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WO2008013030A1 - Composé, générateur d'acide, composition de réserve et procédé pour former un motif de réserve - Google Patents

Composé, générateur d'acide, composition de réserve et procédé pour former un motif de réserve Download PDF

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Publication number
WO2008013030A1
WO2008013030A1 PCT/JP2007/063290 JP2007063290W WO2008013030A1 WO 2008013030 A1 WO2008013030 A1 WO 2008013030A1 JP 2007063290 W JP2007063290 W JP 2007063290W WO 2008013030 A1 WO2008013030 A1 WO 2008013030A1
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Prior art keywords
group
alkyl group
acid
resist composition
resist
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Application number
PCT/JP2007/063290
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English (en)
Japanese (ja)
Inventor
Takeshi Iwai
Makiko Irie
Original Assignee
Tokyo Ohka Kogyo Co., Ltd.
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Publication date
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Publication of WO2008013030A1 publication Critical patent/WO2008013030A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/06—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing halogen atoms, or nitro or nitroso groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C07D333/56—Radicals substituted by oxygen atoms
    • 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 compound suitable as an acid generator for a resist composition, an acid generator comprising the compound, a resist composition containing the acid generator, and a resist pattern using the resist composition. It relates to a 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. Specifically, in the past, ultraviolet rays typified by g-line and i-line were used. Currently, mass production of semiconductor devices using KrF excimer laser and ArF excimer laser has begun. In addition, 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 as a resist material satisfying such requirements.
  • positive chemically amplified resist has increased alkali solubility due to the action of acid as a base resin.
  • the base resin of the resist currently used in ArF excimer laser lithography, etc. it is excellent in transparency around 193 nm, and therefore, a structural unit that generally induces (meth) acrylate force is mainly used.
  • a resin (acrylic resin) contained in the chain is used.
  • (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 !.
  • Patent Document 1 Japanese Patent Laid-Open No. 2003-241385
  • Patent Document 2 JP 2005-100203 A
  • an acid salt-based acid generator having a cation is used to dissolve various components of a resist, and has a low solubility in an organic solvent (resist solvent). is there. Such low solubility in a resist solvent reduces the temporal stability of the resist, and accordingly causes poor lithography properties.
  • the present invention has been made in view of the above circumstances, and is a novel compound suitable as an acid generator for a resist composition, an acid generator comprising the compound, and a resist containing the acid generator. It is an object of the present invention to provide a resist composition and a resist pattern forming method using the resist composition.
  • the first aspect (aspect) of the present invention is a compound represented by the following general formula (bl-3).
  • R "and R 4d are each independently an alkyl group, a acetyl group, an alkoxy group, a carboxy group, a hydroxyl group, or a hydroxyalkyl group; n is an integer of 0 to 3, and n is 0 Is an integer from ⁇ 3, n is an integer from 0 to 2, provided that n, n and n are simultaneously
  • the second aspect (aspect) of the present invention is an acid generator comprising a compound represented by the general formula (b1-3).
  • the third aspect (aspect) of the present invention includes a base material component (A) whose alkali solubility is changed by the action of an acid and an acid generator component (B) which generates an acid upon exposure.
  • a resist composition comprising:
  • the acid generator component (B) is a resist composition comprising an acid generator (B1) comprising a compound represented by the general formula (bl-3).
  • the fourth aspect of the present invention includes a step of forming a resist film on a substrate using the resist composition of the third aspect of the present invention, and the resist A resist pattern forming method including a step of exposing a film and a step of developing the resist film to form a resist pattern.
  • structural unit means a monomer unit (monomer unit) constituting the resin component (polymer).
  • Exposure is a concept that includes radiation exposure in general.
  • alkyl group includes linear, branched and cyclic monovalent saturated hydrocarbon groups.
  • lower alkyl group means an alkyl group having 1 to 5 carbon atoms. "Halony The “lower alkyl group” in the “lower alkyl group” has the same meaning.
  • a novel compound suitable as an acid generator for a resist composition an acid generator comprising the compound, a resist composition containing the acid generator, and a resist pattern using the resist composition A forming method is provided.
  • the compound of the first aspect (aspect) of the present invention is represented by the general formula (bl-3).
  • R 41 , R 42 and R 43 are each independently an alkyl group, acetyl group, alkoxy group, carboxy group, hydroxyl group or hydroxyalkyl group.
  • the alkyl group is preferably a lower alkyl group having 1 to 5 carbon atoms, more preferably a linear or branched alkyl group, a methyl group, an ethyl group, or a propyl group. Particularly preferred is a group, isopropyl group, n-butyl group, or tert-butyl group.
  • the alkoxy group is particularly preferably a methoxy group or an ethoxy group, more preferably a linear or branched alkoxy group, particularly preferably an alkoxy group having 1 to 5 carbon atoms.
  • hydroxyalkyl group examples include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group, which are preferably groups in which one or more hydrogen atoms of the above alkyl group are substituted with a hydroxy group.
  • n is an integer of 0 to 3, preferably 1 or 2, and more preferably 1. n is an integer of 0 to 3, preferably 0 or 1, and more preferably 0.
  • n is an integer of 0 to 2, preferably 0 or 1, and more preferably 1.
  • n, n, and n are not 0 at the same time.
  • R 14 represents a linear, branched or cyclic alkyl. Or a halogenated alkyl group.
  • the linear or branched alkyl group as R 14 preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms. . Most preferably, the cyclic alkyl group as R 14 has 4 to 15 carbon atoms, preferably 4 to 10 carbon atoms, and more preferably 6 to 10 carbon atoms.
  • R 14 is preferably a halogenoalkyl group. That is, in the general formula (bl-3), X— is preferably a halogenated alkyl sulfonate ion.
  • the halogenated alkyl group is one in which part or all of the hydrogen atoms in the alkyl group are substituted with halogen atoms.
  • examples of the halogenated alkyl group include those in which a halogen atom is substituted for the same as the “alkyl group” in R 14 .
  • halogen atom to be substituted examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • alkyl halide it is preferred that 50 to 100% of the total number of hydrogen atoms are substituted with halogen atoms, and it is more preferred that all are substituted! /.
  • the halogenated alkyl group is preferably a linear, branched or cyclic fluorinated alkyl group! /.
  • the linear or branched fluorinated alkyl group has 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. Most preferred.
  • the cyclic fluorinated alkyl group preferably has 4 to 15 carbon atoms, preferably 4 to carbon atoms, more preferably 6 to LO, and most preferably LO.
