the strength of the acid becomes strong.
  • R 4 ′′ is most preferably a linear or cyclic alkyl group or a fluorinated alkyl group.
  • R 5 ′′ and R 6 ′′ each independently represent an aryl group or an alkyl group.
  • At least one of R 5 “and R 6 " represents an aryl group. It is preferred that both R 5 ′′ and R 6 ′′ are aryl groups.
  • Examples of the aryl group of R 5 "and R 6 " include those similar to the aryl groups of,, ⁇ .
  • both R 5 ′′ and R 6 ′′ are a phenol group.
  • sodium salt-based acid generator represented by the formulas (b-1) and (b-2) include trifluoromethanesulfonate or nonafluorobutanesulfonate of diphlo-rhodonium, Bis (4-tert-butylphenol) trifluoromethanesulfonate or nonafluorobutanesulfonate, trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorolob Tansusulfonate, tri (4 methylphenol) sulfurium trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate, dimethyl (4-hydroxynaphthyl) sulfotrifluoromethane Lomethanesulfonate and its heptafluoropropanesulfonate Or its nonafluorobutane sulfonate
  • ohmic salts in which the ionic part of these ohmic salts is replaced with methanesulfonate, n-propanesulfonate, n-butanesulfonate, or n-octanesulfonate can also be used.
  • the oxime sulfonate-based acid generator is a compound having at least one group represented by the following general formula (B-1), and generates an acid upon irradiation with radiation. It is what has.
  • Such oxime sulfonate acid generators are widely used for chemically amplified resist compositions, and can be arbitrarily selected and used.
  • R 31 and R 32 each independently represents an organic group.
  • the organic group of R 31 and R 32 is a group containing a carbon atom, and is an atom other than a carbon atom (for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom) , Halogen atoms (fluorine atoms, chlorine atoms, etc.) etc.
  • a linear, branched or cyclic alkyl group or aryl group is preferable. These alkyl groups and aryl groups may have a substituent.
  • substituents examples thereof include, for example, a fluorine atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms and the like.
  • “having a substituent” means that part or all of the hydrogen atoms of the alkyl group or aryl group are substituted with a substituent.
  • alkyl group 1 to 20 carbon atoms are preferable. 1 to 10 carbon atoms are more preferable. 1 to 8 carbon atoms are more preferable. 1 to 6 carbon atoms are particularly preferable. 1-4 carbon atoms are particularly preferable. Most preferred.
  • a partially or completely halogenated alkyl group (hereinafter sometimes referred to as a halogenated alkyl group) is particularly preferable.
  • the partially halogenated alkyl group means an alkyl group in which a part of hydrogen atoms is substituted with a halogen atom, and the completely halogenated alkyl group means that all of the hydrogen atoms are halogen atoms. It means an alkyl group substituted by.
  • halogen atom examples include a fluorine atom, a chlorine atom, an fluorine atom, and an iodine atom, and a fluorine atom is particularly preferable. That is, the halogenated alkyl group is preferably a fluorinated alkyl group! /.
  • the aryl group is preferably 4 to 20 carbon atoms, preferably 4 to 20 carbon atoms, more preferably 6 to 10 carbon atoms, more preferably LO.
  • a partially or completely halogenated aryl group is particularly preferable.
  • a partially halogenated aryl group means an aryl group in which a part of hydrogen atoms is substituted with a halogen atom, and a fully halogenated aryl group means that all hydrogen atoms are halogenated.
  • R 31 is particularly preferably an alkyl group having 1 to 4 carbon atoms having no substituent or a fluorinated alkyl group having 1 to 4 carbon atoms.
  • the organic group for R 32 is preferably a linear, branched or cyclic alkyl group, aryl group or cyan group.
  • Examples of the alkyl group and aryl group for R 32 include the same alkyl groups and aryl groups as those described above for R 31 .
  • R 32 is particularly preferably a cyano group, an alkyl group having 1 to 8 carbon atoms having no substituent, or a fluorinated alkyl group having 1 to 8 carbon atoms.
  • Examples thereof include compounds represented by B-2) or (B-3).
  • R 34 is an aryl group.
  • R 35 represents an alkyl group having no substituent or a halogenated alkyl group.
  • R 37 is a divalent or trivalent aromatic hydrocarbon group.
  • R 38 is an alkyl group having no substituent or a halogenated alkyl group.
  • the alkyl group or halogenated alkyl group having no substituent for R 33 preferably has 1 to 8 carbon atoms and 1 to 8 carbon atoms. Is more preferred. Carbon number 1 to 6 is most preferred.