  • the fluorination rate of the fluorinated alkyl group (the 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 50 to 100%, and particularly those in which all hydrogen atoms are substituted with fluorine atoms are most preferable because the strength of the acid is increased.
  • 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 a carbon number of , Preferably 2 to 6, more preferably 3 to 5 carbon atoms, and most preferably 3 carbon atoms
  • Y "and ⁇ " each independently represent at least 1 A straight-chain or branched alkyl group in which two hydrogen atoms are substituted with fluorine atoms, and the alkyl group preferably has 1 to L0, more preferably 1 to 7 carbon atoms, Most preferably, it has 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 to 100%, and most preferably all hydrogen atoms.
  • the compound (bl-3) of the first aspect (aspect) of the present invention is represented by, for example, a compound represented by the following general formula (bl-0 31) and a general formula (bl-0-32) below.
  • a compound such as copper (II) benzoate in a solvent such as black benzene and iodine benzene at 80 to 130 ° C, more preferably at 100 to 120 ° C. It can be obtained by reacting for 5 to 3 hours, more preferably 1 to 2 hours.
  • R is the same as R 41 in the formula (bl-3); n is the same as n in the formula (bl-3); It is the same as X— in the formula. ]
  • R 4 and R 4d are the same as R 4 and R 4d in the (BL- 3) formula; n and
  • n is the same as n and n in the above formula (bl-3). However, n, n and n are the same
  • the acid generator of the second aspect of the present invention may have a compound power represented by the general formula (b 1-3). Wherein R 41 , R 42 and R 43 ; n, n and n; X_ are those mentioned in the compound of the first aspect of the present invention.
  • the resist composition of the third aspect (aspect) of the present invention comprises a substrate component (A) whose alkali solubility is changed by the action of an acid (hereinafter referred to as component (A)) and an acid that generates an acid upon exposure. It contains a generator component (B) (hereinafter referred to as component (B)), and the component (B) contains an acid generator (B1) that also has the compound power represented by the general formula (b 13). It is a waste.
  • a polymer material whose alkali solubility is changed by the action of an acid can be used, and a low molecular weight material whose alkali solubility is changed by the action of an acid. Can also be used.
  • the resist composition of the present invention may be a negative resist composition or a positive resist composition! / ⁇ .
  • the resist composition of the present invention is a negative resist composition
  • the component (A) is an alkali-soluble resin
  • a crosslinking agent (C) is further added to the negative resist composition.
  • a negative resist composition when an acid is generated from the component (B) by exposure during resist pattern formation, the exposed portion acts to crosslink between the alkali-soluble resin and the crosslinking agent. Occurs and changes to alkali-insoluble.
  • the coconut resin having a unit derived from at least one of a- (hydroxyalkyl) acrylic acid or ⁇ - (hydroxyalkyl) acrylic acid also having a lower alkyl ester power is selected. It is preferable because a good resist pattern can be formed.
  • a (hydroxyalkyl) acrylic acid is composed of acrylic acid in which a hydrogen atom is bonded to the ⁇ -position carbon atom to which the carboxy group is bonded, and a hydroxyalkyl group (preferably having 1 carbon atom) in the ⁇ -position carbon atom. ⁇ 5 hydroxyalkyl groups) to which (X-hydroxyalkylacrylic acid or both) is attached.
  • crosslinking agent (C) for example, it is usually preferable to use an amino crosslinking agent such as glycoluril having a methylol group or an alkoxymethyl group, which can form a good resist pattern with little swelling.
  • the amount of the crosslinking agent (C) is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the alkali-soluble resin.
  • component (ii) is V, an alkali-insoluble one having an acid dissociable, dissolution inhibiting group, and resist pattern formation Occasionally, when an acid is generated from the component (B) by exposure, the acid releases the acid dissociable, dissolution inhibiting group, so that the component (A) becomes alkali-soluble. Therefore, in the formation of the resist pattern, when the resist film obtained by applying the positive resist composition on the substrate is selectively exposed, the exposed portion turns to alkali-soluble while the unexposed portion Since it remains insoluble in alkali, it can be developed with alkali.
  • the component (A) is preferably a base material component whose alkali solubility is increased by the action of an acid.
  • the resin component (A1) whose alkali solubility is increased by the action of an acid. ) (Hereinafter referred to as the component (A1)) is more preferable. That is, the resist composition of the present invention is preferably a positive resist composition.
  • the resist composition of the present invention can be suitably used as a resist composition for immersion exposure in a resist pattern forming method including an immersion exposure step, and a step of forming a three-layer resist laminate.
  • the resist pattern forming method can be suitably used as a positive resist composition for forming an upper resist film.
  • the (A1) component that is preferably used for the positive resist composition is exemplified. explain.
  • the component (A1) suitably used in a strong positive resist composition preferably has a structural unit (al) derived from an acrylate ester group containing an acid-releasing dissolution inhibiting group.
  • the component (A1) preferably further has a structural unit (a2) derived from an acrylate ester containing a latathone-containing cyclic group.
  • the component (A1) preferably further has a structural unit (a3) from which an ester ester acrylate containing a polar group-containing aliphatic hydrocarbon group is also derived.
  • 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” refers to an acrylic acid ester having a hydrogen atom bonded to a carbon atom at the X position. In addition to stealth, the concept also includes those in which a substituent (atom or group other than a hydrogen atom) is bonded to the carbon atom at position a.
  • Examples of the substituent include a halogen atom, a lower alkyl group, and a halogenated lower alkyl group.
  • Examples of 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 “halogen lower alkyl group” is a group in which at least one or all of the hydrogen atoms of the lower alkyl group are substituted with the halogen atoms.
  • the ⁇ position of the structural unit from which the acrylate power is also derived means a carbon atom to which a carbo group is bonded, unless otherwise specified.
  • the acrylate ester as the lower alkyl group as the substituent at the ⁇ -position, specifically, methyl group, ethyl group, propyl group, isopropyl group, ⁇ -butyl group, isopropyl group, tert-butyl group, pentyl group And a linear or branched lower alkyl group such as an isopentyl group and 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 particularly preferred from the viewpoint of industrial availability.
  • 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 (A1) insoluble in alkali before dissociation, and after dissociation, the entire (A1) component changes to alkali soluble.
  • alkali dissolution inhibiting property that makes the entire component (A1) insoluble in alkali before dissociation, and after dissociation, the entire (A1) component changes to alkali soluble.