  • R 33 is more preferably a fluorinated alkyl group, preferably a halogenated alkyl group.
  • the fluorinated alkyl group in R 33 is preferably fluorinated with 50% or more of the hydrogen atom of the alkyl group, more preferably 70% or more, and even more preferably 90% or more. I like it! /
  • the aryl group of R 34 includes aromatic carbon such as a phenol group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthracyl group, and a phenanthryl group.
  • Etc Among these, a fluorenyl group is preferable.
  • the aryl group of R 34 may have a substituent such as an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, or an alkoxy group.
  • the alkyl group or halogenated alkyl group in the substituent preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms.
  • the halogenated alkyl group is preferably a fluorinated alkyl group.
  • the alkyl group or halogenated alkyl group having no substituent of R 35 preferably has 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms. Most preferred.
  • R 35 is preferably a halogenated alkyl group, more preferably a fluorinated alkyl group, and more preferably a partially fluorinated alkyl group.
  • the fluorinated alkyl group in R 35 preferably has 50% or more of the hydrogen atoms of the alkyl group fluorinated, more preferably 70% or more, and even more preferably 90% or more. This is preferable because the strength of the acid is increased. Most preferably, it is a fully fluorinated alkyl group in which a hydrogen atom is 100% fluorine-substituted.
  • the alkyl group or the halogenated alkyl group having no substituent of R 36 is an alkyl group or a group having no substituent of R 33 described above. Examples thereof are the same as the halogenalkyl group.
  • Examples of the divalent or trivalent aromatic hydrocarbon group for R 37 include groups in which the aryl group strength of R 34 is one or two hydrogen atoms removed.
  • P is preferably 2.
  • oxime sulfonate-based acid generators include ⁇ - (p-toluenesulfo-oxyximino) monobenzyl cyanide, ⁇ - ( ⁇ chlorobenzene-sulfo-oxyoximino) -benzyl cyanide, ⁇ - ( 4-Nitrobenzenesulfo-luoxyimino) -Benzyl cyanide, Hiichi (4-troo 2 trifluoromethylbenzenesulfo-ruximino) Benzyl cyanide, ⁇ - (Benzenesulfo-ruximino) —4-Clorobenzoylcia-do , ⁇ (Benzenesulfo-ruximino) — 2, 4 dichlorobenzil cyanide, ⁇ — (Benzenesulfo-ruximino) — 2, 6 dichlorobenzil cyanide, ⁇ (Benzenes
  • Ruoxime sulfonate-based acid generator As disclosed in JP-A-9-208554 (paragraphs [0012] to [0014], [Chemical Formula 18] to [Chemical Formula 19]), Ruoxime sulfonate-based acid generator, International Publication No. 04-074242 Pan The oxime sulfone and acid generator disclosed in Fret (Example 65 on page 65, 85) can also be suitably used.
  • bisalkyl or bisarylsulfol-diazomethanes include bis (isopropylsulfol) diazomethane, bis (p toluenesulfol) diazomethane, bis (1, Examples thereof include 1-dimethylethylsulfol) diazomethane, bis (cyclohexylsulfol) diazomethane, and bis (2,4 dimethylphenylsulfol) diazomethane.
  • diazomethane acid generators disclosed in JP-A-11-035551, JP-A-11-035552 and JP-A-11-035573 can also be suitably used.
  • poly (bissulfol) diazomethanes include 1,3 bis (phenylsulfol diazomethylsulfol) pronone, 1, 4 disclosed in JP-A-11 322707.
  • the above acid generators may be used alone or in combination of two or more.
  • the content of the entire component (B) in the positive resist composition of the present invention is preferably 0.5 to 30 parts by mass, more preferably 1 to 100 parts by mass of the component (A). ⁇ 20 parts by weight Is done. By setting it within the above range, pattern formation is sufficiently performed. Moreover, since a uniform solution is obtained and storage stability becomes favorable, it is preferable.
  • the positive resist composition further contains optional components to improve the resist pattern shape, post expo sure stability of the latent image formed by tne pattern-wise exposure of the resist 1 ayer, etc. It is preferable to contain a nitrogen-containing organic compound (D) (hereinafter referred to as component (D)).
  • component (D) a nitrogen-containing organic compound
  • aliphatic amines particularly secondary aliphatic amines and tertiary aliphatic amines, can be used arbitrarily from known ones. Is preferred.
  • “aliphatic” in the claims and the specification is a relative concept with respect to aromatics, and is defined to mean a group, a compound, or the like that does not have aromaticity.