  • the acid dissociable, dissolution inhibiting group of the base resin 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, etc .; an acetal type acid dissociable, dissolution inhibiting group such as an alkoxyalkyl group is widely known.
  • (Meth) acrylic acid” means acrylic acid and It means one or both of tacrylic acid.
  • 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 the 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, compound, or the like that does not have aromaticity.
  • Aliphatic branched means that it has no aromaticity and has a branched structure
  • the structure of the “aliphatic branched acid dissociable, dissolution inhibiting group” is not limited to a group consisting of a carbon atom and a hydrogen atom (hydrocarbon group), but is preferably a hydrocarbon group. Yes.
  • 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, etc. Can be mentioned.
  • Aliphatic cyclic group indicates that it has no aromaticity and is 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. And a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as tricycloalkane or tetracycloalkane. Specifically, cyclopentane
  • monocycloalkanes such as cyclohexane, and groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and 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-). And a group having a group and a branched alkylene group having a tertiary carbon atom bonded thereto.
  • R is a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated alkyl group, and R 15 and R 16 are alkyl groups (both linear and branched, preferably 1 to 5). ]
  • halogen atom, lower alkyl group or halogenated lower alkyl group of R in the above formula 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. .
  • 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, this 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 represents a hydrogen atom or a lower alkyl group, n represents an integer of 0 to 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.
  • Examples of the lower alkyl group for R 1 ′ and R 2 ′ include the same lower alkyl groups as those described above for R, and a methyl group that is preferably a methyl group or an ethyl group is most preferable.
  • the acid dissociable, dissolution inhibiting group (pi) is preferably a group represented by the following general formula (pi-1).
  • R 1 ', n, Y is R 1 in the general formula (pi)', n, it is the same as Y. ]
  • Examples of the lower alkyl group of ⁇ include those similar to the lower alkyl group of R above.
  • aliphatic cyclic group a large number of 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 17 and R 18 each independently represent a linear or branched alkyl group or a hydrogen atom
  • R 19 represents a linear, branched or cyclic alkyl group.
  • 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 or a methyl group with a methyl group being preferred.
  • one of R 17 and R 18 is preferably a hydrogen atom and the other is a katyl 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.
  • 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 optionally 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, acetal type acid dissociable, dissolution inhibiting group, and the like.
  • Tertiary alkyl ester type acid dissociable, dissolution inhibiting groups are preferred ⁇
  • R is the same as R in general 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, and the aliphatic cyclic group is the above except that a group in which two or more hydrogen atoms are removed is used.
  • the same explanation as in the “aliphatic cyclic group” can be used.
  • 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
  • ⁇ represents 0 to 3 M represents 0 or 1
  • 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 carbon number 1 Represents a lower alkyl group of ⁇ 5.
  • R in the above general formulas (al-1) to (al-4) is the same as R in the general formulas (al-0-1) to (al-0-2).
  • R 1 ′ and R 2 ′ are preferably at least one 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 for X 1 above.
  • Examples of the aliphatic cyclic group for Y include the same groups as those exemplified above in the explanation of the “aliphatic cyclic group”.
  • the structural unit represented by the general formula (al— 1) is specifically preferred (al— 1 1) to (al— 1— 6) or (al— 1— 35) to (al— It is more preferable to use at least one selected from the structural unit forces represented by 1-41).
  • the structural unit (al) in particular, those represented by the following general formula (al-1 01) including structural units of the formula (al 1 1) to the formula (al 1-4), and the formula (al —
  • the following general formula (a 1—102) including the structural units of (1 35) to (al— 1 -41) is also preferred.
  • 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.
  • the component (A1) preferably has a structural unit (a2) derived from an acrylate ester containing a latathone-containing cyclic group, in addition to the structural unit (al).
  • 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 lathetone-containing cyclic group of the structural unit (a2) has an affinity for the resist film to improve the adhesion of the resist film to the substrate or to have an affinity for a developer containing water when the component (A1) is used for forming the resist film. It is effective in enhancing the sex.
  • any unit can be used without any particular limitation.
  • examples of the latatatone-containing monocyclic group include groups in which y-peptidyl latatone force hydrogen atom is removed.
  • examples of the latathone-containing polycyclic group include groups obtained by removing one hydrogen atom from a polycycloalkane such as a bicycloalkane, tricycloalkane, or tetracycloalkane having a latathone ring.
  • examples of the structural unit (a2) include structural units represented by the following general formulas (a2 ⁇ 1) to (a2 ⁇ 5).
  • R is a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group
  • R ′ is independently a hydrogen atom, a lower alkyl group, or an alkoxy group having 1 to 5 carbon atoms.
  • M is an integer of 0 or 1
  • A is an alkylene group having 1 to 5 carbon atoms or an oxygen atom.
  • R in the general formulas (a2-1) to (a2-5) is the same as R in the general formula (al ") of the structural unit (al).
  • the lower alkyl group for R ′ is the same as the lower alkyl group for R in the structural unit (al).
  • 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.
  • R ′ is preferably a hydrogen atom in view of industrial availability.
  • one type may be used alone, or two or more types may be used in combination.
  • the amount of the structural units within the component (a2) is, (A1) based on the combined total of all structural units constituting the component 5 to 60 Monore 0/0 force S
  • the component (A1) is added to the structural unit (al) or the structural unit.
  • a3 derived from an acrylate ester group containing a polar group-containing aliphatic hydrocarbon group.
  • polar group examples include a hydroxyalkyl group in which at least one hydrogen atom of a hydroxyl group, cyano group, carboxy group, or alkyl group is substituted with a fluorine atom (hereinafter sometimes referred to as “fluorinated alkyl alcohol”).
  • fluorinated alkyl alcohol a fluorine atom
  • a hydroxyl group is 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). It is possible.
  • polycyclic group for example, many resins for resist compositions for ArF excimer lasers have been proposed and can be appropriately selected and used.
  • the structural unit is preferred.
  • the polycyclic group include groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as bicycloalkane, tricycloalkane, and tetracycloalkane.
  • 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.
  • these polycyclic groups a group obtained by removing two or more hydrogen atoms from adamantane, a group obtained by removing two or more hydrogen atoms from norbornane, a group obtained by removing two or more hydrogen atoms from tetracyclododecane, These groups are industrially 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 10 carbon atoms, a hydroxyethyl ester ester of acrylic acid is used.
  • a structural unit represented by the following formula (a3-1) and a structural unit represented by (a3-2) are preferred.
  • the structural unit represented by (a3-3) is preferred.
  • R is a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group, j is an integer of 1 to 3, k is an integer of 1 to 3, and t ′ is 1 to 3] An integer of 3,
  • halogen atom, lower alkyl group, or halogeno-lower alkyl group of R in the general formulas (a3-1) to (a3-3) is bonded to the ⁇ -position of the above acrylate ester. It is the same as the atom, lower alkyl group or halogenated lower alkyl group.
  • 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.
  • the hydroxyl group is preferably bonded to the 3rd position of the adamantyl group.
  • j is more preferably 1, particularly a hydroxyl group 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.
  • the proportion of constituent unit (a3) in component (A1) is based on the total constituent units constituting component (A1). , Preferably from preferred tool 40 mol 0/0 force 5 to 50 mole 0/0, preferably by 5 to 25 mole 0/0 Gasa et al.
  • the structural unit (a3) By containing the structural unit (a3) by setting it to the lower limit value or more, the above-described effects can be sufficiently obtained, and by setting it to the upper limit value or less, it is possible to obtain tolerance with other structural units.
  • the component (Al) includes other structural units (a4) other than the structural units (al) to (a3) as long as the effects of the present invention are not impaired.
  • the structural unit (a4) is not classified into the above structural units (al) to (a3)!
  • other structural units are not particularly limited. Many of them are known to be used in resist resins such as for ArF excimer laser and KrF excimer laser (preferably for ArF excimer laser). Things can be used.
  • 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.
  • R represents a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group.
  • the R halogen atom, lower alkyl group or halogenated lower alkyl group is bonded to the ⁇ - position of the acrylate ester to form V, And the same as a norogen atom, a lower alkyl group or a halogenated lower alkyl group.
  • the proportion of the structural unit (a4) should be 1 to 30 mol% with respect to the total of all the structural units constituting the component (A1). and more preferably is a preferred tool 10 20 mol 0/0! /,.
  • the component (A1) is a rosin component (polymer) whose alkali solubility is increased by the action of an acid, and is suitable as such a rosin component (polymer).
  • a rosin component polymer
  • it is a copolymer having the structural units (al), (a2), and (a3).
  • the structural units (al), (a2), and (a3) forces are also included.
  • the component (A) is particularly preferably a copolymer (A1-1) containing a combination of structural units represented by the following general formula (A1-1). ,.
  • R represents a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group.
  • R 2 is a lower alkyl group.
  • the halogen atom, lower alkyl group, or halogenated lower alkyl group of R in the formula (A1-1) is a halogen atom, lower alkyl group, or halogen atom that may be bonded to the ⁇ -position of the acrylate ester.
  • R is most preferably a hydrogen atom or a methyl group.
  • R 2 is a lower alkyl group, preferably a methyl group or an ethyl group.
  • component (A) as copolymer (A1-1), one type may be used alone, or two or more types may be used in combination.
  • the content of the copolymer (A1-1) in the component (A) is preferably 70% by mass or more, more preferably 80% by mass or more, and most preferably 100% by mass. . When it is at least the lower limit of the range, the lithography properties are further improved when a positive resist composition is obtained.
  • the component (A1) is obtained by polymerizing the monomer for deriving each structural unit by a known radical polymerization using a radical polymerization initiator such as azobisisobutyl-tolyl (AIBN). Obtainable.
  • a radical polymerization initiator such as azobisisobutyl-tolyl (AIBN).
  • component (A1) includes, for example, HS—CH—CH—CH—C (C
  • the mass average molecular weight (Mw) of the (Al) component is not particularly limited, but is preferably 2000 to 50000, more preferably 3000 to 30000 force ⁇ , 5000 ⁇ 20000 power is the most preferred! If it is smaller than the upper limit of this range, it is sufficiently soluble in a resist solvent to be used as a resist, and if it is larger than the lower limit of this range, dry etching resistance and resist pattern cross-sectional shape are good.
  • 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.
  • an alkali-soluble resin component other than the copolymer (A1-1) for example, other high molecular compounds used in conventional positive resist compositions can be used.
  • the content of the component (A1) should be adjusted according to the thickness of the resist film to be formed.
  • the component) includes an acid generator (B1) (hereinafter referred to as the component (B1)) composed of the compound represented by the general formula (bl-3).
  • R 41 , R 42 and R 43 ; n, n and n; X_ are the compounds of the first aspect of the present invention
  • the component (B) is soluble in general resist solvents such as propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), and lactate ethyl (EL).
  • PGME propylene glycol monomethyl ether
  • PGMEA propylene glycol monomethyl ether acetate
  • EL lactate ethyl
  • the component (B1) can be incorporated in a large amount in a resist composition used in a resist pattern forming method including an immersion exposure step and a step of forming a three-layer resist laminate. This is thought to be due to the high transparency (suppression of light absorption) in the exposure wavelength band (especially the wavelength band of ArF excimer laser).
  • the component (B) can be used alone or in combination.
  • the content of the component (B1) in the total component (B) is preferably 40% by mass or more, and more preferably 70% by mass or more. Preferably it is 100% by mass.
  • the resist pattern shape is good.
  • the lithography characteristics are improved.
  • matching with the lower layer film of the resist is good and footing of the resist pattern can be suppressed, which is preferable.
  • 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). It is most preferably 7 to 18 parts by mass.
  • 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). It is most preferably 7 to 18 parts by mass.
  • component (B) an acid generator (hereinafter referred to as component (B2)) other than component (B1) may be used in combination with component (B1). Good.
  • the component (B2) is not particularly limited as long as it is other than the component (B1), and those that have been proposed as acid generators for chemically amplified resists can be used.
  • acid generators include onium salt-based acid generators such as iodine salts and sulfo-um salts; oxime sulfonate-based acid generators; bisalkyl or bisarylsulfol-diazomethanes, There are various known diazomethane acid generators such as (bissulfol) diazomethanes; nitrobenzyl sulfonate acid generators; iminosulfonate acid generators; disulfone acid generators.
  • an acid generator represented by the following general formula (b-0) can be preferably used.
  • R 52 represents a hydrogen atom, a hydroxyl group, A halogen atom, a linear or branched alkyl group, a linear or branched alkyl halide group, or a linear or branched alkoxy group; R 53 has a substituent.
  • u is an integer from 1 to 3.
  • R 51 represents a linear, branched or cyclic alkyl group, or a straight, 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. Good.
  • 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 linear or branched fluorinated alkyl group has 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. Most preferred.