  • An ⁇ aliphatic cyclic group '' means a monocyclic group or polycyclic group having no aromaticity.
  • an aliphatic amine at least one hydrogen atom of ammonia NH must have at least 12 carbon atoms.
  • Examples include amines substituted with alkyl groups or hydroxyalkyl groups below (alkylamines or alkylalcoholamines) or cyclic amines.
  • Examples of the cyclic amine include heterocyclic compounds containing a nitrogen atom as a hetero atom.
  • the heterocyclic compound may be monocyclic (aliphatic monocyclic ammine) or polycyclic (aliphatic polycyclic ammine).
  • aliphatic monocyclic amine examples include piperidine and piperazine.
  • Aliphatic polycyclic amines having 6 to 10 carbon atoms are preferred, such as 1, 5 — diazabicyclo [4. 3. 0] — 5-nonene, 1, 8 — diazabicyclo [5 4. 0] — 7-undecene, hexamethylenetetramine, 1,4-diazabicyclo [2.2.2] octane.
  • 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 includes, as optional components, organic carboxylic acids and phosphorus oxoacids and the like for the purpose of preventing sensitivity deterioration, improving the resist pattern shape, stability with time, and the like.
  • Derivative power Group power At least one selected compound (hereinafter referred to as component (E)) can be contained.
  • organic carboxylic acid for example, acetic acid, malonic acid, citrate, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable.
  • Examples of phosphorus oxoacids and derivatives thereof include phosphoric acid, phosphonic acid, and phosphinic acid. Among these, phosphonic acid is particularly preferred.
  • Examples of derivatives of phosphorus oxoacids include esters in which the hydrogen atom of the oxoacid is substituted with a hydrocarbon group.
  • Examples of the hydrocarbon group include an alkyl group having 1 to 5 carbon atoms and a carbon number of 6 ⁇ 15 aryl groups and the like.
  • phosphoric acid derivatives examples include phosphoric acid esters such as di-n-butyl phosphate and diphenyl phosphate.
  • phosphonic acid dimethyl ester phosphonic acid diol n-butinoreestenole
  • fenenorephosphonic acid phosphonic diphenenolesthenole
  • phosphonic acid diester phosphonic acid diester
  • phosphonic acid esters such as benzyl ester.
  • phosphinic acid derivatives include phosphinic acid esters such as phenylphosphinic acid.
  • one type may be used alone, or two or more types may be used in combination.
  • an organic carboxylic acid is preferred, and salicylic acid is particularly preferred.
  • Component (E) is used in a proportion 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 there are further additives that are miscible as desired, for example, an additional grease for improving the performance of the resist film, and a surfactant for improving the coating property.
  • an additional grease for improving the performance of the resist film for example, a surfactant for improving the coating property.
  • a dissolution inhibitor, a plasticizer, a stabilizer, a colorant, an antihalation agent, a dye, and the like can be appropriately added and contained.
  • the positive resist composition of the present invention can be produced by dissolving the material in an organic solvent (hereinafter sometimes referred to as component (S)).
  • each component to be used it is sufficient if each component to be used can be dissolved into a uniform solution. Any one of conventionally known solvents for chemically amplified resists can be used. Two or more kinds can be appropriately selected and used.
  • latones such as ⁇ -butyrolatatane; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl- ⁇ -amyl ketone, methyl isoamyl ketone, 2-heptanone; ethylene glycol, diethylene glycol, propylene glycol, dipropylene
  • Polyhydric alcohols such as glycol; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate or dipropylene glycol monoacetate; the polyhydric alcohols or having the ester bond
  • Monoalkyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, etc., or ethers such as monophenyl ether
  • Polyhydric alcohols such as compounds having a combination [in these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl
  • organic solvents can be used alone or as a mixed solvent of two or more.
  • PGMEA propylene glycol monomethyl ether acetate
  • PGME propylene glycol monomethyl ether
  • EL EL
  • a mixed solvent in which PGMEA and a polar solvent are mixed 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: 8 to 8: 2. Preferably within range! /.
  • the mass ratio of PGMEA: EL is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2.
  • the mass ratio of PGMEA: PGME is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2, more preferably 3: 7 to 7: Three.
  • a mixed solvent of at least one selected from among PGMEA and EL and ⁇ -petit-mouth rataton is also preferable.
  • the mixing ratio of the former and the latter is preferably 70: 30-95: 5.
  • the amount of component (S) used is not particularly limited, but it is a concentration that can be applied to a substrate, etc., and can be appropriately set according to the coating film thickness. It is used so as to be in the range of 20% by mass, preferably 5 to 15% by mass.
  • the positive resist composition of the present invention has a habit effect when it has excellent depth of focus (DOF) characteristics. The reason is not clear, but is presumed as follows.
  • the component (B1) is used as an acid generator.
  • the cation part of the component (B1) has a substituent! /, But has at least two naphthyl groups. As a result, it can be added more in the resist composition than conventional cation moieties such as triphenylsulfone (TPS). This is thought to be because the transparency to the exposure wavelength band (especially the wavelength band of Ar F excimer laser) is higher.
  • TPS triphenylsulfone
  • the key-on part of the (Bl) component has a three-dimensionally bulky and bulky structure. As a result, it is considered that the acid generation efficiency is suppressed because the diffusion distance of the acid is short compared with the conventional key-on part such as nonafluorobutanesulfonate.
  • the presence density of the acid generator in the resist film can be increased, the acid diffusion length is short, so the resist pattern shape is not deteriorated, and the DOF characteristics are excellent. Guessed.
  • an effect that a resist pattern having a good shape is formed can be obtained.
  • a resist pattern with high rectangularity and good resolution can be formed.
  • the proximity effect is good.
  • Proximity effect indicates the magnitude of the effect of the size of the resist pattern to be formed due to changes in the distance (pitch) between mask pattern patterns. The smaller the proximity effect, the greater the process margin. Improves.
  • line edge roughness which means uneven unevenness of the line side wall
  • LER line edge roughness
  • the resist pattern forming method 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 developing the resist film. And a step of forming a resist pattern.
  • the positive resist composition is applied onto a substrate such as silicon wafer with a spinner or the like, and a pre-beta (post-apply bake (PAB)) of 40 to Apply for 120 seconds, preferably 60-90 seconds.
  • PAB post-apply bake
  • ArF excimer laser light is selectively exposed through a desired mask pattern, and then PEB (post-exposure heating) is preferably performed for 40 to 120 seconds at a temperature of 80 to 150 ° C. Apply for 60-90 seconds.
  • this is developed using an alkali developer, for example, an aqueous 0.1 to 10% by weight tetramethylammonium hydroxide solution. In this way, a resist pattern faithful to the mask pattern can be obtained.
  • An organic or inorganic antireflection film can be provided between the substrate and the coating layer of the resist composition.
  • the wavelength used for exposure is not particularly limited.
  • the positive resist yarn composition according to the present invention is particularly effective for an ArF excimer laser.
  • the polymers (A) -1 to (A) -9 used in the following Examples 1 to 14 and Comparative Examples 1 to 4 were prepared by using the monomers (1) to (14) shown below and using the known dropping polymerization method.
  • the synthesis of the polymers (A) -2 to (A) -9 is carried out by the synthesis method of the polymer (A) -1!
  • the polymer was synthesized by the same method as the polymer (A) -1, except that the monomer for deriving the structural unit of the polymer was used at a predetermined molar ratio.
  • the mass average molecular weight (Mw) and the dispersity (Mw / Mn) were determined on a polystyrene conversion basis by gel permeation chromatography (GPC). .
  • the composition ratio indicating the proportion (mol%) of each structural unit in the polymer was calculated by carbon NMR. In the chemical formula, the number attached to the lower right of the structural unit indicates the ratio (mol%) of each structural unit in the polymer.
  • (B) -2 An acid generator represented by the following chemical formula (B) -2.
  • a contact hole pattern was formed using the obtained positive resist composition solution, and the following evaluation was performed.
  • the organic anti-reflection coating composition “ARC-29A” (trade name, manufactured by Prüs Science) was applied onto an 8-inch silicon wafer using a spinner, and 205 ° C for 60 seconds on a hot plate. By baking and drying, an organic antireflection film having a thickness of 77 nm was formed. On the antireflection film, the positive resist composition solution obtained above was applied using a spinner, pre-betaned at a PAB temperature shown in Table 2 for 60 seconds on a hot plate, and dried. A resist film having a thickness of 150 nm was formed.
  • the optimum exposure dose Eop (mj / cm 2 ) for forming a hole pattern with a diameter of 80 nm is formed at an optimum exposure dose Eop (mj / cm 2 ).
  • the depth of focus (DOm) ( ⁇ m) in the isolated hole pattern obtained within the range of the dimensional change rate of 72 to 88nm) was obtained. The results are shown in Table 2.
  • Examples 1 to 7 according to the present invention were used.