  • the cyclic fluorinated alkyl group is preferably 4 to 12 carbon atoms, preferably 5 to carbon atoms, more preferably 6 to LO, most preferably LO.
  • the fluorination rate of the fluorinated alkyl group (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%. In particular, all hydrogen atoms substituted with fluorine atoms are preferred because the strength of the acid is increased.
  • R 51 is most preferably a linear alkyl group or a linear fluorinated alkyl group.
  • R 52 represents a hydrogen atom, a hydroxyl group, a halogen atom, a linear or branched alkyl group. , A linear or branched alkyl halide 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 among them, a fluorine atom is preferred.
  • the alkyl group is linear or branched, and the carbon number thereof is preferably 1 to 5, more preferably 1 to 4, and most preferably 1 to 3.
  • the halogenated alkyl group is a group in which at least one or all of the hydrogen atoms in the alkyl group are substituted with a halogen atom.
  • the alkyl group herein are the same as the “alkyl group” in 2 above.
  • the halogen atom to be substituted are the same as those described above for the “halogen atom”.
  • 50 to 100% of the total number of hydrogen atoms are preferably substituted with halogen atoms, more preferably all are substituted.
  • the alkoxy group is linear or branched, and the carbon number thereof is preferably 1 to 5, more preferably 1 to 4, and most preferably 1 to 3.
  • hydrogen atom is the most preferred as R 52 .
  • R 53 is an aryl group which may have a substituent, and the structure of the basic ring (matrix ring) excluding the substituent includes a naphthyl group, a phenyl group, an anthracyl group, and the like.
  • a phenyl group is preferred.
  • substituents examples include a hydroxyl group and a lower alkyl group (straight or branched chain, preferably having 1 to 5 carbon atoms, and more preferably a methyl group). Monkey.
  • aryl group for R 53 those having no substituent are more preferable.
  • u is an integer from 1 to 3, preferably 2 or 3, and more preferably 3.
  • 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.
  • R 5 and R 6 each independently represents an aryl group or an alkyl group;
  • R 4 " represents a linear, branched or cyclic alkyl group or a fluorinated group. Represents an alkyl group; at least one of R lw to R 3 ′′ represents an aryl group, and at least one of R 5 ′′ and R 6 ′′ represents an aryl group.
  • to each independently represents an aryl group or an alkyl group. At least one of R to “represents an aryl group. Of,, to”, two or more are preferably aryl groups. R lw to R 3 ”are all aryl groups. Most preferred
  • the aryl group of R lw to R 3 is not particularly limited, for example, an aryl group having 6 to 20 carbon atoms, in which at least one or all of the hydrogen atoms are alkyl groups, It may or may not be substituted with an alkoxy group, a halogen atom, etc.
  • an aryl group an aryl group having 6 to 10 carbon atoms is preferred because it can be synthesized at low cost. That's right.
  • 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. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, nor group, deoxy group, Examples thereof include a force group. Among these, a methyl group is most preferable because it is excellent in resolution from the viewpoint of excellent resolution and is preferably 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, more preferably 1 to 8 carbon atoms, and most preferably 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 linear or branched fluorinated alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. Most preferred.
  • the cyclic fluorinated alkyl group preferably has 4 to 15 carbon atoms, preferably 4 to carbon atoms, more preferably 6 to LO, and most preferably LO. Further, the fluorination rate of the fluorinated alkyl group (ratio of fluorine atoms in the alkyl group) is preferably 10 to 100%, more preferably 50 to 100%. Those substituted with a nitrogen atom are preferred because the strength of the acid increases.
  • R 4 ′′ is most preferably a linear or cyclic alkyl group, or a linear or cyclic 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. All of R 5 “and R 6 " are preferably aryl groups! /.
  • Examples of the aryl group of R 5 "and R 6 " include those similar to the aryl groups of,, ⁇ .
  • alkyl group for R 5 ′′ and R 6 ′′ the same as the alkyl groups for R 1w to R 3 ′′ can be used.
  • R 5 ′′ and R 6 ′′ are most preferably a phenol group.
  • Those similar to - "(1 b) R 4 in the formula is as" the like R 4 of formula (b-2) in.
  • sodium salt acid generator represented by the formulas (b-1) and (b-2) include difluoro-rhodonium trifluoromethanesulfonate or nonafluorobutanesulfonate.
  • 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 anion part is replaced with a caron part represented by the general formula (b-3) or (b-4).
  • a -um salt-based acid generator can also be used (the cation moiety is the same as (b-1) or (b-2)).
  • the oxime sulfonate 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 an atom other than a carbon atom (for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (a fluorine atom, a chlorine atom, etc. ) Etc.).
  • the organic group for R 31 is preferably a linear, branched or cyclic alkyl group or aryl group. These alkyl groups and aryl groups may have a substituent.
  • the place The substituent is not particularly limited, and examples thereof include a fluorine atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms.
  • “having a substituent” means that at least one or all of the hydrogen atoms of the alkyl group or aryl group as the organic group of R 31 are substituted with a substituent.
  • alkyl group as the organic group of R 31 carbon number 1 to 20 is preferable: LO power 1 to 8 carbon is more preferable 1 to 6 is more preferable A preferred carbon number of 1-4 is most preferred.
  • a partially or completely halogenated alkyl group is particularly preferable.
  • the partially halogenated alkyl group means an alkyl group in which at least one of the hydrogen atoms is replaced by a halogen atom, and the fully halogenated alkyl group means that all of the hydrogen atoms are halogenated.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine 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 as the organic group of R 31 is preferably 4 to 20 carbon atoms, preferably 4 to 20 carbon atoms, more preferably 6 to LO, or more preferably LO.
  • a partially or completely halogenated aryl group is particularly preferable.
  • the partially halogenated aryl group means an aryl group in which at least one of the hydrogen atoms is replaced with a halogen atom, and the fully halogenated aryl group means that all of the hydrogen atoms are halogen atoms.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable.
  • 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.
  • organic group for R 32 a linear, branched, or cyclic alkyl group, aryl group, or cyan group is preferable.
  • 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.
  • 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 33 represents a cyano group, an alkyl group having no substituent, or a halogenalkyl group.
  • R 34 is an aryl group.
  • R 35 represents an alkyl group having no substituent or a halogenated alkyl group.
  • R 36 represents a cyano group, an alkyl group having no substituent, or a halogenalkyl 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. p "is 2 or 3.]
  • 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.
  • the halogen atom in the halogenoalkyl group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • R 33 is more preferably a fluorinated alkyl group, preferably a halogenated alkyl group.