  • the shape of the hole was also good, for example, it was confirmed that the cross-sectional shape is highly rectangular and the shape seen from the top is highly round.
  • a line-and-space pattern was formed using the obtained positive resist composition solution.
  • DOF depth of focus
  • LER line edge roughness
  • the resist pattern (hereinafter referred to as the LZS pattern) of 80 nm was formed by developing for 20 seconds, rinsing with pure water for 20 seconds, and performing shake-off drying.
  • 3 refers to the standard deviation ( ⁇ ) of the side length of SEM (manufactured by Hitachi, Ltd., product name: S-9220), the width of the resist pattern of the sample was measured at 32 locations, and the resulting force was also calculated. A triple value (3 ⁇ ) is shown. This 3 ⁇ means that the smaller the value, the more uniform resist pattern that the roughness of the line side wall is smaller is obtained.
  • Example 8 14 according to the present invention using (B) -1 was V ⁇ using (B) -1, and the DOF value was the same as that of Comparative Example 4 It was also confirmed that the DOF characteristics are excellent!
  • Example 814 since the LER value is in the same range or smaller than that in Comparative Example 4, a resist pattern having a uniform width with small line sidewall roughness is obtained. It was confirmed that
  • the positive resist composition of the present invention has excellent depth of focus (DOF) characteristics.
  • the resist pattern formed by the method of the present invention has high rectangularity and good resolution and proximity effect. Therefore, the present invention is extremely useful industrially.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
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  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

Cette invention concerne une composition de réserve positive comprenant un élément résine (A) et un composant générateur d'acide (B). Le composant générateur d'acide (B) comprenant un générateur d'acide (B1) présentant un groupement fonctionnel cationique représenté par la formule générale (b'-1) et un groupement fonctionnel anionique représenté par la formule générale (b-3) et/ou (b-4). [formules chimiques] (b'-1) (b-3) (b-4), R1 et R2 représentent indépendamment l'un de l'autre un groupe naphthyle qui peut comprendre un substituant; R3 représente un groupe alkyle ou aryle; X'' représente un groupe alkylène comprenant de 2 à 6 atomes de carbone, au moins un atome d'hydrogène étant substitué par un atome de fluor; et Y'' et Z'' indépendamment l'un de l'autre représentent un groupe alkyle comprenant de 1 à 10 atomes de carbone, au moins un atome d'hydrogène étant substitué par un atome de fluor.
PCT/JP2007/061284 2006-06-23 2007-06-04 Composition de réserve positive et procédé de formation d'un motif de réserve WO2007148525A1 (fr)

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JP4834505B2 (ja) * 2006-09-26 2011-12-14 富士フイルム株式会社 ポジ型感光性組成物及びそれを用いたパターン形成方法
JP2008225412A (ja) * 2007-03-16 2008-09-25 Jsr Corp 液浸露光用感放射線性樹脂組成物
JP5001192B2 (ja) * 2008-02-18 2012-08-15 東京応化工業株式会社 レジスト組成物、レジストパターン形成方法、新規な化合物および酸発生剤
EP2444845A4 (fr) * 2009-06-16 2013-05-29 Jsr Corp Composition de résine sensible aux rayonnements
JP5452102B2 (ja) * 2009-07-02 2014-03-26 東京応化工業株式会社 レジスト組成物及びレジストパターン形成方法

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JP2005037888A (ja) * 2003-06-26 2005-02-10 Tokyo Ohka Kogyo Co Ltd ポジ型レジスト組成物及びそれを用いたレジストパターン形成方法
JP2005172949A (ja) * 2003-12-08 2005-06-30 Tokyo Ohka Kogyo Co Ltd ホトレジスト組成物およびレジストパターン形成方法
JP2005173468A (ja) * 2003-12-15 2005-06-30 Tokyo Ohka Kogyo Co Ltd 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
JP2005196095A (ja) * 2003-10-23 2005-07-21 Tokyo Ohka Kogyo Co Ltd レジスト組成物およびレジストパターン形成方法
JP2006078760A (ja) * 2004-09-09 2006-03-23 Tokyo Ohka Kogyo Co Ltd 電子線またはｅｕｖ（極端紫外光）用レジスト組成物及びレジストパターン形成方法

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JP2005037888A (ja) * 2003-06-26 2005-02-10 Tokyo Ohka Kogyo Co Ltd ポジ型レジスト組成物及びそれを用いたレジストパターン形成方法
JP2005196095A (ja) * 2003-10-23 2005-07-21 Tokyo Ohka Kogyo Co Ltd 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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