  • the fluorinated alkyl group in R 33 is preferably 50% or more of the hydrogen atom of the alkyl group, more preferably 70% or more, more preferably 90% or more. preferable.
  • the aryl group of R 34 includes an aromatic hydrocarbon such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthracyl group, a phenanthryl group, and the like.
  • Ring force A group in which one hydrogen atom has been removed, and part of the carbon atoms constituting the ring of these groups is substituted with a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom.
  • a roaryl group 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 having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
  • a substituent such as an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
  • the halogen atom in the halogenalkyl group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the alkyl group or halogenialkyl group in the substituent is more preferably 1 to 4 carbon atoms, preferably having a carbon number strength of 8 to 8.
  • 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.
  • the halogen atom in the halogenated alkyl group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • R 35 is more preferably a fluorinated alkyl group, preferably a halogenated alkyl group.
  • the fluorinated alkyl group in R 35 is preferably fluorinated with 50% or more of the hydrogen atoms of the alkyl group being preferred, more preferably 70% or more, and even more preferably 90% or more. Force This is preferable because the strength of the acid generated increases. Most preferred is a fully fluorinated alkyl group in which the hydrogen atom is 100% fluorine-substituted.
  • the alkyl group or halogenated alkyl group having no substituent of R 36 is an alkyl group or a substituent having no substituent of R 33. 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, ex- ( ⁇ -black benzenesulfo-oxyoximino) —Benzyl cyanide, ⁇ - (4-Nitrobenzenesulfo-ruximino) —Benzyl cyanide, 4-trotro 2 trifluoromethylbenzenesulfo-ruximino) Benzyl cyanide, ⁇ - (Benzenesulfo-ruximino) —4—Chloro Oral bendyl cyanide, ⁇ (Benzenesulfo-loxyimino) — 2, 4 Dicndiyl cyanide, ⁇ — (Benzenesulfo-Luoxyimino) — 2, 6 Dicndiyl cyanide, ⁇ (Benzenesulfo-L
  • bisalkyl or bisarylsulfol diazomethanes include bis (isopropylsulfol) diazomethane, bis (p toluenesulfol) diazomethane, bis (1 , 1-dimethylethylsulfol) diazomethane, bis (cyclohexylsulfol) diazomethane, bis (2,4 dimethylphenylsulfol) diazomethane, and the like.
  • 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.
  • one type of acid generator may be used alone, or two or more types may be used in combination.
  • the content of the component (B) in the resist composition of the present invention is 0.5 to 30 parts by mass, preferably 1 to 20 parts by mass with respect to 100 parts by mass of the component (A).
  • pattern formation is sufficiently performed. Further, it is preferable because a uniform solution can be obtained and the storage stability becomes good.
  • the resist composition of the present invention may further include any desired resist pattern shape, post ex posure stability of the latent image rormed by the pattern-wise exposure of the resist layer, etc. It is preferable to contain a nitrogen-containing organic compound (D) (hereinafter referred to as “component (D)”) as a component.
  • component (D) 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.
  • the “aliphatic cyclic group” means a monocyclic group or polycyclic group having no aromaticity.
  • an aliphatic amine at least one hydrogen atom of ammonia NH has 1 or more carbon atoms.
  • Examples include amines substituted with up to 12 alkyl groups or hydroxyalkyl groups (alkylamines or alkylalcoholamines) or cyclic amines.
  • alkylamines and alkylalcoholamines include monoalkylamines such as n-xylamine, n-ptylamine, n-octylamine, n-norlamin, n-decylamine; jetylamine, di-n-propylamine, di-n Dialkylamines such as ptylamine, di-n-octylamine, dicyclohexylamine; —Trialkylamines such as otylamine, tri-n-noramine, tri-n-de-ramine, tri-n-dodecylamine; diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine Emissions, di one n- O click pentanol ⁇ Min, alkyl alcohols ⁇ Min and triethylene one n- Okutanoru Amin like. Among these, tri-n-pentylamine having 5 to 10
  • Examples of the cyclic amine include heterocyclic compounds containing a nitrogen atom as a hetero atom.
  • the heterocyclic compound is a monocyclic compound (aliphatic monocyclic amine). May also be polycyclic (aliphatic polycyclic ammine).
  • aliphatic monocyclic amine examples include piperidine and piperazine.
  • Aliphatic polycyclic amines having 6 to 10 carbon atoms are preferred. Specifically, 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 resist composition of the present invention prevents sensitivity deterioration, resist pattern shape, and placement.
  • Stable stability ⁇ post exposure stability of the latent image formed by the pattern-wishes exposure of the resist layer), etc., as optional components, organic carboxylic acids, phosphorus oxoacids and their derivatives Powerful group force It is possible to contain at least one compound (E) (hereinafter referred to as component (E)) to be selected.
  • 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 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.
  • Examples of the phosphonic acid derivatives include phosphonic acid esters such as phosphonic acid dimethyl ester, phosphonic acid diol n-butenoresestenole, phenolinophosphonic acid, phosphonic acid diphenolinoestenole, and phosphonic acid dibenzyl ester.
  • phosphonic acid esters such as phosphonic acid dimethyl ester, phosphonic acid diol n-butenoresestenole, phenolinophosphonic acid, phosphonic acid diphenolinoestenole, and phosphonic acid dibenzyl ester.
  • phosphinic acid esters such as phenol phosphinic acid Is mentioned.
  • one type may be used alone, or two or more types may be used in combination.
  • component (E) 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 resist composition of the present invention further contains, if desired, miscible additives such as an additional resin for improving the performance of the resist film, a surfactant for improving the coating property, and dissolution.
  • miscible additives such as an additional resin for improving the performance of the resist film, a surfactant for improving the coating property, and dissolution.
  • An inhibitor, a plasticizer, a stabilizer, a colorant, an antihalation agent, a dye, and the like can be appropriately added.
  • the resist composition of the third aspect (aspect) of the present invention can be produced by dissolving the material in an organic solvent (hereinafter sometimes referred to as (S) component).
  • 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 lactic acid ethyl
  • y-butyrolatone are preferred.
  • 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 above-mentioned mixed solvent of PGMEA and PGME and the mixed solvent of ⁇ -butyrolattone are also preferred.
  • 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 resist composition of the present invention can be suitably used as a resist composition for immersion exposure in a resist pattern forming method including an immersion exposure step, and good lithography characteristics can be obtained.
  • the resist composition of the present invention can be suitably used as a positive resist composition for forming an upper resist film in a resist pattern forming method including a step of forming a three-layer resist laminate. Good lithographic properties can be obtained.
  • a compound acid generator (B1) is used to effectively suppress light absorption in the exposure wavelength band (especially the ArF excimer laser wavelength band) and to dissolve various components of the resist. In other words, the solubility in organic solvents (resist solvents) is excellent. Therefore, in the resist composition of the present invention, it is considered that the light absorption is suppressed by blending the component (B1) and the transparency of the resist composition is increased.
  • the component (B1) has good dispersibility in the resist film and is more uniformly distributed in the resist film than a conventional acid generator. For this reason, it is presumed that the acid generated from the component (B1) by exposure can diffuse more uniformly in the resist film than when a conventional acid generator is used.
  • the resist composition of the present invention can be suitably used as a resist composition for immersion exposure in a resist pattern forming method including an immersion exposure step, and good lithography characteristics can be obtained.
  • a resist pattern forming method including a step of forming a three-layer resist laminate it can be suitably used as a positive resist composition for forming an upper resist film, and good lithographic properties are expected to be obtained. .
  • lithography such as line width roughness (LWR), resist pattern shape (especially resist pattern surface roughness), mask error factor (ME F), exposure margin (EL margin), etc. Resist patterns with good characteristics can be formed.
  • LWR line width roughness
  • ME F mask error factor
  • EL margin exposure margin
  • the MEF is a parameter that indicates how faithfully a mask pattern of different size can be reproduced when the mask size (line width and space width) is changed with the same exposure amount and a fixed pitch. Yes, the closer the MEF value is to 1, the better the mask reproducibility.
  • the EL margin is a parameter indicating the amount of change in the pattern size accompanying the change in exposure amount. The larger the value, the smaller the amount of change.
  • the resist pattern forming method of the present invention is the resist of the third aspect (aspect) of the present invention. Forming a resist film on a substrate using a composition, exposing the resist film, and developing the resist film to form a resist pattern.
  • Examples of the resist pattern forming method of the present invention include a resist pattern forming method including a liquid immersion exposure (immersion lithography) step and a resist pattern forming method including a step of forming a three-layer resist laminate. is there. These will be described next.
  • the resist composition according to the third aspect (aspect) of the present invention (hereinafter sometimes referred to as a resist composition for immersion exposure) on a substrate such as silicon wafer is used as a spinner or the like.
  • a pre-beta (post-apply beta (PAB) treatment) is performed to form a resist film.
  • an organic or inorganic antireflection film may be provided between the substrate and the coating layer of the resist composition to form a two-layer laminate.
  • a top coat can also be provided on the resist film.
  • the topcoat is not particularly limited, and those usually used for immersion exposure can be used.
  • a chain alkylene group, and R 5 is a fluorinated alkyl group.
  • CO—O—R 7 (where R 7 is a fluorinated alkyl group)
  • a protective film formed from a composition dissolved in the aqueous solution a composition dissolved in the aqueous solution.
  • main-chain cyclic type of resin means that the structural unit constituting the resin has a monocyclic or polycyclic ring structure, and preferably at least one on the ring of the ring structure, preferably Means that two or more carbon atoms have a constituent unit constituting the main chain (hereinafter referred to as “main-chain cyclic constituent unit”).
  • main chain cyclic structural unit examples include a structural unit derived from polycycloolefin (polycyclic olefin), a dicarboxylic acid anhydride-containing structural unit, and the like. Among them, it is preferable to have a structural unit derived from polycycloolefin (polycyclic olefin, preferably norbornene, etc.) in the main chain.
  • the topcoat provided on the resist film is preferably soluble in an alkali developer. The steps so far can be performed using a known method. The operating conditions and the like are preferably set as appropriate according to the composition and characteristics of the resist composition for immersion exposure to be used.
  • the resist film obtained above is selectively subjected to immersion exposure (Liquid exposure) via a desired mask pattern. Immersion Lithography). At this time, the solvent between the resist film (or top coat) and the lens at the lowest position of the exposure apparatus is larger than the refractive index of air and has a refractive index.
  • the wavelength used for the exposure is not particularly limited, and can be performed using radiation such as an ArF excimer laser, a KrF excimer laser, or an F laser. Immersion exposure according to the present invention
  • the resist yarn composition is effective for KrF excimer laser or ArF excimer laser, especially ArF excimer laser.
  • the space between the resist film (or top coat) and the lens at the lowest position of the exposure apparatus is filled with the immersion medium, and exposure is performed in this state ( Immersion exposure) is performed.
  • a solvent having a refractive index larger than that of air and having a refractive index of a resist film formed by using a resist composition for immersion exposure is preferable.
  • the refractive index of the solvent is not particularly limited as long as it is within the above range.
  • Examples of the solvent having a refractive index larger than the refractive index of air and smaller than the refractive index of the resist film include water, a fluorine-based inert liquid, a silicon-based solvent, and the like.
  • fluorinated inert liquid examples include C HC1 F
  • Examples include liquids mainly composed of fluorine-based compounds such as HF, and boiling point of 70 to 180 ° C.
  • the thing of 80-160 degreeC is more preferable. If the fluorinated inert liquid has a boiling point within the above range, it is preferable that the medium used for immersion can be removed by a simple method after the exposure is completed.
  • perfluorinated alkyl compound in which all the hydrogen atoms of the alkyl group are replaced with fluorine atoms is particularly preferred! /.
  • perfluorinated alkyl compounds include perfluoroalkyl ether compounds and perfluoroalkyl compounds. And amine compounds.
  • examples of the perfluoroalkyl ether compound include perfluoro (2-butyl monotetrahydrofuran) (boiling point: 102 ° C.).
  • examples of the perfluoroalkylamine compound include perfluoroalkylamine compounds. Fluorotributylamine (boiling point 174 ° C).
  • the resist composition of the present invention is particularly sensitive to water and has excellent sensitivity and resist pattern profile shape
  • water is preferably used as a solvent having a refractive index greater than the refractive index of air. It is done. Water is also preferable from the viewpoints of cost, safety, environmental problems, and versatility.
  • post-exposure heating post exposure beta (PEB) treatment
  • PEB post exposure beta
  • an alkaline developer composed of an alkaline aqueous solution.
  • water rinsing is performed using pure water.
  • water is dropped or sprayed on the surface of the substrate while rotating the substrate to wash away the developing solution on the substrate and the resist composition for immersion exposure dissolved by the image solution.
  • drying is performed to obtain a resist pattern in which a resist film (a coating film of a resist composition for immersion exposure) is patterned in a shape corresponding to the mask pattern.
  • the resist pattern forming method including the step of forming a three-layer resist laminate, a lower organic film that can be dry-etched is formed on a substrate, and a material containing an S source element is applied to the lower organic film and heated. Forming an intermediate layer on the intermediate layer, forming an upper resist film on the intermediate layer using the resist composition according to the third aspect of the present invention, and forming a three-layer resist laminate; and Exposing the resist film, developing the upper resist film, and forming a resist pattern.
  • the compound was analyzed by 3 ⁇ 4 NMR.
  • Solubility of the above compounds (bl-31), (bl-34), (bl-40) and di (1 naphthyl) phenol rufomunonafluorobutanesulfonate ((B) -2) was evaluated as follows.
  • the propylene glycol monomethyl ether acetate (PGMEA) solution, propylene glycol monomethyl ether (PGME) solution, and ethyl lactate (EL) solution of each compound were prepared by changing the concentration. After the adjustment, each solution was stirred to measure the concentration at which each acid generator was completely dissolved.
  • Polymer (A) -1 of component (A) used in Examples 5 to 7 and Comparative Example 1 is shown below.
  • Polymer (A) -1 was synthesized by the following procedure. That is, PGMEA was placed in a flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer under a nitrogen atmosphere, and the temperature of the hot water bath was raised to 80 ° C while stirring.
  • the resulting reaction solution was then added dropwise to about 30 times the amount of methanol with stirring to give a colorless precipitate.
  • the resulting precipitate was filtered off and the precipitate was used as a single unit for the polymerization.
  • the body was washed in about 30 times the amount of methanol.
  • the precipitate was filtered off and dried under reduced pressure at 50 ° C. for about 40 hours to obtain polymer (A) -1.
  • the mass average molecular weight (Mw) and dispersity (MwZMn) of the following polymer (A) -1 are also shown.
  • the mass average molecular weight (Mw) and dispersity (MwZMn) were determined on the basis of polystyrene conversion by gel permeation chromatography (GPC).
  • composition ratio was calculated by carbon NMR.
  • the number attached to the lower right of the structural unit indicates the ratio (mol%) of each structural unit in the polymer.
  • a resist pattern was formed using the obtained positive resist composition solution, and the following lithographic characteristics were evaluated.
  • An organic antireflective coating composition “ARC29A” (trade name, manufactured by Brew Science Co., Ltd.) was applied onto an 8-inch silicon wafer using a spinner, and baked on a hot plate at 205 ° C. for 60 seconds. Then, an organic antireflection film having a thickness of 77 nm was formed. Then, the positive resist composition solution obtained above is applied onto the antireflection film using a spinner, and the plate is exposed on a hot plate at 110 ° C. for 60 seconds. A PAB) treatment was performed and dried to form a resist film with a thickness of 150 nm.
  • PEB post-exposure heating
  • TMAH Umuhidorokishido
  • the resist compositions of Examples 5 to 6 and Comparative Example 1 were applied to a resist pattern forming method including the step of forming a three-layer resist laminate and evaluated.
  • a resist laminate was manufactured by the following procedure, and a resist pattern was formed using the resist laminate.
  • a base material solution containing novolak resin is applied onto an 8-inch silicon wafer using a spinner, and soft beta is applied at 230 ° C for 90 seconds to form a lower organic film with a thickness of 270 nm. Formed.
  • a composition for forming a hard mask (feryl silsesquioxane Z hydrogen silsesquioxane / methyl silsesquioxane / methyl silsesquioxane propionate copolymer) on the lower layer is mixed with PGMEA and EL (mass the ratio 6Z4) by dissolving the ones (solid content concentration 2.5 wt 0/0) was applied using a spinner, soft 90 seconds at 90 ° C and beta treatment, followed by 90 seconds at 250 ° C beta By processing, a hard mask layer (intermediate layer) with a thickness of 30 nm was formed.
  • a positive resist layer (upper layer resist film) with a film thickness of 150 nm is formed by performing a beta (PAB) treatment and drying to obtain a resist layered body in which a three-layer resist layer is laminated on the substrate. It was.
  • PAB beta
  • the resist pattern obtained by applying the resist composition of Examples 5 and 6 according to the present invention to a resist pattern forming method including the step of forming a three-layer resist laminate was obtained by It was confirmed that the xantine hard mask forming yarn and the mating with the intermediate layer having a good strength were good and the footing of the resist pattern was suppressed.
  • a novel compound suitable as an acid generator for a resist composition an acid generator comprising the compound, a resist composition containing the acid generator, and a resist pattern using the resist composition A forming method is provided. Therefore, the present invention is extremely useful in industry.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials For Photolithography (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne une composition de réserve contenant un composant de base (A), dont la solubilité en milieu alcalin varie par l'action d'un acide, et un composant générateur d'acide (B), qui génère un acide lorsqu'il est exposé à la lumière. Le composant générateur d'acide (B) contient un générateur d'acide (B1) composé d'un composé représenté par la formule générale (b1-3) ci-dessous. Dans la formule, R41, R42 et R43 représentent indépendamment un groupe alkyle, un groupe acétyle, un groupe alcoxy, un groupe carboxy ou un groupe hydroxyalkyle; n1 représente un entier allant de 0 à 3, n2 représente un entier allant de 0 à 3 et n3 représente un entier allant de 0 à 2, pourvu que n1, n2 et n3 ne sont pas égaux à 0 en même temps; et X-* représente un anion.
PCT/JP2007/063290 2006-07-24 2007-07-03 Composé, générateur d'acide, composition de réserve et procédé pour former un motif de réserve WO2008013030A1 (fr)

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JP6228353B2 (ja) * 2009-12-10 2017-11-08 ローム アンド ハース エレクトロニック マテリアルズ エルエルシーＲｏｈｍ ａｎｄ Ｈａａｓ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ ＬＬＣ 光酸発生剤およびこれを含むフォトレジスト
JP6482344B2 (ja) * 2015-03-24 2019-03-13 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、酸発生剤及び化合物
JP6482342B2 (ja) * 2015-03-24 2019-03-13 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、光反応性クエンチャー及び化合物
KR102455650B1 (ko) * 2015-03-24 2022-10-17 도오꾜오까고오교 가부시끼가이샤 레지스트 조성물, 레지스트 패턴 형성 방법, 산 발생제, 광 반응성 퀀처 및 화합물
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